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Why Hydrogen Energy and Fuel Cell!

Changes in temperature, sea level and Northern Hemisphere snow cover Source: IPCC.

Reason for this is Green House Gas (GHG) Emission Global anthropogenic GHG emissions Source: IPCC

Open-ended energy systems: GHG emission

Quality of Life vs. Energy Usage

Trend in Crude Discoveries, Consumption and Price with Time

Crude oil Discoveries

Year
1960 1980 2000 2020

G bbl/Year
60 30 10 5 X 10 19 J /year 25 120 160 200 US$ / bbl (5.74 GJ) 20 55 30 ?

Crude oil Consumption

Year 1960 1980 2000 2020

Crude Oil Price Note: crude price is highly fluctuating in last few years. 2008/09 - US$ 142 / bbl. In 2010, US$ 65 / bbl bbl: barrels of oil equivalent

Year 1960 1980 2000 2020

Look for Alternatives ! Natural Gas Biomass Solar Water Nuclear H2

Generation Transportation Storage Dispensing Fuel cell

Energy Consumption in Different Types of Passenger Cars

Type

Energy consumption, kJ/km


Well-totank TanktoWell-to-wheel wheel 2777 2314 2834 2136 1915 1543 1615 1653 1157 1111 3471 2691 3257 3560 2394 1794 1856 2755 1928 1851

Gasoline ICE Diesel ICE CNG ICE H2 ICE Gasoline HEV ICE-

694 377 423 1424 479 251 241 1102 771 740

Diesel ICE-HEV CNG-ICE-HEV H2 ICE-HEV H2 FC H2 FC-HEV

Carbon Dioxide Emission From Different Types of Passenger Cars

Fuel Cell Makes Sense Closed Hydrogen Energy System: Min GHG Emission

Fuel Cell

History, Principle & Overview of Fuel Cells



Fuel cell is a device that takes fuel as input and produces electricity as output Converts chemical energy of raw materials into electrical energy Different from battery - A fuel cell will keep on producing electricity as long as fuel is available Similar to a chemical factory which transforms raw material(fuel) into final product (electricity)

A simple fuel cell

Electrochemical half reactions of a H2-O2 fuel cell:

Electrons transferred from the fuel travel through the external circuit (thus constituting an electric current) and do useful work before they complete the reaction Spatial separation achieved by an electrolyte, a material which allows ions to flow but not electrons

Fig: A simple fuel cell with platinum electrodes dipped in sulphuric acid ( an aqueous acidic electrolyte) Basic fuel cell operations

1. 2. 3. 4.

Reactant transport Electrochemical reaction Ionic and electronic conduction Product removal

Advantages

More efficient than combustion engines directly convert chemical energy to electrical energy Mechanically ideal no moving parts , good reliability, long lasting systems Clean and silent operation Easy independent scaling between power (determined by fuel cell size) and capacity ( determined by fuel availability)

Disadvantages

Cost a major issue Fuel availability and storage Durability under stop-start cycles Low volumetric power densities as compared to batteries and combustion engines

Power density comparison of various technologies

Fuel cell and Hydrogen economy : H2 fuel cells coupled with electrolyzers and renewable energy conversion technologies provide a completely closed loop, pollution free energy economy. A schematic of this scheme is shown in fig 1.4.

Types of fuel cells Classification based on type of electrolyte

1. 2. 3. 4. 5.

Phosphoric acid fuel cell (PAFC) Polymer electrolyte membrane fuel cell (PEMFC) Alkaline fuel cell (AFC) Molten carbonate fuel cell (MCFC) Solid oxide fuel cell (SOFC)

Major fuel cell technologies PEMFC Electrolyte Charge carrier PAFC AFC MCFC SOFC

Polymer Liquid KOH Molten Liq.H3PO4immobilized Ceramic Membrane Immobilized carbonate H+ H+ 2000C Platinum H2 OH60-2000C Platinum H2 CO326500C Nickel H2 ,CH4 O265010000C Perovskites H2 ,CH4,CO

Operating 800C Temperature Catalyst Platinum Fuel H2, Compatibility methanol Different Types of Fuel Cells

Basu, S. (Ed.) Recent Trends in Fuel Cell Science and Technology, Springer (2007) Fuel Cell Component

Schematic of Proton Exchange Membrane Fuel Cell

Note the flow of fuel,oxidant, products, ions and electrons through the different components of PEMFC

Polymer Electrolyte Membrane Fuel Cell

Basu, S. (Ed.) Recent Trends in Fuel Cell Science and Technology, Springer (2007) Fuel cell performance

Fuel cell performance can be assessed by current-voltage curves. i-V curves show the voltage output of a fuel cell for a given current load. Ideal fuel cell performance is dictated by thermodynamics Real fuel cell performance is always less than ideal fuel cell performance due to losses. The major types of loss are : 1. Activation loss (losses due to electrochemical reaction)

2. Ohmic loss (losses due to ionic and electronic conduction) 3. Concentration loss (losses due to mass transport)

Combined fuel cell i-V and power density curve

Fuel cell power density increases with increasing current density, Reaches a maximum, and then falls at still higher current densities. Fuel cells are designed to operate at or below the power density maximum. At current densities below the power density maximum, voltage efficiency improves but power density falls. At current densities above the power density maximum, both voltage efficiency and power density fall.

Fuel Cells Types and Chemistry


Alkaline fuel cell (AFC) Anode (Pt/C)

Cathode (Pt/C)

First used in space shuttle by NASA 60% efficiency between 150 200 deg C operating temp. Electrode poisoning is observed in presence of OH-

Proton Exchange Membrane Fuel Cells (PEMFC)

Anode (Pt/C):

Cathode (Pt/C):

Uses a solid polymer electrolyte, usually perfluorosulfonic acid (nafion) membrane. Membrane electrode assembly (MEA ) consists of the anode, cathode, proton exchange membrane (PEM) and gas diffusion layers (GDLs). Nafion allows transport of protons while blocks electrons. Membrane should remain hydrated for efficient transport of protons, and hence PEMFCs cant be operated at higher temperatures Electrode poisoning in presence of OH-

Phosphoric Acid Fuel Cell (PAFC)

Operating principle is similar to that of a PEMFC Phosphoric acid is the electrolyte used, which conducts protons and has good thermal stability Operating temperature varies between 175 200 deg C Used for heavy vehicles such as buses and trucks

Direct Alcohol Fuel Cell (DAFC)

Anode (Pt/C) Cathode (Pt/C) Uses lighter alcohols such as methanol or ethanol instead of hydrogen Can be operated at lower temperatures; 40 80 deg C Might be useful for future portable devices such as laptops, calculators

Molten Carbonate Fuel Cell (MCFC)

Anode (Ni)

Cathode (NiO2)

Molten carbonate salt is used as electrolyte Operates at higher temp., around 650 deg C Hydrocarbons can also be used as fuel, where internal reforming produces H2

Schematic of MCFC

Note the flow of fuel,oxidant, products, ions and electrons through the different components of MCFC Solid Oxide Fuel Cell (SOFC)

Anode (Ni/YSZ)

Cathode (Perovskite/LaMnO3)

Uses hard ceramic electrolyte crystal lattice Operates at higher temp.; 750 1000 deg C O2- migrates through crystal at this high temp. High efficiency upto 60% can be reached Natural gas can be used as a fuel due to internal reforming at this temp.

Schematic of SOFC

Note the flow of fuel,oxidant, products, ions and electrons through the different components of SOFC Regenerative Fuel Cells (RFC)

Water is electrolysed using solar cell Solar energy can be stored as hydrogen, which can be used during night Can be useful for space applications Electrolyser:

Electrolyser:

Anode (Pt/C):

Cathode (Pt/C):

Alkaline fuel cell (AFC) The working principle of an alkaline fuel cell is shown schematically in fig. 1. The alkaline fuel cell generally operates on hydrogen and oxygen gases. The solution of potassium hydroxide in water is used as the electrolyte. At the anode, hydrogen gas reacts with the OH- ions to produce water and electrons. Electrons generated at the anode conduct through a load connected to an external circuit and migrate towards cathode.

Fig.1. Alkaline fuel cell These electrons at cathode react with oxygen and water to produce hydroxyl ions, which diffuse through the electrolyte and reaches anode. The reactions in the AFC are given below

The efficiency of an alkaline fuel cell is about 60% (4) when the operating temperature is about 150 oC to 200 oC. Alkaline fuel cell was first used by NASA in Apollo space shuttle. It was fuelled by hydrogen and oxygen for the power generation while the astronauts used the reaction byproduct, water for drinking purposes. The typical life of a 2 KW AFC is about 5000 hrs. The electrode gets eventually poisoned in the presence of OH- and carbonate is formed in the presence of CO2 in air. Because of these reasons, AFC faces tremendous challenges for its commercialization. The problem of alkaline electrolyte is handled by replacing it with perfluorosulphonic acid membrane, which is discussed in the next section. However, there exists a possibility of poisoning the anode catalyst and the formation of carbonates in the presence of CO2 (5). This problem is tackled by re-circulating the electrolyte after removing the carbonate and the heat of reaction. Recently, many investigators (6) are looking at the possibility of using alcohol as fuel directly feeding it to alkaline fuel cell to generate power. Proton Exchange Membrane Fuel Cells (PEMFC) The proton exchange membrane (PEM) fuel cell as shown in fig. 2, uses a solid polymer electrolyte (perfluorosulphonic acid membrane) in the form of a thin, permeable sheet for the transport of proton (7). Generally, platinum, Pt-black or Pt/Ru catalyst is used as anode and cathode catalysts respectively.

Fig. 2. Proton exchange membrane fuel cell The proton exchange membrane is sandwiched between anode and cathode catalyst, which is pasted on gas diffusion layer made of carbon cloth or paper. The composite structure of gas diffusion layer, anode, proton exchange membrane, cathode and gas diffusion layer is known as membrane electrode assembly (MEA) and is the heart of polymer electrolyte membrane fuel cell. Gas diffusion layer works as substrate for catalyst and ensure the proper distribution of reactants over the catalyst. Hydrogen molecules are stripped at the anode electrode-catalyst into electrons and protons (H+). Electrons are collected at low resistance material, which helps to conduct the electrons from the fuel cell to the outer circuit. This low resistance material is known as the bipolar plate made of graphite and it has channels to supply the reactants over the diffusion layer both on the anode and cathode sides (Fig 2). The protons permeate through membrane and reaches cathode side, where it reacts with oxygen and conducted electrons from the outer circuit to produce water. The proton exchange membrane made of perfluorosulphonic acid allows proton to pass through it and restricts the passage of electrons. The migration of proton in membrane is promoted by sulphonate group present in polytetrafluoroethylene membrane structure through the formation of hydronium ion. Thus, the membrane needs to be hydrated for efficient transport of proton in the form hydronium ion. Moreover, the PEM fuel cell cannot be operated above 80oC because of the water loss from the membrane and subsequent poor conduction of proton. The reaction scheme for proton exchange membrane is shown below:

Phosphoric Acid Fuel Cells (PAFC) The reactions occurring on the anode and cathode are similar to PEMFC as given in equations 4 to 6. A PAFC as shown in fig. 3 consists of an anode and a cathode made of finely dispersed platinum catalyst on carbon and the electrolyte is housed in silicon carbide structure.

Fig.3. Phosphoric acid fuel cell The electrolyte is an inorganic acid, concentrated phosphoric acid (100%), which is like the membranes in PEMFC, conducts proton. Phosphoric acid (H3PO4) is the only common inorganic acid that has enough thermal stability, and very low volatility (150oC) to be considered as an electrolyte for fuel cells (8). The pure 100% phosphoric acid has a freezing point of 42oC, which restricts the operation below this temperature. The operating temperature of the PAFC is in the range of 175oC to 200oC. This was the most commercially developed fuel cell at one point of time. However, the advancement of PEMFC decreased its value in the market. The phosphoric acid fuel cell can be used in large vehicles, such as buses and trucks. Direct Alcohol Fuel Cells (DAFC) The direct alcohol fuel cell (DAFC) is a variant of PEM cell. The direct alcohol fuel cell uses lighter alcohols like methanol or ethanol instead of hydrogen gas. The alcohols dissociate to electrons, hydrogen ions and carbon dioxide at the anode. The positively charged hydrogen ions diffuse from anode to cathode through the polymer electrolyte membrane and electrons migrate toward the cathode through an external circuit. At the cathode, the electrons, hydrogen ions and oxygen from the air react to form water. The reactions involved in direct methanol fuel cell are shown below (9):

The direct alcohol fuel cells are operated at lower temperature (40 oC - 80oC) and thought to be power source in future for portable equipments like laptop, calculator etc. Molten Carbonate Fuel Cells (MCFC) The schematic diagram of a molten carbonate fuel cell is shown in fig.4. The molten carbonate fuel cell uses a molten carbonate salt as the electrolyte (10).

Fig.4. Molten carbonate fuel cell The anode process involves a reaction between hydrogen and carbonate ions to form water and carbon dioxide while releasing electrons at the anode. The electrons migrate towards cathode through the load connected to an external circuit. The cathodic process involves oxygen and carbon dioxide from the oxidant stream with electrons to produce carbonate ions. The need for carbon dioxide in the oxidant stream requires a system for collecting the carbon dioxide from the anode exhaust and mixing it with the cathode feed stream. The reactions occur at 650 oC when salts melt and conduct carbonate ions from the cathode to the anode. The reactions in the molten carbonate fuel cell are given below:

Solid Oxide Fuel Cells (SOFC) The schematic diagram of a solid oxide fuel cell is shown in fig. 5. Solid oxide fuel cells work at even higher temperatures than molten carbonate fuel cells. A solid oxide fuel cell (SOFC) uses a

hard ceramic electrolyte crystal lattice instead of a liquid and operates at temperatures of 750 oC to 1000oC (10).

Fig.5. Solid oxide fuel cell Today's technology employs several ceramic materials as the active SOFC components. The anode is typically formed from an electronically conducting nickel/yttria-stabilised zirconia (Ni/YSZ) cermet (ie, a ceramic/metal composite). The cathode is based on a mixed (ie, both electronic and ionic) conducting perovskite, lanthanum manganate (LaMnO3). Yttria-stabilised zirconia (YSZ) is used for the ion-conducting electrolyte. At this high operating temperature, oxygen ions migrate through the crystal lattice. As hydrogen is passed over the anode, oxide ions moves across the electrolyte to oxidize the fuel. The oxygen is supplied, usually from air, at the cathode. Electrons generated at the anode travel through an external load to the cathode, completing the circuit. Oxygen combines with electrons at cathode to form oxide ions, thus completing the reaction. These cells can reach efficiencies of around 60% and expected to be used for combined heating and power purposes. They can be used potentially for providing auxiliary power in vehicles. The main advantage of SOFC is possibility of internal reforming at 750 oC - 1000oC and hence natural gas can be used as fuel in SOFC. The following reactions occur at the SOFC electrodes:

Regenerative Fuel Cells (RFC) In this type of fuel cells water is electrolyzed with the help of electricity from solar photovoltaic cell

to produce hydrogen and oxygen gases and utilizing these gases in the PEM fuel cell to generate electricity (11). This technology is useful in space application. Further, using this technology solar energy can be stored in the form of hydrogen energy and it will be of use in the night when solar photovoltaic would not work. Fig. 6 depicts the concept of a regenerative fuel cell.

Fig. 6. Regenerative fuel cell system The following reactions describe the water splitting process inside the electrolyser:

Fuel Cells Thermodynamics


Internal energy The energy associated with microscopic movement and interaction between particles on the atomic and molecular scale. Entropy is determined by the number of possible microstates accessible to a system (the number of possible ways of configuring a system) For an isolated system S = k log S:total entropy of the system; K:Boltzmanns constant; O:number of possible microstates accessible to the system

First law The law of conservation of energy

Energy transfer between a closed system and its surrounding via heat(Q) and work (W)

d (Energy) univ = d(Energy) system +d (Energy) surrounding = 0 d (Energy) system = -d (Energy) surrounding dU = dQ dW

Positive work is defined as work done by the system on the surroundings If there is only mechanical work done by a system( eg. Expansion of a system by dV against a pressure, P) (dW)mechanical=pdV

dU = dQ dW

Second law In a system, a process that occurs will tend to increase the total entropy of the universe. dSuniv>=0 For a reversible transfer of heat at contant pressure

dS=dQrev/T

H2-O2 Fuel Cell H2+1/2 O2 ---> H2O ; Grxn=-273 kJ/mol H2 eg 5 mole of O2 is reacted , the extrinsic Gibbs free energy change

Some Important terms Standard State Because most thermodynamic quantities depend on T and p, we need a reference state called as a standard state. Room temperature(298.15K) and Pressure 1 bar=100kPa

Standard state condition are designated by a superscript zero, Reversibility

Reversible implies equilibrium E represents a reversible fuel cell voltage and V represents an operational ( nonreversible ) fuel cell voltage

Heat Potential of a Fuel dH=TdS+Vdp

for a constant pressure process dH=TdS = dU+dW Calculating Reaction Enthalpies

:: enthalpy required to form 1 mole of chemical species i at STP from the reference species Work potential of a fuel: Gibbs free energy

G=H-TS dG = dH TdS
Relationship between Gibbs free energy and Electrical Work

Relationship between Gibbs free energy and voltage

Potential of a system to perform electrical work is measured by voltage (electrical potential) Electrical work done by moving a charge Q ( coulombs) through an electrical potential difference E(volts), Welec

Welec=EQ If the charge is carried by electrons

Q = NF n: number of moles of electrons transferred ; F: Faraday constant

H2-O2 Fuel Cell

Relationship between Gibbs free energy and Electrical Work Standard Electrode Potentials: computing reversible voltage Standard state electrode potential is standard state reversible voltages of various electrochemical half reactions relative to the hydrogen reduction reaction.

Predicting reversible voltage of a fuel cell under non-standard-state conditions Reversible voltage variation with temperature

For molar reaction quantities

Defining ET as the reversible cell voltage at T At cinstant p,

Reversible voltage variation with pressure

Reversible voltage variation with concentration

Fuel cell efficiency

Ideal efficiency of a fuel cell is limited by G Real efficiency is lower than ideal efficiency because of non-ideal irreversible process

Ideal reversible fuel cell efficiency

If work is extracted from a chemical reaction,

For a fuel cell, the maximum amount of energy available to do work is given by Gibbs free energy. Thus the reversible efficiency of a fuel cell is

At room temperature, H2-O2 Fuel Cell

HHV:Higher heating value H2-O2 fuel cell, if H2O(l) is product, it is HHV. If H2O(g) is product, it is LHV. Efficiency is calculated based on HHV Comparison with conventional heat/expansion engine

Real fuel cell efficiency Two main reasons for decrease in fuel cell efficiency:

Voltage losses Fuel utilization

Voltage efficiency of the fuel cell Ratio of the real operating voltage of the fuel cell (V) to the thermodynamically reversible voltage of the fuel cell (E)

Operating voltage depend on the current (i) drawn from the fuel cell: The lighter the current load, the lower the voltage Fuel cell are most efficient at low load

Fuel utilization efficiency of the fuel cell Ratio of the fuel need by the cell to generate electric current and the total products to the fuel cell.

