Journal of The Electrochemical Society, 152 共3兲 A635-A644 共2005兲 A635

0013-4651/2005/152共3兲/A635/10/$7.00 © The Electrochemical Society, Inc.

Analysis of Polarization Curves to Evaluate Polarization

Sources in HydrogenÕAir PEM Fuel Cells
Minkmas V. Williams,*,z H. Russell Kunz,** and James M. Fenton**
Department of Chemical Engineering, University of Connecticut, Storrs, Connecticut 06269, USA

A step-by-step technique to evaluate six sources of polarization, mainly associated with the cathode, in hydrogen/air proton
exchange membrane fuel cells is demonstrated. The six sources of polarization were nonelectrode ohmic overpotential, electrode
ohmic overpotential, nonelectrode concentration overpotential, electrode concentration overpotential, activation overpotential from
the Tafel slope, and activation overpotential from catalyst activity. The technique is demonstrated as applied in the analysis of
hydrogen/air polarization curves of an in-house membrane electrode assembly 共MEA兲 using hydrogen/oxygen polarization curves
as a diagnostic tool. The analysis results are discussed at three cell temperature/relative humidity 共RH兲/oxygen partial pressure
(pO2 , atm兲 conditions at atmospheric pressure: 80°C/100% RHanode/75% RHcathode /pO2 ⫽ 0.136, 100°C/70% RH/pO2 ⫽ 0.064,
and 120°C/35% RH/pO2 ⫽ 0.064, which represent a near fully-humidified, a moderately humidified, and a low humidified con-
dition, respectively. At the higher temperature operating conditions the RH and pO2 decrease resulting in higher electrode ohmic
resistance 共0.020, 0.020, and 0.035 ⍀ cm2, respectively兲, lower limiting current 共2019, 1314, and 819 mA/cm2, respectively兲, and
lower onset current density for significant electrode concentration overpotential 共80, 60, and 40 mA/cm2, respectively兲. The
technique is useful for diagnosing the main sources of loss in MEA development work, especially for high temperature/low
relative humidity operation where several sources of loss are present simultaneously.
© 2005 The Electrochemical Society. 关DOI: 10.1149/1.1860034兴 All rights reserved.

Manuscript submitted March 29, 2004; revised manuscript received September 17, 2004. Available electronically January 31,
2005.

Classification of PEM fuel cell losses.—Useful electrical energy
is obtained from a fuel cell only when a reasonable current is drawn
from it, but the actual cell voltage decreases from its equilibrium
cell voltage because of irreversible losses.1 These losses are called
polarization when the cell voltage is compared with the experimen-
tal equilibrium cell voltage and called overpotential 共␩兲 when it is
compared with the theoretical equilibrium cell voltage according to
the Nernst equation. The terms polarization and overpotential are
often used interchangeably to refer to voltage losses in general.
In proton exchange membrane 共PEM兲 fuel cells, the losses ori-
ginate primarily from the following three sources1: activation over-
potential (␩ act), ohmic overpotential (␩ ohm), and concentration
overpotential (␩ conc). Activation overpotential is associated with
sluggish reaction kinetics and low catalyst activity. Ohmic overpo-
tential is associated with resistance to proton and/or electron trans-
port. Concentration overpotential is associated with reactant trans-
port resistance to the catalytically active sites.
Sources of polarization for the various components of a mem-
brane electrode assembly 共MEA兲 are shown in Table I. The elec-
trode is where the electrochemical reaction occurs and reactants are
consumed. Hydrogen oxidation occurs in the anode electrode and
oxygen reduction occurs in the cathode electrode of a hydrogen/air
PEM fuel cell. The other components of an MEA outside the elec-
trode are called nonelectrode, since there is no reaction and con-
sumption of reactants. Table I shows that each electrode has activa-
tion overpotential, ohmic overpotential 共transport of both proton and
electron兲, and concentration overpotential. In the nonelectrode por-
tion of either the anode or the cathode, there are ohmic overpotential
共transport of electrons only兲 and concentration overpotential when
there is no consumption.
There are other polarization sources beyond the scope of these
primary three sources, called other sources, which are those associ-
ated with hydrogen crossover 关fuel crossover 共through membrane兲兴,
oxidation of platinum, carbon, and other impurities 关mixed potential
共cathode兲兴, and internal short circuit. These other sources are typi-
cally significant only at a low level of current and high cathode
potentials.
Hydrogen crossover is the hydrogen that transports directly from
the anode through the membrane to the cathode 共this is, hydrogen
* Electrochemical Society Student Member.
** Electrochemical Society Active Member.
z
E-mail: minkmas@engr.uconn.edu
that is not oxidized at the anode兲. The rate of hydrogen crossover
depends on electrolyte membrane characteristics, operating condi-
tions, and membrane thickness. Oxidation of platinum, carbon, and
other impurities can occur at high cathode potential. Thus, at low
levels of current and high potentials, the polarization of an electrode
is controlled by a mixed potential2 between the reduction of oxygen
and oxidation of hydrogen that crosses over, platinum, carbon, and
possible impurities. In addition to contributing to the mixed poten-
tial, hydrogen crossover also reduces the net current by the equiva-
lent faradaic current that is lost. If the membrane is designed prop-
erly, the lost current 共⬍5 mA/cm2 under most conditions兲 is
important only at low current density.
An internal short circuit occurs when there is an electrically con-
ductive path through the membrane enabling some electrons pro-
duced at the anode to travel through the membrane instead of by the
external circuit. Influence of a small short circuit is prevalent only at
low current density where the net current is of the same order as the
shorted current. Table I summarizes all these polarization sources
according to the locations where they occur.
Assumptions in the analysis.—The step-by-step analysis tech-
nique is based on a few assumptions; a first order cathode reaction
with respect to oxygen concentration, Butler-Volmer equation kinet-
ics, oxygen transport by Fickian diffusion in gas phase, no signifi-
cant anode polarization, and no electrical short circuit.
The first-order cathode reaction is evaluated at constant ohmic-
corrected potential. The reaction order includes both kinetically and
thermodynamically induced changes in current density with oxygen
concentration. The assumption of negligible anode polarization is
valid since the hydrogen oxidation reaction has orders of magnitude
higher exchange current density (i o) than the sluggish oxygen re-
duction reaction, hydrogen is a much smaller molecule than oxygen
which imposes less concentration polarization, and there is no inert
gas in the anode feed 共typically pure hydrogen兲.3 The assumptions
associated with reaction kinetics and transport have been commonly
used in several previous modeling studies where their validity has
been demonstrated.4,5 First order oxygen reduction reaction has been
verified in phosphoric acid fuel cells.6
If there is an internal short circuit of the cell, this technique
cannot be used because short circuits tend to increase progressively
over time causing errors that cannot be estimated. Verification of no
internal short circuit can be done using a linear sweep voltammetry
technique previously described.7 No short circuit should be verified
before one attempts to analyze any polarization curves.

