-Fuel Cell Systems Explained(Summary of chapter 1-4, 7, 8)

1. Introduction
1.1 Hydrogen fuel cells basic principles
Definition: A fuel cell is an electrochemical device that converts a supplied fuel to electrical energy and heat continuously, so long as reactants are supplied to its electrodes. Neither the electrodes nor the elctrolyte are consumed by the operation of the cell (page 17). Example: Acid electroclyte fuel cell Anode: hydrogen gas ionises, releasing electrons and creating H+ ions. 2H2 4 H+ + 4eCathode: oxygen reacts with the electrons from the electrode and H+ ions from the electrolyte to form water. O2 + 4 H+ + 4e- 2H2O An acid electrolyte allows only H+ ions to pass through. The e- have to pass through an external electric circuit. Certain polymers also allows only positiv ions to pass and can be used as electrolyte, so called proton exchange membranes PEM. Note: For all primary batteries and therefore for fuel cells, are the electrons flowing from the anode to the cathode. Thus the anode is electrical negative and the cathode is electrical positive. Cations: positive ions Anions: negative ions

1.2 What limits the current?

First the activation energy has to be exceeded for an exothermic reaction taken place. If te probability of a molecule having enough energy is low, the reaction rate is slow. The reaction rate can be accelerated by using a catalyst raising the temoerature increasing the electrode surface area (for fuel cells)

The chemical reactions have to take place at the surface of the electrodes, due to removing or supplying electrons. These reactions of the fuel with the electrolyte at the electrode is called a three phase contact. The reaction rate is propotional to the effective surface area of the electrodes. Requirements for the electrodes: high effective surface area (highly porous material) incoporate with a catalyst endure high temperatures in a corrosive environment

1.3 Connecting cells in series bipolar plate

A single fuel cell generates only a small voltage drop (0.7V). In order to generate a useful voltage several cells are connected into series. Such a connection is called a stack. The simplest way to create a series connection would be to connect the edge of each anode to the cathode of the next cell. The problem of such a system is, that the electrons would have to travel through the whole electrode, thus the ohmic resistance would be relative high. A better alternative are bipolare plates. These plates are made of a conducting material (Graphite, stainless steel, some ceramic materials) with connections areas over the surface as well as gas supply channels for the electrodes. The bipolare plates are complex parts and difficult to manufacture, thus the most expensive parts of a fuel cell. In order to optimize the design of bipolare plates several aspects counteracts each other: good electric contact requires a large contact area and a thin plate, to reduce the ohmic resistance. This lead to small narrow gas channels thus bad gas distribution over the electrode and low gas flow rates or high operation pressueres.

1.4 Gas supply and cooling

A major problem of manufacture fuell cells is leakage of the reactant gases. In order to seperate the gases strictly from each other are the electrrodes sealed at the edges with a gasket. External manifolds: gas is supplied through an external lid, that covers the whole side of the stack. + simple structure - cooling of the system. Needs a higher air supply rate for cooling. Makes the cell more inefficient - higher leakage probability. The gasket is not pressed evenly onto the electrodes. Internal manifolds: gas is supplied into the stack through additional supply channels in the bipolare plates. - That requires larger and more complex bipolare plates with extra channels for the reactants supply. These channels are connected to the the gas channels along the electrodes. + solid stack with the gases fed in at the same ends of the electrical connections. + additional cooling channels along the bipolare plates. + lower leakage probability

1.5 Fuel cell types

Besides the practical issuses fuel cells have to fundamental technical problems: slow reaction rate, low current and power hyrogen is not readily available as fuel There are six viable systems of fuel cells: Type Mobile Operating Anode and cathode Application and notes temp. [C] Ion reactions Alkaline AFC
OH -

50-200 30-100 2H24H++4e- (a) O2+4H++4e-2H2O (c)

Space vehicles Vehicles and mobile applications, low power CHP Portable electronic systems, low power but long running time For small CHP plants (hundreds of kW), first commercial one For medium to large CHP (up to MW) For all sizes of CHP (from kW to multi MW)

Proton exchange H + membran PEMFC Direct methanol H + DMFC Phosporic acid PAFC Molten carbonate MCFC
H+

20-90

ca. 220

CO3 2-

ca. 650

O 2Solid Oxide 500-1000 SOFC Advantages and disadvantages are discussed later.

1.6 Other cells Some fuel cells, some not

1. Biological fuel cells use an organic fuel, like methanol or ethanol, and enzymes to produce energy. Not yet commercial 2. Metal air cells (batteries) at the negative electrode the metal reacts with an alkaline electrolyte to form metal oxide or hydroxide. The released eelctrons pass though an external electric circuit to the air cathode, where water and oxygen reacts to hydroxyl ions (see alkaline fuel cell). Metal oxide is dissolved into the electrolyte, which have to be renewed after some time. Consumption of anode and electrolyte. Very good energy densitiy: commercial for low power applications with long running time. Research for higher power for electric vehicles. 3. Reodx flow cells or regenerative fuel cells For charging the reactants are removed from the electrodes and stored in a tank. For discharging the electrolytes are supplied back to the electrodes. Is used for very large capacity rechargeable batteries. The electrocolyte changes during operation and the system cannot work idenfinitely.

1.7 Other parts of fuel cells

The core of a fuel cell power system consists of electrodes, electrolyte and bipolar plate. The additional parts, also called balance of plant BOP, make a up a large contribution to the whole system. They depent on the type of the fuel cell and the used fuel. Circulation of the reactants: pumps, blowers, compressors, intercoolers Electricity output: power electronics, as DC/DC converters, DC/AC inverters Electric motors to drive the devices Fuel storage Fuel processing, desulphurisation Control valves and pressure regulation Controll unit, especially for start-up and shutdown at high temperature devices Cooling system Heat exchanger and pre-heater for high temperature cells humidification of reactant in PEM

1.8 Figures used to compare systems

For the fuel cell: Current density to compare electrodes and electrolytes Specific operating voltage (0.6 0.7V) Power density Note: Electrodes do not scale up properly. If the area is doubled, the current will often not double. The reasons are not yet understood, but realted to even delivery of reactants and removal of products from all over the face of the electrode. For the whole generation system: Power density Specific power cost per kWh Lifetime (difficult to specify) Performance and MTBF (mean time between failures) depends on the age of the electrode and electrolyte. 'Percentage deterioration per hour' Gradual decline in voltage in mV/1000h (somtimes) Efficiency

1.9 Advantages and applications

Disadvantages: mainly the costs Advantages: Efficiency Generally more efficient than combustine engines. Independant of the size of the system. Useful for small local CHP plants Simplicity The basics of a fuel cell is very simple, with few moving parts. Can lead to highly reliable and long-lasting systems. Low emissions Using hydrogen leads to pure water as by-product. A fuel cell can operate with zero emissions. CO2 emission for H2 production is not considered. Silence Fuel cells operate very silent, even with extensive fuel processing Using H2 as fuel can count for disadvantage or advantage. In a future perspective with a limitation of fossil fuels, H2 will be a major fuel.

Fuel cells can be used successfully in CHP plants or in mobile power systems, like vehicles or electronic equipment.

