Electrolyte Resistance Measurement in the Catalyst

Layers of Polymer Electrolyte Fuel Cells using

Electrochemical Impedance Spectroscopy

References
1.

C. Boyer, S. Gamburzev, O. Velev, S. Srinivasan,

A.J. Appelby, Electrochimica Acta, 43, 3703-3709
(1998)

2.

M.C. Lefebvre, R.B. Martin, P.G. Pickup,

Electrochem. and Solid State Letters, 2, 259 (1999)

3.

X. Ren, P.G.Pickup, Electrochimica Acta, 46, 41774183 (2001)

Rohit Makharia, Michael Murphy,

Mark Mathias, John Iaculli, Hubert Gasteiger
General Motors Global Alternative Propulsion Center
10 Carriage Street, Honeoye Falls, NY 14472

-0.4
2

Axes: ohm cm
2
DC Current: 0.12 A/cm

-0.3
-0.2
Z

Performance of Polymer Electrolyte Fuel Cells (PEFCs)

using hydrogen as a fuel is limited mainly by oxygen
reduction reaction kinetics and transport losses (proton
and/or oxygen) at higher current densities. AC impedance
techniques can be used as powerful tools to identify these
rate limiting processes in PEFCs. This work focuses on
using AC impedance to measure the electrolyte resistance
(i.e., proton conductivity) in the catalyst layers of
Membrane Electrode Assemblies (MEAs).
Such
measurements are needed for MEA development,
durability
investigations,
understanding
operating
condition effects and others. This paper describes various
methods and models used to measure electrolyte
resistance. We will evaluate the consistency of the
electrolyte resistance determined using three different
methods and the advantages and disadvantages of each
method will be discussed.

10

-0.1

100

Fit

Data

1k

1
0.1
0.01

10k
0.1

In-Situ Fuel Cell Characterization

Standard MEAs - Figure 1 shows the AC impedance
experimental data and a model fit result of a 50 cm2 cell
running under fully humidified conditions fed with pure
hydrogen and oxygen. Beginning at high frequency, one
can see regions of inductance, electrolyte resistance and
Warburg response. Figure 2 demonstrates that the 45
region is visible once the data of Figure 1 is corrected for
effect of cable inductance. The electrolyte resistance can
be extracted from this region using an appropriate model.
We have also extracted the inductance, pure resistances
(hardware, contact, membrane and diffusion media
resistances) and capacitance of the system. As expected,
the effect of current density on measured electrolyte
resistance was nearly negligible, but the electrolyte
resistance increased with decreasing ionomer loading in
the catalyst layer.
Diagnostic MEAs Boyer et al.1 demonstrated that the
electrolyte resistance could be extracted from specially
prepared MEAs. An inactive layer (containing ionomer
and carbon, with or without Pt) is sandwiched between two
membranes and placed in the path of the proton travel
from the anode to the cathode. High-frequency AC
response of different ionomer loadings in the inactive layer
enables us to determine the electrolyte resistance in the
inactive layer.

Ex-Situ Electrochemical Characterization

Purging the catalyst layer compartment with nitrogen
eliminates kinetics, and the effects of electrolyte resistance
and double layer capacitance determine the electrode
response. Pickup et al.2,3 have performed experiments
using this approach. They explain the deviation of
impedance response of a 45 region due to the
concentration gradient of the ionomer in the catalyst layer.

0.1

0.2

0.3

0.4

0.5

Figure 1: Experimental and model complex-plane

impedance plot using hydrogen/oxygen. Nafion
112 membrane, high stoichiometric ratios,
P=270
kPa, Tcell=80C,
Anode/cathode
Reactant RH = 100%

-0.050

500
1k

-0.025
2k

All experiments were performed on either 5 cm2 or 50 cm2

cells using hydrogen as the anode reactant gas.

Data Corrected
for Lcable
Model Fit

0.025

Raw Data
0.050
0.050

0.075

0.100

0.125

0.150

Z
Figure 2: Experimental and model complex-plane plot in
high-frequency region. Data corrected for cable
inductance reveals 45 region