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Model for Polymer Electrolyte Fuel Cell Operation on Reformate Feed:

Effects of CO, H;2 Dilution, and High Fuel Utilization
To cite this article: T. E. Springer et al 2001 J. Electrochem. Soc. 148 A11

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 Journal of The Electrochemical Society, 148 (1) A11-A23 (2001) A11
S0013-4651/2001/148(1)/A11/13/$7.00 © The Electrochemical Society, Inc.

Model for Polymer Electrolyte Fuel Cell Operation on

Reformate Feed
Effects of CO, H2 Dilution, and High Fuel Utilization
T. E. Springer, T. Rockward, T. A. Zawodzinski,* and S. Gottesfeld**,z
Los Alamos National Laboratory, Electronic and Electrochemical Materials and Devices Group, Los Alamos,
New Mexico 87545, USA

We describe a polymer electrolyte fuel cell model emphasizing operation on hydrocarbon reformate, i.e., the anode feed stream con-
sists of dry H2 concentrations as low as 40%, inlet CO levels of 10-100 ppm, and hydrogen fuel utilization as high as 90%. Refine-
ments of interfacial kinetics equations used in our previous work on CO effects in H2 anodes have yielded a better quantitative fit to
the measured dependence of voltage loss on inlet CO level [in Electrode Materials and Processes for Energy Conversion and Stor-
age, J. McBreen, S. Mukerjee, and S. Srinivasan, Editors, PV 97-13, pp. 15-24, The Electrochemical Society Proceedings Series, Pen-
nington, NJ (1997)]. We calculate anode potential losses by coupling such interfacial kinetic processes to reactant diffusion limita-
tions and ionic resistance in the catalyst layer, and by accounting for the drop in local hydrogen concentration along the flow chan-
nel due to significant fuel utilization. As a result of internal readjustment of cell overpotentials when hydrogen concentration drops
along the flow channel, we show that loss of current, or power, under the realistic condition of constant cell voltage is smaller than
loss of current at constant anode potential. We show that voltage losses associated with CO poisoning are significantly amplified with
diluted hydrogen feed streams and particularly so under high fuel utilization. We make projections on improvements required, qual-
itative and quantitative, in the physical parameters of the anode catalyst surface chemistry to significantly improve “CO tolerance.”
© 2000 The Electrochemical Society. S0013-4651(00)03-119-0. All rights reserved.

Manuscript submitted March 27, 2000; revised manuscript received August 29, 2000.

Recently developed fuel cell power systems for transportation ap-
plications have relied on processing of liquid fuels on board the vehi-
cle to generate a hydrogen-rich gas mixture as the feed stream for a
polymer electrolyte fuel cell (PEFC) stack. Steam reforming of meth-
anol and autothermal reforming of gasoline-like fuels have been the
two most commonly considered and investigated systems of on-board
fuel processing. Methanol has the advantage of a relatively low-tem-
perature steam-reforming process, yielding a gas mixture with hydro-
gen at levels as high as 75% of dry gas composition. Gasoline, on the
other hand, has an advantage of relying on an existing fuel infra-
structure but requires significantly higher temperatures for auto-
thermal processing. The latter process yields typical compositions of
35-40% hydrogen in the dry gas mixture (see, for example, Ref. 1) In
both of these fuel-processing systems, water-shift and fuel cleanup
steps follow the steam or autothermal reforming step. These steps
lower CO levels in the product gas mixture from several percent down
to 10-100 ppm as required for use as an anode feed stream in a PEFC
operating at 80⬚C. The anode feed stream in such systems is thus typ-
ified by hydrogen mole fractions (before humidification) ranging
between 0.4 and 0.75 and by the presence of 10-100 ppm CO, a seri-
ous poison of Pt based anode catalysts operating at 80⬚C.
To quantitatively evaluate PEFC stack losses originating from the
combined effects of hydrogen dilution and CO surface poisoning, a
comprehensive model for a PEFC anode is required. Such a model
should elucidate the effects of H2 dilution alone, particularly under
high fuel-utilization conditions, and then treat the implications of
10-100 ppm levels of CO in diluted hydrogen under high-utilization
conditions. We described in an earlier contribution2 modeling of
anode losses incurred by addition of CO at 10-100 ppm levels to a
neat hydrogen anode feed stream. In this paper, we refine parameters
used for these interfacial kinetic equations to achieve better simulta-
neous fitting of experimental data obtained with a range of CO inlet
levels. We next model effects of dilution of hydrogen in inert dilu-
ents (N2 and CO2) under high fuel-utilization conditions, and final-
ly, we model the effects of CO poisoning under such hydrogen dilu-
tion and high-utilization conditions.
The anode model described in this paper is based on physical prin-
ciples whose input parameters have physical meaning. The model can
** Electrochemical Society Active Member.
** Electrochemical Society Fellow.
*z E-mail: gottesfeld@lanl.gov
guide the proper design and operation of a fuel cell power system. It
can be used to study the effects of total anode pressure, temperature,
hydrogen dilution in N2 and/or CO2, and fuel utilization along the
anode flow field. These effects can also be studied under realistic
reformate anode conditions of 10-100 ppm CO levels and under low
or high power demand. We compare model results to data measured
in our laboratory to determine certain parameter values and to show
the ability of the model to reproduce experimental results.
Some recent experimental work focused on surface catalyst deac-
tivation by low levels of CO. In their studies of hydrogen oxidation on
Pt and Pt alloy (Pt/Sn, Pt/Ru) rotating disk electrodes exposed to
H2/CO mixtures, Gasteiger et al 3,4 showed that a small hydrogen oxi-
dation current is observed well before the onset of major CO oxidative
stripping (ca. 0.4 V) on Pt/Ru. However, they concluded that such cur-
rent observed at low anode overpotential was “too low to be of practi-
cal value.” Nonetheless, both others and we5-7 have found experimen-
tally that it is possible to operate a PEFC with a Pt/Ru anode with CO
levels in the range 10-100 ppm at CO voltage losses of the order of
10–100 mV. Such past5-7 fuel cell measurements were not performed
with diluted hydrogen feed streams under high fuel-utilization condi-
tions, where the effects of a given CO level are amplified, as shown in
this paper. These past results suggested that PEFC operation at signif-
icant current densities may be possible in the presence of 10-100 ppm
CO, even without resorting to air bleeding into the anode feed stream.8
The latter approach has been shown to be highly effective in elimina-
tion of Pt anode catalyst poisoning effects at CO levels as high as 500
ppm, in cells operating at 80⬚C with low Pt catalyst loading, at the cost
of 2-4% in cell fuel efficiency. Air bleeding lowers CO partial pressure
to extremely low levels in the anode plenum by catalytic (chemical)
oxidation of CO by dioxygen at the anode catalyst. In this modeling
work we do not include, however, any description of oxygen bleeding
effects and concentrate on the behavior of the anode with feed streams
of limited flow rate (i.e., under high fuel utilization), consisting of H2
diluted in inerts, with or without CO.
Theoretical Anode Model
We initially address the kinetic equations for the catalyst/ionomer
interface that provides local current generation as a function of local
hydrogen and CO concentrations and the local overpotential. Subse-
quently, we address the mass-transport equations that set the local
conditions at the catalyst surface when a cell is operated with diluted
A12 Journal of The Electrochemical Society, 148 (1) A11-A23 (2001)
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hydrogen and at high fuel utilization. We stress again that this model
is intended to study effects of CO in operation on diluted, highly uti-
lized hydrogen fuel when air bleeding is not used.
Kinetic equations for hydrogen anode.—We would like to use a
single set of kinetic equations for all cases of anode feeds. In either
the presence or absence of CO in the anode gas stream, the same
kinetic equations should still be valid. We would also like the kinetic
equations to predict measured cell performance for a variety of CO
concentrations in the feed stream without changing any model para-
meters, other than xco. The kinetic equations are a small fraction of the
modeling code but, in the presence of CO, have a major effect. Where
we have observed some discrepancies between simpler model predic-
tion and experiment, we have invoked modified assumptions that
apparently better describe the actual physical processes occurring. For
example, we have now made some interfacial rate constants be func-
tions of fractional CO coverage on the catalyst sites. We assume that
isothermal conditions exist, that the feed stream is always saturated
with water vapor, and that the kinetic equations are not affected by the
presence of N2 and CO2 except for their effect on the partial pressures
of H2 and CO.
We assume the four processes expressed in Eq. 1-4 determine the
interfacial kinetics. By itself M corresponds to a vacant catalyst site,
otherwise H or CO is attached to the site
kfc
CO ⫹ M o (M-CO) [1]
bfc(␪CO)kfc
kfh(␪CO)
H2 ⫹ 2M o 2(M-H) [2]
bfhkfh(␪CO)
keh
(M-H) r H⫹ ⫹ e⫺ ⫹ M [3]
kec
H2O ⫹ (M-CO) r M ⫹ CO2 ⫹ 2H⫹ ⫹ 2e⫺ [4]
The first two equations represent the competing processes of CO ad-
sorption and dissociative chemisorption of H2. The forward rate con-
stants for hydrogen and CO adsorption, kfh and kfc, are expressed in
A/cm2 (geometric) atm. The desorption rates are implicit in bfc and
bfh, the ratio of backward to forward rate constants with units of at-
mospheres, i.e., the (inverse) equilibrium constants for processes 1
and 2, respectively. As indicated, we assume that the rate constant kfh
and the backward/forward ratio bfc are functions of CO site occupa-
tion. In other words, the desorption rate for CO and the adsorption rate
for hydrogen are assumed to be functions of ␪CO, whereas it was con-
venient to hold the adsorption/desorption rate ratio for hydrogen and
the adsorption rate for CO constant with CO coverage. The hydrogen
and CO electro-oxidation rate constants keh and kec are expressed in
A/cm2 in Eq. 3-4. The third process (Eq. 3) generates the current den-
sity corresponding to anodic hydrogen oxidation, i.e., the electro-
chemical oxidation of adsorbed hydrogen atoms. The fourth process
(Eq. 4), corresponding to the electrochemical oxidation of CO to CO2,
reaches significant rates particularly at high anode overpotential, gen-
erating at such high overpotential a larger number of CO-free catalyst
sites under steady-state conditions. However, we show that even very
low rates of process (Eq. 4), that would apply at low anode potentials,
can be sufficient to significantly increase the rate of hydrogen electro-
oxidation in the presence of CO. Note that in Eq. 4, the oxygen atom
required for complete electro-oxidation of CO is assumed to originate
from a water molecule. Recent analysis by Cairns’ group9 showed that
the overall stoichiometry implied by Eq. 4, i.e., two electrons per
adsorbed CO molecule, indeed appears to apply at Pt catalysts under
the relevant low anode overpotentials [e.g., <200 mV vs. the reference
hydrogen electrode (RHE)]. An initial step of “water discharge” is a
likely rate-determining step in the electro-oxidation of adsorbed CO
at such low anode potentials, forming an active surface oxygen inter-
mediate, e.g., OHads, that subsequently reacts readily with adsorbed
CO. As further discussed later, different rates for this initial step of
water discharge at a given low anode potential is one possible expla-
nation for different degrees of “CO tolerance” exhibited by various
anode catalysts (e.g., PtRu vs. Pt).
Equations 5 and 6 represent the steady-state catalyst surface bal-
ance of adsorption, desorption, and charge-transfer fluxes of CO and
hydrogen. If the intermediate hydrogen step is second order in catalyst
sites, then n ⫽ 2. If it were first order, then n ⫽ 1. The second-order
solution is given here; the first-order solution, considered by Watan-
abes group,10 is presented in Appendix A. These equations determine
␪CO, the fraction of catalyst sites with adsorbed CO, and ␪h, the frac-
tion with adsorbed H at steady state, at anode potential Va. The fluxes
are also all in units of equivalent current density. The quantity ␳ repre-
sents the molar area density of catalyst sites times the Faraday constant
␳␪˙ CO ⫽ kfc x CO PA (1 ⫺ ␪ CO ⫺ ␪ h )
Va ⫹VNernst
⫺ bfc kfc␪ CO ⫺ kec␪ CO e bc
⫽ 0 [5]
␳␪˙ h ⫽ kfh x h PA (1 ⫺ ␪ CO ⫺ ␪ h ) n ⫺ bfh kfh ␪ nh
 V ⫹ VNernst 
⫺ 2␪ h keh sinh  a  ⫽ 0 [6]
 bh 
Va ⫹VNernst
 V ⫹ VNernst 
jh ⫽ 2 keh␪h sinh  a  , jCO ⫽ 2 kec␪CO e bc [7]
 bh 
Current density expressions for hydrogen and CO oxidation, jh and jCO,
are given in Eq. 7 as a function of anode potential Va referenced to a
standard hydrogen electrode (SHE) corrected for local Nernstian po-
tential shift associated with local values of PH2 different than unity. Va
can be negative if the hydrogen partial pressure is greater than 1 atm.
However, Va ⫹ VNernst will never be negative. We assume a transfer
coefficient of 0.5 for the electro-oxidation of hydrogen, reducing the
Butler-Volmer equation to a hyperbolic sine function that allows the
current to approach zero at zero overpotential. Note that the same over-
potential is assumed at a given anodic potential for both Hads and COads
electro-oxidation. This means that both kfh and kfc describe the rate of
the anodic process at 0 V RHE (at full surface coverage by the corre-
sponding surface species). A Tafel relation can be used for the poten-
tial dependence of current density for CO electro-oxidation (Eq. 7).
If all the rate constants are independent of ␪CO, i.e., kfh and bfc are
constant, then an analytic solution for ␪h and ␪CO is given by Eq. 9
with intermediate variables defined in Eq. 8. From the expressions
for jh and jCO in Eq. 7, the kinetic current densities of hydrogen and
of CO electro-oxidation, can now be evaluated
 V ⫹ VNernst 
s1 ⫽ keh sinh  a 
 bh 
Va
a1 ⫽ e bc kec ⫹ kfc (bfc (b fc ⫹ PA x CO )
 Va 
a2 ⫽  e bc kec ⫹ bfc kfc  a3 ⫽ bfh kfh ⫹ 2 s1 [8]
 