2. Efficiency and open circuit voltgage

2.1 Energy and the EMF of the hydrogen fuel cell
The chemical energy in and output of a fuel cell is not easily derived. Parameters as enthalpy, Hemholtz function, Gibbs free energy or exergy are used. Gibbs free energy energy available to do external work, neglecting any work done by changes in pressure and/or volume. In case of a fuel cell are the moving electrons in the electric circuit meant with external work. Exergy is all external work that can be extracted, including that due to pressure and volume changes Enthalpy Gibbs free energy plus the energy connected to the entropy. The chemical energy has similarities to mechanical potential energy. 1. Reference energy level can be defined as almost anywhere. Working with chemical reactions the reference level with zero energy is defined as pure elements, in the normal state, at standard conditions (25C or 298.15K, 0.1MPa). Using this convention, the terms 'Gibbs free energy of formation', Gf, and 'enthalpy of formation' is used. In case of a hydrogen fuel cell operating at standard temperature and pressure the Gibbs free energy of formation at the input is zero (useful simplification). 2. Energy difference between in and output is the important value. In a fuel cell, the change of the Gibbs free energy of formation, Gf, is the energy released. Given by the equation Gf = Gf of products - Gf of reactants It is convenient to use the molar specific Gibbs free energy of formation, written g f.

Note: The mole is a measure of the amount of a substance in respect to its molar mass. H2 molar mass: 2amu 1 mole = 2g H2O molar mass: 18amu 1 mole = 18g One mole of a substance always has the same number of molecules, given by the Avogardro's number N = 6.022 x 1023. The Faraday's constant gives the charge of one mole of electrons. F = N x e = 6.022 x 1023 x 1.602 x 10-19 C = 96485 C Using the basic reaction of the hydrogen/oxygen fuel cell, it can be seen that one mole of H2 and half a mole O2 deliver one mole of H2O. However, note that the Gibbs free energy of formation is not constant. It depends on the temperature and state (liquid or gas). When the values are negative it means that energy is released. Electromotive force EMF = reversible open circuit voltage OCF In a reversible process in the fuel cell, all Gibbs free energy would be converted into electrical energy. The basic reaction provides two electrons to the electric circuit for each molecule of H 2 used. So for one mole of H2, 2N of electrons pass through the circuit. Flowing charge: -2Ne = -2F [C] The electric work done equals the product of charge times voltage E. In a reversible process, the electric work also equals the Gibbs free energy released.

Given is the electromotive force EMF or reversible open circuit voltage of the hydrogen fuel cell. In practice the voltage would be lower, due to the fact that some irreversibilities also apply even when no current is drawn from the cell. In general

with z is the number of electrons per molecule of fuel.

2.3 Efficiency and efficiency limits

The Gibbs free energy is the part of chemical energy which is converted into electrical energy. However, it is insufficient to calculate the efficiency of a fuel cell only with this part of the chemical energy of the reactants by taken the irreversibilities into account, due to the fact that the Gibbs free energy depends on the temperature, the pressure and other factors. In order to compare a fuel cell with other fuel burning technologies, is the maximum possbile efficiency derived by the ratio of the electrical energy produced per mole of fuel and the change of enthaply of formation, that means the energy amount released as heat by burning the fuel. The maximum possible efficiency level, also named thermodynamic efficiency, is given by f x 100% max = g f / h f depends on the state of the substance, liquid or gas. For gas it is called the higher Note that h heating value HHV, for liquid it it called the lower heating value LHV. The difference betweeen both is the molar enthalpy of vaporisation. Any statement of efficiency should say whether it relates

to the HHV or LHV. If the information is not given, probably the the LHV is used.

Table 2.2 shows the theoretical efficiency limit of a hydrogen fuel cell in respect of the operating temperature. However in practice there are some differences. Voltage losses are less at higher temperatures, so the fuel cell voltage is higher at high temperatures. Waste heat of higher temperature cells can be used. Fuel cells do not always have a higher efficiency limit than heat engines. The mentioned decline in maximum possible efficiency with temperature for the hydrogen fuel cell is not exactly occur for other cell types.

2.4 Efficiency and the fuel cell voltage

The operation voltage of a fuel cell can be related to its efficiency.

For 100% efficient hydrogen fuel cell, the enthalpy of formation is converted into electric energy. Considering the fact that not all fuel is used during operation, the fuel utilisation coefficient is introduced. This is equivalent to the ratio of fuel cell current and the current that would be obtained if all the fuel were reacted. The fuel cell efficiency in respect to the HHV is therefore given by

A good estimation for f is 0.95.

2.5 The effect of pressure and gas concentration 2.5.1 The Nernst equation
As mentioned in 2.1 is the Gibbs free energy change dependant on the temperature and in a more complex relation on the reactant pressure and concentration. In a chemical reaction every reactant and product have their own 'activity'. In case of an ideal gas, the 'activity' is definded as a = P / P0 with P: partial pressure of the gas P0: standard pressure, 0.1MPa The activity of a gas is proportional to its partial pressure. The produced water in a fuel cell can either be a liquid or steam. In case of liquid water, it is a reasonable approximation to assume aH2O=1. The activities of the reactants and products of a chemical reaction jJ + kK mM modify the Gibbs free energy change, given by the equation

0 g f : molar Gibbs free energy change at standard pressure (from gas tables) R = 8.314 j/Kmol molar gas constant T: temperature It can be seen, that when the activities of the reactants increase, g f becomes more negative, so more energy is released. On the other side, if the activity of the product increase, g f becomes less negative, so less energy is released. Substitute this equation in the equation of the EMF gives the Nernst equation.

with

with E0: EMF at standard pressure The Nernst equation gives the EMF dependant on the product and reactant activities. The derived EMF, also called Nernst voltage, is the reversible cell voltage that would exist at a given temperature and pressure. Using the rules of logarithmic functions an the definition of activity, the equation can be simplified.

In nearly all cases will be the pressures partial pressures, that is, the gases will be part of a mixture. It often appears that the pressures at cathode and anode are the same, to simplify the design. Note: In a mixture of gases, the total pressure is the sum of all the partial pressures of the components. From the gas law equation it can be shown, that the volume fraction, molar fraction and pressure fraction of a gas mixture are all equal. Example: CH4 + H2O 3H2 + CO2

The products are three parts of H2 and one part of CO2 by moles and volume. If the reaction takes place at 0.1MPa the partial pressures can be derived PH2 = x 0.1MPa = 0.075MPa PCO2 = x 0.1MPa = 0.025MPa

2.5.3 Fuel and oxidant utilisation

As air passes through a fuel cell, the oxygen is used, and so the partial pressure will reduce. Similarly, the fuel partial pressure will often decline, as the proportion of fuel reduces abd reaction products increase. That makes the logarithmic term in the Nernst equation smaller, and so the EMF will fall. This circumstance will vary over the cell and will be worst at the fuel outlet as the fuel is used. Due to the conducting material of the bipolar plate the voltage is constant over the cell, that means that the current will vary. The current density will be lower nearer the exit where the fuel concentration is lower. The RT term indicates that the voltage drop due to fuel utilisation will be greater for high temperature fuel cells. A high system efficiency normally requires a high fuel utilisation. That counteracts the above described behaviour. The cell voltage, hence the cell efficiency will fall with higher fuel utilisation. Therefore, fuel and oxygen utilisation is an important aspect in the system design and thus needs careful optimisation.