The supply of fuel to a fuel cell is adjusted to the current FC is always supplied with just a bit more fuel than it need at any load

In a hydrogen-oxygen fuel cell system, water is produced as the final product. With pure hydrogen and oxygen at standard conditions, i.e. 1 atm and 298 K, the reversible cell potential obtained is 1.229 V. This is the maximum voltage that can be withdrawn from this system. However, in reality the feed streams, i.e. hydrogen and oxygen are often diluted for several reasons. For example, air can be used as a source of oxygen, which also contains nitrogen. Similarly, the products from water gas shift reaction (CO + H ) can be used as a source for hydrogen. Additionally, pure hydrogen and oxygen can be used at different pressures and temperatures. Therefore, there is a need to understand the dependency of the reversible cell potential on the concentration of various species. In order to build a relationship between the cell potential and concentration of different species, we first recollect the concept of chemical potential learnt in thermodynamics. Chemical potential measures the change in the Gibbs free energy of a system with change in chemistry of the system. It is defined for each species in the system. Chemical potential for a species i in phase a can be related to the Gibbs free energy change as follows
2 2

Nernst Equation Analysis

.................................................................................(1)

where is the chemical potential of species i in phase a and measures the change in the Gibbs free energy of the system with infinitesimal change in the number of molesof species i, while temperature, pressure and the moles of other species are held constant. Also, from thermodynamics the chemical potential of a species i, can be related to its concentration through activity, a
i

.................................................................................(2) where is the chemical potential of species i at standard conditions, i.e. 1 atm and 298 K; ai denotes the activity of species i. The activity of species is a function of its chemical nature. In other words the activity of a chemical species depends on the chemical nature of the species. The following table lists the activity of species depending on their chemical nature. Chemical Nature
Activity ai=pi/po; where pi and p0 are respectively the partial pressure of species i and the standard state pressure, i.e. 1 atm. For example, activity of nitrogen (N2) in air at 1 atm would be partial pressure of N 2 in air. Since air approximately contains 78 % N2(by volume), the activity of N 2 would be 0.78 for 1 atm air pressure. However, if the air pressure is increased to 2 atm, the N2pressure increases proportionally and hence the activity is doubled, i.e. 1.56. ai=i (pi/po); where i is an activity coefficient, while p i and p 0 have the same meanings as defined for the case of an

Ideal gas

Nonideal gas

ideal gas.i is the measure of deviation from ideal behavior (0 < i < 1). The theories are available from thermodynamics to quantify i. Please note that while calculating the activity of N 2 above, we assumed the ideal gas case. However, nonideal behavior of N 2 and air would decrease the activity. ai=ci/co; where ci and c0 are respectively the molar concentration of species i and the standard state concentration, i.e. 1 M (1 mol/L). For example, the acitivity of Na + ions in 0.1 M NaCl is 0.1. However, the activity of Na + ions in 0.1 M Na2 SO4would be 0.2, since 1 mol of Na2SO4 gives 2 moles of Na+ ions (Na2SO4 -------> 2Na+ + SO42-) ai=i(ci/co); where i is an activity coefficient, used to measure the deviation from ideal behavior. As already discussed, 0 <i < 1 and therefore, the activity calculated assuming a nonideal behavior of a species is low compared to that of ideal behavior. ai=1; i.e. the activity of the pure components can be taken as unity. For example the activity of pure aluminum in an aluminum electrode is 1. Also, the activity of liquid water is taken as unity.

Dilute solution

Nonideal solution

Pure components

Table 1. Activity of species depending on their chemical nature Therefore, in order to calculate the Gibbs free energy change of the total system, the contributions from all species are added (Using

Equation 1)

(Using Equation 2)...............................................................(3) For hydrogen-oxygen fuel cell system, we have the following overall reaction It should be noted that the above reaction can be written in the following manner too However, the total Gibbs free energy change calculated for this system would be different for the above two reactions. This is due to the difference in stoichiometric coefficients of H , O2 and H O in the two reactions. Therefore, it becomes necessary to work with molar Gibbs free energy change,g' which is defined on a per mole basis and is therefore intrinsic, i.e. independent of the quantity of the system. For our case, the molar Gibbs free energy change for the
2 2

formation of water is -237 kJ/mol H at standard temperature and pressure. However, if 10 moles of O reacted then the total Gibbs free energy change is given by
2 2

Hence, on a molar basis for species H , the molar Gibbs free energy change for this reaction can be calculated from the chemical potentials of various species participating in the reaction
2

Using Equations 2 and 4, we have

.....................................................................(4)

where standard conditions, i.e. 1 atm and 298 K.

; is the Gibbs free change for the reaction at

...............................................................................................(5) The amount of Gibbs free energy change (g'rxn) can be related to the electrical work by .........................................................(6) where n is the number of moles of electron transferred, F is Faradays constant and Ecell is the potential difference across the cell. It should be noted that the value of n is 2 in our case, since for every one mole of water formed, 2 moles of electrons are transferred. Using Equations 5 and 6, we get

As we discussed previously, the activities of H2 and O2 can be replaced by their respective partial pressure assuming ideal behavior. This assumption leads to

.............................................................................................(7) The above relation clearly shows the dependency of reversible cell potential on the partial pressures of H and O and is known as the Nernst Equation. In general for any arbitrary number of products and reactants, we have
2 2

...........................................................................................(8) where vi denotes the stoichiometric coefficient of ith species involved in the chemical reaction. For example, in our case the stoichiometric coefficient of O is 1/2. The Nernst equation relates the reversible cell potential to the effective concentrations of various species and is therefore, a very significant result. In case of a hydrogen-oxygen fuel cell system, we have n = 2 and hence
2

This expression gives the maximum theoretical voltage across the cell at a particular temperature and pressure. This theoretical voltage is also known as the open circuit voltage (OCV), i.e. the voltage observed when no current is drawn from the cell. When the activities if H2 and O2 are both unity, i.e. the partial pressure of both H2 and O2 is 1 atm, it can be easily seen that the expression reduces to

Both the proton exchange membrane fuel cell (PEMFC) and the solid oxide fuel cell (SOFC) use hydrogen and oxygen as the feed streams, however, the OCV observed is different for the two. This is due to the difference in operating temperatures of PEMFC and SOFC. While the operating temperature range for a PEMFC is 40 to 100C, the SOFCs are operated at very high temperatures ranging from 750-1000C. It should be noted that the temperature dependency of the OCV is not that straightforward as indicated by the Nernst equation and one needs to be careful in analyzing those results. This is because the E0 cell value is also a function of temperature, i.e. changes with change in temperature. The E0 cell decreases with increase in temperature. Therefore, at standard pressure conditions, pH = pO =1 atm, the OCV of a SOFC is lower than that of a PEMFC.
2 2

Partial Pressure of H 2(atm)


1 1 1 1

Partial Pressure of O2(atm) 1 2 3 4

Open Circuit Voltage (V)


1.229 1.233 1.236 1.238

Difference between OCV and E0 cell (mV) 0 4 7 9

1 2 3 4 5 2 3 4 5

5 2 3 4 5 1 1 1 1

1.239 1.242 1.250 1.256 1.260 1.238 1.243 1.247 1.250

10 13 21 27 31 9 14 18 21

Table 2. OCV (at standard temperature condition, i.e. T = 298.15 K) vs. partial pressures of H and O as calculated by Nernst Equation As seen from the values in the table, the OCV increases slightly with increase in pressure of hydrogen and/or oxygen. However, it can be seen that the OCV difference is not very significant even after reaching higher pressures, i.e. 5 atm H and O , only 31 mV voltage difference is observed. Nernst equation also shows that potential difference can be generated with the same redox couple by having different concentrations of species at the anode and the cathode side. This type of arrangement is known as a concentration cell. For example, voltage can be obtained from a hydrogen concentration cell where the anode and the cathode are maintained at different partial pressures of hydrogen. For a hydrogen concentration cell, the following reactions take place
2 2 2 2

1. At anode : H ------> 2H+ + 2e- ; E0a = 0.0 V vs. NHE 2. At cathode :2H+ + 2e- --- --> H ; E0c = 0.0 V vs. NHE 3. Overal : H ----------> H ; E0cell = E0c - E0a = 0 V
2 2 2 2

Fig.1. A schematic representation of a hydrogen concentration cell We can write the following Nernst equation for this hydrogen concentration cell

where (aH2)cathode and (aH2)anode are the activities of H2 at the cathode and anode side respectively. Assuming ideal gas behavior, and replacing the activities of H2 by its partial pressure, we get

where (PH2)cathode and (PH2)anode are the partial pressures of H2 at the cathode and anode side respectively. Replacing the values of E0cell (= 0 V), n (= 2), R (= 8.314 J/(mol-K)), T (= 298.15 K), F (= 96500 C/mol) and (say), in the above equation we get

Therefore, for Ecell (or OCV) to be positive, Q should be less than unity. In other words, (PH2)cathode< (PH2)anode The variation in values of OCV with different values of Q has been listed in Table 3. This clearly shows that OCV increases with decrease in the value of Q. OCV (V)
0 0.059 0.118 0.177 0.236 0.295 0.354 Q 1 10-2 10-4 10-6 10-8 10-10 10-12

Table 3. Variation in OCV with Q This hydrogen concentration cell can produce decent voltage without oxygen and therefore can be used in outer space where oxygen unavailable.

Electrode potential and Electrochemical Potential


It is the electromotive force of a cell built of two electrodes: Suppose,

on the left-hand side (LHS) is the standard hydrogen electrode (SHE, EH 2/H+ = 0.0 V) , and on the right-hand side (RHS) is the electrode the potential of which is being defined.

Note, by convention potential of SHE is zero. We will discuss about SHE in detail little later. ECell =Eeft - Erigh =0- Eright=- Eelectrode Thus, if the potential of RHS electrode is positive then Ecell is negative and if it is negative Ecell is positive. Instead of writing LHS and RHS electrode based on the positive side or negative side of EH2/H+ = 0.0 V, an electrode is named positive (anode) or negative (cathode) electrode. By convention: ECell= (ECathode -EH2/H+)- (EAnode- EH2/H+) ECell= ECathode- EAnode Standard electrode potential ( E), is the measure of individual potential of a reversible electrode at standard state. The basis for an electrochemical cell is always a redox reaction which can be broken down into two half-reactions: oxidation at anode (loss of electron) and reduction at cathode (gain of electron). Electricity is generated due to electric potential difference between two electrodes. This potential difference is created as a result of the difference between individual potentials of the two metal electrodes with respect to the electrolyte. Although the overall potential of a cell can be measured, there is no simple way to accurately measure the electrode/electrolyte potentials in isolation. The electric potential also varies with temperature, concentration and pressure. Since the oxidation potential of a half-reaction is the negative of the reduction potential in a redox reaction, it is sufficient to calculate either one of the potentials. Therefore, standard electrode potential is commonly written as standard reduction potential. Calculation of standard electrode potential The reference electrode; chosen by convention, is the standard hydrogen electrode (SHE): Pt/H2 (a=1)/H+(a=1) Its potential (electrostatic standard) is taken as 0.0 V at all temperature. Similarly, the standard electromotive force (EMF) of the half reactions: 2H++2e- <------->H2 ....................... E0=0.0 V Half cell potentials can be determined by measuring them in whole cells against the SHE. For example, in the system shown in figure 1, measurement of the standard electrode potential of element Ag Pt/H2 (a=1)/H+ (a=1)// Ag+ (a=1)/Ag

the cell potential is 0.799 V and silver is positive. Thus the standard potential of the Ag+/Ag couple is 0.799 V vs. SHE.

Standard electrode potential table/Electrochemical series It is the lists of the all the elements of redox couple according to the magnitude of the electrode potential [1, 2]. It compares the standard-state reversible voltages of various electrochemical half cell reactions relative to the hydrogen reduction reaction. The example shows some of the extreme value of standard cell potential for some elements based on the ranking:

Cathode (Reduction)HalfReaction
Li++(aq) Li(s) K+(aq) K(s) + + e- -> e- ->

Standard Potential E (volts) -3.04 -2.92 -2.76 -2.71 -1.66 -1.63

Ca2+(aq) + 2e- -> Ca(s) Na+(aq) Na(s) Al3+(aq) Al(s) + + e- -> e- ->

Ti2+(aq) + 2e- ->

Ti(s) Mn2+(aq) Mn(s) 2e- -> -1.18 -0.76 -0.71 -0.44 -0.28 -0.25 -0.14 -0.04 0.00 0.34 0.80 0.20 0.36 1.56 2.87

Zn2+(aq) + 2e- -> Zn(s) Cr3+(aq) + 3e- -> Cr(s) Fe2+(aq)+ Fe(s) 2e- ->

Co2+(aq) + 2e- -> Co(s) Ni2+(aq) + 2e- -> Ni(s) Sn2+(aq) + 2e- -> Sn(s) Fe3+(aq) + 3e- -> Fe(s) 2H+ +2e- -> H2 (g) Cu2+(aq) + 2e- -> Cu(s) Ag+(aq) Ag(s) + e- ->

Pt+2(aq) + 2e- -> Pt(s) Cl2 (g) +2e- -> 2CAu3+(aq) + 3e- -> Au(s) F2(g) + 2e- -> 2F(aq)

Table 1. Electrochemical series (at 298 K) To access complete electrochemical series, please refer [1, 2]. The most negative electrode potential represents the strongest reducing agent and the most positive represents the strongest oxidizing agent. Apart from the quantitative information given by the electrochemical series, it also gives the qualitative information e.g. if the two electrochemical couples brought into contact then reaction will proceed in such a manner that the oxidizing member of the couple having higher electrode potential with the reducing member of the couple having electrode potential is thermodynamically favored . Example: Consider the Fe+2-H+ reaction couple from the electrochemical series. Because the hydrogen reduction reaction has a larger electrode potential compared to the iron reduction reaction (0 V > 0.44 V), the net reaction occur as [3]:

Iron would go through oxidation reaction in redox couple with hydrogen reduction reaction. Thus the iron reduction as listed in the table is reversed in the form of oxidation reaction and the potential sign us changed from ve to +ve (+0.44 V). This is the thermodynamically spontaneous reaction direction under standard state conditions as E o= +ve. Thus the reaction would take place spontaneously with the generation of 0.44 V if we consider a fuel cell constructed in such a manner. If Eo = -ve, then we would have applied potential so that the reaction would take place forward direction as shown above and we generally call the process as electrolysis. Instead of Fe ----> Fe+2 + 2e (Eo = 0.44 V), if we consider Cu2+(aq) + 2e ---->Cu(s) (Eo = 0.34 V), then hydrogen reduction reaction would have not taken place spontaneously but in reversed direction i.e., hydrogen oxidation reaction (H2 ----->2H+ + 2e; Eo = - 0.0 V). Eo of the combined oxidation and reduction couple would have been 0.34 V resulting spontaneous reaction in the forward direction. Dominance diagram There is ambiguity in the arrangement of the some elements in electrochemical series because it may form different redox couples, e.g. iron can exists in Fe3+, Fe2+ form. Fe3+(aq)+3e- <---->Fe E0=-0.04 V Fe2+ (aq)+2e- <------>Fe E0=-0.44 V Iron can exists in different forms Fe3+(aq), Fe2+(aq), Fe(s), which depends on the potential they have been exposed. Figure 2 shows the dominance diagram of Fe. It shows which is thermodynamically dominant species at any particular potential. The horizontal lines correspond to the standard potentials of electrode reactions: Fe3+(aq)+e<----->Fe2+(aq) E0=0.771 V Fe2+(aq)+2e-<---->-Fe(s) E0=-0.44 V

Figure 2. Dominance diagram for element iron. The horizontal lines correspond to the standard potentials of electrode reactions: Fe3+ (aq)+e-Fe2+(aq) and Fe2+ (aq)+2e-<------>Fe(s) The diagram reveals that when a potential of 0.0 V is applied to the iron containing solution either by electrode or by any other more concentrated redox couple then iron will exists in the Fe2+ form [2]. Example: a) Let us consider Fe3+/Fe2+ -Cu2+/Cu reaction couple. Fe3+ reduction reaction has the higher potential as compared to the Cu2+ reduction reaction (0.771 V > 0.34 V). So copper would go through the oxidation reaction in redox couple with the iron reduction reaction and the net reaction would occur as:

which thermodynamically favorable reaction(E0>0) with generation of 0.431 V. b) Consider Fe2+/Fe Cu2+/Cu reaction couple. Since copper reduction potential is higher as compared to the iron reduction potential (0.34 V > -0.44 V), so iron would go through oxidation reaction in the redox couple with copper reduction reaction.The net reaction occurred as:

which thermodynamically favorable reaction (E0>0) with generation of 0.78 V. From the above two reactions it shows that the Fe 2+ is the thermodynamically dominant species Electrochemical potential It is a thermodynamic measure that combines the concepts of energy stored in the form of chemical potential and electrostatics. An electrochemical potential difference will inherently provide the driving force for both the transport of charge (electro migration) and the transport of mass (diffusion) by an ion (an ion having both charge and mass will obviously transport both by its movement). Figure 3 shows a hydrogen concentration cell. Hydrogen fuel compartment maintained at a pressure of 50 atm whereas the other compartment maintained at a pressure of 10-8 atm. At room temperature, we can generate almost 0.287 V due to a difference in hydrogen concentration. A voltage develops due to the difference in the chemical potential of both sides. Due to chemical potential gradient, some hydrogen decomposes on the platinum catalyst to protons and electrons. The protons transport to the other compartment via electrolyte and combines with the electrons on the platinum catalyst to reproduce hydrogen gas. If two platinum electrodes are not connected then on the fuel side excess electrons will accumulated while electrons will be depleted on the vacuum side, setting up an electrical potential gradient. This further retards the flow of hydrogen and at equilibrium chemical potential gradient exactly balance by the electrical potential gradient. The concept of chemical and electrical potentials offsetting one another to maintain thermodynamic equilibrium is summarized by the electrochemical potential [3].

In generic terms, electrochemical potential is the mechanical work done in bringing 1 mole of an ion from a standard state to a specified concentration and electrical potential. Also it is the partial molar Gibbs energy of the substance at the specified electric potential, where the substance is in a specified phase. Electrochemical potential can be expressed as [1].

Where, i is the species, zi is the charge number, F is the Faradays constant, a is the electrical potential experienced by the species i. The term zi Fa is the electrical potential energy per mole of species i in phase a The term called chemical potential

Where, ni is the no. of moles of i in phase a. Thus, the electrochemical potential would be

Where, species i.

is the electrochemical free energy and a is the electrical potential experienced by the

Properties of electrochemical potential

For an uncharged species For any substance: For a pure phase at unit activity (e.g. solid Zn, AgCl, Ag, or H 2 at unit fugacity ):

For a electron in a meta(z=-1)l . Activity effects can be neglected because the electron concentration never changes appreciably. For equilibrium of species i between phases a and :

Formulation of cell potential For a reaction at equilibrium

We can derive the Nernst equation from the basis of electrochemical potential. For deriving it we should also include the change in electrochemical potential for the electrons as they move from anode to cathode. Solving for the difference in the electrical potential for the electrons at the cathode versus the anode ( e- )) gives the cell potential E[3]. Consider the H2 O2 fuel cell reaction

At equilibrium

But,

Expanding the above equation, we get

Thus we arrive

which is the Nernst equation of the cell. References 1. Bard J. Allen, Faulkner R. Larry, Electrochemical methods- Fundamentals and Applications, second addition, 2006 2. Keith B. Oldham, Jan C. Myland, Alan M. Bond, Electrochemical Science and Technology, John Wiley and Sons, 2012 3. Ryan P. O'Hayre, Suk-Won Cha, Whitney Colella and Fritz B. Prinz, Fuel cell fundamentals, John Wiley and Sons, 2006

Electrochemical Reactions

Activation over-potential

Electrochemical reactions are redox (reduction-oxidation) reactions that involve transfer of free electrons at the interface of an electron conductor (e.g. metal surface) and an ionic conductor (e.g. electrolyte). Such reactions are either driven by externally applied voltage or voltage may be created by the electro-chemical reaction that occurs spontaneously. The branch of science dealing with electrochemical reactions is electrochemistry. One point may be noted that in chemical reactions no transfer of electrons take place whereas in electrochemical reactions involve transfer of free electrons. Since electrochemistry deals with the transfer of charge between and electrode and a chemical species in an electrolyte, electrochemical processes are necessarily heterogeneous. For example H2<-->2H++2e-...................................................................................................................(1) In (1) above reaction, electron transfer takes place at the interface between the electrode (e.g. Pt) and an electrolyte (e.g. H2SO4 in water). Electrochemical reactions are heterogeneous because H+ cannot exist inside the electrode and free electrons cannot exist inside the electrolyte. Hence, it is a heterogeneous reaction.

