1

FUEL CELLS AND ITS

APPLICATIONS (CHE 694)
Fuel Cell Modeling
By

Abiodun Emmanuel OLAYODE

(1478435)

Department of Chemical & Materials Engineering

Email: olayode@ualberta.ca

Submitted to

Dr. Stojan Djokic

Department of Chemical & Materials Engineering

Office: DONALDEO ICE 12-292

Email: sdjokic@ualberta.ca
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INTRODUCTION
1.1 Background

A need for clean energy cannot be over emphasized in our world today. The ever-increasing
demand for energy due to increasing population means there is a resultant increase in pollution
associated with fossil fuel. Fuel cell (FC); an electrochemical device which converts chemical
energy in fuels into electrical energy and bye-products; such as heat and water, offers a promising
long-lasting solution to this imminent energy challenges. This is because FC is comparatively
clean; highly efficient and durable. In fact, its bye products; water and heat can further be
harnessed, thus, making the fuel cell a unique alternative green source of energy.

1.2 Brief History:

In 1839, Sir William Robert Grove introduced the first Fuel cell, and later its modularity was
introduced by a British scientist, Francis Bacon in 1959, which makes this concept adoptable for
a practical use. In the 1950s, NASA built generator to be used in space1. Although, significant
works have been performed to develop and improve the Fuel cell, more investigations on this
energy source is still required to make it competitive2.

1.3 Importance of Fuel cell

To improve the fuel cell, it is necessary to understand how various parts are affected by a myriad
of variables, and being able to predict effects on the general performance of the fuel cell system.
Fuel cell as a source of energy is potentially attractive due to the advantages it offers which
includes its clean nature compared to fossil fuel because there is no combustion reaction, hence
no release of particulate matter, and green- house gases or very low in case of some types of fuel
cell systems. It is also flexible and scalable based on it modularity, highly efficient and it has high
reliability due to the facts that there are no moving parts. These merits listed and many more
makes the FC a reasonably attractive alternative energy source.
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1.4 Types of fuel cell:

There are different types of FC which can be broadly classified based on the type of electrolyte.
While other classifications are based on the fuel type and operating temperature. However, the
classification by electrolyte encompasses these factors, thereby making it preferred basis for
classification3. These FC are suitable for different use and they are briefly described as follows;

1.4.1 Alkaline Fuel cell (AFC): This FC is fueled with pure hydrogen and oxygen, and its
electrolyte is made-up of highly conductive potassium hydroxide(KOH). Its operating
temperature depends on the concentration of electrolyte; operating at about 250oC for
concentrated KOH and lower temperature for less concentrated electrolyte3

1.4.2 Phosphoric Acid Fuel Cell (PAFC): This type of fuel cell can operate at wide range of
temperature and most developed compared to other types of fuel cells. It has high efficiency and
can be coupled to work with other types of fuel such as the fossil fuel.

1.4.3 Solid-Oxide Fuel Cell (SOFC): It uses a ceramic electrolyte allowing it to operate at high
temperature as high as 982oC3.It is the most applicable FC for industrial purposes. It has high
efficiency which is further improved with co-generation.

1.4.4 Molten Carbonate: This fuel cell also works at high temperature; thus, catalyst poison is
not a concern. It is made-up of a mixed sodium and potassium electrolyte and its electrode is
made of ceramics.

1.4.5 Polymer Electrolyte Fuel Cell (PEFC): This is otherwise known as Proton Exchange Fuel
Cell(PEMFC). It is usually operated at low temperature. It uses hydrogen and oxygen as fuel. The
electrolyte of this fuel cell is a polymer of high ionic conductivity which is in solid- state and hence
simplifies its design. It has an active catalytic site made with platinum.These sites are susceptible
to poisoning from the release of carbon-monoxide gas when operated at high temperature. This
FC has shown potentials to be suitable for automobile application due to its high-power density4.
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1.5 Objective:

In this review, the PEMFC steady-state voltage modeling is discussed, this entails the major losses
and effects on the performance of FC in terms of output voltage. It discusses the solution and
how to manipulate different variables to achieve expected operating output voltage based on
load requirements.

1.5 Paper outline:

In the following chapter, the theory is discussed which elucidates how the fuels works, factors
affecting its operation. In chapter 3, achievement made till date is tersely discussed and followed
by the summary and conclusion of this review.
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BASIC DESCRIPTION
2.1 How do Fuel Cells work?

