Why Hydrogen Energy and Fuel Cell!

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

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

Open-ended energy systems: GHG emission

Quality of Life vs. Energy Usage

Trend in Crude Discoveries, Consumption and Price with Time

Crude oil Discoveries

Year
1960 1980 2000 2020

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

Crude oil Consumption

Year 1960 1980 2000 2020

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

Year 1960 1980 2000 2020

kJ/km Well-totank TanktoWell-to-wheel wheel 2777 2314 2834 2136 1915 1543 1615 1653 1157 1111 3471 2691 3257 3560 2394 1794 1856 2755 1928 1851 Gasoline ICE Diesel ICE CNG ICE H2 ICE Gasoline HEV ICE- 694 377 423 1424 479 251 241 1102 771 740 Diesel ICE-HEV CNG-ICE-HEV H2 ICE-HEV H2 FC H2 FC-HEV Carbon Dioxide Emission From Different Types of Passenger Cars .Look for Alternatives ! Natural Gas Biomass Solar Water Nuclear H2      Generation Transportation Storage Dispensing Fuel cell Energy Consumption in Different Types of Passenger Cars Type Energy consumption.

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

Fuel Cell .

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History. Principle & Overview of Fuel Cells     Fuel cell is a device that takes fuel as input and produces electricity as output Converts chemical energy of raw materials into electrical energy Different from battery . a material which allows ions to flow but not electrons Fig: A simple fuel cell with platinum electrodes dipped in sulphuric acid ( an aqueous acidic electrolyte) Basic fuel cell operations .A fuel cell will keep on producing electricity as long as fuel is available Similar to a chemical factory which transforms raw material(fuel) into final product (electricity) A simple fuel cell  Electrochemical half reactions of a H2-O2 fuel cell:    Electrons transferred from the fuel travel through the external circuit (thus constituting an electric current) and do useful work before they complete the reaction Spatial separation achieved by an electrolyte.

3. 2. Reactant transport Electrochemical reaction Ionic and electronic conduction Product removal Advantages     More efficient than combustion engines – directly convert chemical energy to electrical energy Mechanically ideal – no moving parts .1. 4. good reliability. long lasting systems Clean and silent operation Easy independent scaling between power (determined by fuel cell size) and capacity ( determined by fuel availability) Disadvantages     Cost – a major issue Fuel availability and storage Durability under stop-start cycles Low volumetric power densities as compared to batteries and combustion engines Power density comparison of various technologies .

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

CH4 O265010000C Perovskites H2 .) Recent Trends in Fuel Cell Science and Technology. 5. 3. Springer (2007) Fuel Cell Component .H3PO4immobilized Ceramic Membrane Immobilized carbonate H+ H+ 2000C Platinum H2 OH60-2000C Platinum H2 CO326500C Nickel H2 . 4. S.1. Phosphoric acid fuel cell (PAFC) Polymer electrolyte membrane fuel cell (PEMFC) Alkaline fuel cell (AFC) Molten carbonate fuel cell (MCFC) Solid oxide fuel cell (SOFC) Major fuel cell technologies PEMFC Electrolyte Charge carrier PAFC AFC MCFC SOFC Polymer Liquid KOH Molten Liq. Compatibility methanol Different Types of Fuel Cells Basu.CO Operating 800C Temperature Catalyst Platinum Fuel H2. 2. (Ed.CH4.

oxidant. ions and electrons through the different components of PEMFC .Schematic of Proton Exchange Membrane Fuel Cell Note the flow of fuel. products.

S.Polymer Electrolyte Membrane Fuel Cell Basu. Activation loss (losses due to electrochemical reaction) . The major types of loss are : 1. Springer (2007) Fuel cell performance      Fuel cell performance can be assessed by current-voltage curves. (Ed. Ideal fuel cell performance is dictated by thermodynamics Real fuel cell performance is always less than ideal fuel cell performance due to losses.) Recent Trends in Fuel Cell Science and Technology. i-V curves show the voltage output of a fuel cell for a given current load.

Concentration loss (losses due to mass transport) Combined fuel cell i-V and power density curve     Fuel cell power density increases with increasing current density. Fuel cells are designed to operate at or below the power density maximum.2. At current densities below the power density maximum. voltage efficiency improves but power density falls. Ohmic loss (losses due to ionic and electronic conduction) 3. both voltage efficiency and power density fall. At current densities above the power density maximum. and then falls at still higher current densities. Reaches a maximum. .

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Fuel Cells – Types and Chemistry Alkaline fuel cell (AFC) Anode (Pt/C) Cathode (Pt/C)    First used in space shuttle by NASA 60% efficiency between 150 – 200 deg C operating temp. Electrode poisoning is observed in presence of OH- Proton Exchange Membrane Fuel Cells (PEMFC) .

Membrane electrode assembly (MEA ) consists of the anode. cathode. Membrane should remain hydrated for efficient transport of protons. and hence PEMFCs can’t be operated at higher temperatures Electrode poisoning in presence of OH- Phosphoric Acid Fuel Cell (PAFC) . proton exchange membrane (PEM) and gas diffusion layers (GDLs).Anode (Pt/C): Cathode (Pt/C):      Uses a solid polymer electrolyte. Nafion allows transport of protons while blocks electrons. usually perfluorosulfonic acid (nafion) membrane.

calculators Molten Carbonate Fuel Cell (MCFC)  Anode (Ni)  Cathode (NiO2) . 40 – 80 deg C Might be useful for future portable devices such as laptops. which conducts protons and has good thermal stability Operating temperature varies between 175 – 200 deg C Used for heavy vehicles such as buses and trucks Direct Alcohol Fuel Cell (DAFC)      Anode (Pt/C) Cathode (Pt/C) Uses lighter alcohols such as methanol or ethanol instead of hydrogen Can be operated at lower temperatures.    Operating principle is similar to that of a PEMFC Phosphoric acid is the electrolyte used.

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

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

Anode (Ni/YSZ)

Cathode (Perovskite/LaMnO3)

    

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

Schematic of SOFC

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

  

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

Electrolyser:

Anode (Pt/C):

Cathode (Pt/C):

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

Alkaline fuel cell These electrons at cathode react with oxygen and water to produce hydroxyl ions. there exists a possibility of poisoning the anode catalyst and the formation of carbonates in the presence of CO2 (5). Pt-black or Pt/Ru catalyst is used as anode and cathode catalysts respectively. Generally. which is discussed in the next section.1. 2. The electrode gets eventually poisoned in the presence of OH. . However. It was fuelled by hydrogen and oxygen for the power generation while the astronauts used the reaction byproduct. The reactions in the AFC are given below The efficiency of an alkaline fuel cell is about 60% (4) when the operating temperature is about 150 oC to 200 oC. This problem is tackled by re-circulating the electrolyte after removing the carbonate and the heat of reaction. many investigators (6) are looking at the possibility of using alcohol as fuel directly feeding it to alkaline fuel cell to generate power. permeable sheet for the transport of proton (7). Alkaline fuel cell was first used by NASA in Apollo space shuttle. platinum. Recently. Because of these reasons. water for drinking purposes.Fig. Proton Exchange Membrane Fuel Cells (PEMFC) The proton exchange membrane (PEM) fuel cell as shown in fig. AFC faces tremendous challenges for its commercialization. which diffuse through the electrolyte and reaches anode. uses a solid polymer electrolyte (perfluorosulphonic acid membrane) in the form of a thin.and carbonate is formed in the presence of CO2 in air. The problem of alkaline electrolyte is handled by replacing it with perfluorosulphonic acid membrane. The typical life of a 2 KW AFC is about 5000 hrs.

Gas diffusion layer works as substrate for catalyst and ensure the proper distribution of reactants over the catalyst. . anode. The migration of proton in membrane is promoted by sulphonate group present in polytetrafluoroethylene membrane structure through the formation of hydronium ion. which is pasted on gas diffusion layer made of carbon cloth or paper. cathode and gas diffusion layer is known as membrane electrode assembly (MEA) and is the heart of polymer electrolyte membrane fuel cell. Thus. the PEM fuel cell cannot be operated above 80oC because of the water loss from the membrane and subsequent poor conduction of proton.Fig. Hydrogen molecules are stripped at the anode electrode-catalyst into electrons and protons (H+). A PAFC as shown in fig. 3 consists of an anode and a cathode made of finely dispersed platinum catalyst on carbon and the electrolyte is housed in silicon carbide structure. the membrane needs to be hydrated for efficient transport of proton in the form hydronium ion. The composite structure of gas diffusion layer. This low resistance material is known as the bipolar plate made of graphite and it has channels to supply the reactants over the diffusion layer both on the anode and cathode sides (Fig 2). 2. The protons permeate through membrane and reaches cathode side. which helps to conduct the electrons from the fuel cell to the outer circuit. Proton exchange membrane fuel cell The proton exchange membrane is sandwiched between anode and cathode catalyst. where it reacts with oxygen and conducted electrons from the outer circuit to produce water. Moreover. proton exchange membrane. Electrons are collected at low resistance material. The reaction scheme for proton exchange membrane is shown below: Phosphoric Acid Fuel Cells (PAFC) The reactions occurring on the anode and cathode are similar to PEMFC as given in equations 4 to 6. The proton exchange membrane made of perfluorosulphonic acid allows proton to pass through it and restricts the passage of electrons.

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

A solid oxide fuel cell (SOFC) uses a . The reactions occur at 650 oC when salts melt and conduct carbonate ions from the cathode to the anode.The direct alcohol fuel cells are operated at lower temperature (40 oC . The electrons migrate towards cathode through the load connected to an external circuit. Solid oxide fuel cells work at even higher temperatures than molten carbonate fuel cells. 5.4.80oC) and thought to be power source in future for portable equipments like laptop.4. calculator etc. The molten carbonate fuel cell uses a molten carbonate salt as the electrolyte (10). The need for carbon dioxide in the oxidant stream requires a system for collecting the carbon dioxide from the anode exhaust and mixing it with the cathode feed stream. Molten carbonate fuel cell The anode process involves a reaction between hydrogen and carbonate ions to form water and carbon dioxide while releasing electrons at the anode. Fig. The reactions in the molten carbonate fuel cell are given below: Solid Oxide Fuel Cells (SOFC) The schematic diagram of a solid oxide fuel cell is shown in fig. Molten Carbonate Fuel Cells (MCFC) The schematic diagram of a molten carbonate fuel cell is shown in fig. The cathodic process involves oxygen and carbon dioxide from the oxidant stream with electrons to produce carbonate ions.

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

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

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

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

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

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

First law The law of conservation of energy

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

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

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

dU = dQ –dW

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

dS=dQrev/T

15K) and Pressure 1 bar=100kPa Standard state condition are designated by a superscript zero. Room temperature(298. ΔGrxn=-273 kJ/mol H2 eg 5 mole of O2 is reacted . we need a reference state called as a standard state. Reversibility   Reversible implies equilibrium E represents a reversible fuel cell voltage and V represents an operational ( nonreversible ) fuel cell voltage Heat Potential of a Fuel dH=TdS+Vdp .H2-O2 Fuel Cell H2+1/2 O2 ---> H2O . the extrinsic Gibbs free energy change Some Important terms Standard State Because most thermodynamic quantities depend on T and p.

for a constant pressure process dH=TdS = dU+dW Calculating Reaction Enthalpies :: enthalpy required to form 1 mole of chemical species ‘i’ at STP from the reference species Work potential of a fuel: Gibbs free energy G=H-TS dG = dH – TdS Relationship between Gibbs free energy and Electrical Work Relationship between Gibbs free energy and voltage   Potential of a system to perform electrical work is measured by voltage (electrical potential) Electrical work done by moving a charge Q ( coulombs) through an electrical potential difference E(volts). Welec Welec=EQ If the charge is carried by electrons .

F: Faraday constant H2-O2 Fuel Cell Relationship between Gibbs free energy and Electrical Work Standard Electrode Potentials: computing reversible voltage Standard state electrode potential is standard state reversible voltages of various electrochemical half reactions relative to the hydrogen reduction reaction.Q = NF n: number of moles of electrons transferred . .

Predicting reversible voltage of a fuel cell under non-standard-state conditions Reversible voltage variation with temperature For molar reaction quantities Defining ET as the reversible cell voltage at T At cinstant p. Reversible voltage variation with pressure Reversible voltage variation with concentration .

For a fuel cell.Fuel cell efficiency   Ideal efficiency of a fuel cell is limited by ΔG Real efficiency is lower than ideal efficiency because of non-ideal irreversible process Ideal reversible fuel cell efficiency If work is extracted from a chemical reaction. Thus the reversible efficiency of a fuel cell is At room temperature. H2-O2 Fuel Cell . the maximum amount of energy available to do work is given by Gibbs free energy.

it is HHV. Efficiency is calculated based on HHV Comparison with conventional heat/expansion engine Real fuel cell efficiency Two main reasons for decrease in fuel cell efficiency:   Voltage losses Fuel utilization . if H2O(l) is product. If H2O(g) is product. it is LHV.HHV:Higher heating value H2-O2 fuel cell.

Voltage efficiency of the fuel cell Ratio of the real operating voltage of the fuel cell (V) to the thermodynamically reversible voltage of the fuel cell (E)    Operating voltage depend on the current (i) drawn from the fuel cell: The lighter the current load. the lower the voltage Fuel cell are most efficient at low load Fuel utilization efficiency of the fuel cell Ratio of the fuel need by the cell to generate electric current and the total products to the fuel cell.   The supply of fuel to a fuel cell is adjusted to the current FC is always supplied with just a bit more fuel than it need at any load .

hydrogen and oxygen are often diluted for several reasons. Therefore..... However..78 for 1 atm air pressure. Since air approximately contains 78 % N2(by volume). which also contains nitrogen. the products from water gas shift reaction (CO + H ) can be used as a source for hydrogen...... i. pressure and the moles of other species are held constant....... With pure hydrogen and oxygen at standard conditions...... air can be used as a source of oxygen.. where pi and p0 are respectively the partial pressure of species i and the standard state pressure.. activity of nitrogen (N2) in air at 1 atm would be partial pressure of N 2 in air.... we first recollect the concept of chemical potential learnt in thermodynamics..... a – i ....... For example. Similarly.....56.. 1 atm and 298 K. The activity of species is a function of its chemical nature... However....e..... while temperature. For example.....e. i.. if the air pressure is increased to 2 atm. the activity of N 2 would be 0. 1..... where γi is an activity coefficient...e..... This is the maximum voltage that can be withdrawn from this system........... while p i and p 0 have the same meanings as defined for the case of an Ideal gas Nonideal gas ........ ai=γi (pi/po).. ai denotes the activity of species i. i... The following table lists the activity of species depending on their chemical nature... In other words the activity of a chemical species depends on the chemical nature of the species.....In a hydrogen-oxygen fuel cell system...... from thermodynamics the chemical potential of a species i.. 1 atm.. In order to build a relationship between the cell potential and concentration of different species.................. i.(2) where is the chemical potential of species i at standard conditions... i..... pure hydrogen and oxygen can be used at different pressures and temperatures.............. Chemical Nature Activity ai=pi/po..229 V.. can be related to its concentration through activity.... the reversible cell potential obtained is 1.e. Chemical potential measures the change in the Gibbs free energy of a system with change in chemistry of the system. there is a need to understand the dependency of the reversible cell potential on the concentration of various species.... Also..e... 1 atm and 298 K.. Chemical potential for a species i in phase a can be related to the Gibbs free energy change as follows 2 2 Nernst Equation Analysis . Additionally. in reality the feed streams....(1) where μ α is the chemical potential of species i in phase a and measures the change in the Gibbs free energy of the system with infinitesimal change in the number of molesof species i..... water is produced as the final product... It is defined for each species in the system...... the N2pressure increases proportionally and hence the activity is doubled.

we have the following overall reaction – It should be noted that the above reaction can be written in the following manner too – However.. the activity of liquid water is taken as unity.....e....... As already discussed......1 M NaCl is 0. the activity of the pure components can be taken as unity.. ai=1... in order to calculate the Gibbs free energy change of the total system. For our case..(3) For hydrogen-oxygen fuel cell system.......e. where ci and c0 are respectively the molar concentration of species i and the standard state concentration. the contributions from all species are added – (Using Equation 1) (Using Equation 2)..Δg' which is defined on a per mole basis and is therefore intrinsic... the activity calculated assuming a nonideal behavior of a species is low compared to that of ideal behavior. Dilute solution Nonideal solution Pure components Table 1... the acitivity of Na + ions in 0. For example the activity of pure aluminum in an aluminum electrode is 1... Please note that while calculating the activity of N 2 above.. 0 <γi < 1 and therefore.1 M Na2 SO4would be 0.. independent of the quantity of the system.. Activity of species depending on their chemical nature Therefore.. nonideal behavior of N 2 and air would decrease the activity. the molar Gibbs free energy change for the 2 2 ... For example.ideal gas. the total Gibbs free energy change calculated for this system would be different for the above two reactions.2.. Also. i.. However... i. However.. ai=ci/co.e..γi is the measure of deviation from ideal behavior (0 < γi < 1)... since 1 mol of Na2SO4 gives 2 moles of Na+ ions (Na2SO4 -------> 2Na+ + SO42-) ai=γi(ci/co)..... where γi is an activity coefficient..1. the activity of Na + ions in 0. 1 M (1 mol/L). it becomes necessary to work with molar Gibbs free energy change... we assumed the ideal gas case.. i... used to measure the deviation from ideal behavior... The theories are available from thermodynamics to quantify γi. O2 and H O in the two reactions.. This is due to the difference in stoichiometric coefficients of H . Therefore...