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 A636 Journal of The Electrochemical Society, 152 共3兲 A635-A644 共2005兲
Table I. Classification of polarization sources. Those with gray backgrounds are not determined using the technique described in this study.
Electrode
Primarily Anode Activation
by Ohmic (H⫹, e⫺)
activation Concentration 共with consumption兲
ohmic Membrane
concentration Cathode Activation—␩ activity , ␩ act,Tafel
Ohmic (H⫹, e⫺) ⫺ ␩ ohm,electrode
Concentration 共with consumption兲—␩ conc,electrode
Other sources Mixed potential 共cathode兲
Due to the assumptions, the parameters shown in Table I with
gray background are those that cannot be evaluated in this analysis.
Fortunately in the development of a high performing membrane
electrode assembly these losses are negligible.
Six polarization sources to be evaluated.—The six polarization
sources in the cathode and the membrane to be determined using the
analysis technique are defined as follows:
␩ ohm,nonelectrode—Nonelectrode ohmic overpotential, associated
with all pure resistances outside the cathode electrode; comprises
proton resistance of the membrane, electronic resistance of the gas
diffusion layer, and all contact resistances between components
␩ ohm,electrode—Cathode electrode ohmic overpotential, associated
with resistance of proton and electron transport through the cathode
electrode
␩ conc,nonelectrode—Nonelectrode concentration overpotential, asso-
ciated with oxygen transport resistance through layers where oxygen
is not consumed; the gas diffusion layer and the thin ionomer film at
the cathode electrode surface next to the gas diffusion layer 共GDL兲
␩ conc,electrode—Cathode electrode concentration overpotential, as-
sociated with oxygen transport resistance through the cathode elec-
trode where it is consumed
␩ act,Tafel—Cathode activation overpotential from the Tafel slope,
associated with the oxygen reduction reaction kinetics
␩ activity—Cathode activation overpotential from catalyst activity,
associated with losses at very low current density
Table I also shows the polarization sources that contribute to
each of these six sources of performance loss. By collecting polar-
ization curves using both oxygen and air as reactant, then system-
atically analyzing them together with the six-step analysis technique
yet to be described, these six polarization voltage losses can be
determined.
The technique is demonstrated through analysis of polarization
curves collected from a single MEA at three operating conditions
共change in relative humidity and temperature兲. The MEA prepara-
tion and polarization curve measurement are described below.
Experimental
Preparation of membrane electrode assembly (MEA).—Extruded
Nafion 112 (50 ⫾ 2 ␮m in thickness兲 supplied by Ion Power Corp.
共Bear, DE兲 was used as the electrolyte membrane. Catalyst-coated
membranes were prepared by spraying both the anode and the cath-
ode catalyst layers directly onto the membrane. The cathode cata-
lysts were 46 wt % Pt/C and the anode catalysts were 30.1 wt %
Pt/23.3 wt % Ru/C, each with a Nafion loading of 35 wt %. Both
types of catalyst were supplied by Tanaka Kikinzoku Kogyo 共Tokyo,
Japan兲. Five percent Nafion solution of 1100 EW 共Solution Technol-
ogy, Mendenhall, PA兲 was added into the electrodes. The solvent
used in the catalyst ink preparation was a mixture of water and
methanol. The catalyst ink was magnetically stirred for 24-48 h until
well mixed. Cathode and anode loadings of precious metals were
0.46 and 0.48 mg/cm2 for the cathode and the anode, respectively.
The catalyst-coated membrane was heat treated at 105°C for 3 min.
The gas diffusion layers are double layers consisting of a
macroporous TGPH-120 carbon paper and a microporous layer con-
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Non-electrode
Ohmic (e⫺)
Concentration 共without consumption兲
Ohmic (H⫹) ⫺ ␩ ohm,non-electrode
Ohmic (e⫺) ⫺ ␩ ohm,non-electrode
Concentration 共without consumption兲—␩ conc,non-electrode
Fuel crossover 共through membrane兲
Internal short circuit 共overall兲
taining Vulcan XC-72R 共Cabot Corporation, Billerica, MA兲 and
polytetrafluoroethylene. The gas diffusion layers were prepared in-
house using a silk screening technique in applying the microporous
layer on the macroporous carbon paper similar to what has been
previously described.8 Total thickness of each gas diffusion layer is
0.39 mm. The catalyst-coated membrane was sandwiched between
two gas diffusion layers, without hot pressing, to obtain a 5 cm2
MEA for single-cell polarization measurement. The graphite flow
field used was a single-serpentine pattern with an active area of 6.25
cm2.
Teflon gaskets were used as a seal. They were also used to
achieve a sufficient amount of compression on the MEA so that all
components established intimate contact between each other to
minimize contact losses. Pinch is defined as the difference between
the MEA thickness 共catalyst-coated membrane and two GDLs兲 and
the total thickness of the nearly incompressible gaskets. The higher
the pinch, the more compressive force was obtained through the
compression of the elastic gas diffusion layers. A total pinch of 0.33
mm was used. The torque on all bolts of the cell hardware was 3.4
N m.
Polarization curve measurement.—Polarization curves were ob-
tained by stepping the current from zero to the maximum test cur-
rent density with an increment between 10 and 100 mA/cm2. The
maximum test current density is either the maximum current limit of
the instrument load box or the current density where cell voltage
goes below a minimum set point of 0.1 V. Time spent at each current
density was 5 min. A 10A model 890B Scribner load box 共Scribner
Associates, Southern Pines, NC兲, which has built-in current interrupt
resistance measurement, was used for polarization measurements.
The MEA, prepared as described above, was tested at three dif-
ferent operating conditions, at atmospheric pressure: 80°C cell
temperature/100% RH anode/75% RH cathode, 100°C cell
temperature/70% RH anode/70% RH cathode, and 120°C cell
temperature/35% RH anode/35% RH cathode. Table II summarizes
the three operating conditions in terms of cell temperature, humidi-
fier temperatures, inlet relative humidity 共RH兲, inlet oxygen partial
pressure (pO2 ), and inlet hydrogen partial pressure (pH2 ). The nota-
tions to be used throughout the paper in referring to these conditions
are 80°C/100% RHan/75% RHcat, 100°C/70% RH, and 120°C/35%
RH, respectively. The three conditions represent a near fully humidi-
fied, a moderately humidified, and a low-humidified condition, re-
spectively.
The anode and the cathode gas line temperatures were set at
10°C above the cell temperature to ensure no water condensation in
the inlet gas lines. Even though air is the only practical oxidant for
fuel cells, oxygen was also used for diagnostics. The fuel was pure
hydrogen, certified grade of 99.999%. The following constant reac-
tant utilization conditions were used as the current was varied: 33%
hydrogen utilization, 25% oxygen utilization for air, and 5% oxygen
utilization for oxygen. Since current density is assumed uniform
throughout the whole active area of the MEA in this analysis, the
technique can be used with reasonable accuracy up to reactant uti-
lizations of 60%. Beyond this, there is a significant difference of
reactant concentration between the inlet and the exit of the flow
 Journal of The Electrochemical Society, 152 共3兲 A635-A644 共2005兲 A637

Table II. Three operating conditions where polarization curves are collected, all at atmospheric pressure „V eq is the equilibrium cell voltage
calculated from the Nernst equation….

