Fuel Cell: Chemical Energy Sources

Fuel Cells Introduction Principle Classifications Performance Analysis of fuel cell Heat generated by fuel cells Advantages of the fuel cells Limitations of fuel cells Application of fuel cells

Fuel Cell: Introduction

An electrochemical device that converts chemical energy directly into electricity and heat.. Fuel cell operates on pure H2 andO2 (air) to produce electricity with water and heat as by-products. It differs from conventional electric cell in two respects: (1) reactants hydrogen and oxygen are supplied from outside which are consumed; electrodes and electrolyte are not consumed. (2) electrical energy stored in the form of chemical energy after discharge needs to be recharged so that chemical energy is built up for reconversion into electrical energy to cater to demand. But fuel cell needs no recharging ; as long as reactants are fed it continues to provide electricity to the load through an external circuit. Its efficiency does not depend on size; according to power output requirement, size varies . It is modular in construction. . As conversion from chemical into electrical takes place isothermally its efficiency is theoretically higher than Carnot Engine whose efficiency is limited as it has to reject some heat to the sink while operating between a higher heat sources and the sink. Fuel cellfirst demonstrated (1959) by F. T. Bacin & C. Frost of Cambridge Unv

Principle of operation of fuel cell:

Although practical fuel cell differs in design details, the essential principles are same. When two permeable nickel electrodes ( allow gasses to diffuse through but not the electrolyte) embedded with catalyst are immersed in a conducting electrolyte (eg.KOH solution for alkaline cell) with anode( negative electrode, as per fuel cell convention) fed with hydrogen and cathode (positive electrode)with oxygen (air), negative charges are developed at cathode where as positive charges build up at anode thus developing an emf between these two electrodes under the equilibrium reactions between the electrolyte and the electrodes. However, when the electrodes are connected through external circuit with electrical resistance ( i.e. load), 2 electrons flow from cathode to anode via the electrical circuit for every hydrogen molecules consumed. Differences from primary( dry) and secondary ( storage battery) cells.

At cathode the electrons on reaching there through external circuit react with oxygen and water from electrolyte to form hydroxyl ions ( OH-);Hydrogen ( hydrogen ion) can diffuse through the permeable nickel electrode to move into electrolyte where H+ ions combines with OH- and to form water(H2O) .The catalyst enables the hydrogen molecule to be absorbed on the electrode surface as hydrogen reacts with hydroxyl ions in the electrolyte to form water. The net reactions are flow of electrons through external circuit and chemical combination of hydrogen and oxygen. This process goes on as long as reactants are fed externally to the electrodes. At Anode, 2H2 4 H+ + 4e- which flows through external circuit At cathode, O2+2 H2O + 4e- 4(OH-) + heat 4 H+ +4 OH-4H2O Net reaction, 2H2 + O2 H2O + heat

 8.3. Cell Type: hydrogen fuel cell called Hydrox are two types: 1) Low temperature Cell: Electrolyte temperature is 900C and cell pressure up to 4 atm. 2) High Pressure Cell: Temperature and pressure are up to 3000C and 45 atm. A single hydoxyl cell produces 1.23V at 1 atmosphere and 250C. By connecting a number of cells it is possible to have 100 to 1000V and power 1kw to 100Mw. The current depends on the physical size of the cell. the output of the cell varies with pressure, so to increase the cell output , gas pressure is raised. The optimum size of the cell is about 0.27 m3 per kw. The gases in the hydroxyl cell must be free from CO2 as the latter reacts with KOH to form potassium carbonate(K2CO3) which increase electrical resistance of the cell thereby lowers output voltage. Fuel cells are most suited for low voltage and high current application .

 Based on a) Temperature range of operation: low (25-1000C), medium (100-5000C), high temperature (5oo-10000C), very high temperature > 10000C b) Fuel and oxidant combination: e.g. hydrogen and oxygen, alcohol and oxygen, fossil fuel and oxygen c) Electrolyte: e.g. aqueous, non- aqueous, H2SO4 ( acidic), molten carbonate, KOH( alkaline) d) Direct/ indirect fuel e) Power ratings f) Application g) The cell may be divided into basic categories according to (1) whether the product of reaction must be disposed of in the cathode plenum space or in the anode plenum space and (2)whether the current flow through the electrolyte is a transfer of negative ions from the cathode to the anode or (3) a transfer of positive ions in the opposite direction from anode through electrolyte to cathode.