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

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

Using Equations 2 and 4, we have –

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

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

; is the Gibbs free change for the reaction at

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

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

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

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

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

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

Partial Pressure of H 2(atm)
1 1 1 1

Partial Pressure of O2(atm) 1 2 3 4

Open Circuit Voltage (V)
1.229 1.233 1.236 1.238

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

1 2 3 4 5 2 3 4 5

5 2 3 4 5 1 1 1 1

1.239 1.242 1.250 1.256 1.260 1.238 1.243 1.247 1.250

10 13 21 27 31 9 14 18 21

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

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

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

295 0. OCV (V) 0 0. .118 0.236 0.177 0. This clearly shows that OCV increases with decrease in the value of Q.15 K). and replacing the activities of H2 by its partial pressure. Q should be less than unity.where (aH2)cathode and (aH2)anode are the activities of H2 at the cathode and anode side respectively. for Ecell (or OCV) to be positive. F (= 96500 C/mol) and (say). Assuming ideal gas behavior.314 J/(mol-K)). we get – where (PH2)cathode and (PH2)anode are the partial pressures of H2 at the cathode and anode side respectively. Replacing the values of E0cell (= 0 V). n (= 2).354 Q 1 10-2 10-4 10-6 10-8 10-10 10-12 Table 3. T (= 298. In other words. in the above equation we get – Therefore. Variation in OCV with Q This hydrogen concentration cell can produce decent voltage without oxygen and therefore can be used in outer space where oxygen unavailable.059 0. R (= 8. (PH2)cathode< (PH2)anode The variation in values of OCV with different values of Q has been listed in Table 3.

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

04 -2. Thus the standard potential of the Ag+/Ag couple is 0.-> e. Standard electrode potential table/Electrochemical series It is the lists of the all the elements of redox couple according to the magnitude of the electrode potential [1.-> Ti2+(aq) + 2e. It compares the standard-state reversible voltages of various electrochemical half cell reactions relative to the hydrogen reduction reaction. 2].-> Ca(s) Na+(aq) Na(s) Al3+(aq) Al(s) + + e.66 -1.63 Ca2+(aq) + 2e.-> Standard Potential E° (volts) -3.92 -2.799 V vs.799 V and silver is positive.-> .76 -2.the cell potential is 0.71 -1.-> e. The example shows some of the extreme value of standard cell potential for some elements based on the ranking: Cathode (Reduction)HalfReaction Li++(aq) Li(s) K+(aq) K(s) + + e. SHE.

the net reaction occur as [3]: .80 0.Ti(s) Mn2+(aq) Mn(s) 2e.-> Sn(s) Fe3+(aq) + 3e. Example: Consider the Fe+2-H+ reaction couple from the electrochemical series.-> -1.-> Cr(s) Fe2+(aq)+ Fe(s) 2e. 2].00 0.-> Pt(s) Cl2 (g) +2e.56 2.25 -0.-> 2CAu3+(aq) + 3e.36 1.-> Co(s) Ni2+(aq) + 2e.14 -0.-> 2F(aq) Table 1.g.87 Zn2+(aq) + 2e.71 -0.44 -0.44 V).76 -0. it also gives the qualitative information e.-> Pt+2(aq) + 2e.34 0. please refer [1. The most negative electrode potential represents the strongest reducing agent and the most positive represents the strongest oxidizing agent.18 -0. Because the hydrogen reduction reaction has a larger electrode potential compared to the iron reduction reaction (0 V > 0.20 0.28 -0.-> Fe(s) 2H+ +2e. Apart from the quantitative information given by the electrochemical series.-> Zn(s) Cr3+(aq) + 3e. if the two electrochemical couples brought into contact then reaction will proceed in such a manner that the oxidizing member of the couple having higher electrode potential with the reducing member of the couple having electrode potential is thermodynamically favored .-> Ni(s) Sn2+(aq) + 2e.-> Au(s) F2(g) + 2e. Electrochemical series (at 298 K) To access complete electrochemical series.04 0.-> Co2+(aq) + 2e.-> Cu(s) Ag+(aq) Ag(s) + e.-> H2 (g) Cu2+(aq) + 2e.

Eo = .771 V > 0. hydrogen oxidation reaction (H2 ----->2H+ + 2e. Fe3+ reduction reaction has the higher potential as compared to the Cu2+ reduction reaction (0. The horizontal lines correspond to the standard potentials of electrode reactions: Fe3+ (aq)+e-Fe2+(aq) and Fe2+ (aq)+2e-<------>Fe(s) The diagram reveals that when a potential of 0.e.0. which depends on the potential they have been exposed. Figure 2 shows the dominance diagram of Fe.44 V if we consider a fuel cell constructed in such a manner.44 V Iron can exists in different forms Fe3+(aq).Iron would go through oxidation reaction in redox couple with hydrogen reduction reaction. Thus the reaction would take place spontaneously with the generation of 0. Dominance diagram for element iron. It shows which is thermodynamically dominant species at any particular potential. then we would have applied potential so that the reaction would take place forward direction as shown above and we generally call the process as electrolysis. Example: a) Let us consider Fe3+/Fe2+ -Cu2+/Cu reaction couple. iron can exists in Fe3+.<------>Fe E0=-0. Eo of the combined oxidation and reduction couple would have been 0.34 V resulting spontaneous reaction in the forward direction. Thus the iron reduction as listed in the table is reversed in the form of oxidation reaction and the potential sign us changed from –ve to +ve (+0.0 V is applied to the iron containing solution either by electrode or by any other more concentrated redox couple then iron will exists in the Fe2+ form [2].. So copper would go through the oxidation reaction in redox couple with the iron reduction reaction and the net reaction would occur as: .04 V Fe2+ (aq)+2e.g. Fe2+ form. This is the thermodynamically spontaneous reaction direction under standard state conditions as E o= +ve. Dominance diagram There is ambiguity in the arrangement of the some elements in electrochemical series because it may form different redox couples. The horizontal lines correspond to the standard potentials of electrode reactions: Fe3+(aq)+e<----->Fe2+(aq) E0=0. Fe(s). Fe3+(aq)+3e.44 V).34 V). e.0 V).44 V Figure 2. If Eo = -ve. then hydrogen reduction reaction would have not taken place spontaneously but in reversed direction i.34 V).771 V Fe2+(aq)+2e-<---->-Fe(s) E0=-0. if we consider Cu2+(aq) + 2e ---->Cu(s) (Eo = 0.<---->Fe E0=-0. Instead of Fe ----> Fe+2 + 2e (Eo = 0.44 V). Fe2+(aq).

At room temperature. A voltage develops due to the difference in the chemical potential of both sides. some hydrogen decomposes on the platinum catalyst to protons and electrons. If two platinum electrodes are not connected then on the fuel side excess electrons will accumulated while electrons will be depleted on the vacuum side. The concept of chemical and electrical potentials offsetting one another to maintain thermodynamic equilibrium is summarized by the electrochemical potential [3].which thermodynamically favorable reaction(E0>0) with generation of 0. From the above two reactions it shows that the Fe 2+ is the thermodynamically dominant species Electrochemical potential It is a thermodynamic measure that combines the concepts of energy stored in the form of chemical potential and electrostatics. The protons transport to the other compartment via electrolyte and combines with the electrons on the platinum catalyst to reproduce hydrogen gas. b) Consider Fe2+/Fe – Cu2+/Cu reaction couple.34 V > -0.287 V due to a difference in hydrogen concentration.78 V. . Due to chemical potential gradient.The net reaction occurred as: which thermodynamically favorable reaction (E0>0) with generation of 0. Hydrogen fuel compartment maintained at a pressure of 50 atm whereas the other compartment maintained at a pressure of 10-8 atm. An electrochemical potential difference will inherently provide the driving force for both the transport of charge (electro migration) and the transport of mass (diffusion) by an ion (an ion having both charge and mass will obviously transport both by its movement). we can generate almost 0. so iron would go through oxidation reaction in the redox couple with copper reduction reaction.431 V. Since copper reduction potential is higher as compared to the iron reduction potential (0. setting up an electrical potential gradient.44 V). This further retards the flow of hydrogen and at equilibrium chemical potential gradient exactly balance by the electrical potential gradient. Figure 3 shows a hydrogen concentration cell.

Also it is the partial molar Gibbs energy of the substance at the specified electric potential. is the electrochemical free energy and Φa is the electrical potential experienced by the . F is the Faraday’s constant. Where. The term zi FΦa is the electrical potential energy per mole of species i in phase a The term called chemical potential Where. species i. electrochemical potential is the mechanical work done in bringing 1 mole of an ion from a standard state to a specified concentration and electrical potential. the electrochemical potential would be Where. Φ a is the electrical potential experienced by the species i. Electrochemical potential can be expressed as [1]. of moles of i in phase a.In generic terms. zi is the charge number. where the substance is in a specified phase. ni is the no. Thus. i is the species.

Solving for the difference in the electrical potential for the electrons at the cathode versus the anode (Δ φ e.Properties of electrochemical potential    For an uncharged species For any substance: For a pure phase at unit activity (e.)) gives the cell potential E[3]. Activity effects can be neglected because the electron concentration never changes appreciably. Ag. or H 2 at unit fugacity ):   For a electron in a meta(z=-1)l . For equilibrium of species i between phases a and ß : Formulation of cell potential For a reaction at equilibrium We can derive the Nernst equation from the basis of electrochemical potential. AgCl. .g. solid Zn. For deriving it we should also include the change in electrochemical potential for the electrons as they move from anode to cathode. Consider the H2 –O2 fuel cell reaction At equilibrium But.

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

... For example H2<-->2H++2e-.... Pt) and an electrolyte (e............... Since electrochemistry deals with the transfer of charge between and electrode and a chemical species in an electrolyte.. The branch of science dealing with electrochemical reactions is electrochemistry. where oxidation takes place and the cathode.............. electron transfer takes place at the interface between the electrode (e..... it is a heterogeneous reaction..........g...g...... Electrochemical reactions are heterogeneous because H+ cannot exist inside the electrode and free electrons cannot exist inside the electrolyte...... electrolyte)... electrochemical processes are necessarily heterogeneous........ H2SO4 in water)..... ..g.....(1) In (1) above reaction....Electrochemical Reactions Activation over-potential Electrochemical reactions are redox (reduction-oxidation) reactions that involve transfer of free electrons at the interface of an electron conductor (e.. One point may be noted that in chemical reactions no transfer of electrons take place whereas in electrochemical reactions involve transfer of free electrons.... These reactions occurring at the anode and cathode are called half-cell reactions which together constitute the full electrochemical cell.. Such reactions are either driven by externally applied voltage or voltage may be created by the electro-chemical reaction that occurs spontaneously...... Figure 1: Electrochemical reaction at the electrode-electrolyte interface showing heterogeneous nature of the reaction Any electrochemical cell has two electrodes called the anode. metal surface) and an ionic conductor (e.......... Hence.......g....... where reduction takes place....

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

...........(4) Where... only these will participate in the reaction) multiplied by the rate at which these transform into the final products........ u1 is the reaction rate in the forward direction..... Therefore......................(3) Where P* is the probability of finding a reactant species in the activated state.. we need to find out the reaction rate in the forward direction............. As such..... Reaction Rate For any chemical reaction................................... However............................ Net Reaction Rate The net rate of reaction is given by: Net rate = forward rate – reverse rate u=u1-u2..Thermodynamic treatment from statistical mechanics tells that probability of finding a species in an activated nature is exponentially dependant on the size of the activation barrier: .. the net reaction rate can be given as .......... T is temperature (K) and R is the universal gas constant................. this is still not the net reaction rate.......(5) Where............. it is not just the product that is important but also the rate at which it forms............... ?G 1 is the energy barrier (energy gap between the reactants and the activated species)........ reaction rate is given by: u1=CRtP*......................... C R is the reactant surface concentration (mol/cm2) and t is the transformation rate from activated state to final products............... Quite intuitively............ This can be understood and calculated as follows: The reaction rate is the number of reactant species available to participate in the reaction multiplied by the probability that they will be found in the activated state (because...................................... because the reverse reaction is happening too... u is the net rate of reaction and ??2 is the rate of reaction in reverse direction.....................

............. if Q (coulomb) is the charge transferred in time t (sec)........................... we know that current is charge transferred per unit time..........(8) Exchange Current Density Now.........(7) Using equation 7 to substitute ΔG2 in equation 6 ............. t2 and ΔG2 are the transformation rate and activation barrier for the reverse direction and C P is the product surface concentration.......................................... the net reaction rate can be given as: ................................................................................ then the current is given by the relation ............(9) If an electrochemical reaction results in the transfer of n electrons................................. then ............................................ Hence.....................................................(6) Where....... Gibbs energy change for the entire reaction can be given as ......................................................

. we need to understand the equilibrium state of a reaction by analyzing the energies of the system............... the forward current density can be ............. For this............ That is.... Butler-Volmer Equation: Generally.(11) Similarly............................... the forward and reverse current densities should be equal. there is no net current density. But.... it is i mportant to deviate from equilibrium........... where the energies of the reaction are balanced........ Also note that at equilibrium..... Since electrochemical reaction takes at the interface of electrolyte-electrode................................... no net current is extracted from the cell under operation.... the reverse current density can be given as ........... the electrical energy increases (Figure 3 (b)) as the distance from in interface increases (development of charge ensues with eaccumulating up at the electrode and H+ in the electrolyte..From above relation........... we aim to get some useful net current from the cell under operation............... For this................ F is the Faraday's constant and expressed as is the rate of electrochemical reaction (mol s-1)...... This current density at equilibrium is known as the exchange current density.. it is wise to express in terms of current density than simply current...... At this point.................(12) Note that i is current and j is current density............. in an electrochemical cell....... the chemical free energy of the above reaction step decreases as the distance from the interface (catalyst-hydrogen) increase........... For understanding this approach.... This charge accumulation continues till the resultant potential difference (ΔΦ) .................................(10) Where........................ we can take the earlier example only (Equation 1) One of the steps involved here is the chemi-desorption of the adsorbed hydrogen on the catalyst surface (denoted by cat below) cat-H --> cat+e++H+ As shown in Figure 3 (a).

