Journal of The Electrochemical Society, 157 共12兲 B1795-B1801 共2010兲 B1795

0013-4651/2010/157共12兲/B1795/7/$28.00 © The Electrochemical Society

Active Area Determination of Porous Pt Electrodes Used in

Polymer Electrolyte Fuel Cells: Temperature and Humidity
Effects
Rakel Wreland Lindström,*,z Katrin Kortsdottir, Maria Wesselmark,**
Alejandro Oyarce, Carina Lagergren,* and Göran Lindbergh*
Applied Electrochemistry, School of Chemical Science and Engineering, Kungliga Tekniska Högskolan,
SE-10044 Stockholm, Sweden

This paper discusses the proper measure of the electrochemically active area 共ECA兲 of carbon supported Pt catalyst in polymer
electrolyte fuel cells employing in situ cyclic voltammetry. The charges of the hydrogen underpotential deposition 共Hupd兲 and CO
stripping peaks obtained in situ are compared, and the influence of operation temperature 共25–80°C兲 and relative humidity
共40%–90%兲 is discussed. The results show that the charges of the Hupd decrease with rising temperature, while the corresponding
charges of the CO stripping peak are essentially independent of temperature, at least at high relative humidity. The unexpectedly
small Hupd charges are explained by the significant overlap with the hydrogen evolution reaction in a fuel cell at elevated
temperatures. According to our results, it is proposed that a more reliable value of Pt ECA is estimated from the CO stripping
charge. However, with decreasing humidity the charges of both Hupd and CO stripping peaks decrease, which is probably an effect
of increasing blockage of Pt active sites by hydrophobic domains in the electrode ionomer. Some implications of varying cell
conditions on the estimated Pt ECA and its correlation with fuel cell activity are discussed in an example from a fuel cell
degradation test.
© 2010 The Electrochemical Society. 关DOI: 10.1149/1.3494220兴 All rights reserved.

Manuscript submitted May 7, 2010; revised manuscript received August 12, 2010. Published October 14, 2010.

In fuel cell experiments it is valuable to be able to determine the
catalyst active area in situ. With the increased focus on degradation,
it is even more important to make an accurate determination of the
changes in active area before and after degradation tests. It is gen-
erally considered that a good estimation of the platinum active area
can be made from the hydrogen underpotential deposition 共Hupd兲
charge. The area over the two cathodic peaks, from the double layer
charge to the minimum just before the onset of hydrogen evolution,
is assumed to correspond to 77% of a full monolayer 共mL兲 of ad-
sorbed hydrogen on polycrystalline platinum, which averaged over
the three crystal base planes corresponds to about 210 ␮C cm−2.1,2
This method was originally defined in an acidic solution at room
temperature. For porous electrodes used in fuel cells, the electro-
chemically active area 共ECA兲 is often expressed per milligram of
catalyst nanoparticles and measured over the desorption peak共s兲 or
as an average between the adsorption and desorption peak共s兲.
The normal conditions of a running fuel cell are significantly
different from the case in acidic solution at room temperature. A fuel
cell is generally operated at an elevated temperature, and instead of
an aqueous solution electrolyte, with free mobility of ions, a solid
polymer, in this case Nafion, with sulfonic acid 共SO−3 兲 groups, situ-
ated on a side chain of the polymer, is employed. These attract
protons and form a hydrophilic network in which water and protons
can be transported via nanometer wide water channels through the
membrane.3 In contrast, the perfluorated backbone of Nafion is
highly hydrophobic and constitutes the framework for the membrane
channel system. The proton conductivity of the membrane, which is
related to the number of open channels through the membrane, is
determined by the water content.
The gas diffusion electrodes consist of a noncompact mixture of
Pt nanoparticles deposited on porous carbon support, carbon black
or other types of carbon structures, and about 30–40 wt % ionomer,
i.e., polymer fibers that must wet the catalyst particles for electro-
chemical activity. The optimum Nafion content for the cathode elec-
trode has previously been shown to be 36 wt %.4 Further, for full
utilization of the platinum, electron conductivity, via the gas diffu-
sion layer 共GDL兲 and the carbon particle network, is required be-
* Electrochemical Society Active Member.
** Electrochemical Society Student Member.
z
E-mail: rakel2@kth.se
tween the active platinum surfaces and the current collectors. During
fuel cell operation, the reactants, hydrogen and oxygen, must be
continuously supplied via gas channels and pores in the GDL and
the electrodes to reach the active platinum surfaces. In addition, the
gases contain a considerable amount of water vapor that will form a
thin water film over all solid matter in the cell.
In a liquid electrolyte, such as sulfuric or perchloric acid or al-
kaline solution, the appearance of the Hupd on polycrystalline Pt or
Pt/C catalysts differs slightly between different electrolytes, both in
the peak positions and the relative size of the two peaks. It was
proposed by Markovic and co-workers5,6 that this is a consequence
of the adsorption of anions that are adsorbed in the double layer
region and are replaced by adsorbed 共or replace desorbing兲 hydro-
gen at the potentials of the peaks. Sulfate, for example, is strongly
bonded to the Pt surface, resulting in defined Hupd peaks in the
voltammogram. Generally, the peak positions are shifted negatively
with increasing temperature, both in aqueous solution7-9 and in con-
tact with Nafion.10 The Hupd charge on Pt, polycrystalline and single
crystal, has been shown to be practically unaffected by temperature
in aqueous solution.7,11-15 However, in fuel cells operated at elevated
temperatures, a significant decrease in the charge has been observed
when the temperature is increased.16-18
Several studies have been performed to investigate the interac-
tions between Nafion and the platinum surface and the influence on
the Hupd,10,19-22 where most of them were performed on Nafion-
coated Pt in H2SO4 共aq兲. Maruyama et al.19 reported that recast
Nafion did not reach the expected exchange current densities, even
though they found a higher hydrogen solubility in Nafion compared
to 0.1 M HClO4. The lower electrochemical activity for Nafion was
explained by blocking of the catalyst by electrochemically inactive
fluorocarbon domains in the Nafion ionomer, even though these do-
mains showed excellent hydrogen solubility. The same argument
was used by Chou et al.,22 who compared the Hupd on a Nafion-
coated Pt surface with one without a Nafion-coating. The Hupd
charge measured from cyclic voltammetry 共CV兲 for the bare surface
in 0.5 M H2SO4 was 50% larger compared to the coated one at
room temperature. Also, Jiang and Kucernak20 observed a suppres-
sion of the Pt hydrogen and oxygen electrochemistry by Nafion
when comparing 0.5 M H2SO4 electrolyte with water saturated
Nafion. Possible effects of ionic or organic impurities were confuted
in their study. However, according to Strmcnik et al.,21 impurities
can play an important role in the electrode activity. Liu et al.23 have

