INTERNATIONAL JOURNAL OF ENERGY RESEARCH Int. J. Energy Res. 2005; 29:11331151 Published online in Wiley InterScience (www.interscience.wiley.com).

DOI: 10.1002/er.1144

Analysis of electrochemical impedance spectroscopy in proton exchange membrane fuel cells

Parthasarathy M. Gomadam and John W. Weidnern,y
Center for Electrochemical Engineering, Department of Chemical Engineering, University of South Carolina, Columbia, SC 29208, U.S.A.

SUMMARY A literature review of electrochemical impedance spectroscopy (EIS) analysis of proton exchange membrane fuel cells (PEMFCs) is presented. Emphasis is placed on the papers that analyse the impedance response of the cathode and anode half-cells of the PEMFCs based on a continuum-mechanics approach. The other type of analysis, which is based on the equivalent-circuits approach, is addressed for comparison. The relative advantages and disadvantages of the two approaches are discussed. Papers dealing with continuum-mechanics-based EIS modelling of general electrochemical systems are briey reviewed. Copyright # 2005 John Wiley & Sons, Ltd.
KEY WORDS:

impedance; EIS; fuel cell; porous electrode; catalyst layer; Nyquist plot; linear kinetics; Tafel kinetics; equivalent circuit

1. INTRODUCTION A schematic of a proton exchange membrane fuel cell (PEMFC) stack is shown in Figure 1 along with blown-up views of the seven-layer membrane electrode assembly and the catalyst region. The reactant gases, hydrogen and oxygen/air, are own into the fuel cell through the ow-elds. The ow-elds are normally made of a light, electronically conducting material (e.g. graphite) with channels grooved in them for gas ow. From the ow-elds the gases diuse through the gas-diusion layers (GDLs) into the catalyst layers, where electrochemical reactions (hydrogen oxidation in the anode and oxygen reduction in the cathode) occur. The GDLs are made of porous carbon paper or cloth allowing simultaneous gas and liquid ows. The catalyst layers are made of a porous mixture of the ionomer and platinum-loaded carbon particles, allowing contact between the solid, ionomer, and gas phases. The Naon1 ionomer membrane, made of immobile sulphonate anions and mobile protons, serves to conduct the protons generated by hydrogen oxidation from the anode catalyst layer to the cathode catalyst layer. In the cathode catalyst layer the protons combine with the oxygen entering through the GDL to
n

Correspondence to: John W. Weidner, Center for Electrochemical Engineering, Department of Chemical Engineering, University of South Carolina, Columbia, SC 29208, U.S.A. y E-mail: weidner@engr.sc.edu

Copyright # 2005 John Wiley & Sons, Ltd.

Received 8 February 2005 Revised 14 March 2005 Accepted 17 March 2005

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H2 flow

O2 flow

H2 flow

O2 flow

H2 flow

O2 flow

H2 flow

Catalyst Catalyst O2 flow Carbon Platinum Ionomer + Gas Pores

GDL Membrane

Figure 1. A schematic of a PEMFC stack, showing the seven-layer membrane electrode assembly and the catalyst pore structure in detail.

form water. The generated water is transported out of the fuel cell by diusion/permeation through the cathode GDL into the ow-eld and by back-diusion through the membrane towards the anode side. According to Gasteiger and Mathias (2003) PEMFCs show excellent performance given the right composition and operating conditions. However, todays PEMFCs do not operate well under extreme conditions (e.g. low humidity, high temperature, excessive gas contaminants) nor are they cost-eective. In order to compete with the currently used power sources (e.g. internal combustion engines) PEMFCs must operate over a wide range of conditions and meet stringent cost requirements. As laid out by the authors, some of the desirable properties of PEMFCs are that the operating temperature should be made higher than 1208C for ecient heat rejection, the ionic conductivity of the membrane should be increased by over ten times at low relative humidities, the platinum loading in the catalyst layers should be steeply reduced, the GDL should be better tailored and optimized to allow fast gas transport while facilitating fast water removal, and the catalyst should be made more tolerant to poisons. These properties can be achieved by altering the materials used to make the fuel cell components, their composition, cell design, and processing and operating conditions. Therefore, numerous researchers are involved in characterizing fuel cell materials and their components as functions of the above variables
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Figure 2. Measured in-plane ionic and electronic resistivities for various treatment types used in catalyst layer preparation: 1. Proton form, as prepared; 2. Proton form, extracted with water; 3. Proton form, acid boiled; 4. Tetrabutylammonium form, unpressed, acid boiled; 5. Tetrabutylammonium form, pressed, acid boiled. Reproduced by permission of The Electrochemical Society (Saab et al., 2003).