T humidifier T humidifier Inlet RH Inlet RH Inlet pO2 Inlet pO2 Theoretical Theoretical Theoretical
T cell Cathode Anode Cathode Anode in oxygen in air Inlet pH2 V eq in oxygen V eq in air Tafel slope
共°C兲 共°C兲 共°C兲 共%兲 共%兲 共atm兲 共atm兲 共atm兲 共V兲 共V兲 共mV/dec兲
80 80 73 75 100 0.650 0.136 0.532 1.176 1.153 70
100 90 90 70 70 0.307 0.064 0.307 1.119 1.094 74
120 90 90 35 35 0.307 0.064 0.307 1.112 1.086 78

fields that additional correction to accommodate spatial current dis- V cell ⫽ V eq ⫺ 关 ␩ activity ⫹ ␩ act,Tafel ⫹ ␩ conc,electrode ⫹ ␩ conc,nonelectrode
tribution throughout the active area would be needed.
Cell internal resistance was measured and recorded at current ⫹ ␩ ohm,electrode ⫹ ␩ ohm,nonelectrode兴 关3兴
densities higher than 100 mA/cm2 using the current interruption
technique of the load box along with the Scribner V.3.1b Fuel Cell Even though these six sources of polarization are coupled and
Software 共Scribner Associates, Southern Pines, NC兲. Resistance val- cannot be separated completely from each other, the analysis tech-
ues at lower than 100 mA/cm2 were not measured, because the nique to be described below provides a reasonable estimation of
voltage loss in that small current range was too small to accurately
measure.
Results
Polarization curves.—Figure 1a, b, and c show polarization
curves 共plotted as cell voltage as a function of the logarithm of
current density兲 using air and oxygen in comparison at the 80 the
100, and the 120°C conditions, respectively. The polarization curves
at the 120°C/35% RH condition are used in demonstrating the tech-
nique. Six polarization sources are extracted from the air polariza-
tion curve with the use of the oxygen polarization curve as a diag-
nostic tool.
Demonstration of the six-step analysis technique.—When a fuel
cell is operated at a current density higher than zero, the cell voltage
departs from the equilibrium cell voltage due to cell polarization in
the amount represented by overpotential. The actual cell voltage can
be written as

V cell ⫽ V eq ⫺ ␩ 关1兴

where V cell is the experimental cell voltage from an experimental

polarization curve, V eq , the theoretical equilibrium cell voltage, ␩,
the total overpotential, and V eq equals the difference between the
cathode equilibrium potential and the anode equilibrium potential.
V eq is a function of operating conditions, i.e., oxygen partial pres-
sure, hydrogen partial pressure, water partial pressure, and cell tem-
perature, according to the Nernst equation9
1/2
RT pH2 pO 2
V eq ⫽ V 0eq ⫹ ln 关2兴
2F pH2 O

where V 0eq is the equilibrium cell voltage at the cell operating tem-
perature and unit activity of reactants and products 共V兲, T, the cell
operating temperature 共K兲, R, the ideal gas constant ⫽ 8.314 共J/mol-
K兲, F, the Faraday’s constant ⫽ 96,485 共C/equiv兲, pH2 , the inlet
hydrogen partial pressure 共atm兲, pO2 , the inlet oxygen partial pres-
sure 共atm兲, pH2 O , the inlet water partial pressure of the cathode
共atm兲.
It is important to note that the theoretical equilibrium cell voltage
V eq is not the same as the experimental equilibrium cell voltage
known as the open circuit voltage (V ocv). V ocv is the equilibrium cell
voltage as a result of a cathode mixed potential between the reduc-
tion of oxygen and the oxidation of hydrogen that crosses over to the
cathode, platinum, carbon, and other impurities, therefore V ocv is Figure 1. Polarization curves and cell internal resistance (R nonelectrode , ob-
usually significantly lower than V eq . tained from current interruption technique兲 of oxygen and air in comparisons
Since the total overpotential 共␩兲 comprises the six sources of at 共a兲 80°C/100% RHan/75% RHcat, 共b兲 100°C/70% RH, and 共c兲 120°C/35%
polarization defined above, Eq. 1 can be written as RH, all at atmospheric pressure.