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 B1796 Journal of The Electrochemical Society, 157 共12兲 B1795-B1801 共2010兲

studied porous electrodes in a fuel cell at varying relative humidity

共RH兲 and found that the Hupd charge was nearly independent of
water activity. Xu et al.,24 however, saw an increase in the Hupd
charge when increasing the relative humidity from 20% up to 72%,
but observed no further increase above 72%.
Another common method for the determination of the active area
is to use stripping of an adsorbed CO monolayer from a CO satu-
rated aqueous solution. CO adsorbs with approximately 0.8 mL 25
on polycrystalline platinum, as revealed by electrochemical strip-
ping and infrared spectroscopy in ultrahigh vacuum.26 Bett et al.2
determined the CO molecule/H atom ratio electrochemically as ap-
proximately 0.9. The charge of the oxidation peak is generally taken
to be equivalent to two electrons per CO molecule, which results in
a charge about twice that of the Hupd peak. Similar to Hupd, a linear
negative shift is observed for the CO stripping peak potential with
increasing temperature in aqueous electrolyte15,27 in contact with
Nafion10 as well as in a fuel cell.28 The CO oxidation charge has
generally been observed as fairly constant when increasing
temperature.10,15,17,27 Some studies have experienced a decrease of
the CO oxidation charge at temperatures above 60°C and attribute
the difference to thermal desorption of CO in the time period be-
tween the adsorption and stripping procedure.10,15 Shinozaki et al.17
concluded that the most accurate determination of active platinum
surface area was made by CO adsorption and that the most reliable
result was obtained at a temperature of 40°C or lower. Ioroi et al.28
studied the effect of relative humidity on CO oxidation in a fuel cell
and found that the charge of the oxidation peak was almost indepen-
dent of relative humidity, although the peak potential shifted nega-
tively with increased humidification up to saturation.
In this paper we have compared the electrochemically active sur-
face area determined from hydrogen adsorption/desorption with that Figure 1. 共Color online兲 Experimental setup: gas humidifiers and gas flow
determined by CO monolayer oxidation peak charges for a conven- meters 共1兲, heated stainless steel tube system with Swagelok connections
tional porous Pt/C electrode in a single fuel cell setup, at varying including valves enabling a shift between pure and contaminated gas flow
temperatures and relative humidity. We also give an example on 共2兲, fuel cell hardware at controlled temperature connected to a potentiostat
共3兲.
how the present cell conditions can influence the determination of
the electrochemically active surface area and what information can
be obtained by using CO stripping as a diagnostic tool after an
accelerated fuel cell degradation test. This paper is an approach to which the gas entered from the center. With an approximate cell
correlate the results from simplified and well studied model and volume of 0.1 cm3 and gas flows around 1 mL/s, the residence time
single crystal electrodes with the more realistic fuel cell system, of the gas was about 0.1 s over the electrode. The hardware was
where contributions from the solid electrolyte, the gas diffusion coupled to the humidifiers as shown in the schematic sketch in Fig.
electrodes, and humidified gas may contribute to the overall reaction 1.
behavior. In this design it was possible to switch between pure humidified
nitrogen gas flow and a humidified carbon monoxide-containing gas
Experimental 共2% CO balanced with Ar兲. To avoid hydrogen crossover the inlet
MEA preparation.— A Nafion 115 membrane, purchased from gas on the combined counter and reference electrode 共CE兲 was 5%
DuPont, was cleaned by boiling, first in 3% H2O2 共aq兲 solution for H2 balanced with Ar, giving rise to a potential shift of −0.045 V
1 h, followed by 1 h in 0.5 M H2SO4, and finally boiled in three versus the relative hydrogen electrode 共RHE兲 according to Nernst’s
successive Milli-Q baths for a few minutes. The membrane was then equation. All graphs shown in this paper are corrected for this shift.
dried in an oven at 70°C for 15 min and pressed flat at 130°C just
before applying the catalyst. The electrode ink was prepared by Electrochemical characterization.— Cyclic voltammetry curves
mixing the Pt/C powder 共20 wt % Pt/Vulcan XC-72 from ETEK兲 were recorded with a PAR273A potentiostat, controlled by Cor-
with 5 wt % Nafion solution 共from DuPont兲 using Milli-Q water and rWare software. Before experiments the MEAs were activated at
isopropanol in equal volumetric amounts as solvent, giving 36 wt % 80°C and 90% RH according to the following protocol:
Nafion in the dry electrode. The ink was ultrasonicated and stirred a兲 Cycling in N2 共50 cycles at 100 mV/s兲 between 0.1 and 1.2 V
for 24 h before 20 ␮l was pipetted on the membrane placed on a versus RHE with 5% H2 on the CE.
heated table 共90°C兲 for evaporation of the solvents. The resulting b兲 Cycling in O2 共50 cycles at 100 mV/s, 5 cycles at 10 mV/s
electrode had an approximate area of 0.3 cm2 and a loading of and 5 cycles at 1 mV/s兲 between 0.5 and 0.9 V versus RHE with H2
on the CE.
0.17 mg Pt. A commercial gas diffusion electrode from ETEK 共30%
c兲 A second cycling in N2 共50 cycles at 100 mV/s兲 between 0.1
Pt/C on a GDL兲 with a diameter of 16 mm was used as a combined
and 1.2 V versus RHE with 5% H2 on the CE.
reference and counter electrode. A GDL from Carbel, also 16 mm in
Stripping curves were recorded with CV, in the potential window
diameter, was used for the working electrode 共WE兲. The membrane
electrode assembly 共MEA兲, including the GDLs, was hot pressed at between 0.05 and 1.2 V, at a sweep rate of 10 mV/s. After a cycle in
130°C for 30 s. humidified N2 gas, the potential scan was stopped at 0.15 V and the
gas flow shifted to CO-containing gas for CO adsorption during
The cell assembly.— The MEA, including the GDLs, was 2 min. Thereafter, the inlet gas was shifted back to nitrogen for
mounted in a modified ElectroChem Inc standard fuel cell hardware 5 min, to flush out remaining CO in the cell, before subsequent
with own design of the graphite plates using a spiral gas channel stripping. Measurements were made at temperatures between 25 and
共1 mm wide and deep channels兲 over a circular area of 2.0 cm2, in 80°C and at different levels of relative humidity 共40%–100%兲.