 a a a k P x ⫹ a2s2 ⫺ a2s ⫺ a k P x 
 1 2 3 fh A H 1 1 1 1 2 fh A H 
␪H ⫽
kfh (bfh a12 ⫺ a2 PA x H )

kfc PA x CO  a1b fh kfh ⫹ a1s1 ⫺ 2

a2 bfh kfh PA x H ⫹ 2 a2 kfh PA x H s1 ⫹ a12 s12 
 
␪ CO ⫽ [9]
kfh (bfh a12 ⫺ a2 PA x H )
 Journal of The Electrochemical Society, 148 (1) A11-A23 (2001) A13
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(A solution for first-order kinetics at uncovered sites is given in

Appendix A.)
As indicated in Eq. 1, bfc is next made a function of ␪CO. By using
a Temkin isotherm11 Eq. 10 allows the free energy of CO adsorption
to decrease linearly with ␪CO. Use of a Temkin isotherm was advo-
cated originally by Bellows and Marcuchi-Soos12 as a means to
achieve a better fit to the experimentally observed variation of the
critical current with CO level. ␦(⌬GCO) is the difference in adsorption
free energy assumed between ␪CO ⫽ 1 and ␪CO ⫽ 0. Conrad et al.13
have found the binding energy for CO on single-crystal Pd decreased
from 35 kcal/mol at zero coverage to 5 kcal/mol at saturation cover-
age of 0.8. For Pt a decrease from 30 kcal/mol at a surface coverage
of ␪CO ⫽ 0.12-10 kcal/mol at ␪CO ⫽ 0.69 has been found. Other
researchers14 have found the heat of adsorption of CO on Pt 111 to
decline with increasing coverage from 32 to 12 kcal/mol. Thus in
Eq. 10 we express the CO adsorption-to-desorption rates ratio as
␦( ⌬Gco )
␪ co [10]
bfc ⫽ bfc0 e RT

Because the model has been found relatively insensitive to the actu-
al forward rate kfc, we consider it constant. The variation of bfc with
␪CO in Eq. 10, using a ␦(⌬GCO) value of 20 kcal/mol, is needed to
reproduce the proper dependence of the “critical current density”
(current at which the anode potential begins to increase steeply) on
CO partial pressure.
In Eq. 2 we indicate that we also want the H2 dissociative chemi-
sorption rate constant to be a function of ␪CO. This proposed relation
is needed to explain, with the same model, anode polarization results
obtained with hydrogen greatly diluted in inerts (e.g., nitrogen) and
anode polarization results obtained with neat hydrogen containing
10-100 ppm CO. The results with diluted hydrogen imply very high
rates of hydrogen dissociative chemisorption on a CO-free anode
catalyst surface. We found experimentally (to be discussed) that with
only 6% hydrogen in the flow channel, the kinetic limiting rate
derived from the dissociative chemisorption step still significantly
exceeds 1 A/cm2, i.e., it must be of the order of 10 A/cm2, at least.
Consideration of the combined effects of hydrogen dilution by more
than an order of magnitude (6/100) vs. the standard state of 1 atm,
and the limited anode catalyst utilization calculated with such a
diluted hydrogen feed stream (see the following discussion), leads to
the conclusion that kfh must significantly exceed 100 A/cm2, i.e., be
of the order of 1000 A/cm2 under the standard condition PH2 ⫽
1 atm. However, based on the recorded effects of CO, kfh apparently
falls sharply in the presence of partial catalyst surface coverage by
CO, otherwise, limiting currents of less than 1 A/cm2 would not be
expected from Eq. 6 (assuming n ⫽ 2) even at high surface coverage
by CO, contrary to experimental observation of “critical currents.”
To generate an effect of ␪CO on kfh, as required to explain the exper-
imental results, we propose a surface catalyst model described in
Appendix B. Figure 1 shows a plot of bfc and kfh as functions of ␪CO,
using values of ␦(⌬GCO), ␦(⌬EH), and p (see Eq. 10 and B-2) re-
quired to explain our experimental results both without and with CO.
Figure 1. Plot of bfc and kfh as functions of ␪CO (see Eq. 10 and B-2) using
␦(⌬GCO)/RT ⫽ 6.8, ␦(⌬EH)/RT ⫽ 4.6 and p ⫽ 5.
calculates a local current density and anode potential along the
anode flow field, where the local concentrations in the flow channel
have been determined by inlet flow conditions and cell current.
We show in the next section how the current distribution down the
flow channel and the average current density can be calculated as a
function of fuel utilization using this 1D model. (Obviously, the 1D
model also describes the current density of the total cell for the case of
“zero” fuel utilization or very high anode flow rate). Under significant
fuel utilization conditions, we apply the 1D model repeatedly for each
of the various dashed 1D sections in Fig. 2. In each section, the back-
ing inlet composition, the current density, and the anode overpotential
assume different values, even though the cell voltage remains constant
along the flow channel. To avoid confusion, we let J represent current
density in the 1D model with the local value for J varying along the
flow channel, and I represents the average cell current density. As
shown in Fig. 2, the remaining (non-anode) part of the cell is includ-
ed here without detail. We include in this 1D PEFC model a “standard
cathode-membrane voltage,” shown in Fig. 3, which is the cell voltage
vs. current relationship expected at zero anode loss. This standard
curve is used to determine the anode potential at a fixed overall cell
voltage, based on the local anode conditions and all other cell voltage