2.5.4 System pressure

When the system pressure is known, the Nernst equation can be rewritten, using PH2 = P with constant depending on the molar masses and concentration of H2 PO2 = P with constant of O2 PH2O = P with constant of H2O as

It can be seen, thet the EMF of the fuel cell is depending on the system pressure P. A hihgher pressure leads to a higher voltage. For high temperature fuel cells, for example SOFC at 1000C, the predictions of the Nernst equation correlate with practise. For lower temperatures, as in a PAFC at 200C, the voltage change is even bigger. This occurs due to increasing pressure also reduces the losses at the electrodes, especially at the cathode. A similar effect occurs from switching from air to oxygen (). The voltage losses at the cathode decline for pure oxygen.

2.6 Summary
reversible OCV or EMF

max efficiency

f x 100% max = g f / h

efficiency of working H2 fuel cell relative to HHV

Nernst equation The pressure and the concentration of the reactants affects the Gibbs free energy, and thus the voltage, given by the Nernst equation.

3. Operational fuel cell voltage

3.1 Introduction
The operating voltage of a fuel cell is always below the theoretical open circuit voltage derived in chapter 2. Figure 3.1 shows the performance of a typical hydrogen fuel cell operating at 70C and normal air pressure.

Note:

even the open circuit voltage is less than the theoretical value there is a rapid initial fall afterwards the voltage falls less rapidly and mor linear there may be a higher current density at which the voltage falls rapidly again

For a higher temperature fuel cell the graph changes. The reversibel 'no loss' voltage is smaller, but the difference between the 'no loss' voltage and the operational voltage is less, due to the initial voltage drop is significant smaller.

Figure 3.2 shows the performance of a SOFC operating at 800C.

Note: the OCV is equal or just a litle less than the theoretical vallue the intial fall in voltage is very small, and the graph more linear there may be a higher current density at which the voltage falls rapidly again The focus of chapter 3 is on the questions: What causes the voltage to fall below the reversible value and how can this situation be improved?

3.2 Terminology
Commonly five terms are used to describe this voltage difference: Overvoltage or overpotential Polarisation Irreversibility Losses Voltage drop Every term is used in the book!

3.3 Fuel cell irreversibilities causes of voltage drop

The characteristic shape of the voltage/current density graphs results from four major irreversibilities. 1. Activation losses caused by the slowness of the reactios at the electrode. Voltage is used to drive the reactions. Nonlinear. 2. Fuel crossover and internal currents caused by unused fuel diffusion and electron flow through the electrolyte. Small losses. 3. Ohmic or resistive losses caused by the ohmic resistance of the electrodes and interconnections. 4. Mass transport or concentration losses caused by a change in the reactants concentration at the surface of the electrodes. Modelled by the Nernst equation.

3.4 Activation losses 3.4.1 The Tafel equation

The Tafel equation and plots are experimental results. Tafel observed, that the overvoltage at the surface of an electrode follows similar pattern for different chemical reactions: The plot of the voltage against the logarithmen of the current density is approximatly a straight line. Tafel plots

Tafel equation

The constant A is higher for slow chemical reactions. The exchange current density i0 is higher if the reaction is faster. The current density i0 can be considered as the current density at which the overvoltage begins to move from zero. The equation is only true for i0 > i.

3.4.2 The constants in the Tafel equation

For a hydrogen fuel cell, the constant A is given by with : charge transfer coefficient The charge transfer coefficient varies from 0 to 1 and amount of electrical energy that is used to change the electrochemical reaction rate. The value of depends on the electrode material. The impact of the temperature in the equation is far outweighted by the effect of i0 with changing temperature and thus is not considered. Indeed we shall see, that the key to making the activation overvoltage as low as possible is i0, which can vary by several orders of magnitude. Even at zero current density the electrochemical reaction at the electrodes is taken place, but the reverse reaction is also taken place at the same rate. There is an equilibrium. Thus, there is an continual forwards and backwards flow of electrons from and to the electrolyte. This current density is the exchange current density i0. If i0 is high, that means, that the surface of the electrode is more active, and thus it is easier to direct the current densit in a particular direction. The exchange current density is crucial in controlling the performance of the fuel cell electrode and should be as high as possible.

In order to get the current instead of the voltage the Tafel equation is cahnged in the ButlerVollmer equation The importance of i0 can be seen in the following graph for values of 0.01, 1.0 and 100mA/cm2.

Measurements of i0 shows a great variation in respect of the e;ectrode material. For hydrogen fuel cells are the values at the oxygen electrode (cathode) lower by a factor of 105. Therefore is the overvoltage at the anode negligible compared to the cathode. For other fuel cells, for example a DMFC, the anode overvoltage is not negligible. In these cases the equation for the total overvoltage combine the voltage drops at both electrodes. I can be expressed as

with

3.4.3 Reducing the activation voltage

In order to reduce the activation voltage it is most important to increase i0. This can be done by Raising the cell temperature Using more effective catalysts Increasing the roughness of the electrode (increased surface) Increasing reactant concentration (pure O2 instead of air) (more effective occupation of the surface by reactants) Increasing the pressure (more effective occupation of the surface by reactants) Increasing the value of i0. Has the effect of raising cell voltage by a constant amount at most currents, and so lead to raising OCV. The last two points explain the difference between thearetical and practical OCV. In low and medium temperature fuel cells, activation overvoltage is the most important irreversibility and cause a voltage drop at the electrodes. Mainly at the cathode for hydrogen fuel. At higher temperatures and pressures the activation overvoltage becomes less important.

3.5 Fuel crossover and internal currents

Even if the electrolyte is designed toconduct only ions, it always occurs that a small amount of electrons pass through it. In practical fuel cells the fact that a certain amount of fuel diffuse unused through the electrolyte is more important. The unused fuel will react directly with oxxygen at the cathode and no current is produced. These effects fuel crossover and internal current are essentially equivalent. One diffused hydrogen molecule effects in the same way as two electrons of internal current. The amount of these losses will be very small in respect to the irreversebilities. However,, in low temoerature fuel cells it causes a very noticeable drop of OCV, about 0.2V (20%) for a PEM. Noticeable in the steep initial falls of the voltage plots. A small change in fuel crossover and/or internal current, caused for example, by a change in humidity of the electrolyte, can cause a large change in the OCV. Measurements of the internal current are problematic, but can be done by the measurement of the fuel consumption. The consumption rate of hydrogen [moles/s] is related to the current by the following equation. The equation of the cell voltage can be refined, including the internal current density in.

To conclude, the effect of internal current is much less for high temperature cells, because i0 is much higher. For low temperature cells internal current and fuel diffusion is usually not of great importance in terms of operating efficiency, but it has a marked effect on the OCV.

3.6 Ohmic losses

The losses occured by the electrical resistance of the electrodes and the interconnection and by the resistance against the flow of ions in the eelctrolyte. The ohmic voltage loss is important in all types of fuel cells, especially in SOFC, and is mainly caused by the electrolyte. However the electrical resistance of the electrodes and bipolar plates is not negligible. The voltage drop is given by Ohm's law, using the current density and the area-specific resistance. Vohm = i x r with i in [mA/cm2] r in [kcm2] There are three ways of reducing the internal resistance: highly conductiv electrode material design and material of the bipolar plate or interconnection electrolyte as thin as possible (but have to prevent shorting of the electrodes, wide enough to provide a flow of electrolyte, physical robust, due to electrodes are built on it)

3.7 Mass transport and concentration losses

Due to the electrochemical reactions at the eelctrodes, hydrogen and oxygen are consumed. That leads to a change in concentration, which leads on the other hand to a change in partial pressure of the reactants, which results in a voltage drop over the cell. The pressure changes depend on the current drawn from the cell and the physical characteristics of the gas supply system, relating to the fluid resistance, the flow rate and the design of the gas supply along the electrodes. There is no overall satisfactory analytical solution to this problem. One theoretical approach is mentioned, which shows the effect of reducing the partial pressure on the OCV.

