F784 Journal of The Electrochemical Society, 166 (12) F784-F795 (2019)

0013-4651/2019/166(12)/F784/12/$38.00 © The Electrochemical Society

Three and Four-Electrode Electrochemical Impedance

Spectroscopy Studies Using Embedded Composite Thin Film
Pseudo-Reference Electrodes in Proton Exchange Membrane
Fuel Cells
∗,z
Alex Szendrei, Taylor D. Sparks, and Anil Virkar
Department of Materials Science & Engineering, University of Utah, Salt Lake City, Utah 84112, USA

One and two pseudo-reference electrode proton exchange membrane fuel cell devices were fabricated using composite thin film
composed of Nafion and Ag paste as the reference electrode. Three and four-electrode electrochemical studies were performed
isolating different parts of the cell. Summing the scans utilizing the reference electrode(s) resulted in good agreement with the
two-electrode scan across the entire cell. A DC current was passed through the cell under constant resistive load conditions. The
equations necessary to determine the cell and the anode/cathode-reference impedance under constant resistive load are presented.
A high frequency depressed arc present in the spectra of the entire cell had contributions from both the anode-reference and the
cathode-reference scans. Reactance present in the four-electrode measurements isolating a section of the membrane further suggests
that the high frequency depressed semicircle in the cell scan can, at least in part, be attributed to the membrane. The present work
shows that by using embedded pseudo-reference electrodes, the polarization behavior of cathode and anode can be investigated
independently and unambiguously without the need for de-convolution of spectra across the entire cell.
© 2019 The Electrochemical Society. [DOI: 10.1149/2.0771912jes]

Manuscript submitted March 7, 2019; revised manuscript received June 17, 2019. Published July 17, 2019.

Proton exchange membrane fuel cells (PEMFCs) are attractive located in the same plane as one of the active electrodes. Many of the
power sources, due to their high power densities, low operating tem- findings are based on computational studies where Laplace’s equation
peratures, and clean reaction products when hydrogen is used as a fuel. is solved for a given set of boundary conditions.17,18 However, these
Applications range from stationary power to transportation.1,2 Despite studies treat the electrolyte as a conductor, where the differences in the
their many applications, challenges in low temperature fuel cells in- chemical potential of electrons are neglected.19 Although, the veracity
clude finding a new electrolyte material that will increase the operating of the magnitude of deviation in accuracy is debatable, it is generally
temperature and reduce cost,3–5 decreasing the cathode polarization,6 believed that the studies are useful in diagnosing the problem. The ac-
and increasing the lifetime.7,8 curacy is found to depend on the location of the pseudo-reference elec-
Electrochemical impedance spectroscopy (EIS) is a popular char- trode relative to the active (current carrying) electrode(s).14,15,17,20–22
acterization technique in PEMFC research.9 In the most simple of Poor alignment between active electrodes can also lead to a decrease
electrochemical systems, EIS can be used to study and model funda- in accuracy.14,15,17,23 Contributions to the error are attributed to plac-
mental kinetic parameters. In more complex systems, the interpretation ing the pseudo-reference electrode in a region where the potential is
can be ambiguous, having many possible explanations.5,9,10 However, not uniform.15,17,24 The AC potential distribution will be a function of
even when the interpretation behind a spectral feature is difficult, EIS frequency, with the primary and the secondary current distributions
is still a good comparative tool to investigate electrode and electrolyte present at high and low frequencies, respectively.17 The equipotential
performance when engineering electrochemical devices and qualita- lines, assumed equivalent with the electrostatic potential, will shift as
tive deductions can be made.10 EIS measurements represent an in- the frequency changes between the two current distributions.15
verse problem, where the physical observable (spectra) is known, but The dynamic hydrogen electrode is one type of pseudo-reference
the causal contributions to the physical observable are unknown. As electrode which is believed to yield accurate 3-electrode results.8,14,24
an example, consider the Nyquist plot in Figure 1. Two equivalent However, this requires additional electronic components. It has also
circuits, labeled A & B in the figure, can explain the resulting spec-
trum equally well. In the Figure, RM is the electrolyte resistance, and
the parallel RC elements represent the modeled electrode impedance.
Circuit B represents identical behavior of the two electrodes, while cir-
cuit A represents a situation where the impedance is dominated by one
electrode in the system, while the other electrode has zero polariza-
tion resistance. Thus, from the measured EIS spectra, it is not possible
to determine which of the two equivalent circuits is representative of
the actual system. Real systems are far more complex which makes
unambiguous de-convolution of EIS spectra even more challenging.
Two methodologies have been used for estimating the individual
electrode impedance contributions in fuel cell studies. Symmetric elec-
trode feeding is an ex situ technique and involves using the same
gas composition on both sides of the cell.1,8,11–14 However, this re-
quires an assumption of nearly equivalent performance from both ac-
tive electrodes.14,15 Also, electrodes are not symmetric when under
load. On the other hand, using a pseudo-reference electrode is an in
situ technique to isolate the impedance of different parts of the cell.8,16
The latter methodology is the more desirable of the two.8 Multiple
problems with 3-electrode studies have been reported when thin solid
state electrolytes are used. In these studies the reference electrode is

Figure 1. An example Nyquist plot with two corresponding equivalent cir-

∗ Electrochemical Society Fellow. cuits that describe impedance spectra by a semicircle. The inverse problem of
z determining the equivalent circuit from the measured spectra thus is not unique.
E-mail: anil.virkar@utah.edu