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 Journal of The Electrochemical Society, 157 共12兲 B1795-B1801 共2010兲
10
25
5
I 30
II
Current density / mA (mg Pt) −1
60
80
0
−5
−10
−15
0 0.2 0.4 0.6
Potential vs RHE / V
Figure 2. 共Color online兲 Base CV for 20% Pt/Vulcan electrode 共0.17 mg Pt兲
in a nitrogen flow humidified to 90% RH, recorded at a sweep rate of
10 mV s−1. The temperatures in °C are indicated in the figure.
Further, a support degradation test was conducted, where the
electrode was activated over night by potential cycling in oxygen
2000 times between 0.6 and 0.9 V versus RHE followed by degra-
dation in a potentiostatic degradation test at 1.4 V versus RHE for
3 h in nitrogen. Prior to and after the degradation tests, polarization
curves in oxygen, cyclic voltammetry in nitrogen, as well as CO
stripping curves were performed according to the same protocol as
described above, except that the sweep rate used for CO stripping
was 20 mV/s. In addition, polarization curves were recorded with
100% hydrogen on both working electrode and counter electrode
using the slope to determine the resistance of the fuel cell. The
current densities in the support degradation test example are all cor-
rected for the cell resistance.
ECA estimation.— The Hupd charge was calculated from the in-
tegral over the desorption peaks in the Hupd region using the CO
stripping curve, for which the peaks are completely suppressed, as a
baseline. It was considered that the charge of the adsorption peaks
was more difficult to estimate due to the overlap with the onset of
hydrogen evolution. The integral of the area from the onset of the
hydrogen evolution 共 ⬃ 0.1 V兲 to the maximum value in the double
layer charge 共 ⬃ 0.35 V兲 was approximately the same for the ad-
sorption and desorption, within an error of 10%. The charge of the
CO stripping peak was estimated in a similar manner using the
corresponding base CV 共in nitrogen gas兲 as a baseline.
Results and Discussion
The base CV of Pt/C MEA.— Figure 2 shows typical cyclic vol-
tammetry curves obtained in flowing nitrogen humidified to 90%
RH at 25–80°C. The two characteristic hydrogen adsorption and
desorption peaks typical for polycrystalline Pt in sulfuric acid solu-
tion as well as carbon supported Pt are present in the curve obtained
at 25°C. The symmetric peaks 共adsorption and desorption兲 at 0.25 V
共II兲 shift negatively with increasing temperature in accordance with
literature on studies performed in solution6-9,11-14 and using Nafion
membranes as electrolyte.10,28 The peaks at 0.15 V 共I兲 disappear as
the temperature rises, and at 80°C only one pair of peaks at 0.2 V is
apparent.
The onset of the hydrogen evolution seen in our voltammograms
is shifted positively compared to those obtained in acidic
solutions.7,15 This shift is argued to be caused by the deviation from
standard conditions in the inert nitrogen atmosphere resulting in a
more positive equilibrium potential. This effect is dynamic and
causes a variation in the equilibrium potential due to the evolution
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B1797
and consumption of hydrogen during the potential sweep, as previ-
ously suggested by Schneider et al.29 Further, mass transport from
80 60 the electrode surface facilitates an increase in the hydrogen evolu-
tion potential. Biegler et al.1 found that the onset of hydrogen evo-
lution in liquid electrolyte started at more positive potentials for a
25 smooth polycrystalline platinum electrode compared to a rough
30
platinum black electrode. An additional positive shift in the onset
potential of the hydrogen evolution could also be revealed on the
smooth electrode upon stirring heavily, confirming that the hydrogen
evolution was indeed mass transport controlled. Using a segmented
fuel cell at room temperature, Schneider et al.29 showed that the