Figure 1: Electrochemical reaction at the electrode-electrolyte interface showing heterogeneous nature of the reaction Any electrochemical cell has two electrodes called the anode, where oxidation takes place and the cathode, where reduction takes place. These reactions occurring at the anode and cathode are called half-cell reactions which together constitute the full electrochemical cell.

Understanding Potential A general electrochemical reaction can be displayed as follows: Oxspecies+e- <--->Respecies.....................................................................................................(2) Where Oxspecies and Respecies are the oxidized and reduced form of the same chemical entity. Voltage (potential) is a measure of electron energy. By manipulating the voltage in an electrochemical reaction, course of above reaction can be influenced. For example, if the potential in above reaction is made more negative than the equilibrium potential, then reaction will be biased in the forward direction. On the other hand, if the electrode potential is made relatively more positive than the equilibrium potential, the reaction will be biased in the reverse direction. Thus, voltage applied to an electrochemical cell decides the course a reaction will take. Activation Energy For any reaction to occur spontaneously, the change in Gibbs energy should necessarily be negative. Even if the Gibbs free energy decreases from reactants to products, the reaction rates are finite because of impedance which is known as activation barrier (Figure 2). This impedance is a barrier that needs to be overcome for the chemical reaction to occur (please go to module 5 in-situ analyses for electrochemical impedance analyses). Lower the activation energy, easier it is for reactants to convert from reactants to products. Transition state theory states that only a species in activated state can undergo transition from reactant to product. Hence, it is necessary to first overcome the activation energy before conversion into products.

Figure 2: Gibbs Energy change for an electrochemical reaction. Activation barrier makes the reaction rate finite.

Thermodynamic treatment from statistical mechanics tells that probability of finding a species in an activated nature is exponentially dependant on the size of the activation barrier:

....................................................................................................(3) Where P* is the probability of finding a reactant species in the activated state, ?G 1 is the energy barrier (energy gap between the reactants and the activated species), T is temperature (K) and R is the universal gas constant. Reaction Rate For any chemical reaction, it is not just the product that is important but also the rate at which it forms. Therefore, we need to find out the reaction rate in the forward direction. This can be understood and calculated as follows: The reaction rate is the number of reactant species available to participate in the reaction multiplied by the probability that they will be found in the activated state (because, only these will participate in the reaction) multiplied by the rate at which these transform into the final products. As such, reaction rate is given by: u1=CRtP*....................................................................................................(4) Where, u1 is the reaction rate in the forward direction, C R is the reactant surface concentration (mol/cm2) and t is the transformation rate from activated state to final products. However, this is still not the net reaction rate, because the reverse reaction is happening too. Net Reaction Rate The net rate of reaction is given by: Net rate = forward rate reverse rate

u=u1-u2....................................................................................................(5)
Where, u is the net rate of reaction and ??2 is the rate of reaction in reverse direction. Quite intuitively, the net reaction rate can be given as

....................................................................................................(6) Where, t2 and G2 are the transformation rate and activation barrier for the reverse direction and C P is the product surface concentration. Gibbs energy change for the entire reaction can be given as

....................................................................................................(7) Using equation 7 to substitute G2 in equation 6 , the net reaction rate can be given as:

.........................................................................................(8) Exchange Current Density Now, we know that current is charge transferred per unit time. Hence, if Q (coulomb) is the charge transferred in time t (sec), then the current is given by the relation

...................................................................................................(9) If an electrochemical reaction results in the transfer of n electrons, then

.................................................................................................(10)

Where, F is the Faraday's constant and expressed as

is the rate of electrochemical reaction (mol s-1).From above relation, the forward current density can be

....................................................................................................(11) Similarly, the reverse current density can be given as

....................................................................................................(12) Note that i is current and j is current density. Since electrochemical reaction takes at the interface of electrolyte-electrode, it is wise to express in terms of current density than simply current. Also note that at equilibrium, there is no net current density. That is, the forward and reverse current densities should be equal. This current density at equilibrium is known as the exchange current density. At this point, no net current is extracted from the cell under operation. Butler-Volmer Equation: Generally, in an electrochemical cell, we aim to get some useful net current from the cell under operation. For this, it is i mportant to deviate from equilibrium, where the energies of the reaction are balanced. For this, we need to understand the equilibrium state of a reaction by analyzing the energies of the system. For understanding this approach, we can take the earlier example only (Equation 1) One of the steps involved here is the chemi-desorption of the adsorbed hydrogen on the catalyst surface (denoted by cat below) cat-H --> cat+e++H+ As shown in Figure 3 (a), the chemical free energy of the above reaction step decreases as the distance from the interface (catalyst-hydrogen) increase. But, the electrical energy increases (Figure 3 (b)) as the distance from in interface increases (development of charge ensues with eaccumulating up at the electrode and H+ in the electrolyte. This charge accumulation continues till the resultant potential difference ()

counterbalances the difference in free energies between the reactant and product state. The combined effect of these two energies can be seen in figure 3 (c) where the net effect leads to equal forward and reverse reaction rates.

This build up of the charge, neutralizes the difference between the two reaction rates by decreasing the activation energy barrier for the reverse reaction and increasing the activation energy barrier for the forward reaction rate. As such, while the forward reaction rate decreases, the reverse reaction rate increases. This makes it difficult to extract a net current from the cell. Now, it can be stated that

...................................................................................................(13) We know that the sum of interfacial electric potential difference at anode and cathode yield the overall thermodynamic equilibrium voltage. These anode and cathode interfacial potentials are called Galvani potentials. The exact magnitude of these Galvani potentials is not known. We had earlier studied that voltage plays a crucial role in deciding the course of a reaction. This is because charged species are involved in the

reaction and this free charge species are sensitive to voltage which changes the free energy of these species upon bringing up a change in the voltage. As a result, this changes the size of the activation barrier. Now, voltage will play a crucial role in extracting a net current from the electrochemical reaction. Reducing the Galvani potential at both anode and cathode reduces the forward reaction activation barrier and at the same time, increases the reverse reaction activation barrier. This results into a net forward reaction and hence, a net current can be obtained from the electrochemical cell. By looking at the figure 4(b), it can be seen that if the Galvani potential is reduced by a value of , the forward reaction activation barrier is reduced by F and the reverse reaction activation barrier is increased by (1-)F (figure 4(c)). Here, is called the charge transfer coefficient and it denotes how a change in Galvani potential changes the activation barrier for forward and reverse reactions thus producing a net cell current.

We already know that at equilibrium, the current density is given by the exchange current density. Moving away from equilibrium and taking into account the changes in activation barrier, the new current densities can be written as follows:

...................................................................................................(14)

...................................................................................................(15)

The net current j is therefore,j1-j2 (subtracting eq. 15 from 14)

...................................................................................................(16) We also need to take into account the change in reactant and product surface concentration; owing to change in voltage that changes the reaction rate. This change in concentration can be taken care of by introducing actual surface concentrations CR* and CP*. Accordingly, eq. (16) becomes:

...................................................................................................(17) Where, j0 is the current density measured at surface concentrations CR and CP. Eq. 17 is called the Butler-Volmer equation and denotes the relationship between current density, surface concentration and activation voltage loss in an electrochemical loss. We can conclude from the above equation that the current density increases exponentially with activation over-voltage (). Activation Over-potential Activation over-potential represents the voltage that is sacrificed to overcome the activation barrier to extract a net current from an electrochemical reaction. The over-potential is the extra voltage needed to reduce the energy barrier of the reaction (usually the rate determining step) so that the reaction proceeds at a desired rate. Thus, higher is the voltage sacrificed, higher is the current density obtained. The magnitude of this activation loss is governed by reaction kinetic parameters and j0. Having a high j0 is highly favored. This can also be shown from Figure 5, which shows the plot for cell voltage versus current density.

Tafel Equation

Figure 5: Voltage versus current density at different exchange current densities

The ButlerVolmer equation (17) often is quite complex to deal with owing to its exponential nature. Thus, it creates unnecessarily complications which can be resolved by making some simplifications under certain conditions. We consider here two cases: 1. is very small: For small ? (less than 15 mV at room temperature), a Taylor series expansion of the Butler-Volmer equation (17) yields:

..........................................................................................................(18) Approximation being made here is that ex1+x for small values of x. Eq. 18 displays linear relationship between current density and over-potential for small disturbances from equilibrium. 2. is very large: When is very large (> than 50-100 mV at room temperature), only the forward reaction rate contributes significantly to current density. In other words, the reaction becomes irreversible and the eq. 17 is simplified to :

.........................................................................................................(19) Solving for yields,

.........................................................................................................(20) A plot of and ln (j) should be a straight line with intercept as - RT/anF ln(j0 ) with slope RT/aNF . Eq. 20 is known as the Tafel equation. Tafel equation is important to calculate transfer coefficient a and exchange current density j0 from the slope and intercept as shown in figure 6.

Figure 6: plot of activation over-potential and current density. At low over-potential, Tafelequation deviates from its linear nature.

Concentration Polarization
Transport processes in fuel cells: By this time, we are aware that in fuel cells the following processes occur simultaneously.

Mass Transport Heat Transport Momentum Transport Charge (electron and ion) Transport

All these processes are very complex and have interlinkages and dependencies to each other as per the scheme shown.

These transport processes of the fuel cell are equally important and responsible for the desired output of an efficient fuel cell. The understanding of all the above processes in a fuel cell requires the knowledge of multicomponent, multiphase, and multidimensional transport processes. The basic knowledge may be gathered from the fundamental books on heat transfer, mass transfer, fluid mechanics, and mass transfer. However, here we would like to present a simplistic view of the essential knowledge required to understand the fuel cell.Objective of this section is to make you understand the various transport processes and their impact on the fuel cell. Revisiting some of the basic concepts: Consider a mixture of volume V, containing N different species. The concentration of a species i may be described by anyone of the following ways, molar concentration(Ci)

Where, ni represents the number of moles of species i in the mixture and

Mass concentration(i)
Where, mi represents the number of moles of species i in the mixture and

Where, Wi represents the molecular weight of species i in the mixture.

Mole fraction(Xi) Where C is total molar concentration. Mass fraction(Yi)

Where

is the total mass concentration.

Concept of Average and Diffusion Velocity:

Vi is the velocity (absolute) of different species with respect to the stationary coordinate. The average velocity of the species in the mixture can be defined as:

Mass- average velocity (v)

Thus the mass-average velocity is averaged by the proportional amount of mass of each species in the mixture.

Mass- average velocity (v*)

Thus the molar-average velocity is averaged by the proportional amount of moles of each species in the mixture. It is to be noted that diffusion is the relative motion of a species with respect to the average motion of a mixture as a whole. Thus,

Mass- average velocity Mass- average velocity Bulk motion: v or v* Diffusion: vi or vi*

Therefore, the total mass flux and total molar flux of the species i relative to the stationary coordinate become,

Diffusion Law: Consider a typical case of a fuel cell, which has a non-reacting mixture containing two species i,& j. The rate of mass transfer for species i diffusing through j follows Ficks Law. For unidirectional flux in x-direction,

The above equation is the Ficks Law in terms of mass flux and conveys that the diffusion mass flux arises from the mass concentration gradient. The negative sign shows that the diffusion flux is in the direction of decreasing concentration.In a similar way, the equation can be written for the molar concentration gradient,

The proportionality constant Dij is called binary diffusivity, or the diffusion coefficient of the species

i with respect to species j. The unit of diffusivity is m2/s. Table:A few relevant values (approx.) of binary coefficient required in fuel cell are shown in table at 25o C and 1 atm. Pressure. Species Dij(m2/s) j Air (g) Air (g) H2O(l) H2O(l) H2O(l) H2O(l) 0.41 X 10-4 0.21 X 10-4 0.12 X 10-8 0.20 X 10-8 0.24 X 10-8 0.63 X 10-8 0.26 X 10-8

Species i H2 (g) O2 (g) CO2 (g) CO2 (g) O2 (g) N2 (g)

C2H5OH(l) H2O(l)

Now, we would see that the momentum and heat transport laws are very similar to the mass transport and equivalent laws are Newtons Law and Fourier Law, respectively. Consider a flow situation where the flow is over a solid surface (x-z plane) in an orderly (laminar) and smooth manner in the x-direction, the velocity, temperature and concentration of species i changes in the y-direction. Note: The reader may get the details in any standard book on fluid mechanics, heat transfer, and mass transfer. Newton's Law of Viscossity (momentum transport)

Where Md,y is the the momentum flux , v is the kinematic viscosity (m 2/s) and vX is the velocity in x-direction. The Fourier law can be represented by the following equation for the heat transfer in the ydirection, Fourier's Law

Where, qy is the heat flux, is the thermal diffusivity (m 2/s). These transport properties are related to each other by some non-dimensional ratios.After this brief discussion on the transport properties, we will now focus on concentration polarization in the fuel cell. Polarization: Activation Polarization Ohmic Polarization Concentration Polarization Recall that during the explanation of the activation polarization, we have assumed that the concentration of the reactant is constant and independent of the cell current density. However, in real situation when we draw the current, the concentration of the reactant decreases at the reaction site. Once the concentration of the reactant decreases, the low availability of the reactant at the reaction site leads to the reduction of corresponding voltage. If we further keep on drawing the current the reactant concentration depleted and at a certain current the cell voltage drops down to zero voltage. This maximum current is known as the limiting current.

The reactant does not continued to be transported to the reaction site because of limitation of the certain processes. A few major processes include the slow diffusion in the gas phase in the electrode pores (problem aggravates in case of flooded electrode), slow diffusion of the product through reactant from the active sites and vice-versa. These losses are known as reaction losses. Moreover, the concentration of the reactant decreases along the flow channel from inlet to outlet, which adds to the increases in the voltage loss. The combined effect of the Nernst loss and reaction loss is known as concentration loss or concentration polarization. Concentration loss = Nernst loss + reaction loss

Quantifying Concentration Polarization The quantification of the concentration polarization may be done by simplified or by rigorous engineering approach. In this NPTEL course we will be limited to the simplified approach only. Consider an electrode prepared with backing layer and catalyst layer. It may be assumed that the catalyst layer is very thin as compared to the backing layer. Thus the thickness of the catalyst layer may be considered negligible. The reactant concentration at the inlet is considered to be C o. We know that the reactant is transported from the flow channel through convection and to the electrode by diffusion. If the concentration of reactant at the end of the backing layer is Cc, and at the surface of the electrode is Ce, the rate of the mass transfer at steady-state can be calculated as shown below.

The mass transfer rate from flow channel to the electrode surface through convection is,

Where N is the mass transfer rate (mol/s), A is the electrode area and h mis the mass transfer coefficient. Similarly, the mass transfer rate from electrode surface to the catalyst surface by diffusion is,

Where, Deff is the effective diffusion coefficient as the diffusion will be from the porous media. In case of a porous electrode with porosity of and without any water flooding D eff will be defined by the Bruggmanns correlation

At steady state these mass transfer rates will be same thus eliminating C e from the above two equation,

Where, R is the total mass transfer resistant of the reactant to the catalyst layer. By this time, we know that due t the different resistances the rate of mass transfer of the reactant to the catalyst site or reaction site is N. once the reactant is reached to the reaction site the electrochemical reaction will occur which result in the current and we are aware that the current generation and the rate of reactant transport is linked by the Faradays law,

Where, J is Current Density. On substituting the value of rate of mass transfer (N) in the above equation,

Thus by the above relation we can find out that the current density is proportional to the reactant concentration difference in the inlet and the catalyst layer as well as the concentration of the inlet concentration of the reactant. Here we can see that if the current density increases, C c will reduce and at the maximum current density the value of Cc becomes zero.Therefore, the maximum possible current density (limiting current density; J L) when all the reactant supplied to the catalyst layer is consumed by the electrochemical reaction, can be found out at C c = 0,

It can be emphasized at this moment that the limiting current at a particular design and operating condition is fixed at a certain value. However, by improving the design and operating conditions the limiting current may be improved by analyzing the above equation. Increase in mass transfer coefficient (hm) will improve JL: How to improve the mass transfer coefficient? The flow conditions must be improved in the flow channel. Increase in effective diffusivity (Deff) will improve JL: Issues of design and operating condition! The effective diffusivity is the function of temperature and porosity of the electrode (or gas diffusion layer) and thus can be improved by these improving these factors. On combining J and JL,

It is very interesting relation and can easily provide the real concentration of the reactant at the catalyst surface if the current density and limiting current density are known for a particular fuel cell at the operating conditions. The above equation may be rearranged to,

Now, to quantify the concentration overpotential, consider Nernst equation for a single reactant species,

If the reactant concentration at the inlet and at the catalyst surface if same then the cell voltage (E) will be maximum (EO). Thus,

A few points must be noted for the previous equation, 1. 2. 3. 4. The equation is valid at higher current densities. Reactant transport should be the rate limiting process. The pores of the gas diffusion layer are assumed to be free of water droplets. Other physico-chemical processes are ideal and do not affect the system considered.

Note: Detailed knowledge of the concentration polarization in terms of individual mass transport into the fuel channel, diffusion of the reactant from the fuel channel to the interface of gas diffusion layer and catalyst layer, and diffusion of the reactant into the catalyst layer (for high and low current densities), removal of the product from the reaction sites etc. All these processes can evaluated with the complex mathematics along with various co-relations. These processes are beyond the scope of the NPTEL course.

Ohmic Overpotential
In a typical operation of a fuel cell, the electrons flow through the external load while the ions move across the electrolyte to complete the whole circuit. Therefore, ion transport across the electrolyte is essential for current flow. The current can be related to the charge on the ions transported through the electrolyte by i=njzjF................................................................................................................................ ..(1) where denotes the current, is the molar transfer rate of ion, i.e. the number of moles of ions transported across the electrolyte per unit time, is Faradays constant (96,500 C/mol) and is the charge number of the ion. In case of a proton exchange membrane fuel cell (PEMFC) the H+ ion is transported across the solid polymer electrolyte (generally the Nafion membrane)and therefore, zj= +1. On the other hand, O2- ion moves through the electrolyte (typically yttria stabilized zirconia) in a solid oxide fuel cell (SOFC), and therefore, we have zj= -2. The ions can be transported by three mechanisms namely, the convection, diffusion and migration. The details of these mechanisms are discussed below 1) Convective Transport In this case, the mass transfer of ions occur as a result of net motion of the electrolyte (e.g., stirred liquid solutions). Convective transport can itself be classified into forced and natural convection based on the cause of transport. Forced convection results from an externally controlled fluid motion while natural convection is a result of buoyant forces resulting from a density gradient. For example, the fluid flow under a pressure drop can be regarded as a forced convection, while the upward movement of less dense water, in the case of boiling water, is an example of natural convection. Forced convection can be represented mathematically by the following equation nj,i=Cjvj................................................................................................................................ .(2)

where is the molar flux rate of species j in the ith direction , is the molar concentration of the jth species, is the velocity field vector of the fluid. In general, the velocity field vector of the fluid is represented by

where vx,vy and represent the components of velocity along the X, Y and Z axis respectively. The convective transport of jth species can be represented by the following set of equations a) Along X axis: nj,x=Cjvx b) Along Y axis: nj,y=Cjvy strain c) Along Z axis: nj,z=Cjvz In natural convection, the transport depends on the density difference which arises through several reasons, e.g. temperature difference, etc. The analysis for natural convection is therefore, much more complex. 2) Diffusive Transport In this case, the mass transfer of ions take place due to concentration gradient across the electrolyte.