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 Journal of The Electrochemical Society, 166 (12) F784-F795 (2019)
been argued by some authors that an embedded reference electrode
may increase the heterogeneous nature of the current distribution.14,24
In this work we fabricated MEAs with a mixed phase film, com-
posed of silver paste and Nafion, embedded in the electrolyte. The film
had the same lateral dimensions as the active electrodes. This served
as a pseudo-reference electrode. Given that the reference electrode is
between the active electrodes, the reference electrode should be in a
region of uniform potential. Evidence for the veracity of the EIS mea-
surements is presented and the physical/chemical interpretation of the
spectra is also discussed in terms of our results and the current liter-
ature. We also present a novel methodology for making 3-electrode
measurements under a resistive load.
Experimental
Membrane electrode assembly (MEA) fabrication.—Nafion
115 membranes (Fuel Cell Store), approximately 127 μm thick when
dry, were cut to the desired dimensions and preconditioned by rins-
ing the membranes in a warm (80–100°C) 0.5 M H2 SO4 solution for
1 hour. The membranes were then rinsed in DI water multiple times
at room temperature to remove the excess acid solution. The Nafion
sheets were then placed in DI water (80–100°C) for 1 hour. Wet mem-
branes were placed in between two stainless steel mesh screens and
dried in a vacuum drying oven (Across International) at 60°C and at
a gauge pressure of −711.2 mm of Hg between 0.5–1 h.
The catalyst layer slurry was prepared by mixing 10 wt% Pt on Vul-
can (Fuel Cell store) with 5 wt% ionomer solution (Sigma Aldrich,
EW = 1100) in a 2:1 (catalyst/ionomer) by mass ratio. The suspension
was rigorously stirred for a few hours and sonicated for 30 minutes.
The catalyst layer slurry was painted onto Teflon treated carbon paper
(Toray: TGP-H-060) and dried under ambient conditions until a cata-
lyst loading of 2 mg of Pt/cm2 was achieved. The area of the carbon
paper, which served as the gas diffusion layer (GDL), was 5.9 cm2 .
The pseudo-reference electrode slurry was prepared by mixing
0.355 g of Ag paste (Structure Probe Inc.) per 1 mL of the 5% ionomer
solution. The solvent of the ionomer solution was a mixture of water
and aliphatic alcohols. The Ag paste from Structure Probe Inc. was
chosen because no high temperature heat-treatment is needed to pre-
pare an electrically conductive film. Many commercial platinum pastes
contain inorganic fluxes or glass and are designed for use in ceramic
electrolyte systems. In order to make a conductive film, excessive heat
treatments would be required, which would not suit our system.15 The
suspension was sonicated for approximately 30 minutes and then rig-
orously stirred for 2–3 days under ambient conditions. The suspension
was stirred without a lid to allow the evaporation of the solvent and
thus lead to a corresponding increase in the viscosity of the suspen-
sion. Once the desired viscosity was achieved, the pseudo-reference
electrode slurry was painted onto the dried Nafion membranes of the
same lateral dimensions as the GDLs. A small amount of the Ag paste
was applied to the corners of the Ag/Nafion film to make contact with
a silver wire.
The membranes with Ag/Nafion films were air dried overnight
and then dried in a vacuum oven at 80°C and at a gauge pressure of
−711.2 mm of Hg for 1 hour. In order to make a one pseudo-reference
electrode device, a membrane with a Ag/Nafion film was laminated
with a dried Nafion membrane without a composite film and two
electrodes (i.e. the catalyst layer and GDL). A two pseudo-reference
electrode device was fabricated by laminating two membranes with
a Ag/Nafion film and one dried Nafion membrane without a com-
posite film, which was placed between the two membranes with the
Ag/Nafion film and two electrodes. In concept, it should be possible to
use thinner Nafion membranes (50 microns) which are commercially
available so that the final laminated MEA has the same thickness as
those typically used commercially or in research. A 0.127 mm di-
ameter Ag wire (Alfa Aesar) was placed in the assembly to make
contact with the pseudo-reference electrode(s). To prevent movement
of the various components during lamination, the components were
adhered to a gasket using high temperature Kapton tape (Digi-Key
Electronics). Two gaskets were used to isolate the MEA components
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F785
to prevent adhesion of the Nafion to the aluminum platens. Lamina-
tion was performed using a hydraulic press (Carver) at 140–150°C
and under 4450 Newtons force for 10 minutes. See Figure 2 for draw-
ings of a laminated one pseudo-reference electrode MEA and a two
pseudo-reference electrode MEA.
Scanning electron microscope (SEM) analysis and sample
preparation.—A cross section of an embedded reference electrode
MEA was prepared by cutting a MEA with a razor blade after
lamination.25 In order to image the microstructure of the film the
Ag/Nafion slurry was painted onto a pretreated piece of Nafion and
dried according to the procedure described above. Both samples were
analyzed with a scanning electron microscope using a Field Emission
and Ion (FEI) Nova NanoSEM.
Electrical testing of MEAs.—MEAs were loaded into two end-
plates with two current collectors, two graphite single sided flow-field
plates with a serpentine pattern, and gaskets to enable a tight seal.
Clamping bolts, torqued to 20 N.m,26 held the apparatus together. An
850e Fuel Cell Test system (Scribner Associates Inc.) controlled the
gas flow rate and the temperatures of the cell and the bubblers. The