onset of hydrogen evolution in nitrogen humidified gas flow is de-
pendent on the flow rate and on the position in the cell along the
flow channel. The onset potential shifted more negatively with no
flow or when it was measured deeper into the cell, leading to a
simultaneous appearance of a well defined desorption peak 共I兲. This
evidences that the off transport of evolved hydrogen counteracts the
0.8 1 1.2 electrode reaching its equilibrium, since the removal of evolved hy-
drogen by inert gas must be compensated for by the formation of
hydrogen, causing an increase in the hydrogen evolution current and
consequently in the overlap of the hydrogen evolution and the Hupd
region. In a recent study, Schneider et al.30 found similar results at
an elevated temperature 共70°C兲, although more pronounced com-
pared to their previous study at room temperature.29
In our measurements the gas flow velocity was controlled before
the gases were heated up in the humidifier and in the gas lines. Due
to the gas expansion with rising temperature in the cell, the actual
flow velocity through the cell must also increase. It is therefore
argued that the disappearance of the weakly adsorbed/desorbed hy-
drogen peaks 共I兲 with temperature is partly due to an increasing off
transport of evolved hydrogen and so, an increasing overlap of the
hydrogen evolution reaction with the hydrogen adsorption and de-
sorption peaks. Varying the flow of nitrogen between 25 and
140 mL/min had no effect on the size or shape of the peaks. How-
ever, setting the flow too low resulted in unstable curves, where
either crossover of hydrogen from the opposite site or permeation of
oxygen from the surrounding air influenced the curves. Stopping the
gas flows completely resulted in the reappearance of a nicely re-
solved desorption peak 共I兲.
The platinum oxide region also changes with temperature. In
accordance with Jiang and Kucernak10 and Chaparro et al.,18 both
the oxidation and reduction currents increase with temperature,
which may be explained by the combined effect of faster kinetics of
the oxide growth and the presence of more water in the gas at higher
temperatures. A similar observation can be made when altering the
level of humidity. At 80°C 共Fig. 3 and 5兲, the platinum oxidation
and reduction peaks increase as the level of humidity rises, similar
to the increase of the hydrogen desorption and adsorption peaks. The
strong dependence of humidity on the currents for Pt oxide forma-
tion is generally accepted and well documented 共see, e.g., Ref. 24兲,
while the behavior of the hydrogen adsorption and desorption peaks
with variations in humidity is not as clear. The increase of the Hupd
charge with increased humidity is in accordance with observations
made by Xu et al.,24 while Liu et al.23 found the Hupd charge nearly
independent of relative humidity.
A summary of the peak shift and the total H desorption charges,
as functions of temperature, is given in Fig. 3. A linear relationship
between the peak 共II兲 position and the temperature is observed. Fur-
ther, an increase in the temperature results in a strong decrease of
the Hupd charge density, most likely due to the overlap with the
hydrogen evolution reaction as discussed above. The Hupd is also
affected by the relative humidity. With rising relative humidity, the
peak potentials are shifted negatively, accompanied by a linear in-
crease in the Hupd charges. The effect of humidity on the charges is,
however, significantly smaller than that of temperature.
An attempt was made to analyze the effect of sweep rate on the
base CV, but due to the relatively high resistance in our cell system,
the larger currents generated during the faster sweep rates gave rise
to a significant hysteresis of the peaks. As a result a detailed inves-
 B1798 Journal of The Electrochemical Society, 157 共12兲 B1795-B1801 共2010兲