Mathematically, the diffusive transport can be quantified by the following equation

...............................................................................................................(3) where ni,jis the molar flux rate of species j in the ith direction , is the diffusivity of jth species along

the ith direction , is the molar concentration of the jth species, is the position field vector. In general, we have xi=xi+yj+zk................................................................................................................(4) The negative sign on the right-hand-side (RHS) of the equation 3 signifies that the direction of transport is opposite to the increase in concentration. In other words, mass transfer of species j, occurs in the direction of decreasing concentration of species j. As discussed for the case of convective transport, equations 3 and 4, yield three scalar equations in the three axes, X, Y and Z. Therefore, we have

a) Along X axis:

b) Along Y axis:

c) Along Z axis: 3) Migration Here, the mass transport of charged species is driven by an external electric field. In addition to convection and diffusion, the ions can be transported across the electrolyte by an applying an external electric field. The transport equation for migration is given by

..........................................................................................(5)

where nj,i is the molar flux rate of species j in the ith direction ,zj is the charge number of the ion,Dj,i is the diffusivity of jth species along the ith direction,Cj is the molar concentration of the jth species, F is Faradays constant (96,500 C/mol), is the universal gas constant (8.314 JK1mol-1), is the absolute temperature (in Kelvin), xi is the position field vector, and, is the electric potential. The negative sign signifies that the transport of positively charged jth species is in the direction of decrease in the potential field. On the other hand, the transport of a negatively charged species would be in the direction of increase in the potential field. On similar basis, as discussed for the case of convective and diffusive transport, we have the

following equations along the three axes, X, Y and Z

a) Along X axis:

b) Along Y axis:

c) Along Z axis: Therefore, the net transport of the species j across the electrolyte can be represented by the summation of contributions from the convection, diffusion and the migration. This leads us to the following equation

.....................................................................................(6) This equation can be expanded to the following equations in the X, Y and Z directions.

a) Along X axis:

b) Along Y axis:

c) Along Z axis: Using Equations 1 and 6, we get the following expression for the total current

Where,

, is known as the mobility of the jth species in the electrolyte.

Thus, the ion mobility of a particular species is related to its diffusion coefficient, and this equation is popularly known as Nernst Einstein relation. Additionally, the mobility also depends on the ionic charge, operating temperature and pressure, ionic concentration and size.

.....................................................................................(7) This is the general equation to calculate the total current in any electrochemical system. It should be noted that at open circuit voltage (OCV), there is no net current drawn from the system and therefore, at OCV the above equation reduces to

Hence at OCV, the convective transport of the species in the electrolyte is balanced by diffusion and migration. Further, in case of static electrolyte, there is no velocity field, i.e. the velocity field vector is zero. Therefore, in case of static electrolyte the left-hand-side (LHS) of the above equation reduces to zero and we have

Therefore, the diffusion and migration transport balance each other and there is zero current.The mobility of an ion can be related to its conductivity by the following equation

where the symbol have their usual meanings as defined already; and is the absolute value of zj. This expression helps us to understand the ion conduction process in an electrolyte a) As the charge number zj. is increased, the total current carried per ion increases proportionally, increasing the effective conductivity. b) As the mobility of the charge carriers increases, the conductivity increases. c) As the concentration of charge carriers (participants in the ion exchange) increases, the ionic conductivity increases, although this trend does not hold for highly concentrated solutions. It should be noted that in electrochemical systems, the term overpotentials and/or polarization are often used to indicate inefficiency. In other words, this overpotential results in loss of the voltage

that the system can achieve at a particular current density. In case of a SOFC, a ceramic electrolyte is used, while a solid polymer electrolyte is employed for a PEMFC. The details of ohmic losses in both the cases are discussed here. Ceramic Electrolytes in SOFCs In a SOFC, O2- ions move from the cathode to anode through a ceramic electrolyte, typically yttria (Y2O3) stabilized zirconia (ZrO2), termed YSZ. Ceramics are generally inorganic nonmetallic materials synthesized by action of heat and subsequent cooling. Besides yttria, several other oxide materials have been used to dope YSZ, such as Yb2O3, Nd2O2, and Sc2O3. Doped YSZ conducts negative O2- ions, which are transported through oxygen vacancies in the zirconia structure. Yttria is typically added around 10 mol % to stabilize ZrO2as pure YSZ in not a good ion conductor. High electrolyte temperature is required for sufficient oxygen ion conductivity in the solid-state ceramic electrolyte, since oxygen ion mobility is almost negligible till 650 oC. This is the why the SOFCs are operated at very high temperatures, i.e. between 600 1000oC. Therefore, there lies a challenge in finding new materials which can be used as electrolytes in SOFC. Presently, researchers have been successful in improving the ion conductivity by doping YSZ with several oxide materials, as discussed above. The YSZ exhibits mixed (electrical and ionic) conductivity; however, the electrical conductivity is pretty low for typical operating conditions in the SOFC. The ionic and electrical conductivity of 8% mole fraction yttria YSZ, (ZrO2)0.92(Y2O3)0.08, has been reported in literature

.....................................................................................(8)

.....................................................................................(9) where KB is the Boltzmann constant (8.61 10-5 eV/K = 1.38 10-23 J/K), T is the absolute temperature, and PO2 is the partial pressure of oxygen; kBT should only be in eV to use the above equations. A plot of the ionic conductivity of (ZrO2)0.92(Y2O3)0.08, as a function of temperature is shown in Figure 1. As it is clearly evident from Equations 8 and 9, the ionic and electrical conductivity of the ceramic electrolyte increases with increase in temperature, however, increasing the partial pressure of oxygen would decrease the electrical conductivity. The conductivity can be related to the voltage drop by ohms law V=IR The total current through the circuit can be calculated by multiplying the current density, i with the geometric surface area of the electrode, and hence we have

.........................................................................................(10) Where,l is the electrolyte thickness, generally around 50 microns. As it can be seen clearly, a lower electrolyte thickness and a higher ionic conductivity would decrease the ohmic drop. In order to increase the power output from the fuel cell, we need to reduce the ohmic loss as much as

possible. However, thin film electrolytes (electrolyte thickness, l< 25 m), are not very stable during operation.

Fig. 1. Ionic Conductivity of (ZrO2)0.92(Y2O3)0.08 vs. temperature Solid Polymer Electrolytes in PEMFCs In a solid polymer electrolyte, ion mobility is a result of an electrolyte solution integrated into an inert polymer matrix. Generally, the solid electrolytes are perflourinated ionomers with a fixed side chain of sulfonic acid bonded covalently to the inert, but chemically stable, polymer polytetrafluoroethylene (PTFE) structure. As a result, the membrane consists of two very different sub-structures a) hydrophilic and ionically conductive phase related to the bonded sulfonic acid groups that absorbs water b) hydrophobic and relatively inert polymer matrix that is not ionically conductive but provides chemical stability and durability. The most widely studied perflourinated ionomers for fuel cells is Nafion, developed by DuPont, a U.S. based company. When Nafion is hydrated, H3O+-SO3- groups enable motion of H+ ions. Dry perflourinated ionomers act as insulators, therefore PEMFCs typically operate with hydrated Nafion membranes to facilitate ion transport and reduce ohmic losses. People have tried to understand the fundamental nature of proton transport through the Nafion membrane and reported two mechanisms, depending upon the water content in the membrane a) When the water content is low, the ionically conductive hydrated portion of the membranes behaves as nearly isolated clusters, and proton transport is dominated by diffusion. b) When the proton content is high, a proton hopping mechanism is verified, where protons hop from one H3O+ to another along a connected pathway in the ionomer structure. The molecular weight of Nafion cant be determined accurately due to differences in processing and solution morphology. Instead, the equivalent weight (EW) and material thickness are used to describe most commercially available membranes. The EW is calculated by the following equation

.........................................................................................................(11) where k is the number of tetrafluoroethylene groups per chain. Generally, Nafion, 11, electrolyte is used for fuel cell operations, where 11 represents an EW of 1100, while the last digit indicates the thickness of dry membrane in thousandths of an inch. For example, Nafion 112 represents a 0.002 inch (or 51 m) thick membrane with 1100 EW. However, it should be noted that thickness of the membrane depends on the water content of the membrane. In other words, the thickness changes when exposed to different relative humidity environments. The ionic conductivity through Nafion is a function of its water content. Therefore, one first needs to quantify the water content of the membrane. In general the water uptake, ?, is defined in terms of water molecules per sulfonic acid site, i.e.

.........................................................................................................(12) In literature, the water uptake of Nafion 1100 EW membrane at 30 C is reported as

.........................................................................................................(13) where a (0 < a = 1) is the relative humidity (RH), which is a function of temperature. Figure 2 below shows the graphical representation of water uptake, ?, as a function of relative humidity. It can be seen clearly, for 0 < a = 1, i.e. between zero and 100 percent RH, the water uptake of the membrane increases with increase in RH. It should be noted that the water uptake of the Nafion membrane is much higher, when equilibrated with liquid water and therefore, the above relation can only be used when the membrane is equilibrated with water vapor.

Fig. 2. Water uptake, , vs. relative humidity at 30 C Although, the water uptake of the Nafion 1100 EW membrane depends on temperature, the equation can be still be used to good effect to quantify the water content of the Nafion membrane at higher temperatures. However, it should be noted that water uptake of the membrane decreases with increase in temperature. The water uptake of the Nafion membrane can further be related to its ionic conductivity as follows

.....................................................................................................(14) where T is absolute temperature (in Kelvin) and ? is the water uptake as defined above and can be quantified using equation 13. The Nafion membrane, though has negligible electrical conductivity unlike ceramic electrolytes and hence, we have ..................................................................................................................(15)

Fig. 3. Ionic conductivity vs. temperature at different RH values

Fig. 4. Ionic conductivity vs. RH at different temperature values Figures 3 and 4 depict the variation in ionic conductivity with temperature and various RH values. The increase in temperature clearly increases the ionic conductivity. Moreover, the increase in RH considerably increases the ionic conductivity. This can be attributed to the transition from diffusion to hopping transport mechanism because of increasing water content in the membrane. Since we now know the ionic conductivity through the Nafion membrane, the voltage drop can be calculated using ohms law as discussed in the case of a SOFC. Therefore, we have

Where, l is the wet membrane thickness and is the current density. It should be noted that thickness of a membrane depends on its water content. Generally, the dry membrane thickness is only known to us and thus needs to be determined based on the RH environment, before calculating the ohmic overpotential. Transport of Electricity: Ohmic Polarization The ohmic polarization arises due to electrical resistance in the cell components, including

Resistance to the flow of ions in the electrolyte (ionic resistance) Resistance to the flow of electrons and ions in the catalyst layer (ionic and electronic resistance) Resistance to the flow of electrons through the electrode-backing layer, or gas- diffusion layer (electronic resistance), and Resistance to the flow of electrons through the interface contact and the terminal connections (electronic resistance)

Ohmic polarization can be determined by Ohms law, ohm=IR where R is the sum of electronic, ionic, and contact resistance. For practical fuel cells, ohmic polarization is mainly caused by ionic resistance in the electrolyte. In fuel cell literature, the use of electrical resistance of the cell components, including electrolytes, is often avoided and reciprocal resistance or conductance is commonly used. The conductance is simply the inverse of resistance, Conductance: =1/R The resistance R depends on the material property as well as the geometry of the conductor as follows, R= L/A =The specific resistance (resistivity) is a material property, representing the capability of the material in the transport of electricity. L = Where L is the length of the conducting path, A is the cross-sectional area of the conductor normal to the conducting path and the electrical field has been assumed uniform in arriving the above equation.

Area specific resistance = A R Specific conductance (or conductivity) = 1/(S/cm) Inverse of sp. resistance Details of Mass and Electricity Transport in Electrolyte As discussed earlier that the ohmic polarization is contributed by many components. However, in fuel cell the ohmic polarization is largely contributed by the electrolyte. The electrolyte transports the ions, that means the mass as well as the charge (or electricity) are transported by the electrolyte. Therefore, the transport processes in the electrolyte will be discussed in the electrolyte. The Mass transfer in the electrolyte is very similar to reactant transfer to the electrode as described earlier. However, only exception is that the mass transfer arises in the electrolyte is by the motion of mobile ionic species in the electric field set up between the anode and cathode. The motion of charged species in the electric field is known as migration of the ions. Thus in order to understand the complex behaviour of transport in the electrolyte, the discussion is divided into 3 situation to make it simplified. In the first situation, it will be considered that the mass transfer of the ionic species in the electrolyte is purely due to the diffusion and there is no electric field between the anode and cathode. In the second situation, it will be considered that the mass transport of the ionic species in the electrolyte is due to migration only. That is the transporting species is having charge and electric field is set up between the anode and cathode. In the third situation, the transport of charged species will be considered due to simultaneous diffusion and migration. Based on the previous discussion, the three situations are written below, 1. Mass transfer by diffusion 2. Mass transfer by migration 3. Mass transfer by simultaneous diffusion and migration of ions

All above three situations are described in the following discussion one by one. Mass transfer in Electrolyte by Diffusion of Ionic Species Consider the situation of a mobile ionic species, i, that is being discharged at an electrode surface.

The transfer process for the ionic species is thus created by the concentration difference (diffusion mechanism). A representative concentration profile is shown in the adjacent figure.

The rate of diffusion towards the electrode surface for the ionic species i is, in terms of molar flux (Ficks law)

Di is the diffusion coefficient of the ionic species, i, with respect to the electrolyte solution and is mainly a function of nature & molecular size of the species, temperature, and electrolyte viscosity.

Thus current density corresponding to the rate of ion transport is,

Where, i is the thickness of the diffusion layer adjacent to the electrode surface. The typical value of the diffusion layer is in the rage ~300 micrometer). The limiting current density can be obtained at Ci,s = 0

where L,i is the diffusion layer thickness at limiting current density. If the diffusion layer thickness could be assumed almost invariant (which may not be necessarily true), then i = L,i

Assuming all other processes at the electrode are reversible, the voltage loss due to lowering of the ion concentration at the electrode surface can be estimated from the Nernst equation,

Mass transfer in Electrolyte by Diffusion of Ionic Species In the earlier discussion, the charge on the species did not matter. However, while discussing migration the charge on the species matters. The electrolyte may have positively and negatively charged species along with the neutral species. Thus, Electrolyte

Positive ion Negative ion Neutral species (eg. water) for electrolyte

Ions are constantly in random thermal motion. However, they start to accelerate in the direction of the electric field once an external field is set-up across the electrolyte layer. Acceleration is retarded by: viscous and electrical forces (mainly from ionic interactions). Terminal velocity: (Driving forces = Retarding forces)

Electrical field is represented by the gradient of the electrical potential in the x-direction ui is the mobility (ionic velocity/potential gradient) of the ion (m2.mol/J.s). The negative sign reflect that positively charge ion (ni > 0) moves in the direction of decreasing potential. The molar flux due to terminal velocity,

Thus the current density arises,

Where, conductivity of the ion i is the transport property of the ion in the electrolyte is defined as

Then,

Which is simply an expression of Ohms law The eq. is valid when Ci is uniform throughout At this moment, the question comes that if all the charged species are involved then how to know the effect of individual species. In this concern, the total current density J resulting from the migration of all the ions in the electrolyte is equal to the sum of the contribution made by the transport of each of the ionic species or,

On comparing this equation with the previous one, we can find out that the conductivity of the electrolyte may be written as,

The migration of each ionic species in the electrolyte contributes to the total current density carried by the electrolyte. In order to quantify the relative contributions, the transference number of the ionic species, i, is defined as the fraction of the total current density that is carried by the given ionic species, i, or

Substituting J and Ji,

Since k is transport property, t is also a transport property of the electrolyte If we integrate the equation, across the electrolyte layer thickness, we obtain the ohmic overpotential due to the electrolyte,

On integration,

The relationship is valid only if the concentration is uniform in the electrolyte. Mass Transfer by Simultaneous Diffusion and Migration of Ions Total molar flux for the ion i under the combined effect of diffusion and ion migration,

Total molar flux for the ion i under the combined effect of diffusion and ion migration, Corresponding current density,

When a fuel cell reach a steady state, all the current is carried by the transport of ions that participate in the electrode reactions For all other ions present in the electrolyte, their flux due to the electric field effect (migration) is counterbalanced by the flux due to the concentration gradient (diffusion) and no net transport of electricity arises from the motion of these ions. At this point we may emphasize that both the diffusion coefficient Di and the ion mobility ui are the transport property of the ionic species i through the electrolyte solution and they may be related to each other. Consider a situation where there is no net current flow (J=0) through the electrolyte, that is, the current arising from the ion diffusion due to the concentration gradient and from the ion migration in an applied electric field reaches the same magnitude, but in the opposite direction. Thus thermodynamic equilibrium is attained and the conc. of the ion i is given by the thermodynamic Boltzmann distribution.

Where Ci, , is the concentration of the ionic species i corresponding to zero (0) local potential ( ). On the other hand, at J=0 and integrating the below written equation, from Ci, , at =0 to Ci at

&phie, we obtain,

On comparing with the equation written in the previous slide,

u =D /RT
i i

The relation is known as the Nernst-Einstein relation. It relates the transport processes of ionic species by diffusion and migration in an electrolyte and provides an important link between mass diffusion and electrical conductance. It should be pointed out that the Nernst-Einstein relation is valid even when the total current through the electrolyte does not reduce to zero value, although it was derived when J=0. This is because both ui and Di are the (transport) properties of the ion i in the electrolyte. Considering equations

On rearranging

On integrating from the surface where x=0, =1 and Ci = Ci,s and in the bulk electrolyte sufficiently away from the electrode surface where = 2 and C =C i, ,

It may be noted that the above equation is the basis of current interruption method, that we will discuss in characterization techniques. At this point we may think if diffusion and migration is considered then why not the convection process. Of course, we will discuss that also. The mass transfer, that is, the movement of material from one location in solution to another, arises from atleast by one of them, 1. Migration 2. Diffusion 3. Convection

The mass transfer to an electrode is governed by the Nernst-Planck equation, written for 1-D mass transfer along the x-axis as,

The above equation is known as Nernst-Planck Equation

Modelling of fuel cell: current-voltage predictions


Need Of modeling

A virtual prototypes of fuel cell, which helps in fabrication Insight into the electrochemistry of the fuel cell & processes that takes place in the heart of the fuel cell Optimize the design parameters of fuel cell system

A combination of modeling and experimentation can reduce the cost and accelerate the pace of building and understanding prototype systems[1]. This will further help in commercialization of fuel cell.

development process [2]

Figure 1: Flow chart of fuel cell development process Characteristics of a good model [2] A good model should balances,

Robustness: model should able to predict fuel cell performance under a large range of operating conditions and physical parameters. Accuracy: it can be developed by using the correct assumptions, correct physical quantities and input parameters, correct governing equations, and validation with experimental data. Computational efforts: time required for calculation should be less, but sometimes for accuracy, computational efficiency is compromised.