Classification of fuel cells:

 Based on electrolyte( most common):

Alkaline Fuel Cell(AFC) Direct Methanol Fuel Cell(DMFC) Phosphoric Acid Fuel Cell (PAFC) Proton/Polymer Exchange Membrane Fuel Cell(PEMFC) 5) Molten Carbonate Fuel Cell (MCFC) 6) Solid Oxide Fuel Cell (SOFC) 7) Zinc air Fuel Cell (ZAFC) 8) Regenerative Fuel Cell (RFC) 8.4.1. Alkaline Fuel Cell(AFC): Electrolyte: KOH, Electro catalyst: nickel, silver, Nobel metals: discussed earlier under sec.8.1. 1) 2) 3) 4)

 Direct Methanol Fuel Cell(DMFC): Polymer is an electrolyte; Fuel is liquid methane supplied at cathode and oxygen at anode; Chemical reactions are : At Anode: CH3OH + H2OCO2+ 6H+ + 6e+ At Cathode: 3/2 O2 + 6H+ + 6e+ 3 H2O Net Reaction: CH3OH + 3/2 O2 CO2 + H2O Efficiency of these cells is approximately 40% at operating temperature 500C-1200C. Main disadvantage of the cell is that more active catalyst is required for low temperature conversion of methane, hence it increases cost and weight. Phosphoric Acid Fuel Cell (PAFC):Reactions at electrodes: (Correct the diagrams) At Anode : 2H2 4H+ + 4e+ At Cathode: O2 + 4H+ + 4e+ 2 H2O Net reactions: 2H2 + O2 2 H2O PAFC operates 1500C-2200C and efficiency over 40% which can be improved to 85% in co-generation plant ; it offers lowest cost of electricity and has capacity range 50 to 200kw. The waste water from PAFC has high temperature capable of heating water and generating steam atm. Pressure.

 Proton/Polymer Exchange Membrane Fuel Cell(PEMFC): Fuel is hydrogen and charge carriers are hydrogen ions( protons); electrolyte is solid polymer membrane( plastic film) in the form of screens that allow protons to permeate but not hydrogen and oxygen thereby prevent them coming in contact. Reactions are : At Anode : 2H2 4H+ + 4e+ At Cathode : O2 + 4H+ + 4e+ 2 H2O Net reactions: 2H2 + O2 2 H2O the cell operates at 40-600C. Advantages: a) For a given volume it generates more power ( i.e. higher power density) b) Rapid start c) Less expensive d) Because of solid electrolyte , PEMFC cell has less problem with corrosion e) High ionic conductivity; Good mechanical stability; Longer life

 Molten Carbonate Fuel Cell (MCFC): Electrolyte is a molten mixture of lithium carbonate and sodium carbonate. The operating temperature is high, 6500C; These salts are heated to this temperature and become conductive to (CO3)- - ; A hydrocarbon fuel methane or kerosene is used. At fuel electrode (anode): (CO3)- - + H2 H2O+ CO2 + 2e+ ; At oxygen electrode (cathode): CO2 +2e++ O2(CO3)- Overall reaction: H2(g)+ O2 (g)+CO2(cathode) H2O(g) + CO2 ( anode) MCFCs are second generation fuel cells, have efficiency around 60%. The byproducts heat can be used to generate high pressure steam for commercial applications.

 Solid Oxide Fuel Cell (SOFC): At hydrogen electrode: 2H2 + 2O-- 2H2O+ 4e+ At oxygen electrode: O2 +4e+ 2O Overall reaction: 2H2+ O2 2H2O ; it has lower efficiency around 45% due to higher operating temperature; However operating I cogeneration plant efficiency can be increased to 80%. Material used in SOFC should be able to function at high temperature . Westinghouse has developed a tubular style SOFC that operate at 10000C.

 Regenerative Fuel Cell (RFC): is on in which the fuel cell product, e.g. water in the hydrogen-oxygen fuel cell is recovered into its reactants i.e hydrogen and oxygen, by one of the several processes such as thermal, RES( such as wind, solar), electrolysis, photochemical or radiochemical. The RFC operates in closed cycle. There are two stages in a RFC: The overall efficiency of RFC is the product the efficiencies of these two stages:
1) Conversion of fuel cell reactants into products while producing electricity 2) Reconversion of fuel cell products into reactants

The principle of photo chemically RFC( ref. next slide) is briefly explained : The sequences of reactions are mentioned in the slide. The nitrous oxide (NO) chlorine fuel cell in which the overall reaction is
2NO+ Cl2 2NOCl. The product nitrosyl chloride is decomposed photo chemically to chlorine and nitrous oxide. The cell electrical output is 0.21V , current obtainable is low.

