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Electrochemical Impedance Study on Estimating the Mass Transport Resistance in the Polymer

Electrolyte Fuel Cell Cathode Catalyst Layer.

Samuel Cruz-Manzo and Rui Chen

Department of Aeronautical and Automotive Engineering, Loughborough University, LE11 3TU, UK

Abstract

In this study the mass transport resistance in the cathode catalyst layer (CCL) of a polymer electrolyte

fuel cell (PEFC) is estimated using electrochemical impedance spectroscopy (EIS) measurements.

Experimental impedance measurements for a 6 cm2 PEFC operated with two different relative

humidity (RH) values in the cathode and different partial pressure of oxygen in He/O2 and N2/O2 gas

mixture were carried out. A mathematical model predicting the CCL impedance response, derived in

the authors’ previous study, is applied to EIS measurements to calculate the CCL mass transport

resistance. The experimental results show the presence of an overlapped second semicircle at low

frequencies which is attributed to an increase in the time constant to diffuse oxygen through the CCL

when the PEFC is operated at low oxygen partial pressure, p(O2) ≤ 20 %, in He/O2 or N2/O2 gas

mixture. The results also show that oxygen diluted with nitrogen can reduce the steady state oxygen

concentration in the CCL-gas diffusion layer (GDL) interface and can increase CCL mass transport

resistance. It is possible, as such, to harness capabilities from both modelling and real-world EIS data

in a complementary manner.

Keywords: PEFC, EIS, mass transport resistance, cathode catalyst layer, impedance model
 1. Introduction

Polymer Electrolyte Fuel Cells (PEFCs) are the best candidates to be considered as the future source

of propulsion for automobiles because they are able to produce high power density at low temperature

and are not bound by the Carnot cycle. A PEFC converts the chemical energy of a fuel such as

hydrogen gas into electrical energy. The study of mass transport resistance in the PEFC is of crucial

interest, because the electrochemical reaction during hydrogen oxidation and oxygen reduction

(redox) is affected by concentration gradients in the reactants supplied across the gas diffusion layer

(GDL) and catalyst layer (CL), for example. GDLs and CLs contain a tortuous pore network for the

supply and removal of reactant gases and product water, respectively. External gas humidification is

desirable to ensure an appropriate humidification of the ionomer in the CL and the polymer electrolyte

membrane (PEM). A high relative humidity (RH) enhances the ionic conductivity in the PEM and

improves catalyst utilization and overall performance. Nevertheless, a high RH can result in pore

saturation in the GDL and CL which will impede reactant transport. Electrochemical Impedance

Spectroscopy (EIS) is an experimental technique that can be applied in-situ to separate the physical

processes in the PEFC that occur at different rates through a frequency response plot. One of the

challenges in EIS research is to quantify the mass transport limitations between the CCL and the

GDL. The Randles circuit [1] has been broadly used in impedance plots to estimate mass transport

limitations in PEFC EIS measurements. However, it has not been clear how to define whether this

effect of oxygen transport limitation is dominated by the CCL or the GDL. In the authors’ previous

study [2], a mathematical model based on electrochemistry theory was developed to simulate the

impedance spectrum of the cathodic side of a PEFC. The objective of the current study is to estimate

the mass transport resistance in the cathode catalyst layer (CCL) using EIS measurements and the

mathematical model developed in a previous study. To validate this work, experimental impedance

measurements for a 6 cm2 PEFC operated with two different relative humidity (RH) values in the

cathode and different partial pressure of oxygen in He/O2 and N2/O2 gas mixture were considered. It is

possible as such to harness capabilities from both modelling and EIS in a complementary manner.
 2. Experimental

A 6 cm2 PEFC was operated at 500 mAcm2, 80 ºC, 20 psig anode and cathode inlet pressures, 100%

RH for the anode and 100/30 % RH for the cathode. The flow rates were kept constant throughout

the experiment at 125.5 sccm on the anode and 313 sccm on the cathode. The cell was allowed to sit

at the required current on pure oxygen for 5 minutes and then the AC responses were measured. The

gas was then switched to 80 % O2 in helium, held for a few minutes and then switched to 80 % O2 in

nitrogen. The concentrations were then stepped down to 60, 40, 20, and 10 % O2 in helium followed

by nitrogen with impedance measurements taken at each point. The MEA was a developmental

sample from Johnson Matthey Fuel Cells with 0.4 mg Pt/cm² on both anode and cathode. The

thickness of the CLs was 10 μm. The membrane was a commercial 30 µm perfluorinated sulphonic

acid membrane. The gas diffusion layers were based on wetproofed Toray TGP-H-060.