A basic fuel cell model[3] The real output voltage (V) of fuel cell can be calculated subtracting all the overvoltage losses from the thermo-dynamically predicted voltage

............................................................................................(1)
where, Ethermo =thermodynamically predicted voltage of fuel cell act =activation losses due to reaction kinetics ohmic =ohmic losses from the ionic and electronic resistance conc

=concentration losses due to mass transport

Using the expression for conc , act , ohmic from the previous chapter, the net j - v behaviour can br given as,

................................................(2) Here we use the Tafel equation for the fuel cell kinetics, therefore Eq.(2) means this model is only valid for j>>j o.For modelling at low current density region, full form of Butler - Volmer equation should be used. In this model there are seven fitting parameters: A, C,A, C,,A,Rohmicand jL, where the values of ,, are related to and j0

Graphical representation of the factors that contributes to fuel cell performance

Figure 2: Graphical representation of all the losses

A 1D FUEL CELL MODEL (ANALYTICAL)

This model is more sophisticated than the basic model. It is based on the flux balance concept. Flux balance allows us to keep tracks of all the species flowing in, out and through the fuel cell. The model is well suited for polymer electrolyte fuel cell (PEMFC) and solid oxide fuel cell (SOFC). In the present models, we only concentrated on fuel cell species transport and determine the species concentration profiles, electrochemical losses and j-V curve.

Flux Balance in Fuel Cells PEMFC

Figure 3shows the flux details needed in 1D model. Individual fluxes are represented by the numbers. Infuel cells, all species transport flux are related to the single charcter flux-the current density or charge flux of the fuel cell.From the figure 2 one can write as,

flux-flux5=flux1 - flux4 = flux8 - flux 13 ....................................................................(3) mathematically,

...........................................................(4) where, j is the cell current density (A/cm2), F is Faraday's constant (96,484 C/mol), N is the molar flux (mol/s.cm 2) , r is the generation term due to electrochemical reaction

Figure 4: Flux detail diagram of SOFC

is the net hydrogen flux (in - out) in the anode, i.e., the amount consumer in the oxidation reaction. Similarly, oxygen at cathode is the water generation rate due to oxygen reduction reaction at cathode. water flux balance in the PEMFC is given as,

is the net flux of

................................................(5)

water flux through the membrane is given by the balance between electro-osmotic drag and back diffusion water fluxes.Flux 5 represent the

flux due to water generation. Mathematically above equation can be written as,

...................................................(6)

where, is the net flux into the anode catalyst layer, across the membrane layer, and into the cathode catalyst layer respectively and j/2F term represent the water generation rate.

Let (unknown) is the ratio between the water flux across membrane and charge flux across the membrane is hiven as,

..............................................................................................(7) Putting Eq. (7) in Eq. (6) one can gets,

.............................................................................................(8) On combining eq. (5) - (8), all the flux in the fuel given as,

............................................(9)
SOFC flux balance

Figure 4 shows the flux detailed diagram of SOFC. Similar to PEMFC model, the flux balance equation for SOFC is given as,

.............................................(10)

Overall flux balance in SOFC is simpler compared to PEMFC because water produced at the anode and does not transport through the membrane, hence no need of water balance . The water flux at the anode equal to the charge flux. The species transport through membrane is only of oxygen ions (O2-). Water flux at the cathode is zero. The water generates at the anode is in vapor form because of high temperature. In PEMFC model, water present in liquid form and transport through the membrane. So, water balance across the membrane is necessary.

Figure 4: Flux detail diagram of SOFC Model Assumptions

To simplify the model, some assumptions are made which are as follows: 1. convective transport is ignored. Although, convection is dominant phenomena in fuel cells.Bur here, for iD model convection is not cosidered along x-axis . 2. Diffusion transport in flow channel is ignored.Convection is dominant phenomena in flow channel, since convection is ignored (assumption 1)) in flow channel , diffusion can also be ignored. 3. Ohmic losses only due to electrolyte membrane. 4. For H2 - O2 fuel cells, anode activation losses is much smaller than cathode activation losses. Hence, anode reaction kinectics is ignored. 5. Catalyst layer are assumed as extremely thin like 'interface'(no thickness).Hence convection, diffusion and conduction processes in catalyst layer are ignored. 6. Water assumed to be exists as water vapor.For SOFC, this assumption is valid because SOFC operates at high temperature. In PEMFC, water exist in water vapor and in liquid form.

Governing Equations

Equations that deal specificially with phenomena in a fuel cell areDeacy's equation for fluid flow in conduits and porous media, Fick's law of diffusion, Stefan-Maxwell equation for multispecies diffusion, Fourier's Law for heat conduction, Faraday's Law for relationship between electrical current and consumption of reactants in an electrochemical reaction, Butler-Volumer equation for relationship between electrical current and Potential Ohm's Law of electrical current conduction.

For the present model, simplified version of equations are used by choosing appropriate assumptions.By solving these equations we can determine concentration profiles, activation overpotential (act), ohmic overpotential (act), and concentration overpotential (act). For the present model, simplified version of equations are used by choosing appropiate assumptions.By solving these equation we can determine cocentration profiles, activation overpotential (act), ohmic overpotential (ohmic), and concentration overpotential(conc) . Electrode layer Species transport (H2,O2,N2,H2O) in this layer is given by simlified Fick's Law of diffusion,

......................................................................(11) In case of gaseous reactants, above equation can be written as,

.....................................................................(12) where, Ni is the molar flux (mol/s-cm2) of the species i, Ci is the concentration (mol/cm3) of the species i,pi=pxi is the partial pressure (Pa) of the species i,p is the total pressure of the gas,x i is the mole fraction of the species i, is the effective binary diffusivity (cm2/s) between species i and j, it can be determine using the nominal binary diffusity, Dij and void fraction, by Bruggeman's correction,

.......................................................................................(13) Electrolyte layer Governing equations for species transport in the electrolyte.From Eq.(10) oxygen ion flux can be given as,

.......................................................................................................(14) From assumption 3, ohmic overpotential is given by,

..............................................................................(15)

where, LM is the electrolyte thickness, KM is the electrolyte conductivity (S/cm) which is given as,

...............................................................................(16) where, A (K/ohm) and activation energy, Gact(J/mol) are usually determine experimently. For PEMFC, water and proton (H+) both transport through the membrane electrolyte.Proton flux is given by Eq.(4) nd water flux through the membrane can be describe as combined effect of back diffusion and electroosomotic drag,

..................................................................(17)

...................................................................(18)

...................................................................(19)

Where, ndrag is the electroosmotic drag coefficient, dry is the density (g/am3) of dry membrane, Mm is the molecular weight, Dmis the diffusivity(cm2/s) of water inmembrane, is the water content membrane. Sustitute Eqs. (18) and (19) in Eq. (17), one gets,

..........................................................................(20)
Ohmic overpotential is determined as,

..............................................................................................(21) Resistance of the membrance, Rm is given by,

..............................................................................................(22) Membrance conductivity, KM for Nafion membrane is expressed as [3],

where, can be determine using Eq.(20) Catalyst layer Cathode side kinetics is represented by modified form of Butler-Vilmer equation,

................................................................(23)

.........................................................................(24) For an ideal gas(p=CRT), the above equation becomes,

................................................................(25) where, p0=1atm Modeling Examples 1d SOFC Model

Figure 5 shows the 1D schematic of SOFC. Anode: H2,H2O transport is given by Eq. (12)

...............................................................(26)

................................................(27)

Figure 5: Schematic of SOFC Using Eq. (10), H2, H2O flux are related with cell current density. Integrating Eq.(26) and (27), gives linear profile of H2,H2O concentration at anode,

.....................................................................(28)

......................................................................(29)
At interface 'a', values of xH2,xH2O are known. Solving Eqs. (28) and (29) at interface 'b' yields,

....................................................................(30)

...........................................................(31)
where, tA is the thickness of the anode Cathode Siimilarly, one can obtained oxygen profile at cathode,

....................................................(32) At interface 'c', Eq. (32) yields,

......................................................(33) Combine Eqs. (25) and (33), cathode overpotential is given as,

.....................................(34) Electrolyte From Eqs. (15) and (16), ohmic loss is given by,

.................................(35)) Finally, a real SOFC voltage is written as,

.............................(36)

............................(37) PEMC Model Figure 6 shows the 1D schematic of PEMFC

Reactants (H2, H2O, O2, N2) transport in flow channel is by convection and in electrodes by diffusion. Electrons transport is through the external circuit, whereas ions transport through membrane electrolyte.

In membrane, water transport is by electroosmotic drag and back diffusion

Anode

Figure 6: Schematic of PEMFC Similar to SOFC model, H2, H2O fluxes described as,

........................................................................................(38)

...........................................................................................(39) Using Eq. (9), the solution of the above equations,

..........................................................................................(40)

.......................................................................................(41) here, is unknown. At interface 'b', Eq. (40) and (41) yields,

....................................................................................(42)

...............................................................................(43)
Cathode Oxygen concentration profile at cathode interface 'c' is expressed as

...............................................................................(44)
water concentration profile at cathode interface 'c' is given as,

...........................................................................(45)
where, tc is the thickness of the cathode. Similar to SOFC model, cathodic overpotential is determine using Eqn (34) Membrance electrolyte: To calculate ohmic overpotential, water profile in membrane is required. Substitute Eq. (7) in Eq. (20) and integrate, Eq.(20) becomes,

........................................................(45)

At interface 'b'

.......................................................................(46)

At interface 'c'

.......................................................................(47)

Nation watrer content can be relate with the water activity as,

......................................................................(48)

......................................................................(49)

......................................................................(50)
Combining Eqs.(43) and (48) and Eqs. (45) and (49) gives,

.....................................................................(51)

........................................(52)

From Eqs. (46),(47),(51) and (52), two unknowns, and B in Eq.(45),the conductivity, KM profile in membrance can calculated by Eqs.(23) and (45). Resistance in membrane is calculated by Eq. (22), hence ohmic overpotential is determine as,

..................................................................(53) Finally, fuel voltage is given as,

.............................................................(54) Direct Methanol Fuel Cell Modeling (DMFC) [4]

Figure 7 shows the schematic diagram of DMFC. Complete oxidation of methanol (fuel at anode) takes place and product obtained is CO2 via 6 e- release. Model consider the mass transport in the anode compartment. Kinetics and ohmic effect considered in the catalyst layer. Influence of different parameters on anode performance is investigated.

Figure 7: Schematic diagram of the anode bonded PEM DMFC Mathematical Model

A membrane region of solid polymer electrolyte (PEM), protons produced at the catalyst layer are transported via migration through it. Active catalyst region(catalyst layer) on which oxidation of glucose takes place, it formed as a thin film of proton conductive ionomer (e.g. Nafion) and carbon supported catalyst (e.g. Pt-Ru/C) uniformly dispersed in the ionomer. A diffusion region (diffusion layer) composed of highly porous and electronically material (collect the electrons generated at the catalyst layer

into the current collector).

Figure 8 : Schematic illustration of catalyst layer [5] Model Assumptions

Steady state, isothermal conditions were considered . Anode and cathode compartment have the same pressure . Anode and cathode compartment assumed as mixed reactor . Two phase flow in anode channel is neglected .

The electro-osmotic drag coefficient of the water for PEM is taken as fully hydrated, therefore it depend only on temperature . Concentration of oxygen taken high, so assumed constant concentration at cathode compartment so no need of mass balance .

Electrochemical Cell Reactions

Governing Equations Methanol transport in flow channel

.....................................................................................(55)
Mass transport in diffusion layer water flux balance equation is given as,

.....................................................................................(56)
Methanol flux equation is expressed as,

.....................................................................(57)

.................................................................(58)

..............................................................(59)
Integrating Eq. (59) gives,

...............................................................(60)
Combining Eqs. (55) and (66)

................................................................(67)

where,

is the mass transfer coefficient,

is the superficial velocity of water


Mass transport in catalyst layer Electrochemical reaction rate described by Tafel type Butler-Volumer Equation,

..........................................................................(68)
Methanol flux equation given as,

..........................................................................(69)
Flux balance of water is expressed as,

...........................................................................................(70)
Methonal, flux in catalyst layer decrease along z-axis due to its oxidation at the catalytic site, therefore material balance of methonol,

.............................................................................................(71)
Anodic over potential at any location within the catayst layer is written as,

.............................................................................................(72)
Ohm's law for solid phase,

.............................................................................................(73)
Ohm's law for ionomer phase,

.............................................................................................(74)
Variation of the over potential within in the catalyst layer given by,

.............................................................................................(75)
Mass transport in PEM Water transport through the PEM results from both the electro-osmotic drag and diffusion, i.e.

Water flux caused by elctro-osmotic drag, at constant cell temperature is given by,

...................................................................................................(76) Water flux caused by water concentration gradient in the PEM,

....................................................................................................(77) At higher current density enhanced water accumulation at cathode reaction raise its concentration on the cathodic side into fully hydrated state, also anode is in fully hydrated condition, so we can neglect Ndrag Final water flux equation is expressed as,

............................................................................................(78)
Similarly as anode diffusion layer, methanol flux in membrane given as,

........................................................................................(79)
Solution Procedure

................................(80)

...........................................(81) These equations can br transferred into first order equation as,

.......................................................................................(82)

.......................................................................................(83)

..............................................(84)

..............(85)

Dependent variables:

Boundary Conditions Diffusion layer is ionically insulated, so that the protonic current density must be zero at the diffusion layer/catalyst layer interface(z-0),

................................................................................(86) Material balance of methonal at diffusion layer/catalyst layer interface(z=0)

................................(87)
In shooting technique appropriate initial guess is given to the variable and iterate it until the final value due to initial guess will match with the actual final value. At catalyst layer/PEM interface(z=lc), the protonic current density must be equal to the cell current density l

.......................................................................................(88) The flux through the catalyst layer is partly consumed in electrochemical reaction and remaining pass through the membrane sa menthonol crossover, therefore,

Intial value of i is known , others variables values are unknown so for solve these equations, proper shooting technique is used. Base - case parameterrs values

Results [4] Anode overpotential of DMFC:Catalyst Pt-Ru, Methanol concentration in feed- 2 M

Methanol concentration variation with in the diffusion layer and catalyst layer at various current density

Variation of methanol crossover with current density at various feed concentrations

Effect of current density on anodic overpotential at various current density

Variation of reaction rate within the catalyst layer at different values of

and

at cell current density of 0.3 A/cm2

Vriation of anodic overpotential with effective protonic conductivity

at different current density

References 1. 2. 3. 4. 5. Modeling of fuel cell, http://www.aip.org/tip/INPHFA/vol-7/iss-4/p14.pdf Frano Barbir, PEM Fuel Cells: Theory and Practice, 2005, Elsevier Inc. Ryan O'Hayre, Suk-Won Cha, Whitney Colella, Fritz B. Prinz, Fuel Cell Fundamentals, 2nd Edition, 2008, Wiley. K.T. Jeng, C.W. Chen, Modeling and simulation of a direct methanol fuel cell, Journal of Power Sources 112 (2002) 376-375. Lixin You, Hongtan Liu, A parametric study of the cathode catalyst layer of PEM fuel cells using a pseudo-homogeneous model, International Journal of Hydrogen Energy 26 (2001) 991999

Fuel Cell Components


In this particular section, we will discuss about the fuel cell components. We would consider the components of polymer electrolyte membrane fuel cells as it is the most widely used fuel cell and have a potential to use in wide variety of applications as discussed at the beginning. Moreover, the PEMFC components are more or less same for the other type of low temperature fuel cells. The major components of the fuel cell are, 1. 2. 3. 4. Polymer electrolyte membrane (membrane) Bipolar plate Gas diffusion layer (electrode) Catalyst

The following figure shows a representative cost break up of the major components in the PEMFC. We have already discussed time to time about all the components. However, as it can be seen that bipolar plate is the most costly among others, we will discuss a few more information on bipolar plate little later.

We also know that at present the Nafion (a trademark of DuPont) is the most suitable membrane for the PEMFC and in order to make the PEMFC commercially viable there should be some other competitive membrane in the market. Therefore, some more information on the membrane is also provided in this section apart from bipolar plate. Electrolytes The use of polymeric membranes as electrolytes in fuel cells has received a tremendous impetus in the recent past. The PEM fuel cell gained prominence after an ion exchange resin was incorporated as an electrolyte for space application by General Electric (GE), in 1959 with the testing of phenolic membranes, prepared by polymerization of phenolsulfonic acid with formaldehyde. These membranes had low mechanical strength and a short lifetime of a few hundred hours and power density of a few hundred kW.m-2.

During 19621965, GE attempted to improve the power density by developing partially sulfonated polystyrene sulfonic acid membranes (prepared by dissolving polystyrene sulfonic acid in ethanol stabilized chloroform followed by sulfonation at room temperature). This membrane exhibited a better water uptake and an improved power density of 0.40.6 kWm-2 that enabled its application in NASAs Gemini flights. However, this membrane exhibited brittleness in the dry state. In the late sixties, cross-linked polystyrene-divinylbenzene sulfonic acid membrane/polymer was prepared in an inert matrix by GE. The life of the membrane ranged from 1000 to 10,000 h and the power density attained was 0.750.8kWm-2 [Costamagna, 2001]. In 1970s, DuPont developed a perfluorosulfonic acid called Nafion that not only showed a twofold increase in the specific conductivity of the membrane but also extended the lifetime by four orders of magnitude. The Dow Chemical Company and Asahi Chemical Company synthesized advanced perfluorosulfonic acid membranes with shorter side chains and a higher ratio of SO3H to CF2 groups [Guarau, 2000].

P. Costamagna, S. Srinivasan, J. Power Sources 102 (2001) 242252. V. Guarau, F. Barbir, H. Liu, J. Electrochem. Soc. 147 (7) (2000) 2468.

Currently PEMFC finds a wide range of applications due to its perceived simplicity of design and weight advantages, combined with optimum compatibility [Neburchilov, 2007]. Membrane materials used till date for PEM fuel cells can be classified as,

fluorinated polymer membranes, hydrocarbon membranes, acidbase blends.