and have reported signicant eects. For example, Saab et al. (2003) observed a strong dependence of the electronic and ionic conductivities of composite fuel cell electrodes on their composition and processing conditions (see Figure 2). The techniques used by researchers for characterizing fuel cells and their components involve applying a current or voltage input and observing the response. While fuel cells are ultimately characterized by their steady-state currentvoltage responses, the great deal of extra information obtained from transient responses is valuable for property measurements. The use of a variety of transient techniques such as potential stepping, potential sweeping, current interrupt, and electrochemical impedance spectroscopy (EIS) are reported in the literature (e.g. Saab et al., 2002, 2003; Li and Pickup, 2003; Jaouen et al., 2003; Jaouen and Lindbergh, 2003). Among these, EIS is the technique most widely used for measuring transport properties (e.g. ionic conductivity of the membrane) in fuel cells. Researchers in PEMFCs use EIS to measure the overall impedances of the cathode side, the anode side, as well as the whole fuel cell, through which the fuel cell health is diagnosed along with measurements of transport properties. While EIS is a standard technique to obtain such information in other elds of electrochemistry such as batteries, electrodeposition, and corrosion, fuel cells lend themselves especially to probing with this technique because of their nearly steady-state operation. Numerous experimental papers exist in the literature that obtain and analyse impedance data on PEMFCs. However, on modelling impedance behaviour and on mathematically analysing impedance data, papers are fewer. Nevertheless, mathematical analysis has been shown to be of paramount importance if the extracted information about the materials or the transport properties of the cell were to be accurate (Gomadam et al., 2003). In this work, we review these papers for the variety of mathematical modelling and analyses of impedance data
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presented on PEMFCs and discuss the information obtained therein. While the popular equivalent-circuits-based approach is outlined and briey discussed, the more fundamental continuum-mechanics-based approach to impedance modelling is reviewed in detail.

2. AN OVERVIEW OF EIS The EIS experiment involves applying a small sinusoidal voltage or current perturbation around a steady-state value and measuring the resulting current or voltage along with the phase angle. Using this data the real and imaginary impedances are calculated and plotted against each other for dierent perturbation frequencies in what are called Nyquist impedance spectra. Although other types of plots}such as, the Bode plots, where the magnitude of the impedance and the phase angle are plotted against frequency, the ColeCole plots, where the squares of the real and imaginary impedances are plotted against each other}are also used in the literature, the Nyquist plots are the most common way of analysing impedance data. However, in Nyquist plots the frequency dependence of the impedance remains hidden. For this reason, Bode plots, which provide explicit information on the frequency dependence of the impedance, are often used. The EIS technique forms a good diagnostic tool for evaluating performance owing to its ability to separate the impedance responses of the various transport processes occurring simultaneously in PEMFCs (Li and Pickup, 2003). Generally, the high-frequency region (>100 Hz, in general) of an impedance spectrum reects the charge transport in the catalyst layer, whereas the low-frequency region (50.01 Hz, in general) represent mass transport in the GDL, the catalyst layer, and the membrane. The relative importance of the transport processes depend on the steady-state value of the overpotential at which the EIS experiment is conducted. At low overpotentials when the mass transport resistance is not signicant, the main contributor to the impedance is the charge transport in the catalyst layer. At moderate overpotentials proton, gas, and water transport begin to contribute to the total impedance of the cell. At high overpotentials gas diusion in the GDL and the catalyst layer become dominant, especially when air is used as the oxidant. In the various layers of the fuel cell one or more of the transport processes described above are important depending on cell design and operating conditions. For example, electron conduction, water transport, and gas diusion are important in the GDL, and proton conduction and water transport are important in the membrane. However, all these processes coupled with distributed electrochemical reaction are important in the catalyst layer. This distinguishes the catalyst layer from the other components in terms of the mathematical complexity of the analysis, arising primarily due to its porous nature. Mathematical models of PEMFCs existing in the literature dier fundamentally in the level of complexity with which the porous catalyst layer is treated. With respect to EIS there are broadly two ways: (a) equivalentcircuits-based and (b) continuum-mechanics-based.

