Comparison of Fuel Cell Electrolyte Resistance
Measurement Techniques
One of the key performance drivers for fuel cells is the
resistance of the electrolyte. The electrolyte is the
medium in which the ions produced at one electrode
migrate to the other electrode in order to complete the
electrical circuit. The passage of ions within a phase of
finite resistance gives rise to a voltage loss referred to
as ohmic polarization. Regardless of whether one
considers the electrolyte to be the solid polymer in a
proton exchange membrane (PEM) fuel cell, a
high-temperature ionically-conductive oxide in a solid
oxide fuel cell (SOFC), or an acid-soaked matrix in
phosphoric acid fuel cell (PAFC), electrolyte resistance
is an important metric for fuel cell performance. This
article examines and compares presently available
methods for measuring the resistance of the electrolyte
within a fuel cell. The fuel cell can be modeled by the
equivalent circuit shown in Figure 1. This is a
simplified version of the Randles equivalent circuit, a
model commonly applied to electrochemical systems
in which contact resistance and other effects are small
enough to ignore. For simplicity, assume that the
polarization resistance of one electrode (say the
cathode) is much larger than that of the other electrode
(the anode), so that one can legitimately omit circuit
elements associated with one of the electrodes (the
anode in this example). Polarization Resistance is the
reaction equivalent, Double-Layer Capacitance is the
interfacial capacitance of the cathode and Electrolyte
Resistance is the resistive component of the fuel cell to
be evaluated. The Voltage Source element is an ideal
DC voltage source (zero internal impedance, constant
voltage) with a potential equal to the open-circuit
voltage of the fuel cell. This element does not affect
AC analysis but allows the model to approximate the
DC behavior of the fuel cell.
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Comparison of Fuel Cell Electrolyte Resistance Measurement Techniques
Reedited from April/May 2005 issue of Fuel Cell Magazine
Fig.1 Simplified equivalent circuit for a fuel cell
Note that the values of these equivalent circuit
components are a function of the cell's operating
current or voltage, making the fuel cell an electrically
non-linear device. The sum of the electrolyte and
polarization resistances can be determined from the
slope of the linear portion of the DC voltage-current
(V-I) characteristic curve (polarization curve) of the
cell. The electrolyte resistance is a particularly
important measure of single fuel cell (or fuel cell stack)
electrical performance since it quantifies internal cell
losses. It is desirable to monitor electrolyte resistance
during electrolyte development and subsequent
manufacture of stacks because ohmic losses generate
waste heat that must be removed from the fuel cell,
resulting in a decrease in overall electrical efficiency.
In addition, because fuel cell current densities are quite
high in comparison to other electrochemical processes,
even small amounts of ohmic resistance (milliohms)
have a significant effect on overall efficiency.
Unfortunately, electrolyte resistance cannot be directly
measured by conventional DC methods when installed
in a fuel cell, nor can DC methods isolate electrolyte
resistance from polarization resistance. Furthermore,
because the resistivity of the electrolyte is a function of
the operating conditions (temperature, current density,
etc.) it is imperative that its resistance be determined
under operating conditions.
Fortunately, the electrode / solid electrolyte interface
has a large capacitance associated with it (the
Double-Layer Capacitance in Figure 1) that allows an
AC measurement to be used to determine the
electrolyte resistance separately from the polarization
resistance. This may be performed several different
ways, but all have some traits in common:
1. All methods impose a changing electrical
condition on the fuel cell.
2. All methods measure current or voltage
waveforms resulting from that change.
3. All methods require an accurate voltage
measurement directly at the cell terminals using a Fig.2 Typical current interrupt waveform

four-terminal (Kelvin) method.

The four methods generally used for electrolyte
resistance measurement are current interrupt (iR), AC
resistance, electrochemical impedance spectroscopy
(EIS) and high frequency resistance (HFR) methods. A
comparison of these methods follows a discussion of
the measurement principle, and the pros and cons of
each.
Current Interrupt Method
This time-domain AC technique, developed over 50
years ago, quickly interrupts the fuel cell current and
rapidly measures the terminal voltage before and
during the interruption. This is shown schematically in
Figure 2. Because the cell voltage is a combination of
the charged anode and cathode potentials less the
resistive drop of the electrolyte, the cell voltage rises
by the amount of the drop across the electrolyte. The
AC Resistance Method
This method uses an AC resistance measurement
device, such as an external AC milliohm meter, to
apply a fixed, single high frequency sine wave
(typically ~1 kHz) to the fuel cell under test to measure
the total impedance magnitude of the cell and the load
in parallel at that frequency. The set-up is shown in
Figure 3. The ohmic resistance of the electrolyte can be
extracted after correcting for the impedance of the
load.
Fig.3 Equipment set-up for electrolyte resistance by AC Resistance

cell ohmic resistance, dominated by the electrolyte, is measurement technique. Note that the electronic load is in

the ratio of the change in voltage (ΔV) due to the parallel with the fuel cell and therefore its impedance contributes

interrupt to the cell current. Advantages of this method to the observed AC resistance.

include a single data value which is easily interpreted.