.............. This makes it difficult to extract a net current from the cell.... while the forward reaction rate decreases. it can be stated that ............ The combined effect of these two energies can be seen in figure 3 (c) where the net effect leads to equal forward and reverse reaction rates................. Now..... As such.counterbalances the difference in free energies between the reactant and product state...... The exact magnitude of these Galvani potentials is not known.... These anode and cathode interfacial potentials are called Galvani potentials....... the reverse reaction rate increases.... ΔΦ neutralizes the difference between the two reaction rates by decreasing the activation energy barrier for the reverse reaction and increasing the activation energy barrier for the forward reaction rate...(13) We know that the sum of interfacial electric potential difference at anode and cathode yield the overall thermodynamic equilibrium voltage..... We had earlier studied that voltage plays a crucial role in deciding the course of a reaction... This build up of the charge............. This is because charged species are involved in the ..............

............ As a result...... Reducing the Galvani potential at both anode and cathode reduces the forward reaction activation barrier and at the same time............. This results into a net forward reaction and hence.................. increases the reverse reaction activation barrier........ voltage will play a crucial role in extracting a net current from the electrochemical reaction. Moving away from equilibrium and taking into account the changes in activation barrier. this changes the size of the activation barrier................................ Here.......... a net current can be obtained from the electrochemical cell...reaction and this free charge species are sensitive to voltage which changes the free energy of these species upon bringing up a change in the voltage................ α is called the charge transfer coefficient and it denotes how a change in Galvani potential changes the activation barrier for forward and reverse reactions thus producing a net cell current......(14) ..(15) ... it can be seen that if the Galvani potential is reduced by a value of η........ We already know that at equilibrium...................... By looking at the figure 4(b)................ the forward reaction activation barrier is reduced by αηFη and the reverse reaction activation barrier is increased by (1-α)ηFη (figure 4(c))......... Now.. the current density is given by the exchange current density.............. the new current densities can be written as follows: ..............

....... owing to change in voltage that changes the reaction rate......................... eq....... We can conclude from the above equation that the current density increases exponentially with activation over-voltage (η)..... Activation Over-potential Activation over-potential represents the voltage that is sacrificed to overcome the activation barrier to extract a net current from an electrochemical reaction. 15 from 14) . Eq...... This change in concentration can be taken care of by introducing actual surface concentrations CR* and CP*....... (16) becomes: . Thus............................ which shows the plot for cell voltage versus current density.................. j0 is the current density measured at surface concentrations CR and CP. higher is the voltage sacrificed.....(17) Where.............. higher is the current density obtained.....The net current j is therefore. Accordingly.... The magnitude of this activation loss is governed by reaction kinetic parameters and j0............ The over-potential is the extra voltage needed to reduce the energy barrier of the reaction (usually the rate determining step) so that the reaction proceeds at a desired rate................ This can also be shown from Figure 5. 17 is called the Butler-Volmer equation and denotes the relationship between current density.........................(16) We also need to take into account the change in reactant and product surface concentration. surface concentration and activation voltage loss in an electrochemical loss. Having a high j0 is highly favored........................... .j1-j2 (subtracting eq.

..........................(18) Approximation being made here is that ex˜1+x for small values of x....... Thus....... 2...η is very small: For small ? (less than 15 mV at room temperature).......................................... it creates unnecessarily complications which can be resolved by making some simplifications under certain conditions.............(19) Solving for η yields......... η is very large: When η is very large (> than 50-100 mV at room temperature).......... 18 displays linear relationship between current density and over-potential for small disturbances from equilibrium. We consider here two cases: 1........ only the forward reaction rate contributes significantly to current density........ a Taylor series expansion of the Butler-Volmer equation (17) yields: ...................Tafel Equation Figure 5: Voltage versus current density at different exchange current densities The Butler–Volmer equation (17) often is quite complex to deal with owing to its exponential nature....... ........ the reaction becomes irreversible and the eq.................. In other words................ Eq....................... 17 is simplified to : .

.......RT/anF ln(j0 ) with slope RT/aNF ....................(20) A plot of η and ln (j) should be a straight line with intercept as . Tafelequation deviates from its linear nature......................... At low over-potential................ Tafel equation is important to calculate transfer coefficient a and exchange current density j0 from the slope and intercept as shown in figure 6.............. Eq........... 20 is known as the Tafel equation.... Figure 6: plot of activation over-potential and current density............. ...

The basic knowledge may be gathered from the fundamental books on heat transfer. These transport processes of the fuel cell are equally important and responsible for the desired output of an efficient fuel cell. containing N different species. multiphase.Objective of this section is to make you understand the various transport processes and their impact on the fuel cell. molar concentration(Ci) Where. fluid mechanics. The concentration of a species i may be described by anyone of the following ways. and mass transfer. here we would like to present a simplistic view of the essential knowledge required to understand the fuel cell. The understanding of all the above processes in a fuel cell requires the knowledge of multicomponent. we are aware that in fuel cells the following processes occur simultaneously. However. ni represents the number of moles of species i in the mixture and Mass concentration(ρi) Where. . Wi represents the molecular weight of species i in the mixture. and multidimensional transport processes.     Mass Transport Heat Transport Momentum Transport Charge (electron and ion) Transport All these processes are very complex and have interlinkages and dependencies to each other as per the scheme shown. mass transfer.Concentration Polarization Transport processes in fuel cells: By this time. mi represents the number of moles of species i in the mixture and Where. Revisiting some of the basic concepts: Consider a mixture of volume V.

Concept of Average and Diffusion Velocity: Vi is the velocity (absolute) of different species with respect to the stationary coordinate. Mass fraction(Yi) Where is the total mass concentration.Mole fraction(Xi) Where C is total molar concentration. Mass.average velocity (v*) . The average velocity of the species in the mixture can be defined as: Mass.average velocity (v) Thus the mass-average velocity is averaged by the proportional amount of mass of each species in the mixture.

It is to be noted that diffusion is the relative motion of a species with respect to the average motion of a mixture as a whole. Thus. The negative sign shows that the diffusion flux is in the direction of decreasing concentration. The rate of mass transfer for species i diffusing through j follows Fick’s Law. Diffusion Law: Consider a typical case of a fuel cell.average velocity Bulk motion: v or v* Diffusion: vi or vi* Therefore. which has a non-reacting mixture containing two species i. the equation can be written for the molar concentration gradient.Thus the molar-average velocity is averaged by the proportional amount of moles of each species in the mixture.average velocity Mass.In a similar way. or the diffusion coefficient of the species . the total mass flux and total molar flux of the species i relative to the stationary coordinate become. The proportionality constant Dij is called binary diffusivity. The above equation is the Fick’s Law in terms of mass flux and conveys that the diffusion mass flux arises from the mass concentration gradient.& j. Mass. For unidirectional flux in x-direction.

respectively. This maximum current is known as the limiting current. heat transfer.41 X 10-4 0.12 X 10-8 0. Consider a flow situation where the flow is over a solid surface (x-z plane) in an orderly (laminar) and smooth manner in the x-direction. Once the concentration of the reactant decreases. Polarization: Activation Polarization Ohmic Polarization Concentration Polarization Recall that during the explanation of the activation polarization.i with respect to species j. The Fourier law can be represented by the following equation for the heat transfer in the ydirection. Pressure. . we have assumed that the concentration of the reactant is constant and independent of the cell current density. in real situation when we draw the current. temperature and concentration of species i changes in the y-direction. we would see that the momentum and heat transport laws are very similar to the mass transport and equivalent laws are Newton’s Law and Fourier Law. the velocity. the concentration of the reactant decreases at the reaction site.26 X 10-8 Species i H2 (g) O2 (g) CO2 (g) CO2 (g) O2 (g) N2 (g) C2H5OH(l) H2O(l) Now.20 X 10-8 0. The unit of diffusivity is m2/s. Newton's Law of Viscossity (momentum transport) Where Md. Note: The reader may get the details in any standard book on fluid mechanics.After this brief discussion on the transport properties.24 X 10-8 0. If we further keep on drawing the current the reactant concentration depleted and at a certain current the cell voltage drops down to zero voltage. α is the thermal diffusivity (m 2/s). the low availability of the reactant at the reaction site leads to the reduction of corresponding voltage. However.y is the the momentum flux . we will now focus on concentration polarization in the fuel cell. These transport properties are related to each other by some non-dimensional ratios. qy is the heat flux.21 X 10-4 0. v is the kinematic viscosity (m 2/s) and vX is the velocity in x-direction. and mass transfer. Fourier's Law Where. Species Dij(m2/s) j Air (g) Air (g) H2O(l) H2O(l) H2O(l) H2O(l) 0.) of binary coefficient required in fuel cell are shown in table at 25o C and 1 atm. Table:A few relevant values (approx.63 X 10-8 0.

The combined effect of the Nernst loss and reaction loss is known as concentration loss or concentration polarization. Consider an electrode prepared with backing layer and catalyst layer. and at the surface of the electrode is Ce. We know that the reactant is transported from the flow channel through convection and to the electrode by diffusion. . which adds to the increases in the voltage loss. In this NPTEL course we will be limited to the simplified approach only. Concentration loss = Nernst loss + reaction loss Quantifying Concentration Polarization The quantification of the concentration polarization may be done by simplified or by rigorous engineering approach. the rate of the mass transfer at steady-state can be calculated as shown below. It may be assumed that the catalyst layer is very thin as compared to the backing layer. If the concentration of reactant at the end of the backing layer is Cc. the concentration of the reactant decreases along the flow channel from inlet to outlet. Moreover. Thus the thickness of the catalyst layer may be considered negligible. These losses are known as reaction losses. The reactant concentration at the inlet is considered to be C o. A few major processes include the slow diffusion in the gas phase in the electrode pores (problem aggravates in case of flooded electrode). slow diffusion of the product through reactant from the active sites and vice-versa.The reactant does not continued to be transported to the reaction site because of limitation of the certain processes.

once the reactant is reached to the reaction site the electrochemical reaction will occur which result in the current and we are aware that the current generation and the rate of reactant transport is linked by the Faraday’s law. By this time. Thus by the above relation we can find out that the current density is proportional to the reactant concentration difference in the inlet and the catalyst layer as well as the concentration of the inlet concentration of the reactant. C c will reduce and at the maximum current density the value of Cc becomes zero. On substituting the value of rate of mass transfer (N) in the above equation. A is the electrode area and h mis the mass transfer coefficient. Where N is the mass transfer rate (mol/s). Where. J L) when all the reactant supplied to the catalyst layer is consumed by the electrochemical reaction. R is the total mass transfer resistant of the reactant to the catalyst layer.Therefore. Where. the maximum possible current density (limiting current density. Deff is the effective diffusion coefficient as the diffusion will be from the porous media. can be found out at C c = 0. we know that due t the different resistances the rate of mass transfer of the reactant to the catalyst site or reaction site is N. Where.The mass transfer rate from flow channel to the electrode surface through convection is. Similarly. J is Current Density. the mass transfer rate from electrode surface to the catalyst surface by diffusion is. . In case of a porous electrode with porosity of φ and without any water flooding D eff will be defined by the Bruggmann’s correlation At steady state these mass transfer rates will be same thus eliminating C e from the above two equation. Here we can see that if the current density increases.

It is very interesting relation and can easily provide the real concentration of the reactant at the catalyst surface if the current density and limiting current density are known for a particular fuel cell at the operating conditions. If the reactant concentration at the inlet and at the catalyst surface if same then the cell voltage (E) will be maximum (EO). A few points must be noted for the previous equation. 2. removal of the product from the reaction sites etc. The pores of the gas diffusion layer are assumed to be free of water droplets. . Now. by improving the design and operating conditions the limiting current may be improved by analyzing the above equation. Thus. Increase in mass transfer coefficient (hm) will improve JL: How to improve the mass transfer coefficient? The flow conditions must be improved in the flow channel. 3. consider Nernst equation for a single reactant species. These processes are beyond the scope of the NPTEL course. The equation is valid at higher current densities. The above equation may be rearranged to. 1.It can be emphasized at this moment that the limiting current at a particular design and operating condition is fixed at a certain value. diffusion of the reactant from the fuel channel to the interface of gas diffusion layer and catalyst layer. All these processes can evaluated with the complex mathematics along with various co-relations. However. to quantify the concentration overpotential. Increase in effective diffusivity (Deff) will improve JL: Issues of design and operating condition! The effective diffusivity is the function of temperature and porosity of the electrode (or gas diffusion layer) and thus can be improved by these improving these factors. Note: Detailed knowledge of the concentration polarization in terms of individual mass transport into the fuel channel. and diffusion of the reactant into the catalyst layer (for high and low current densities). Other physico-chemical processes are ideal and do not affect the system considered. Reactant transport should be the rate limiting process. On combining J and JL. 4.

.. is an example of natural convection...... the convection............. the fluid flow under a pressure drop can be regarded as a forced convection. Convective transport can itself be classified into forced and natural convection based on the cause of transport. the electrons flow through the external load while the ions move across the electrolyte to complete the whole circuit....e.. i... The ions can be transported by three mechanisms namely........ we have zj= -2.... stirred liquid solutions).. ion transport across the electrolyte is essential for current flow. In general........i=Cjvj..... Y and Z axis respectively....... the number of moles of ions transported across the electrolyte per unit time.. The convective transport of jth species can be represented by the following set of equations – a) Along X – axis: nj...................... the mass transfer of ions occur as a result of net motion of the electrolyte (e. The analysis for natural convection is therefore. 2) Diffusive Transport – In this case..... . the transport depends on the density difference which arises through several reasons.. is Faraday’s constant (96.. On the other hand..... and therefore.... Forced convection can be represented mathematically by the following equation – nj................. . The current can be related to the charge on the ions transported through the electrolyte by – i=njzjF...........g...... is the molar concentration of the jth species........g........ temperature difference....... the mass transfer of ions take place due to concentration gradient across the electrolyte. O2. is the velocity field vector of the fluid...x=Cjvx b) Along Y – axis: nj...y=Cjvy strain c) Along Z – axis: nj...................(1) where denotes the current. in the case of boiling water....... while the upward movement of less dense water.... The details of these mechanisms are discussed below – 1) Convective Transport – In this case...... diffusion and migration........ Therefore......... much more complex... is the molar transfer rate of ion..........................(2) where is the molar flux rate of species j in the ith direction . e. For example.....Ohmic Overpotential In a typical operation of a fuel cell.500 C/mol) and is the charge number of the ion.. In case of a proton exchange membrane fuel cell (PEMFC) the H+ ion is transported across the solid polymer electrolyte (generally the Nafion membrane)and therefore... zj= +1...vy and represent the components of velocity along the X... etc...ion moves through the electrolyte (typically yttria stabilized zirconia) in a solid oxide fuel cell (SOFC).. ......... the velocity field vector of the fluid is represented by – where vx........ Forced convection results from an externally controlled fluid motion while natural convection is a result of buoyant forces resulting from a density gradient...........z=Cjvz In natural convection.

.. xi is the position field vector..(4) The negative sign on the right-hand-side (RHS) of the equation 3 signifies that the direction of transport is opposite to the increase in concentration.................. On the other hand...314 JK1mol-1)........................ X..... As discussed for the case of convective transport........(3) where ni..jis the molar flux rate of species j in the ith direction . is the absolute temperature (in Kelvin).(5) where nj..Cj is the molar concentration of the jth species........... The transport equation for migration is given by – ............ occurs in the direction of decreasing concentration of species j.........i is the molar flux rate of species j in the ith direction .............zj is the charge number of the ion.............. equations 3 and 4.. the diffusive transport can be quantified by the following equation ............................. is the universal gas constant (8........................... the ions can be transported across the electrolyte by an applying an external electric field.. yield three scalar equations in the three axes........................500 C/mol)... Y and Z........... as discussed for the case of convective and diffusive transport........ In general.......... φ is the electric potential. mass transfer of species j...............i is the diffusivity of jth species along the ith direction. In addition to convection and diffusion......Mathematically......Dj. is the position field vector.............. we have – xi=xi+yj+zk.... On similar basis. we have – a) Along X – axis: b) Along Y – axis: c) Along Z – axis: 3) Migration – Here.... The negative sign signifies that the transport of positively charged jth species is in the direction of decrease in the potential field....... we have the ..... F is Faraday’s constant (96....... the mass transport of charged species is driven by an external electric field....... and..................... the transport of a negatively charged species would be in the direction of increase in the potential field.. In other words.... is the molar concentration of the jth species.. is the diffusivity of jth species along the ith direction .. Therefore.