How were the flow rates controlled?

3. Model description

In the authors’ previous study [2], a mathematical model was developed based on fundamental

electrochemical and diffusion theory to simulate the impedance spectrum of the cathodic side of a

PEFC operated for any zone of the polarisation curve, as such:

Z PEFC = LH (iω ) + Re +
[RC + ZW ]γ 1 coth(γ 1 x ) (1)
1 + Y (iω ) [RC + ZW ]
P

With γ 1 = R p  1 P
+ Y (iω ) 
 RC + Z W 

RP is the resistance to the flow of ions in the electrolytic phase of the CCL; RC represents the charge

transfer resistance during the oxygen reduction reaction (ORR) and is defined as RC = b / j0 exp(η SS / b) ,

where b is the Tafel slope, η SS represents the activation overpotential, and j0 is the exchange current;

ZW = RW tanh (iωTW ) / (iωTW ) is defined as the Warburg impedance and describes diffusion across a
0.5 0.5

finite dimension in the frequency domain, with RW = RTδ / (z 2 F 2 co* D ) defined as resistance for the
diffusion process and TW = δ 2 / D defined as the time constant to diffuse oxygen through the CCL; Y

represents a parameter related to capacitance, superscript P represents a parameter to correct the

inhomogeneity in the distribution of charge between the electrode-electrolyte inteface; ω is the

angular frequency; i is the imaginary component in impedance; LH represents the inductance in the

electrical cables in the measurement system; and Re represents the total ohmic resistance to flow

electrons and ions in the bipolar plate, GDL and PEM. In the authors’ previous study [3] a reference

electrode inserted in a PEFC operated with 100% RH in the anode and a multichannel frequency

response analyser allowed the separation of the impedance response of the cell and cathode. The

results showed that anode mechanisms (hydrogen oxidation reaction) have not contribution in EIS

measurements at low frequencies where oxygen transport limitations are commonly manifested [3,4].

Springer et al. [5] reported that there is a negligible difference in impedance response when

measuring the cathode impedance relative to the anode or relative to a reference electrode place on the

side of the anode. The anode contribution, neglecting any contaminant within the hydrogen supplied

such as CO which affects the PEFC performance [6], can be considered negligible in these EIS

measurements. Therefore Eq. 1 will be used to estimate the mass transport resistance in the CCL. The

use of Eq. 1 with EIS measurements have already been demonstrated in previous studies [2,3,4]. The

modelling predictions of Eq.1 can be compared with the experimental impedance curves for a PEFC

operated with different partial pressure of oxygen in He/O2 and N2/O2 gas mixture and two RH (100

%, 30 %) in the cathode. The simulated data from Eq. 1 were compared with the measured EIS data

using a Graphic User Interface (GUI) developed in Matlab®. The use of the GUI with Eq. 1 for EIS

analysis has already been demonstrated in the authors’ previous study [2]. The parameters of Eq. 1

were manually adjusted with experimental EIS measurements using the GUI to achieve a good

agreement between the experimental and simulated data. In Eq. 1 there are some parameters that can

also be estimated through a graphical interpretation of the Nyquist plot, as reported in a previous

study [3]. This allows the reduction of the number of parameters to be fitted in the measured EIS

spectra. The least-squares fitting method was used in order to find the best fit between the model and

the measured data.

 4. Results and Discussion

The aim of this section is to estimate the mass transport resistance in the CCL when using O2 diluted

in He and N2. For partial pressure of oxygen p(O2) > 20% in He/O2 or N2/O2 gas mixture, the kinetic

and diffusion processes masked one another in the impedance plot. In EIS measurements carried out

with p(O2) ≤ 20 % in He/O2 or N2/O2 gas mixture an overlapped second semicircle at low frequencies

which can be attributed to oxygen diffusion effect was apparent, as shown in Fig. 1. In this study only

EIS measurements with p(O2) ≤ 20 % in He/O2 or N2/O2 gas mixture were considered, as shown in

Fig. 1, as it was possible to quantify accurately the charge transfer and mass transport resistances

using Eq. 1.