1D anode model and consideration of fuel utilization.—We turn

now to a description of the transport processes in PEFC anodes oper-
ated on reformate at high fuel utilization. These transport processes
determine the local concentration and local interfacial potential dif-
ference at an anode catalyst site located within the catalyst layer.
Limited rates of such transport processes could be significant
sources of voltage loss for operation with diluted hydrogen. Figure
2 is a schematic diagram of a general PEFC model that is the subject
of this paper. Depicted along the left and right sides of the diagram
are anode and cathode flow channels through which reactant gases
flow vertically downward. Lying horizontally across the cell
between the two flow channels is a series of differential one-dimen-
sional fuel cell sections. A typical 1D section model is depicted at
the bottom. This 1D model has specified anode gas composition at
its left side, an anode gas-diffusion-backing region, a catalyst layer
region, and a “standard cathode-membrane” region. The 1D model Figure 2. PEFC anode model schematic.
A14 Journal of The Electrochemical Society, 148 (1) A11-A23 (2001)
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would be measured at constant anode potential. This is a result of the

“overpotential trade-off” described previously.
As shown at the bottom of Fig. 2, the 1D model consists of three
sections; gas diffusion backing, catalyst layer, and the “standard
cathode-membrane.” We now describe the assumptions and equa-
tions for these sections.

Anode backing layer.—The backing usually consists of carbon

cloth filled with wetproof carbon powder. We assume the gas mole-
cules transported through the backing collide with other gas mole-
cules at much higher frequency than with the surrounding backing
materials. Then the total pressure remains constant and the Stefan-
Maxwell equations (Eq. 11) describe the shift in component mole
fractions xi as a function of steady-state component fluxes ␾i
through the backing. Indexes 1-5 correspond to H2, CO, N2, CO2,
and H2O respectively. If water vapor remained unsaturated with no
liquid water in the backing, the five linear first-order differential
equations can be solved analytically. With the constraint on the fifth
equation, there must be a flux of water vapor ␾5 (Eq. 13) through a
hydrophobic component of the backing that is a function of the mole
Figure 3. Standard cathode-membrane polarization curve, Vstd, used in this
paper to convert the “anode model” to a “cell model.” Vstd ⫽ 0.8177 ⫺
fractions. A corresponding return flux of liquid must flow through
0.1897Jtot ⫺ 0.0176 ⫻ ln[Jtot] ⫺ 1.0077 ⫻ 10⫺5 exp[5.3687]. Vstd is equiv- part of the cross-sectional area. The treatment of saturated water
alent to cell polarization with no anode losses. vapor in a cathode model has been described previously.15 Eliminat-
ing ␾5 from the first four equations makes them nonlinear. Howev-
er, a linear solution with an error of only about 1% is introduced by
losses (represented by the standard curve) at a given current density. holding ␾5 constant at the inlet mole fractions. Resolving the ana-
Such consideration of current continuity through each segment of the lytic solution at the exit conditions for ␾5 verifies this, and averag-
cell converts the PEFC anode model to a PEFC cell model. ing the two solutions eliminates most of the error
Addressing the changing anode conditions as a cell, rather than
∂x i xi ⌽ j ⫺ x j⌽ i
∑
anode, problem reveals an interesting “trade-off” that takes place in V ␶T
reality between anode and other voltage losses. As the H2 mole frac- 1 ⱕ i ⱕ 4: ⫽ S
∂z ⑀TS DSij
tion decreases, the constant cell voltage condition for the 1D model j⫽1
forces an increase in local anode overpotential at the expense of low-
∑ ␣ (x ⌽ ) VS ␶T
ering in combined cathode-membrane overpotential, resulting in a ⫽ ij i j ⫺ x j ⌽ i ; ␣ ij ⫽ [11]
relatively smaller decrease in local current density than that expected ⑀TS DSij
j⫽1
at constant anode potential. This is explained by the example given in
Fig. 4. This figure describes solutions for base-case parameters JH J
(Table I) of the 1D model (discussed in detail later) for a range of ⌽1 ⫽ ; ⌽ 2 ⫽ CO ; ⌽ 3 ⫽ 0; ⌽ 4 ⫽ 0 [12]
2F 2F
concentrations of hydrogen below 40%, representative of flow chan-
∂x 5
∑␣
nel concentrations. Two current density vs. mole fraction curves are
⫽0⫽ 5 j ( x5 ⌽ j ⫺ x j ⌽ 5 );
shown, one at constant Vcell and one at constant Vanode. As seen in ∂z
Fig. 4, current and power losses incurred from hydrogen dilution j⬆1
under conditions of constant overall cell voltage (that always apply to
the segments of a cell in a stack) are seen to be smaller than those that ⌽ 5 ⫽ x 5 ( ␣ 51⌽1 ⫹ ␣ 52 ⌽ 2 ) / ∑␣
j⬆5
5jx j [13]

Anode catalyst layer.—We assume the catalyst layer has a uni-

form effective ionic conductivity ␴ and uniform effective diffusion
coefficients DH and DCO for hydrogen and CO. Local generated
kinetic ionic current densities, jH and jCO from hydrogen and CO
conversion, respectively, are expressed as equivalent A/cm2 per geo-
metric electrode area. Both jH and jCO are functions of CH and CCO
and local overpotential ␩

Table I. The base-case parameters used for the anode model.