X........ diffusion and the migration. ............following equations along the three axes.... a) Along X – axis: b) Along Y – axis: c) Along Z – axis: Using Equations 1 and 6.................... the net transport of the species j across the electrolyte can be represented by the summation of contributions from the convection...............(6) This equation can be expanded to the following equations in the X....... is known as the mobility of the jth species in the electrolyte... Y and Z directions.... This leads us to the following equation – .. Y and Z – a) Along X – axis: b) Along Y – axis: c) Along Z – axis: Therefore.. we get the following expression for the total current – Where.... ...............

...e.. operating temperature and pressure..... the diffusion and migration transport balance each other and there is zero current. the ion mobility of a particular species is related to its diffusion coefficient.... the mobility also depends on the ionic charge..................Thus... the total current carried per ion increases proportionally.. at OCV the above equation reduces to – Hence at OCV. there is no net current drawn from the system and therefore.... the velocity field vector is zero.... and is the absolute value of zj. and this equation is popularly known as Nernst – Einstein relation. In other words... This expression helps us to understand the ion conduction process in an electrolyte – a) As the charge number zj...... Additionally.. is increased. the conductivity increases.. It should be noted that in electrochemical systems. i. It should be noted that at open circuit voltage (OCV). c) As the concentration of charge carriers (participants in the ion exchange) increases..... there is no velocity field.. the convective transport of the species in the electrolyte is balanced by diffusion and migration..... Further.... the ionic conductivity increases.. in case of static electrolyte the left-hand-side (LHS) of the above equation reduces to zero and we have – Therefore.. although this trend does not hold for highly concentrated solutions.... ..... the term overpotentials and/or polarization are often used to indicate inefficiency..The mobility of an ion can be related to its conductivity by the following equation – where the symbol have their usual meanings as defined already... in case of static electrolyte. this overpotential results in loss of the voltage . b) As the mobility of the charge carriers increases...... ionic concentration and size. Therefore...(7) This is the general equation to calculate the total current in any electrochemical system.... increasing the effective conductivity.....

. as a function of temperature is shown in Figure 1......... i with the geometric surface area of the electrode......... and hence we have – .... while a solid polymer electrolyte is employed for a PEMFC. As it can be seen clearly........ Therefore.......... Nd2O2..... Besides yttria...that the system can achieve at a particular current density...08....... there lies a challenge in finding new materials which can be used as electrolytes in SOFC.... Yttria is typically added around 10 mol % to stabilize ZrO2as pure YSZ in not a good ion conductor. kBT should only be in eV to use the above equations. a lower electrolyte thickness and a higher ionic conductivity would decrease the ohmic drop... The YSZ exhibits mixed (electrical and ionic) conductivity.... the ionic and electrical conductivity of the ceramic electrolyte increases with increase in temperature....(8) .. the electrical conductivity is pretty low for typical operating conditions in the SOFC.. and PO2 is the partial pressure of oxygen... as discussed above. has been reported in literature – .......... such as Yb2O3..ions........(10) Where....08....... Presently. increasing the partial pressure of oxygen would decrease the electrical conductivity.... (ZrO2)0........ The details of ohmic losses in both the cases are discussed here...........38 × 10-23 J/K)..... however.. and Sc2O3...... O2...... since oxygen ion mobility is almost negligible till 650 oC... generally around 50 microns............. Doped YSZ conducts negative O2...e.. The conductivity can be related to the voltage drop by ohm’s law – ΔV=IR The total current through the circuit can be calculated by multiplying the current density.. As it is clearly evident from Equations 8 and 9. termed YSZ...... which are transported through oxygen vacancies in the zirconia structure......92(Y2O3)0...........ions move from the cathode to anode through a ceramic electrolyte..61 × 10-5 eV/K = 1. typically yttria (Y2O3) stabilized zirconia (ZrO2).l is the electrolyte thickness............ In case of a SOFC....................... i. a ceramic electrolyte is used.... In order to increase the power output from the fuel cell...... This is the why the SOFCs are operated at very high temperatures.. Ceramic Electrolytes in SOFCs In a SOFC..... High electrolyte temperature is required for sufficient oxygen ion conductivity in the solid-state ceramic electrolyte..............92(Y2O3)0.. A plot of the ionic conductivity of (ZrO2)0. between 600 – 1000oC........... however....... T is the absolute temperature.. researchers have been successful in improving the ion conductivity by doping YSZ with several oxide materials.... Ceramics are generally inorganic nonmetallic materials synthesized by action of heat and subsequent cooling.(9) where KB is the Boltzmann constant (8... we need to reduce the ohmic loss as much as . several other oxide materials have been used to dope YSZ.. The ionic and electrical conductivity of 8% mole fraction yttria YSZ.........

and proton transport is dominated by diffusion. are not very stable during operation. Instead.groups enable motion of H+ ions. the solid electrolytes are perflourinated ionomers with a fixed side chain of sulfonic acid bonded covalently to the inert. where protons hop from one H3O+ to another along a connected pathway in the ionomer structure.S. As a result. Fig. therefore PEMFCs typically operate with hydrated Nafion membranes to facilitate ion transport and reduce ohmic losses. When Nafion is hydrated. The EW is calculated by the following equation . 1. developed by DuPont. However. the ionically conductive hydrated portion of the membranes behaves as nearly isolated clusters. depending upon the water content in the membrane – a) When the water content is low.08 vs. The most widely studied perflourinated ionomers for fuel cells is Nafion. polymer polytetrafluoroethylene (PTFE) structure. temperature Solid Polymer Electrolytes in PEMFCs In a solid polymer electrolyte. a proton hopping mechanism is verified. ion mobility is a result of an electrolyte solution integrated into an inert polymer matrix. but chemically stable. Generally. Ionic Conductivity of (ZrO2)0.92(Y2O3)0. H3O+-SO3. thin film electrolytes (electrolyte thickness. People have tried to understand the fundamental nature of proton transport through the Nafion membrane and reported two mechanisms. b) When the proton content is high. the equivalent weight (EW) and material thickness are used to describe most commercially available membranes. the membrane consists of two very different sub-structures – a) hydrophilic and ionically conductive phase related to the bonded sulfonic acid groups that absorbs water b) hydrophobic and relatively inert polymer matrix that is not ionically conductive but provides chemical stability and durability. l< 25 µm). based company. Dry perflourinated ionomers act as insulators.possible. a U. The molecular weight of Nafion can’t be determined accurately due to differences in processing and solution morphology.

....... which is a function of temperature... – .... For example........... one first needs to quantify the water content of the membrane. is defined in terms of water molecules per sulfonic acid site.. However.......................... Nafion........ electrolyte is used for fuel cell operations...... 11×..e..(13) where a (0 < a = 1) is the relative humidity (RH)....... Nafion 112 represents a 0..... i... i.................... for 0 < a = 1. Figure 2 below shows the graphical representation of water uptake........ It can be seen clearly.........(11) where k is the number of tetrafluoroethylene groups per chain...... ?... the thickness changes when exposed to different relative humidity environments........... ............. The ionic conductivity through Nafion is a function of its water content..............– .......................................... when equilibrated with liquid water and therefore... as a function of relative humidity........... the water uptake of Nafion 1100 EW membrane at 30° C is reported as – .. Generally.....002 inch (or 51 µm) thick membrane with 1100 EW................. Therefore... In other words.. ?.............(12) In literature........................................... In general the water uptake.e.... it should be noted that thickness of the membrane depends on the water content of the membrane..... the water uptake of the membrane increases with increase in RH..... It should be noted that the water uptake of the Nafion membrane is much higher.. while the last digit indicates the thickness of dry membrane in thousandths of an inch..... where 11 represents an EW of 1100.. the above relation can only be used when the membrane is equilibrated with water vapor........... between zero and 100 percent RH.....

.... 2.................... it should be noted that water uptake of the membrane decreases with increase in temperature.......... Water uptake... λ... The water uptake of the Nafion membrane can further be related to its ionic conductivity as follows – ................................... vs.......................(14) where T is absolute temperature (in Kelvin) and ? is the water uptake as defined above and can be quantified using equation 13....... the equation can be still be used to good effect to quantify the water content of the Nafion membrane at higher temperatures..... relative humidity at 30° C Although.......................................... we have – .. However...................... The Nafion membrane...................(15) .Fig. though has negligible electrical conductivity unlike ceramic electrolytes and hence..... the water uptake of the Nafion 1100 EW membrane depends on temperature...........................

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

or gas. ionic. we have – Where. ηohm=IR where R is the sum of electronic. Since we now know the ionic conductivity through the Nafion membrane. Ionic conductivity vs. l is the wet membrane thickness and is the current density. A is the cross-sectional area of the conductor normal to the conducting path and the electrical field has been assumed uniform in arriving the above equation. before calculating the ohmic overpotential. L = Where L is the length of the conducting path. and Resistance to the flow of electrons through the interface contact and the terminal connections (electronic resistance) Ohmic polarization can be determined by Ohm’s law. and contact resistance. .diffusion layer (electronic resistance). Transport of Electricity: Ohmic Polarization The ohmic polarization arises due to electrical resistance in the cell components. the dry membrane thickness is only known to us and thus needs to be determined based on the RH environment. It should be noted that thickness of a membrane depends on its water content. RH at different temperature values Figures 3 and 4 depict the variation in ionic conductivity with temperature and various RH values. the voltage drop can be calculated using ohm’s law as discussed in the case of a SOFC. including     Resistance to the flow of ions in the electrolyte (ionic resistance) Resistance to the flow of electrons and ions in the catalyst layer (ionic and electronic resistance) Resistance to the flow of electrons through the electrode-backing layer. Moreover. the increase in RH considerably increases the ionic conductivity. Therefore. including electrolytes. ohmic polarization is mainly caused by ionic resistance in the electrolyte.Fig. In fuel cell literature. the use of electrical resistance of the cell components. R=Ρ L/A Ρ=The specific resistance (resistivity) is a material property. is often avoided and reciprocal resistance or conductance is commonly used. Conductance: γ=1/R The resistance R depends on the material property as well as the geometry of the conductor as follows. For practical fuel cells. The increase in temperature clearly increases the ionic conductivity. Generally. 4. This can be attributed to the transition from diffusion to hopping transport mechanism because of increasing water content in the membrane. representing the capability of the material in the transport of electricity. The conductance is simply the inverse of resistance.

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

and electrolyte viscosity.The transfer process for the ionic species is thus created by the concentration difference (diffusion mechanism). in terms of molar flux (Fick’s law) Di is the diffusion coefficient of the ionic species. temperature. δi is the thickness of the diffusion layer adjacent to the electrode surface. The limiting current density can be obtained at Ci. The typical value of the diffusion layer is in the rage ~300 micrometer). If the diffusion layer thickness could be assumed almost invariant (which may not be necessarily true).i . Thus current density corresponding to the rate of ion transport is. then δi = δL. A representative concentration profile is shown in the adjacent figure. i.s = 0 where δL.i is the diffusion layer thickness at limiting current density. Where. with respect to the electrolyte solution and is mainly a function of nature & molecular size of the species. The rate of diffusion towards the electrode surface for the ionic species i is.

Thus the current density arises. The negative sign reflect that positively charge ion (ni > 0) moves in the direction of decreasing potential. water) for electrolyte Ions are constantly in random thermal motion.Assuming all other processes at the electrode are reversible. However.s). they start to accelerate in the direction of the electric field once an external field is set-up across the electrolyte layer. Thus. the voltage loss due to lowering of the ion concentration at the electrode surface can be estimated from the Nernst equation. However. Terminal velocity: (Driving forces = Retarding forces) Electrical field is represented by the gradient of the electrical potential in the x-direction ui is the mobility (ionic velocity/potential gradient) of the ion (m2. Acceleration is retarded by: viscous and electrical forces (mainly from ionic interactions). while discussing migration the charge on the species matters. Electrolyte    Positive ion Negative ion Neutral species (eg. Mass transfer in Electrolyte by Diffusion of Ionic Species In the earlier discussion.mol/J. The electrolyte may have positively and negatively charged species along with the neutral species. . the charge on the species did not matter. The molar flux due to terminal velocity.

Where. the total current density J resulting from the migration of all the ions in the electrolyte is equal to the sum of the contribution made by the transport of each of the ionic species or. Which is simply an expression of Ohm’s law The eq. i. The migration of each ionic species in the electrolyte contributes to the total current density carried by the electrolyte. is valid when Ci is uniform throughout At this moment. t is also a transport property of the electrolyte If we integrate the equation. Since k is transport property. the question comes that if all the charged species are involved then how to know the effect of individual species. In this concern. we obtain the ohmic overpotential due to the electrolyte. or Substituting J and Ji. . is defined as the fraction of the total current density that is carried by the given ionic species. On comparing this equation with the previous one. the transference number of the ionic species. i. across the electrolyte layer thickness. In order to quantify the relative contributions. we can find out that the conductivity of the electrolyte may be written as. conductivity of the ion i is the transport property of the ion in the electrolyte is defined as Then.

The relationship is valid only if the concentration is uniform in the electrolyte. from Ci. Mass Transfer by Simultaneous Diffusion and Migration of Ions Total molar flux for the ion i under the combined effect of diffusion and ion migration. Total molar flux for the ion i under the combined effect of diffusion and ion migration. Corresponding current density. that is. at φ=0 to Ci at . but in the opposite direction. their flux due to the electric field effect (migration) is counterbalanced by the flux due to the concentration gradient (diffusion) and no net transport of electricity arises from the motion of these ions.On integration. Consider a situation where there is no net current flow (J=0) through the electrolyte. at J=0 and integrating the below written equation. Where Ci. is the concentration of the ionic species i corresponding to zero (0) local potential ( Φ). all the current is carried by the transport of ions that participate in the electrode reactions For all other ions present in the electrolyte. When a fuel cell reach a steady state. On the other hand. the current arising from the ion diffusion due to the concentration gradient and from the ion migration in an applied electric field reaches the same magnitude. of the ion i is given by the thermodynamic Boltzmann distribution. Thus thermodynamic equilibrium is attained and the conc. At this point we may emphasize that both the diffusion coefficient Di and the ion mobility ui are the transport property of the ionic species i through the electrolyte solution and they may be related to each other. . .

we obtain. It relates the transport processes of ionic species by diffusion and migration in an electrolyte and provides an important link between mass diffusion and electrical conductance.&phie. u =D /RT i i The relation is known as the Nernst-Einstein relation. On comparing with the equation written in the previous slide. . ∞ .s and in the bulk electrolyte sufficiently away from the electrode surface where φ = φ2 and C =C i. It should be pointed out that the Nernst-Einstein relation is valid even when the total current through the electrolyte does not reduce to zero value. although it was derived when J=0. φ =φ1 and Ci = Ci. This is because both ui and Di are the (transport) properties of the ion i in the electrolyte. Considering equations On rearranging On integrating from the surface where x=0.

The mass transfer. Diffusion 3.It may be noted that the above equation is the basis of current interruption method. written for 1-D mass transfer along the x-axis as. At this point we may think if diffusion and migration is considered then why not the convection process. Migration 2. arises from atleast by one of them. Convection The mass transfer to an electrode is governed by the Nernst-Planck equation. the movement of material from one location in solution to another. we will discuss that also. that is. Of course. 1. The above equation is known as Nernst-Planck Equation . that we will discuss in characterization techniques.

This will further help in commercialization of fuel cell. which helps in fabrication Insight into the electrochemistry of the fuel cell & processes that takes place in the heart of the fuel cell Optimize the design parameters of fuel cell system A combination of modeling and experimentation can reduce the cost and accelerate the pace of building and understanding prototype systems[1]. .Modelling of fuel cell: current-voltage predictions Need Of modeling    A virtual prototypes of fuel cell.

development process [2] .

