EXPERIMENT 3. PROTON EXCHANGE MEMBRANE FUEL CELLS H2/Air Fuel Cell Perform !"e Te#$i!%&Tem'er $ure !

( Rel $i)e Humi(i$* effe"$# Objective The objective of this laboratory is to implement basic experimental and analysis techniques to demonstrate and characterize the performance of a hydrogen PEM fuel cell as a function of temperature and reactant gas humidity levels. BACKGROUND A fuel cell is similar to a battery it uses an electrochemical process to directly convert chemical energy to electricity. !ut" unli#e a battery" a fuel cell ideally $ill not reduce its po$er output as long as fuel and oxidant supply is provided. The technical and environmental advantages offered by the fuel cell li#e high performance characteristics" reliability" durability and clean po$er attract a great deal of interest for commercial applications. Among the fuel cells, PEMFC is particularly interesting for use as a laboratory experiment due to safety and operational advantages. It includes a solid polymer electrolyte that reduces corrosion and avoids electrolyte lea age. A lo! operating temperature is re"uired to allo! "uic start up. #here is no toxic emission and it sho!s a fairly good performance. In Figure $, you can see the cross sectional diagram of a single%cell PEMFC.

Fi%ure +. Cro## #e"$io! of

PEMFC

&n 'igure %" as you can see the membrane is in contact $ith the anode catalyst layer and the cathode catalyst layer. Each catalyst layer is in contact $ith a gas diffusion layer. The heart of the PEM'( is MEA )membrane*electrode*assembly+ $hich includes the membrane" catalyst layers and the gas diffusion layers. 'or the operation of the PEM'( H2 gas as fuel is fed into the anode side of the PEM'(. The oxidant in a fuel cell is O2 )in air or as pure gas+ is fed to the cathode side of the fuel cell. &n order to see ho$ these reactants flo$ through the fuel cell" $e should have a loo# at the components of the fuel cell.

Fi%ure 2. Com'o!e!$# of "ell "urre!$ le (#

#i!%le "ell fuel "ell. ,T-e -e $er#. re !o$ #-o/!0.

!( )ol$ %e #e!#e le (#

As you can see in Figure &, the reactants '(& and )&* flo! through channels machined into graphite plates and migrate through gas diffusion layers to the catalyst surface on both sides of the MEA. +ith the help of the noble metal catalyst in the anode, ( & is oxidi,ed to form protons and electrons. #he protons move through the proton exchange membrane and the electrons travel from the anode through an external circuit causing a flo! of electric current, to the cathode. At the cathode catalyst layer, )& combines !ith the protons that pass through the membrane and !ith the electrons that travel through the external circuit to form !ater and heat. Fuel cells are not limited by the Carnot cycle efficiency as is the case !ith chemical combustion reactions. #he typical overall efficiency for a PEMFC is -./ assuming the availability of pure (&. Fuel cell performance #he fuel cell performance is obtained from Cell voltage '0* vs. current density 'mA1cm&* curves. In Figure 2, you can see a representative fuel cell performance curve at &- oC and $ atm.

Fi%ure 3. Re're#e!$ $i)e fuel "ell 'erform !"e "ur)e !( + $m.

$ 21 2C

#he primary techni"ue for characteri,ing the performance of fuel cell is measurement of the cell voltage as a function of current density. 0oltage '0* vs. current density 'A1cm&* and po!er density '+1cm&* vs. Current density curves to a large extent define the performance characteristics of fuel cell and yield information about cell losses under the operating conditions employed. For a given cell, operating conditions such as the cell temperature, and the composition, flo! rate, temperature and relative humidity of the reactant gases can be readily varied. #he effects of such variations on cell performance can be analy,ed to better characteri,e the properties of the fuel cell. At lo! current densities the ma3ority of the losses are due to inetic limitations at the electrocatalyst surface. In the case of a PEM fuel cell operating !ith pure hydrogen fuel, the high energy barrier associated !ith oxygen reduction reaction at the cathode is the dominate source of losses in the fuel cell at lo! current densities. Cathodic activation losses dominate in this case because the exchange current density, i ., for )& reduction on Pt is approximately $,... times less than the .