The fundamental working principles of fuel cells remain the same which is through
electrochemical reaction involving the transport of charged species between electrode through
conductor and electrolyte. This can be described using a reduction-oxidation reaction. Fuel cell
generally has 3 major components; the electrodes, electrolyte and load as shown in Figure 1. For
the electrode we have the anode which is the positive terminal where the oxidation of hydrogen
usually takes place for FC, and the cathode; the negative terminal where the reduction of oxygen
happens. The sum of these half reactions gives the full or complete reaction as shown in equation
(1-3) in the case of H2/O2 PEMFC.

Heat-1

load electrodes

e- e-
e e Heat-2
- -
H+
Oxygen supply
Hydrogen supply H+ H+
e e e
Water
- - -
Heat-3
Active catalytic sites Polymer
Anode Electrolyte Cathode

Figure 1. Typical PEMFC showing its components and working illustrations.

Anodic half reaction: H2 2H+ + e- (1)

Cathodic half reaction: O2 + 4H+ + 4 e- 2H2O (2)
Complete reaction: H2 +1/2 O2 H2O (3)
In general, the operation process of fuel cell involves the supply of hydrogen to the anode where
heterogenous reaction takes at the platinum catalytic site and electrolyte interface. At these
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catalytic sites the rate of reaction is favored due to the reduction of the energy barrier. The
hydrogen is oxidized to release Hydrogen ion (H+) and electrons (e-). The released charged
species, H+ and e-, are then selective transported, internally through the electrolyte and
externally through a conductor respectively. The electrons from the anode travels through the
conductor to the cathode, likewise, the hydrogen ion travels to the cathode. At the cathode,
oxygen is supplied, and reduced at the catalytic site, reacting with the released electrons and
hydrogen ion to produce water. Heat is also released as a bye-product of these reactions at
different sections of the FC due to resistances to the flow of the charged species and due to
operating temperature.

2.2 Fuel Cell Components and Functions

2.2.1 Anode: For the PEMFC, it is usually made of carbon with active platinum catalyzed
reaction sites5. This engineered site accelerates the rate of chemical reaction by reducing the
activation energy. At the anode, pressurized hydrogen gas is stripped into its constituent
components as represented by the anodic half reaction in equation (1) above, where H + and e-
are produced following the steps highlighted below6;

1o: Mass transport of H2 gas to the electrode

2o: Adsorption of H2 onto the electrode surface; H2(near surface) + M = MH2

3o: Separation of H2 molecule;

4o: Transfer of electrons from chemisorbed H atoms to the electrode and release of H + ion into
the electrolyte

5o: Mass transport of H+ away from the electrolyte; 2H+(near electrode)

2.2.2 Cathode: Similar to the anode; the materials are the same, but the reduction half reaction
which completes the electrochemical reaction takes place at the cathode where oxygen
combines with released electron form the anode and hydrogen ion to generate water as a bye-
product. The half reaction is provided in equation (3) above.
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2.2.3 Electrolyte: The PEMFC has a solid state Nafion-polymer electrolyte which has a
perflourinated side as well as sulfonated side group, allowing its stability, and the same time
limiting it to work at low temperature5. It serves to preferentially allow the flow of ions from the
region of high concentration to a lower concentration towards the cathode. For an ideal and
highly efficient electrolyte membrane, no electron should flow through the electrolyte, however,
due to material limitations there are leakages and internal flow of electrons which reduces the
performance and efficiency of the PEMFC.

2.2.4 Conductor and external load: The conductor selective allows the flow of electrons and
this is driven by the electromotive force (EMF). This action of electrons flow produces the
electricity which powers the externally connected load.

The combination of this individual components make-up the fuel cell.

There are limitations to the easy and complete conversion of the residual chemical energy in fuel
to electrical energy right from the first point of action, which is the anode. These limitations
leading to various losses or overpotential reduces the performance, efficiency of PEMFC and
these losses will be discussed in the following section.