bc 0.06 V ᐉcl 5 ⫻ 10⫺4 cm

bh 0.032 V ␴ 0.03 S cm⫺1
bfc0 1.510⫺8 atm kec 1 ⫻ 10⫺8 A cm⫺2
bfh 0.5 keh 4.0 A cm⫺2
DCO 5.34 ⫻ 10⫺5 cm2 s⫺1 kfc 10 A cm⫺2 atm⫺1
DH 2 ⫻ 10⫺4 cm2 s⫺1 kfh 4000 A cm⫺2 atm⫺1
Figure 4. 1D model calculations of the variations of anode potential and cell ⑀/␶ 0.26 Tcell 80⬚C
current density with dry hydrogen mole fraction. Current density is shown for K1 0.8177 V ␦(⌬GCO)/RT 6.8
two cases of (---) constant cell voltage of 0.6 V and (—) constant anode K2 0.1897 ⍀ cm2 Pa 1-3 atm
potential. The constant anode potential corresponds to a H2 mole fraction of K3 0.0176 ⑀/␶ 0.26
0.4. With fall in hydrogen concentration, cell current is seen to fall to a less- K4 1.0077 ⫻ 10⫺5 V ␦(⌬EH)/RT 4.6
er extent under the (realistic) conditions of constant cell voltage, as compared K5 5.3687 cm2 A⫺1
with conditions of constant anode potential. ᐉB 0.03 cm
 Journal of The Electrochemical Society, 148 (1) A11-A23 (2001) A15
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tions of cell voltage and gas composition at the anode flow field/back-
∂ 2 CH jH ᐉ cl 2 FPATS xHF/ B DH
⫽ ; I Dh ⫽ ; ing interface. We next develop a method for obtaining integrated cell
∂y 2 IDh VST ᐉ cl current generated along the flow field where the backing entrance mole
fractions vary as hydrogen and CO are utilized along the flow channel.
xHB/ CL ∂CH Let w be the normalized position variable along the flow field.
CH (0) ⫽ ; (1) ⫽ 0 [14]
xHF/ B ∂y Along the flow field the H2 mole fraction changes so that the rate of
change of H2 flow equals the equivalent H2 current produced per unit
∂ 2 CCO jCO ᐉ cl F/B
2 FPATS xCO DCO length of w. A similar relation for CO exists. We consider as CO cur-
2 ⫽ I ; IDCO ⫽ ; rent that which arises from Eq. 4. We express as f the molar flow of
∂y DCO VS T ᐉ cl
the feed stream normalized to that of a unit area of the fuel cell and
B/ CL
xCO ∂CCO expressed in terms of equivalent current density for hydrogen, or CO
CCO (0) ⫽ ; (1) ⫽ 0 [15] (i.e., multiplied by two times the Faraday constant F). Utilization u is
F/B
xCO ∂y the fraction of fuel gas consumed producing cell current
∂ 2 Va ( jH ⫹ jCO )ᐉcl ∂Va u ⫽ Iave/(xHIN ⫹ x CO
IN
)f IN ⫽ 1 ⫺ [(xH ⫹ xCO)f ]/[(xHIN ⫹ x CO
IN
)f IN] [20]
⫽ ; (0) ⫽ 0; Va (1) ⫽ Vanode [16]
∂y 2 ␴ ∂y The mole fractions xH and xCO correspond to the location where the
Accumulated ionic current densities JH and JCO range from zero average current density reaches Iave, which can be any value of u be-
at the backing interface to the total current density at the membrane tween 0 and 1.
interface. The total current density from H2 and CO electro-oxida- Because only H2 and CO are consumed along the flow field, the
tion at the membrane interface is equal to the respective fluxes times total molar flow rate everywhere is
2F at the backing interface 1 ⫺ x HIN ⫺ x CO
IN
f ⫽ fIN [21]
tot ∂CH tot 1 ⫺ x H ⫺ x CO
J H ⫽ 2 F⌽1 ⫽ ⫺I Dh (0); J CO ⫽ 2 F⌽ 2
∂y and the combined mole fraction of the reacting species is
∂CCO ( x HIN ⫺ x CO
IN
)(1 ⫺ u)
⫽ ⫺I DCO x H ⫹ x CO ⫽ [22]
∂y y⫽0 1 ⫺ ( x HIN ⫺ x CO
IN
)u
[17]
We wish to specify utilization and then determine the total current
␴ ∂␩ density Jtot. Because we do not know the feed rate fIN to achieve this
J tot ⫽ J Htot ⫹ J CO
tot
⫽ [17]
ᐉcl ∂y y⫽1
utilization, it is convenient to switch the integration variable from w,
the position down the flow channel, to u⬘(w), the local utilization
At the membrane interface a relationship for the “standard cathode- down the flow channel
membrane” voltage Vstd as a function of current density is supplied w

∫ (I
to determine Vanode for a given cell voltage, Vcell dw
( x HIN ⫹ x CO
IN
) fIN u ′( w ) ⫽ H ⫹ ICO )dw or
Vanode ⫽ Vstd(Jtot) ⫺ Vcell [18] du ′
0
As explained previously, the purpose of introducing this polarization ( x HIN ⫹ x CO
IN
) fIN
relation for the cathode and membrane in an anode model is to eval- ⫽ [23]
I H ⫹ ICO
uate the anode under the valid constant-cell-voltage condition. To
generate Vstd as a function of current density (Fig. 3), we used an Equating the loss of hydrogen and CO along the flow field to the cur-
experimental PEFC voltage vs. current density relationship using rent produced, we obtain
neat hydrogen feed and an air cathode, corrected for the small anode df
overpotential associated with neat hydrogen operation. The resulting ⫽ ⫺ I H ⫺ ICO [24]
“standard cathode-membrane” voltage vs. current curve was then dw
represented mathematically, choosing a form suggested by Kim dx H f df dx dx
⫽ ⫺ IH ⫽ x H ⫹ f H ⫽ ⫺( I H ⫹ ICO ) x H ⫹ f H
et al.16 that can be fit well with five parameters dw dw dw dw
Vstd(Jtot) ⫽ K1 ⫺ K2Jtot ⫺ K3 ln(Jtot) ⫺ K4 exp [K5Jtot] [19] [25]
dx CO f df dx CO
Equation 19 is used in conjunction with Eq. 18 to determine the local ⫽ ⫺ ICO ⫽ x CO ⫹ f
dw dw dw
value of Vanode and Vstd that generates equal current densities at the
anode and the cathode at a specified cell voltage and local H2 con- dx
⫽ ⫺( I H ⫹ ICO ) x CO ⫹ f CO [26]
centration. dw
To solve the previous nine equations a banded matrix solution By substituting Eq. 21, 23, and 24 into 25 and 26, we obtain deriva-
similar to Newman’s BAND routine was used.17 The catalyst layer tives of w, xH, and xCO with respect to u⬘. However, fIN is not known
region (Eq. 14-16) was divided into a number of nodes, typically 21, so we divide it into w and use the relation that w ⫽ 1 when u ⫽ u⬘
and implicit difference equations were programmed at each node for
each variable. Equations 14-16 plus Eq. 11-13 and 18 for backing  
and cathode technically define the problem. However, the solution d  1 ⫽ 1
[27]
stability was greatly improved by explicitly integrating the current
sources jH and jCO backward through the catalyst layer to get JHtot and ( IN
)
du ′  x H ⫹ x CO fIN 
IN

I H ( x H , x CO ) ⫹ ICO ( x H , x CO )
tot. Passing the total current density from backing to membrane end
JCO
dx H (1 ⫺ x H ⫺ x CO )[ x H ICO ⫺ (1 ⫺ x H ) I H ]( x IN ⫹ x CO
IN
)
of the catalyst layer forced the same current density to be used in the ⫽ [28]
backing and “standard cathode-membrane” and to be consistent with du ′ (1 ⫺ x HIN ⫺ x COIN
)( I H ⫹ ICO )
the current generation. This required introducing three more vari-
ables or “concentrations” to the banded matrix. dx C (1 ⫺ x H ⫺ x CO )[ x CO I H ⫺ (1 ⫺ x CO ) ICO ]( x HIN ⫹ x CO
IN
)
⫽
du ′ (1 ⫺ x H ⫺ x CO )( I H ⫹ ICO )
IN IN
Calculation of cell current under high hydrogen utilization.—The
1D anode model gives us hydrogen and CO current densities as func- [29]
A16 Journal of The Electrochemical Society, 148 (1) A11-A23 (2001)
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Equations 27-29 may be integrated using the fourth-order Runge
Kutta method. The 1D model determines IH and ICO as functions of
Vcell, xH, and xCO. The integration begins at u ⫽ 0 (where fIN is infi-
nite) with xHIN and xCO
IN
and ends at the maximum value of u desired.
We could eliminate Eq. 28 by taking xH from Eq. 22 using xCO
obtained by integrating Eq. 29. The integral of Eq. 27 allows us to
determine the fIN as a function of u. The total current density as a
function of u is then
Iave(u) ⫽ (xHIN ⫹ xCO
IN
)fIN(u)u [30]
Results and Discussion
Interfacial kinetics at a Pt anode catalyst in the presence of
CO.—Critical current density and fit for a range of xCO.—We start
the discussion of our model results with an examination of the inter-
facial reactivity predicted for a hydrogen anode in the presence CO.
We discuss here the general features of this interfacial kinetics
model, while highlighting the effects of the refinement made here vs.
the first version presented in Ref. 1. The model results shown in the
relevant figures are all quantified for a Pt anode catalyst, although
they may also apply for Pt alloy catalysts by making appropriate
changes to the values of one or two of the surface chemistry/electro-
chemistry parameters. We refer to the possible nature of such
changes in several of the examples shown.
A set of IR-corrected cell polarization curves, measured for a
H2/air fuel cell employing a Pt anode catalyst, at various added con-
centrations of CO into the neat H2, is shown in Fig. 5. There is a
region of low current density for which little voltage loss is observed
as a result of addition of CO to hydrogen. This is followed by a much
steeper decline in cell voltage and eventual leveling off at an almost
constant, low cell voltage. The range of little polarization loss at low
current densities is dependent on CO concentration. The lower the
level of CO, the higher is the current density achievable at minimal
voltage loss.
Table I lists the set of representative interfacial-kinetics-model
parameters selected to match such experimental data. Note that the
values chosen reflect basic documented characteristics of this inter-
facial system, e.g., equilibrium coverage by CO is substantial (at
80⬚C) at partial pressures of CO as low as 10-100 ppm (see value
chosen for bfc). The choice of parameters describes a catalyst surface
Figure 5. Measured iR-corrected cell voltage on Pt anode with H2/air fuel
cell at 80⬚C and high stoichiometric flow of hydrogen with various concen-
trations of CO. Experimental conditions: cell active area 5 cm2; temperature:
80⬚C (cell)/105⬚C (anode)/90⬚C (cathode); Pt catalyst loading 0.2 mg/cm2 on
each side; Nafion 117 membrane.
with (i) highly preferential adsorption of CO from a CO/H2 mixture
and (ii) a much higher specific rate per catalyst site at low anodic
potentials for hydrogen electro-oxidation vs. CO electro-oxidation.
These two key features determine the behavior of Pt-based PEFC
anode catalysts when exposed to a mixture of hydrogen with CO in
the 10-100 ppm range.
In the polarization curves of Fig. 5, we refer to the highest cur-
rent density available without a major loss in cell voltage (i.e., a
sharp increase in anode overpotential) as the “limiting” or “critical”
current. This critical current indicates control of the overall rate of
the anode process at the Pt catalyst by the limited rate of the disso-
ciative chemisorption of hydrogen (Eq. 2) occurring on a limited
number of CO-free Pt surface sites. To obtain a simple analytical
expression for this limiting current density, we consider a somewhat
extreme case of the rate of CO electro-oxidation, kec ⫽ 0 (kec is very
small in reality at a Pt catalyst). When kec ⫽ 0, the limiting, or crit-
ical current density, jhl, from Eq. 5-7 when ␪h approaches zero, is
given by
n
 bfc 
jhl ⫽ kfh x h PA (1 ⫺ ␪ CO ) n ⫽ kfh x h PA   [31]
 fc
b ⫹ x CO A 
P
This represents, at given CO partial pressure and cell tempera-
ture, a limit on the current density that can be generated by the anode
with acceptable voltage losses. An interesting conclusion from
Eq. 31 is that for a fixed CO mole fraction, if the order n for free cat-
alyst sites is greater than unity, a lower overall anode pressure PA
increases the limiting current density jhl. This assumes that the CO
partial pressure is equal to or greater than bfc, a condition necessary
for serious poisoning effects. The finding that a limiting current den-
sity of hydrogen oxidation could arise at low anode overpotentials in
the presence of CO was described in the 1975 work by Vogel et al.18
for phosphoric acid fuel cell anodes. In that case the fuel cell tem-
perature was significantly higher (190⬚C) and the relevant CO con-
centrations were much higher (about 1%).
Figure 6 shows a computed set of cell polarization curves using
the system parameter values in Table I. The dashed curves represent a
constant value of bfc, and the solid curves represent the case of bfc in-
creasing with ␪CO to correspond to a decrease of CO adsorption ener-
gy with increasing CO coverage, as described in Fig. 1. Comparing
Fig. 6 to Fig. 5, we see that with constant bfc the performance at high
(250 ppm) CO concentration is predicted to be significantly poorer
than that observed. Assuming bfc varies with ␪CO according to Eq. 10
Figure 6. Cell polarization as function of current density calculated for base
case parameters in Table I for different CO concentrations in the anode feed
stream: (---) constant bfc ⫽ 4.5 ⫻ 10⫺6 atm; (—) use the Fig. 1 relation for
␪CO-dependent bfc. Kinetics order (Eq. 6), n ⫽ 2.
 Journal of The Electrochemical Society, 148 (1) A11-A23 (2001) A17
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raises the critical current density at higher CO concentration and also