V. Neburchilov, J. Martin, H. Wang, J. Power Sources 169 (2007) 221238 A brief description on each type of membrane system is given below. Fluorinated polymer membranes The perfluorinated sulfonic acid (PFSA) membranes have been the subject of intense research and are the key polymers used currently in portable fuel cell applications [Motupally, 2000]. Nafion by DuPont is a perfluorinated polymer and used most extensively in fuel cells. Similar polymers are Flemion produced by Asahi Glass and Aciplex-S produced by Asahi Chemical. S. Motupally, A.J. Becker, J.W. Weidner, J. Electrochem. Soc. 147 (9) (2000) 31713177. Among the three major types, the DuPont product is considered to be superior because of its high proton conductivity, good chemical stability and mechanical strength [Neburchilov, 2007]. However, Nafion and related polymers are still being intensely researched upon for improving the proton conductivity and chemical stability along with longevity of 60,000 h at 80 0C. The PFSA membranes are associated with some major limitations such as high cost of membrane, requirement of supporting system and temperature related issues. V. Neburchilov, J. Martin, H. Wang, J. Power Sources 169 (2007) 221238

Requirements of supporting equipment for uses with PFSA membranes, such as the hydration system add considerable cost and complexity to the vehicle power train [Neburchilov, 2007]. Membrane dehydration, reduction of ionic conductivity, decreased affinity for water, loss of mechanical strength due to softening of polymer backbone and increased parasitic losses through high fuel permeation are some of the other serious issues associated with these membranes [Neburchilov, 2007]. V. Neburchilov, J. Martin, H. Wang, J. Power Sources 169 (2007) 221238 With regard to the application in direct methanol fuel cells (DMFC), Nafion exhibits a high methanol permeability, which drastically reduces the DMFC performance and renders it unsuitable for DMFCs [Sakari, 1985]. Efforts are directed to eliminate the disadvantages such as methanol crossover problems and loss of hydration above 1000C. The influence of addition of different additives, such as silica, titanium dioxide, in Nafion, was studied to improve the retention of water in the membrane and to enable the operation of the fuel cell at higher temperature. T. Sakari, H. Takenaka, N. Wakabayashi, Y. Kawami, K. Tori, J. Electrochem. Soc. 132 (1985) 1328. Perfluro-sulphonic Acid Membrane

Polymer Electrolyte Membrane for PEMFC

Polymer electrolyte membrane (PEM) is a solid electrolyte and thus has various advantages compared to liquid electrolyte.

allows simple and compact cell structure and operation no free corrosive liquid; minimum corrosion of cell components can be made very thin thus ohmic losses can be minimized able to withstand large pressure differentials and thus control is easy as well as expensive , precision sensors and control units can be avoided) insensitive to orientation and therefore ideal for mobile application no CO2 poisoning issue acid concentration of the electrolyte is fixed during membrane fabrication quick start-up thus ideally suitable for transportation no need of electrolyte maintenance to refurbish or regenerate the electrolyte

However, the PEMs have certain disadvantages also, which are given below,

Low temp. operation results in low quality of waste heat Noble metal catalysts are required CO poisoning is an issue

Qualitatively the PEM should have the following main properties related to the low temperature fuel cell:

ionic (protonic or hydroxyl) conductivity should be as high as possible, chemical stability should be high , thermal stability should high to sustain in the operating temperature , mechanical properties (strength, and flexibility ) should be high enough to have good processability and can bear the fuel cell assembly condition , low fuel permeability is required, Moderate water drag is required, fast kinetics for electrode reactions should be supported, and The cost must be low and the raw materials must be ready availability.

Some information on Nafion

Nafion is a trademark of DuPont, USA, and work as an excellent proton exchange membrane for PEMFC. It is a sulfonated tetra fluoro-ethylene copolymer. Tetra fluoro-ethylene is the backbone of the Nafion and therefore it has very good chemical resistance and mechanical strength The sulphonic acid groups provide the proton conductivity to Nafion. The Nafion can hold or absorb large quantity of water in it. Once they absorb the water, the H+ (proton) of sulphonic group becomes hydrated and the hydrated proton can move quite freely with in the material. The water is essential for the protonic conductivity of the Nafion. Therefore, the fuel cell made up of Nafion can not work at higher temperatures. Thus the general operating temperature of the PEMFC is around 80oC.

Nafion solution as well as membrane are available in the market. Nafion115 and Nafion117 are widely used as fuel cell membranes. The various important nomenclature of the Nafion is given below,

Eg., Nafion115 The first two digits multiplied by 100 gives the equivalent weight of the polymer. In this case it will be 11x100=1100. The last digit gives us the thickness of the membrane in mil. One mill is 1000 part of an inch. Thus, in this case, the thickness of the Nafion115 membrane would be 5/1000 inch (or aorund112 micrometer). Basics of equivalent weight Equivalent weight = Atomic (formula) wt./valence (gm/mol) Valence is number of electrons that the species can donate or accept . Thus the equivalent weight of hydrogen or oxygen will be, H=1/1; O=16/2=8

The sulfonic group (SO3H+) in nafion has a valence of 1 since only one proton can be accepted Equivalent weight of nafion is equal to the average weight of the polymer chain structure that can accept one proton.

Hydrocarbon polymer membranes Despite its shortcomings, Nafion is still the polymer of choice for most PEFC and DMFC applications. However, it has been suggested that in order to produce materials that are less expensive than Nafion, some sacrifice in material lifetime and mechanical properties may be acceptable, provided the cost factors are commercially realistic [Neburchilov, 2007]. Hence the use of hydrocarbon polymers, even though they had been previously abandoned due to low thermal and chemical stability, has attracted renewed interest. V. Neburchilov, J. Martin, H. Wang, J. Power Sources 169 (2007) 221238 Hydrocarbon membranes provide some definite advantages over PFSA membranes and have the potential to compete with Nafion membranes. They are less expensive, commercially available and their structure permits the introduction of polar sites as pendant groups in order to increase the water uptake [Kreuer, 2001]. Poly(vinyl alcohol) (PVA) membranes are known to be good methanol barriers. Based on this observation, a method of crosslinking PVA was suggested so that the extent of swelling in water could be controlled. Presence of aromatic hydrocarbon in the backbone of hydrocarbon polymer enhances its performance at high temperature [Smitha, 2005].

K.D. Kreuer, J. Membr. Sci. 185 (2001) 13. B. Smitha, S. Sridhar, A.A. Khan, J. Membr. Sci. 259 (2005) 1026.

Aromatic hydrocarbons can be: (a) incorporated directly into the backbone of a hydrocarbon polymer, or (b) polymers modified with bulky groups in the backbone.

Polyarylenes are high temperature rigid polymers with glass transition temperature, Tg, >200 0C owing to the presence of inflexible and bulky aromatic groups. The aromatic rings offer the possibility of electrophilic as well as nucleophilic substitution. Polyethersulfones (PESF), polyether ketones (PEK) with varying number of ether and ketone functionalities (such as PEEK, PEKK, PEKEKK, etc.), poly(arylene ethers), polyesters and polyimides (PI) are some of the relevant examples of main chain polyarylenes [Gowariker, 1999]. V.R. Gowariker, N.V. Vishwanathan, J. Sridhar, Polymer Science, New Age International, New Delhi, 1999. Acid-base polymer membranes Acidbase complexes have been considered as one of the alternative for high temperature fuel cell operations. In general, an acid component is incorporated into an alkaline polymer to promote proton conduction. Poly(2,21-(m-phenylene)-5,51-bibenzimidazole)/phosphoric acid (PBI/H3PO4) complex is both intriguing and promising at the same time. It has shown a great deal of potential for medium temperature fuel cell applications and hence many attempts were made to understand and optimize this particular system.

Fuel Cell Catalysts


The electro-catalysts have a central part in the fuel cell and impact the efficiency, durability, and cost of the cell to a large extent. Carbon supported platinum or platinum alloys are commonly used as catalyst on both the anode and the cathode of PEMFC. The oxygen reduction reaction (ORR) taking place on the cathode has sluggish kinetics, which give a major contribution to the efficiency loss of the fuel cell. High amount of catalyst is required on the cathode to reach sufficient activity compared to the fast hydrogen oxidation reaction on the anode. Platinum is used as an active catalyst for not only hydrogen electrooxidation at anode but also used for oxygen electroreduction at cathode of PEMFC. However, the use of bulk platinum (e.g. Ptsheet or foil) neither yields good performance of the PEMFC nor it is economical due to low surface area per unit weight of platinum. In order to increase the surface area per unit weight, the nanoscale Pt particles are dispersed on supporting materials. The researchers are using the Pt based bimetallic, ternary catalyst, and other non-presious metal to decrease the use of Pt and improving the support material. The regular transition elements are good candidates as electrocatalysts, like, palladium, rhodiam, ruthenium, iridium, and osmium are used by various reaserchers to decrease the use of Pt. The platinum poisons by trace amounts of carbon monooxide and sulphur compounds, therefore losing its efectiveness as an electrocatalyst. Non -noble metal catalysts are more tolerant to these impurities. In general, the high temperature operation of the fuel cell reduces the effect of catalyst poisoning. However, the cell operation may be limited due to various other reasons. High electrocatalytic activity of a catalyst is generally achieved by a high surface area per unit mass of the catalyst. It is possible if we reduce the size of the catalyst particle. However, it may not be beneficial by reducing the size of the particles only but also there is a need to provide the active sites open to the reantant gases. It may be done by providing more porosity to the catalyst bed. The porosity may be developed without much hamperring the active sites of the catalyst, if the catalyst patricles are loaded on support material. It is well known that the electrocatalytic activity in the PEMFC were improved using the supported metal catalyst as compared to the unsupported bulk metal catalyst The carbon (Vulcan XC-72) is used commercially as a support material for the platinum in PEMFC application. Generally, the requirements for catalyst support material are high surface area, high electrical conductivity, high electrochemical stability and good interaction with catalyst under fuel cell operating conditions. Even a small increase in the eletrical conductivity of the support materials may improve the PEMFC performance significantly.

The above figure shows a catalyst for PEMFC, consist of platinum dispersed on carbon particle. As we are aware that the triple phase boundary is necessary for the transport of the species due to the reaction at electrode. The reactant reaches at the electrode and involves in the electrochemical reaction. The products thus formed have to be transported away from the catalyst site in order to keep the site free for further reaction. The reactant and product of the electrochemical reaction involves reactant, electron, ionic species, and any by product.

The figure on the left side shows a typical electrode system for hydrogen electro-oxidation in a representative way. Whereas, the figure at the right side shows the detailed transport of the various species from the triple phase boundary, infact the triple phase point is shown. A good interaction between catalyst and support materials improves the catalyst eficiency and decreases the loss of catalyst with time during operation of the fuel cell. The support material may affact the formation of platinum particales size during the preparation of metal catalyst. It is known that the electrochemical surface area (ESA) of electrocatalyst depends upon the support material as well as Pt particles size. Higher the ESA, better the PEMFC performance. The support material affect the Pt particles distribution during the synthesis of electrocatalyst. Therefore, the selection of catalyst support material is most important towards determining the ESA, stability, durability, and overall performance of the PEMFC. As discussed earlier, the carbon (Vulcan XC-72) is generally used commercially as a support material for the platinum in PEMFC application. However, during dynamic operation of the cell, there is a deterioration of the fuel cell performance, partly caused by the loss of electrochemically active surface area. The mechanism for the loss of platinum surface area has been widely investigated and can basically be described by the dissolution or detachment of Pt from carbon substrate and further re-deposition onto existing Pt particles or diffusing into the membrane or other inactive parts of the membrane electrode assembly. The detachment and mobility of the platinum is affected by the corrosion of the carbon support, which has been shown to be very severe not only on the cathode but also at the anode. Moreover, carbon cannot be used as the support in catalysts for PEM-water electrolysis and regenerative fuel cells because its corrosion occurs easily at the high oxygen-evolution potential. Moreover, low surface area (around 250 m2g-1) carbon material may not sufficient to accomodate Pt nanoparticles. Moreover, due to corrosion of carbon, Pt nanoparticle on the carbon support agglomerates and looses the suport material (carbon). Therefore, the electrochemical active sites reduce and as a result the performance of the PEMFC also reduce with the fuel cell operation time. Moreover, the researchers focus has shifted towards carbonaecous nanomaterials support for PEMFC catalyst due to their faster electron ransfer and high electrocatalyctic activity. e The carbon nanotube, carbon nanofiber, and graphene have been wiedly used as a carbon nanomaterial for catalyst support in PEMFC. These carbon nanostructures are basically allotrops of carbon atoms with high specific surface area, high electrical conductivity, and relatively good stability towards electrochemical environment. Due to the changes in the hybridization structure of source bulk materials, the electronical, mechanical, and physical properties of the nanomaterials are quite different and improved. In the recent efforts, it has been found that carbonless multifunctional active catalyst supports for

the PEMFC and electrolyser electro-catalysts may enhance the activity, utilization as well as the stability of the electro-catalyst.

Bipolar Plate for PEMFC


Why bipolar plate is required? The main functions of the bipolar plates in a PEMFC system are

to to to to to

support the membrane electrode assembly (MEA) robustly, distribute reactant gases uniformly over the active areas, conduct current between adjacent cells, remove heat from adjacent cells, and prevent leakage of reactant gases.

What are the materials available for bipolar plate? The following table summarizes the different material available for the bipolar plate as well as their advantages and disadvantages. Material Metal Advantages 1. High electrical conductivity 2. High mechanical strength Disadvantages 1. Corrosive 2. High contact resistance 3. High density 1. Uneven expansion 2. High density 1. Low mechanical strength 2. High H2 permeability 3. Machining of flow field 1. Long processing time 2. High production temperature 3. Cost ineffective 4. High porosity

Coated metal

1. High electrical conductivity 2. High mechanical strength

Graphite bipolar plate

1. High electrical conductivity 2. Good corrosion resistance

Carbon-carbon composite

1. Moderate electrical conductivity 2. Good corrosion resistance

Carbon-polymer composite

1. Moderate electrical conductivity 2. Good corrosion resistance 3. Good mechanical strength

1. Long processing time

If we have to develop a bipolar plate for the PEMFC then we should have a fair idea of the requirement of the bipolar plate. Thus to have a feel the following table shows that if one have to work on carbon/resin composite bipolar plate then the developed bipolar plate should have achieved properties. How to measure these properties are discussed in the proceeding sections with a focus on a few of the properties. Required properties Low weight Density Target Values < 0.4 kgkW-1 < 2.0 gcm-3

High flexural strength Highly flexible High electrical conductivity High thermal conductivity Low gas permeability High corrosion resistance High shore hardness

> 50 MPa * 35 % deflection at mid-span > 100 Scm-1 > 10 Wm-1K-1 < 210-6 cm3sec-1cm-2 at 80C and 3atm < 1 Acm-2 > 40*

OHayre et al., Fuel Cell Fundamentals, John Wiley 2009

Fuel cell characterization


Why to characterize fuel cell? This topic is one of the most important topics of the fuel cell technology. The fuel cell characterization is of particular importance to the fuel cell developers, scientists and researchers. Once the fuel cell is prepared, it is required to access whether a fuel cell is good or bad from the pool of the developed cells. It is required to know whether the fuel cell is comparatively inferior or superior to the competitive cell either prepared by others or the improvement from the previous cells. In order to distinguish between inferior or superior fuel cell, the characterization techniques are very straight forward by using i-v characteristics of the fuel cell. If a fuel cell performance is not upto the expectation or if you want to make it more effective, you must understand and to be able to quantify the different losses occurring in the fuel cell. The fuel cell characterization can be divided into two broad categories,

1. In-situ characterization Insitu characterization means the fuel cell is fabricated and now you would like to performance of the fuel cell. You may also be interested to know how much losses are occurring in the fuel cell, quantity of the losses, location of the losses etc. Thus we have to characterize the fuel cell in the ready form. On careful analysis, we may understand that the in-situ characterization can use the electrochemical variables of V, I, and time to characterize the performance of fuel cell under operating conditions. A few major in-situ characterization techniques are ,

1. 2. 3. 4.

Current voltage measurements Current interruption technique Cyclic voltammetry Electrochemical impedance spectroscopy

2. Ex-situ characterization Once we know that the performance of the fuel cell is not upto the desired standard then we have to find out the route cause. We need to identify the problematic component(s) as well as the reasons of ill-performance. Thus we need to characterize the component for its properties. Moreover, before using and developing a component for the fuel cell, it is to be characterize fully in order to know the desired properties. Some of the properties in which we are be interested are kinetic properties (?out, jo, a etc.), ohmic properties (Rohmic, electrolytic R etc.), mass transport properties (J L, Deff, ?P etc.), parasitic losses (jleak, side reactions, crossover), electrode structure (?,

tortuosity, etc.), catalyst structure (TPB, conductivity, AE, etc), flow structure (pressure drop, gas distribution, conductivity, etc.), heat generation/ heat management, water management, life time issues (degradation, cycling, startup/shut-down, corrosion, etc.), and many more. Various characterization techniques may be followed depending upon the individual components of the fuel cell. A some of them are shown below, Electrolyte : Proton conductivity; cross-over etc. Bipolar plate : Mechanical and chemical strength; flow field design; electrical conductivity etc. Catalyst : Surface area; selectivity etc. Gas diffusion layer : Porosity; hydropholicity; hydrophilicity; strength etc. However, we will focus on just a few of the most widely used characterization techniques in the forthcoming slides.

In-situ characterization
1. Current Voltage measurement Current-voltage measurement or polarization curve provides overall quantitative evaluation of fuel cells performance. It is very useful technique and provides an information of various losses like activation polarization, ohmic polarization, and mass transfer limitations or concentration polarization. With the help of polarization curve we can understand various processes happening in the fuel cell. For example, if at zero current the difference in the corresponding voltages of two similar direct methanol fuel cells indicate that the difference in the voltage may be because of the anode side fuel (methanol) crossover through the electrolyte to cathode side. Similarly, different concentration polarization may indicate about the slow transfer of the reactant to the electrode. For details, please refer to the earlier discussion on the polarization curve. 2.Current Interruption Technique The method separates the contribution of ohmic and non-ohmic processes of the fuel cell. This technique is very simple as compared to the other techniques like cyclic voltammetry, and electrochemial impedance spectrometry, etc. In the next slide an illustration is provided for the better understanding. Consider a current A1 is flowing through a fuel cell is abruptly interrupted as shown in figure (a). The resulting voltage-time response is shown in the figure (b). The interruption of the current causes an immediate rebound in the voltage, followed by an additional, time-dependent rebound in the voltage.

Illustration of current interruption technique The immediate voltage rebound from V1 to V2 is associated with the ohmic resistance of the fuel cell. The time-dependent rebound is associated with capacitive nature of the much slower reaction and mass transport processes. The recovery time for this process is slow and thus it takes time to come to the open circuit voltage (V3) corresponding to A1. If we recall the following equation discussed before to understand it.

For zero current the ohmic part contribution gets zero. However, the reactant molecules and ionic species takes some time to get re-oriented due to the removal of electric field.. 3. Cyclic Voltammetry (CV) The cyclic voltammetry has become a very popular technique for initial electrochemical studies of new systems and has proven a very useful in in obtaining information about fairly complex electrode reactions. In the technique, the potential of an electrochemical system swept back and forth between two voltage limits and the response of the current is measured against the voltage. In general the voltage is changes linearly with a predefined rate (V/s).

Illustration of the CV: The voltage is scanned from V1 to V2 and then back to V1 For a reversible electrochemical reaction the CV recorded has certain well defined characteristics.