.. ...    Robustness: model should able to predict fuel cell performance under a large range of operating conditions and physical parameters. and validation with experimental data.................. but sometimes for accuracy... ηact .Figure 1: Flow chart of fuel cell development process Characteristics of a good model [2] A good model should balances......... A basic fuel cell model[3] The real output voltage (V) of fuel cell can be calculated subtracting all the overvoltage losses from the thermo-dynamically predicted voltage ............ correct physical quantities and input parameters.....(1) where........ Ethermo =thermodynamically predicted voltage of fuel cell ηact =activation losses due to reaction kinetics ηohmic =ohmic losses from the ionic and electronic resistance ηconc =concentration losses due to mass transport Using the expression for ηconc ...... Computational efforts: time required for calculation should be less....... correct governing equations.. ηohmic from the previous chapter........v behaviour can br given as.. computational efficiency is compromised.............. Accuracy: it can be developed by using the correct assumptions.... the net j ...

.. full form of Butler ... where the values of μ... μC...(2) Here we use the Tafel equation for the fuel cell kinetics.........γ.For modelling at low current density region.(2) means this model is only valid for j>>j o.  ......Rohmicand jL... βC.. In this model there are seven fitting parameters: μA.Volmer equation should be used...βA....A....β..... therefore Eq..........γ are related to α and j0 Graphical representation of the factors that contributes to fuel cell performance ...

Figure 2: Graphical representation of all the losses A 1D FUEL CELL MODEL (ANALYTICAL)     This model is more sophisticated than the basic model. . The model is well suited for polymer electrolyte fuel cell (PEMFC) and solid oxide fuel cell (SOFC). Flux balance allows us to keep tracks of all the species flowing in. we only concentrated on fuel cell species transport and determine the species concentration profiles. out and through the fuel cell. In the present models. It is based on the flux balance concept. electrochemical losses and j-V curve.

.(3) mathematically.......(4) where.flux 13 . r is the generation term due to electrochemical reaction .......... Individual fluxes are represented by the numbers........... N is the molar flux (mol/s................. all species transport flux are related to the single charcter flux-the current density or charge flux of the fuel cell.........cm 2) .......Flux Balance in Fuel Cells PEMFC   Figure 3shows the flux details needed in 1D model...............484 C/mol)...... flux-flux5=flux1 ... ....flux4 = flux8 .......From the figure 2 one can write as....... F is Faraday's constant (96.... Infuel cells........................... j is the cell current density (A/cm2).....

e....Flux 5 represent the .......... oxygen at cathode is the water generation rate due to oxygen reduction reaction at cathode. water flux balance in the PEMFC is given as.............. is the net flux of  ....(5)  water flux through the membrane is given by the balance between electro-osmotic drag and back diffusion water fluxes.... Similarly. the amount consumer in the oxidation reaction...out) in the anode..............Figure 4: Flux detail diagram of SOFC  is the net hydrogen flux (in .. i..

......................................  Let ς (unknown) is the ratio between the water flux across membrane and charge flux across the membrane is hiven as..... across the membrane layer.(7) Putting Eq........... ...... (6) one can gets................. .......(8) On combining eq...... Mathematically above equation can be written as..........flux due to water generation................... ...... is the net flux into the anode catalyst layer.............................................................(8).......... all the flux in the fuel given as..............................(9) SOFC flux balance .......(6) where............ ................. and into the cathode catalyst layer respectively and j/2F term represent the water generation rate.... (5) . (7) in Eq.............................

.... ..(10)   Overall flux balance in SOFC is simpler compared to PEMFC because water produced at the anode and does not transport through the membrane.... In PEMFC model.. Figure 4: Flux detail diagram of SOFC Model Assumptions ... The species transport through membrane is only of oxygen ions (O2-)... Water flux at the cathode is zero....... The water generates at the anode is in vapor form because of high temperature..... water balance across the membrane is necessary......... water present in liquid form and transport through the membrane.  Figure 4 shows the flux detailed diagram of SOFC... The water flux at the anode equal to the charge flux. Similar to PEMFC model...... the flux balance equation for SOFC is given as.... hence no need of water balance .... So.

H2O) in this layer is given by simlified Fick's Law of diffusion.Bur here. For the present model. Although. Faraday's Law for relationship between electrical current and consumption of reactants in an electrochemical reaction. Hence.To simplify the model. For H2 . . simplified version of equations are used by choosing appropriate assumptions. 5. Stefan-Maxwell equation for multispecies diffusion. water exist in water vapor and in liquid form. Electrode layer Species transport (H2.By solving these equations we can determine concentration profiles. diffusion can also be ignored. ohmic overpotential (ηohmic).Hence convection. Diffusion transport in flow channel is ignored. activation overpotential (ηact). since convection is ignored (assumption 1)) in flow channel . convection is dominant phenomena in fuel cells. Water assumed to be exists as water vapor. Fourier's Law for heat conduction. and concentration overpotential (ηact). anode reaction kinectics is ignored. convective transport is ignored. diffusion and conduction processes in catalyst layer are ignored. Ohmic losses only due to electrolyte membrane. For the present model.O2.For SOFC. and concentration overpotential(ηconc) . 2. simplified version of equations are used by choosing appropiate assumptions. Butler-Volumer equation for relationship between electrical current and Potential Ohm's Law of electrical current conduction.O2 fuel cells. anode activation losses is much smaller than cathode activation losses. 4. some assumptions are made which are as follows: 1. 6. for iD model convection is not cosidered along x-axis . Catalyst layer are assumed as extremely thin like 'interface'(no thickness). In PEMFC. ohmic overpotential (ηact). this assumption is valid because SOFC operates at high temperature. activation overpotential (ηact). Governing Equations         Equations that deal specificially with phenomena in a fuel cell areDeacy's equation for fluid flow in conduits and porous media. 3. Fick's law of diffusion.Convection is dominant phenomena in flow channel.N2.By solving these equation we can determine cocentration profiles.

... .........................pi=pxi is the partial pressure (Pa) of the species i.................. above equation can be written as...................................................(12) where........From Eq........(15) ......................... .................. is the effective binary diffusivity (cm2/s) between species i and j. .....................................................p is the total pressure of the gas............ ε by Bruggeman's correction...... Ci is the concentration (mol/cm3) of the species i.......................................................x i is the mole fraction of the species i................(14) From assumption 3...............(10) oxygen ion flux can be given as..... ohmic overpotential is given by...................... Dij and void fraction........... ......................(13) Electrolyte layer Governing equations for species transport in the electrolyte........... it can be determine using the nominal binary diffusity........................(11) In case of gaseous reactants.......... Ni is the molar flux (mol/s-cm2) of the species i......

.......... ndrag is the electroosmotic drag coefficient. ΔGact(J/mol) are usually determine experimently..........(18) . water and proton (H+) both transport through the membrane electrolyte................... For PEMFC....................... .... ...(17) ...................... Mm is the molecular weight..(19) Where. LM is the electrolyte thickness................. Dmis the diffusivity(cm2/s) of water inmembrane............. ...... KM is the electrolyte conductivity (S/cm) which is given as.............. Ρdry is the density (g/am3) of dry membrane................................... one gets......Proton flux is given by Eq............. A (K/ohm) and activation energy...... λ is the water content membrane........................... Sustitute Eqs..............where...........(4) nd water flux through the membrane can be describe as combined effect of back diffusion and electroosomotic drag........ (17).. (18) and (19) in Eq....................(16) where............

... ......................(21) Resistance of the membrance...........................................................................................(23) ...................................................... Rm is given by........... ...................(24) For an ideal gas(p=CRT)..............(20) Catalyst layer Cathode side kinetics is represented by modified form of Butler-Vilmer equation..................... where....... the above equation becomes.................................. .............................................. KM for Nafion membrane is expressed as [3]............................................ ........ λ can be determine using Eq...........................(20) Ohmic overpotential is determined as........(22) Membrance conductivity.

............................(25) where.... (12) ....(27) ...............................................................................(26) ............ p0=1atm Modeling Examples 1d SOFC Model   Figure 5 shows the 1D schematic of SOFC.H2O transport is given by Eq...... Anode: H2..............................................

......... Integrating Eq............ H2..... H2O flux are related with cell current density........(28) .xH2O are known.. (10)..... values of xH2...... ............. gives linear profile of H2.........(26) and (27).........Figure 5: Schematic of SOFC Using Eq....... Solving Eqs........H2O concentration at anode......................................(29) At interface 'a'... (28) and (29) at interface 'b' yields.......... ........

..... (32) yields.......................... one can obtained oxygen profile at cathode.........................(31) where..(32) At interface 'c'.............. ......(33) Combine Eqs....................... Eq..................(30) .... (25) and (33)................................................................ ... tA is the thickness of the anode Cathode Siimilarly......... cathode overpotential is given as................................ ............

............(34) Electrolyte From Eqs.......(35)) Finally..... a real SOFC voltage is written as......... whereas ions transport through membrane electrolyte. ohmic loss is given by........ ................. .......... N2) transport in flow channel is by convection and in electrodes by diffusion..(36) ....................... O2......... Electrons transport is through the external circuit........ (15) and (16)................... . H2O.(37) PEMC Model Figure 6 shows the 1D schematic of PEMFC   Reactants (H2.......

...........................(38) ................ . In membrane.....................(39) Using Eq..................................................... H2. the solution of the above equations..... H2O fluxes described as....................... ............................... water transport is by electroosmotic drag and back diffusion Anode Figure 6: Schematic of PEMFC Similar to SOFC model....... (9)..

................................................ (40) and (41) yields.......................................................................(43) Cathode Oxygen concentration profile at cathode interface 'c' is expressed as ..................................................(44) water concentration profile at cathode interface 'c' is given as..............................(41) here................................. Eq.........................................................................................(42) ...... At interface 'b'. ς is unknown................................ .................. ...................(40) .............................

.......................................................................... (7) in Eq....................(45) where............... tc is the thickness of the cathode................................................... ...............(46) At interface 'c' ...... Eq....(45) At interface 'b' ................ Similar to SOFC model........................ water profile in membrane is required.(47) Nation watrer content can be relate with the water activity as.............. cathodic overpotential is determine using Eqn (34) Membrance electrolyte: To calculate ohmic overpotential...............(20) becomes... (20) and integrate..........(48) ............ Substitute Eq.............. .............................................................

............................ ..... ...... KM profile in membrance can calculated by Eqs...................... hence ohmic overpotential is determine as...(52)   From Eqs...............the conductivity......(54) Direct Methanol Fuel Cell Modeling (DMFC) [4] .. Resistance in membrane is calculated by Eq.................(23) and (45)............................................... (46)...(50) Combining Eqs.............. (22).........(49) .......... (45) and (49) gives................. .............. ζ and B in Eq.....................................(53) Finally...................................(51) .........(45)........................(51) and (52)....(47)................. two unknowns...............(43) and (48) and Eqs..... fuel voltage is given as...............................

Nafion) and carbon supported catalyst (e. it formed as a thin film of proton conductive ionomer (e. Kinetics and ohmic effect considered in the catalyst layer. protons produced at the catalyst layer are transported via migration through it.release.g. Active catalyst region(catalyst layer) on which oxidation of glucose takes place. Model consider the mass transport in the anode compartment. A diffusion region (diffusion layer) composed of highly porous and electronically material (collect the electrons generated at the catalyst layer .     Figure 7 shows the schematic diagram of DMFC. Pt-Ru/C) uniformly dispersed in the ionomer. Figure 7: Schematic diagram of the anode bonded PEM DMFC Mathematical Model    A membrane region of solid polymer electrolyte (PEM). Influence of different parameters on anode performance is investigated. Complete oxidation of methanol (fuel at anode) takes place and product obtained is CO2 via 6 e.g.

Figure 8 : Schematic illustration of catalyst layer [5] Model Assumptions     Steady state. Anode and cathode compartment assumed as mixed reactor . Anode and cathode compartment have the same pressure . . isothermal conditions were considered . Two phase flow in anode channel is neglected .into the current collector).

..............(55) Mass transport in diffusion layer water flux balance equation is given as.......... therefore it depend only on temperature ........  The electro-osmotic drag coefficient of the water for PEM is taken as fully hydrated................... so assumed constant concentration at cathode compartment so no need of mass balance . Concentration of oxygen taken high...(56) Methanol flux equation is expressed as........................................ ................................. Electrochemical Cell Reactions Governing Equations Methanol transport in flow channel .. ...............................................

.......................................(60) Combining Eqs....... ...........................(58) ........(57) ............................................................................................................................................ (59) gives.......................(59) Integrating Eq........... (55) and (66) .....................(67) ...................................................

........... .. flux in catalyst layer decrease along z-axis due to its oxidation at the catalytic site.......(70) Methonal... is the mass transfer coefficient....................................... ...................... is the superficial velocity of water Mass transport in catalyst layer Electrochemical reaction rate described by Tafel type Butler-Volumer Equation........... .................................................(68) Methanol flux equation given as...........................(69) Flux balance of water is expressed as................................ therefore material balance of methonol.where............................................

................................. ..............................(75) Mass transport in PEM Water transport through the PEM results from both the electro-osmotic drag and diffusion...................................................................................... i...........(71) Anodic over potential at any location within the catayst layer is written as..(73) Ohm's law for ionomer phase....... ................................................................................ ..........(74) Variation of the over potential within in the catalyst layer given by......................e............... ........................................................................................... ...........................................(72) Ohm's law for solid phase...........................................

............................. ...Water flux caused by elctro-osmotic drag........... methanol flux in membrane given as......................... . at constant cell temperature is given by...(77) At higher current density enhanced water accumulation at cathode reaction raise its concentration on the cathodic side into fully hydrated state..(76) Water flux caused by water concentration gradient in the PEM...................................................... ........................................ .............(79) Solution Procedure ...........(78) Similarly as anode diffusion layer...................................................................... also anode is in fully hydrated condition..................... so we can neglect Ndrag Final water flux equation is expressed as.........................................................................................................

.............................................................................(82) ..(84) ........................................(85) Dependent variables: .........(80) ............... ...............................................................................................................(83) ..............................................(81) These equations can br transferred into first order equation as...........

.. proper shooting technique is used.... the protonic current density must be equal to the cell current density l ................. so that the protonic current density must be zero at the diffusion layer/catalyst layer interface(z-0)........................ Intial value of i is known ..................Boundary Conditions Diffusion layer is ionically insulated.. At catalyst layer/PEM interface(z=lc)... therefore............... others variables values are unknown so for solve these equations..........case parameterrs values ......................................(86) Material balance of methonal at diffusion layer/catalyst layer interface(z=0) ..........................(87) In shooting technique appropriate initial guess is given to the variable and iterate it until the final value due to initial guess will match with the actual final value.......(88) The flux through the catalyst layer is partly consumed in electrochemical reaction and remaining pass through the membrane sa menthonol crossover....... Base . ....................................

.

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

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

Variation of methanol crossover with current density at various feed concentrations .

Effect of current density on anodic overpotential at various current density .

Variation of reaction rate within the catalyst layer at different values of and at cell current density of 0.3 A/cm2 .

2nd Edition.aip.T. Fritz B. International Journal of Hydrogen Energy 26 (2001) 991–999 . Elsevier Inc. A parametric study of the cathode catalyst layer of PEM fuel cells using a pseudo-homogeneous model. Chen.W. 5. 2008. 3. Modeling and simulation of a direct methanol fuel cell. Modeling of fuel cell. C. Lixin You.pdf Frano Barbir. K. Hongtan Liu.org/tip/INPHFA/vol-7/iss-4/p14. Fuel Cell Fundamentals. Journal of Power Sources 112 (2002) 376-375. Prinz. PEM Fuel Cells: Theory and Practice. Whitney Colella. Wiley. Ryan O'Hayre. 2.Vriation of anodic overpotential with effective protonic conductivity at different current density References 1. 4. http://www. Suk-Won Cha. 2005. Jeng.