lowers it relatively at lower concentrations. This feature of ␪CO depen-
dence on bfc (that we added here to our model, see Ref. 2 for com-
parison), is supported by the documented variation of the heat of
adsorption of CO with CO coverage on Pt and is seen (Fig. 6) to pro-
vide a better fit to the actual experimental behavior. Interestingly, a
similar improvement in the fit to variation of the critical current den-
sity with xCO was achieved if first-order kinetics in free catalyst sites
was assumed in the H2 dissociative chemisorption step, as shown in
Fig. 7. Indeed, with bfc held constant (at a smaller value), the match
to Fig. 5 data appears to be better with n ⫽ 1 than with n ⫽ 2. Exper-
imentally, we have observed, however, poorer performance at higher
overall anode pressure, as seen below in Fig. 7, and (as explained pre-
viously in this section) Eq. 31 indicates that n should therefore be
greater than unity. Hence, use of n ⫽ 2 with variable bfc for modeling
appears to be preferable, although we chose to include Fig. 7 as a pos-
sible indication that reality may lie somewhere between n ⫽ 1 and 2
for the effective order of free catalyst sites in the kinetics of Eq. 2.
[Note: Differential pressure effects on oxygen crossover could not
contribute significantly to the trends seen in Fig. 8, considering the Figure 8. Measured performance with Pt anode at high stoichiometric feed
very low rates of oxygen crossover through the Nafion 1135 mem- rate of 40% H2 with 10 and 20 ppm CO at three anode gauge pressures (air
brane-based membrane electrode assembly (MEA)]. cathode pressure constant at 60 psig). Decreased performance seen with
increasing total anode pressure indicates kinetic order n in free catalyst sites
Interfacial kinetics at a Pt anode catalyst with CO.—Calculated (Eq. 6) is greater than 1. Experimental conditions: cell area 5 cm2; H2 160
effects of variations in key interfacial parameters.—As explained pre- sccm; air 550 sscm; temperature 80⬚C (cell)/105⬚C (anode/90⬚C (cathode); Pt
viously, the current obtained in the low-polarization region is appar- catalyst loading 0.2 mg/cm2 on each side; Nafion 1135 membrane used for
ently generated by hydrogen oxidation at a small fraction of uncovered MEA preparation.
(by CO) catalyst sites. The availability of such uncovered sites is relat-
ed primarily to the equilibrium coverage of the catalyst by CO at the
relevant temperature (i.e., by CO partial pressure and bfc) and by any age as a function of anode potential. The rate of CO electro-oxidation
marginal rate of CO electro-oxidation at low anode overpotentials (i.e., as a function of applied potential is kept at the base-case level of 3 ⫻
by kec). To quantify the possible effects of such factors, we now exam- 10⫺10 A/cm2 at 0 V RHE in all cases, and under such conditions the
ine calculated variations in the polarization curve brought about by rate of CO stripping is calculated to be well below ␮A/cm2 (geom.) in
variations in these model parameters using second-order kinetics at the potential domain of interest (<0.2 V). An increase of bfc, i.e., a drop
free catalyst sites. We specifically explore effects of variations in base- of the equilibrium constant for CO adsorption even to the limited
case values of these parameters for a 40% H2, 50 ppm CO anode feed extent shown in Fig. 9, could substantially improve the performance at
stream at 1 atm, assuming zero fuel utilization. Figure 9 shows the the 50 ppm CO level, as indicated by the fivefold increase of the cal-
effect of varying bfc, the (inverse the) equilibrium constant for CO culated limiting kinetic current density of hydrogen electro-oxidation.
adsorption when bfc is constant (——) and when bfc assumes the ␪CO-
dependent form of Fig. 1 (----). We use the base-case value of bfc0 and
a factor of ten higher. The constant bfc values are chosen to have the
same value as the ␪CO-dependent values at the broad maxima in the
␪CO vs. Vanode curve. Consequently, the constant bfc values exhibit a
ratio of only 2.8. The upper half of Fig. 9 shows the hydrogen and CO
current density and the lower half shows the hydrogen and CO cover-

