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Electrochimica Acta 50 (2005) 2469–2474

An electrochemical impedance spectroscopy study of fuel cell electrodes
E. Bradley Easton∗ , Peter G. Pickup
Department of Chemistry, Memorial University of Newfoundland, St. John’s, NL, Canada A1B 3X7

Received 22 August 2004; received in revised form 19 October 2004; accepted 19 October 2004
Available online 30 November 2004

Abstract

Electrochemical impedance spectroscopy (EIS) was used to study the capacitance and ion transport properties of fuel cell catalyst layers.
It was found that limiting capacitance correlates with active area. The capacitance per gram of catalyst was calculated and is proposed as a
measure of catalyst utilization. Results obtained with catalyst layers immobilized on glassy carbon electrodes agree very well with results
obtained with gas diffusion electrodes. EIS was also used to study ion conductivity and active area in fuel cell electrodes that contain the
electroactive probe Os(bpy)3 2+ . Together, these results validate the hypothesis that the non-ideal behavior of fuel cell electrodes is due to
variations of conductivity across the layer, rather than variations in capacitance.
© 2004 Elsevier Ltd. All rights reserved.

Keywords: Fuel cell; Electrochemical impedance spectroscopy; Ion transport

1. Introduction cellent electronic conductors, we also assume that Relectronic
is negligible compared to Rionic , and therefore should have
Electrochemical impedance spectroscopy (EIS) is a pow- a negligible effect on the impedance of the electrode [4,11].
erful technique that can provide a vast amount of information We can also subtract the electrolyte resistance (Relectrolyte )
in a short period of time and has been applied to proton ex- since it would only shift the plot along the real axis. Based
change membrane fuel cells (PEMFC) in a number of recent upon these assumptions, the impedance response of a PEMFC
studies [1–9]. The cathode impedance typically dominates electrode can be simulated for any ionic conductivity profile
the PEMFC impedance when pure hydrogen is used at the an- [10,12]. Noticeably absent from this model is charge trans-
ode. Previous work in our lab has shown that the impedance fer resistance. This is because all impedance experiments are
of fuel cell electrodes closely corresponds to that of porous performed under nitrogen as opposed to oxygen, which sim-
electrodes, which can be modeled by a finite transmission- plifies the impedance response of the electrode.
line equivalent circuit, shown in Fig. 1. Although Nyquist type plots are the most common, we
The model is described in detail elsewhere [10]. Briefly, find it more informative to convert them into capacitance
the circuit consists of two parallel resistive rails, one plots [12]. This type of plot can better show how conductiv-
for electron transport through conducting carbon particles ity (resistivity) varies across the catalyst layer. This is because
(Relectronic ), the other for ion transport in the catalyst layer the capacitance axis can also be considered to approximate
(Rionic ). The rails are connected by capacitors representing a distance axis since the capacitance is uniformly distributed
the differential capacitance of the electrolyte-catalyst (Pt and across the layer. In practice, the capacitance measured by
C). We assume that this capacitance is uniformly distributed EIS will include both double layer capacitance and Faradaic
throughout the catalyst layer. Since carbon particles are ex- pseudo-capacitance terms for both the Pt and carbon surfaces.
However, within the potential range studied, these surface
∗ Corresponding author.
Faradiac processes can be modeled as capacitances in paral-
E-mail addresses: brad.easton@dal.ca (E.B. Easton), lel with the double layer capacitance. Also, we can assume
ppickup@mun.ca (P.G. Pickup). that their relative contributions do not vary greatly between

0013-4686/$ – see front matter © 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2004.10.074
2470 E.B. Easton, P.G. Pickup / Electrochimica Acta 50 (2005) 2469–2474