3. EQUIVALENT-CIRCUITS-BASED ANALYSES The equivalent-circuits-based analysis involves reducing the transport processes into electrical analogues made of networks of resistors and capacitors, and sometimes, inductors. The values
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C dl Re
(a)

C dl,1 Ri R ct,1 R e,1

R ct

Re

Re

Re

R ct

R ct C dl C dl

R ct C dl

R ct C dl

(b)

Ri

Ri

Ri

Ri

Figure 3. Equivalent circuits for: (a) a PEMFC with catalyst layers in planar form; and (b) a half-cell with catalyst layer in porous form. Ri ionic resistance, Re electronic resistance, Rct charge-transfer resistance, Cdl double-layer capacitance. The resistances and capacitance of the electrode on the right are distinguished with the subscript 1.

of the resistances and capacitances are obtained by tting the eective impedance of the network to experimental data. This method provides us with a quick visualization tool to understand system behaviour and limitations. Figure 3 shows typical equivalent circuits of (a) a fuel cell treating the catalyst layer in planar form, and (b) the catalyst layer in porous form. In the planar form, the catalyst layers are described by the parallel combination of the charge-transfer resistance, Rct and Rct,1, with the double-layer capacitances, Cdl and Cdl,1, respectively. The resistances (Re and Re,1) at the ends describe the electronic resistance due to the GDLs and the ow-elds, while the resistance (Ri) in the middle describes the ionic resistance of the membrane. The boxed region shows the equivalent circuit of a half-cell obtained by considering a reference electrode placed in the membrane. In Figure 3(b) the equivalent circuit of this half-cell is shown with the catalyst layer in porous form. The parallel combination of Rct and Cdl, used to represent the entire catalyst layer in the planar form, now represents the local interface in every volume element of the porous catalyst layer. Two adjacent volume elements are separated by electronic and ionic resistances. This results in the ladder-like circuit called the transmission-line model, which is widely used to capture the impedance response of porous electrodes. A more empirical way of achieving this is to replace the normal double-layer capacitance (Cdl) in the planar form with a distributed capacitance. The distributed nature is introduced by expressing the impedance of the double-layer capacitance as the impedance of the normal capacitance raised to the power of an empirical parameter called the constant phase element (Lasia, 1999). The Nyquist impedance responses of the half-cell in its planar form, the half-cell in its porous form, and the full cell are shown in Figures 4(a)(c), respectively. Figure 4(a) shows a semi-circle
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Figure 4. Sample Nyquist plots presented for: (a) the half-cell in planar form shown boxed in Figure 3(a); (b) the half-cell in porous form shown in Figure 3(b); and (c) the full cell shown in Figure 3(a).

with a high-frequency intercept equal to the ionic resistance of the membrane, and a lowfrequency intercept equal to the sum of the ionic resistance of the membrane and the chargetransfer resistance of the catalyst layer. The frequency dependence of the impedance depends on the double-layer capacitance. In the case of the transmission-line model for the porous catalyst layer (Figure 4(b)) the high-frequency intercept is the sum of the ionic resistance of the membrane and a function of the ionic and electronic resistances of the catalyst layer. On the other hand, the low-frequency intercept is the sum of the ionic resistance of the membrane and a function of the ionic, electronic, and charge-transfer resistances of the catalyst layer. Further, the frequency dependence of the impedance is qualitatively dierent from the planar case, showing a high-frequency straight line of unit slope and an asymmetric semi-circle (Lasia, 1999). These features of the impedance spectrum of a porous electrode will be discussed in greater detail when reviewing the theoretical analyses published by Gomadam et al. (2003). Note that while charge-transfer resistances are often described normally as pure resistances, complex reaction mechanisms result in non-resistive behaviours. For example, Antoine et al. (2001) show that the oxygen reduction reaction occurring in fuel cells involves an adsorption step giving rise to an inductive behaviour at low frequencies (around 0.6 Hz). Using the model based on equivalent circuits, one can extract the above resistances and capacitances from an EIS experiment conducted on a half-cell. However, because of the lack of a reliable reference electrode, measurements are often made only on full cells. The impedance response of a full cell is a combination of the responses of the anode and cathode half-cells as shown in Figure 4(c). The gure shows that if the time-constants of the two half-cells are very dierent, two distinct semi-circles appear such that the high-frequency intercept gives the ionic plus electronic resistances, the moderate-frequency intercept gives the charge-transfer resistance with the lower time-constant, and the low-frequency intercept gives the charge-transfer resistance with the higher time-constant. On the other hand, if the time-constants of the
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Figure 5. Capacitance vs resistance plots of a porous electrode with: (a) uniformly distributed ionic resistance; and (b) linearly increasing ionic resistivity. Reproduced by permission of The Electrochemical Society (Lefebvre et al., 1999).