2.4 Theory: Model

This section provides the mathematical frame work for the description of steady state PEMFC
performance in terms of output voltage. PEMFC can be affected by many factors which includes,
temperature, concentration and or pressure, composition amongst other myriads of variables. In
general terms, from an extensive research work, a relationship exists between the output voltage
of FC and current density which shows how implicitly these numerous variables affects its voltage
output. The manipulation of these various conditions results into different behavior which can
be estimated from fuel cell modeling and represented by a simple, yet complex, curve. A typical
cell voltage and current density (i-V) curve is shown in Figure 2 below. The modeling of fuel cell
can be simple; describing limited conditions at steady-state, and complex; comprising of a
dynamic-state with various parameters being considered. As mentioned in the introductory
chapter, the simple steady-state
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1.4
Ideal Fuel cell voltage
1.2
V- i curve
1

Region 3: Concentration loss

Voltage,V

Region1: Activation loss

0.8

0.6

0.4
Region 2: Ohmic loss

0.2

0
0 200 400 600 800 1000
Current density,i, (mA/cm2)

Figure 2: Characteristic voltage-current density curve which describes the behavior of FC

performance (adapted from CHE 649 assignment, 2017).

modeling is considered in this review. This covers the modeling of the open circuit voltage when
the FC is not working (reversible voltage), and the irreversible voltages which consist of the 3-
major losses. The coupling of these losses together with the reversible voltage gives a classical
steady-state voltage modeling of the FC. This model has 3-regions which will be discussed
individually in the following sections.

Understanding how various condition results into different magnitude of voltage loss does not
only help to operate at the optimal condition, but also help with the design, material selection
and development of FC to achieve targeted voltage output. Therefore, the modeling of FC serves
as a good fundamental tuning method to investigate the performance of FC and how to improve
it based on simulated conditions.

FC voltage can be categorized as reversible voltage which is obtained when the FC is not
connected, i.e. non-operating. This is also referred to as the open circuit voltage (OCV) or
thermodynamic voltage which is lower than the ideal voltage (maximum theoretical voltage).
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This OCV is affected by the operating pressure, temperature and composition of fuel and fuel cell
system. For example, at standard temperature and pressure. The ideal voltage of FC, Eo, is 1.229V.
The OCV is lower than this value due to energy barrier that must be overcome for spontaneity of
reaction as well as loss of fuel due to fuel cross over and internal currents. In addition, the OCV
is further affected by the thermodynamic quantities. For the irreversible voltage which comprises
of the 3-major losses due to activation, ohmic and mass or concentration transport, the FC must
be operating, i.e. connected, close-circuit-voltage, before it is experienced.

Total voltage of FC = Reversible voltage(Vr) + Irreversible voltage (Vir) (5)

Vir = (overpotentials)

Vir = (Activation loss + Ohmic loss+ Concentration loss) (6)

The Vir is a negative value since it is related to potential energy lost in various parts of the FC.
Therefore, the summation of the reversible and irreversible voltages gives the total FC voltage.
These irreversible losses are extensively discussed in the following section to understand the
causes, and the direct implication in terms of magnitude of the losses. The mathematical
equations which describes these losses is the basic steady-state FC modelling.

2.4.1 Activation Loss: For reaction to start and proceed a certain minimum energy needs to be
overcome. the energy expended to overcome this barrier is a loss of the residual potential and
maximum recoverable energy stored in the fuel as chemical energy. This causes the slow rate of
reaction at the surface of the electrodes. To sustain the continuity of reaction, certain amount of
energy in terms of voltage is lost to continuously transfer electrons from the anode to the
cathode. Activation loss is denoted by Vact or act and it is a function of current density. It happens
at low current density and the Tafel equation below describes this phenomenon and the
parameters that can affect the rate of reaction as implicit functions.

act = A log(io/i) (7)

where io =Z*F*Crs f exp(-G/RT) (8)

where Z- electron transfer, F- Faraday constant, R- gas constant; T- Temperature

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Crs- Concentration of reactants; G- Gibbs free energy; A=Tafel coefficient; i-current

density and io -exchange current density.

From equation (7), activation loss is strongly affected by current density and from the relationship
the higher the exchange current density, the lower the activation loss experienced. A typical
relationship between current density and activation loss is shown in Figure 3. To manipulate this
exchange current density in other to achieve certain voltage loss is therefore a function of
concentration of reactant gas, temperature and the activation barrier and surface area. Through
the knowledge of variables that could be manipulated, activation loss can be controlled to meet
required load conditions or output voltage.