temperature of the cell was monitored with a T-type thermocouple.
Heating cuffs (Scribner Associates Inc.) were placed around the nuts
in the gas line to prevent condensation of water vapor upstream from
the cell. The gas flow rate and bubbler temperature were 0.1 L/min
and 37°C, respectively, for both the anode and the cathode. The cell
temperature was maintained at 40°C. Thus, the relative humidity of
the gas mixtures was 85%.27 Before electrical testing was performed,
preconditioning of the cell was conducted according to the procedure
described by Spiegel.6
DC potential and current were measured using Keithley 2000 me-
ters automated with LabVIEW software. The input impedance of the
Keithley 2000 was ≥10 GΩ. The shunt resistor for the ammeter was
0.1 Ω. A decade resistor box (PPM Inc.) was used when passing DC
current through the cell. EIS testing was performed using a Solartron SI
1287 electrochemical interface, with a corresponding input impedance
of >10 GΩ and 50 pF. A SI 1260 Impedance/gain-phase analyzer was
used as the frequency response analyzer (FRA). The frequency was
swept over a range of 100 kHz to 0.1 Hz with an amplitude of 10 mV.
Results and Discussion
Drawings of a one and two pseudo-reference electrodes device,
showing the electrochemical reactions at each electrode in galvanic
cell mode, are shown in Figure 2. A contiguous embedded Ag/Nafion
film allows for the passage of H+ ions through the cell and an elec-
trically conductive phase allows for electrical potential measurements
on the cell. The embedded electrode should be thin so as not to per-
turb the system greatly. An SEM image, shown in Figure 3a, is a cross
section of an embedded pseudo-reference electrode device. Measure-
ments across the electrolyte indicate that the Ag/Nafion film comprised
about 3% of the electrolyte thickness when dry. Given the methodol-
ogy of preparation and application of the slurry, there is likely some
sample variance with respect to the thickness of the Ag/Nafion film.
Two phases, corresponding to the Ag (white phase) and the Nafion
(dark gray phase), are also clearly observed, as expected. Any additive
organics from the paste, that were not evaporated, are likely indistin-
guishable from the Nafion. The image also shows that good lamina-
tion was achieved and that the Nafion phase is continuous across the
whole electrolyte (from the anode to the cathode). Figure 3b shows
the microstructure of the Ag paste. Some agglomerated particles are
observed; however, some submicron particles are also observed. Note
that the appearance of the film may change after lamination as the
Nafion chains modify their confirmation. In some instances the con-
ductive film’s resistance increased slightly after lamination; however,
the corner to corner resistance of the film, as measured by a multimeter,
was only a few ohms before and after lamination.
A cell with one pseudo-reference electrode was tested at OCV
and also under constant resistive load conditions using O2 /H2 O as the
 F786 Journal of The Electrochemical Society, 166 (12) F784-F795 (2019)
Figure 2. Drawings of a one (left) and a two (right) embedded pseudo-reference electrode MEAs.
Figure 3. SEM images of (a) the cross section of an embedded pseudo-
reference electrode MEA and (b) the Ag/Nafion film on a pretreated Nafion
substrate. The thin line in the center of (a) is the Ag + Nafion pseudo-reference
electrode.
cathode gas. The cell potential (Figure 4a), the reference electrode
potential with respect to the anode (Figure 4b), and the DC Current
(Figure 4c) are shown under various loads during the first 10 minutes
after applying the load to the cell. The results show good stability with
respect to the DC current and potentials, although there does appear to
be greater variation in the potential and the current as the magnitude
of the DC current is increased. A change in DC potential with respect
Figure 4. Electrical measurements on the MEA at various resistive loads, showing (a) the DC cell potential, (b) the DC potential between the anode and the
embedded pseudo-reference electrode, and (c) the DC current.
to time will be an issue in EIS measurements only if the magnitude
of the change is sufficient to alter the impedance also.14,24 From the
data presented here, it is clear that the magnitude of the drift observed
was not significant. The variance in the potential between the pseudo-
reference electrode and the anode (Figure 4b) may be due to a change
at the reference electrode, but it may also be from the anode and/or
the changing ohmic drop of the electrolyte (i.e. a potential difference
is measured). The cell potential also shows the most variance at the
largest DC current measured. This is expected upon switching loads,
because the water balance will change, leading to a period of instability
in current and potential measurements.6
Small signal perturbation was performed under voltage control.
When a nonzero DC current was desired, the cell was connected to
a resistive load, RL . This resistive load is external to the EIS mea-
suring hardware. This deviates from most studies where DC potential
(potentiostat) or current (galvanostat) control is mediated by opera-
tional amplifier circuits. A schematic showing a simplified equivalent
circuit where the impedance of the entire cell, Zcell , and a three elec-
trode measurement where the cathode and electrolyte impedance to
the reference electrode is isolated, are shown in Figures 5a and 5b,
respectively. Figure 5c shows the electrical connections to an MEA
for the equivalent circuit represented by Figure 5b.
In the circuit analysis that follows, a horizontal bar accent refers
to a DC value and a sinusoidal accent indicates an AC value. The