half-cells are comparable, the two semi-circles merge and, therefore, the two charge-transfer resistances are not separable. Numerous papers have been published using the equivalent-circuits analysis to measure properties of PEMFCs from impedance data. For example, Saab et al. (2002, 2003) studied the eect of ionic and electronic conductivities of catalyst layers as functions of processing and operating conditions, Abe et al. (2004) studied the eect of humidity in oxygen gases on the performance of a PEMFC, Ciureanu and Wang (1999) studied hydrogen oxidation at a PEMFC anode with and without CO, Wang et al. (2001) studied CO poisoning in the anode, and Li and Pickup (2003) studied the eect of Naon1 loading in the cathode catalyst layer. All these papers use the analysis explained above to extract physical properties from EIS data. Only very few papers (Lefebvre et al., 1999; Waraksa et al., 2003) provide alternative methods of analyses based on the equivalent-circuits approach. Lefebvre et al. (1999) developed a new method of analysing impedance data so as to obtain information about the ionic conductivity proles in catalyst layers. Assuming a constant doublelayer capacitance, they showed that analysing impedance data in the form of eective capacitance vs resistance plots, as shown in Figure 5, reveals semi-quantitatively how the ionic conductivity varies across the catalyst layer. They demonstrated this approach by extracting a non-uniform ionic conductivity prole of the catalyst layer from its measured impedance response. The approach involved tting measured impedance data with simulations using various assumed ionic conductivity proles. Waraksa et al. (2003) developed a transmission-line model for the EIS response of porous oxygen electrodes with discrete particles. Their model was based on an array of parallel, non-uniform, transmission lines, incorporating physically realistic elements, such as discrete particles of variable sizes and adjustable multilayer stacking geometries. Using this analysis Chen et al. (2003) studied the EIS response of porous oxygen electrodes with discrete particles and compared two titanium-oxide-based catalyst supports.
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The popularity of the equivalent-circuit approach stems from the fact that it is mathematically simple and easy to use. However, this method normally involves oversimplied representations of the components of electrochemical systems. Therefore, this method cannot always be used to accurately describe the system and estimate parameters, especially in porous electrodes. Further, because the various transport processes occur simultaneously in porous electrodes, converting the estimated resistances and capacitances into physically meaningful parameters is dicult. For these reasons, a more fundamental, continuum-mechanics-based approach is preferred (Gomadam et al., 2003) while the equivalent-circuit approach is good for a quick visualization tool and, perhaps, as a rst approximation. However, when certain simplifying restrictions (e.g. invariant physical properties, linear kinetics, no mass-transfer limitations) are enforced, the continuum-mechanics approach reduces to the equivalent-circuit approach (Springer and Raistrick, 1989; Eikerling and Kornyshev, 1999).