large percentage of Nafion was chosen to ensure good proton
conductivity and to avoid the use of other solvents in the ink
preparation.
The preparation of gas diffusion electrodes containing
Os(bpy)3 2+ electroactive probe (0.80 mg cm−2 20% Pt/C,
0.98 mg cm−2 Nafion, and 0.15 mg cm−2 Os(bpy)3 -
Cl2 ·6H2 O) is described in detail elsewhere [16]. Half-cell
electrochemical measurements were performed in a three-
electrode configuration by exposing the 1 cm2 test electrode
Fig. 1. Finite transmission-line equivalent circuit describing the impedance to a 0.5 M H2 SO4 electrolyte with a Pt wire counter electrode
behavior of a PEMFC electrode. and a Ag/AgCl reference electrode. For measurements in
fuel cells, membrane and electrode assemblies (MEAs) were
electrodes and that total capacitance is a relative measure- prepared by hot-pressing the 1 cm2 electrode and a similar
ment of electrochemically active area. This assumption is Pt black catalyzed electrode onto each side of a Nafion
supported by cyclic voltammetry studies [13]. membrane. Electrochemical experiments were performed
The main objectives of this work were to establish a re- on these MEAs in a two-electrode configuration with
lationship between the liming capacitance and active area, humidified hydrogen passing over the Pt black electrode,
validate measurements taken on fuel cell electrodes and which serves as both counter and reference electrodes, and
study their ionic conductivities. In one case, we studied the nitrogen passing over the test electrode. The impedance of
impedance behavior of catalyst layers immobilized on glassy the anode is assumed to be negligible. The MEA was run as
carbon electrodes following a procedure developed by Go- a H2 /O2 fuel cell (with O2 passing over the test electrode)
jkovic et al. [14]. This method has proved useful to study fuel for 30 min at 0.5 V immediately before the impedance
cell catalyst layers under carefully controlled conditions [15]. measurements were performed.
The impedance response was studied as a function of cata-
lyst layer thickness and dc bias potential. In another case, we 2.2. Pt particle size
studied the impedance response of gas diffusion electrodes
containing Os(bpy)3 2+ electroactive probes (which was ion Powder X-ray diffraction (XRD) spectra were acquired
exchanged into the Nafion binder). Previous work in our lab using a Rigaku Ru 200 diffractometer using Cu K␣ radi-
has shown that electroactive probes are useful for studying ation (0.15405 nm). Average particle sizes were estimated
the activity of fuel cell electrodes [16]. One of the advan- from the spectral line broadening using commercial software
tages of using an electroactive probe is that it can serve as a (Jade 1994, Materials Inc.) that uses the Scherrer equation
reference point for impedance studies. and includes an instrument calibration parameter.

2. Experimental 3. Results and discussion

2.1. Electrochemical experiments 3.1. Catalyst layers immobilized onto glassy carbon
electrodes
Electrochemical experiments were performed at ambient
temperatures in a typical three-compartment cell using 0.5 M Cyclic voltammetry (CV) is the most common technique
H2 SO4 (aq.) as the electrolyte, a Ag/AgCl reference electrode to characterize active areas of Pt catalyst. CVs were obtained
and a Pt counter electrode. Electrochemical measurements for electrodes with various amounts of catalyst ink applied.
(CV, EIS) were performed using a Solartron (Schlumberger) Fig. 2 shows the CVs obtained with 1–6 ␮L of ink. Good
1286 electrochemical interface and 1250-frequency response definition of the hydrogen adsorption/desorption peaks was
analyzer controlled using custom software. Impedance Spec- obtained when a small amount of ink (1–3 ␮L) was used,
tra were collected using Z-plot software (Scribner Associates which allowed for easy integration of the area under the H-
Inc.) and obtained over a frequency range of 100 kHz to 1 Hz adsorption waves. However, these peaks became less defined
at a dc bias potential of 0.2 V versus Ag/AgCl unless other- as more ink is added, so much so that accurate integration
wise stated. was not possible when 5 and 6 ␮L of ink was used. The lack
Catalyst ink was prepared at a concentration of of peak definition may be due to increased resistivity in the
0.0222 mg ␮L−1 by mixing 20% Pt/Vulcan XC72 carbon catalyst layer when larger volumes are used. Nonetheless,
black (11.1 mg, Etek) and 5% Nafion solution (500 ␮L, So- for 1–4 ␮L, the charge under the H-adsorption wave does
lution Technology) thoroughly with a magnetic stirrer and scale well with ink volume, as shown in Fig. 3. From this, we
sonication to ensure homogeneity. Volumes of this catalyst calculate a value of 0.0396 mC ␮g−1 of catalyst.
ink (1–6 ␮L) were applied via a syringe onto a 0.071 cm2 Pt utilization was calculated as the ratio of the area of
glass carbon electrode and allowed to dry before use. Such a electroactive Pt, estimated from the charge under the H-
E.B. Easton, P.G. Pickup / Electrochimica Acta 50 (2005) 2469–2474 2471

Fig. 4. Nyquist plots obtained at a dc bias potential of 0.2 V vs. Ag/AgCl
for electrodes with various amounts of catalysts ink applied.