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 A638 Journal of The Electrochemical Society, 152 共3兲 A635-A644 共2005兲
each source. The inlet hydrogen partial pressure, inlet oxygen con-
centration, and the calculated V eq for air and oxygen are summarized
in Table II. With a known V eq , each of those polarization sources
can be determined step-by-step as follows:
Step 1. Determination of the nonelectrode ohmic overpotential
(␩ohm,nonelectrode).—The ohmic loss due to the nonelectrode portion is
determined through measuring the nonelectrode ohmic resistance
(R nonelectrode), using a technique called current interruption. In the
current interruption technique, current is interrupted from the elec-
trochemical cell for a short time, on the order of microseconds, so
that the voltage drop across the nonelectrode components is reduced
to zero 共as the current is zero兲, and the measured polarization is that
of the electrode itself. The electrode polarization is typically mea-
sured a few microseconds after the current is interrupted. When the
interrupted time is that short, the exponential decay due to leakage
across the double-layer capacitance in the form of the faradaic reac-
tions taking place at the electrode can be assumed negligible.
It is important to note that the cell voltage after the current is
interrupted equals that of the electrode only when there is negligible
electrical resistance in the electrode. If the electrical resistance in the
electrode is not negligible, the current interrupt resistance will not
only consist of the nonelectrode resistance, but also additional elec-
trical resistance that cannot be deconvoluted using this analysis
technique. In most cases the Pt/C catalyst provides sufficient elec-
tron conductivity and the gas diffusion layer is sufficiently smooth
that the electrical ohmic loss in the electrode is negligible. However,
one needs to be aware that an extremely poor electrode or an ex-
tremely rough gas diffusion layer can induce errors in the nonelec-
trode resistance.
The cell voltage before and after the interruption gives the value
of R nonelectrode , therefore
␩ ohm,nonelectrode ⫽ iR nonelectrode
where R nonelectrode is the nonelectrode ohmic resistance, also called
cell internal resistance, determined from the current interruption
technique, and i, the operating current density.
R nonelectrode comprises the proton resistance of the membrane
electrolyte, electrical resistance of the GDL, and all contact resis-
tances. R nonelectrode can be assumed to be the proton resistance of the
membrane, but only when the catalyst and GDL have sufficient elec-
tron conductivity and the cell is assembled with an optimum pinch
to ascertain negligible contact resistance.10
The cell voltage corrected for the nonelectrode ohmic overpoten-
tial according to the first step, step 1, is defined as corrected voltage
V corr1
V corr1 ⫽ V cell ⫹ ␩ ohm,nonelectrode
⫽ V cell ⫹ iR nonelectrode
⫽ V eq ⫺ 关 ␩ activity ⫹ ␩ act,Tafel ⫹ ␩ conc,electrode
⫹ ␩ conc,nonelectrode ⫹ ␩ ohm,electrode兴
The experimental values of R nonelectrode at the 120°C/35% RH
condition are shown on the right axis of Fig. 1c. Since the resistance
is not measured at lower than 100 mA/cm2 due to the accuracy limit
of the load box, the resistance value at 100 mA/cm2 is used in
obtaining V corr1 for current densities below 100 mA/cm2. Figure 2
shows the polarization curves after step 1 共ⵜ is V corr1 for air and ⵜ
is V corr1 for oxygen兲 and step 2 corrections for ohmic overpotentials
at the 120°C/35% RH condition 共step 2 is discussed below兲.
Step 2. Determination of the cathode electrode ohmic overpotential
(␩ohm,electrode).—␩ ohm,electrode is determined based on two governing
phenomena at high current density that are first order with oxygen
concentration, the oxygen reduction reaction and Fick’s law of dif-
fusion using a parameter called the current ratio. The current ratio is
defined as the ratio of the current density obtained from the oxygen
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Figure 2. Polarization curves using oxygen and air at the 120°C/35% RH
condition, atmospheric pressure, where V cell ⫽ experimental polarization
curve, V corr1 ⫽ V cell corrected for ␩ ohm,nonelectrode and V corr2 ⫽ V corr1 cor-
rected further for ␩ ohm,electrode . R electrode is found to be 0.035 ⍀ cm2. Tafel
slope is found from the 10-100 mA/cm2 range of the oxygen V corr2 polariza-
tion curve to be 72 mV/dec.
polarization curve to that from the air polarization curve at the same
cell voltage.
When the current is truly first order with oxygen concentration,
as governed by those two phenomena, the current ratio equals 4.8
共4.8 is the ratio of inlet mole percent oxygen in pure oxygen to that
in air兲. This is the case when there are no ohmic overpotentials and
there is adequate oxidant flow rate 共if the utilization is too high,
⬎60%, then the exit oxygen partial pressure is significantly less than
关4兴
the inlet oxygen partial pressure兲. Also recall that there are two
kinds of ohmic overpotentials, that of the electrode (␩ ohm,electrode)
and that of the nonelectrode (␩ ohm,nonelectrode). Therefore, if the ex-
perimental current ratio, with sufficient oxidant flow rate, at high
current density 共⭓400 mA/cm2兲 determined from V corr1 , after
␩ ohm,nonelectrode is already eliminated, is less than the first order value
of 4.8, there is an indication of significant ohmic resistance in the
electrode (R electrode).
Based on that rationale, the value of R electrode is obtained using an
iterative procedure. The correct value of R electrode makes the plot of
关 V corr1 ⫹ iR electrode兴 vs. current density of both oxygen and air yield
a current ratio of the first order value of 4.8. After correcting for
R electrode , the current is first order with the oxygen concentration at
high current density. Thus
关5兴
关6兴 ␩ ohm,electrode ⫽ iR electrode 关8兴
where R electrode is the electrode ohmic resistance, obtained from the
关7兴 iterative procedure described.
For the iterative procedure to be valid there has to be one ratio of
oxygen concentration representing the whole current density range.
This is true only when the polarization curve is collected at constant
utilization, not constant flow rate.
For a more accurate value of R electrode , the ratio of oxygen con-
centration between oxygen and air should be calculated from the
log-mean average values, between inlet and exit, instead of from the
inlet values 共that result in the ratio of 4.8兲. The average values are
calculated based on the oxygen and mass balance at the inlet and
exit of the cathode flow field. The calculation takes into account the
amount of water entering the cell 共which is set by the inlet relative
humidity and reactant flow rates兲, cell temperature, and the amount
of water produced at each current density.
In most cases the Pt/carbon catalyst and gas diffusion layer pro-
vide sufficient electron conductivity for negligible electrical resis-
tance in the electrode that proton resistance is the predominant com-
 Journal of The Electrochemical Society, 152 共3兲 A635-A644 共2005兲
ponent of R electrode . The cell voltage corrected further from V corr1 for
the electrode ohmic overpotential according to step 2 is labeled
V corr2
V corr2 ⫽ V corr1 ⫹ ␩ ohm,electrode 关9兴
⫽ V cell ⫹ iR non-electrode ⫹ iR electrode 关10兴
⫽ V eq ⫺ 关 ␩ activity ⫹ ␩ act,Tafel ⫹ ␩ conc,electrode
⫹ ␩ conc,nonelectrode兴 关11兴
In Fig. 2, the current ratio based on V corr1 is less than the first
order value of 4.8 共for example, at V corr1 of air at 400 mA/cm2, the
current ratio equals 1300/400 ⫽ 3.3) suggesting significant
␩ ohm,electrode . Based on the iterative procedure described, the
R electrode that makes the current ratio first order with oxygen concen-
tration is found to be 0.035 ⍀ cm2. V corr2 (V corr1 ⫹ iR electrode) is the
V corr1 corrected for the R electrode found giving the first-order current
ratio of 4.8 at high current density 共for example, at V corr2 of air at
400 mA/cm2, the current ratio equals 1900/400 ⫽ 4.8). The itera-
tive procedure should be implemented at high enough current den-
sity that cell polarization reaction is governed by both reaction ki-
netics and oxygen transport, typically current densities higher than
100 mA/cm2 with air. The R electrode of 0.035 ⍀cm2 is the effective
electrode resistance, not the sheet resistance of the layer.
The plots of V corr2 for oxygen and air in Fig. 2 关共䊐兲 is V corr2 for
air and 共䊏兲 is V corr2 for oxygen兴 are the polarization curves that are
first order with oxygen concentration at high current density, as gov-
erned by first-order reaction kinetics and Fick’s law of diffusion,
after all ohmic overpotentials are eliminated.
Step 3. Determination of non-electrode concentration overpotential
(␩conc,nonelectrode).—In determining ␩ conc,nonelectrode , the limiting cur-
rent density (i lim) needs to be evaluated. The limiting current density
is the current obtained when the oxygen concentration at the cathode
catalyst surface approaches zero, which represents the maximum
operating current density of the cell. The i lim is indicative of the
concentration polarization through layers where oxygen is not con-
sumed; the gas diffusion layer and the thin ionomer film at the
cathode electrode surface next to the GDL. The existence of the thin
ionomer film is dependant on the manufacturing technique of the
electrode. The majority of the ionomer that is added to the electrode
is mixed thoroughly inside the electrode 共which contributes to the
electrode concentration polarization, see step 4兲, while some iono-
mer forms a thin film at the electrode surface as a result of some
electrode manufacturing techniques including spraying. The film is
typically in the order of a few nanometers in thickness, although
extremely hard to physically evaluate accurately.
The Butler-Volmer equation represents cell voltage in the
activation-control region 共no significant ohmic, concentration, and
other losses兲 as follows
i ⫽ i o exp关共 V eq ⫺ V 兲 /b 兴 关12兴
where b is the Tafel slope in the kinetically control region, called
kinetic Tafel slope, which is determined experimentally from the
oxygen polarization curve 共details described in step 4兲, i o , the ex-
change current density, obtained from extrapolating Tafel slope B to
V eq , and V, the cell voltage 共in this case it is V corr2 , after eliminat-
ing all ohmic resistances兲.
The theoretical basis for evaluating the limiting current is based
on a first order oxygen reduction reaction, the Butler-Volmer equa-
tion kinetics, Fick’s first law of diffusion, and the limiting current