Assumption: Introduction a limiting current density i1 at which the hydrogen consumption rate is equal to the max. supply rate. At i1 the pressure would have reached zero. P1 is the pressure when i is zero. If we assume a linearly fall from P1 to P(i1), tha the pressure at any current density is given by

Substitution in above equation delivers the voltage drop due to mass transport.

The negative sign is due to the fact that it is a voltage drop. The term RT/2F will be different for each reactant and is in general substitute by the constant B. This theoretical approach has many limitations, like: supply of air instead of pure oxygen lower temperature cells mixed fuel production and removal of reaction products build-up nitrogen in air systems An empirical approach is more favourable, because it provides an equation which delivers much better results and will be used in the rest of the chapter. With m is about 3x10-5 V and n is about 8x10-3 cm/mA. The mass transport or concentration losses are important when Hydrogen is supplied by a reformer. The reaction rate on a demand change is too slow. The supply at the air cathode is not well circulated. Build-up nitrogen can block the oxygen supply at high currents. Water is not removed qickly enough in PEMFC.

3.8 Combining the irreversebilities

The operating voltage of a fuel cell at a current density i is given by

with

E: reversible OCV in: internal and fuel crossover equivalent current density A: slope of the Tafel line i0: exchange current density m & n: constants in the mass-transfer overvoltage r: area-specific resistance This equation can be simplified, due to in is usually very small and has little impact on operating losses of fuel cells at working currents, so it will be cancelled. The term of the activation overvoltage can be rewritten as

The second part is constant and is included in a real, practical OCV.

Finally we get a simple equation, that fits excellent results in respect to real fuel cells.

Example:

3.9 The charge double layer

Whenever two differnet materials are in contact, there is a build-up of charge on the surfaces or a charge transfer over the junction. In electrochemical systems, the charge double layer is formed by diffusion effects, by the reactions between electrons in the electrodes and ions in the electrolyte and by an applied voltage. The probability of electrochemical reaction taking place depends on the density of the different charges at the double layer; more charges lead to higher current. The charge seperation at the double layer generates an electric voltage, in case of a fuel cell the activation overvoltage. Adding catalysts to the electrodes increases the probability of a reaction; a higher current canflow without such a build-up voltage. The charge double layer can be seen as an electric capacitor, a storage of electric energy. Due to the capacitive behaviour of the double layer, will a fuel cell react on a cureent change in two steps. 1. Immediate change in operating voltage due to the internal resistance. 2. Smoothly move to the final equilibrium value due to the capacitance.

3.10 Distinguishing the different irreversebilities

How can the different kinds of voltage losses be distinguished in respect to conditions they mainly occur? Eperiments using specialised electrochemical test equipment such as half cells Electrical impedance spectroscopy AC current with variable frequency is applied to the cell, the voltage is measured and the impedance is calculated. Higher frequencies means less impedance of the capacitors. Plots of the impedance over the frequencies shows the values of the equivalent electric circuit elements, thus the mass transport and activation losses can be seperated. Current interrupt technique is an alternative, which delivers accurate quantitative results but also quick qualitative indications. It can be performed using low cost electronic equipment. A current is applied and suddenly cut of. The voltage will follow in the above mentioned steps: 1. Immediate change in operating voltage due to the internal resistance. 2. Smoothly move to the final equilibrium value due to the capacitance. The ohmic losses and the activation overvoltage can be seperated from each other. The following graph shows a sketch of the voltage change.

To summarize the irreversibilities due to their importance in different conditions. Concentration and mass transport losses are important only at higher currents. The should be very small in well designed systems. In low temperature hydrogen fuel cells activation overvoltage and ohmic losses are important Fuel cells using mixed fuel, as methanole, the activation overvoltage at anode and cathode dominates. In higher temperature fuel cells the ohmic losses are the major factor.

4. Proton Exchange Membrane Fuel Cell PEMFC

A PEMFC, also called solid polymer fuel cell, consists of an ion conducting polymer electrolyte bonded at each side with a catalysed porous electrode. These membrane electrode assemblies MEAs are very thin and connected in series with bipolare plates. The mobile ion is an H+ ion or a proton. The basic reactions are at the anode 2H2 4 H+ + 4eand at the cathode O2 + 4 H+ + 4e- 2H2O The polymer electrolyte works at low temperature, so that the fuel cell can start very quickly. Further advantages are, that the design can be very compact, no corrosive fluid hazards are used and the cell works in every direction. This means that the PEMFC is very suitable for a wide range of applications, like vehicles and portable electronics, but can also be used in CHP power plants. Similarities for applications: electrolyte electrode structure and catalyst Differences for applications: water management cooling the fuel cell connecting the cells in series operating pressure used reactants

4.2 How the polymer electrolyte works

The basicly used material for the electrolyte is fluoroethylene. The established industrial polymer electrolyte is Nafion from the company Dupont. The construction of the electroclyte material consists of the following steps. The starting material is the polymer polyethylene. 1. The hydrogen in PE is substituted through fluorine, to get polytetrafluoroethylene PTFE, also known as Teflon. This process is called perfluorination. PTFE is durable and resistance against chemical attacks. It is also highly hydrophobic, waterrepellent. 2. The PTFE polymer is sulphonated, that means a side chain, ending with sulphonic acid HSO3 is added to the molecul. The resulting structure is caleed anionomer, due to the ionical bond of the H+ and SO3- ions. The ionic bondage results in a clustering of the side chains in the overall structure.Another important property is, that HSO3 is highly hydrophyllic, attracts water. In conclusion, we are creating water attracting areas in a water repellent material. Within these hydrated regions, H+ ions are relatively weakly bonded and are able to move (dilute acid). Even if these areas are seperated, it is still possible for the H+ ions to move along the the supporting long molecules. From the fuel cell use, the main features of Nafion are: chemically highly resistant mechanically strong, thin films are possible acidic absorb large quantities of water if well hydrated, H+ ions are able to move quite freely through the material

4.3 Electrodes and electrode structure

The electrodes in a PEMFC are essentially the same, a high porous conducting material with platinum as catalyst. To built the single cells, first the platinum catalyst is formed of small platinum particals, which are added onto bigger carbon-based particals. In the seperate electrode method, this powder is fixed on corbon cloth or carbon paper, which builts the basic structure of the electrode. Also PTFE is added due to its hydrophobic property, so that the water as the reaction product is expelled from the surface. Additional the carbon cloth/paper acts as a gas diffusion layer and diffuses the gas onto the catalysts. To form the fuel cell, two of these electrodes are hot pressed on each side of the electrolyte membran. The result is a complete MEA. The alternative method involves building the electrode directly onto the electrolyte. The platinum on carbon catalyst is fixed directly to the electrolyte by rolling or spraying. The electrode is directly manufactured on the membrane.Then the gas diffusion layer is added ,which provides the electrical connection between the carbonsupported catalyst and the bipolar plate, carries the water away and also forms a protective layer for the thin catalyst layer. The final result is shown in figure 4.7, beginning from the left side: electrolyte molecules, platinum/carbon katalyst, carbon cloth or paper. In order to increase the performance the electrolyte material is spread out over the catalyst, to promote the three-phase contact between, the reactant gas, electrolyte abd electrode catalyst.