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 Journal of The Electrochemical Society, 166 (12) F784-F795 (2019) F787

Figure 5. EIS circuit analysis under resistive load. Measuring (a) the AC potential across the cell, (b) the AC potential across the cathode-reference electrode, and
(c) the AC potential across the cathode-reference electrode, showing the connections to an MEA.

four leads from the SI 1287 to the cell are shown in Figure 5. RE1
and RE2 are floating voltage measuring leads. The DC component
of the voltage is nullified in the SI 1287. The WE and CE leads are
connected to the anode and the cathode of the cell, respectively. Note
that in our experiments the SI 1287 DC potential, V̄P , is the same as
the cell potential, V̄cell ,28 which is the DC potential between the points
where RE1 and RE2 are connected in Figure 5a. Given V̄p = V̄cell ,
the cell does not see the signal source as a load and all DC current,
I¯DC , is contained in the cell/load resistor circuit external from the EIS
hardware. In Figures 5a and 5b a DC potential, V̄o, is displayed in the
cell. The numerical value of V̄o will change with the load resistance.
The DC source V̄o, which varies with current, is the intercept on the
voltage axis for a tangent drawn to the voltage current curve at I¯DC .29
Allowing V̄o to vary with load permits Equation 1 to be satisfied even
with large DC currents and both DC and AC sources can be shown in
the equivalent circuit,
V̄cell = V̄o − I¯DC Zcell ( f = 0) [1]
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where Zcell ( f = 0) is the impedance of the cell when the frequency is
zero. The impedance of the cell at any given frequency, Zcell , is simply
the sum of ZAR , the anode impedance and the electrolyte impedance
to the embedded electrode, and ZCR , the cathode impedance and the
electrolyte impedance to the embedded electrode. The equivalent cir-
cuit is sufficient for EIS analysis. A more detailed equivalent circuit
showing discretized Nernst potentials across the electrode/electrolyte
interface and in the electrolyte has been previously described.30
Note that in the measurement setup the load resistor provides a
parallel path for the AC current, I˜RL . It is only in the limiting condi-
tion of the impedance of the load, ZRL , being much greater than Zcell
that the measured AC current, Ĩ Total = Ĩ cell + Ĩ RL , is approximately
equivalent to the AC current through the cell, Ĩ cell . Equation 2 is used
for determining the cell impedance from the output values of the in-
strument, Zout put
cell , from the experimental setup seen in Figure 5a and
defined mathematically in Equation 3,
1 1 1
= − [2]
Zcell Zout
cell
put
Z RL
 F788 Journal of The Electrochemical Society, 166 (12) F784-F795 (2019)

magnitude and the phase angle of impedance element i are denoted by

|Zi | and θi and defined by Equations 7 and 8, respectively,

Zi = |Zi | cos (θi ) + jˆ |Zi | sin (θi ) [6]

 
  |Zcell |
|Zi | = Zout put 
  [7]
i Zout put 
cell

θi = θout
i
put
+ θcell − θout
cell
put
[8]
√
where jˆ is the imaginary number ( jˆ = −1). The magnitudes and the
out put
phase angles of Zcell , Zcell , and Zi out put
are given by |Zcell |, |Zout
cell |,
put

|Ziout put
|, θcell , θcell , and θi
out put out put
, respectively. This is an important
correction when the aforementioned limit is not obeyed. In the case of
open circuit measurements, no correction is needed because all of the
AC current passes through the cell. Further details of the derivations
are given in the appendixes.
Figure 6 shows the impedance behavior of the resistive loads and
lead impedance (ZRL ) used in the experiments without the cell. The
Nyquist plots show vertical line behavior and a net positive reactance
at high frequencies, indicating a resistor and an inductor in series as an
Figure 6. EIS spectra of the resistive load/leads used to pass a DC current appropriate model. Figure 7 shows Zcell and Zout cell
put
under a resistive
through the cell. load of 10.3 Ω and 1.58 Ω. Considering the EIS data obtained using
the 10.3 Ω resistor (Figure 7a), the deviation between Zcell and Zout cell
put

is mainly at lower frequencies. At high frequencies both show net in-

Zout put
=
Ṽ cell
[3] ductive reactance with both the real (Z  ) and the negative imaginary
cell
Ĩ Total (−Z  ) components nearly equivalent. The convergence at high fre-
quencies results because the 10.3 Ω load impedance is much greater
where Ṽ cell is the phasor voltage across the cell and Ĩ Total is the phasor than the cell impedance at high frequencies. The parasitic inductance
current representing the total AC current passing through the cell and in the lead/resistor path is much greater than the parasitic inductance
the resistive load. A general expression for an impedance element in in the fuel cell hardware. This is supported by comparing the data in
the cell, Zi (corresponding to either ZAR or ZCR in the one pseudo- Figure 6 and Figure 7a.
reference electrode device), is shown in Equations 4, where Ṽ i is the Considering the spectra in Figure 7b, we see a difference in Z’ for
phasor voltage across element i in the cell. The output impedance from Zcell and Zout put
throughout the entire frequency range. In this case,
the instrument, Zouti
put
, is defined by Equation 5. cell
the load resistance is closer to the Z’ of the cell. Comparing-Z’’ for the
Ṽ i two plots at high frequencies, again we see the imaginary components
Zi = [4] are approximately equivalent for the same reason stated above.
Ĩ cell Figure 8 shows the results for the 2-electrode anode-cathode (Zcell ),
Ṽ i 3-electrode anode-reference (ZAR ), and the 3-electrode cathode-
Zout
i
put
= [5] reference (ZCR ) scans using humidified H2 /O2 for different loads for a
Ĩ Total single pseudo-reference electrode device. Figure 8a shows the results
Note that the difference in Equations 4 and 5 is in the denominator at open circuit. In this plot, the anode-reference spectrum is barely
of the two expressions. It can be shown that from the polar coordinates visible. This is because the impedance of the cell and of the cathode-
of Zcell , Zout put ouput
cell , and Zi that the rectangular coordinates (which are reference are much larger at low frequencies at open circuit. Figure 8b
used for Nyquist plots) for Zi can be determined using Equation 6. The shows the same set of results as Figure 8a with the range in the axes

Figure 7. EIS spectra of Zcell and Zout

cell
put
using (a) 10.3 Ω and (b) 1.58 Ω external load.