Theroectical or Ideal voltage

io =10-2
Voltage, V

io =10-5

io =10-8

Current density, (mA/cm2)

Figure 3: Voltage vs current density graph showing the effect of exchange current density and
activation loss

2.4.2 Ohmic losses: This loss is described by the 2nd region of the characteristic i-V curve shown
above in Figure (2). This loss is associated to the energy expended to overcome the resistances
to the transport of charged species (electrons and hydrogen ions). The electrons are transported
through the externally connected conductor and must overcome the resistance to flow. The ions
also must overcome the resistance to flow through the electrolytic membrane. Lastly there are
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interconnection resistances due to the connections between electrodes and conductor as well as
electrodes and membrane. The total resistance to the transport of charged species is therefore
a contribution of the electrodes-conductor; electrodes-electrolyte interconnectivity resistances,
the electron-conductor resistance and the ion-electrolyte resistance.

RT = Rinter + Re + Ri (9)

Following Ohms Law, the overpotential voltage can be estimated as shown in equations (10-11)

Vohm = ohm = IRT (10)

This ohmic loss can also be describe as function of current density.

Vohm = ohm = iART (11)

Therefore, the extent of ohmic loss depends largely on the materials conductivity for the
electrode, conductor and electrolyte and their connectivity. Of all these resistances, the ionic
resistance is more impactful ref. Hence, choosing a high ionic conductive electrolyte is essential
to reduce the impact of ohmic loss on the overall FC voltage.

2.4.3 Concentration loss: This is simply the voltage loss due to fuel depletion arising from the
limitation of porous electrode. If supply of fuel is shortened or reduced from external source, cell
performance is greatly influenced by concentration loss. For a constant supply however, the
depletion can be attributed to microstructural limitation of the electrode. Concentration loss is
also a function of current density. Like the activation loss which is affected by the exchange
current density, concentration loss Is affected by limiting current density iL, and the mathematical
expression to model this is given in equation (12)., an analogue of the Tafel equation for the
activation loss.

conc = (RT/ZF)* ln[iL /( iL -i)] (12)

valid when i < iL

Thus, it can be said that the maximum operating current density is the limiting current density,
iL, in which FC output voltage becomes zero, following a downward impulse trend as shown below
in Fig. (4).
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Voltage, V

Limiting current density, iL

Current density, (mA/cm2)

Figure 4: Typical concentration loss profile.

The summation of these voltages including the reversible voltage give the mathematical
expression that describes the performance of FC according to equation (13):

V = Ethermo act- ohmic - conc (13)

It should be noted that in this review, leakage current is not modeled and the impact of fuel cross
and internal current is considered negligible.

.
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Major Achievements
The description of FC behavior using modeling, key parameters have been identified and
significant development have been made to improve the performance, cost and durability of fuel
cell according to the report by the US Department of Energy (DOE), ( #ref). In this report there
have been significant reduction in the cost of automotive fuel cell using the PEMFC by more than
50%. This reduction in cost of production of FC is because the platinum contents have been
reduced.

Also, a more durable FC lasting for 2500hrs against 950hr from 2006 have been reported. These
are a few of many significant improvements made to make the FC competitive, with low cost,
high performance, durability and efficiency.
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Conclusion
Fuel cell modeling is an importance tool for the design of fuel cell to selectively choose and
develop materials in other to improve the performance of fuel cell. Operating at high current
density is crucial for high performance and efficiency. This model serves as the foundation for
the development of more sophisticated dynamic models encompassing the fuel cell and fuel cell
adjunct external systems.

Recommendation
The following are recommendations based on the crucial parameter identified from modeling of
fuel cell which is limited to steady-state PEMFC voltage modeling.

1. Specially engineered indented electrode surface should be considered. This increases the
area compared to a smoothed surface.
2. Designing the polymer membrane of PEMFC to have strips of immobilized electrons at
the surface. This will improve the selective passage of ions through it, reducing the effect
due to internal current and fuel cross over.
3. Improving the electrolytic membrane to accommodate operations at higher temperature
will also improve its performance and avoid catalyst poisoning, thus, improve durability.
4. Improving the conductivity of the electrolyte would significantly reduce Ohmic losses.
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(1) Fuel Cell Technology Showcase - History of Fuel Cells.

(2) Husar, A.; Strahl, S.; Riera, J. Experimental Characterization Methodology for the
Identification of Voltage Losses of PEMFC: Applied to an Open Cathode Stack. 2009.

(3) Maroju, P. Modeling of a Fuel Cell. 2002.

(4) Ceraolo, M.; Miulli, C.; Pozio, A. Modelling static and dynamic behaviour of proton
exchange membrane fuel cells on the basis of electro-chemical description. 2003, 113.

(5) Seyezhai, R. Mathematical Modeling of Proton Exchange Membrane Fuel Cell. 2011, 20
(5), 16.

(6)