4.4 Water management in the PEMFC

Wtaer management is a crucial aspect in designing a PEMFC. The PEM requires a sufficient water content, the proton conductivity is directly proportional to it. On the other side, should the electrodes and the gas diffusion layer not be flooded and blocked. In an ideal case, the product water would diffuse evenly through the electrolyte and keep it at a correct level of hydration. But there are several complications: Electro-osmotic drag + H moving from anode to cathode, drag H2O with them, especially at high current densities. The anode side of the PEM can dry out. Drying effect of air at high temperatures At approximatly 60C the air will always dry out the elctrodes faster than H2O is produced. Solution: Humidify the reactants before entering the fuel cell. Correct water balance throughout the whole cell Dry air may ente the cell, but it can become saturated in the cell and can not dry off any more excess water. Important for designing larger stacks. Fortunately, all water movements are predictable and controllable. Water production and water drag are directly proportional to the current. The water evaporation can be predicted. The back diffusion of water from cathode to anode depends on the thickness of th PEM and the relative humidity of each side. The preceded external of humidification of the reactants is also controllable.

4.4.2 Air flow and water evaporation

In a PEMFC it is common to remove the product water by the air flow through the cell (expect the special case: using pure O2). That means, that air is always fed at an higher rate into the cell, than needed to provide the O2 for the reactions (> stoichiometric rate). In practice, the stoichiometry will be at least 2. Problems arise because the drying effect of air is highly non-linear in relation to the temperature. The amount of water vapour in air varies greatly, depending on temperature, location, weather conditions and other factors. One way of describing it is the humidity ratio, the ratio of water vapour in respect to the other gases in air, also called absolute humidity or specific humidity. = mw / m a with mw : mass of water ma: mass of dry air The relative humidity of air gives a good impression of the drying effect of air and is defined as = Pw / Psat with Pw : partial pressure of water Psat : saturated vapour pressure (the air is fully humiditied, it can not hold any more water) The problem in case of a fuel cell is, that Psat varies with temperature in a highly non-linear way. It increases more rapidly with incresing temperature.

Another way of describing the water content is the dew point, the temperature to which the air have to be cooled in oeder to reach saturation. Example: Pw = 12.35kPa dew point T = 50C (see table 4.1) Sometimes it is necessary to humidify the gases going into the cell, so the mass of H2O added has to be calculated. To do so, note that the mass of a species in a mixture is proportional to the product of molecular mass and partial pressure of the species.

And so we get with

P = Pa + Pw

Note that the mass of water is inversely proportional to the total air pressure P, so higher air pressure requires less added water to achieve the same humidity.

4.4.3 Humidity of PEMFC air

The air flow in a PEMFC must be dry enough to evaporate the product water but also wet enough not to dry the PEM out, thus it have to be carefully controlled. The humidity should be between 80 and 100%. In the following section a theoretical formula is derived to set up proper conditions for the humidity required. The partial pressure of a gas is proprtional to the number of molecules (molar fraction)

due to the assumption, that all water is removed by the cathode air supply, the following equations can be used.

With Pe: electrical Power of the stack Vc: voltage of a single cell O2: supply or use rate of oxygen : air stoichiometry The exit flow rate of the non-oxygen components of air is the same as in the inlet. The non-oxygen components amount to 79% of the air. This will be graeter than the oxygen molar flow rate by the factor 0.79/0.21 = 3.76. Substituting the molar flow rates in the first equation delivers

The water vapour pressue at the outlet only depends on the air stoichiometry and the air pressure at the exit. This eqution gives the worst case conditions, not water vapour in the inlet. If the realtive humidity of the excess air is too dry, it could be changed by lowering temperature increase losses lowering air flow rate and hence reduce cathode performance increasing pressure more enrgy for the compressor None of these options is really attractive. Another option is to extract the water of the excess air and supply it to the reactants at the inlet. This requires additional equipment, extra costs, but is often justified by an increased performance. The water pressure can be derived, taking the humidity of the inlet air into account, is given by with

4.4.4 Running PEM fuel cells without extra humidification

It is possible to run a PEM fuel cell at the right conditions without external humidification, by choosing suitable operating temperatures and air flowrates.

Note that humidities are lower at greater airflow. At higher temperatures the relative humidity falls sharply. Note that if the relative humidity of the excess air is below 100% the fuel cell has given all its water, but the air is not yet saturated. That means the fuel cell dries out. On the other side a relative humidity greater than 100% is basically impossible, because the air stream would contain condensed water and the electrons would become flooded. At temperatures above 60C, the relative humidity of the exit air is below 100% at all reasonable values of . Above this temperature extra humidification of the reactants is essential in PEMFC operating. This causes the difficulties in choosing the optimum operating temperature; higher temperatur means better performance but also increasing humidification problems. The key is to set the stoichiometry so that the relative humidity of exit air is about 100% and design a balanced water distribution within the cell.

4.4.5 External humidification - principles

Small fuel cells can be operated without external humidification, they will perform, even with the correct air flowrate and temperature, muc =h worse than a identical humidified cell. Operating temperatures over 60C are desirable to reduce the cathode activation losses. Considering the additional equipment and costs for extra humidification, it is still more economic to operate the fuel cell at maximum possible power density. However, water as a additional input is not desirable. The water has to be extracted from the exit air flow. That requires a water condensation or seperation system in the exit path. The intrnal recycling of water also ensures the purity of the water. Note: air & hydrogen are often humidified. Process involvs evaporating water in the incoming gas. This will cool the gas. Desired in pressurized systems. Benefits of increasing humidity improve the performance especially at operating at higher pressures.

4.4.6 External humidification methods

In this operation process no industrial standard has been yet emerged. In the following section eight different methods will be outlined. 1. In laboratory test systems the reactants are humidified by bubbling them through water (sparging) 2. Direct injection of water as a spray in th reactants flow. Easy to control, but expensive and inefficient due to additional pumps and valves. Cools the gas. 3. Metal foam to make a fine water spray. No pumps and other devices needed. 4. Direct watering of the PEMFC (used in the past) Wicks are constructed as part of the gas diffusion layer and draw water directly into the cell. Selfregulating, because no water is drawn if the wicks are saturated. Problem: Sealing the cell and no cooling effect 5. Direct injection of liquid water and distribution by the reactants. Requires an efficient flow field design of the bipolar plate. Good results are reported, though the reactants have to be driven at pressure. Problem: no cooling effect All the mentioned methods requires liquid water. There are other methods which don't need a water condensation and seperation system. 6. Rotating piece of water absorbing material Absorbs water in the exit, rotates and evaporates it in the inlet. Problem: system is bulky, needs to be powered and controlled. 7. Membrane Exiting warm, damp air passes the membrane, water is condensed, liquid water passes through the membrane and is evaporated by the dry gas at the inlet. A PEM membrane can be used. Advantage: evenly spread humidity, simple, no moving parts Disdvantage: no control 8. Self-humidification, by using a modified electrolyte which also produces water. A catalyst is added in the PEM, some amount of the reactants diffuse through the electrolyte and combine to water. The improved performance justifies the fuel loss.