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 Journal of The Electrochemical Society, 166 (12) F784-F795 (2019)
Figure 8. EIS spectra showing the 2-electrode anode-cathode (Zcell ) scan, 3-electrode anode-reference scan (ZAR ), and the 3-electrode cathode-reference scan
(ZCR ) at (a) open circuit, (b) open circuit with the axes modified, using (c) 10.3 Ω, (d) 2.65 Ω, and (e) 1.58 Ω resistor. Frequencies corresponding to a few data
points are labeled.
modified to highlight the high frequency behavior of Zcell and ZCR ,
and show ZAR throughout its entire frequency range. Figure 8c through
Figure 8e show the results under load. In Figure 8e, the corresponding
frequencies for a few data points are labeled.
The anode-cathode scans throughout the loads investigated re-
vealed 2 arcs: one depressed and an incomplete arc at high frequen-
cies and a larger more complete semicircle at lower frequencies. The
cathode-reference scans also show the same number of arcs. From
Figure 8, we see there are contributions from both the anode-reference
and the cathode-reference scans to the high frequency feature in the
anode-cathode spectrum.
The low frequency semicircle in the anode-cathode spectra re-
veals similar shape and trend with respect to load as that present
in the cathode-reference spectra. In both the anode-cathode and the
cathode-reference scans, the diameter of the low frequency semicircle
decreases as the load resistance decreases (increase in DC current and
cell overpotential). Thus, we see a relatively greater contribution from
the anode-reference scan to the cell impedance as the overpotential
increases.
The high frequency intercept observed for the anode-reference and
the cathode-reference spectra are approximately equal and about half
that of the 2-electrode cell scan at open circuit. This can be observed
in Figure 8b. Assuming the high frequency intercept can be attributed
to the membrane ohmic resistance, this would be the expected result
for a reference electrode embedded between two Nafion sheets where
the membrane conductivity is not a function of position, which would
imply uniform hydration throughout the membrane.24 Similar findings
were reported by Li and Pickup using a dynamic hydrogen reference
electrode (DHE) embedded between two membranes.24 Further details
on the features of the spectra with respect to their physical/chemical
origins are discussed in what follows.
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F789
Figure 9 shows the sum of the anode-reference and the cathode-
reference scans, Zsum
cell , as defined by Equation 9, and the two-electrode
method capturing the cell impedance for the loads investigated.
Ṽ AR Ṽ CR
cell =
Zsum + = ZAR + ZCR [9]
Ĩ cell Ĩ cell
The results show that the two spectra nearly overlap, yielding confi-
dence in the veracity of the 3-electrode measurements. This implies
that the use of the two phase film spanning the active electrode area is a
good pseudo-reference electrode and that the potential was uniform in
the region. This also shows that using the embedded pseudo-reference
electrode, it is possible to measure electrode kinetics of cathode and
anode separately. In order to further analyze how well Zsumcell compares
to Zcell , the percent difference, P, was calculated with respect to the
impedance magnitudes,
  
abs ZSum 
cell − |Zcell |
P= × 100 [10]
|Zcell |
where |Zsum
cell | is the magnitude of the sum of the anode-reference and
the cathode-reference scans and abs is used to denote that the abso-
lute value in the curly brackets used in the calculation. The percent
difference is plotted against frequency (logarithmic) in Figure 10. The
high frequency measurements above 50 kHz show the most error.
This is the frequency region where the net reactance is in the fourth
quadrant of the Nyquist plots, indicating dominance from the graphite
blocks/current collectors from the fuel cell hardware and any uncom-
pensated impedance from the leads. It is possible that the current car-
rying leads were inadvertently placed at different locations between
scans, which led to the error seen in Figures 9 and 10.31 It is also pos-
sible that there could have been mutual-inductance during these high
 F790 Journal of The Electrochemical Society, 166 (12) F784-F795 (2019)

Figure 9. EIS of Zsum

cell and Zcell at (a) open circuit, using (b) 10.3 Ω, (c) 2.65 Ω, and (d) 1.58 Ω resistor.