condition of zero oxygen concentration at the catalyst surface.
Modifying the Butler-Volmer equation on this basis leads to a modi-
fied Butler-Volmer equation as follows
i/ 共 1 ⫺ i/i lim兲 ⫽ i o⬘ exp关共 V eq ⫺ V corr2 兲 /b⬘ 兴 关13兴
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A639
Figure 3. Polarization curves using air at the 120°C/35% RH condition,
atmospheric pressure, where V cell ⫽ experimental polarization curves,
V corr1 ⫽ V cell corrected for ␩ ohm,nonelectrode , V corr2 ⫽ V corr1 corrected further
for ␩ ohm,electrode , V corr3 ⫽ V corr2 corrected further for ␩ conc,nonelectrode , V corr4
⫽ V corr3 corrected further for ␩ conc,electrode , V corr5 ⫽ V corr4 corrected further
for ␩ act,Tafel , V corr6 ⫽ V corr5 corrected further for ␩ activation ⫽ V eq . V corr3 is
the line (R 2 ⫽ 0.989) representing the plot of V corr2 vs. log关i/(1-i/ilim) 兴
whose slope, called slope of the i lim plot B ⬘ , is found to be 138 mV/dec (i lim
here is 819 mA/cm2兲. The current density at the intersection between V corr3
and V corr4 , the breaking current density (i b) represents the minimum current
density where ␩ conc,electrode starts to occur, which is 40 mA/cm2 here.
where b⬘ is the slope of the modified Buttler-Volmer equation cor-
recting for i lim 共called slope of the i lim plot兲, i ⬘o , the modified ex-
change current density, obtained from extrapolating slope of the i lim
plot b ⬘ to V eq .
The value of b ⬘ may or may not equal the kinetic Tafel slope b in
Eq. 12 depending on whether ␩ conc,electrode ⭓ 0 共explained in the
next step兲. Equation 13 is similar to Eq. 12, except that a correction
for the finite limiting current is added; i becomes i/(1 ⫺ i/i lim).
i lim is found using an iterative procedure based on Eq. 13. The
correct value of i lim makes the plot of log关i/(1-i/ilim) 兴 vs. V corr2 a
straight line following the modified Butler-Volmer equation. The
resulting straight line on the semilog plot represents the cell voltage
corrected further from step 2 for ␩ conc,nonelectrode to V corr3 . The dif-
ference between the straight line and V corr2 at the same current den-
sity is ␩ conc,nonelectrode , which cannot be written in an explicit form of
the current density
V corr3 ⫽ V cell ⫹ iR nonelectrode ⫹ iR electrode
⫹ ␩ conc,nonelectrode共implicit) 关14兴
⫽ V eq ⫺ 关 ␩ activity ⫹ ␩ act,Tafel ⫹ ␩ conc,electrode兴
关15兴
Figure 3 shows polarization curves of only air, the oxidant gas of
interest, at the 120°C/35% RH condition after each step of correc-
tion, with the V cell , V corr1 , and V corr2 curves identical to those
shown and discussed earlier in Fig. 2. The sharp decrease of V cell at
high current density suggests that there is significant ␩ conc,nonelectrode .
Using the iterative procedure described, the i lim that makes the semi-
log plot of V corr2 vs. log关i/(1 ⫺ i/ilim) 兴 become a straight line 共shown
as V corr3 ) according to Eq. 13, is found to be 819 mA/cm2. The slope
of the i lim plot b⬘ is 138 mV/dec 共the implication of this value is
discussed in step 4兲. Extrapolating b ⬘ to V eq results in i ⬘o of 5.3
 A640 Journal of The Electrochemical Society, 152 共3兲 A635-A644 共2005兲
⫻ 10⫺1 mA/cm2 共the implication of i o⬘ is explained with Eq. 26 yet
to be described兲. V corr3 is the polarization curve with no ohmic over-
potentials and no ␩ conc,nonelectrode .
Step 4. Determination of the cathode electrode concentration
overpotential (␩conc,electrode).—A comparison between the slope of
the i lim plot (b ⬘ ) to the kinetic Tafel slope 共b兲 is used to determine
␩ conc,electrode . The kinetic Tafel slope is determined from the
activation-control portion of the oxygen polarization curve. The de-
cade of 10–100 mA/cm2 is the best to assume activation control in
an oxygen polarization curve, because the maximum current density
is low enough that concentration overpotentials can be assumed neg-
ligible while the minimum current density is high enough that the
interference from mixed potential and hydrogen crossover can also
be assumed negligible. Hydrogen crossover was measured in our
previous work7 at the three operating conditions of 80, 100, and
120°C. The highest crossover was 1.3 mA/cm2 at the 120°C/35%
RH condition using a similar membrane electrode assembly. The
small hydrogen crossover verifies its negligible effect on the kinetic
Tafel slope determined from the decade of 10-100 mA/cm2.
It is more desirable to determine the kinetic Tafel slope from
polarization curve data in a range broader than one decade, espe-
cially in studies where kinetic information is the main interest. Ad-
ditional data between 1-10 mA/cm2 is useful, although one needs to
be careful that mixed potential and hydrogen crossover are not sig-
nificant in that low range by verifying that the polarization curve
still does not deviate from the straight Tafel line. Measurement of
actual hydrogen crossover at each operating condition to correct for
the deviation from the straight Tafel line at the low current density
decade will help extend the kinetically controlled region of the po-
larization curve to more than one decade.
The kinetic Tafel slope is the slope, in mV/dec, of the experi-
mental cell voltage (V) plotted vs. log i in the kinetically controlled
region of the polarization curve, according to a rearranged form of
Eq. 12. Figure 2 shows the kinetic Tafel slope at the 120°C/35% RH
condition taken from the kinetically controlled 10-100 mA/cm2
range of the oxygen polarization curve to be b ⫽ 72 mV/dec. The
experimental kinetic Tafel slope is close to the theoretical Tafel
slope of 78 mV/dec at 120°C, based on the first order Butler-Volmer
equation kinetics and a transfer coefficient of 0.5 共calculated theo-
retical Tafel slope at the three conditions are tabulated in Table II兲.
It has been shown theoretically11,12 and experimentally13 for the
oxygen reduction reaction that a polarization curve, plotted as a
function of the logarithm of current density, starts to follow a slope
which is twice the kinetic Tafel slope 共often called the double Tafel
slope, 2b兲 when the electrode experiences oxygen concentration
overpotential. Thus when a slope of the i lim plot b ⬘ is between the
kinetic Tafel slope and the double Tafel slope, there is a significant
transport resistance of oxygen within the electrode.
The b ⬘ in Fig. 3, 138 mV/dec, is about twice that of the kinetic
Tafel slope, 72 mV/dec, indicating significant electrode concentra-
tion overpotential. The cell voltage corrected further from step 3 for
␩ conc,electrode is named V corr4 , which is the true activation control
polarization curve following the kinetic Tafel slope. The value of
␩ conc,electrode equals the difference between V corr4 and V corr3 .
The current density where the kinetic Tafel slope line (V corr4 in
Fig. 3兲 intersects that which follows the slope of the i im plot (V corr3
in Fig. 3兲 is called the breaking current density, i b . The i b is the
current density beyond which there is significant ␩ conc,electrode that
can be determined from Eq. 16
␩ conc,electrode ⫽ 共 b ⬘ ⫺ b 兲 ⫻ log共 i/i b兲 关16兴
Equation 16 is valid only at a current density higher than i b .
According to Fig. 3, the intersection of V corr3 and V corr4 is i b ⫽ 40
mA/cm2, revealing that below this current density there is no
␩ conc,electrode at the 120°C/35% RH condition. V corr4 can be written as
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V corr4 ⫽ V cell ⫹ iR nonelectrode ⫹ iR electrode
⫹ ␩ conc,nonelectrode共implicit) ⫹ 共 b ⬘ ⫺ b 兲 ⫻ log共 i/i b兲
关17兴
⫽ V eq ⫺ 关 ␩ activity ⫹ ␩ act,Tafel兴 关18兴
Step 5. Determining the cathode activation overpotential from the
Tafel slope (␩act,Tefel).—The activation overpotential due to the ki-
netic Tafel slope (b ⫽ 72 mV/dec in Fig. 2兲 represents the cell
voltage loss through oxygen reduction reaction kinetics for every
decade of increased current density. 10 mA/cm2 is chosen as a ref-
erence for the starting current density of the kinetic-controlled Tafel
region, because it is low enough that concentration overpotentials
can be assumed negligible and high enough that the interference
from mixed potential and hydrogen crossover can be assumed neg-
ligible. The ␩ act,Tafel is then defined as voltage loss due to the reac-
tion kinetics at current density higher than the reference 10 mA/cm2
␩ act,Tafel ⫽ b ⫻ log共 i/10兲 关19兴
The cell voltage corrected further from step 4 for ␩ act,Tafel is named
V corr5
V corr5 ⫽ V cell ⫹ iR nonelectrode ⫹ iR electrode
⫹ ␩ conc,nonelectrode共implicit) ⫹ 共 b ⬘ ⫺ b 兲 ⫻ log共 i/i b兲
⫹ B ⫻ log共 i/10兲 关20兴
⫽ V eq ⫺ 关 ␩ activity兴 关21兴
In Fig. 3, the kinetic Tafel slope B of 72 mV/dec is used to
calculate the ␩ act,Tafel resulting in V corr5 shown. V corr5 is independent
of current density and equals the cell voltage at 10 mA/cm2 or 0.874
V at the 120°C/35% RH condition.
Step 6. Determination of the cathode activation overpotential from
catalyst activity (␩activity).—The loss left from the last step is only
the difference between V eq and the cell voltage at 10 mA/cm2
(V @10 mA/cm2 ). This difference is not fundamentally meaningful be-
cause there is no theoretical basis besides that 10 mA/cm2 is chosen
as the starting current density of the Tafel region. V @10 mA/cm2 is a
reasonable indication of catalyst activity for comparing different
electrodes at one operating condition, but not an accurate indication
for comparing several operating conditions due to differences in
V eq . However, for convenience V @10 mA/cm2 is used as a representa-
tive of the catalyst activity and an additional parameter truly repre-
sentative of the catalyst activity at various conditions is described in
a later section
␩ activity ⫽ V eq ⫺ V @10 mA/cm2 关22兴
The cell voltage after all the six steps of correction is V eq
V corr6 ⫽ V eq ⫹ iR nonelectrode ⫹ iR electrode ⫹ ␩ conc,nonelectrode共implicit)
⫹ 共 b ⬘ ⫺ b 兲 ⫻ log共 i/i b 兲 ⫹ b ⫻ log共 i/10兲
⫹ 共 V eq ⫺ V @10mA/cm2 兲 关23兴
⫽ V eq 关24兴
In Fig. 3, the difference between each step of correction shows
the amount of each associated polarization source. The differences
between V corr1 and V cell , V corr2 and V corr1 , V corr3 and V corr2 , V corr4
and V corr3 , V corr5 and V corr4 , and V corr6 and V corr5 equal
␩ ohm,nonelectrode , ␩ ohm,electrode , ␩ conc,nonelectrode , ␩ conc,electrode , ␩ act,Tafel ,
and ␩ activity , respectively. Figure 2 and 3 demonstrate the applica-
tion of the technique to quantitatively determine six sources of po-
larization 共two of ohmic, two of concentration, and two of activa-
tion兲 of the air polarization curve at the 120°C/35% RH condition.
 Journal of The Electrochemical Society, 152 共3兲 A635-A644 共2005兲 A641