Figure 7. Modeled performance prediction as in Fig. 6 but using first-order
kinetics in free catalyst sites (n ⫽ 1 in Eq. 6). bfc is fixed here and lowered
to 5 ⫻ 10⫺7 atm.
Figure 9. Effect of increase in base case bfc on fractional CO and Hads cov-
erage (bottom) and hydrogen current density (top). CO concentration is 50
ppm in 40% H2, 35% N2, 25% CO2 at 1 atm. The constant bfc value for the
base case is 4.8 ⫻ 10⫺6 and bfc0 is 1.5 ⫻ 10⫺8 for the ␪-dependent curve.
These are increased by a factor of 10 in the “⫻10 case.” Other model para-
meters have values as in Table I. The abscissa shows anode overpotential vs.
RHE.
A18 Journal of The Electrochemical Society, 148 (1) A11-A23 (2001)
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This increase takes place, as seen from the figure, as a result of lower-
ing of steady-state CO coverage from 0.83 to 0.63 at Vanode near 0.1 V
vs. RHE. This change in bfc might be achieved experimentally by rais-
ing the temperature of the PEFC with a given anode catalyst, or, alter-
natively, by developing novel anode catalysts of lower affinity to CO
at 80⬚C, while maintaining high hydrogen electro-oxidation activity.
Figure 10 shows calculated effects of raising the rate constant for
electrochemical stripping of CO, kec, (process described by Eq. 4) by
one or two orders of magnitude above the very low level of
10⫺8 A/cm2 (geom.) at 0 V, assumed in the base-case. The figure
describes a calculation for 100 ppm CO in H2. The top part of Fig. 10
shows calculated CO stripping currents, the middle part shows the
corresponding steady-state CO coverage as a function of anode
potential, and the bottom part shows the resulting hydrogen oxida-
tion currents as a function of anode potential. Other parameters are
kept at base-case levels (see Table I). It is evident from these curves
that low CO stripping current density of less than 100 ␮A/cm2
(geom.) (i.e., sub ␮A/cm2 Pt), can translate into quite significant
effects on steady-state CO coverage in the relevant anode potential
range and, consequently, into significant hydrogen oxidation current
densities. For example, for the case of kec ⫽ 10⫺8, jCO at an anode
potential of 0.28 V is approximately 100 ␮A/cm2 (geom). This re-
sults in a lowering of CO steady-state coverage to a level sufficient
to enable a hydrogen oxidation current density of 1 A/cm2 at the
same anode potential. The strong effect, of what is still a very low
CO electro-oxidation rate, is a consequence of the high rate of the
hydrogen electro-oxidation process per catalyst site available.
Calculated effects of hydrogen dilution in the complete absence
of CO.—We next address the effects of hydrogen dilution (in inerts)
as projected by our model calculations. Losses associated with lim-
ited protonic conductivity and/or limited hydrogen diffusivity in the
anode catalyst layer generally increase during operation with diluted
hydrogen feed streams because of a redistribution of current genera-
Figure 10. Effect of increase by factor 10, or 100, in rate constant for CO
electro-oxidation on CO electro-oxidation current (top), CO surface coverage
(middle), and hydrogen electro-oxidation current (bottom). Other model
parameters have values as in Table I. The abscissa shows anode overpotential
vs. RHE.
tion through the catalyst layer. We use the model to illustrate this
point by setting base-case parameters for the model and then observe
the implications of varying some of them. Table I lists the base-case
parameters we have selected. Certain of the parameters, such as cat-
alyst layer resistance, Rcl, effective catalyst layer diffusion coeffi-
cients DH and DCO, and gas diffusion backing porosity/tortuosity fac-
tor e/t could be inferred from results of our fuel cell cathode model19
modified for the different gases.
Figure 11 shows a comparison of the anode potential calculated
as a function of current density for neat hydrogen and for 10%
hydrogen in nitrogen at two different values of catalyst layer specif-
ic protonic conductivity, 0.1 and 0.01 S/cm. Note that at 1 A/cm2 the
anode overpotential penalty for hydrogen dilution by a factor of ten
increases from 75 to 100 mV between the higher and lower conduc-
tivity catalyst layers. In Fig. 12 we see the catalyst layer profiles for
the four cases in Fig. 11 depicted at a current density of 1 A/cm2. The
overall anode potential (top plot) is higher for the 10% dry H2 cases,
and the increase in Va across the catalyst layer is more pronounced
in the lower conductivity cases. This is caused by the faster drop in
reactant concentration in the 10% H2 cases that moves peak current
generation toward the backing side of the catalyst layer, consequent-
ly passing the protonic current through greater ionic resistance. A
diluted feed stream is thus seen to generate an increased anode polar-
ization originating from combined concentration and resistance
polarization.
We next compare our 1D model calculations with experimental
anode polarization data obtained with various dilutions of hydrogen
in nitrogen in the range of 30-6% hydrogen under very low fuel uti-
lization. An air cathode was used and anode dilution loss (“anode
overvoltage”) was defined as the lowering of cell voltage vs. that of
the same cell with a neat hydrogen anode. Figure 13 shows the ex-
perimental data. The indicated mole fractions are for dry gas, but the
gas was then fully saturated with water vapor at the cell temperature
of 80⬚C. At low hydrogen concentrations, we see a sharp rise in
anode potential expected to be caused by the limited rate of diffusion
in the backing layer. Figure 14 shows the model predictions for
anode polarization corresponding to the conditions of Fig. 13. A
good match is obtained with the base-case parameters for the inter-
facial process and the anode catalyst layer. Whereas the limiting-cur-
rent behavior could be fully accounted for with the physical backing
properties as shown, it is interesting to note that interfacial kinetics
can also generate, in principle, a limit on jh of kfhxhPA. This follows
from Eq. 6 and 7 for large values of ␩. A high value of kfh0 of 4000 A
cm⫺2 atm⫺1, invoked in our model for the process of hydrogen dis-
sociative chemisorption on CO-free Pt, was dictated by lack of indi-
Figure 11. Anode polarization calculated for neat and 10% H2, at higher and
lower catalyst layer resistance. Assumed conditions are dry gas pressure of
2 atm, 80⬚C; Vanode is vs. SHE.
 Journal of The Electrochemical Society, 148 (1) A11-A23 (2001)
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Figure 12. Distribution in anode catalyst layer of potential, H2 concentration,
and current production at 1 A/cm2 for the four cases in Fig. 11. The backing
interface is at y ⫽ 0 and the membrane interface is at y ⫽ 1.
cation of such kinetic rate limits in operation with the highly diluted
H2 feed streams. Current limits resulting from hydrogen adsorption
were evident in our model calculations if a significantly lower value
of kfh0 were used. (Mass transport in the catalyst layer exacerbates
the effects of dilutions as high as employed in the experiment depict-
ed in Fig. 13 and increases the tendency to generate limiting currents
at lower kfh values.)
Cell losses with realistic feed streams.—As a first step we illus-
trate in this section the consequences of high fuel utilization in oper-
Figure 13. Measured anode loss caused by hydrogen dilution at various
dilutions of hydrogen in nitrogen at 3 atm, 80⬚C (5 cm2 cell). Anode catalyst
Pt/C at 0.2 mg Pt cm⫺2. Anode feed humidified at 105⬚C. Hydrogen flow rate
very high.
A19
Figure 14. Model prediction for results in Fig. 12 using ⑀/␶ ⫽ 0.09 for the
anode backing. Other parameters are from Table I.
ation on a diluted hydrogen inlet stream, still in the absence of CO.
We have selected operating conditions of 1.5 atm pressure, 80⬚C
temperature, 0.6 V cell voltage, and a reformate mixture of 40% H2,
25% CO2, 0% CO, and 35% N2. Basic cell parameters are given in
Table I. Figure 15 describes the predicted performance of this cell as
the hydrogen utilization is varied from 0 to a maximum of 0.9. The
top curve plots the feed rate in equivalent current density for the case
where u⬘ is the utilization at the anode outlet (u ⫽ u⬘). The middle
curve plots the H2 mole fraction at the specified utilization. For the
bottom curve of Fig. 15, because there is a distribution of anode
potentials along the feed path, we describe an effective anode loss,
analogous to Eq. 18 for the 1D model, by means of an effective
anode potential Van,eff which at some average cell current Iave, is
defined as
Van,eff ⫽ Vstd(Iav) ⫺ Vcell [32]
In the bottom plot we show the values of Jlocal and Van,local, the local
current density and anode potential when utilization has reached u⬘,
together with the values of Iave and Van,eff. Jlocal and Van,local, in the
lower part of Fig. 15, correspond to solutions of 1D model sections
depicted in Fig. 2. Each solution uses the overall cell voltage of
0.6 V and an H2 mole fraction xH (top part of Fig. 15) for the corre-
sponding value of u⬘. We see the local current density drops about
32% as the dry mole fraction drops from 0.4 to about 0.053. This rel-
atively small change is sustained because of the relatively large
increase in anode potential from 34 to 102 mV [and the low Tafel
slope for the hydrogen oxidation reaction (HOR)]. This increase in
anode overpotential occurs together with an equivalent decrease in
overvoltage across the cathode membrane, as required to sustain the
constant Vcell of 0.6 V. Such interplay between anode and cathode
overpotentials down the flow channel reduces the penalty for higher
utilization. Although examination of expected local current and
potential variations is instructive, in operation we observe only Iave
and Van,eff. The loss of average cell current and, hence, cell power
density, as a result of raising (40%) H2 utilization from 0 to 90%, is
seen to be only 9.3% at cell voltage of 0.6 V. This is a remarkably
small penalty for high fuel utilization with such a diluted (40% H2)
inlet feed stream, explained basically by the very high interfacial
kinetics of the HOR that enables us to achieve high currents in spite
of very low local concentrations of hydrogen.
To examine more closely the combined implications of hydrogen
dilution and high fuel utilization, the effective anode potential Van,eff,
as defined in Eq. 32, is plotted as a function of current density in
Fig. 16 and 17 for a range of fuel dilution and fuel utilization. (In
Fig. 16, Vloss becomes negative at 3 atm pressure, because the standard
A20 Journal of The Electrochemical Society, 148 (1) A11-A23 (2001)
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Figure 15. Local H2 mole fraction, current density, and anode potential along
the anode flow field plotted as a function of local utilization. Operating con-
dition is 1.5 atm, 40% H2, 25% CO2, 0% CO, and 35% N2 at a cell voltage
of 0.6 V and maximum fuel utilization u ⫽ 0.9. Other parameters are in
Table I.
anode is defined for PH2 ⫽ 1 atm). Figure 16 conditions are replotted
in more familiar terms of cell voltage vs. current density in Fig. 18.
The results of Fig. 18 reveal a cell voltage loss from operation on dilut-
ed hydrogen feed streams at high fuel utilization that can be described
as significant but not overwhelming. Loss near the maximum power
point, relative to operation on neat hydrogen, of either current or volt-
age with the other held constant is about 10% in the most demanding
case of 40% H2 at 90% utilization. The corresponding loss encoun-
tered with 75% H2 inlet is smaller than 5%. If the implication of oper-
ation with gasoline reformate were only the need of a PEFC stack of
Figure 16. Calculated effective anode loss in the absence of CO for three
anode feed streams of neat H2, 75% H2, and 40% H2 (no CO) at utilization
of 0, 0.5, and 0.9.
Figure 17. Same as Fig. 16 but at 3 atm anode pressure.
10% larger volume than that required for operation on neat hydrogen,
it would not amount to a technology barrier of any real significance.
However, having reached such an optimistic conclusion, we note that
both from ourselves and from reports by others to date, it appears that
reaching 90% fuel utilization with such diluted hydrogen feed streams
has not been so straightforward in reality. In the context of stack rather
than single-cell operation, this may reflect nonuniformity of anode
feed flow between cells in the stack under high overall fuel utilization,
bringing about high polarization in some “fuel-starved” cells. We view
the results of the model as indication that a loss of only 10% in max-
imum power between using neat hydrogen and 40% H2 at 90% fuel
utilization should be reachable. However, this apparently requires (i)
sufficiently humidified anode catalyst layers of good transport charac-
teristics, (ii) properly designed anode backing layers, (iii) properly
designed anode manifolds and flow fields, and (iv) that the CO level
in the feed stream is practically zero.
We move now to calculations that consider all causes for anode
loss with realistic anode feed streams: a dilute inlet stream containing
CO and operation under high fuel utilization. Cell voltage vs. current
density plots, calculated for diluted feed streams containing CO, are
shown in Fig. 19 through 21. Whereas dilution and high utilization do
not penalize cell performance very much in the absence of CO, as can
be seen in Fig. 18, the voltage loss under similar conditions could be
large when some CO is present. This amplifying effect that hydrogen
Figure 18. Calculated cell polarization curves for three anode feed streams
of neat H2, 75% H2, and 40% H2 (no CO), under fuel utilization of 0%, 50%,
and 90%.
 Journal of The Electrochemical Society, 148 (1) A11-A23 (2001)