frequency perturbations.31 This would violate the condition of
causality, which is an implicit assumption in all impedance
measurements.16,31 High frequency measurements are hard to repro-
duce unless strict repetition with respect to the placement of the lead
wires is adhered to. Excluding frequencies above 50 kHz, the percent
error, as estimated by Equation 10, was less than 3%.
Figures 9 and 10 show good agreement between Zsum cell and Zcell be-
low 50 kHz. It should be noted that there appeared to be an increase in
error with extended use of the MEAs (data not shown). The reason for
the degradation in performance over time will be the subject of fur-
ther study. In some cases we also observe an increase in error at low
frequencies (most easily observed in Figures 9b and 10b). This may
be attributed to nonstationary behavior,32 where the electrode active
area/composition is changing during the measurement. Recalling that
the period is greater at lower frequencies, it is expected that the as-
sumption of an invariant system during the measurement is less valid
in this region.5,10
Figure 11a shows the results for the 2-electrode anode-cathode
(Zcell ), 3-electrode anode-reference (ZAR1 ), 3-electrode cathode-
reference (ZCR2 ), and 4-electrode membrane (ZM ) scans using humidi-
fied H2 /O2 at OCV in an MEA using two pseudo-reference electrodes.
ZAR1 represents the impedance of the anode and the electrolyte up to
pseudo-reference electrode 1, ZCR2 is the impedance of the cathode
and the electrolyte up to pseudo-reference electrode 2, and ZM is the
impedance of the electrolyte between reference electrodes 1 and 2.
ZM is obtained by placing the current carrying leads at the anode and
the cathode and connecting the floating potential measuring leads to
the two pseudo-reference electrodes embedded in the polymer elec-
trolyte. Pseudo-reference electrode 1 was adjacent to the anode and
pseudo-reference electrode 2 was adjacent to the cathode. See Fig-
ure 2 for a schematic of the MEA. Figure 11b shows the same results
as Figure 11a with the axes modified to more clearly observe ZAR1
and ZM . The impedance results for the electrode-reference scans are
similar to that of the one pseudo-reference electrode MEA discussed
above. What is gained by the use of two pseudo-reference electrodes
is that the impedance behavior of a portion of the membrane can be
measured exclusively. It is interesting to note that there appears to be
some net capacitive reactance in the high and mid-frequency region
of ZM , with some pseudo-inductance at lower frequencies. It should
also be noted that the high frequency region of ZM does not cross
into the fourth quadrant. This indicates that the parasitic inductance
is mainly from the current collector, plate, GDL, etc. Figure 11c and
sum
Figure 11d show the comparison of Z̈cell and Zcell as a Nyquist plot
sum
and the error analysis, respectively, where Z̈cell is defined by Equa-
tion 11. Note the error analysis for the two pseudo-reference device
was performed using Equation 10 with the substitution of |Zsum cell | for

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 Journal of The Electrochemical Society, 166 (12) F784-F795 (2019) F791

Figure 10. Error analysis at (a) open circuit, using (b) 10.3 Ω, (c) 2.65 Ω, and (d) 1.58 Ω resistor.

sum sum sum

Z̈cell , where Z̈cell is the magnitude of Z̈cell . Both Figures 11c and 11d
show good agreement, with the exception of the high frequency mea-
surements. This is expected as discussed earlier. The results for both
the one reference electrode and the two reference electrodes MEAs
indicate that this good agreement is reproducible using a thin film
embedded pseudo-reference electrode in PEMFCs.
sum
Z̈cell = ZAR1 + ZM + ZCR2 [11]
The cathode-reference scans for the membrane with one embed-
ded reference electrode are shown in Figure 12, with both the Nyquist
(Figure 12a) and the phase angle Bode plot (Figure 12b) represented.
As mentioned above, there is a decrease in the diameter of the low
frequency semicircle in the cathode-reference scans with increasing
DC current. This is clearly seen in the Nyquist plots collecting all of
the cathode-reference scans in one plot (Figure 12a). The phase angle
bode plot (Figure 12b) shows a decrease in the maximum of −θCR and
a right horizontal shift in the low frequency peak, indicating a higher
characteristic frequency, with a decreasing load resistance. Thus, the
low frequency arc in the cathode-reference scans across all loads was
attributed to the oxygen reduction reaction (ORR). The semi-circle
discussed above has long been suspected to come from the ORR from
2-electrode studies using symmetric electrodes and in H2 /O2 gas feed-
ing modes.12–14,33–35 This further confirms that the ORR is the domi-
nating feature in the impedance response at low overpotentials.13,14,33
It has been argued by Paganin et al. that under conditions of high cell
polarization, mass transport polarization of O2 through the Nafion,
which coats the Vulcan/platinum particles in the catalyst layer, as pre-
dicted by the flooded agglomerate model, may occur even when no
mass transport features are observed in the EIS spectra.34
The high frequency incomplete and depressed arc in the anode-
cathode scans seen in Figure 8 has been the subject of some con-
troversy. Interpretation has been exacerbated by its absence in some
studies.8,12,14 Pourcelly et al. found that the high frequency semicir-
cle disappeared with increasing water content in the electrolyte.36
Paganin et al. attributed the behavior to distributed ionic resistance
in the catalyst layer.34 Other studies suggest that the phenomena
may be due to electrolyte contributions.12,35,36 Many authors have ob-
served that there appears to be no obvious dependence of the fea-
ture on overpotential.8,33 Our results also indicate a negligible change
with overpotential. A close-up of the phase angle Bode representa-
tion for the cathode-reference high frequency arc is shown in Fig-
ure 13. The results indicate an ill-defined characteristic frequency. As
mentioned above, our results from the one reference electrode de-
vice indicate that the high frequency arc from the two-probe scans has

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 F792 Journal of The Electrochemical Society, 166 (12) F784-F795 (2019)

Figure 11. EIS results from an MEA with two embedded pseudo-reference electrodes at open circuit. Showing (a) the Nyquist plots of all four scans (Zcell , ZAR1 ,
sum
ZCR2 , and ZM ), (b) the Nyquist plots of all four scans with the axes modified, (c) the Nyquist plots of Zcell and Z̈cell , and (d) the error analysis.

Figure 12. Cathode-reference scans (ZCR ) under different loading conditions showing (a) the Nyquist plots and (b) the phase angle bode plots.