(i) The voltage separation between the current peaks is

(ii)The ratio of the peak currents is equal to one (iii)The positions of peak voltage do not alter as a function of voltage scan rate

(iv)The peak currents are proportional to the square root of the scan rate Note: Subscript p denotes the peak, superscripts a and c denote the anodic and cathodic components , and v denote the voltage scan rate 4. Electrochemical Impedance Spectroscopy (EIS) Electrochemical Impedance Spectroscopy is also called AC Impedance or just Impedance Spectroscopy. It is a method of characterization of the electrochemical system. It utilizes the modeling of the electrochemical system into the electrical circuit of resistances, capacitances, or

other electrical components. EIS is a recent tool in corrosion and solid state laboratories and its usefulness lies in the ability to distinguish the dielectric and electric properties of individual contributions of components under investigation. The polarization curve provides general quantification of fuel cell performance. However, the EIS can be used for accurate quantification. It is a very common method to distinguish the different losses in the fuel cell. Basics of the EIS We know that like resistance, the impedance is a measure of the ability of a system to impede the flow of electrical current (electron or ions). However, impendance can deal with time or frequency dependent phenomena unlike resistance. The resistance is the ratio of voltage to current, similarly the impedance is also the ratio of time dependant voltage to time dependant current. In EIS technique, we provide a sinusoidal voltage perturbation to the fuel cell and the response is measured. As the EIS is modelled using electrical components, we would first learn the basics of the electrical components generally used for the fuel cell under sinusoidal perturbation. At first we will refresh the complex theory, If V(t) is the potential at time t, V0 is the amplitude of the signal, and ? is the radial frequency. The relationship between radial frequency ? (expressed in radians/second) and frequency f (expressed in Hertz (1/sec)). = 2f

Thus the impedance becomes,

As there is a phase shift between the voltage and current for a sinusoidal input, we generally represent the same in a complex plane shown in the next slide. Some of the equations related to complex numbers are as follows:

Electrical Components and their Impedance

Registor, R V=IR Let V = V0sin(t), then I = V0sin(t)/R So, current and voltage are in the same plane to each other and hence the impedance of a registor is R only. 2.Capacitor, C q = CV Let V = V0sin(t) I = CV0cos(t) = CV0 sin (t + 900) So, current leads voltage by 90o and hence impedance of a capacitor = 1/jC Inductor, L V= L.dl/dt Similarly, - V0cos(t) =LI = V0sin(t - 90o) So, current lags voltage by 900 and hence Impedance of an Inductor = j?L 4. Warburg Element, W It represents the diffusion part of an electrochemical cell, associated with a double layer capacitance. Impedance, ZW = Aw/+Aw/j Series and parallal combination of electrical components Very few electrochemical cells can be modeled using a single equivalent circuit element. Instead, EIS models usually consist of a number of elements in a network. Both serial and parallel combinations of elements occur. Impedances in Series: Zeq = Z1 + Z2 + Z3

Impedances in Parallal: 1/Zeq =1/ Z1 +1/ Z2 +1/ Z3

Representation of impedance spectroscopy The impedance so obtained from the study can be plotted in two different kinds. They are, i) Nyquist Plot:

The expression for Z(?) is composed of a real and an imaginary part. If the real part is plotted on the X-axis and the imaginary part on the Y-axis of a chart, we get a Nyquist plot. Notice that in this plot the Y-axis is negative and that each point on the Nyquist plot is the impedance Z at a particular frequency. On the Nyquist plot the impedance can be represented as a vector of length |Z|. The angle between this vector and the X-axis is f. Nyquist plots have one major shortcoming. The frequency at any point cannot be determined from the plot. Low frequency data are on the right side of the plot and higher frequencies are on the left. This is true for EIS data where impedance usually falls as frequency rises (this is not true of all circuits). The Nyquist plot shown in the next slide is for a RC circuit. The semicircle is characteristic of a single time constant. Electrochemical Impedance plots often contain several time constants. Often only a portion of one or more of their semicircles is seen. RC Circuit

1/Z =1/R +1/j Corresponding Nyquist Plot

ii) Bode Plot: Another popular presentation method is the Bode plot. The impedance is plotted with log frequency on the X-axis and both the absolute values of the impedance ( Z = Z0) and phase shift on the Y-axis. The Bode plot for the RC circuit is shown below. Unlike the Nyquist plot, the Bode plot explicitly shows frequency information.

A typical representation of fuel cell The fuel cell, which has three major parts, anode, electrolyte and cathode, can be expressed in terms of resistance, capacitance and the Warburg element. Resistances develop mainly due to the resistance to the transport of ions or electrons. And hence we see the electrolyte section being shown as a resistance model with small resistances in the anode and cathode part to account for the resistance to the electron movement. An electrical double layer generally exists at the interface between an electrode and its surrounding electrolyte. This double layer is formed as ions from the solution to the electrode surface. Charges in the electrode are separated from the charges of these ions. The separation is very small and is in the order of nanometers. These charges separated by an insulator forms a capacitor. In order to have a feel of the capacitance value, it is known that a bare metal immersed in an electrolyte will generate around 25F per cm2 of the metal electrode area. The value of the double layer capacitance depends on many variables such as electrode potential, temperature, ionic concentrations, types of ions, oxide layers, electrode roughness, impurity adsorption, etc. A representative Nyquist plot for a fuel cell: The typical values on the plot is just a typical value.

The Warburg element accounts for the diffusion layer formed at the cathode section and hence resisting the flow of hydronium ions to the cathode. Now, we see that there exist two semicircles in the Nyquist plot for the given model. This shows that the system has two time constants, one for the cathode side and another for the anode side. While at the later section of the graph, it takes a linear form owing to the Warburg element coming into play. The diameter of each of the semicircle represents the resistance of that particular part of the cell. As we know that the kinetics at the anode is much faster than at the cathode so we have a larger resistance value for the cathode than for the anode, which is evident from the diameter of the respective semicircles. In fact for actual fuel cell system, the smaller semicircle is too small to be visualized and in many cases removed to make the system simpler to analyze

Ex-situ characterization
We will discuss a few of the important ex-situ characterization of the major components of the fuel cell. 1. Electrolyte Characterization for proton conductivity In this section we will see how to find out the proton conductivity of the cationic solid electrolyte (proton exchange membrane). Through plane conductivity of the membrane can determined in a conductivity cell shown in the next slide. The conductivity measurement can be performed in a two-electrode AC impedance mode using a LCR mete.

Proton conductivity set-up for cationic solid polymer electrolyte Conductivity measurements should be performed at a particular temperature after equilibrating the membrane in de-ionized water for 24 hours. The membrane should be located at the centre of the conductivity cell, having two chambers filled with 0.5 M H2SO4 solution. Both the compartments should have a platinum electrode (say, 0.5 cm2 each). The electrical resistance of membrane (R1) can be measured using LCR meter. The electrical resistance of the 0.5 M H2SO4 solution (R2) without the membrane can be measured. The electrical resistance, R, of the membrane can be calculated by subtracting the value of R2 from R1.

where L, R, and A denote the distance between the electrodes (cm), the measured resistance (ohm), and the effective area of the membrane (cm2) perpendicular to ion flow, respectively. Bipolar plate

i. Electrical conductivity As discussed in the bipolar plate section, the electrical conductivity is one of the most important properties of the bipolar plate. In this section, we would discuss about how to measure the electrical conductivity of a composite bipolar plate made up of carbon materials and polymer matrix. Electrical conductivity of the bipolar plate can be measured as per the ASTM C611 method using conventional four probe technique at a constant current supply. The schematic of the electrical conductivity measurement set-up is shown in the figure on the next slide. Electrometer may be used as the constant current source.

Bipolar plate conductivity measurement set-up The electrical conductivity of the sample can be calculated by the following equation,

Electrical Conductivity where, l (cm) and b (cm) are the width and thickness of the sample, respectively. The constant current supplied through the sample is represented by i (A) and V (V) is the voltage drop between two points separated by a distance d (cm) along x-direction. The set-up was used to measure the in-plane and through-plane electrical conductivity by changing the orientation of the bipolar plate. ii. Flexural strength The flexural strength of the composite bipolar plates are important properties as the

bipolar plates may undergo high bending force during clamping within the fuel cell hardware. The three-point flexural strength of the bipolar plate can be used to evaluate with the help of an universal testing machine.

Bipolar plate flexural strength measurement set-up The movable anvil will start applying load to the specimen at the speci?ed crosshead rate, and the simultaneous load-de?ection data can be monitored with the help of a computer. The break load and the maximum deflection should be recorded accordingly. The flexural strength of the composite bipolar plate can be calculated using following equation,

where P = load at a given point on the load deflection curve in N, L = support span distance in mm, b = width of the test sample in mm, d = depth of the test sample in mm. iii. Shore hardness The shore hardness is another important mechanical property of the composite bipolar plate. Shore hardness of a composite bipolar plate can be measured with the help of a scleroscopic hardness tester as per the ASTM C886. It is a dynamic indentation type hardness test in which a diamond tipped hammer is allowed to fall vertically from a fixed height over the test specimen. The height of the rebound of the diamond tipped hammer was noted down and it was equal to the shore hardness of the composite bipolar plate.

3. Catalyst The usual methods of catalyst characterization may be used like surface area, particle size etc. However, as the catalyst is to be used in electrochemical system, the electrochemical activity as well as electrochemical surface area is very important properties of the catalyst rather electrocatalyst. The cyclic voltammetery is very important technique to find the electrocatalyst activity as well as electrochemical surface area. A typical example of two different catalysts are shown in the next slide, where CV was used to evaluate the electrochemical active surface area

Cyclic voltammetry of Pt/G and Pt/C electrocatalysts Where Pt/G and Pt/C are platinum supported on graphene and carbon, respectively. The figure on previous slide shows the cyclic voltammetry result for Pt/G and Pt/C. The electrochemical surface area (ESA) can be calculated by the following equation using charge of the hydrogen adsorption peak in the cyclic voltammetry curve after base line fitting by least square method.

The charge constant for poly-crystalline Pt surface for hydrogen adsorption is 210 Ccm2. The high electrochemical surface area is favorable for fuel cell catalyst oxidation and reduction reaction. The ESA for Pt/G and Pt/C can be determined as 61.58 and 54.76 m2g-1Pt, respectively. Thus, the Pt/G has more than 10% ESA than the Pt/C catalyst. From the previous figure it can be seen that the forward peak current density of Pt at the potential of 0.146 V is 0.04 Acm-2, which is nearly four times compared to Pt/C

(0.01Acm-2 at 0.066 V). Therefore, the electrochemical activity of Pt/G is also superior than that of Pt/C. 4. Gas diffusion layer Gas diffusion layer (GDL) is one of the vital components of the polymer electrolyte membrane fuel cell (PEMFC). The GDL is placed in between the bipolar plate and the catalyst layer of the fuel cell. The GDL of PEMFC is generally composed of microporous substrate and microporous layer (MPL) of carbon black. The MPL functions as a substrate for the catalyst layer by providing reduced ohmic resistance between the catalysts layer and the microporous substrate. The MPL works as a non-permeable support to the catalyst particles during catalyst deposition. However, it should be porous enough to pass the gases without imparting much resistance to the gas flow. The properties of the GDL can be altered by MPL. The most important desired properties of the MPL coated GDL are high electrical conductivity, high corrosion resistance, and high porosity. Therefore, pressure drop, porosity

High Temperature Fuel Cell: Solid Oxide Fuel Cell



What is Solid Oxide Fuel Cell (SOFC)? SOFC Components and Properties! Configuration of SOFC!

SOFC Ceramic Ion Conductors: Early Work Walther Nernst (1897) that the conductivity of pure oxides rises very slowly with temperature and remains relatively low, whereas the mixtures possess an enormously much greater conductivity Nernst mass (85% ZrO2 + 15% Y2 O3 )

W. Nernst Electrical GlowLight U.S. Patent 623,811. April 25, 1899 Reference: Solid State Fuel Cells: Evolution and Trends, Presentation by S. C. Singhal Solid Oxide Fuel Cells ( SOFCs ) A solid oxide fuel cell (SOFC) is a device that converts gaseous fuels (hydrogen, natural gas, gasified coal) via an electro-chemical process directly into electricity.

Advantages of SOFC

SOFCs are over 60% efficient (conversion of fuel to electricity) making them the most efficient fuel cell currently being developed. The efficiency makes them a good candidate for a distributed power source (generator or power plant). There are no liquids that cause safety and environmental problems. The reactions in SOFC require a high temperature. The advantage is that this creates a byproduct of heat.

Cell Reactions Anode H2 + O2- < ---------> H2 O + 2eCH4 +4 O2- < ---------> 2H2 O + CO2+8eCathode 1/2O2+2e- <---------> O2Overall Cell Reaction H2 +1/2 O2 + <------------>H2 O
0
2 2

E=E +RT/2F [ln(PH /PH 0)] +RT/2F[ln(PO


CH4+ 2 O2 2 H2O + CO2
0

1/2

E=E +RT/8F [ln(PcH /PH 0


4 2

PCO2)] +RT/2F[ln(PO2 2]

SOFC Electrolyte: Yttria-Stabilized Zirconia

Y O -------->2Y
2 3

Zr

+3OxO+Vo

YZr denotes Y in the Zr site with the apparent negative charge, and VO is the vacancy in the oxygen site with double positive charge. OxO is the lattice oxygen, i.e., oxygen in the oxygen site with net charge of zero.

Yttria is used as dopant for stabilizing the cubic phase of zirconia; a fully (cubic) stabilized zirconia is obtained with aY2O3-content of >7 mol% Y3+ have lower valency than zirconium ion (Zr 4+), induces the generation of oxygen vacancies for charge compensation. Substitution of Zr4+ with Y3+causes negative net charge in the lattice(for every mole of yttria incorporated into the zirconia lattice, charge neutrality condition prevailed by forming an oxygen vacancy) For an effective operation of a fuel cell, with the electrolyte within this range of thickness, the ionic conductivity of the electrolyte material must be higher than 0.1 S cm-1.

Different Electrolyte Material

Zirconia based

Ceria based

Lanthanum oxide based

Bismuth oxide based

Excellent Stability in oxidizing and reducing Good environment Excellent Good compatibility with cathode compatibility with Mechanical stability Materials High Conductivity cathode Materials (3YSZ) well stsdied material Electronic Ga evaporation at conduction at low lowpO2 Formation ofstable Lower Ionic Conductivity pO2 Poor secondry phases In compatible mechanical with NiO strength Different Electrolytes Zirconia electrolytes: (8YSZ, 3YSZ, ScSZ,CaSZ etc.) Ceria electrolytes :(GDC, SDC, YDC, CDC etc.) Lanthanum based electrolytes : LSGM LaXSr(1-X)GaYMg(1-Y)O3 LaALO3-based La1-xCax ALO3 ,La1-xBaxAlO3

High Conductivity

Thermodynamic instability in reducing atmosphere Volatilization of Bi2O3 High corrosion activity Poor mechanical

Bismuth oxide-based: Bi2V0.9Cu0.1O5.5-,(Bi2O3)x(Nb2O5)1-x Pyrochlorores - based: YZr2O7, Gd2Ti2O7 Barium brownmillerites : BaZrO3, Ba2In2O7, Ba3InxAOy (A=Ti,Zr,Ce,Hf) ,Ba3Sc2ZrO8 State-of-theart SOFC Bench mark properties for component materials 1.Cathode Composition Porosity Condutivity TEC Dimensions :LSM (La0.9Sr0.1 :40% (pore size 20-50 m) :100 S/cm at 1000oC :10-12 ppm/ oC :ID-14mm, Wall -2mm, L-160mm

2.Electrolyte
Composition Porosity Condutivity TEC Dimensions 3.Anode Composition Porosity Condutivity TEC Dimensions 4.Interconnect Composition Porosity Condutivity TEC Dimensions Requirement for the cathode :LCM [La0.95Mg0.05(CrO3)] :Nil, permeability should be zero :5 - 10 S/cm at 1000oC :10 - 12 ppm/ oC :W - 5 mm, L - 125mm , t~100m : Ni-YSZcermet (Ni - 60% by wt) :40% (pore size 20 - 50 m) :1000 - 1500 S/cm :10 - 12 ppm/ oC :OD - 18.1 mm, t~100m, L~125 mm : YSZ [(ZrO2)0.92(Y2O3)0.08 :Nil, permeability should be zero :lonic~0.1S/cm :10.5 ppm/ oC :Film thickness-50 m, L-125mm

high electronic conductivity Chemically comatible with neighbouring cell component (usually the electrolyte) Should be porous Stable in an oxidizing environment

Large triple phase boundary Catalyze the dissociation of oxygen Adhesion to electrolyte surface Thermal expansion coefficient similar to other SOFC materials

Requirement for the anode

Electrically conductive High electro - catalytic activity Large triple phase boundary Stable in a reducing environment Can be made thin enough to avoid mass tranfer losses, but thick enough to provide area and distribute current Thermal expansion coefficient similar neighbouring cell component Fine particle size Able to provide direct internal reforming (if applicable)

Requirements for the interconnect

Stable under high temperature oxidizing and reducing environment Very high electrical conductivity High density with "no open porosity" Strong and high creep resistances for planar configurations Good thermal conductivity Phase stability under temperature range Resistant to sulfur poisoning, oxidation and carburization Low materials and fabrication cost

Interconnect Ceramic Interconnect for High temperature SOFC (High material cost, sintering difficulties) eg: Doped Lanthanum Chormites and doped Yttrium chromites Metallic Interconnects (easy fabrication, high electrical and thermal conductivity) High chrome alloys (C5rFe1Y2O3) Ferritic stainless steel for temperature SOFC Iron super alloys Nickel super alloys Critical Issues Chromium evaporation (in Cr based interconnects)

Requirements for the sealing materials

Electrically insulating Thermal expansion compatibility with other cell components Chemically and physically stable at high temperatures Gastight Chemically compatible with other components Provide high mechanical bonding strength Low cost

Materials Glass ceramic materials - SrO-La2O3-Al2O3-SiO2 SOFC:Designs 1. Tubular Design o Pioneered by Siemens - Westinghouse 2. Planar Design o Convectional 'electrolyte supported' concept o Cathode supported design o Newer - Anode supported concept 3. Monolithic design

Planar SOFC Feature Power density at 800 C


o

Value 1.935 W/cm over kW/L over kW/Lkg 1 minute 5 seconds 31 hours
2

References Berkeley Lawrence Lab (2) Allied-Signal Aerospace (3) Allied-Signal Aerospace (3) Keele University (4) Keele University (5) Univ. of California (6)

Stack power per volume Stack power per mass Warm -up: to 800 C
o

or to operationg temperature Cool - down, 1000 to 800oC

Table 1 Recent results reported by distinguidhed SOFC laboratories Features Operating temperature Start -up (ambient to operating temp.) Stack power per volume stack power per mass Fuel Reforming Cooling Duty lifetime Projections (550oC)600oC to 800oC less than 2 minutes 2 kW/L 2 kW/kg unleaded gasoline, diesel, Mwthanol integrated internal and in situ air. heat rejection by exhaust 5,000 hours

Table 2 Projected trends of development of SOFCs for transporatation

Planar SOFC Preparation of Anode and Electrolyte suspension for Tape Casting

Cell Testing Unit

Experimental Setup

PGSTAT 3

Cathode LSM:YSZ

Comparison of SOFCs
Cell Type Primary application Electrolyte Operating temp Charge carrier Cell component Catalyst Primary fuel Start up time Power Density (k W/m) Fuel cell efficency PEMFC Automotive and stationary power Polymer (plastic membrane) 50 - 100OC H+ Carbon based Platinum H2 second - minutes 3.8 -6.5 50-60% HT - SOFC Vehicle auxillary power Yttria stabilized Zirconium Oxide (YSZ) 700 - 1000OC O2Ceramic Perovskites H2,CO Hours 0.1 - 1.5 55-65% IT - SOFC Vehicle auxillary power Cation doped cerium oxide (GDC, SDC) 500-700OC O3 Ceramic Perovskites H2,CO Hours 3-4 55-65% LT - SOFC Vehicle auxillary power Two phase composite made by mixing Cation doped cerium oxide and either salts(eg: GD CNaCl) or carbonates SD-M2CO3(M-Li, Na, K) 300-600OC H+,OO2Salt based+ceramic Carbon based+ceramik Salt and carbon H2 Minutes 3-8 55-65%

Hydrogen Generation
Hydrogen is the fuel for low temperature fuel cell. However, for high temperature fuel cells hydrocarbon may be fed to fuel cell instead of hydrogen. Hydrocarbon may be reformed in-situ in the fuel cell from the hydrocarbon. It can be understood that the generation of hydrogen is one of the important processes for the fuel cell application. We may generate hydrogen from any hydrogen atom containing species (eg., hydrocarbon and water) using various techniques. A few of the important techniques are listed in the next slide.