1.2 0.3 20
25
80
15 60
1
30
−1

−1
0.25
10

Current density / mA (mg Pt)

Charge density / mC (mg Pt)

Peak potential vs RHE / V

0.8

5
0.6 0.2
0

0.4
−5
0.15
0.2
−10

0 0.1 −15
20 30 40 50 60 70 80 0 0.2 0.4 0.6 0.8 1 1.2
Temperature / °C Potential vs RHE / V

Figure 3. 共Color online兲 The dependence of the Hupd charges 共from the
positive desorption charge兲 on temperature and humidity, and peak potentials
for the strongly bonded desorption peak II. The symbols are related to rela-
tive humidity as follows: 90% RH 共䊏兲 60% RH 共⽧兲 and 40% RH 共䉱兲, filled
symbols are the charge densities and unfilled are the peak potentials.
Figure 4. 共Color online兲 CO stripping curves obtained for a 20% Pt/Vulcan
electrode 共0.17 mg Pt兲 in a nitrogen flow humidified to 90% RH, recorded at
a sweep rate of 10 mV s−1, after CO monolayer adsorption for 2 min in 2%
CO 共Ar balanced兲 at 0.15 V followed by nitrogen purging for another 5 min.
The temperatures in °C are indicated in the figure and the corresponding base
CVs are plotted in thin lines 共see Fig. 2兲.

tigation of the effect of the sweep rate on either the charge of the
peaks or the peak potential could not be made. The peak current
should, however, be essentially unaffected by the distortion and was
as expected found to increase linearly with the square root of the
sweep rate.
To summarize, a large deviation of the Hupd is found when
changing the experimental conditions using the same MEA. An ob-
servation that brings up the question of what is a proper measure of
the platinum active area in a fuel cell and if the electrochemically
active surface area is changing with temperature and humidity. For
comparison, the surface area was also determined employing CO
stripping.
CO monolayer oxidation.— In order to obtain a good measure of
the active surface area at fuel cell relevant conditions, CO stripping
was performed directly in the fuel cell and not in the sulfuric or
perchloric acid aqueous solutions, generally used as a standard. The
gaseous system has an advantage in the possibility to increase the
CO concentration above the saturation level of CO in acidic water
solution. Further, CO adsorption is very rapid on the platinum sur-
MEA from the anode/reference electrode 共H2 balanced with Ar兲
most likely interfered with the data. These complications hindered
any analysis of the displacement.
Figure 5 shows the dependence of relative humidity on the CO
stripping behavior. The positive shift in CO stripping potential with
decreased relative humidity is in accordance with Ioroi et al.,28 who
found that the shift in peak potential was linear with the partial
pressure of water vapor. The potential shift and the broadening of
the peaks are argued to be effects of a smaller amount of water, and
consequently less OHad on the surface, which is needed for the CO
oxidation to take place according to a Langmuir–Hinshelwood reac-
tion mechanism. This effect can be compared to the effect of pH,
since it is known that the potential of the CO stripping peak obtained
in alkaline solution is more negative than the one obtained in acidic
15
90
10
−1

face, and after switching to inert gas flow 共here nitrogen兲 the cell is 60
Current density / mA (mg Pt)

easily purged from any remaining CO. Figure 4 shows the CO strip-
ping curves obtained at 90% RH for the same temperatures pre- 5 90
40
sented in Fig. 2. 60
Upon CO adsorption, the hydrogen desorption peaks are sup- 40
pressed, indicative of a saturated monolayer of CO on the platinum
0
surface. At high humidity and a potential sweep rate of 10 mV/s, the
monolayer is oxidized to CO2 in a distinct peak between 0.6 and
0.8 V, depending on the temperature. The negative shift in the peak
potential with increasing temperature is in accordance with observa- −5
tions made in a fuel cell,28 water immersed Nafion,10 and in acidic
solution.15,27 In agreement with previous fuel cell studies,17,18,28 no
distinct prepeaks were observed in our experiments in contrast to −10
typical CO stripping curves in acidic solution15 and for water im- 0 0.2 0.4 0.6 0.8 1 1.2
mersed Nafion.10 The prepeak observed in the latter study10 is prob- Potential vs RHE / V
ably due to higher pH, as the CO was supplied from a CO saturated
Figure 5. 共Color online兲 CO stripping curves obtained for a 20% Pt/Vulcan
neutral water solution, as shown in Ref. 31. During the adsorption electrode 共0.17 mg Pt兲 in a nitrogen flow at 80°C, recorded at a sweep rate of
the displacement charge was monitored, but it was difficult to obtain 10 mV s−1, after CO monolayer adsorption for 2 min in 2% CO 共Ar bal-
reliable reproducible data as the displacement was very rapid and anced兲 at 0.15 V followed by nitrogen purging for another 2 min. The dif-
within the time frame of adjusting the valves, with the result of a ferent levels of relative humidity are indicated in the figure and the corre-
noisy signal. In addition, crossover of hydrogen gas through the sponding base CVs are plotted in thin lines.