Furthermore, there is no requirement for additional Like the current interrupt technique, this method only
equipment because the interrupt is brought about by provides a single data point. An advantage is that the
the load. The primary disadvantage of the iR method is cell is minimally disturbed electrochemically by the
that it imposes a significant perturbation on the cell, if measurement, but unfortunately accurate results cannot
only for a short duration (~ 10s μsec). Users of this be obtained without exact gain-phase characterization
method are also cautioned that iR data is degraded of the impedance of the electronic load at the operating
when long cell cables are used due to 'ringing' caused conditions of the fuel cell during the AC measurement
by cable inductance. (DC voltage, DC current and frequency) using
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Comparison of Fuel Cell Electrolyte Resistance Measurement Techniques
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additional external frequency analysis equipment.
Additionally, the zero-phase condition of the parallel
load-fuel cell combination measured by the milliohm
meter is not meaningful since it is not the zero-phase
impedance of the cell (the load has a complex
impedance in parallel with the complex impedance of
the cell). The only way to separate the actual cell
impedance is to use the measured load impedance and
reported magnitude and phase data of the milliohm
meter to calculate the impedance of the cell itself. The
difficulties of this technique stem from the millohm
meter not being intended to measure energy sources
under load.
High Frequency Resistance Method (HFR)
In the HFR method to determine electrolyte resistance,
a small AC signal is applied to the electronic load to
modulate the DC load current, as illustrated in Figure 4.
The resulting magnitude and phase of the AC voltage
and current response are measured by a frequency
response analyzer. A single, high frequency is used,
typically on the order of 1 kHz. This method is actually
a subset of the method described below wherein a
broad range of frequencies are employed. It is the Real
(Z') component of the impedance that is of interest,
usually displayed in milliohms. Looking at the
equivalent circuit in Figure 1, the double-layer
capacitance will act as a very low resistance for high
frequency signals. If a high frequency current is
applied and the corresponding voltage measured, the
resistance of the electrolyte is the ratio of these values.
The HFR measurement minimally disturbs the cell
from its operating condition, both in magnitude and
duration, and therefore it is suitable for routine,
periodic application during normal fuel cell operation
with the result displayed in real time.
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Comparison of Fuel Cell Electrolyte Resistance Measurement Techniques
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Fig.4 Equipment set-up for HFR and EIS measurement
techniques. The AC signal imposed on the cell is done by
modulating the load
The optimum measurement frequency can vary with
the electrochemical system under study and its
selection must be made with care. Selection of the
proper frequency is best accomplished by examining
the phase difference between the applied current and
measured voltage. When this difference is zero, the cell
is functioning in purely resistive manner. It should
ideally be the frequency at which imaginary
component of the impedance is zero (Z'' = 0). In terms
of a Nyquist plot, this condition exists when the
impedance data cross the real axis (Figure 5) at high
frequency (small Z'). If the Nyquist plot does not cross
the Real axis at high frequency, the highest frequency
before the plot deviates from the semicircular shape
may be used or the intercept of the data fit to a
semicircle or other model may be used. Typical HFR
measurement frequencies range from 500 Hz to 3 kHz.
In any case, the same frequency must be used for valid
data comparison.
Note that the method for choosing the HFR frequency
requires that the test system also have Electrochemical
Impedance Spectroscopy capability. This is generally
not a problem because a true frequency response
analyzer can measure over a wide range of frequencies,
so a test system capable of true HFR measurement will
also be capable of performing EIS measurements.
Electrochemical Impedance Spectroscopy (EIS)
Method
The EIS technique is an extension of the HFR method
previously described and differs in two ways. Whereas
HFR employed measurement at a single frequency and
generally only examined the real component of the
impedance, EIS involves imposing the AC perturbation
over a broad range of frequencies - typically 10 kHz to
1 Hz or lower - and monitoring the resulting variations
in magnitude and phase of the cell voltage and current
with a frequency response analyzer in order to
determine the complex impedance (Z' and Z'') of the
fuel cell. This results in a rich data set from which
several parameters may be extracted. The amplitude
and phase of the signals may be plotted in Bode and
Nyquist formats for analysis and modeling. Figure 5
shows an idealized Nyquist plot of the equivalent
circuit shown in Figure 1. This method may be used to
determine electrolyte resistance as well as provide
information about kinetics and mass transport within
the fuel cell.
Fig.5 Idealized Nyquist plot of the impedance of a fuel cell
Unlike the previously mention techniques, EIS
provides the advantage of a large amount of potentially
useful information about the cell. Like the AC and
HFR resistance method, the cell under test is
minimally disturbed from its operating condition and
therefore not electrochemically changed by the
measurement. Modeling software is available to allow
accurate analysis of the electrical and reaction
characteristics of the fuel cell which can provide
insight into fundamental kinetic and transport
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Comparison of Fuel Cell Electrolyte Resistance Measurement Techniques
Reedited from April/May 2005 issue of Fuel Cell Magazine
processes within the cell. Disadvantages include the
need to interpret the spectra produced and the cost of
the equipment required to make the measurement.
Comparison of Techniques
The objective for each method is to determine the
electrolyte resistance of the fuel cell. The two
techniques most easily compared are the Current
Interrupt and HFR methods. In practice, the results
from these two techniques usually correlate well if the
HFR measurement frequency is properly chosen. There
are, however, inherent differences in the two methods:
the current interrupt method introduces a large
perturbation to the fuel cell and looks at its
time-domain response where as the HFR method
applies a small signal and uses the frequency domain
response of the cell. Discrepancies between results
obtained form these two methods derive from whether
the current distribution present during the current
interruption or impedance measurement is the same as
the current distribution during standard DC operation
of the cell. In the current interrupt technique, after the
interrupt, the "true" cell voltage is only measured if the
current is zero everywhere within the cell and on the
surface of the electrodes. This condition exists for a
uniform double layer charge. If however, the electrode
double layer was non-uniformly charged when the
current was flowing, then after the interruption, current
will flow through the electrolyte from one part of the
electrode surface to the other to redistribute the surface
charge. This current flow just after the interruption will
create an ohmic voltage drop within the cell which will
introduce an error in the resistance measurement. That
is, the measured
ΔV will not equal the true voltage drop due to ohmic
resistance when the cell is operating under DC current.
This artifact is most likely to occur for primary current
distributions. If the polarization resistance of the
electrodes is large relative to the electrolyte resistance,
the current distribution is more uniform and the of the Electrochemical Society, 117, 507 (1970).