exchange current density for hydrogen oxidation of the li"uid fuel is sluggish and for this type of fuel cell, activation losses on both the anode and cathode are significant. As the current density increases, the ohmic 'i4* voltage drop !ithin the cell becomes significant. #his is evident in the linear portion of the polari,ation curve at intermediate current densities. If current interrupt 'or some other method* is used to measure the ohmic resistance ' 4 ohm in 5%cm& * of the cell, the voltage data can be corrected for the ohmic voltage loss by adding the product of the each current density to generate the i4%compensated polari,ation curve. Electrochemical Thermodynamics #he electrochemical oxidation and reduction reactions in a ( &1)& fuel cell dictate the best%attainable performance of a fuel cell. A!o(e re "$io!3 0, C $-o(e re "$io!3 %2,3, 1 ,01 1 , e* 0,3 ,01 1 , e*

T-e o)er ll re "$io!3 0, 1 %2,3, 0,3

As you can see from the above reactions, for every mole of ( & fuel consumed, the cell consumes ..- mole of ) & and produces $ mole of !ater. In addition, & moles of e%6s are produced. 4ecall from your thermodynamic bac ground7 d89 %:d# ; 0dP < d+Elect. At constant temperature and pressure7 d89 %d+Elect.

+Elect.9=8.rxn +Elect.9 % E Q >9 n F constant*

'electrical !or 'E? potential,

done by moving charge > 'coulombs* >9 charge*

through an electrical potential difference* 'n? number of moles of e %6s produced, F? Faraday@s

#he conductivity of perfluorinated membranes such as AafionB is strongly dependent on the level of hydration in the membrane. Co! ionic conductivity due to lo! membrane !ater content causes high ohmic voltage loss leading to reduced cell performance. #herefore, in practice, reactant gases are humidified to maintain a !ell%hydrated membrane to prevent excessive dehydration despite formation of !ater at the cathode as the product of reaction. An excess of !ater, ho!ever, could flood the electrode, resulting in severe transport limitations and reducing 'and1or interrupting* the performance and po!er output of the cell. Care must be ta en to maintain the proper !ater balance to ensure lo! ohmic losses and mass transport losses. +hen proton exchange membranes are sub3ected to temperatures above $..D( at atmospheric pressure" their conductivity decreases significantly due to dehydration. )!ecause $ater boils at $..D( at % atm" humidifier de$ points must be belo$ this temperature to ensure that some reactant partial pressure is maintained" thereby lo$ering the inlet relative humidity to less than %445+. This problem can be alleviated by operation the cell at higher pressures" although pressurization is not desirable for fuel cell systems due to the parasitic compressor po$er requirement. The resistance of the membrane can also increase due to dehydration at the anode. This occurs $hen electro*osmotic drag of $ater by protons migrating through the membrane exceeds transport of neutral $ater molecules in the opposite direction from the cathode to the anode. This phenomenon is most prominent at high current densities" typically 6 % A2 cm&. The rate of electro*osmotic drag of $ater from anode to cathode depends on the inherent properties of the ionomer and the operating temperature but not on the thic#ness 7

of the membrane. 0o$ever" thinner membranes tend to establish a more uniform distribution $ith the overall effect that thinner membranes tend to less susceptibility of anode dehydration at high current density. Factors affecting the performance of a single-cell fuel cell: 8oltage vs.current density relationship )'igure -+ Efficiency 9eactant utilization Po$er density

The :ernst equation is used to calculate theoretical cell voltage )E theor+ at non*standard conditions )conditions $herein the activity of the reactants and2or products are not equal to %+. !ased on the 0,23, cell;

E theor = E 4 theor +)

) PH , +) PO, +% 2 , RT + ln nF PH ,4

Etheor< theoretical cell voltage at non*standard concentrations and at temperature T" volts E4theor< theoretical cell voltage at standard concentrations and at temperature T" volts 9< gas constant )=.-%. >2mol?+ T< temperature" ? '< 'araday@s constant" A7.=/ (2equivalent n< moles of electrons produced per mole of 0 , reacted )n<, for the PEM'( rxn." equivalent2mole+ The above equation assumes that the activity of the species is equal to the partial pressures of the species. Voltage vs.Cu ent densit! elationshi" #$ola i%ation cu ves&

Bhen an external resistance )C3AD+ is applied to the cell" nonequilibrium exists and a net current flo$s through the load. The net rate of an electrochemical reaction is proportional to the current density )current of the electrochemical system2active area of the device+. The cell voltage becomes smaller as the net reaction rate increases because of the irreversible loses. These loses are due to #inetic activation resistance" ohmic resistance and transport resistance. Cell '((icienc!