We also know that at present the Nafion (a trademark of DuPont) is the most suitable membrane for the PEMFC and in order to make the PEMFC commercially viable there should be some other competitive membrane in the market. as it can be seen that bipolar plate is the most costly among others. we will discuss a few more information on bipolar plate little later.m-2. Polymer electrolyte membrane (membrane) Bipolar plate Gas diffusion layer (electrode) Catalyst The following figure shows a representative cost break up of the major components in the PEMFC. the PEMFC components are more or less same for the other type of low temperature fuel cells.Fuel Cell Components In this particular section. Moreover. we will discuss about the fuel cell components. However. These membranes had low mechanical strength and a short lifetime of a few hundred hours and power density of a few hundred kW. Electrolytes The use of polymeric membranes as electrolytes in fuel cells has received a tremendous impetus in the recent past. prepared by polymerization of phenol–sulfonic acid with formaldehyde. in 1959 with the testing of phenolic membranes. The major components of the fuel cell are. some more information on the membrane is also provided in this section apart from bipolar plate. We would consider the components of polymer electrolyte membrane fuel cells as it is the most widely used fuel cell and have a potential to use in wide variety of applications as discussed at the beginning. . 3. We have already discussed time to time about all the components. 4. 1. Therefore. The PEM fuel cell gained prominence after an ion exchange resin was incorporated as an electrolyte for space application by General Electric (GE). 2.

Power Sources 169 (2007) 221–238 A brief description on each type of membrane system is given below. combined with optimum compatibility [Neburchilov. V. Costamagna.J. Currently PEMFC finds a wide range of applications due to its perceived simplicity of design and weight advantages. J.6 kWm-2 that enabled its application in NASA’s Gemini flights. 2000]. 147 (9) (2000) 3171–3177. Wang. the DuPont product is considered to be superior because of its high proton conductivity. Srinivasan. In 1970s. GE attempted to improve the power density by developing partially sulfonated polystyrene sulfonic acid membranes (prepared by dissolving polystyrene sulfonic acid in ethanol stabilized chloroform followed by sulfonation at room temperature). A. H. Nafion® by DuPont is a perfluorinated polymer and used most extensively in fuel cells. The Dow Chemical Company and Asahi Chemical Company synthesized advanced perfluorosulfonic acid membranes with shorter side chains and a higher ratio of SO3H to CF2 groups [Guarau. J. Wang. Among the three major types. 2001]. 2007]. Soc. Weidner. Neburchilov.75–0. However. this membrane exhibited brittleness in the dry state. Martin.During 1962–1965. V. Becker.    fluorinated polymer membranes.4–0. H. V. Power Sources 169 (2007) 221–238 . However. H. cross-linked polystyrene-divinylbenzene sulfonic acid membrane/polymer was prepared in an inert matrix by GE. Neburchilov. J. The life of the membrane ranged from 1000 to 10. Power Sources 102 (2001) 242–252. Similar polymers are Flemion® produced by Asahi Glass and Aciplex-S® produced by Asahi Chemical.000 h and the power density attained was 0.000 h at 80 0C. Barbir. Fluorinated polymer membranes The perfluorinated sulfonic acid (PFSA) membranes have been the subject of intense research and are the key polymers used currently in portable fuel cell applications [Motupally. J.   P. requirement of supporting system and temperature related issues. Liu. S.W. The PFSA membranes are associated with some major limitations such as high cost of membrane. 2000]. 2007]. Motupally. Electrochem. J. S. DuPont developed a perfluorosulfonic acid called “Nafion®” that not only showed a twofold increase in the specific conductivity of the membrane but also extended the lifetime by four orders of magnitude. Electrochem. Nafion® and related polymers are still being intensely researched upon for improving the proton conductivity and chemical stability along with longevity of 60. J. J. hydrocarbon membranes. J. Martin. Membrane materials used till date for PEM fuel cells can be classified as. This membrane exhibited a better water uptake and an improved power density of 0.8kWm-2 [Costamagna. acid–base blends. Guarau. good chemical stability and mechanical strength [Neburchilov. F. Soc. 147 (7) (2000) 2468. In the late sixties.

which drastically reduces the DMFC performance and renders it unsuitable for DMFCs [Sakari. Membrane dehydration. loss of mechanical strength due to softening of polymer backbone and increased parasitic losses through high fuel permeation are some of the other serious issues associated with these membranes [Neburchilov. J. The influence of addition of different additives. decreased affinity for water. Nafion® exhibits a high methanol permeability. Kawami.Requirements of supporting equipment for uses with PFSA membranes. such as silica. Sakari. 1985]. Electrochem. J. H. Wang. V. K. H. Power Sources 169 (2007) 221–238 With regard to the application in direct methanol fuel cells (DMFC). was studied to improve the retention of water in the membrane and to enable the operation of the fuel cell at higher temperature. J. reduction of ionic conductivity. T. N. 2007]. in Nafion®. Y. Perfluro-sulphonic Acid Membrane Polymer Electrolyte Membrane for PEMFC . 132 (1985) 1328. 2007]. Wakabayashi. Martin. Efforts are directed to eliminate the disadvantages such as methanol crossover problems and loss of hydration above 1000C. Takenaka. Tori. titanium dioxide. Soc. Neburchilov. such as the hydration system add considerable cost and complexity to the vehicle power train [Neburchilov.

the H+ (proton) of sulphonic group becomes hydrated and the hydrated proton can move quite freely with in the material. Some information on Nafion       Nafion is a trademark of DuPont. which are given below. Once they absorb the water. and work as an excellent proton exchange membrane for PEMFC. Nafion solution as well as membrane are available in the market. thermal stability should high to sustain in the operating temperature .Polymer electrolyte membrane (PEM) is a solid electrolyte and thus has various advantages compared to liquid electrolyte. the PEMs have certain disadvantages also. and flexibility ) should be high enough to have good processability and can bear the fuel cell assembly condition . . mechanical properties (strength.    Low temp. Moderate water drag is required. and The cost must be low and the raw materials must be ready availability. Nafion115 and Nafion117 are widely used as fuel cell membranes. Tetra fluoro-ethylene is the backbone of the Nafion and therefore it has very good chemical resistance and mechanical strength The sulphonic acid groups provide the proton conductivity to Nafion. Therefore. low fuel permeability is required. The water is essential for the protonic conductivity of the Nafion. operation results in low quality of waste heat Noble metal catalysts are required CO poisoning is an issue Qualitatively the PEM should have the following main properties related to the low temperature fuel cell:         ionic (protonic or hydroxyl) conductivity should be as high as possible. precision sensors and control units can be avoided) insensitive to orientation and therefore ideal for mobile application no CO2 poisoning issue acid concentration of the electrolyte is fixed during membrane fabrication quick start-up thus ideally suitable for transportation no need of electrolyte maintenance to refurbish or regenerate the electrolyte However. It is a sulfonated tetra fluoro-ethylene copolymer. Thus the general operating temperature of the PEMFC is around 80oC. The Nafion can hold or absorb large quantity of water in it. fast kinetics for electrode reactions should be supported.         allows simple and compact cell structure and operation no free corrosive liquid. The various important nomenclature of the Nafion is given below. chemical stability should be high . USA. the fuel cell made up of Nafion can not work at higher temperatures. minimum corrosion of cell components can be made very thin thus ohmic losses can be minimized able to withstand large pressure differentials and thus control is easy as well as expensive .

The last digit gives us the thickness of the membrane in mil. or (b) polymers modified with bulky groups in the backbone. the thickness of the Nafion115 membrane would be 5/1000 inch (or aorund112 micrometer). Membr. even though they had been previously abandoned due to low thermal and chemical stability. in this case. One mill is 1000 part of an inch. Nafion115 The first two digits multiplied by 100 gives the equivalent weight of the polymer.A. it has been suggested that in order to produce materials that are less expensive than Nafion. B. However. Khan. They are less expensive. 185 (2001) 13. . a method of crosslinking PVA was suggested so that the extent of swelling in water could be controlled. J. has attracted renewed interest. Thus the equivalent weight of hydrogen or oxygen will be.   K. Sridhar. some sacrifice in material lifetime and mechanical properties may be acceptable. 2001]. provided the cost factors are commercially realistic [Neburchilov. Poly(vinyl alcohol) (PVA) membranes are known to be good methanol barriers. Aromatic hydrocarbons can be: (a) incorporated directly into the backbone of a hydrocarbon polymer. 2007]. Basics of equivalent weight Equivalent weight = Atomic (formula) wt. V. J. Presence of aromatic hydrocarbon in the backbone of hydrocarbon polymer enhances its performance at high temperature [Smitha. O=16/2=8   The sulfonic group (SO3H+) in nafion has a valence of 1 since only one proton can be accepted Equivalent weight of nafion is equal to the average weight of the polymer chain structure that can accept one proton. A. Smitha.D. In this case it will be 11x100=1100. H. Power Sources 169 (2007) 221–238 Hydrocarbon membranes provide some definite advantages over PFSA membranes and have the potential to compete with Nafion® membranes. Kreuer.. 2005]. Hence the use of hydrocarbon polymers. Martin. J. Wang. Hydrocarbon polymer membranes Despite its shortcomings. Membr. Sci. Based on this observation./valence (gm/mol) Valence is number of electrons that the species can donate or accept . Neburchilov. 259 (2005) 10–26. commercially available and their structure permits the introduction of polar sites as pendant groups in order to increase the water uptake [Kreuer. Nafion® is still the polymer of choice for most PEFC and DMFC applications. J. Thus. S.Eg. Sci. H=1/1.

Poly(2.21-(m-phenylene)-5. . Vishwanathan.). polyether ketones (PEK) with varying number of ether and ketone functionalities (such as PEEK. It has shown a great deal of potential for medium temperature fuel cell applications and hence many attempts were made to understand and optimize this particular system. In general. 1999. poly(arylene ethers). polyesters and polyimides (PI) are some of the relevant examples of main chain polyarylenes [Gowariker. Tg. N. J. New Delhi.51-bibenzimidazole)/phosphoric acid (PBI/H3PO4) complex is both intriguing and promising at the same time. an acid component is incorporated into an alkaline polymer to promote proton conduction. >200 0C owing to the presence of inflexible and bulky aromatic groups.V. 1999]. Gowariker. Polymer Science. Sridhar. V. PEKEKK. etc. Polyethersulfones (PESF). New Age International. The aromatic rings offer the possibility of electrophilic as well as nucleophilic substitution.Polyarylenes are high temperature rigid polymers with glass transition temperature. Acid-base polymer membranes Acid–base complexes have been considered as one of the alternative for high temperature fuel cell operations. PEKK.R.

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

it has been found that carbonless multifunctional active catalyst supports for . carbon cannot be used as the support in catalysts for PEM-water electrolysis and regenerative fuel cells because its corrosion occurs easily at the high oxygen-evolution potential. durability. It is known that the electrochemical surface area (ESA) of electrocatalyst depends upon the support material as well as Pt particles size. carbon nanofiber. Therefore. Pt nanoparticle on the carbon support agglomerates and looses the suport material (carbon). The mechanism for the loss of platinum surface area has been widely investigated and can basically be described by the dissolution or detachment of Pt from carbon substrate and further re-deposition onto existing Pt particles or diffusing into the membrane or other inactive parts of the membrane electrode assembly. e The carbon nanotube. and overall performance of the PEMFC. In the recent efforts. low surface area (around 250 m2·g-1) carbon material may not sufficient to accomodate Pt nanoparticles. better the PEMFC performance. As discussed earlier. The support material affect the Pt particles distribution during the synthesis of electrocatalyst. The support material may affact the formation of platinum particales size during the preparation of metal catalyst. infact the triple phase point is shown. the carbon (Vulcan XC-72) is generally used commercially as a support material for the platinum in PEMFC application. Whereas. the researchers focus has shifted towards carbonaecous nanomaterials support for PEMFC catalyst due to their faster electron ransfer and high electrocatalyctic activity. the selection of catalyst support material is most important towards determining the ESA. which has been shown to be very severe not only on the cathode but also at the anode. and graphene have been wiedly used as a carbon nanomaterial for catalyst support in PEMFC. high electrical conductivity. Moreover. stability. The detachment and mobility of the platinum is affected by the corrosion of the carbon support. the electronical. A good interaction between catalyst and support materials improves the catalyst eficiency and decreases the loss of catalyst with time during operation of the fuel cell. during dynamic operation of the cell. Moreover. Moreover. Moreover. there is a deterioration of the fuel cell performance. the figure at the right side shows the detailed transport of the various species from the triple phase boundary. and relatively good stability towards electrochemical environment. However. Due to the changes in the hybridization structure of source bulk materials. due to corrosion of carbon. Therefore. mechanical. the electrochemical active sites reduce and as a result the performance of the PEMFC also reduce with the fuel cell operation time. Higher the ESA. partly caused by the loss of electrochemically active surface area. These carbon nanostructures are basically allotrops of carbon atoms with high specific surface area. and physical properties of the nanomaterials are quite different and improved.The figure on the left side shows a typical electrode system for hydrogen electro-oxidation in a representative way.

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

High density 1. Required properties Low weight Density Target Values < 0.0 g·cm-3 . Good corrosion resistance Carbon-carbon composite 1. High H2 permeability 3. Low mechanical strength 2. Good corrosion resistance 3. Moderate electrical conductivity 2. Material Metal Advantages 1. Long processing time 2. High mechanical strength Graphite bipolar plate 1. Moderate electrical conductivity 2. High electrical conductivity 2. High density 1. remove heat from adjacent cells. conduct current between adjacent cells. Machining of flow field 1. Corrosive 2. What are the materials available for bipolar plate? The following table summarizes the different material available for the bipolar plate as well as their advantages and disadvantages.Bipolar Plate for PEMFC Why bipolar plate is required? The main functions of the bipolar plates in a PEMFC system are      to to to to to support the membrane electrode assembly (MEA) robustly. Good corrosion resistance Carbon-polymer composite 1. High production temperature 3. How to measure these properties are discussed in the proceeding sections with a focus on a few of the properties. Cost ineffective 4. High porosity Coated metal 1. High electrical conductivity 2. Uneven expansion 2. distribute reactant gases uniformly over the active areas. Good mechanical strength 1. High electrical conductivity 2. and prevent leakage of reactant gases. High contact resistance 3. Long processing time If we have to develop a bipolar plate for the PEMFC then we should have a fair idea of the requirement of the bipolar plate. High mechanical strength Disadvantages 1.4 kg·kW-1 < 2. Thus to have a feel the following table shows that if one have to work on carbon/resin composite bipolar plate then the developed bipolar plate should have achieved properties.

Fuel Cell Fundamentals.. John Wiley 2009 .High flexural strength Highly flexible High electrical conductivity High thermal conductivity Low gas permeability High corrosion resistance High shore hardness > 50 MPa * 3–5 % deflection at mid-span > 100 S·cm-1 > 10 W·m-1·K-1 < 2×10-6 cm3·sec-1·cm-2 at 80°C and 3atm < 1 µA·cm-2 > 40* O’Hayre et al.