Table III. Characteristic parameters of the in-house MEA tested at the three cell temperatureÕrelative humidity conditions:
80°CÕ100% RHanÕ75% RHcat, 100°CÕ70% RH, and 120°CÕ35% RH. These parameters are used to calculate polarization sources shown in Table
IV.

Related overpotential Characteristitics Unit 80°C 100°C 120°C

Equilibrium cell voltage, air, V eq V 1.153 1.094 1.086

Open-circuit voltage, air, V ocv V 0.968 0.956 0.963
Inlet cathode relative humidity % 75 70 35
Inlet anode relative humidity % 100 70 35
Ohmic, nonelectrode Nonelectrode ohmic resistance, R nonelectrode ⍀ cm2 0.063 0.085 0.223
Ohmic, electrode Electrode ohmic resistance, R electrode ⍀ cm2 0.020 0.020 0.035
Concentration, nonelectrode Limiting current, air, i lim mA/cm2 2019 1314 819
Concentration, electrode Slope of the i lim plot, air, B ⬘ mV/dec 115 138 138
Concentration, electrode Breaking current density, air, i b mA/cm2 80 60 40
Activation, Tafel Kinetic Tafel slope, B mV/dec 65 70 72
Activation, activity 共not theoretical兲 Voltage at 10 mA/cm2, air, V @10 mA/cm2 V 0.885 0.869 0.874
Activation, activity 共extrapolated兲 Exchange current density, i o , air mA/cm2 3.3 ⫻ 10⫺4 4.5 ⫻ 10⫺4 6.8 ⫻ 10⫺4
Meaningless Modified exchange current density, i ⬘o , air mA/cm2 1.1 ⫻ 10⫺1 5.8 ⫻ 10⫺1 5.3 ⫻ 10⫺1
Activation, activity 共extrapolated兲 Exchange current density, i o , oxygen mA/cm2 1.0 ⫻ 10⫺3 8.9 ⫻ 10⫺3 1.4 ⫻ 10⫺2
Activation, activitya Catalyst activity, air, i @␩⫽260 mV mA/cm2 7 33 40
Activation, activity Current ratio at V corr2 at 10 mA/cm2 of air - 4 4 3.5
a
True indication of catalyst activity.

Discussion i b , the modified exchange current density i o⬘ of air is found to be

Representative equations.—From the analysis steps, the overall
polarization curve can be described by two separate equations, one
for current densities smaller than i b , and one for current densities
starting greater than i b . At
i ⬍ ib
V calculate ⫽ V eq ⫹ b log共 i o兲 ⫺ b log共 i 兲 ⫺ iR electrode ⫺ iR nonelectrode
关25兴
The exchange current density i o is determined from extrapolating
the kinetic Tafel slope b to V eq of each operating condition. The i o is
not to be taken as an accurate parameter, especially when extrapo-
lated from an air polarization curve where the Tafel region is estab-
lished only in a narrow range of current density 共this is further
described in the Catalyst Activity section below兲. At
i ⭓ ib
V calculate ⫽ V eq ⫹ b ⬘ log共 i ⬘o 兲 ⫺ b ⬘ log关 i/ 共 1 ⫺ i/i lim兲兴 ⫺ iR electrode
⫺ iR nonelectrode 关26兴
V eq is the theoretical equilibrium cell voltage calculated from the
Nernst equation 共Table II兲. The parameters b ⬘ , i lim , R electrode , and
R nonelectrode are obtained from the steps described previously. The
parameter i ⬘o is a modified exchange current density obtained from
extrapolating b ⬘ to V eq in step 3. It is important to note that in the
case of a high performance cell where there is no concentration
overpotential, Eq. 26 becomes Eq. 25 for the whole range of current
density 共equivalent to very large i b and i lim).
When b ⬘ equals 2b 共double Tafel slope兲 there is significant con-
centration polarization in the electrode and the value of i o⬘ is a func-
tion of both the true exchange current density and the effective
diffusion coefficient of oxygen in the electrode. However, in the
case when the slope b ⬘ is between b and 2b, the parameter i o⬘ is not
a meaningful parameter.
By extrapolating the kinetic Tafel slope b to V eq , using data at
current densities lower than i b where there is no concentration over-
potentials, the exchange current density i o of air is found to be 3.3
⫻ 10⫺4 , 4.5 ⫻ 10⫺4 , and 6.8 ⫻ 10⫺4 mA/cm2 for the 80, 100, and
120°C conditions, respectively. However, by extrapolating the slope
of the i lim plot b ⬘ to V eq , using data at current densities greater than
1.1 ⫻ 10⫺1 , 5.8 ⫻ 10⫺1 , and 5.3 ⫻ 10⫺1 mA/cm2 for the three
conditions, respectively 共both i o and i ⬘o of air are tabulated in Table
III兲. It is clear that the intercept based on b ⬘ , with imbedded
␩ conc,electrode , is significantly higher than that based on b. This shows
that one needs to verify negligible concentration and ohmic overpo-
tentials before attempting to determine an exchange current density
to not mistakenly obtain a meaningless i ⬘o that contains mass-
transport effects.
V calculate is obtained for current densities up to i b by substituting
i o , b 共found in step 4兲, R electrode 共step 2兲, and R nonelectrode 共step 1兲 into
Eq. 24. V calculate is obtained for current densities greater than i b by
substitute i o⬘ , b ⬘ , i lim 共step 3兲, R electrode , and R nonelectrode into Eq. 26.
Figure 4 shows the comparison between the experimental cell
voltage (V cell) and the calculated cell voltage (V calculate) for the
whole range of current density for the three operating conditions.
The overall correlation coefficient R 2 is 0.988, 0.977, and 0.991 for
the 80, 100, and 120°C curves, respectively. The two equations give
good accuracy over the whole polarization curve verifying that the
analysis method is representative of the polarization phenomena oc-
curring in the cell.
It is important to note that if one attempts to curve-fit Eq. 25
and 26 to an experimental polarization curve to simultaneously de-
termined all the parameters (i o , i o⬘ , b, b ⬘ , i lim , R electrode , and
R nonelectrode), the obtained parameters will not be representative of
the polarization phenomena even when the correlation coefficient R 2
is very close to unity. It is important to extract each representative
parameter from the appropriate portion of the polarization curve,
where the associated phenomenon governs, according to the step-
by-step technique described to obtain meaningful parameters.
Six sources of polarization.—The analysis technique has been
applied to all air polarization curves shown in Fig. 1 at the three
operating conditions of 80°C/100% RHan/75% RHcat, 100°C/70%
RH, and 120°C/35% RH with a use of each associated oxygen po-
larization curve as a diagnostic tool. The characteristic parameters of
the MEA at the three conditions are summarized in Table III. These
characteristic parameters include nonelectrode ohmic resistance
(R nonelectrode), electrode ohmic resistance (R electrode), limiting current
(i lim), slope of the i lim plot (b ⬘ ), breaking current density (i b),
kinetic Tafel slope 共b兲, cell voltage at 10 mA/cm2, exchange current
density i o , and modified exchange current density i o⬘ . The calcu-