measured voltage error will be fairly accurate. 2. C. Lagergren, G. Lindbergh and D. Simonsson, "Investigation of Porous

Knowledge of the relative magnitude of the Electrodes by Current Interruption," Journal of the Electrochemical Society,

polarization resistance and electrolyte resistance for a 142, 787 (1995).

given fuel cell system is beneficial when evaluating the 3. F.N. Buchi, A. Marek and G.G. Scherer, "In Situ Membrane Resistance

applicability of the interrupt method. Measurements in Polymer Electrolyte Fuel Cells by Fast Auxiliary Current

In the HFR method, the electrolyte resistance is Pulses," Journal of the Electrochemical Society, 142, 1895 (1995).

determined from the real component of the impedance 4. C.-G. Lee, H. Nakano, T. Nishina, I. Uchida and S. Kuroe, "Characterization

measured at high frequency. However, total electrolyte of a 100 cm2 Class Molten Carbonate Fuel Cell with Current Interruption,"

resistance may change with current redistribution. Journal of the Electrochemical Society, 145, 2747 (1998).

Therefore, the AC signal should be small relative to the 5. Springer, Zawodzinski, Wilson and Gottesfeld, "Characterization of Polymer

DC current such that imposition of the AC signal on electrolyte Fuel Cells using AC Impedance Spectroscopy," Journal of the

the cell does not itself significantly influence the Electrochemical Society, 143, 587 (1996).

current distribution. The resistance measured in this 6. M. Lefebvre, R. Martin and P. Pickup "Characterization of Ionic Conductivity

instance will be similar to that experienced under pure Profiles within Proton Exchange Membrane Fuel Cell Diffusion Electrodes by

DC conditions and the electrolyte resistance Impedance Spectroscopy," Electrochemical and Solid State Letters, 2, 259

determined with the impedance method will be (1999).

accurate. The Electrochemical Impedance Method 7. The Measurement and Correction of Electrolyte Resistance in Electrochemical

produces a spectrum of data, a superset of that from the Tests, ASTM STP 1056, L. Scribner, S.R. Taylor, Eds., 1990.

HFR method. The Real (Z') impedance measured using 8. H.P. Hack, P.J. Moran, and J.R. Scully, "Influence of Electrolyte Resistance on

EIS at the frequency used for an HFR measurement Electrochemical Measurements and Procedures to Minimize or Compensate

should be identical to that for the latter. The data from for Resistance Errors," in The Measurement and Correction of Electrolyte

the AC Resistance method is not directly comparable Resistance in Electrochemical Tests, ASTM STP 1056, L. Scribner, S.R. Taylor,

to that produced by the other methods due to the Eds., ASTM International: Philadelphia, PA (1990).

artifacts imposed by the parallel-connected electronic

load.

Conclusion
Each of the four methods described may be used to
determine the ohmic resistance of the fuel cell
electrolyte, and in case of EIS, valuable information
about other cell parameters. However, users of these
techniques should be cognizant of differences in these
methods in order to properly apply and interpret the
results if accurate and useful measurement of cell
resistance is to be obtained.

References

1. J. Newman, "Ohmic Potential Measured by Interrupter Techniques" Journal

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Comparison of Fuel Cell Electrolyte Resistance Measurement Techniques
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