Reversible Fuel Cell: is a cell that is designed to consume chemical A to produce electricity and chemical B, and be reversed to consume some electricity to produce chemical A from chemical B. For example, a hydrogen fuel cell uses hydrogen and oxygen to produce electricity and water; a reversible hydrogen cell could also use electricity and water to produce hydrogen and oxygen. Performance analysis of a fuel cell: The emf(E) that will drive the electrons through external load, is proportional to Gibbs free energy change; E=-G/(ne. F) volts, where, G= change in Gibbs free energy(g/mol) ; ne= no. of electrons per mole of fuel= 2 for hydrogen; F= Faradays constant= 96487 coulomb per mole. Also, -G= T ln(a2/a1), where , a1 and a2 are the activities at electrode 1 and 2. E= T ln(a2/a1).. Nernst equation. G = H - TS kcal /mole ( by definition: G= H-TS and as temperatures of flow stream at entrance and exist are taken same), where H=change of enthalpy for reaction known as heat of reaction, S = change of enthalpy; TS =Q: isothermal heat transfer;

Thermal efficiency, T = Free energy / heat of reaction= G / H=1T(S/ H); For, reversible emf of the cell, the efficiency , i= nFE/H = -( ItE/ H ), where = current and t time for which current flows; For maximum efficiency, the process is should be reversible. Overall efficiency of a reversible of fuel cell, o= T loss factor Power output of a reversible fuel cell, Prev = gmax / (molar mass of hydrogen); Molar mass of hydrogen = 2.016 kg/mol Actual electrical power output, P= Prev o The rate of heat release, Q = Prev P Losses from fuel cell: In fuel cell, all the available energy can not be converted into electricity; some are lost in the form of heat energy. The losses occur as follows: 1) Activation losses: ability o the cell to dissociate and drive in chemical reactions. These depend on the temperature and , the type and the amount of the catalyst.

2) Fuel cross-over losses are caused by leakages and diffusion of fuels. 3) Ohmic and resistance losses are the result of the electrical resistance of the cell to current 4) Mass transfer losses ( concentration losses) occur when the ability to maintain adequate concentration of hydrogen and oxygen in the fuel cell, is limited by high demand. Conversion efficiency: the electrical energy generated by a fuel cell depends on what oxygen at atm. pressure is 56.67 kcal ( 237 kJ) at 250C . The heat energy of reaction( enthalpy) under the same condition is 68.626 kcal. The theoretical efficiency of conversion is 56.67/ 68.626 i.e. 83%. The discharge voltages observed in actual cells are always below the theoretical value which can be calculated from the reaction free energy at 56.67/ 68.626 kcal 56.67/ 68.626 kcal 250C and at 1atm (1.23V); he difference increases with increasing strength of the current drawn from the cell. The difference between the theoretical voltage and the actual voltage is known as polarization or overvoltage.

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Efficiency of fuel cells are high compared to other power sources. Fuel cells are simple, safe, compact and noiseless. Fuel cells dont have moving parts. Fuel cells are pollution free. Only, if fuel source is hydrocarbon, some CO2 is produced. Whatever heat is is produced as by-product can be utilized or dissipated in the environment without causing thermal pollution. The unit is lighter, smaller and requires little maintenance as no moving parts are there. No overhead lines are required for transmission, as it can be installed near the user point. A fuel cell gives a few times more electrical energy per unit weight as compared to a turbo-generator or storage battery. A variety of fuel cell with fuels such as methane, ammonia, LPG, biogas or coal gas can be used. Long life span

10) Quick start, even in sub-freezing temperature down to -400C. 11) It is odorless and quiet for application. 12) The space requirement for fuel cell power plant is considerably less as compared to conventional power plants.

8.10 Limitations of fuel cells:

a) The developments or initial costs are high. It is necessary to work at high temperatures and pressure or use costly catalysts for the reactions to take place at high speed to give high current densities required for the economic plant. b) Low voltage and low service life.

 Applications of Fuel cells: I. Domestic use : Generally up to 5kw capacity-e.g. home appliances, street lights; up to 25w for laptop, cell phone, toys, hearing aids, digital camera, watches, calculators etc. II. Commercial, industrial and Central power stations: 300kw5Mw III. Automobile vehicles( cars, buses, trucks) locomotives( commuter trains, mining trains), submarines: 5-300kw IV. Special applications e.g. military, space craft Recent Development: Hydrogen-oxygen and hydrocarbon oxygen cells will be used to an increasing extent in special military and space projects. DNES has funded the import of a 200kw PAFC system from ONSI to evaluate its operation. DMFC is underway in IISC. SPIC-SC is working on PEMFC. First electric car with a fuel cell REVA-EV is at developmental stage. IISC is working on DMFC and also SOFC.