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dilution and high fuel utilization could have on the extent of surface
poisoning by CO can be understood by examining Eq. 31. This equa-
tion shows that the H2 electro-oxidation “limiting” or “critical” cur-
rent density is directly proportional to H2 mole fraction and is not
affected by anode potential. For operation at high fuel utilization, the
hydrogen mole fraction drops along the flow channel to well under
the inlet level, which could itself be as low as 0.4. However, the CO
mole fraction typically remains the same or actually rises, because
CO is not consumed to a significant extent (very low rates of the
process in Eq. 4 at relatively low anode potentials). Figure 15 shows
that the mechanism to correct for the local fall in hydrogen concen-
tration in the absence of CO is a rise in anode potential along the flow
channel. The local current density consequently recovers significant-
ly by boosting the rate of the reaction described by Eq. 3. However,
in the presence of CO, the local “critical” current density at some seg-
ment along the flow channel would be determined by the reaction rate
of Eq. 2, rather than of Eq. 3. The local current in the presence of CO
is therefore proportional to the local low mole fraction of H2 and can-
not be increased above the critical value by raising the local anode
potential. Figure 19 (top, left) shows that at just 10 ppm CO, the crit-
ical current density at a Pt anode catalyst at 80⬚C is 0.8 and 0.4 A/cm2
in operation on 75% hydrogen inlet at 0 and 90% fuel utilization,
respectively. The same figure (bottom, left) shows, for the more dilute
40% hydrogen inlet with just 10 ppm CO, critical current densities of
0.5 and 0.2 A/cm2 at 0 and 90% fuel utilization, respectively. Effects
of a very low inlet CO level of just 10 ppm are thus seen to be sig-
nificantly amplified when the inlet feed is diluted and the fuel uti-
lization is high. Under similar conditions, the situation in cells with
Pt anode catalysts is projected to be much worse at an inlet level of
50 ppm, as seen in the two panels on the right in Fig. 19. Our model
projections depicted in Fig. 19, of strong effects of fuel utilization on
cell performance in the presence of CO, still await full comparison
with experiment. However, trends seen with increased fuel utilization
in the presence of CO are along the lines projected, as can be seen,
for example, from the exceptionally low cell currents measured under
such conditions with 100 ppm CO (see curve on left side of Fig. 21).
Operation with “critical” anode current densities as low as 0.5 A/cm2,
or below, is quite impractical and, consequently, a catalyst with much
better “CO tolerance” is required to provide sufficient performance
under such realistic operation conditions, particularly in the case of
40% hydrogen at high utilization. Alternatively, the air bleeding8
which is apparently employed by most PEFC stack developers to
maintain high performance on reformate feed streams provides a rad-
ical solution by lowering xCO in the anode to practically zero, using
chemical oxidation of CO by dioxygen within the anode.
Figure 19. Fuel utilization effect on cell polarization in presence of CO, cal-
culated using base case parameters at 1 atm, 75% (top) or 40% H2 (bottom)
inlet, with 10 ppm (left), or 50 ppm CO (right). In each case the polarization
curve is calculated for four fuel utilization levels of 0, 0.5, 0.8, and 0.9.
A21
The interfacial parameters we have used in this model up to this
point have been set to match experimental data for (unalloyed) Pt
catalysts. The question remains for improved anode catalysts, known
for better “CO tolerance,” whether the same strong amplification of
CO-related loss is also observed with dilute feed streams at high fuel
utilization. Figure 20 shows the polarization curves for the identical
conditions as the bottom, right plot in Fig. 19, except that kec has
been increased from 1 ⫻ 10⫺8 to 1 ⫻ 10⫺6 A/cm2. This amounts to
an assumption that the advantage of the improved catalyst over Pt is
a significantly higher rate of CO electro-oxidation at low anodic po-
tentials. While still low, such somewhat higher kec values can have a
significant effect on steady-state ␪CO and, hence, on the rate of hy-
drogen oxidation at the CO-covered catalyst surface at a given low
anode potential (see Fig. 10). Figure 20 exhibits milder drops of po-
tential within each polarization curve and smaller penalties with
increased fuel utilization. This is because the assumed increase in
rate of CO electro-oxidation has removed the exclusive control of
the rate of hydrogen electro-oxidation by a chemical process (Eq. 2),
making hydrogen electro-oxidation now under the mixed control of
processes Eq. 2 and 3. Polarization curves with such qualitative pat-
terns of softer drops of cell voltage with current density in the pres-
ence of CO have been reported for PEFCs with PtRu or PtMo anode
catalysts.20 Further possible improvements can be invoked, beyond
what is presented by Fig. 20, with a stronger increase of kec as well
as an increase of bfc. It has been our practical experience, however,
that at 50 ppm CO, the only effective way to avoid excessive voltage
losses under operation with dilute hydrogen at significant fuel uti-
lization is air bleeding. To put the issue of “CO tolerance” in practi-
cal perspective, we finally present in Fig. 21 a recent result for the
performance of a PEFC (single cell) with an inlet of 40% H2 with
100 ppm CO at 70% fuel utilization. This performance was achieved
with an air bleed into the anode inlet at a level of 4%. In terms of the
key parameters of the model described here, the effect of air bleed is
to lower xCO to practically zero by chemical oxidation of CO
adsorbed on anode catalyst sites according to 2COads ⫹ O2 ⫽ 2CO2.
Conclusions
Model for a PEFC with an anode operating on reformate.—We
described here a model for a PEFC with a hydrogen anode that oper-
ates at high fuel utilization on diluted hydrogen feed streams contain-
ing CO. The components of the feed stream, other than hydrogen, can
be carbon dioxide, nitrogen, and carbon monoxide. We assume the
gas mixture is saturated with water vapor at the specified temperature.
The model incorporates diffusion losses in the anode gas diffusion
layer, and diffusion and ohmic losses in the anode catalyst layer, to
define the distribution of hydrogen reactant as a function of location
Figure 20. Fuel utilization effect on cell polarization in the case of 40% H2
feed stream containing 50 ppm CO, calculated for a catalyst which is associ-
ated with 100 times higher kec.
A22 Journal of The Electrochemical Society, 148 (1) A11-A23 (2001)
S0013-4651(00)03-119-0 CCC: $7.00 © The Electrochemical Society, Inc.
along the catalyst layer at given composition in the flow channel adja-
cent to the backing. Having defined local hydrogen and CO concen-
trations, the model provides detailed equations for interfacial kinetics
that apply for hydrogen electro-oxidation at Pt in the presence of CO.
Some refinements of the interfacial kinetic equations employed
by us previously1 to describe anode deactivation in presence of CO
were explored. For the dissociative chemisorption of H2, we first
assumed in Eq. 1 simultaneous involvement of two adjacent Pt cata-
lyst sites (Tafel mechanism).1 When comparing to measured polar-
ization losses, the “critical current” projected by the model dropped
too sharply with a rise in inlet ppm CO. The fit was significantly
improved by introducing a Temkin isotherm to allow the equilibrium
constant for CO adsorption to drop with ␪CO, i.e., allowing the model
parameter bfc to be smaller at higher ␪CO, in line with solid/gas liter-
ature reports. We also found that using a mechanism that assumes
initial H2 adsorption on a single Pt site (Heyrovsky mechanism), the
“critical current” variation with CO concentration could be matched
by assuming bfc independent of ␪CO. The latter result may suggest
that both Tafel and Heyrovsky mechanisms could possibly be oper-
ative. However, a key criterion for order higher than unity in free cat-
alyst sites is met experimentally: measured voltage losses are exac-
erbated with increased total anode pressure at a given ppm CO. This
suggests that the Tafel mechanism with coverage-dependent adsorp-
tion energy for CO is, most probably, the preferred description for
the HOR process in the presence of CO at a Pt catalyst. Along sim-
ilar lines, to use the same kinetic equations of the model both with-
out and with CO, we had to invoke an activation energy for the dis-
sociative chemisorption of hydrogen on Pt that decreases substan-
tially over a group of surface sites around every site covered by CO.
Finally, we provided a method to calculate the cell voltage loss
expected when the anode feed stream consists of diluted hydrogen
and the cell is operated under high fuel utilization. We pointed to the
redistribution of losses along the flow channel, as segments of the
cell closer to the outlet would exhibit higher anode overpotential to
correct, in part, for lower local hydrogen concentrations. Corre-
spondingly, cathode and membrane overpotentials were smaller near
the outlet, maintaining the same overall cell voltage at each point
along the flow channel.
Conclusions
PEFC with anode operating on reformate.—The power loss from
PEFC operation on dilute hydrogen feed streams, as low as 40% in
hydrogen, under high fuel usage, as high as 90%, should not exceed
10% of the stack power obtained in operation on neat hydrogen, as
Figure 21. Fuel tolerance to CO, demonstrated experimentally at 70% fuel
utilization with inlet feed of 40% H2 containing 100 ppm CO. Bleeding air at
4% by volume into such anode feed stream with 100 ppm CO, is seen to
restore the performance back very close to the same level recorded with CO-
free, 40% H2 feed. Precious metal loading in the anode of this cell was
0.6 mg/cm2.
long as the anode feed stream is completely free of CO. One inter-
esting reason for this rather “forgiving” behavior of the cell is that
under constant voltage conditions, the cell tends to readjust anode
losses vs. losses in the remainder of the cell as the hydrogen con-
centration drops along the anode flow channel at high fuel usage.
In contrast, when the level of CO is even as low as 10 ppm, the
losses incurred by CO are amplified significantly as a result of lower-
ing the local concentration of hydrogen and therefore become worse
with a more diluted feed stream and with higher fuel usage levels.
Replacement of Pt by PtRu, or similar, as anode catalyst, is likely
to enable operation with 10 ppm CO in neat hydrogen, and possibly,
in reformate at low fuel utilization. It is less likely that such an anode
catalyst would be sufficient, however, to resolve the “tolerance” prob-
lem even at 10 ppm CO (not to mention higher CO levels) with dilut-
ed anode feed streams and under high fuel utilization. Air bleed there-
fore appears for the moment the most radical approach to minimize
voltage losses in realistic PEFC operation on reformate, for reasons
that become clearer from our model calculations.
Acknowledgments
The authors are indebted to Dr. Mark Paffett for helpful discus-
sions on the effect of hydrogen adsorption rate in the presence of
CO. We also appreciate suggestions from Dr. Richard Bellows that
the model critical current density dependence on CO concentration
might better fit experiment if we used a Temkin rather than a Lang-
muir isotherm. The U.S. Department of Energy, Office of Advanced
Automotive Technology, supported this work.
Los Alamos National Laboratory assisted in meeting the publication
costs of this article.
Appendix A
First-Order Kinetics of a CO Anode
Because the second-order model decreases current more abruptly with
Vanode than the measured data, we also calculated first-order kinetics for Eq. 5-
7. Equation 6 becomes Eq. A-1. The intermediate variables are different
␳␪˙ h ⫽ k fh x h PA (1 ⫺ ␪ CO ⫺ ␪ h ) ⫺ bfh k fh ␪ h
 V ⫹ VNernst 
⫺ 2␪ h k eh sinh a  ⫽ 0 [A-1]
 bh 
Va ⫹VNernst
 V ⫹ VNernst  bc
j h ⫽ 2 k eh ␪ h sinh a  , jCO ⫽ 2 k ec ␪ CO e [A-2]
 bh 
V
 V ⫹ VNernst  a
s2 ⫽ 2 keh sinh a  , a4 ⫽ e bc kec ⫹ kfc bfc
 bh 
a5 ⫽ a4(bfh ⫹ xhPA) ⫹ bfhkfcxCOPA, a6 ⫽ a4 ⫹ kfcxCOPA,
a7 ⫽ kfha5 ⫹ s2a6 [A-3]
a3 k fh x h PA k x P (b k ⫹ s2 ) [A-4]
␪h ⫽ ; ␪ CO ⫽ fc co A fh fh
a7 a7
Appendix B
In deriving a relationship between kfh and ␪CO, we target a unified de-
scription of the hydrogen electro-oxidation rates observed in anode operation
on feed streams of (i) CO-free, very dilute hydrogen (e.g., 5% H2, 95% N2)
and (ii) hydrogen (or “reformate”) containing 10-200 ppm CO. Assuming, as
we did, that the “site-blocking” effect of CO on hydrogen adsorption is
described as (1 ⫺ ␪CO ⫺ ␪h)2 (see Eq. 6), further dependence of kfh on ␪CO in
Eq. 6 is dictated by measured anode activity on the two feed streams de-
scribed previously. If site blocking according to (1 ⫺ ␪CO ⫺ ␪h)2 were the
only effect on the rate of dissociative chemisorption, the very high value of
kfh, concluded from measured anode activity with CO-free diluted hydrogen,
is not compatible with the appearance of limiting currents significantly lower
than 1 A/cm2 in the presence of CO. Hence, we reach our conclusion that a
significant drop of kfh with ␪CO must be added in Eq. 6. The catalyst surface
model described in this Appendix targets a variation of kfh vs. ␪CO of the type
seen in Fig. 1, i.e., a strong drop of kfh with ␪CO at lower CO coverage (␪CO <
0.3), following by leveling off at higher CO coverage. This pattern was found
 Journal of The Electrochemical Society, 148 (1) A11-A23 (2001) A23
S0013-4651(00)03-119-0 CCC: $7.00 © The Electrochemical Society, Inc.