) Cu ent e((icienc!
i = Actual current produced Theoretical current that should be produced for a given feed rate

Voltage e((icienc!
E Actual cell voltage = (ECC Theoretical cell voltage E T0E39

v =

*a+i,u, Cell Voltage

Theoretica lcell voltage Thermoneutral potential

max

The phenomena of maximum cell voltage here should be clarified. The total chemical energy of a fuel cell reaction is given by the change of enthalpy of the reaction. &f all the chemical energy could generate electricity" the cell voltage $ould be %..= 8 based on the heat of formation of liquid $ater at standard conditions. This is called the thermoneutral potential. 0o$ever" only the change in the Fibbs free energy contributes to the theoretical cell voltage. The difference bet$een these t$o quantities is energy that is liberated as $aste heat. This effect ma#es a maximum possible efficiency. The 38E9ACC 'GEC (ECC E''&(&E:(H; i v max $o-e densit!. i V Utili%ation o( eactants
:=
.
.

& n'

N < reactant consumption or product production rate )mole2s+

&< current" A )(oulomb2s+ n< moles of electrons exchanged per mole of species" equivalent2mole '< 'araday@s constant" A7.=/ (oulomb2equivalent Io" from the above relation
N H, =
.

% )n< , eq2mole 0,+ ,F

N O, =

% .F

)n< . eq.2mole 3,+

Procedure /. C l"ul $e $-e flo/ r $e# of H2 !( ir i! L/mi! for + A/"m2. 2. *easu e cell "e (o ,ance #cell voltage vs. cu ent densit!& at di((e ent o"e ating conditions #"ola i%ation cu ves&. Chec0 the e" oducibilit! o( the esults. NO1'. Do not (o get that !ou -ill be given a 2ui% at the 3beginning4 o( the (i st da!5 :ote that JJ2JJ2JJ represents the Anode humidifier temperature 2 (ell temperature2 (athode humidifier temperature. DA6 / a. '((ect o( O"e ating 1e,"e atu e at /778 elative hu,idit! Bith 74274274 K =42=42=4 conditions using air at the cathode" ma#e the Ican (urrent Experiments and obtain the follo$ing; 'ull Performance curve; (urrent density from 4 to E44 mA2cm, at -/ mA2cm, increments. 4. Effe"$ of G # Flo/r $e3 Bith a cell temperature of =4 4(" vary the gas flo$rate and ma#e 'ull Performance curve analysis. DA6 2 '((ect o( Cell Hu,idi(ication at constant cell te,"e atu e Bith a cell temperature of =4 4(" by estimating the temperatures for anode and cathode humidifier temperatures from steam tables at 745 relative humidity" ma#e 'ull Performance curve analysis.

3. Re#ul$#

!( A! l*#i# Calculate the hydrogen and oxygen partial pressure,

A! l*#i# of Fuel Cell Perform !"e theoretical reversible potential at each condition. Calculate the theoretical reversible cell voltage at each temperature. Compare the theoretical reversible cell voltage E theor to the experimentally observed open circuit voltage. Explain !hat open circuit voltage is (alculate po$er at 4./ 8 (ompare ho$ cell resistance changes $ith temperature at %445 humidification. Bhich operating parameter Ltemperature or humidification* has a greater influence on the performance of the cellM Bhat is the effect of gas flo$rate on performanceM Bhat is the proton conductivity of nafionM 0o$ many electrons are generated in an experiment of %/ minutes at a flo$ rate of % slpm hydrogen.M Bhat is the maximum current that can be generated at this flo$rateM Bhat is the concentration of hydrogen in the laboratory room after a period of , hours at a flo$rate of % slpm and a conversion of /45M Bhat is the efficiency of the fuel cellM

%4

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