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 A642 Journal of The Electrochemical Society, 152 共3兲 A635-A644 共2005兲
Figure 4. Comparison of the experimental cell voltage (V cell) and the cal-
culated cell voltage (Vcalculated) of air operation, according to Eq. 25 for i
⬍ i b and Eq. 26 for i ⭓ i b , using all parameters obtained from the six-step
analysis described at 共a兲 80°C/100% RHan/75% RHcat (R 2 ⫽ 0.988), 共b兲
100°C/70% RH (R 2 ⫽ 0.977), and 共c兲 120°C/35% RH (R 2 ⫽ 0.991), all at
atmospheric pressure.
lated V eq , experimental V ocv , and inlet relative humidity at each
condition are also tabulated for simpler understanding of the results
that follow.
Higher-temperature operation increases ohmic resistance both of
the electrode and the nonelectrode due to the lower cell relative
humidity causing higher proton resistance of the Nafion membrane
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and of Nafion in the electrode. The difference between the 80 and
the 100°C conditions is not big because the relative humidity de-
creases only slightly on the cathode. There is a dramatic increase of
nonelectrode resistance from 0.085 ⍀ cm2 at the 100°C/70% RH to
0.223 ⍀ cm2 at the 120°C/35% RH from the big decrease in relative
humidity. This phenomenon is also reflected in the relative electrode
resistances of the three cases.
Concentration overpotentials both in the electrode and the non-
electrode increase at higher temperature conditions as seen from the
lower i lim and higher b ⬘ . Higher concentration overpotentials are
due to lower oxygen permeability through the Nafion ionomer film
at the cathode electrode surface as relative humidity decreases14 and
lower inlet oxygen partial pressure 共Table II兲. Similar results have
been observed previously.8 The breaking current density where
␩ conc,electrode starts to occur is also lower at higher temperatures con-
firming the more difficult oxygen transport in the electrode at lower
relative humidity and oxygen partial pressure.
The current ratio at low current density, taken at V corr2 of air at
10 mA/cm2, is less than the first order value of 4.8 for all the con-
ditions 共4, 4, and 3.5 for the 80, 100, and 120°C conditions, respec-
tively. These values are tabulated in Table III兲. These lower than first
order current ratios indicate that the oxygen reduction reaction is
less than first order with oxygen concentration. The reaction order is
closer to first order at lower temperature and higher relative humid-
ity.
The kinetic Tafel slope b is 65, 70, and 72 mV/dec at 80, 100,
and 120°C, respectively. These slopes are close to the theoretical
values of 70, 74, and 78 mV/dec based on a transfer coefficient of
0.5. All parameters reported in Table III are used to calculate the
polarization sources to be reported in Table IV.
Catalyst activity.—Catalyst activity is an important parameter
that has not been determined in the steps previously described. Ex-
change current density i o is the theoretical parameter representing
catalyst activity. However, i o is obtained from extrapolating the
Tafel slope B from the kinetically control region 共typically starting
at around 10 mA/cm2兲 several decades to V eq . The extrapolation
over several decades of current density has inherent potential for
errors (i o is typically on the order of 10⫺2 to 10⫺6 mA/cm2兲.15,16
The exchange current density i o of oxygen has been found, from
extrapolating the kinetic Tafel slope from the 10–100 mA/cm2 de-
cade to V eq , to be 1.0 ⫻ 10⫺3 , 8.9 ⫻ 10⫺3 , and 1.4 ⫻ 10⫺2
mA/cm2 for the 80, 100, and 120°C conditions, respectively. The
ratio between i o of oxygen and that of air 共both shown in Table III兲
significantly changes with operating conditions. The ratios are about
3, 5, and 21, at the 80, 100, and 120°C conditions, respectively,
indicating that the values are highly inaccurate.
Another more practical parameter representative of catalyst ac-
tivity is the current density at a fixed appropriate overpotential,
which is large enough that mixed potential and hydrogen crossover
are insignificant, but small enough to not be interfered by concen-
tration overpotentials. An ideal overpotential to choose is that which
results in a current density in the range between the beginning of the
Tafel region 共about 10 mA/cm2兲 and i b , where concentration over-
potential starts occurring. Reasonable overpotentials are between
200 and 300 mV.17 The chosen overpotential is subtracted from the
theoretical equilibrium cell voltage tabulated in Table II.
For the polarization curves at the three conditions shown in Fig.
1, an overpotential of 260 mV was chosen for determining the cata-
lyst activity. Figure 5 shows air polarization curves in the low cur-
rent density range, based on V corr2 共with no ohmic overpotentials兲, at
the three conditions. Activation-control Tafel lines are plotted on the
curves up to i b . The catalyst activity, which is the current density at
the selected 260 mV overpotential, is 7, 33, and 40 mA/cm2, at the
80°C/100% RHan/75% RHcat, the 100°C/70% RH, and the 120°C/
35% RH conditions, respectively.
A 260 mV overpotential results in a catalyst activity at the 80°C
condition of less than the beginning of the experimentally verified
Tafel region 共10 mA/cm2兲 so extrapolating the kinetic Tafel slope to
 Journal of The Electrochemical Society, 152 共3兲 A635-A644 共2005兲 A643

Table IV. Polarization sources in air operation at the three cell temperatureÕrelative humidity conditions at current densities of 400 mAÕcm2 and
600 mAÕcm2.