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 Journal of The Electrochemical Society, 166 (12) F784-F795 (2019)
Figure 13. The phase angle Bode plots for the cathode-reference scans (ZCR ),
under different loading conditions, with emphasis on the high frequency
features.
contributions from both the cathode-reference and the anode-reference
scans. Furthermore, results from the two reference electrode cell show
a net capacitive reactance in the high and mid-frequency region in the
membrane (ZM , in Figure 11b). From the evidence presented above,
it is reasonable to conclude that the reactance in the high frequency
feature at the very least has contributions from the membrane. There
is an interesting low frequency inductive feature in ZM (Figure 11b).
Schneider et al. observed similar phenomena in their EIS spectra. The
low frequency loop seemed to increase in prominence as the hydration
of the membrane is decreased.37 They reasoned that the inductive loop
present in EIS spectra in dehydrated MEAs is due to a changing ionic
resistance in the membrane at low frequencies. In the low frequency
region, more of the AC current is faradaic; thus, the AC current in this
frequency region may change the water content of the membrane.37
Given that our cells would be classified as sub-saturated with respect
to water content, the aforementioned physical explanation could be
applicable here. The high lamination temperature can also cause in-
complete rehydration of the electrolyte.38
Figure 14. Anode-reference scans (ZAR ) under different loading conditions, showing (a) the Nyquist plots, and (b) the phase angle bode plots.
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F793
The anode-reference scans for the loads investigated are shown in
Figure 14, where Figure 14a shows the Nyquist representation and
Figure 14b shows the phase angle Bode plot. We do not see any ob-
vious dependence of the arc on overpotential as observed for the low
frequency arc in the cathode-reference scans. Examining the plots in
the complex plane representation (Figure 14a), it appears that the plot
using the 1.58 Ω load resistor shows a diminished diameter. However,
examining Figure 14b, there is no obvious shift in the characteristic
frequency as seen in the case of the low frequency arc in the cathode-
reference scans. The appearance of an attenuated diameter of the arc
using the 1.58 Ω load resistor may merely be a consequence of the
higher inductive load seen during this scan (see Figures 14b and 8e).
Based on the present data, we cannot conclude with a high degree of
confidence that the smaller diameter can be attributed to the higher
DC current used in this scan. This invariance has been observed in
symmetric H2 /H2 cells.12 By diluting H2 gas with N2 , some authors
have observed an increase in the diameter of the arc.3,20 The spectra for
ZAR captured the impedance of the anode and part of the membrane;
however, based on the data from the single pseudo-reference electrode
device alone we cannot determine which is the dominating feature, or
if two features of similar magnitude are overlapping.
The two pseudo-reference electrode cell may offer greater clarity.
We assume similar thicknesses of the membrane between the two em-
bedded reference electrodes, the anode to Reference 1, and the cathode
to Reference 2 since three Nafion membranes identical thickness were
laminated. Furthermore, we assume that each section of the membrane
has equivalent impedance. Then the impedance of the anode, ZA , can
be calculated from ZAR1 and ZM using Equation 12.
ZA = ZAR1 − ZM [12]
The Nyquist plots showing ZA , ZAR1 , and ZM at OCV are depicted in
Figure 15, in which ZA is obtained by point by point subtraction at each
frequency. The high frequency intercept of ZA is close to the origin as
expected. This is consistent with the expectation since the electronic
resistance of the active anode layer is very small due to the presence
of high conductivity carbon. Although two distinct semicircles appear
in ZAR1 , from the application of Equation 12 we see that it would be
incorrect to assign one semicircle of ZAR1 to the membrane and the
other to the hydrogen oxidation reaction (HOR). Given the results from
the analysis of the two pseudo-reference electrode device we conclude
that ZAR , for the one pseudo-reference electrode device, is composed
of two features of similar magnitudes.
The observation of invariance in the diameter of ZAR with respect
to DC current for the one pseudo-reference device can be explained
in reference to both membrane and electrode kinetic attributions. A
 F794 Journal of The Electrochemical Society, 166 (12) F784-F795 (2019)

ware used in the EIS experiments. Rishabh Sahani helped prepare the
one-reference electrode MEA. Ashley Kennedy and Danielle Beatty
read the manuscript and gave useful suggestions about the syntax and
format.

Appendixes
The following appendixes give further details on the equations for the determination of
Zcell , ZCR , and ZAR when the cell is connected to a resistive load. In the following analysis
we have assumed linear circuit behavior and the applicability of Kirchhoff’s current and
voltage laws. Basic network circuit theory analyses are used.14

Appendix A
Determination of Zcell .—Consider the circuit schematic in Figure 5a. We want to
determine the impedance of the cell, Zcell , under a resistive load, RL . The cell voltage,
Vcell , is simply a superposition of the DC and AC signals shown in Equation A1,

Vcell = V̄cell + Ṽ cos (ωt + φV ) [A1]

where V̄cell is the DC component of the cell potential, Ṽ is the amplitude of the voltage
perturbation, ω is the angular frequency, t is time, and φV is the phase of the AC signal.
Figure 15. Nyquist plots showing the two scans ZAR1 and ZM with the calcu-
Note that the second term on the right hand side of Equation A1 is the AC component of
lated spectrum ZA .
the cell potential. Writing the AC component of Vcell in complex exponential notation,
     