4.5 PEMFC cooling and air supply 4.5.1 Cooling using the cathode air supply
PEM reaches normally efficincies of around 50%, so half of the chemical energy is changed in heat. The heat produced by a PEM, if the product water is evaporated within the cell is

The way the heat is removed depends greatly on the size of the fuel cell, beolow 100W it is possible to cool the cell and evaporate the water by air, without using any fan, only due to a open cell design. The fact that damp air is less dense than dry air aids the circulation process. For more compact types a small fan blows the reactants and cooling air through the cell, though a large proportion of heat is lost through natural convection and radiation. For systems with a power higher than 100W, seperate cooling is needed.

4.5.2 Seperate reactant and cooling air

Is best shown with a specific example. fuel cell power Pe [W] single cell voltage Vc = 0.6V operating temperature T = 50C cooling air enters at 20C and leaves at 50C (best possible case!) 40% of generated heat is removed by the air, rest is radiated. Entry air humidity 70% 40% of the heat rate (equation above) is removed by air of the specific heat capacity c p, with the flowing rate and a temperature change T. With cp = 1004 J/kgK T = 30K Vc = 0.6V The reactant air flow rate is given (see appendix A2.2).

If the reactant air and cooling air are the same, the equation would be the same. This gives an exit air humidity at 50C of 26%, that means that the relative humidity decreases, and so the PEM will quickly dry out. In order to reduce to a desired value of 3 to 6, the air flow rate has to be reduced and a seperate cooling system is required. Seperate cooling is achieved by adding cooling channels in the bipolar plates of adding additional cooling plates in the cell. Air cooling works for cell powers up to 2 kW.

4.5.3 Water cooling of PEMFC

For larger fuell cells water cooling is more useful, due to the higher cooling effect of water. The operation process are basically the same as for external air cooling. Cooling channels or additional cooling plates distribute the water in a seperate cooling circuit in the cell. Water cooling is, for example, in cases of heat recovering in small CHP plants more preferable.

4.6 PEMFC connection the bipolare plate

Bipolar plates are difficult to manufacture, and made up almost all volume and mass of a fuel cell, thus they are also a high proportion of the cost of a PEMFC stack.

4.6.2 Flow field patterns on the bipolar plates

In the bipolar plate the reactants are fed over the electrode in a fairly dimple pattern or parrallel grooves. The parallel system has the problem that impurities, like notrogen, can block one groove, and therefore leading an area of the electrode unsupplied. This leads to a more serpentine pattern. The problem with this pattern is the longer path length abd the large numbers of turns in the gas flow. That means more work and thus more energy is needed to push the gas through. The grooves are very narrow, less than 1mm2. In order for water droplets not to form, the system is arranged so that the pressure drop along a channel is greater than the surface tension holding a water droplet in place. That has to work even when the gas suuply is stopped. The latest development by Ballard is a rectangular plate, several times longer than wide, with long straight channels, which have a high pressure drop and no inefficient bends and turns.

4.6.3 Making bipolar plates for PEMFCs

The bipolare plate has many tasks in the cell. Collecting and conducting the current from the anode to the cathode of the next cell, evenly distributing the fuel to the anode and oxygen/air to the cathode and sometimes carrying a cooling fluid. Furthermore keeping all the gases and fluids apart from each other and contain the reactant gases within the cell. Requirements: electric conductivity > 10 S/cm heat conductivity > 20 W/mK with additional cooling and > 100 W/mK without gas permeability < 10-7 mbarL/scm2 corrosion resistant stiff, flexural strength > 25 Mpa low costs slim for min stack volume light for min stack weight short production time The materials and production method used, varies considerably. In terms of easier manufacture the plates are often made in two halves. Then, the cooling channels can be cutted and don't have to be drilled into the plate. The most commonly used materials and methods are: machining of graphit paper ellectrically conductive, reasonably easy to machine, low density Disadvantages: long machining time, brittle so careful handling needed, porous so a few mm thickness is needed inection molding of graphite filled polymer cheap, short production time Disadvantages: poor conductivity, needs further developments compression moulding of a graphite and thermoplastic polymer granules higher proportion of graphit, so better conductivity, but not so fast as injection moulding. Carbon-carbon composite the complex shape of the surface is moulded and then applied to a solid carbon back plate, in order to get a higher stiffness, lower gas premeability and sufficiently flat plate. Stainless steel good electrical and heat conductor, not porous so thin, can be machined easily. Disadvantages: heavy, expensive Perforated or foamed metal

flow field is made of foamed metal, with a sponge-like structure. Then a thin solid metal plate is added between two foamed plates. A corrocsive resistant coating is added. Cooling plates can be made in the same way. One porous metal slice between two solid plates. Advantage: already available material, cutting and moulding the plastic deals only process steps

4.6.4 Other topologies

Fuel cell stacks construction using bipolar plates gives very good electrical connection between the cells, but are expensive and difficult to manufacture. In cases of lower current densitiesa compromise with higher electrical resistance but therefore cheaper and simpler is helpful. Such a compromise is shown in figure 4.20. A system of three cells in series, consisting a cheap plastic body and requires only on chamber for the fuel and on for the air. It is not a compact system, but the potential leaks are much reduced and due to the free circulation, humidification is not a problem.

Another problem is the possible imbalance of this system. The single cells are some way apart. If one cell becomes rather warmer, this would lead to more rapid water evaporation, and so to higher resistance and higher temperatures. The cell got in a vicious circle and would end up dried.

4.7 Operating pressure

Running a fuel cell at higher pressure will increase the power of the cell, mainly by reducing the cathode activation losses. But it also involves consumption of power for the additional equipment as compressors and turbines. A typical value of power consumption is about 20%.

4.7.2 Simple cost/benefit analysis of higher operating pressures

We have seen, that V is proportional to the logarithm of the pressure rise.

We also saw, that the activation overvoltage is related to the exchange current by a logarithmic functio. So we can say, that if the pressure is increased from P1 to P2, then there is a gain in voltage and power.

with

C: voltage gain constant, depeding on the change of i0 with the pressure, R, T and F. I: current n: number of cells

On the other side we have the power consumption of the compressor and the electric propulsion.

with

T1: entry temperature c: compressor efficiency m: motor and drive efficiency : air flow rate The air flow rate is connected to the electric power, the cell voltage and the air stoichiometry, by Substituting the electric power by nIVc and the air parameters cp and , we get the power losses.

The highlighted part is the voltage loss. We can get now the voltage change for a rise of the pressure by The following plot shows two graphs, a realistic and optimistic one, for the different parameters.

It can be seen, that for the realistic values, the nett voltage will always be less for higher pressures. The made derivation is a quite simple one and a lot of other factors have to be included to get a realistic view of the effect of ibcreased pressures.

4.7.3 Other factors affecting the choice of pressure

Gains: fuel reforming system reduction in size, the waste heat of the burner can be used to drive the compressor humidification easier for hot inlet air, that needs cooling. Compression goes always with a temperature rise, about 150C. Less water is needed to humidify the air and cool it to suitable temperature. It is very difficult to arrange proper PEMFC humidification ta temperatures above 80C unless the system is pressurized in larger fuel cells the flow paths of the reactants is long and narrow, so a certain pressure is already needed to drive the gases through the cell. Disadvantages: size, weight, cost of the additional equipment. Rising noise, due to the operation of compressors and electric motors. Using pure oxygen nstead of air, the choice of operating pressure will be made under complete different aspects and can be much higher.