Hydrogen production techniques

Hydrogen from hydrocarbon

Since hydrogen doesn't exist on earth in free form, we must separate it from other chemical species. We can separate hydrogen atoms from biomass, or natural gas molecules. Hydrogen can be produced from natural gas with approximately 80% efficiency, or from other hydrocarbons to a varying degree

of efficiency.

Hydrogen from water

Water is the another greatest source of hydrogen. High purity (ideally 100%) hydrogen can be produced from water.

We will briefly discuss about the reforming of hydrocarbon and electrolysis. The details of the processes may be read from some other source. Reforming of hydrocarbon The aim of the reforming is to generate hydrogen rich gas by hydrocarbons. The reforming may be done with or without catalyst. Three types of major reforming process are,

Steam reforming (SR) Partial oxidation reforming (POR) Auto thermal reforming (ATR)

Steam reforming (SR)

Steam is used to reform the hydrocarbon (say natural gas) using a catalyst.

CH4+H2O -------------> 3H2+CO ; h=(+)

The above reaction is strongly endothermic. In subsequent reaction the CO can further be converted to CO2 and the process is known as water-gas-shift reaction,

The above reaction is mildly exothermic. The above process do not need air, thus the product is not diluted with nitrogen.

CO+H2O -------------> H2+CO2 ; h=(-) Partial Oxidation Reforming (POR)

Partial reforming is the another technique for generation of hydrogen by hydrocarbon for fuel cell. As the name indicates, less oxygen (stochiometry) is required to carryout POR. POR does not require catalyst if it is carried out at high temperature. Catalyst is required for the partial oxidation at low temperature, the process is then known as catalytic partial oxidation reforming (CPOR). A typical POR is shown below,

CH4+1/2O2----------------->CO+2H2 ; h=(-) Autothermal Reforming (ATR)

It is another technique for hydrogen generation. The name suggests that the temperature is not required externally. However, the thermal energy requirement is met by the system itself. The idea is that if the endothermic steam reforming reaction and the exothermic POR occur together, there should not be any need of heat addition or removal to/from the system.

Hydrogen Generation Through Electrolysis

Generation of hydrogen using electrolysis is one of the oldest technique. In fact the concept of fuel cell came during the electrolysis of water by Sir William Grove in 1839. In electrolysis, the energy (or electrical current) is required to dissociate water molecules into hydrogen and water.

The hydrogen formed in electrolysis is the purest form of hydrogen. Electrolytic cell is used for the electrolysis of water.

Electrolysis reactions in cationic electrolyte Cathode Reaction:

4 H + 4e <--------> 2H2
+ -

Anode Reaction:

2H O <--------> O + 4 H + 4 e
2 2

Overall Cell Reaction:

2 H O <----------> 2H + O
2 2

Electrolyte (cationic or anionic) is placed between anode and cathode of the cell and the electrical current is given by the DC power source. Hydrogen is generated at cathode, whereas oxygen is generated at anode of the electrolytic cell.

Electrolytic Cell

Hydrogen Storage
Hydrogen may be a prospective source or energy carrier for the future because it is clean and sustainable. Hydrogen can be produced from a variety of feedstock. These include fossil resources, such as natural gas and coal, as well as renewable resources, such as biomass and water, when we use the energy input from renewable energy sources (e.g. solar, wind, hydro-power, etc.). Many process technologies like chemical, biological, electrolytic, photolytic, and thermo-chemical may be used for the hydrogen production. Each technology is in a different stage of development, and each offers unique opportunities, benefits and challenges. Local availability of feedstock, the maturity of the technology, market applications and demand, policy issues, and costs may influence the choice and timing of the various options for hydrogen production. Several technologies are already available commercially for the industrial production of hydrogen. However, major problem with hydrogen is its efficient storage system. The most common method to store hydrogen in gaseous form is in steel tanks, although lightweight composite tanks designed to endure higher pressures are also becoming popular. Gaseous hydrogen cooled to near cryogenic temperatures is another alternative that can be used to increase the volumetric energy density of gaseous hydrogen. In this course, we will discuss about a few of the techniques in which the hydrogen can be stored. The major techniques are shown below, 1. 2. 3. 4. 5. Composite tanks Cryogenic liquid hydrogen (LH2) Chemical hydrides Carbon based materials Metal hydrides

Composite tanks There are several advantages with composite tanks. Their low weight meets key targets and the tanks are already commercially available, well-engineered and safety-tested, since extensive prototyping experience exists. Standard size tanks are available worldwide with specific code for pressures in the range of 350-700 bar. Composite tanks does not require internal heat exchanger and may be used for cryogas with extra fittings. Their main disadvantages are the large physical volume required, the fact that the ideal cylindrical shape makes it difficult to conform storage to available space, their high cost (500-600 USD/kg H2), and the energy penalties associated with compressing the gas to very high pressures. Figure in the next slide show a representative sketch of a composite tank.

There are also some safety issues that still have not been resolved, such as the problem of rapid loss of H2 in an accident. The long-term effect of hydrogen on the materials under cyclic or cold conditions is also not fully understood. Hence, there is still need for more research and development specifically:

Research on material embrittlement, using new ad hoc fracture mechanics techniques. Development of stronger and lower-cost construction materials, especially carbon fibers. Development of an efficient and clean (i.e. without oils) 1000-bar compressor. The consideration of hydride-type compressors utilizing waste heat or solar energy. Development of techniques that recover the compression energy during vehicle operation.

Cryogenic liquid hydrogen (LH2) Cryogenic hydrogen, usually simply referred to as liquid hydrogen (LH 2), has a density of 70.8 kg/m3 at normal boiling point (253C). (Critical pressure is 13 bar and critical temperature is 240C.) The theoretical gravimetric density of liquid H2 is 100%, but only 20 wt.% H 2 can be achieved in practical hydrogen systems as of today. On a volumetric basis, the respective values are 80 kg/m3 and 30 kg/m3. This means that liquid hydrogen has a much better energy density than the pressurized gas solutions mentioned above. However, it is important to recall that about 30-40% of the energy is lost when liquid H2 is produced. The other main disadvantage with liquid H2 is the boil-off loss during dormancy, plus the fact that super-insulated cryogenic containers are needed. The main advantage with liquid H 2 is the high storage density that can be reached at relatively low pressures. Liquid hydrogen has been demonstrated in commercial vehicles (particularly by BMW), and in the future it could also be coutilized as aircraft fuel, since it provides the best weight advantage of any H 2 storage. Further research needed in this area is as follows:

Efficient liquefaction processes (hydride compressors, magnetic and acoustic cooling, etc.). Developing systems that automatically capture the boil-off (e.g. via hydrides) and reliquefying the fuel. Minimizing costs and improving the insulated containers.

Chemical hydride Some of the chemicals may be used to store the hydrogen gas. For example, Sodium borohydride (NaBH4) can be used to store the hydrogen gas. In order to release the hydrogen, the sodium borohydride solution can be catalytically hydrolyzed as per the reaction shown below,

NaBH4 (liq.) + 2H2O (liq.) ---------> 4H2 (gas) + NaBO2 (solid) The theoretical maximum hydrogen energy storage density for this reaction is 10.9 wt.% H 2. The main advantage with using NaBH4 solutions is that it allows for safe and controllable onboard generation of H2. The main disadvantage is that the reaction product NaBO 2 must be regenerated back to NaBH4 off-board. The use of NaBH4 solutions in vehicles may be prohibitively expensive. The required cost reduction is unlikely because of the unfavorable thermodynamics. However, NaBH 4 solutions may be used in high-value portable and stationary applications. Further research required as follows:

Approaching the ideal energy density (10.9 wt.% H 2) by optimizing the H2O needed in the reaction and management of H2O in the fuel cell system. NaBO2 removal, regeneration, and replacement methods.

Carbon based materials Carbon-based materials have received a lot of attention in the research community over the last decade. Carbon based materials mainly include graphene, fullerenes, and carbon nano-tubes. H2 is stored on these carbon allotropes by molecular physisorption. However, it is useful only at cryogenic temperatures. Pure H-chemisorptions has been demonstrated to be stored upto 8wt.% H2 with catalyst, but the covalent-bound H is liberated only at impractically high temperatures (above 400C with catalyst). Room temperature adsorption up to a few wt.% H2 is occasionally reported, but has not been reproducible. This requires a new bonding mechanism with energies between physisorption and strong covalent chemisorption. Hence, the potential for H2 storage in carbon-based materials is yet to be established practically; therefore further research may be emphasized on,

Theoretical modeling studies of H on carbon nanostructures and in bulk phase. New C-H bonding mechanism has to be explored and, if theoretically so, how to achieve it in practice. Study on carbon-metal composites capable of catalysing H2 dissociation and so-called spill over. Minimizing production costs for promising carbons (e.g. graphene, graphite nanofibers and nanotubes). Measuring H2 uptake and release from carbon samples has to be standardized.

5. Metal hydride The chemically bound hydrogen storage material is metal hydrides. Many metals and alloys will reversibly react with hydrogen to form a hydride. A generic reaction is given in the figure on next slide. The regeneration of the metal can be accomplished either by increasing the temperature or by reducing the pressure. To understand this behavior it is helpful to consider the pressure composition isotherm (PCI) for a metal hydride.

Reversible reaction of hydrogen with metal The PCI figure in the next slide shows that as the pressure increases the hydrogen uptake increases. The PCI plot also shows that there is a plateau above which pressure the metal will hydride and in a closed system will continue to hydride until the pressure of the system decreases down to that of the plateau pressure. The stored hydrogen can be released by reducing the pressure of the system to a level below that of the plateau pressure. The plateau pressure is also temperature dependent, and increases with temperature. Thus a hydride stable under a certain temperature and pressure will decompose when the temperature is increased to a level where the plateau pressure is now higher than the system pressure. The temperature needed for a 1 bar plateau pressure, T(1 bar), is a useful characteristic of metal hydrides as this gives an indication of the minimum working temperature for a store based on that material.

Pressure-composition Isotherm Some of the common metal hydrides are LiH, MgH2, as well as Gallium, indium, thallium ,and lanthanide hydrides .

Balance of plant and Power electronic ans system integration


Fuel Cell System We are at the end of the fuel cell course and now can easily understand that not only the fuel cell is necessary but also the peripheral components are necessary. The peripheral components are necessary in order to have the fuel cell work efficiently as well as the efficient and effective utilization of the electrical energy by the fuel cell for an application. When we talk about the fuel cell system it includes many sub-systems. These sub-systems are, 1. Fuel cell stack Thermal management 2. Fuel delivery/processing Power electronics

All the subsystem (peripherals) except the fuel cell stack known as balance of plant (BOP). They described below.

Balance of Plant (BOP) Fuel Cell System: For most practical fuel cell applications, unit cells must be combined in a modular fashion into a cell stack to achieve the voltage and power output level required for the application. Generally, the stacking involves connecting multiple unit cells in series via electrically conductive interconnects.

In addition to the stack, practical fuel cell systems require several other sub-systems and components; the so-called balance of plant (BoP). Together with the stack, the BoP forms the fuel cell system. The precise arrangement of the BoP depends heavily on the fuel cell type, the fuel choice, and the application. In addition, specific operating conditions and requirements of individual cell and stack designs determine the characteristics of the BoP. Still, most fuel cell systems contain Fuel Preparation: Except when pure fuels (such as pure hydrogen) are used, some fuel preparation is required, usually involving the removal of impurities and thermal conditioning. In addition, many fuel cells that use fuels other than pure hydrogen require some fuel processing, such as reforming, in which the fuel is reacted with some oxidant (usually steam or air) to form a hydrogen-rich anode feed mixtur Air Supply: In most practical fuel cell systems, this includes air compressors or blowers as well as air filters. Thermal management: All fuel cell systems require careful management of the fuel cell stack temperature. Water management: Water is needed in some parts of the fuel cell, while overall water is a reaction product. To avoid having to feed water in addition to fuel, and to ensure smooth operation, water management systems are required in most fuel cell systems. Electric power conditioning equipment: Since fuel cell stacks provide a variable DC voltage output that is typically not directly usable for the load, electric power conditioning is typically required. Some More Facts on BOP A single fuel cell is capable of producing very low voltage (say 1 V). Therefore, a typical fuel cell design needs many individual cells to form a stack to produce significant or useful voltage. A fuel cell stack can be configured with many group of cells in series and parallel connections to further tailor the voltage, current, and power as per the requirement for a particular applicatio In a typical fuel cell configuration, the number of individual cells contained within the stack is more than 50 and varies mainly with the design of the stack. The combination of many stack may provide the useful power for a particular application. One can understand that as the number of cells in a stack increases the complexity also increases. The stack performance depends on the performance of individual cells within the stack. The extra components or peripherals (or BOP) contribute significantly to the performance, and economy of the fuel cell power system. The BOP is generally depends on the type of fuel cell as well as the fuel used. Like in case of high temperature fuel cells the thermal

management is of great concern. The waste heat can be used in combined heat and power (CHP) cycle. We have already discussed about the humidification as well as role of heating and cooling of the feed . If we have a fuel cell stack then what are the peripherals required to obtain a useful power for an application. We will learn about different BOP components in brief and discuss in detail about a few of the important BOP components. As we know that the fuel and oxidant is required to be fed through the fuel cell stack. To accomplish this we need to have pumps or blowers or compressors along with the electrical motors. The fuel can be obtained from various sources and thus may need to be cleaned for any unwanted impurities. For example, hydrogen obtained from the steam reforming of methanol contains many impurities such as CO2 and CO. If the H2 contaminated with CO is passes to the PEMFC stack then it will poison the catalyst very fast. Therefore, cleaning of the fuel is important depending upon the fuel cell type and catalyst used. Similarly, air should be filtered properly if it i s used as an oxidant Moreover, before feeding the fuel, there should be proper storage of the fuel is required. It becomes more important if the fuel cell system is designed for a mobile application. We have already discussed earlier about the hydrogen storage. If fuel storage is not required then the system must have the fuel processing unit, which should be capable of generating the fuel for the application. The various kind of control valves will be required to control the fuel and oxidant to the fuel cell stack. Sophisticated control valves, and control unit is required especially for the dynamic application. The time lag of the valves are of utmost importance. The complication becomes more and more as deal with the high temperature fuel cell system where start-up and shut-down is very important. Moreover, seals and gaskets are also required to prevent leakage of fluids and to maintain the pressure in the system. Gaskets are generally used between two static surfaces to prevent to provide a seal and the sealing is an important issues for all the fuel cells especially high temperature fuel cells (SOFC and MCFC) as well as for fuel processing component Therefore, high temperature seals are very important and the development n this area is going on considering the performance of the seal towards, temperature, load swings, cycles, rapid transient temperature and pressure, and thermal gradients. The research and development work on corrosion resistance, hermitic, solid-state, and glass seals are advancing in a great pace. Once the stack is ready along with the proper pipelines and flow system. The fuel processor in combination with the fuel cleaning system will provide the feed to the fuel cell stack. The stack will generate the output, which will be direct current (DC) output, which may rarely be suitable for direct connection to an electrical appliance. Therefore, we have to modify or regulate the fuel cell output to the desired electrical power. This modification is known as power conditioning.

Depending upon the requirement we may need:

DC/DC convertor or voltage regulator DC/AC inverter

Power Conditioning In BOP, we will mostly focus about the power conditioning. We will first discuss about the power regulation then power inversion ion brief. Power Regulation In our day-to-day life we have seen that we require electrical power at a specified voltage level that is stable over time also. However, the electrical power provided by a fuel cell is neither stable nor have desired voltage output. Because a single cell may pro vide hardly 0.7V at operating conditions . Therefore, for a desired voltage output we have to make a fuel cell stake with series connection of the cells. Even then we may not get the desired voltage for the application. For a practical size (number of cells) of the fuel cell stack We have already discussed that a fuel cell can provide high electrical current. Therefore, if we some how convert the electrical current into voltage, we may achieve the higher voltage or desired voltage. Thus the concept of energy conservation may be used for converting some of the electrical current into electrical voltage. Moreover, the fuel cell voltage is highly dependant on the temperature, pressure, humidification, and flow rate, of the reactant feed to the fuel cell as well as the dynamics of the load. In order to increase as well as to keep the the cell voltage stable at the expense of current, DC/DC convertors are used A DC/DC convertor use the fluctuating DC fuel cell voltage as input and converts it to a stable DC voltage output which is fixed at a specified voltage as shown in the figure.

Based on the input voltage to the DC/DC the voltage may be stepped to the convertors specified value, of course within a certain limit.

In step-up convertor the, the fuel cell voltage is stepped up to a higher fixed output voltage, whereas in step-down convertor, the fuel cell voltage is stepped down to a lower fixed output voltage. In any of the case the power of the fuel cell must be conserved. It can be understood from the following diagram (for step-up convertor),

Figure A in the previous slide shows that the voltage is stepped up by a factor of 2, whereas in the process the current was reduced by a factor of 2, in order to keep the power conserved. It is done by a DC/DC convertor which as the 100% efficiency to do this job. Figure B in the same slide shows that the voltage was stepped up by a factor of two but the current was reduced by more than a factor of

2. Therefore, the power was reduced slightly. This power is consumed by the DC/DC convertor to do the job as the efficiency of the convertor may not be 100%. So depending upon the efficiency of the DC/DC convertor the power reduces. In general, the efficiency of a carefully designed DC/DC falls in between 80-95%. DC/AC Inverters Most of the residential appliances and utilities require single phase AC power rather than DC power. For the utilities of the industrial application we may need three phase AC power. Therefore, DC output of the fuel cell should be converted to the AC power before utilizing it. We are aware that the inverter technologies are well developed and are being utilized greatly. For example, in household battery backup power supply the inverters are used. Their efficiencies are quite good and a careful design of the inverter may be upto 95% efficient . The details of inverters may be found in any standard text book on power electronics. Power Supply Management System The power supply management system is the heart of the BOP. It is used to control and manage the electrical power of the fuel cell system as per the requirement of the load. A typical example is a vehicle run by fuel cell power. It can be easily understood that the power requirement of the vehicle is dynamic in nature. Once we move the vehicle from stationary condition or when vehicle on moving uphill the requirement of the power increased. Whereas at a constant speed the requirement may be very low as compared to the previous condition. The question arises that how to get and control the requirement of the dynamic power from the fuel cell. The source of power are the reactants to the fuel cell. During high demand, the requirement of the current density increases (in turn power density). Thus to achieve the high current density the reactant supply has to be increased. The power management system senses the requirement and accordingly send the reactants to the fuel cell system. Not only the reactants but the power management system also controls the temperature, humidity, fuel reforming system etc. to the fuel cell. It is infact the mind of the system and very essential part of the fuel cell system..

Commercialization Aspects 1 kW Stationary System

Honda FCX Clarity Specification (for U.S.) Length width Car Height Weight Max Speed Cruising Range Type Stack Max Power Volume weight Motor Max Power Max Torque Type Fuel Tank Pressure Outer Volume Inner etimated mm mm mm kg km/h km ----kW L kg kW N-m -----atm L L 4,835 1,845 1,470 1,625 160 620 PEFC 100 62 67 100 256 H2 gas 350 171 18