4.1 Diffusion Time Constant

The presence of the overlapped semicircle at low frequencies is attributed to an increase in the time

constant TW = δ 2 / D to diffuse oxygen through the CCL [3]. The diffusion time constant is related to

the three principal modes of transport of O2 in the CCL: gas-phase diffusion in the CCL pore,

diffusion in the liquid-water film surrounding a catalytic agglomerate, and diffusion in the ionomer of

the agglomerate. The diffusion time constant for EIS measurements at p(O2) > 20 % in He/O2 or N2/O2

gas mixture and 100 % and 30 % RH and calculated through Eq. 1 resulted in 0.003 s. For EIS

measurements carried out at p(O2) ≤ 20 % in He/O2 or N2/O2 gas mixture an average value was

calculated for 100 % and 30 % RH conditions. The average diffusion time constants for 100 % and 30

% RH were 0.08 s and 0.14 s respectively. Springer et al. [5] concluded that it is not possible to

visualize the charge transfer and mass transport effects in PEFC EIS measurements with time

constants of 10-4 and 10-3 orders of magnitude, and with either air or oxygen as a gas reactant. The

finite diffusion distance δ for oxygen to reach the reaction sites in the CCL forms a complicated

network of multi-phase parallel and serial paths and change in dimension for different CCL

composition (e.g. nafion loading, porosity, tortuosity) and at different fuel cell operating conditions

(current density, temperature, relative humidity, etc.) [7]. Assuming that the finite diffusion distance

is the thickness of the CCL to simplify the analysis, the effective diffusion coefficient D for EIS
measurements at p(O2) > 20 % in He/O2 or N2/O2 gas mixture at 100 % and 30 % RH was calculated

to be 3.33x10-8 m2/s. For p(O2) ≤ 20 % in He/O2 or N2/O2 gas mixture at 100 % RH the effective

diffusion coefficient was calculated to be 1.25x10-9 m2/s and at 30 % RH was 7.143x10-10 m2/s. These

values present the same order of magnitude as the diffusion coefficients for diffusivity of oxygen in

gas phase 2.68x10-8 m2/s, liquid-water phase 2.00x10-9 m2/s and ionomer phase 2.83x10-10 m2/s as

reported by Malevich et al. [1]. It can be concluded that the main contribution to oxygen transport in

the CCL for p(O2) > 20 % in He/O2 or N2/O2 gas mixture at 100 % and 30 % RH is through the porous

media. For p(O2) ≤ 20 % in He/O2 or N2/O2 gas mixture at 100 % RH the main contribution to oxygen

transport is through the water film surrounding a catalytic agglomerate and at 30 % RH the main

contribution is through the ionomer surrounding the agglomerate in the CCL.

4.2 Mass transport resistance in Cathode 100 % RH

The mass transport resistance RW in the CCL expressed in Eq. 1 relates the change in oxygen

concentration during the ORR from the GDL-CCL interface at steady state to the CCL-PEM interface

at the frequency domain. RW is a function of the steady state oxygen concentration cO* at the CCL-

GDL interface. The steady state oxygen concentration can depend upon the conditions of the reactant

supply to the cell and the physical properties of adjacent porous transport layers such as the GDL and

microporous layer (MPL). Tab. 1 shows that CCL mass transport resistance calculated from EIS and

Eq. 1 is reduced by using He/O2 gas mixture, and increases with a decrease in p(O2). The diffusivity

of O2 diluted in N2 at 80o C has been reported [8] to be 2.8x10-5m2/sec and the diffusion coefficient of

water vapour in N2 is 3.9x10-5m2/sec; the oxygen diffusivity in He is 1.13x10-4m2/sec and the

diffusion coefficient of water vapour in He is 3.14x10-4m2/sec under the same conditions. So, when

the background gas in the cathode is switched to N2 from He, an increase in mass transport limitations

can be expected. The steady state oxygen concentrations cO* calculated from Eq. 1 are shown in Tab.1.

The increase of CCL mass transport resistance RW when O2 is diluted with N2 is due to a decrease in

the steady state oxygen concentration cO* , as shown in Tab.1. The low diffusivity of O2 diluted in N2

in the GDL can decrease the steady state oxygen concentration cO* at the CCL-GDL interface and
increase the mass transport resistance in the CCL. It is well known that the EIS technique can separate

the charge transfer resistance from mass transport losses. This effect can be noticeable when EIS

measurements in PEFCs reflect two semicircles. The one at high-medium frequencies is related to the

charge transfer resistance during the ORR and decreases with increasing current density. The other

one, at low frequencies, is related to oxygen transport limitations and increases with increasing

current density [3,9]. The charge transfer resistance RC calculated from EIS measurements and using

Eq. 1 is similar at the same p(O2) in He/O2 or N2/O2 gas mixture. This effect can be observed in the

spectra shown in Fig. 1a at frequencies from 2 kHz to 40 Hz. The charge transfer resistance increased

with decreasing p(O2) in He/O2 or N2/O2 gas mixture because the charge transfer during the ORR also

depends on the distribution and amount of chemical species (oxygen, ions, and electrons) in the CCL

electrode-electrolyte interface. Figure 1a shows that EIS spectra increase by using O2 diluted in N2

and also by reducing O2.