4. CONTINUUM-MECHANICS-BASED ANALYSES The continuum-mechanics approach involves mathematical descriptions of phenomena derived from conservation equations using rst principles. A number of continuum-mechanics-based impedance models have been published for electrochemical systems. However, a vast majority of them are for planar electrodes, which are often not applicable to the porous catalyst layers of PEMFCs since they do not predict the qualitative features of impedance spectra measured on porous electrodes. Owing to the mathematical complexity associated, only a few papers have been published that analyse the impedance response of porous electrodes based on continuummechanics. De Levie (1967) developed impedance models for porous electrodes by treating them either as made of uniform cylindrical pores ooded with electrolyte or as a macrohomogeneous superposition of the solid and solution phases. Following them, Darby (1966) developed an impedance model for porous gas-diusion electrodes. An error in Darbys model predicted that the occurrence of reactions inside the pores will result in inductance loops in the Nyquist spectra, which was later corrected by Keddam et al. (1984). Rangarajan (1969) developed an impedance model for porous electrodes with potential and concentration gradients and derived analytical solutions for linear kinetics. Cachet and Wiart (1985) developed an approximate solution for the impedance of a porous electrode with potential and concentration gradients under conditions of Tafel kinetics. Paasch et al. (1993) extended the above models by including time delay. Lasia (1995) developed an impedance model for porous electrodes with potential gradients only in the solution phase and with ButlerVolmer kinetics for nite and semi-innite pores. Lasia (1997) later extended the work by including concentration gradients in the pore. In a more recent paper, Lasia (2001) discussed the nature of the two semi-circles observed on the Nyquist spectra in the presence of concentration gradients. Lasia (1999) summarizes impedance modelling for planar and porous electrodes. Continuum-mechanics-based EIS models using the macrohomogeneous representation of porous electrodes have been published in many elds of electrochemistry, especially, in Li and Li-ion batteries. In this representation the porous electrode is treated to be a continuous superposition of electronic and ionic phases, with average properties (Newman and Thomas-Alyea, 2004). Doyle et al. (2002) developed an impedance model for a Li-polymer cell sandwich incorporating charge and mass transport in the solid and solution phases. Meyers et al. (2002) developed an impedance model for a porous intercalation electrode by combining a
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single-particle impedance model to the impedance response of a porous electrode. Guo et al. (2002) applied the model of Doyle et al. (2002) to estimate the solid-phase diusion coecient of Li and analysed the eect of design variables on the accuracy of the estimated parameter. Devan et al. (2004) developed an analytical solution to the impedance response of a porous Li-ion battery electrode under the presence of concentration gradients in the solution phase. Most of the above impedance models were developed for ooded porous electrodes, where the pores are considered to be lled with electrolyte. However, the electrodes used in fuel cells have pores lled partly with the electrolyte and partly with the reactant gas. Relatively fewer models exist in the literature that deal with continuum-mechanics-based analysis of such gas-diusion electrodes. Such models as applicable to PEMFCs are reviewed below in detail. Springer and Raistrick (1989) calculated the impedance of a dierential element of the pore wall based on a ooded-agglomerate model for the catalyst layer of PEMFCs. Assuming negligible ohmic drops in the electronic and ionic phases and a uniform reaction distribution, they integrated the dierential impedance over the pore length to obtain the total impedance of the gas-diusion electrode. However, the reaction rate distribution in a porous electrode depends on the perturbation frequency; lower the frequency, more uniform the distribution. Consequently, their model predictions, accurate only at relatively low frequencies, show qualitative errors at high frequencies. For example, the high-frequency straight line in the Nyquist plots, characteristic of porous electrodes, cannot be predicted by this model. At low frequencies, the model predicts a Warburg straight line arising due to semi-innite diusion of oxygen in the agglomerate. They combined the ooded-agglomerate impedance model in series with a model for a thin electrolyte lm surrounding the agglomerate. Using this complete agglomerate model they calculated the pore wall impedance for dierent steady-state currents. They also developed transfer functions that simplied the numerical tting procedure of model predictions to experimental data. An important conclusion made in their work was that the agglomerate itself does not lead to a steady-state-limiting current behaviour, but rather to a doubling of the eective Tafel slope when current penetration of the agglomerate region is incomplete. This is because until current penetration of the agglomerate is complete there will be a region of the agglomerate with a non-zero reactant concentration and, therefore, a limiting current does not occur. They showed that it is the thin electrolyte lm, either by itself or in conjunction with the agglomerate, that ultimately leads to a diusionlimited current. In a later paper, Springer et al. (1996) developed an impedance model for the cathode side of a PEMFC. In contrast to their previous work, they based this model on macrohomogeneous porous electrode theory for charge transport in the catalyst layer and used StefanMaxwell multicomponent diusion equations for oxygennitrogenwater transport in the GDL. The predicted Nyquist impedance spectra showed two loops in general}the higher frequency loop determined by charge transport in the catalyst layer and the lower frequency loop determined by mass transport in the GDL. They showed that the lower frequency loop does not appear if pure oxygen is fed to the cathode instead of air. Comparing the model predictions to impedance data measured under large steady-state currents of operation, they concluded that for PEMFCs in general: (a) a high catalyst utilization is achieved with thin-lm catalyst layers made of ionomer//Pt/C composites; (b) the limited protonic conductivity in the composite cathode catalyst, in conjunction with the nite oxygen permeability in this layer, contributes signicantly to the cathode impedance in the medium current density domain; and (c) cell humidication has a profound eect on the physical properties several cell components. They also showed that the
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eects of insucient humidication on electrocatalysis and on catalyst layer protonic conductivity may supersede the most commonly considered eects on membrane conductivity. Eikerling and Kornyshev (1999) analysed the impedance behaviour of a PEMFC cathode catalyst layer by considering it to be governed by two transport processes}proton migration and oxygen diusion. For the transport processes they identied characteristic lengths, whose magnitudes relative to the catalyst layer thickness determines the relative importance of the transport processes. For situations when only one of the transport processes is limiting, they derived analytical solutions to the impedance response of the catalyst layer at open-circuit and under load considering both linear and Tafel kinetics. However, when both processes are limiting simultaneously, analytical solutions do not exist and only numerical solutions were presented. Based on this analysis they identied the following diagnostic criteria characterizing catalyst layers: (a) When the characteristic lengths of both the transport processes are large the catalyst layer operates under kinetic control. This results in a semi-circle in Nyquist plot, the diameter of which gives the kinetic resistance. Further, under Tafel kinetics, the kinetic resistance decreases with increase in load current; (b) When proton transport is limiting the Nyquist plot shows an asymmetric semi-circle with a 458 straight line at high frequencies; and (c) When oxygen diusion or both the transport processes are limiting the impedance spectra shows two semi-circles overlapping or separate. The semi-circle occurring at lower frequencies arises due to oxygen diusion. Jaouen et al. (2003) developed an impedance model for the gas-diusion cathode of PEMFCs by combining the spherical agglomerate model for oxygen diusion with the macrohomogeneous porous electrode model for charge transport. In this model, only pure-oxygen feed were considered and concentration gradients across the GDL and the catalyst layer we assumed negligible. For these conditions, they calculated the impedance under Tafel kinetics for ORR, for which they dened a Tafel impedance, Zt  dV=dlog I; and used it in place of the traditional impedance, Z  V=I or dV=dI: A distinguishing property of the Tafel impedance is that its value is independent of load current under kinetic control. Using this model they discussed the relative importance of kinetics, mass transfer, and proton migration for dierent load currents of fuel cell operation. They predicted Nyquist spectra for conditions of diusion limitation, migration limitation, and diusionmigration limitation, as shown in Figures 6(a), (b), and (c), respectively. It was observed with Figure 6(a) that the low-frequency intercept at high load currents (diusion control) was identically equal to twice the value for low load currents (kinetic control). Note that this was also predicted by Springer and Raistrick (1989). When proton migration is limiting (Figure 6(b)) a straight line was observed at high-frequencies although the low-frequency intercepts showed the same behaviour as the diusion control case. When both diusion and migration are limiting (Figure 6(c)) the Nyquist curves show the same general shape as migration control. However, the low-frequency intercept at high load currents reaches four times that at low load currents. The authors address the common practice of using the high-frequency intercept of the Nyquist plot to obtain the IR drop of the electrolyte. They show that unless the IR drop is a linear function of the current density of operation, the highfrequency intercept cannot be directly used to obtain the IR drop. Instead, one has to use the integral of the IR drop over the current range considered. In the second part of their paper (Jaouen and Lindbergh, 2003), they use the above model to extract charge- and mass-transport properties from impedance data measured on a PEMFC under load currents ranging from 1 to 400 mA cm2. The parameters obtained indicated that the electrode is limited by both diusion and migration. Further, they concluded that the spherical
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Figure 6. Predicted impedance spectra at various current densities for: (a) diusion limitation; (b) migration limitation; and (c) diusion and migration limitation. Reproduced by permission of The Electrochemical Society (Jaouen et al., 2003).