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 Journal of The Electrochemical Society, 157 共12兲 B1795-B1801 共2010兲
1.2
1 1
−1
Charge density / mC (mg Pt)
0.8
0.6
0.4
0.2
0 argued that the CO adsorption is not an electrochemical process and
20 30 40 50 60 70
Temperature / °C
Figure 6. 共Color online兲 The dependence of the CO monolayer oxidation
charges on temperature and humidity 共subtracted from the corresponding
base CV兲 and peak potentials for the CO stripping peak. The symbols are
related to relative humidity as follows: 90% RH 共䊏兲 60% RH 共⽧兲 and 40 %
RH 共䉱兲, filled symbols are the charge densities and unfilled are the peak
potentials.
solution.31 The observed tilt in the CV shows that the cell resistance
increases with decreasing amount of water in the system, mainly due
to losses in ion conductivity in the membrane. However, an in-
creased contact resistance as the pressure over the cell decreases
with less swelling of the membrane at low humidity cannot be ruled
out.
Figure 6 summarizes the effect of temperature and humidity on
the CO stripping charges and peak potentials. The most striking
observation is that in comparison to the Hupd, the charge of the COad
oxidation peak is independent of temperature for a well humidified
cell. At the same relative humidity, using the same adsorption and
purging periods, the charge of the stripping peak is almost constant.
These results are in contrast to Jiang and Kucernak,10 who found a
decrease in the charge of the CO stripping peak as the Hupd charge
decreased at higher temperatures. Comparing the charges of the Hupd
and the CO stripping peak at 80°C and 90% RH, we were at first
surprised that the CO oxidation peak appeared to be much too large
in comparison to the Hupd area. Only at 25°C did the CO oxidation
peak have a charge corresponding to that expected from the Hupd.
In order to ensure that the inert gas purging time was sufficient in
our setup, its effect on the CO stripping peak was investigated.
Prolonging the time caused a decrease in the size of the peak, but no
steady state value was obtained. After 1 h of nitrogen purging, 90%
of the original peak remained, which is still three times that ex-
pected from the Hupd. Purging over night in humidified nitrogen flow
at 0.15 V, followed by a positive potential sweep, resulted in an
absent CO stripping peak. There was, however, a slight increase in
the positive sweep current at high potentials, probably due to oxida-
tion of contaminants adsorbed during the night. Based on these ob-
servations we concluded that the removal of nonadsorbed CO was in
fact very rapid in our setup and the gradual loss of adsorbed CO
with time was due to oxidation with traces of oxygen in the system.
Lower relative humidity decreases the charges of the CO strip-
ping peak especially for the higher temperatures, as can be seen in
Fig. 6. The same influence of humidity is also found for the charges
of the Hupd 共Fig. 3兲. The decreased charges are proposed to be due to
lower wetting, and consequently, less active area available in the
electrode under drier conditions. In order to investigate if the
amount of ionomer in the electrode would influence this behavior,
experiments were also performed with an electrode with only
26 wt % Nafion instead of the optimized composition of 36 wt %
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B1799
1.1 used in the rest of the study. Similar results were obtained for this
electrode as the previous one. The CO and Hupd peak positions were
shifted with temperature and relative humidity, and the charges of
the Hupd peak were decreased with both increased temperature and
decreased relative humidity. The CO stripping peak was shifted to
more negative potential with increased temperature and humidity in
Peak potential vs RHE / V
0.9 a similar manner as observed for the optimized electrode, and the
charge was essentially independent of temperature at high humidity,
while a decrease was seen at lower humidity. However, this decrease
0.8 of the CO stripping charge was significantly larger for the lower
Nafion content in the electrode than for the higher Nafion content,
which supports the hypothesis that the decreased charges of the CO
0.7 stripping peak with decreased relative humidity are caused by lower
wetting of the catalyst at drier conditions.
The question remains of how to interpret the discrepancy be-
0.6 tween the CO stripping and Hupd charges with increasing tempera-
ture while both charges decrease with lower humidity. It may be
80
may take place at all Pt surface independent of whether the platinum
particle is in contact with the polymer electrolyte or not, while the
Hupd forms from protons or water and is only possible in contact
with the electrolyte. However, protons are formed during the oxida-
tion of the CO adlayer and thus the surface must be in contact with
the electrolyte, electrical contact alone is insufficient. The counter
ions in Nafion are the sulfonic acid groups, bonded in the membrane
framework, and in contrast with liquid electrolyte, they cannot mi-
grate in the liquid surface film. Consequently, the charge balance
can only be maintained as long as the protons are formed in the