Fig. 2. CVs (100 mV s−1 ) obtained in 0.5 M H2 SO4 (aq.) with 1–6 ␮L of
catalyst ink applied.

adsorption waves (0.21 mC cm−2 ), to the total area of Pt esti-
mated from the mean particle size (radius r), on the assump-
tion that the particles are spheres with surface area 4πr2 .
Based upon an average Pt particle size of 3.2 nm determined
from XRD experiments, Pt utilization was estimated to be ca.
109%, when 1–4 ␮L of ink was applied.
Fig. 4 shows Nyquist plots obtained with various amounts
of catalyst ink applied onto the electrode. From these we can
see that the ionic resistance increases with the volume of
ink applied (an enlarged view of the high-frequency region
is shown in Fig. 5). However, there appears to be a larger
increase in resistance for electrodes containing 4–6 ␮L of
catalyst ink. This may be in part to due to a less homogenous
catalyst layer when large volumes of ink are applied since Fig. 5. Expansion of the high-frequency region of Fig. 4.
successive layers of ink was required to apply the larger vol-
umes of ink. The increased resistivity also explains the CV tained for 1–6 ␮L of catalyst ink applied. It can be seen that
results. for 1–3 ␮L of ink, the initial slope (up to half the total capac-
This increase in ionic resistivity can be better visualized itance) of each plot is very similar; indicating that the resis-
through capacitance plots. Fig. 6 shows capacitance plots ob- tivity of each is similar. However, plots obtained for 4–6 ␮L

Fig. 6. Capacitance plots obtained at a dc bias potential of 0.2 V vs. Ag/AgCl
Fig. 3. Variation of average hydrogen adsorption charge and limiting capac- for electrodes with (a) 1–3 ␮L of catalyst ink applied and (b) 4–6 ␮L of
itance as a function of the mass of catalyst applied. catalyst ink applied.
2472 E.B. Easton, P.G. Pickup / Electrochimica Acta 50 (2005) 2469–2474

Fig. 7. Mass normalized capacitance plots obtained for electrodes with dif- Fig. 8. Comparison of capacitance plots obtained at a dc bias potential of
ferent volumes of catalyst ink applied at a dc bias potential of 0.2 V vs. 0.2 V vs. Ag/AgCl with 2 ␮L of catalyst ink immobilized onto a 0.071 cm2
Ag/AgCl. glassy carbon electrode, to that obtained with a 1 cm2 gas diffusion electrode
equivalent to ca. 2.2 ␮L of catalyst ink.

show much lower slopes, indicating higher resistivity. This tential is set at a potential where Faradaic processes occur,
is perhaps better seen in Fig. 7 where the capacitances have then an increase in capacitance will be observed. We have
been normalized by dividing them by the mass of catalyst therefore studied the effect of dc bias potential on the EIS
applied. Here, the increasing resistivity is clearly visible. response of electrodes prepared from the Pt/C/Nafion ink de-
It can also be seen from the normalized capacitance plots scribed above.
that the limiting capacitance does scale well with the quantity Fig. 9 shows a plot of limiting capacitance versus dc bias
of catalyst applied. A plot of limiting capacitance as a func- potential. There is a large increase in capacitance between
tion of the mass of catalyst applied is shown in Fig. 3. From −0.2 and 0.0 V that can be attributed to the hydrogen adsorp-
this, we calculate a capacitance of 0.037 mF ␮g−1 of catalyst tion/desorption process on Pt. There are also smaller peaks at
and 0.196 mF cm−2 of Pt. These are useful parameters that higher potentials, which are shown in the inset of Fig. 9. The
can be applied to fuel cell electrodes to determine utilization. peak at ca. 0.3 V can be attributed to the presence of the elec-
The linearity of this plot indicates that even though thicker trochemistry of quinone groups present on the carbon surface
electrodes have higher resistivity, the active area per gram [17]. The peak between 0.6 and 0.9 V can be attributed to the
of catalyst of each electrode is approximately the same. This electrochemistry associated with oxide formation/stripping
would not necessarily be the case in an operating fuel cell on the Pt surface.
electrode, since a fuel cell electrode would not be as well These plots indicate that EIS data should not be acquired
hydrated as one exposed to sulfuric acid solution, nor would at potentials below 0.1 V (versus Ag/AgCl). While there are
it contain such a large percentage of Nafion. some Faradaic processes present above 0.1 V, the magnitude
Comparison of these results with those obtained with gas
diffusion electrodes is desired to validate the application of
EIS to fuel cell electrodes. To do this, a 1 cm2 gas diffusion
electrode, containing 0.85 mg cm−2 of ETEK 20% Pt/C, and
1.1 mg cm−2 (57%) of Nafion was prepared and tested in the
same electrolyte. This loading corresponds to the equivalent
of ca. 2.2 ␮L of catalyst ink applied onto a 0.071 cm2 elec-
trode. Fig. 8 compares the capacitance plot obtained with the
1 cm2 gas diffusion electrode to that obtained with 2 ␮l of
catalyst ink on the 0.071 cm2 electrode. The results are very
similar. The slight differences can be attributed to the differ-
ences in the Nafion content (65% versus 57%) and the ap-
proximate nature of the calculation. Nevertheless, this shows
that impedance measurements taken on gas diffusion elec-
trodes correlate well with data obtained by the more con-
trolled Nafion/catalyst ink on glassy carbon method. Fig. 9. Limiting capacitance as a function of dc Potential. Data obtained us-
The dc bias potential at which EIS is acquired can have a ing 1 ␮L of catalyst ink. The inset shows an expansion of the region between
significant effect upon the data collected. If the dc bias po- 0 and 1.2 V.
E.B. Easton, P.G. Pickup / Electrochimica Acta 50 (2005) 2469–2474 2473