agglomerate model used to describe oxygen diusion is valid, although the model could not t data obtained at load currents higher than 200 mA cm2. This was attributed non-uniform electrode thickness and/or the inuence of the anode, which was not included in the model. They also observed that at low humidities, a second loop appeared on the low-frequency side, which was attributed to the membrane not behaving as an ideal resistor under dynamic conditions. Guo and White (2004) extended the pure-oxygen-feed impedance model of Jaouen et al. to consider air feed and including concentration variations across the GDL and the catalyst layer. The transport of three components, namely, nitrogen, oxygen, and water, in the gas phase was treated using the StefanMaxwell equations for multicomponent diusion. The model predictions showed signicant concentration variations in the GDL and the catalyst layer. Further, the eect of pure-oxygen feed and air feed were compared using the predicted dimensionless Nyquist impedance spectra as shown in Figure 7. These comparisons were made between high-pressure air feed and low-pressure oxygen feed so that the partial pressures of oxygen in the feed were the same. For small operating current densities both air-fed and oxygenfed cathodes exhibited the same impedance prole and a normal Tafel slope, indicating the absence of gas-phase transport limitations. However, with increase in load current the oxygen cathode began to display an increasing Tafel slope. For very high load currents an almost quadric Tafel slope was predicted on the oxygen-fed cathode, caused by a combined limitation from slow ionic conduction and slow dissolved oxygen diusion in the agglomerate. For the airfed cathode, besides the increasing Tafel slope observed from the high-frequency impedance loop, a second impedance loop began to grow adding an extra Tafel slope.
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Figure 7. Comparison of the simulated normalized impedance responses of an air cathode with those of an O2 cathode. Both the air ow and O2 ow have the same partial pressure of O2. Reproduced by permission of The Electrochemical Society (Guo and White, 2004).