Figure 1 Comparison between experimental and simulated. Experimental ◊ 20%O2-80%He; □ 20%O2-80%N2; ○

10%O2-90%He; ∆ 10%O2-90%N2; - Simulated; a) Cathode 100% RH, b) Cathode 30% RH

4.3 Mass transport resistance in Cathode 30 % RH

In the same way as the preceding subsection for 100% RH, the parameters that account for the mass

transport resistance RW and charge transfer resistance RC were estimated through Eq. 1. Figure 1b

shows the comparison between the simulated spectra from Eq.1 and the measured data at 30 % RH.

At 30 % RH the mass transport resistance in the CCL is less than that accounting for the 100 % RH

case as shown in Tab. 1. This can be attributed to the low water content in the GDL which increases

the steady state oxygen concentration cO* in the CCL-GDL interface, as shown in Tab.1. The charge

transfer resistance RC is higher at 30 % RH than for the 100 % RH case. Similar results were reported

by Xu et al. [10]; the authors carried out EIS measurements at different cathode RH (20, 35, 50, and
72%) in a 5 cm2 PEFC. The CCL comprises Pt/C/ionomer agglomerates. Each agglomerate is

considered to be surrounded by a film of water. At high RH the water film that surrounds the

agglomerate increases and consequently improves catalyst utilisation in the CCL. This argument is

supported by the superscript P from Eq. 1 and shown in Tab. 1. When P=1, a pure capacitive effect is

present in the CCL [11] and therefore there is a homogeneous charge distribution between the

electrode-electrolyte interface. At 100 % RH there is an increase in P when compared with the 30%

RH condition. A homogenous charge distribution between dissimilar materials improves the charge

transfer during the ORR reaction.

Cathode 100% RC P RW Cathode 30% RC P RW

cO* cO*
RH Ω.cm 2
Ω.cm 2
RH Ω.cm 2
Ω.cm 2

mol/cm3 mol/cm3
-5
20%O2-80%He 0.7944 0.9444 0.1018 1.549x10 20%O2-80%He 0.9571 0.7546 0.0982 2.810x10-5
20%O2-80%N2 0.7944 0.9693 0.1963 8.033x10-6 20%O2-80%N2 0.9571 0.7669 0.1227 2.249x10-5
-6
10%O2-90%He 0.9518 0.9632 0.4172 3.779x10 10%O2-90%He 0.9815 0.8896 0.2454 1.343x10-5
10%O2-90%N2 0.9518 0.9528 1.2025 1.311x10-6 10%O2-90%N2 0.9815 0.8896 0.5153 5.355x10-6
Table 1 Parameters estimated using Eq. 1 and EIS measurements

5 Conclusions

This study demonstrates that it is possible to attain a deeper understanding of the internal

phenomenological processes in the PEFC by coupling the experimental EIS technique with the

fundamental electrochemical theory. Experimental tests were carried out on a 6 cm2 single cell

operated at 80oC and RH of 100 % for anode and RH of 100/30 % for cathode. Different partial

pressure of oxygen in He/O2 and N2/O2 gas mixture was considered as background gases. A

mathematical model predicting the CCL impedance response, derived in the authors’ previous study,

was applied to EIS measurements to quantify the mass transport resistance of the CCL. The results

showed that it is possible to separate the CCL mass transport resistance and charge transfer resistance

in EIS measurements when a PEFC is operated with low oxygen partial pressure p(O2) ≤ 20 % in

either He/O2 or N2/O2 gas mixture. The results also showed that the low diffusivity of O2 diluted in N2

in the GDL can decrease the steady state oxygen concentration cO* at the CCL-GDL interface and
increase CCL mass transport resistance. This study can be applied when studying the effect of

different GDL structures on equilibrium oxygen concentration at GDL-GDL interface. A further study

has to be conducted to examine the effect of oxygen transportation in every single phase of the CCL

on EIS measurements. This is the aim of a future work.

Acknowledgements

The provision of the data used in this work by Johnson Matthey Fuel Cells is gratefully

acknowledged. The authors also acknowledge Miss. Kathleen McLoughlin for helping with the

English Language.

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