4.8 Reactant composition

In larger systems the hydrogen fuel will frequently come from some kind of fuel reforming system. These systems nearly always involve a reaction, like the water shift reaction, producing carbon monoxide. CO has a great negative effect on the performance of the cell, by poisoning the electrodes. CO covers the platinum, preventing the hydrogen fuel from reaching it.This happens even in very low concentrations, as 10ppm CO. In the end CO has to be removed of the fuel stream, which requires additionel processing. Small quantities, around 2%, of hydrogen or oxygen are added to the fuel stream. This reacts with the CO. However, any oxygen not reacting with CO will react with hydrogen, and thus wasting fuel. Gas clean-up unit is used. Pure oxygen is mainly used in air independant systems, as submarines or spacecraft. Advantages: no loss OCV rises, due to higher partial pressure of oxygen (Nernst equation) actication overvoltage decreases limiting current increases, thus reducing the mass transport and concentration losses, because of the absence of nitrogen.

7. Medium and high temperature fuel cells

Even if the no loss OCV decreases with increasing temperature outweigh the advantages the disadvantages at high temperatures. Electrochemical reactions take place more quickly. Noble metal catalysts are often not needed. Enough heat in the exit gases to extract hydrogen from readily available fuels. Heat of the exit gases can be used for heating buildings, processes and other facilities, in CHP plants. Heat of the exit gases can be used to drive turbines and generate electricity. Three types of medium and high temperature cell are considered. PAFC, MCFC and SOFC. PAFC: operates at around 200C and needs a noble metal catlyst, and so, like the PEM is poisoned by any CO in the fuel gas, thus its fuel processing system is necessarily complex. MCFC: operates at around 650C. The main problem is the degradation of cell components over long periods. But it shows great promises for the use in CHP plants.

SOFC:
operates between 650C and 1000C. Since it is a solid state device, it has many advantages due to its mechanical simplicity and can be used in a wide range of applications. The advantages mentioned above consider mostly the use of the waste heat. PAFC, MCFC and SOFC must always be thought of as a integral part of a complete fuel processing and heat generating system. The common features of all three types are: used fuel needs processing fuel utilisation fuel is a mixture, in which the hydrogen is used. This means that the concentration will decrease, what reduces the local cell voltage. Exit gases carry a large amount of heat, which can be further converted into electricity and

thus leads to higher efficiency. Heat can also be used to preheat fuel and oxidant. Ensure high electrical and thermal efficiency and reduce the exergy losses are the key aspects in designing such a system.

7.2 Common features 7.2.1 An introduction to fuel reforming

The production of hydrogen from hydrocorabons usually involves steam reforming. The steam reforming reaction with natural gas is an endothermic reaction, that means heat needs to be suuplied for a suficient reaction rate. In most cases fuel reforming takes place at about 500C and can be used from the exhaust gases of the fuel cell itself. The PAFC requires additional burning of fuel to achieve that temperature, what reduces the effcicncy to 40-45%. For the MCFC and the SOFC efficiencies over 50% can be achieved. In a PAFC as in a PEM must the reformed gas further processed with the gas shift reaction, due to reducing the CO content in the gas. An aspect considering all fuel cells using hydrocarbonat,as natural gas, is the desulphurisation of the fuel .Even small amounts of sulfur deactivate the electrodes. This proces also needs heating up the fuel over 350C. The higher operation temperatures of theMCFC and the SOFC allows the basic steam reaction taken place in the fuel cell stack itselfs. Furthermore the steam neede is already present in the stack. The exhaust steam at the anode is used for the fuel reforming. That simplifies the design of MCFC and SOFC.

7.2.2 Fuel utilisation

Fuel utilisation has always to be taken into account when the hydrogen is fed in a mixture to the stack. As the gas mixture passes through the cell, the hydrogen is utilised, the other components simply pass through unconverted, and so the hydrogen concentration falls. At the end of the cell the partial pressure of hydrogen will be very low and thus lower the cell voltage. From the Nernst equation we can get the voltage change in respect of a change in hydrogen pressure.

If the partial pressure of hydrogen falls from P1 to P2, the voltage change will always be negative. The RT term means that this drop will be greater for higher temperatures. The same occur for the oxygen utilisation from the air. Figure 7.1 shows the effect of it in four cases. 1. Standard hydrogen fuel cell operating at 1bar with pure hydrogen and oxygen. 2. Using air at the cathode and a mixtue of 4 parts hydrogen and 1 part carbon dioxide at the anode. 3. Nernst exit voltage for 80% fuel utilisation and 50% air utilisation. 4. Nernst exit voltage for 90% fuel utilisation and 50% air utilisation.

Sometimes the voltage drop can be reduced, by using opposite flow direction (counteer-flow), so high oxygen concentration at the point of the cell with low hydrogen concentration. A factor ignored yet, is that in MCFC and SOFC the product steam ends up at the anode, hydrogen is replaced by steam. This will also cause a fall of the OCV. The important conclusion is, that in the case of reformed fuel containing carbon dioxide or when internal reforming is applied, all the hydrogen can nevver be consumed in the fuel cell itself. Some hydrogen must pass right through the cell and can be used later to provide energy to process the fuel or to be burnt to increase the heat energy. To find an optimum, extensive modelling is needed.

7.2.3 Bottoming cycles

Bottoming cycles mean the use of waste heat from a fuel cell axhaust gases to drive some kind of heat engine, for example boiler and steam turbine or a gas turbine. These combined cycle systems offer an elegant way of producing very efficient systems of generating electricity. However, the Gibbs free energy for hydrogen decreases with temperature. So the highest theoretical possible efficiency is at ambient temperature.

On the other side are the losses high at abient temperature and so the practical efficiency would be well below that limit. To reduce the voltage losses we have to raise the temperature, but this reduces the Gibbs free energy. If we assume now a revrsible process operating at high temperature, the waste heat can also be converted into electricity. Using thermodynamic basics and the Carnot limit we get the same maximum efficiency as mentioned above. Figure 7.2 shows the efficiency limit of fuel cell, a heat engine and a combined cycle. Note that the temperature limit of the heat engine is the combustion temperature of the fuel.

A fuel cell operating at around 800-1000C can approach the theoretical maximum efficiency, as

well as heat engines. Figure 7.3 sketches a possible combined cycle system based on an SOFC.

The work done by the two compressors are the major losses in the system. Assuming realistic values such a system can reach efficiencies of around 60%. Working at higher pressures offers the possibilties to reach even higher pressuers.

7.2.4 The use of heat exchangers -exregy and pinch technology

In fuel cell systems are process streams that need heating and others need cooling. A challenge for the designer is to use the available heat in the most efficient way. The hot gas streams, which need to be cooled deliver their heat over heat exchangers to the streams which need it. Exergy may be defined as a kind of energy which can be converted into work, like the potential energy. Energy is conserved in all processes, exergy only in reversible processes. Real processes are irreversible, so that exergy is always partly consumed to give enthaply. The exergy is measured by the change out of the thermodynamic equilibrium (reference state). Note: The higher the temperature, the higher the exergy. For a SOFC and PEMFC having the same power output and efficiency, the heat, so the enthaply content, of the exhaust streams will be the same. However the heat produced by the SOFC would be at higher temperature and therefore has a higher exergy. It can be converted into usefl energy. Pinch analysis or pinch technology is a methodology that can be applied to fuel cell systems for deciding the optimum arrangement of heat exchangers and other units so as to minimise the exergy loss. 1. Defining the required chemical processes and set up a system configuration, showing all hot and cold process streams. Calculating the enthalpy content for each process and building heating and cooling curves. 2. Sum them together to derive a total heating and a total cooling curve. 3. Slid the curves together at the y-axis and note the point the curves pinch together, so the

minimum difference. This so-called pinch temperature defines the target for the optimum process design, since in a real system heat cannot transferred from above or below this temperature. Other considerations taken into account are the materials of the BOP components and their mechanical layout.