appropriate for accounting for the experimental results. Very strong varia- T temperature, K
tions of Si, the initial sticking probability for dissociative chemisorption of Ts standard temperature 273.15, K
diatomic molecules, have indeed been observed experimentally at low cover- u, u⬘(w) utilization, local utilization Itot /(xHIN ⫹ xIN
CO)/f
IN

age of site-masking agents,21 including the case of H2 on Pt. Monte Carlo Va local anode potential in catalyst layer, V
simulations21 accounted for such observations in terms of domains of sever- Vanode anode potential at membrane interface, V
al surface atoms affected by the “masking agent” and a domain of several sur- VNernst Nernst potential RT ln(PAxh), V
face atoms required for a diatomic molecule to stick effectively. Vs standard molar volume, cm3 mol⫺1
The model described here is based on a similar assumption of an ad- w fractional distance along flow field
sorbed CO molecule having an effect on the rate of dissociative adsorption of x mole fraction
hydrogen at a number of CO-free adjacent sites. The activation energy for y fractional distance through catalyst layer
dissociative chemisorption of H2 is locally increased from the zero CO cov- z distance through backing, cm
erage value by a constant amount ␦(⌬⌭⌯) on sites on and within some radius Superscripts
around each CO-containing site. Let there be a total number of n sites per unit
IN flow field gas inlet
area. Assume p contiguous sites (p ⬇ 4-6) plus the occupied site contribute
INA 1D model backing gas inlet along flow field
to the fraction of coverage ␪A that suffers the ␦(⌬EH) shift. There are n␪CO-
covered sites per unit area, leaving n(1-␪CO) sites available for each CO-cov- Subscripts
ered site to affect. The probability that any single CO site will affect any of H, CO, CO2, N, W components of hydrogen, CO, CO2, N2, and water,
the n(1-␪CO) unoccupied sites is p/n(1 ⫺ ␪CO). Then the probability that any respectively
available site is not affected by all CO occupied sites is h, co components of hydrogen, CO
n␪CO Greek
 p  ␣ij Stefan-Maxwell coefficients, cm s mol⫺1
1 ⫺ ␪ A ⫽ 1 ⫺
 n(1 ⫺ ␪ CO  ␦(⌬EH) change in activation energy for hydrogen dissociative ad-
sorption near CO occupied site
n(1⫺␪co ) p␪co
⋅ p␪co
␦(⌬GCO) variation of free energy of adsorption of CO between zero
 p  p (1⫺␪co ) ⫺
(1⫺␪co ) and full coverage of CO, J mol⫺1
⫽ lim 1 ⫺ ⫽e
n(1 ⫺ ␪ CO  flux of component i in backing, mol cm⫺2 s⫺1
[B-1] ⌽i
n→∞ 
␳ molar area density of catalyst sites, mol cm⫺2
The following function dependence of kfh on ␪CO results ␴ catalyst layer conductivity, ⍀⫺1 cm⫺1
␪CO, ␪h fractional coverage, CO, hydrogen
 ␦( ⌬EH ) 
k fh (␪ CO ) ⫽ k fh0 exp ⫺ ␪A  References
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