2. we may understand that the in-situ characterization can use the electrochemical variables of V. electrolytic R etc. I. location of the losses etc. you must understand and to be able to quantify the different losses occurring in the fuel cell. The fuel cell characterization is of particular importance to the fuel cell developers. ohmic properties (Rohmic. Deff. scientists and researchers. You may also be interested to know how much losses are occurring in the fuel cell. electrode structure (?. ?P etc. before using and developing a component for the fuel cell. Current voltage measurements Current interruption technique Cyclic voltammetry Electrochemical impedance spectroscopy 2. Thus we have to characterize the fuel cell in the ready form. . it is to be characterize fully in order to know the desired properties. It is required to know whether the fuel cell is comparatively inferior or superior to the competitive cell either prepared by others or the improvement from the previous cells. it is required to access whether a fuel cell is good or bad from the pool of the developed cells. a etc. The fuel cell characterization can be divided into two broad categories. 4. We need to identify the problematic component(s) as well as the reasons of ill-performance. parasitic losses (jleak. Some of the properties in which we are be interested are kinetic properties (?out. Once the fuel cell is prepared. On careful analysis. If a fuel cell performance is not upto the expectation or if you want to make it more effective.). Ex-situ characterization Once we know that the performance of the fuel cell is not upto the desired standard then we have to find out the route cause. In-situ characterization In–situ characterization means the fuel cell is fabricated and now you would like to performance of the fuel cell. Thus we need to characterize the component for its properties. mass transport properties (J L. In order to distinguish between inferior or superior fuel cell. 1. and time to characterize the performance of fuel cell under operating conditions. jo. crossover). 1.). side reactions. Moreover.Fuel cell characterization Why to characterize fuel cell? This topic is one of the most important topics of the fuel cell technology. quantity of the losses. A few major in-situ characterization techniques are . 3. the characterization techniques are very straight forward by using i-v characteristics of the fuel cell.).

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

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

the potential of an electrochemical system swept back and forth between two voltage limits and the response of the current is measured against the voltage. the reactant molecules and ionic species takes some time to get re-oriented due to the removal of electric field. 3. . In general the voltage is changes linearly with a predefined rate (V/s). The time-dependent rebound is associated with capacitive nature of the much slower reaction and mass transport processes. The recovery time for this process is slow and thus it takes time to come to the open circuit voltage (V3) corresponding to A1. In the technique. Cyclic Voltammetry (CV) The cyclic voltammetry has become a very popular technique for initial electrochemical studies of new systems and has proven a very useful in in obtaining information about fairly complex electrode reactions. However. For zero current the ohmic part contribution gets zero. If we recall the following equation discussed before to understand it..Illustration of current interruption technique The immediate voltage rebound from V1 to V2 is associated with the ohmic resistance of the fuel cell.

superscripts a and c denote the anodic and cathodic components . or . (i) The voltage separation between the current peaks is (ii)The ratio of the peak currents is equal to one (iii)The positions of peak voltage do not alter as a function of voltage scan rate (iv)The peak currents are proportional to the square root of the scan rate Note: Subscript p denotes the peak. and v denote the voltage scan rate 4.Illustration of the CV: The voltage is scanned from V1 to V2 and then back to V1 For a reversible electrochemical reaction the CV recorded has certain well defined characteristics. Electrochemical Impedance Spectroscopy (EIS) Electrochemical Impedance Spectroscopy is also called AC Impedance or just Impedance Spectroscopy. It utilizes the modeling of the electrochemical system into the electrical circuit of resistances. capacitances. It is a method of characterization of the electrochemical system.

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

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

R V=IR Let V = V0sin(ωt). current leads voltage by 90o and hence impedance of a capacitor = 1/jωC Inductor.V0cos(ωt) =ωLI = V0sin(ωt . associated with a double layer capacitance. then I = V0sin(ωt)/R So. Both serial and parallel combinations of elements occur.dl/dt Similarly. current lags voltage by 900 and hence Impedance of an Inductor = j?L 4.Registor. ZW = Aw/√ω+Aw/j√ω Series and parallal combination of electrical components Very few electrochemical cells can be modeled using a single equivalent circuit element. Impedance. W It represents the diffusion part of an electrochemical cell. 2. Instead.90o) So. L V= L. C q = CV Let V = V0sin(ωt) I = CωV0cos(ωt) = ωCV0 sin (ωt + 900) So. Impedances in Series: Zeq = Z1 + Z2 + Z3 Impedances in Parallal: 1/Zeq =1/ Z1 +1/ Z2 +1/ Z3 .Capacitor. current and voltage are in the same plane to each other and hence the impedance of a registor is R only. . EIS models usually consist of a number of elements in a network. Warburg Element.

This is true for EIS data where impedance usually falls as frequency rises (this is not true of all circuits). i) Nyquist Plot: The expression for Z(?) is composed of a real and an imaginary part. Electrochemical Impedance plots often contain several time constants. On the Nyquist plot the impedance can be represented as a vector of length |Z|. The angle between this vector and the X-axis is f.Representation of impedance spectroscopy The impedance so obtained from the study can be plotted in two different kinds. Low frequency data are on the right side of the plot and higher frequencies are on the left. RC Circuit 1/Z =1/R +1/jω Corresponding Nyquist Plot . Often only a portion of one or more of their semicircles is seen. Notice that in this plot the Y-axis is negative and that each point on the Nyquist plot is the impedance Z at a particular frequency. The Nyquist plot shown in the next slide is for a RC circuit. Nyquist plots have one major shortcoming. we get a “Nyquist plot”. The semicircle is characteristic of a single “time constant”. If the real part is plotted on the X-axis and the imaginary part on the Y-axis of a chart. The frequency at any point cannot be determined from the plot. They are.

it is known that a bare metal immersed in an electrolyte will generate around 25µF per cm2 of the metal electrode area. oxide layers.ii) Bode Plot: Another popular presentation method is the “Bode plot”. electrode roughness. . the Bode plot explicitly shows frequency information. These charges separated by an insulator forms a capacitor. And hence we see the electrolyte section being shown as a resistance model with small resistances in the anode and cathode part to account for the resistance to the electron movement. In order to have a feel of the capacitance value. The Bode plot for the RC circuit is shown below. types of ions. A typical representation of fuel cell The fuel cell. capacitance and the Warburg element. The separation is very small and is in the order of nanometers. Resistances develop mainly due to the resistance to the transport of ions or electrons. This double layer is formed as ions from the solution to the electrode surface. The value of the double layer capacitance depends on many variables such as electrode potential. Unlike the Nyquist plot. Charges in the electrode are separated from the charges of these ions. etc. temperature. ionic concentrations. The impedance is plotted with log frequency on the X-axis and both the absolute values of the impedance ( Z = Z0) and phase shift on the Y-axis. impurity adsorption. anode. can be expressed in terms of resistance. An electrical double layer generally exists at the interface between an electrode and its surrounding electrolyte. electrolyte and cathode. which has three major parts. A representative Nyquist plot for a fuel cell: The typical values on the plot is just a typical value.

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

The membrane should be located at the centre of the conductivity cell.Ex-situ characterization We will discuss a few of the important ex-situ characterization of the major components of the fuel cell. where L. R.5 cm2 each). Through plane conductivity of the membrane can determined in a conductivity cell shown in the next slide. The electrical resistance of membrane (R1) can be measured using LCR meter.5 M H2SO4 solution. the measured resistance (ohm). 0. Proton conductivity set-up for cationic solid polymer electrolyte Conductivity measurements should be performed at a particular temperature after equilibrating the membrane in de-ionized water for 24 hours. Both the compartments should have a platinum electrode (say. Electrolyte Characterization for proton conductivity In this section we will see how to find out the proton conductivity of the cationic solid electrolyte (proton exchange membrane). R. of the membrane can be calculated by subtracting the value of R2 from R1. Bipolar plate . The electrical resistance. respectively. and the effective area of the membrane (cm2) perpendicular to ion flow. having two chambers filled with 0. 1. The electrical resistance of the 0. and A denote the distance between the electrodes (cm). The conductivity measurement can be performed in a two-electrode AC impedance mode using a LCR mete.5 M H2SO4 solution (R2) without the membrane can be measured.

i. we would discuss about how to measure the electrical conductivity of a composite bipolar plate made up of carbon materials and polymer matrix. l (cm) and b (cm) are the width and thickness of the sample. Bipolar plate conductivity measurement set-up The electrical conductivity of the sample can be calculated by the following equation. The set-up was used to measure the in-plane and through-plane electrical conductivity by changing the orientation of the bipolar plate. In this section. The schematic of the electrical conductivity measurement set-up is shown in the figure on the next slide. Electrical conductivity of the bipolar plate can be measured as per the ASTM C611 method using conventional four probe technique at a constant current supply. Electrical conductivity As discussed in the bipolar plate section. the electrical conductivity is one of the most important properties of the bipolar plate. respectively. The constant current supplied through the sample is represented by i (A) and V (V) is the voltage drop between two points separated by a distance d (cm) along x-direction. Flexural strength The flexural strength of the composite bipolar plates are important properties as the . Electrometer may be used as the constant current source. Electrical Conductivity where. ii.

bipolar plates may undergo high bending force during clamping within the fuel cell hardware. Shore hardness The shore hardness is another important mechanical property of the composite bipolar plate. . The three-point flexural strength of the bipolar plate can be used to evaluate with the help of an universal testing machine. The height of the rebound of the diamond tipped hammer was noted down and it was equal to the shore hardness of the composite bipolar plate. It is a dynamic indentation type hardness test in which a diamond tipped hammer is allowed to fall vertically from a fixed height over the test specimen. Bipolar plate flexural strength measurement set-up The movable anvil will start applying load to the specimen at the speci?ed crosshead rate. d = depth of the test sample in mm. Shore hardness of a composite bipolar plate can be measured with the help of a scleroscopic hardness tester as per the ASTM C886. b = width of the test sample in mm. The break load and the maximum deflection should be recorded accordingly. iii. where P = load at a given point on the load deflection curve in N. The flexural strength of the composite bipolar plate can be calculated using following equation. and the simultaneous load-de?ection data can be monitored with the help of a computer. L = support span distance in mm.

the electrochemical activity as well as electrochemical surface area is very important properties of the catalyst rather electrocatalyst. as the catalyst is to be used in electrochemical system.3. The cyclic voltammetery is very important technique to find the electrocatalyst activity as well as electrochemical surface area. However. From the previous figure it can be seen that the forward peak current density of Pt at the potential of 0. Thus. particle size etc.76 m2·g-1Pt. The figure on previous slide shows the cyclic voltammetry result for Pt/G and Pt/C. respectively. A typical example of two different catalysts are shown in the next slide. where CV was used to evaluate the electrochemical active surface area Cyclic voltammetry of Pt/G and Pt/C electrocatalysts Where Pt/G and Pt/C are platinum supported on graphene and carbon.146 V is 0. The ESA for Pt/G and Pt/C can be determined as 61. which is nearly four times compared to Pt/C . The charge constant for poly-crystalline Pt surface for hydrogen adsorption is 210 µC·cm2. the Pt/G has more than 10% ESA than the Pt/C catalyst.58 and 54. respectively. Catalyst The usual methods of catalyst characterization may be used like surface area. The electrochemical surface area (ESA) can be calculated by the following equation using charge of the hydrogen adsorption peak in the cyclic voltammetry curve after base line fitting by least square method.04 A·cm-2. The high electrochemical surface area is favorable for fuel cell catalyst oxidation and reduction reaction.

Gas diffusion layer Gas diffusion layer (GDL) is one of the vital components of the polymer electrolyte membrane fuel cell (PEMFC). The MPL works as a non-permeable support to the catalyst particles during catalyst deposition. The most important desired properties of the MPL coated GDL are high electrical conductivity. Therefore. Therefore.(0. the electrochemical activity of Pt/G is also superior than that of Pt/C. porosity .066 V). The properties of the GDL can be altered by MPL. it should be porous enough to pass the gases without imparting much resistance to the gas flow. 4. The MPL functions as a substrate for the catalyst layer by providing reduced ohmic resistance between the catalysts layer and the microporous substrate. and high porosity. high corrosion resistance.01A·cm-2 at 0. pressure drop. The GDL is placed in between the bipolar plate and the catalyst layer of the fuel cell. The GDL of PEMFC is generally composed of microporous substrate and microporous layer (MPL) of carbon black. However.

Patent 623. gasified coal) via an electro-chemical process directly into electricity. whereas the mixtures possess an enormously much greater conductivity” “Nernst mass (85% ZrO2 + 15% Y2 O3 )” W.811. natural gas. April 25. C. Singhal Solid Oxide Fuel Cells ( SOFCs ) A solid oxide fuel cell (SOFC) is a device that converts gaseous fuels (hydrogen.High Temperature Fuel Cell: Solid Oxide Fuel Cell    What is Solid Oxide Fuel Cell (SOFC)? SOFC Components and Properties! Configuration of SOFC! SOFC Ceramic Ion Conductors: Early Work Walther Nernst (1897) “that the conductivity of pure oxides rises very slowly with temperature and remains relatively low. . 1899 Reference: Solid State Fuel Cells: Evolution and Trends.S. Presentation by S. Nernst “Electrical GlowLight” U.

The efficiency makes them a good candidate for a distributed power source (generator or power plant).< ---------> 2H2 O + CO2+8eCathode 1/2O2+2e.< ---------> H2 O + 2eCH4 +4 O2. The reactions in SOFC require a high temperature.<---------> O2Overall Cell Reaction H2 +1/2 O2 + <------------>H2 O 0 2 2 E=E +RT/2F [ln(PH /PH 0)] +RT/2F[ln(PO CH4+ 2 O2 2 H2O + CO2 0 2 1/2 ] E=E +RT/8F [ln(PcH /PH 0 4 2 2 PCO2)] +RT/2F[ln(PO2 2] SOFC Electrolyte: Yttria-Stabilized Zirconia . Cell Reactions Anode H2 + O2.Advantages of SOFC     SOFCs are over 60% efficient (conversion of fuel to electricity) making them the most efficient fuel cell currently being developed. There are no liquids that cause safety and environmental problems. The advantage is that this creates a byproduct of heat.

    Yttria is used as dopant for stabilizing the cubic phase of zirconia. induces the generation of oxygen vacancies for charge compensation..1 S cm-1. the ionic conductivity of the electrolyte material must be higher than 0. .Y O -------->2Y 2 3 Zr +3OxO+Vo YZr denotes Y in the Zr site with the apparent negative charge.e. OxO is the lattice oxygen. i. with the electrolyte within this range of thickness. charge neutrality condition prevailed by forming an oxygen vacancy) For an effective operation of a fuel cell. a fully (cubic) stabilized zirconia is obtained with aY2O3-content of >7 mol% Y3+ have lower valency than zirconium ion (Zr 4+). oxygen in the oxygen site with net charge of zero. and VO is the vacancy in the oxygen site with double positive charge. Substitution of Zr4+ with Y3+causes negative net charge in the lattice(for every mole of yttria incorporated into the zirconia lattice.

) Lanthanum based electrolytes : LSGM LaXSr(1-X)GaYMg(1-Y)O3 LaALO3-based La1-xCax ALO3 . ScSZ. CDC etc.Different Electrolyte Material Zirconia based Ceria based Lanthanum oxide based Bismuth oxide based Excellent Stability in oxidizing and reducing Good environment Excellent Good compatibility with cathode compatibility with Mechanical stability Materials High Conductivity cathode Materials (3YSZ) well stsdied material Electronic Ga evaporation at conduction at low lowpO2 Formation ofstable Lower Ionic Conductivity pO2 Poor secondry phases In compatible mechanical with NiO strength Different Electrolytes Zirconia electrolytes: (8YSZ.) Ceria electrolytes :(GDC. YDC. SDC.La1-xBaxAlO3 High Conductivity Thermodynamic instability in reducing atmosphere Volatilization of Bi2O3 High corrosion activity Poor mechanical . 3YSZ.CaSZ etc.