7.4 The molten carbonate fuel cell MCFC

The electrolyte is a molten mixture of alkali metal carbonates, usually lithium and potassium or lithium and sodium, which is retained in a ceramic matrix of LiAlO2. At the operation temperature of 600-700C the alkali carbonates form a highly conductive molten salt, with CO32- as mobile ion. Unlike other fuel cells, CO2 and O2 needs to be supplied at the cathode. Figure 7.9 shows the principal function of a MCFC with the electrode reactions.

The Nernst reversible potential, taken the CO2 transfer into account, is given by

In practice the CO2 produced at the anode is externally recycled to the cathode. The anod exhaust gas is fed to a burner, which converts any unused fuel into water and CO2. The exit flow of the burner is then supplied with fresh air to the cathode inlet. The process also pre-heat the reactant air. Another method of reuse the CO2 is a membrane seperator. The advantage of this method is unused fuel gas can be recycled to the anode or used for other purposes. If an external supply of CO 2 is already existing this can also be used. MCFC doesn't need nobel metal catalysts, due to the high operating temperature. Nickel (anode) and nickel oxide (cathode) is used. Furthermore it is also able to convert CO directly and reform hydrocarbon fuels directly. The high operating temperature of MCFCs provides the opportunity for achieving higher overall system efficiencies and greater flexibility in use of available fuels compared to low temperature cells. Unfortunately, the higher temperatures and the aggresive medium of molten carbonate electrolyte also place severe demands on the corosion stability and life of the cell components.

7.4.2 Implications of using a molten carbonate electrolyte

MCFC uses a liquid electrolyte that is immobilised in a porous ceramic matrix. The electrolyte interfacial boundaries are established by a balance in capillar pressures in the MCFC. By properly co-ordinating the pore diameters in the electrodes and in the electrolyte matrix, the electrolyte distribution is established. The smaller pores in the matrix remain completely filled, while the bigger pores in the electrodes are partially filled. The electrolyte management is a critical point to achieve hich performance and endurance.

7.4.3 Cell components in a MCFC

Electrolyte MCFC electrolytes contain typically 60wt% of carbonate constrained in a matrix of 40wt% LiOALO2. The ohmic resistance of the electrolyte and especially the ceramic matrix has an important effect on the operating voltage. They account for around 70% of the ohmic losses, which depends mainly on the thickness t of the electrolyte according to V = 0.533 x t The ceramic matrices can nowadays be made quite thin (0.25 0.5mm), by using tapecasting methods, what counteracts the long-term stability, which is obtained with thicker materials. Note that, in contrast to the other types, the final preperation is carried out once the stack components are assembled. The whole package is heated up slowly. At its melting temperature the carbonate is absorbed by the matrix. That leads to a significant shrinkage of the stack. Damages due to the shrinkage have to be provided. In addition, a reducing gas has to be supplied to the anode, while heating up, to ensure that the nickel anode remains in the reduced state. Heating and cooling of a MCFC needs time to avoid cracking the electrolyte matrix. It is also necessary to protect the anode at lower temperatures of oxidation with inert gas. Therefore they are best used in continous processes. Anodes Anodes are made of porous sintered NiCr/NiAl alloy, with a thickness of 0.4 to 0.8mm and a porosity of 55 75%. Cr is added in order to reduce the sintering of the Ni during cell operation. It leads on the other side to bigger pores, so less surface area and finally to a performance drop, due to redistribution of carbonate from the electrolyte. Cr also reacts with the Li in the electrolyte ovr the time. To overcome this, Al is added, to improve the creep resistance in the anode and reduce electrolyte losses. The anodes have achieved a commercial acceptable stability but are very expensive. A high surface area of the anode is not required, because the anode reaction is fast in respect to the cathode reaction. Because of this the anode is partially flooded to provide a reservoir for carbonate. Nowadays, using the tape cast structure it is possible to control the pore distribution; Small pores close to the electrolyte, larger pores near the fuel gas channels. However, long term electrolyte loss is still a significant problem with MCFC. Cathodes The major problem with the cathode is that the nickel oxide has a small, but significant, solubility in molten carbonate, thus metallic nickel can precipitate out in the elctroclyte, that can cause internal short circuits with a subsequent loss of power. The precipitated nickel can act as a sink for nickel ions, which promates further dissolution. This problem can be reduced by using basic carbonates, operating at atmospheric pressure and low CO2 partia; pressure. Non-porous components The bipolare plates for a MCFC are usually made of stainless stell, which is coated at the anode side with nickel, due to the reducing environment at the anode, and with a thin layer of aluminium to avoid corrosion. The sealing is achieved by connecting the bipolare plate with the liquid electrolyte outside the electrochemically active area.

7.4.5 Internal reforming

The principal variations of internal reforming in a MCFC are direct internal reforming DIR and indirect internal reforming IIR. DIR offers a higher cell performance. The product of the reforming reaction, hydrogen, is directly consumed by the electrochemical reaction, therefore the reforming reaction is shifted in the forward direction. This leads to a higher conversion of hydrocarbon than would normally expected. A thigh fuel utilisation in a DIR MCFC nearly 100% of methane is

converted into hydrogen at operating temperature. IR eliminates the costs of an external reformer and thus systems efficiency is improved, but the cell configuration can get more complex. IR is only possible with an additional metal catalyst, due to the low anode surface area. Key requirements for the MCFC reforming catalyst area-specific sustained activity to achieve the desired cell performance and lifetime resistance to poisons in the fuel resistance to alkali/caronate poisoning

7.4.6 Perfomance of MCFC

The performance curve of a MCFC is defined by cell pressure, temperature, gas composition and utilisation. State of the art MCFCs operate in the range of 100 200mA/cm2 and 750 900mV per cell. Influence of pressure The reversible voltage change in respect to a pressure change is given by the Nernst equation. In practice the voltage gain is greater because of the reduced cathode polarisation. Increasing the operating pressure ofMCFCs result in enhanced cell voltages because of the increase in the partial pressure of the reactants, increase in gas solubilities and increase in mass transport. Another advantage of a pressurized system is that the exiting gases can be used to drive a gas turbine. On the other side compressing requires a lot of power and undesirable side reactions can occur. Higher pressure also inhibits the steam reformation if internal reforming is used. In practice the benefits of increasing pressure only outweigh the disadvantages up to 5bar. To provide gas crossover between the electrdodes and leakage the pressure differences between the electrodes as well as to the outside should be as small as possible. Therefore, the stack is enclosed in a pressure vessel. Influence of temperature The reversible voltage of a MCFC decreases with higher temperature due to the decrease of Gibbs free energy and the change in equilibrium gas composition at the anode. Under real conditions the effect of cathode polarisation dominates; Increasing temperature, decreasing cathode polarisation and this leads to higher operating voltages of the MCFC. However above 650C the effect is negligible small and undesired side effects, as electrolyte evaporation and corrosion, rise. Generally 650C is considered as an optimum operating temperature.

7.5 The solid oxide fuel cell SOFC