In an earlier paper, Guo et al. (2003) developed an impedance model for a PEMFC cathode with a non-uniform ionic conductivity. Porous electrode theory was used to derive the governing equation for the impedance response of the cathode at open-circuit conditions. The inuence of an assumed ionic conductivity prole on the error in the estimation of total double-layer capacitance of the catalyst layer was also investigated. Further, a characterization of the ionic conduction of the catalyst layer was conducted using impedance measurements. The increase of ionic conductivity in the catalyst layer of an air-fed cathode with increase in ionomer loading was revealed from both impedance data and surface area measurements. A nonlinear parameter estimation method was used to extract the ionic resistance from the high-frequency region of the impedance data at open-circuit potential conditions. The assumed ionic conductivity distribution in the active layer was found to vary with ionomer loadings. We recently developed the theoretical analysis required to extract charge-transport properties from impedance or time-dependent polarization data on composite (i.e. porous) electrodes (Gomadam et al., 2003). The experiments considered in this theory involved perturbing the composite under three dierent congurations around open-circuit. Although these congurations have been considered before by researchers for measuring some transport properties, their analysis allows using combinations of these congurations to accurately obtain all the transport properties of composite electrodes. The three congurations considered are shown schematically in Figure 8. In Conguration I, the reference electrode is placed in the electrolyte at a point near the face of the composite working electrode (i.e. at x 0) and the other side of the composite is supported by a metallic current collector (i.e. at x L). In Conguration II, the composite is
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Figure 8. Schematic of a composite electrode (shown shaded) under three dierent congurations labelled I, II and III. The electrolyte lls the unshaded area between the current collectors as well as the pores in the composite. In all the three congurations, current ows between points A and B, while the resulting potential dierence is measured between points C and D. Reproduced by permission of The Electrochemical Society (Gomadam et al., 2003).

bounded by current collectors on either side, while in Conguration III, it is bounded by two reference electrodes. In all the three congurations, a current, I, ows between points A and B, while the resulting potential dierence, V, is measured between points C and D. Using porous electrode theory, we obtained analytical solutions for the frequency response of the three congurations in terms of dimensionless impedances as   2 s=k k=s cosh nAC I Z RO 1 1 nAC sinh nAC  k1 cosh n  AC 12 s nAC sinh nAC

Z RO

II

 s1 cosh n  AC Z III RO 1 2 k nAC sinh nAC where nAC r ak s i0 nf Cdl oj L ks

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RO

1 1 k=s

Figure 9(a) shows Nyquist plots of the composite for the three congurations simulated using Equations (1)(4), with k=s 1:25 and n 10: Here, n is a dimensionless parameter signifying the ratio of ohmic resistance of the electrode relative to its charge-transfer resistance at steadystate. It is equal to the steady-state value of nAC, obtained by substituting o 0 in Equation (4). In each of the three congurations, the Nyquist plots are characterized by a high-frequency real intercept equal to RO, a high-frequency straight line of unit slope, and a low-frequency real intercept equal to the steady-state polarization resistance of the composite. The values of the low-frequency intercepts, RI ; RII ; RIII ; for the three congurations are obtained by substituting 1 1 1 o 0 in Equations (1)(4), respectively. These intercepts and the Nyquist spectra are functions of the two parameters, k/s and n. Nevertheless, the qualitative shapes of the Nyquist plots of Congurations II and III do not change with n. In contrast, Figure 9(b) shows that the shape of the Nyquist plot of Conguration I varies signicantly with n. The low-frequency real intercept, approaches innity as n ! 0. At n 0; the Nyquist plot does not come back towards the real axis at all. Rather, it behaves as a purely capacitive system, whose impedance tends to innity. Except for some limiting conditions, the impedance of a composite electrode is a combination of s, k, i0, and Cdl. Therefore, these parameters must be obtained from a set of data rather than a single data point. For example, these parameters can be obtained by tting the analytical expressions derived here to the entire impedance spectrum, measured on any one of the congurations. Which conguration is chosen depends on how sensitive its response is to the parameter of interest. When the eect of one unknown parameter on the impedance of a conguration is much greater than another parameter, then that conguration cannot be used to determine the latter parameter with condence. One has to use alternative congurations, wherein the response is dominated by the parameter of interest. Since one often does not know the relative importance of the parameters a priori, it is prudent to determine the parameters from the responses of multiple congurations. Such use of multiple congurations to determine dierent parameters has been considered by Saab et al. (2002, 2003) for fuel cells and by Shibuya et al. (1996) for Li-ion batteries. Impedance measurements on normal PEMFCs, which have large cross-sectional areas and small path lengths for current ow, often show low signal-to-noise ratios. Secondly, based on the time-constant of the process of interest, the measured impedance data may not be well resolved over the range of frequencies allowed by the instrument or by competing processes. For these reasons, our analysis considered thin and long electrode samples, which dramatically improve the signal-to-noise ratio, as shown by Saab et al. (2002). Moreover, by varying the length of the sample the time-constant of the process can be varied so as to obtain reliable impedance data in the frequency range allowed by the instrument. In a recent paper (Gomadam and Weidner, submitted), we extended the open-circuit analysis, mentioned above, to allow for in-situ property measurements under load. Impedance under load with Tafel kinetics for Conguration I has been analysed by many researchers (Springer and Raistrick, 1989; Springer et al., 1996; Jaouen et al., 2003; Guo and White, 2004). However, we considered linear and Tafel kinetics for all the three congurations and their combinations under load. Analytical solutions were derived for most of these combinations, while simple numerical solutions were obtained for more complex situations
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Figure 9. (a) Nyquist plots obtained for the three congurations simulated using Equations (1)(3), with k=s 1:25 and n 10; and (b) for the same value of k/s, as n decreases or as charge-transfer resistance increases, the low-frequency intercept of Conguration I also increases, eventually tending to innity as n ! 0. Reproduced by permission of The Electrochemical Society (Gomadam et al., 2003).