vicinity of the Nafion solid electrolyte. However, due to the rela-
tively fast surface diffusion of adsorbed CO 共and possibly adsorbed
H2兲 from isolated Pt sites to sites in contact with proton conductive
ionomer, the electrochemical reactions can possibly proceed. In con-
clusion, if the same physical requirements must be fulfilled by the
two reactions, it seems more likely that the measured Hupd in a fuel
cell is an underestimation of the electrochemically active surface
area. The decreasing Hupd charge is proposed to be due to an in-
creasing overlap with the hydrogen evolution reaction, which in-
creases as the peak positions of the hydrogen adsorption and desorp-
tion peaks shift negatively with increasing temperature in
combination with a very slight positive shift for the hydrogen reduc-
tion peak. If so, the active area determination measured from CO
monolayer would be a more accurate one. The slightly decreasing
charges for both the Hupd and the CO stripping peak with decreasing
humidity support the hypothesis that with less water in the Nafion,
the relative blocking of Pt active surface by hydrophobic domains in
the Nafion increases.
Example—degradation test at 1.4 V.— As mentioned in the in-
troduction, the loss of electrochemically active Pt area is often used
as a measure of the degradation of the Pt/C electrodes. However, the
apparent loss of Pt active area is not always connected to a loss in
performance. Figure 7a shows the polarization curves of a conven-
tional E-tek electrode, before and after an accelerated carbon sup-
port degradation test, constituted of a potentiostatic hold at 1.4 V for
3 h at 80°C and 90% RH in nitrogen gas flow. According to the
inset voltammograms, the double layer capacitance increases drasti-
cally during the test, most likely due to the formation of surface
oxides on the carbon, and the Hupd charge decreases. However, as
indicated by the polarization curve, the performance is only de-
creased in the high current region, presumably due to transport limi-
tations in the electrode.32 Interestingly, after the cell was restarted
after having been switched off and left at rest during the night at
room temperature, without any gas flowing through, an increase in
performance was seen, with higher current densities in almost the
whole potential range. In addition, the Hupd charges are regained,
whereas the increase in double layer capacitance remains, as can be
seen in the inset in Fig. 7a. Obviously, the active area was not lost
by the test, even though the Hupd appeared to disappear in the CV.
To better analyze this, CO stripping was performed after each stage.
 B1800
1 over the night. At the same point, a better performance than before
0.9
Potential / V vs RHE
0.06
Current density / (A mg Pt) -1
0.8
0.7
-0.06
0 1.2
0.6 -4
Potential / V vs RHE
10
(a)
0.04
Current Density / A mg Pt) -1
0.02
0 that CO stripping is better to use for determination of the platinum
-0.02
-0.04
0 0.2
(b)
Figure 7. 共Color online兲 Example:degradation test at 1.4 V with a 20%
Pt/Vulcan electrode 共0.16 mg Pt兲 at 80°C and 90% relative humidity, 共a兲
Polarization curves in oxygen and cyclic voltammetry in nitrogen in the inset
共i兲 before, 共ii兲 after 3 h at 1.4 V, and 共iii兲 after 12 h at rest at room tempera-
ture. Scan rate in oxygen 50 mV s−1 and in nitrogen 100 mV s−1. 共b兲 CO
stripping curves in a nitrogen flow recorded at a sweep rate of 10 mV s−1,
after CO monolayer adsorption for 2 min in 2% CO 共Ar balanced兲 at 0.15 V
followed by nitrogen purging for another 2 min 共i兲 before, 共ii兲 after 3 h at
1.4 V, and 共iii兲 after 12 h at rest at room temperaure.
The corresponding CO stripping curves 共20 mV/s兲 recorded before
directly after the potentiostatic test and after rest during the night are
displayed in Fig. 7b.
The most interesting observation is the positive shift in the CO
oxidation peak potential for the curve taken directly after the test.
The shift and the broadening of the peak resemble the shift observed
for lower humidity in Fig. 5. We propose that the observed shift in
Fig. 7b is a consequence of drying of the electrode during the test,
since water is readily oxidized to oxygen gas at 1.4 V. The dry
conditions decrease the proton conduction of the ionomer as water
channels are contracted, which generally leads to increased resis-
tance and decreased performance for oxygen reduction on the
electrode.23 However, the polarization curves are all iR-corrected by
measurements with a symmetric H2 /H2-cell after each polarization
curve, and the resistance cannot explain the lowered performance at
higher current densities. Another consequence of the increased re-
sistance is an increasing hysteresis of the peaks in the CV, i.e., in the
positive going sweep direction a positive shift is found for the peak
potentials. After the stop and when the original conditions are reset,
the CO stripping peak potential is shifted back to the original posi-
tion. This may be partly explained by the regained Nafion structure
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Journal of The Electrochemical Society, 157 共12兲 B1795-B1801 共2010兲