Ṽ cos (ωt + φV ) = Re Ṽ ex p jˆ [ωt + φV ] = Re Ṽ cell ex p jˆωt [A2]
tenuous change of the high frequency depressed semicircle with re- √
spect to load, which we attribute largely to the membrane, was also where jˆ = −1 and Ṽ cell is the phasor voltage of the AC signal across the cell. Bold
observed for ZCR . The phase angle bode plot capturing the frequency letters are used to indicate that the corresponding variables are phasors. The Re notation
used before the curly brackets indicates the real component of the complex number.
range of the high frequency feature of the ZCR in Figure 13 is the clear-
The cell impedance, Zcell , is given by A3; however the output from the instrument
est representation of the consistent behavior observed. There may also determines the impedance of the parallel combination of the cell and the load resistor,
be invariance in the characteristic frequency with respect to the hydro- Zout put
cell , defined by A4.
gen electrode kinetics in the range of DC currents investigated. The
exchange current density for the HOR is much higher than the ORR.12 Ṽ cell
Zcell = [A3]
If the current densities investigated in the experiments did not exceed Ĩ cell
the exchange current density of the HOR in our system, the linear ap- Ṽ cell
proximation of the Butler-Volmer equation under the conditions tested Zout
cell
put
= [A4]
Ĩ Total
would be appropriate for the HOR reaction.
In the above equations, Ĩ cell is the phasor current of the AC signal through the cell and
Ĩ Total is the total phasor current, which is represented in the output impedance from the
Conclusions instrument. From basic circuit theory, Zcell can be represented by Equation A5, where ZRL
is the impedance of the load resistor and leads from the cell to the decade resistor box.
A composite pseudo-reference electrode composed of conductive
Ag paste and Nafion was embedded inside a polymer electrolyte. 1 1
= out put −
1
[A5]
MEAs incorporating one and two pseudo-reference electrodes were Zcell Zcell ZRL
fabricated and tested using humidified H2 and O2 . EIS measurements
In order to perform subtraction of complex numbers, rectangular coordinates are used.
were performed using the pseudo-reference electrode(s) in three and In the case of Equation A5, Zout put
and ZRL must be multiplied by their complex con-
cell
four-electrode scans. Summing the spectra utilizing the reference jugates. This is equivalent to the subtraction of their corresponding admittances. Once
electrode(s) resulted in good agreement with spectra capturing the the admittance of the cell, Y cell , is determined, it is easy to find Zcell . The mathematical
impedance of the entire cell. This yields evidence that the approach relationships between the real and the imaginary impedance components to the real and
was successful in separately measuring the anode and the cathode the imaginary admittance components are given in Equations A6 to A9.39
impedances. In order to pass a DC current through the cell, a resistive
Z
load was used. A circuit analysis of the measurement system with a Y = [A6]
Z  2 + Z  2
resistive load was used to derive equations to describe the cell and the
anode/cathode-reference impedances. The results from the three and Z 
Y  = − [A7]
the four-electrode EIS measurements yield evidence to suggest that Z  2 + Z  2
the high frequency semicircle observed in the two-electrode cell scans Y
can, at least in part, be attributed to the electrolyte. By subtracting the Z = [A8]
Y  2 + Y  2
membrane impedance, the impedance corresponding to the anode re-
Y 
action was determined. The high frequency intercept was nearly zero Z  = − [A9]
Y + Y  2
2
indicating that it was possible to measure anode kinetics free of any
ohmic contributions. Here, Z  and Y  are the real components of the impedance and the admittance, respec-
tively, and Z  and Y  are the imaginary components of the impedance and admittance,
respectively.
Acknowledgments With both Zcell and Zout
cell
put
known, it is straightforward to convert to polar coordinates
to find their corresponding magnitudes (|Zcell | and |Zout put
cell |) and phase angles (θcell and
This work was supported in part by the US Department of En- θout
cell
put
). The relationships between the rectangular coordinates and the polar coordinates
ergy, Office of Basic Energy Sciences under grant number DE-FG02- for a complex number are shown in Equations A10 and A11.
06ER46086, and in part by the National Science Foundation under
grant numbers NSF-CBET-1604008 and NSF-DMR-1742696. The |Z| = Z  2 + Z  2 [A10]
authors would like to express gratitude to Rachel Svoboda and Brian

Z
Sayers of Solartron for useful discussions on the hardware and the soft- θ = tan−1 [A11]
Z 

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 Journal of The Electrochemical Society, 166 (12) F784-F795 (2019) F795

Appendix B where Zi is the impedance of element i in the cell. This is the desired quantity under a
resistive load. The impedance values given by the instrument are Zout i
put
, which is the ratio
Determination of Ĩ Total .—The goal of this section is to find an equation for Ĩ Total
of the phasor voltage of the AC signal across element Zi and Ĩ Total . The magnitudes and
from the polar coordinates of Zcell and Zout put
cell . Equation A3 can be written as Ṽ cell = the phase angles of Zi and Zout
i
put
are given by |Zi |, |Zout
i
put
|, θi , and θout
i
put
respectively.
Zcell Ĩ cell . Substitution of this expression into Equations A4 and solving for Ĩ Total yields
Equation B1.
      ORCID
Zcell |Zcell | ex p jˆθcell
Ĩ Total = Ĩ cell = Ĩ cell  out put   out put  [B1]
Zout put Z  exp jˆθ Taylor D. Sparks https://orcid.org/0000-0001-8020-7711
cell cell cell
Anil Virkar https://orcid.org/0000-0003-4530-6807
Using commercial EIS hardware and software, the rectangular and polar coordinates of
the impedance are readily determined. Thus, from the analysis in appendixes A and B,
Ĩ Total
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[C11] Hill Education.

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