(e.g. ButlerVolmer kinetics, two-dimensional distributions). The impedance-under-load theory, developed for conditions of no concentration gradients, was modied for the case when concentration gradients exist. Analytical solutions were obtained in spite of relaxing this assumption since we recognized that under mass-transfer-limiting conditions the potential drops in the catalyst layer are negligible compared to the large overpotential for reaction. The various conditions treated (linear kinetics, Tafel kinetics, presence of concentration gradients) allow the use of the model to measure properties at all load currents or voltages of operation of PEMFCs.
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Figure 10. Simulated Nyquist plots of impedance under load for Conguration I under Tafel conditions.

The same governing equations as open-circuit are applicable under load, except: (i) the initial conditions for the dependent variables are their pseudo-steady-state proles under load; (ii) the governing equations, if nonlinear, are linearized around their steady-state values to obtain the solutions for impedance. When linear kinetics applies, the mathematical analysis and the solutions for impedance under load are identical to that at open-circuit. However, for Tafel kinetics, the mathematical analysis is more complex, although analytical solutions were still obtained as plotted in Figure 10. The gure shows sample Nyquist impedance spectra simulated for Conguration I as a function of load current applied also on Conguration I. The Nyquist curves follow the same qualitative trends as in open-circuit, namely, an asymmetric semi-circle with a straight line of unit slope at high frequencies, a high-frequency real intercept equal to the eective ohmic resistance of the composite, and a low-frequency real intercept equal to the total resistance (i.e. ohmic plus kinetic). The gure also shows that as the load current is decreased the low-frequency intercept or the total resistance of the composite increases. Considering that the ohmic resistance is a constant, this means that the kinetic resistance increases with decrease in load current; a distinguishing feature of Tafel kinetics. For impedance under load with linear kinetics, the same parameter estimation technique as open-circuit is applicable. However, with Tafel kinetics, the kinetic parameters obtained from the low-frequency intercept are dierent. Under Tafel conditions, the kinetic resistance of the composite depends on the load current and the transfer-coecient (a). Therefore, the lowfrequency intercept obtained from an impedance experiment under a given load gives the transfer-coecient. Using this transfer-coecient in the steady-state currentvoltage relationship for the porous composite gives the exchange-current density ai0. The impedance-under-load experiment can also be performed with two congurations}one operating under load and the other being perturbed. Thus, with the three congurations considered here, we obtain nine dierent combinations. Further, it is often more convenient to arrange the perturbed conguration perpendicular to the load conguration, as we proposed in the paper. However, the analysis then becomes two-dimensional with only numerical solutions possible unless simplifying assumptions are enforced.

5. CONCLUSIONS A literature review of EIS analysis of PEMFCs is presented. Papers that analyse the impedance response of the cathode and anode half-cells of the PEMFCs based on the
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continuum-mechanics approach are reviewed in detail. Papers dealing with EIS analysis based on the equivalent-circuits approach are briey addressed along with the relative advantages and disadvantages of the two approaches. Papers dealing with continuum-mechanics-based EIS modelling of general electrochemical systems are also briey reviewed.

NOMENCLATURE a Cdl f F i0 I j L n R RO Rct Re Ri RI ; RII ; RIII 1 1 1 T V x Z Zi, Zimag Zr, Zreal Zt Z I ; Z II ; Z III Greek letters k nAC o s =ionic conductivity (S m1) =as dened in Equation (4) =frequency (Hz) =electronic conductivity (S m1) =specic area for electrochemical reaction (m2 m3) =double-layer capacitance (F m2) =F/RT (V1) =Faradays constant (C mol1) =exchange-current density (A m2) =current (A) p = 1 =electrode length (m) =number of electron transfers in electrochemical reaction =universal gas constant (J mol1 K1) =as dened in Equation (5) =charge-transfer resistance (O) =electronic resistance (O) =ionic resistance (O) =low-frequency intercepts of Congurations I, II, III, respectively =temperature (K) =voltage (V) =position (m) =impedance (O, O m or no units, as applicable) =imaginary part of Z (O, O m or no units, as applicable) =real part of Z (O, O m or no units, as applicable) =Tafel impedance (V) =dimensionless impedance of Congurations I, II, III, respectively

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