125mm .9Cu0.50 μm) :1000 .95Mg0.Interconnect Composition Porosity Condutivity TEC Dimensions Requirement for the cathode :LCM [La0. permeability should be zero :5 . Ba2In2O7.92(Y2O3)0.1S/cm :10. t~100μm : Ni-YSZcermet (Ni .08 :Nil. Gd2Ti2O7 Barium brownmillerites : BaZrO3. Ba3InxAOy (A=Ti.1 :40% (pore size 20-50 μm) :100 S/cm at 1000oC :10-12 ppm/ oC :ID-14mm.1500 S/cm :10 .1 mm. L-160mm 2.05(CrO3)] :Nil.10 S/cm at 1000oC :10 .Zr.12 ppm/ oC :OD .(Bi2O3)x(Nb2O5)1-x Pyrochlorores . L .5 mm.1O5.60% by wt) :40% (pore size 20 .Ce.Bismuth oxide-based: Bi2V0. L-125mm     high electronic conductivity Chemically comatible with neighbouring cell component (usually the electrolyte) Should be porous Stable in an oxidizing environment . t~100μm. Wall -2mm.Ba3Sc2ZrO8 State-of-theart SOFC Bench mark properties for component materials 1.5 ppm/ oC :Film thickness-50 μm.Anode Composition Porosity Condutivity TEC Dimensions 4.18.Electrolyte Composition Porosity Condutivity TEC Dimensions 3.Hf) . permeability should be zero :lonic~0.Cathode Composition Porosity Condutivity TEC Dimensions :LSM (La0.based: YZr2O7.9Sr0.5-δ.12 ppm/ oC :W . L~125 mm : YSZ [(ZrO2)0.

    Large triple phase boundary Catalyze the dissociation of oxygen Adhesion to electrolyte surface Thermal expansion coefficient similar to other SOFC materials Requirement for the anode         Electrically conductive High electro . oxidation and carburization Low materials and fabrication cost Interconnect Ceramic Interconnect for High temperature SOFC (High material cost.catalytic activity Large triple phase boundary Stable in a reducing environment Can be made thin enough to avoid mass tranfer losses. but thick enough to provide area and distribute current Thermal expansion coefficient similar neighbouring cell component Fine particle size Able to provide direct internal reforming (if applicable) Requirements for the interconnect         Stable under high temperature oxidizing and reducing environment Very high electrical conductivity High density with "no open porosity" Strong and high creep resistances for planar configurations Good thermal conductivity Phase stability under temperature range Resistant to sulfur poisoning. high electrical and thermal conductivity) High chrome alloys (C5rFe1Y2O3) Ferritic stainless steel for temperature SOFC Iron super alloys Nickel super alloys Critical Issues Chromium evaporation (in Cr based interconnects) . sintering difficulties) eg: Doped Lanthanum Chormites and doped Yttrium chromites Metallic Interconnects (easy fabrication.

Monolithic design .Westinghouse 2. Tubular Design o Pioneered by Siemens .SrO-La2O3-Al2O3-SiO2 SOFC:Designs 1.Requirements for the sealing materials        Electrically insulating Thermal expansion compatibility with other cell components Chemically and physically stable at high temperatures Gastight Chemically compatible with other components Provide high mechanical bonding strength Low cost Materials Glass ceramic materials .Anode supported concept 3. Planar Design o Convectional 'electrolyte supported' concept o Cathode supported design o Newer .

000 hours Table 2 Projected trends of development of SOFCs for transporatation .down.) Stack power per volume stack power per mass Fuel Reforming Cooling Duty lifetime Projections (550oC)600oC to 800oC less than 2 minutes 2 kW/L 2 kW/kg unleaded gasoline. 1000 to 800oC Table 1 Recent results reported by distinguidhed SOFC laboratories Features Operating temperature Start -up (ambient to operating temp. Mwthanol integrated internal and in situ air. of California (6) Stack power per volume Stack power per mass Warm -up: to 800 C o or to operationg temperature Cool . heat rejection by exhaust 5.935 W/cm over kW/L over kW/Lkg 1 minute 5 seconds 31 hours 2 References Berkeley Lawrence Lab (2) Allied-Signal Aerospace (3) Allied-Signal Aerospace (3) Keele University (4) Keele University (5) Univ. diesel.Planar SOFC Feature Power density at 800 C o Value 1.

Planar SOFC Preparation of Anode and Electrolyte suspension for Tape Casting Cell Testing Unit .

Experimental Setup PGSTAT 3 .

Cathode LSM:YSZ .

OO2Salt based+ceramic Carbon based+ceramik Salt and carbon H2 Minutes 3-8 55-65% .SOFC Vehicle auxillary power Yttria stabilized Zirconium Oxide (YSZ) 700 .1.1000OC O2Ceramic Perovskites H2.CO Hours 3-4 55-65% LT .SOFC Vehicle auxillary power Cation doped cerium oxide (GDC. SDC) 500-700OC O3 Ceramic Perovskites H2.8 -6.1 . K) 300-600OC H+.Comparison of SOFCs Cell Type Primary application Electrolyte Operating temp Charge carrier Cell component Catalyst Primary fuel Start up time Power Density (k W/m) Fuel cell efficency PEMFC Automotive and stationary power Polymer (plastic membrane) 50 .5 55-65% IT .SOFC Vehicle auxillary power Two phase composite made by mixing Cation doped cerium oxide and either salts(eg: GD CNaCl) or carbonates SD-M2CO3(M-Li.CO Hours 0.5 50-60% HT . Na.minutes 3.100OC H+ Carbon based Platinum H2 second .

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

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

of efficiency. Three types of major reforming process are. . The details of the processes may be read from some other source. Hydrogen from water   Water is the another greatest source of hydrogen. The reforming may be done with or without catalyst. In subsequent reaction the CO can further be converted to CO2 and the process is known as water-gas-shift reaction.    Steam reforming (SR) Partial oxidation reforming (POR) Auto thermal reforming (ATR) Steam reforming (SR)  Steam is used to reform the hydrocarbon (say natural gas) using a catalyst. Δh=(+)   The above reaction is strongly endothermic. High purity (ideally 100%) hydrogen can be produced from water. We will briefly discuss about the reforming of hydrocarbon and electrolysis. Reforming of hydrocarbon The aim of the reforming is to generate hydrogen rich gas by hydrocarbons. CH4+H2O -------------> 3H2+CO .

. A typical POR is shown below. Catalyst is required for the partial oxidation at low temperature. Δh=(-) Partial Oxidation Reforming (POR)      Partial reforming is the another technique for generation of hydrogen by hydrocarbon for fuel cell. In electrolysis. the energy (or electrical current) is required to dissociate water molecules into hydrogen and water. thus the product is not diluted with nitrogen. Δh=(-) Autothermal Reforming (ATR)     It is another technique for hydrogen generation. the process is then known as catalytic partial oxidation reforming (CPOR). As the name indicates. CH4+1/2O2----------------->CO+2H2 . the thermal energy requirement is met by the system itself. In fact the concept of fuel cell came during the electrolysis of water by Sir William Grove in 1839. The name suggests that the temperature is not required externally. The idea is that if the endothermic steam reforming reaction and the exothermic POR occur together. there should not be any need of heat addition or removal to/from the system. less oxygen (stochiometry) is required to carryout POR. CO+H2O -------------> H2+CO2 . POR does not require catalyst if it is carried out at high temperature. Hydrogen Generation Through Electrolysis    Generation of hydrogen using electrolysis is one of the oldest technique. The above process do not need air. However.  The above reaction is mildly exothermic.

 The hydrogen formed in electrolysis is the purest form of hydrogen. Electrolysis reactions in cationic electrolyte Cathode Reaction: 4 H + 4e <--------> 2H2 + - Anode Reaction: 2H O <--------> O + 4 H + 4 e 2 2 + - Overall Cell Reaction: 2 H O <----------> 2H + O 2 2 2   Electrolyte (cationic or anionic) is placed between anode and cathode of the cell and the electrical current is given by the DC power source. Electrolytic cell is used for the electrolysis of water. . whereas oxygen is generated at anode of the electrolytic cell. Hydrogen is generated at cathode.

Electrolytic Cell .

photolytic. biological. Local availability of feedstock. Hydrogen can be produced from a variety of feedstock. Many process technologies like chemical. Their low weight meets key targets and the tanks are already commercially available. and the energy penalties associated with compressing the gas to very high pressures. Composite tanks Cryogenic liquid hydrogen (LH2) Chemical hydrides Carbon based materials Metal hydrides Composite tanks There are several advantages with composite tanks. In this course.g. well-engineered and safety-tested. as well as renewable resources. Gaseous hydrogen cooled to near cryogenic temperatures is another alternative that can be used to increase the volumetric energy density of gaseous hydrogen. electrolytic. 4. we will discuss about a few of the techniques in which the hydrogen can be stored. such as biomass and water. market applications and demand. These include fossil resources. solar. although lightweight composite tanks designed to endure higher pressures are also becoming popular. benefits and challenges. The most common method to store hydrogen in gaseous form is in steel tanks. Figure in the next slide show a representative sketch of a composite tank. when we use the energy input from renewable energy sources (e. the maturity of the technology. 3. the fact that the ideal cylindrical shape makes it difficult to conform storage to available space. major problem with hydrogen is its efficient storage system. hydro-power. and costs may influence the choice and timing of the various options for hydrogen production. etc. However. . Their main disadvantages are the large physical volume required. 1. Each technology is in a different stage of development. Composite tanks does not require internal heat exchanger and may be used for cryogas with extra fittings.). wind. and thermo-chemical may be used for the hydrogen production. 2. Standard size tanks are available worldwide with specific code for pressures in the range of 350-700 bar. since extensive prototyping experience exists. and each offers unique opportunities. such as natural gas and coal. policy issues. 5. The major techniques are shown below.Hydrogen Storage Hydrogen may be a prospective source or energy carrier for the future because it is clean and sustainable. Several technologies are already available commercially for the industrial production of hydrogen. their high cost (500-600 USD/kg H2).

usually simply referred to as liquid hydrogen (LH 2).8 kg/m3 at normal boiling point (–253°C). The consideration of hydride-type compressors utilizing waste heat or solar energy.e. Development of an efficient and clean (i. Further research needed in this area is as follows:    Efficient liquefaction processes (hydride compressors. Chemical hydride Some of the chemicals may be used to store the hydrogen gas. Development of stronger and lower-cost construction materials.There are also some safety issues that still have not been resolved. there is still need for more research and development specifically:      Research on material embrittlement. Development of techniques that recover the compression energy during vehicle operation. without oils) 1000-bar compressor. Sodium borohydride (NaBH4) can be used to store the hydrogen gas. Hence. and in the future it could also be coutilized as aircraft fuel. it is important to recall that about 30-40% of the energy is lost when liquid H2 is produced. However. plus the fact that super-insulated cryogenic containers are needed. etc. For example. The main advantage with liquid H 2 is the high storage density that can be reached at relatively low pressures. Liquid hydrogen has been demonstrated in commercial vehicles (particularly by BMW). using new ad hoc fracture mechanics techniques. Developing systems that automatically capture the boil-off (e. (Critical pressure is 13 bar and critical temperature is – 240°C. . but only 20 wt. This means that liquid hydrogen has a much better energy density than the pressurized gas solutions mentioned above. Cryogenic liquid hydrogen (LH2) Cryogenic hydrogen.g. the respective values are 80 kg/m3 and 30 kg/m3. the sodium borohydride solution can be catalytically hydrolyzed as per the reaction shown below. magnetic and acoustic cooling. In order to release the hydrogen. such as the problem of rapid loss of H2 in an accident. has a density of 70. The long-term effect of hydrogen on the materials under cyclic or cold conditions is also not fully understood. especially carbon fibers.) The theoretical gravimetric density of liquid H2 is 100%. The other main disadvantage with liquid H2 is the boil-off loss during dormancy.). On a volumetric basis.% H 2 can be achieved in practical hydrogen systems as of today. via hydrides) and reliquefying the fuel. since it provides the best weight advantage of any H 2 storage. Minimizing costs and improving the insulated containers.

therefore further research may be emphasized on. However.g. Room temperature adsorption up to a few wt. The use of NaBH4 solutions in vehicles may be prohibitively expensive. 5. . Further research required as follows:   Approaching the ideal energy density (10. To understand this behavior it is helpful to consider the pressure– composition isotherm (PCI) for a metal hydride. The regeneration of the metal can be accomplished either by increasing the temperature or by reducing the pressure. regeneration. This requires a new bonding mechanism with energies between physisorption and strong covalent chemisorption.% H 2. the potential for H2 storage in carbon-based materials is yet to be established practically. However. Measuring H2 uptake and release from carbon samples has to be standardized.) + 2H2O (liq.9 wt.% H 2) by optimizing the H2O needed in the reaction and management of H2O in the fuel cell system. graphene. Study on carbon-metal composites capable of catalysing H2 dissociation and so-called “spill over”. New C-H bonding mechanism has to be explored and. NaBO2 removal. but has not been reproducible. Metal hydride The chemically bound hydrogen storage material is metal hydrides. how to achieve it in practice.) ---------> 4H2 (gas) + NaBO2 (solid) The theoretical maximum hydrogen energy storage density for this reaction is 10.9 wt. Hence. The main disadvantage is that the reaction product NaBO 2 must be regenerated back to NaBH4 off-board. graphite nanofibers and nanotubes). A generic reaction is given in the figure on next slide.NaBH4 (liq. and replacement methods. and carbon nano-tubes. if theoretically so. Minimizing production costs for promising carbons (e. Carbon based materials Carbon-based materials have received a lot of attention in the research community over the last decade. The main advantage with using NaBH4 solutions is that it allows for safe and controllable onboard generation of H2.% H2 with catalyst.% H2 is occasionally reported. Many metals and alloys will reversibly react with hydrogen to form a hydride. H2 is stored on these carbon allotropes by molecular physisorption.      Theoretical modeling studies of H on carbon nanostructures and in bulk phase. The required cost reduction is unlikely because of the unfavorable thermodynamics. but the covalent-bound H is liberated only at impractically high temperatures (above 400°C with catalyst). it is useful only at cryogenic temperatures. fullerenes. Pure H-chemisorptions has been demonstrated to be stored upto 8wt. NaBH 4 solutions may be used in high-value portable and stationary applications. Carbon based materials mainly include graphene.

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

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

When we talk about the fuel cell system it includes many sub-systems. Fuel cell stack Thermal management 2. These sub-systems are. They described below. 1. Fuel delivery/processing Power electronics All the subsystem (peripherals) except the fuel cell stack known as balance of plant (BOP).Balance of plant and Power electronic ans system integration Fuel Cell System We are at the end of the fuel cell course and now can easily understand that not only the fuel cell is necessary but also the peripheral components are necessary. . The peripheral components are necessary in order to have the fuel cell work efficiently as well as the efficient and effective utilization of the electrical energy by the fuel cell for an application.

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

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

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

. we will mostly focus about the power conditioning. the fuel cell voltage is highly dependant on the temperature. Because a single cell may pro vide hardly 0. of the reactant feed to the fuel cell as well as the dynamics of the load. For a practical size (number of cells) of the fuel cell stack We have already discussed that a fuel cell can provide high electrical current. Even then we may not get the desired voltage for the application. However.Depending upon the requirement we may need:   DC/DC convertor or voltage regulator DC/AC inverter Power Conditioning In BOP. if we some how convert the electrical current into voltage. we may achieve the higher voltage or desired voltage. Moreover. In order to increase as well as to keep the the cell voltage stable at the expense of current. for a desired voltage output we have to make a fuel cell stake with series connection of the cells. humidification. Therefore. We will first discuss about the power regulation then power inversion ion brief. Thus the concept of energy conservation may be used for converting some of the electrical current into electrical voltage. the electrical power provided by a fuel cell is neither stable nor have desired voltage output. Therefore. DC/DC convertors are used A DC/DC convertor use the fluctuating DC fuel cell voltage as input and converts it to a stable DC voltage output which is fixed at a specified voltage as shown in the figure.7V at operating conditions . pressure. and flow rate. Power Regulation In our day-to-day life we have seen that we require electrical power at a specified voltage level that is stable over time also.

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

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

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

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

Commercialization Aspects 1 kW Stationary System .

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845 1.Honda FCX Clarity Specification (for U.835 1.) Length width Car Height Weight Max Speed Cruising Range Type Stack Max Power Volume weight Motor Max Power Max Torque Type Fuel Tank Pressure Outer Volume Inner etimated mm mm mm kg km/h km ----kW L kg kW N-m -----atm L L 4.S.470 1.625 160 620 PEFC 100 62 67 100 256 H2 gas 350 171 18 .