80°C/100% RHan/75% RHcat 100°C/70% RH 120°C/35% RH

b b
Overpotential 共mV兲 i ⫽ 400
a
i ⫽ 600
a Percent i ⫽ 400
a
i ⫽ 600
a Percent i ⫽ 400
a
i a ⫽ 600 Percentb

␩ ohm,non-electrode ⫽ iR non-electrode 25 38 33 34 51 37 89 134 29

␩ ohm,electrode ⫽ iR electrode 8 12 11 8 12 9 14 21 4
␩ conc,non-electrode 共inexplicit兲 0 1 3 0 1 2 19 99 51
␩ conc,electrode ⫽ (B ⬘ ⫺ B)log(i/ib) 35 44 23 56 68 26 66 78 7
␩ act,Tafel ⫽ B log(i/10) 104 116 30 112 124 27 115 128 8
␩ activity ⫽ V fq ⫺ V @10 mA/cm2 268 268 0 225 225 0 212 212 0
Total 440 478 100 435 481 100 516 671 100
a
i ⫽ current density where overpotentials are determined 共in mA/cm2兲.
b
Percent ⫽ Percent of total increase in overpotential 共when current density is increased from 400 to 600 mA/cm2兲 that is attributed to each specific source
of polarization.

lower current density is needed. However, higher overpotentials than
260 mV will result in catalyst activity that is interfered with by
concentration polarization at the 120°C condition 共higher than the i b
of 40 mA/cm2兲. The overpotential of 260 mV is not ideal for evalu-
ating catalyst activity at all three conditions, but it is an appropriate
compromise in this case. One needs to be careful in choosing this
overpotential for a fair comparison of catalyst activity when a wide
range of operating conditions are of interest. For fundamental cata-
lyst activity studies, oxygen is typically used instead of air due to its
broader activation-control region that gives more accurate catalyst
activity. Catalyst activity is reported for air in this work to complete
the air polarization analysis with that concern in mind.
Catalyst activity, as summarized in Table III, is significantly
higher at the 100°C condition 共33 mA/cm2兲 than at the 80°C condi-
tion 共7 mA/cm2兲 because the higher temperature promotes the reac-
tion. The catalyst activity at the 120°C condition 共40 mA/cm2兲 is not
much higher than that at the 100°C condition because of the signifi-
cantly lower relative humidity, which reduces proton activity and
affects the reaction kinetics. Detailed examination of oxygen reduc-
tion reaction kinetics as a function of cell temperature and relative
humidity has been previously studied and will be published by our
group shortly.17
Figure 5. The low current density range for air polarization curves based on
V corr2 , 共with no ohmic resistances兲 which is corrected for both R nonelectrode
and R electrode in comparison at the 80°C/100% RHan/75% RHcat, the 100°C/
70% RH, and the 120°C/35% RH conditions. The catalyst activity, the cur-
rent density at 260 mV overpotential, equivalent to at V corr2 of 0.893, 0.834,
and 0.826 V 共shown as arrows on the left axis兲, is 7, 33, and 40 mA/cm2 for
the 80, 100, and 120°C conditions, respectively. Activation-control Tafel
lines are plotted with the kinetic Tafel slope B 共from Table III兲 up to i b .
The current ratio at low current density, as determined from
V corr2 of air at 10 mA/cm2, is indicative of reaction order. The cur-
rent ratios are 4, 4, and 3.5, for the 80, 100, and 120°C conditions,
respectively 共last line in Table III兲. The current ratios slightly devi-
ate from the first order value of 4.8, especially at the 120°C condi-
tion. A more accurate reaction order should be determined from a
straight Tafel line over a current density range wider than what was
obtained in this work, by correcting for hydrogen crossover and
mixed potential due to platinum oxidation and also by collecting
polarization data at less than 10 mA/cm2. A more detailed investi-
gation of reaction order at high temperature and low relative humili-
ties has been studied and will be published by our group shortly.17
Losses at different current densities.—Table IV reports overpo-
tentials at two different current densities, 400 and 600 mA/cm2.
These values represent a range of applicable current density for the
operation of a cell stack with a significant power density and a
reasonably high voltage efficiency. The total overpotentials at 600
mA/cm2 are 38, 46, and 155 mV higher than at 400 mA/cm2 at the
80, 100, and 120°C conditions, respectively. The total increase in
overpotential comprises contributions from several polarization
sources, whose percentages of the total increase are reported in the
third column for each operating condition.
Table IV shows that at the 80 and the 100°C conditions, three
main polarization sources contribute to the total increase in overpo-
tential as the current density increases: ␩ ohm,nonelectrode 共mainly mem-
brane proton resistance兲, ␩ conc,electrode , and ␩ act,Tafel , with the mem-
brane proton resistance being the largest contributor. However, at
the 120°C condition, only two main sources contribute to the total
increase in overpotential: ␩ ohm,nonelectrode and ␩ conc,nonelectrode , with
the ␩ conc, nonelectrode being the largest contributor.
This analysis demonstrates that at different operating conditions
there are different controlling polarization losses that obstruct effi-
cient fuel cell operation at higher current density. The controlling
polarization loss also depends on the current density range and char-
acteristics of each MEA. For this specific MEA, the controlling
polarization loss at operating current densities beyond 400 mA/cm2
at the 120°C condition is not the membrane ohmic resistance loss,
but the nonelectrode concentration overpotential. These results show
that a detailed polarization breakdown is useful in diagnosing the
biggest obstacle to higher performance.
The analysis technique described is not mathematically vigorous
and does not give perfect accuracy for all the parameters, but when
used with appropriate assumptions and care, it is a useful tool for
MEA diagnostics and development. The first order reaction with
oxygen concentration is a big assumption required for the analysis
described here. Since the current ratio at low current density indi-
cates a reaction order of less than first order with oxygen concen-
tration, further modification of the technique to more appropriately
accommodate cases of non-first order reaction should be developed.

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 A644 Journal of The Electrochemical Society, 152 共3兲 A635-A644 共2005兲
Use of additional oxygen concentration.—It has been shown that
at least one additional oxygen concentration is needed in order to
analyze an air polarization curve using this technique. Oxygen is the
best diagnostic gas because it gives more accurate activation polar-
ization information than air because of its lower concentration po-
larization. However, additional oxygen concentrations such as 4%
O2 /N2 or 10.5% O2 /N2 can be useful in checking the accuracy of
the parameters.
Limiting current can be found for a lower oxygen concentration
and a ratio of that i lim with i lim,air can be used to determine if the first
order assumption is consistent. An R electrode can be determined by the
same trial and error procedure of step 4 using air and a lower oxy-
gen concentration. This R electrode can then be compared with the
R electrode obtained from air and oxygen data. However, one must be
aware that the activation control region with a straight Tafel line of
a gas with lower concentration will be shorter than that of air due to
more concentration polarization. In some cases, a straight Tafel line
might not be established at all, as i b becomes smaller than the mini-
mum measured current density 共10 mA/cm2兲.
Conclusions
An analysis technique to evaluate six sources of polarization
losses in hydrogen/air proton exchange membrane fuel cells has
been described. The step-by-step technique is based on the follow-
ing few assumptions: a first order cathode reaction with respect to
oxygen concentration, Butler-Volmer equation kinetics, oxygen
transport by Fickian diffusion, no significant anode polarization, and
no electrical short circuit. The six sources of polarization are non-
electrode ohmic overpotential, electrode ohmic overpotential, non-
electrode concentration overpotential, electrode concentration over-
potential, activation overpotential from the Tafel slope, and
activation overpotential from catalyst activity.
The technique has been demonstrated with polarization curves
obtained from an in-house MEA tested at three different operating
conditions, ranging from 80 to 120°C in cell temperature, from 35 to
100% in anode inlet relative humidity, and from 35 to 75% in cath-
Downloaded on 2014-06-25 to IP 157.182.150.22 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).
ode relative humidity. For accurate analysis results, polarization
curves are required to be collected using both oxygen and air as
oxidant at constant utilization to as high current density as possible.
Testing of membrane electrode assemblies 共MEAs兲 for effects of
a changing parameter of interest is difficult since the consistent con-
trol of all other parameters to ascertain no change in anything, but
the studied parameter is difficult. Applying this technique in under-
standing polarization curves for differently constructed MEAs al-
lows systematic comparison of the polarization sources associated
with various operating conditions and membrane electrode assembly
structures.
University of Connecticut assisted in meeting the publication costs of this
article.
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