Fig. 11. Conductivity profiles used to simulate the EIS data shown in Fig. 10.

initial slope of the capacitance plot is also observed in the
Fig. 10. Comparison of (a) capacitance plots and (b) Nyquist plots obtained
with nitrogen bathed 1 cm2 gas diffusion electrode containing the Os(bpy)3 2+
half-cell. This clearly indicates that there is better ionic con-
electroactive probe in both the half-cell and fuel cell MEA. Experimental ductivity in the half-cell compared to the fuel cell, agreeing
data is shown as open symbols, lines represent simulated data obtained using with our inferences from the CV. Based on the relationship
the conductivity profiles shown in Fig. 11. Half-cell data was obtained at a dc of 0.196 mF cm−2 established between the capacitance and
bias = 0.2 V vs. Ag/AgCl, fuel cell data was obtained at a dc bias = 0.425 V Pt area for this catalyst, the active Pt area in the fuel cell can
vs. NHE.
be estimated to be 64 cm2 .
is much lower than that for hydrogen adsorption/desorption To further study the differences in conductivity between
and should therefore have a smaller effect on the data col- the fuel cell and half-cell configurations, data was simulated
lected. from a conductivity profile to fit these experimental results us-
ing a Microsoft Excel spreadsheet [12]. The simulated fits to
3.2. Electrodes containing Os(bpy)3 2+ electroactive the impedance data are displayed in Fig. 10. The conductivity
probes profiles that simulated these fits are shown in Fig. 11. These
profiles are reasonable and are similar to those previously
One of the advantages of using an electroactive probe is reported [4,9,10,13]. Good fits were obtained, especially at
that it will provide an alternative method determination of the high-frequencies. The distance into the layer is based upon an
fraction of the catalyst layer that is electrochemically active. estimate of 55% of a 30 ␮m layer being electroactive (from
When the Os(bpy)3 2+ electroactive probe is incorporated into Ref. [16]). From this we see that in both cases the conduc-
the catalyst layer, a well defined Os(II/III) peak is observed tivity close to the electrolyte is similar and declines as you
during a CV experiment, which can be easily integrated. The move further away from the electrolyte. This is the experi-
area under the Os(II/III) peak is related to the fraction of the mental observation and it indicates that the catalyst layer is
catalyst layer that is electroactive, in the same manner that better hydrated close to the membrane. This can be explained
the area under the H-adsorption peaks are related to catalyst by electro-osmotic drag and the evaporation of water into the
utilization. backing layer. The similarity of the conductivities close to the
Fig. 10(b) shows Nyquist plots obtained in both a half-cell electrolyte indicates that the presence of H2 SO4 (aq.) in the
and in a fuel cell for electrodes containing Os(bpy)3 2+ elec- half-cell electrode does not appear to add significantly to its
troactive probes. Capacitance plots are shown in Fig. 10(a). conductivity. However, there is a much sharper decline in con-
The most obvious aspect of the capacitance plots is the higher ductivity when the electrode is used in a fuel cell. This is a re-
limiting capacitance obtained in the half-cell. This indicates sult of less catalyst layer hydration when used in the fuel cell.
that a significantly smaller fraction of the catalyst layer is
electrochemically active in the fuel cell. Based on the values
of the limiting capacitance, only ca. 65% of the catalyst layer 4. Conclusions
that is electroactive in the half-cell is electroactive in the fuel
cell. This value is slightly higher than that obtained by cyclic EIS is a powerful tool to study PEMFC catalyst layers. Ac-
voltammetry and integration of the Os(II/III) peak (ca. 55%, tive area and ionic conductivity within the catalyst layer has
Ref. [16]). This discrepancy is most likely due to slight vari- been studied as a function of catalyst layer thickness using
ation in catalyst loading between electrodes and/or variation EIS. We have shown that there is a relationship between the
of the hydration state within the catalyst layers. A steeper limiting capacitance and the mass of catalyst. The capacitance
2474 E.B. Easton, P.G. Pickup / Electrochimica Acta 50 (2005) 2469–2474

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