the degradation test is seen in the polarization curves, indicating that
the high potential hold in the test resulted in an improvement of the
cell, possibly due to changes of the morphology of the electrode.
These phenomena will be discussed in a forthcoming paper.33
iii Comparing the charges of the CO stripping peak before, directly
after, and after the stop, only a small variation was evident; the
variation was from 25 through 22 to 23 mC. The charge of the H
desorption peak, however, varied from 9.6 through 6.5 to 6.4 mC
共using the stripping curve as baseline兲 during the test. In accordance
i
ii with the previous results at 80°C, the charge of the CO oxidation
peak is much larger than expected from the 1:2 relation. This can be
understood by the underestimation of the Hupd at this temperature in
a gaseous flow cell, as has been discussed. The loss of charge di-
rectly after the test, which remains after the stop, shows that the test
-3 -2 -1 0 does result in some loss of platinum active area. However, it should
10 10 10 10
Current density / A (mg Pt) -1 be noted that the hydrogen desorption peak smears out directly after
the test, and without the CO stripping curve as baseline the Hupd
charges would have been estimated as much smaller. The large loss
iii of Hupd apparent in the cyclic voltammogram recorded at a fast
sweep rate directly after the test, shown in the inset in Fig. 7a, is
argued to be due to increased resistance and a decrease of the inter-
ii face between catalyst and ionomer in the cell at lower humidity. As
i a result, the peaks are smeared out and the overlap with the in-
creased double layer capacitance caused by carbon surface oxides.
To conclude, the risk for overlap with hydrogen evolution and
double layer charges when determining the Hupd charge suggests
active area in a fuel cell.
This example clearly shows that the active area of carbon-
supported platinum in contact with Nafion electrolyte is not easy to
determine and is strongly dependent on the present conditions in the
cell. For a correct comparison of electrodes or the effect of various
treatments, it is important that the experimental conditions are kept
the same, especially the level of humidity. The example also dem-
0.4 0.6 0.8 1 1.2
onstrates that CO stripping experiments can be used as a diagnostic
Potential / V vs RHE
tool to follow the effect of different electrochemical treatments used
for instance in accelerated degradation tests.
Conclusions
The results show that there are considerable differences between
experiments in a fuel cell, with a gas diffusion electrode and Nafion
electrolyte, and the classical measurements in acidic or alkaline
aqueous solutions. The most striking observation is that the hydro-
gen region changes significantly with temperature as well as with
humidity. Compared to sulfuric acid solution where increased tem-
perature only affects the peak positions but not the peak areas,7 the
charges in the fuel cell setup decrease strongly with temperature.
However, the peak charges for the COad oxidation are about the
same, independent of temperature in the fuel cell and, similar to
experiments in sulfuric acid solution, the CO stripping potential is
shifted linearly with temperature.10,15,27,28
It is suggested that the decreased charge of the Hupd with in-
creased temperature is connected to the overlap with the hydrogen
evolution reaction in a gas flow cell. With increasing temperature,
the overlap is more pronounced since the hydrogen peaks are shifted
to more negative potential, while the onset of hydrogen evolution is
almost constant. The small decrease in both charges, Hupd and CO
stripping peak, at lower humidity confirms that with less water in the
Nafion ionomer, the blocking of the electrochemically active Pt sur-
face by hydrophobic domains in the polymer electrolyte increases.
From the strong influence of temperature and humidity on the
Hupd in a fuel cell and as clearly visualized in our example of a
potentiostatic corrosion test at 1.4 V, we conclude that determina-
tion of the electrochemically active surface area of platinum using
the charge of the Hupd region is not a good measure of the Pt loss
after degradation of a fuel cell. Both the parameter study and the
accelerated degradation test show that CO stripping is less affected
by, and better defined at, various fuel cell conditions than the Hupd.
 Journal of The Electrochemical Society, 157 共12兲 B1795-B1801 共2010兲
As the Hupd is close to the potential for the onset of hydrogen evo-
lution, an overlap between these reactions cannot be avoided. We
therefore propose that CO stripping is a more accurate measure of
the active area in a fuel cell. If the Hupd area will be used, a rela-
tively good estimation is achieved when the temperature is de-
creased to room temperature and water saturated gases at a very low
or, preferably, zero flow rates are used, as suggested in Ref. 29.
Acknowledgments
The work was supported by the Swedish Research Council, the
Swedish Energy Agency, and the MISTRA fuel cell program.
Kungliga Tekniska Högskolan assisted in meeting the publication costs of
this article.
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