Characterisation tools development for PEM electrolysers

Electrochemical impedance spectroscopy (EIS), current interrupt (CI) and current mapping (CM) were investigated as in-situ characterisation tools for PEM electrolysers. A 25 cm² cell with titanium anode and carbon cathode plates were utilised in this study. A commercial MEA consisting of 1 mg IrO₂/cm² on the anode and 0.3 mg Pt/cm² on the cathode was used. The electrocatalyst was deposited on Nafion^® membranes. The electrochemical losses in a PEM electrolyser namely: activation, ohmic and mass transfer losses were identified using EIS and CI and both the advantages and disadvantages of the methods were discussed. The current distribution over the membrane electrode assembly (MEA) at different current densities was measured using the current mapping method. It is also shown that under the given experimental conditions the current density decreases along the serpentine flow field.     

Polymer electrolyte membrane fuel cell contamination: Testing and diagnosis of toluene-induced cathode degradation

The effects of toluene contamination on the performance of polymer electrolyte membrane (PEM) fuel cells were investigated, using various levels of toluene concentration in the air streams, under different operational conditions and with different catalyst loadings. Constant-current polarization and electrochemical impedance spectroscopy (EIS) were conducted to analyze the poisoning behaviour of toluene. The severity of the contamination effect increased with an increase in both the current density and the toluene concentration, but decreased with an increase in both the relative humidity (RH) and the cathode-side Pt loading. The toluene-poisoned fuel cell could not be fully recovered by replacing toluene-contaminated air with pure air. EIS measurements revealed that both kinetic resistance and mass transfer resistance increased as a result of toluene contamination, while membrane resistance remained unchanged. However, the increase in kinetic resistance was a major contributor to cell performance degradation.     

AC impedance technique in PEM fuel cell diagnosis—A review

Because the AC impedance technique, also known as electrochemical impedance spectroscopy (EIS), is being utilized by more and more researchers in proton exchange membrane (PEM) fuel cell studies, the technique has developed into a primary tool in such research. In this paper the recent work on PEM fuel cells using the AC impedance technique is reviewed. Both in situ and ex situ impedance measurements are discussed, with primary focus on the in situ measurements. Within the domain of in situ studies, various methods for measuring the impedance of a PEM fuel cell are examined, and typical impedance spectra in several common scenarios are presented. Representative applications of the AC impedance technique in PEM fuel cell research are also discussed. Finally, the necessity of a time domain rapid AC impedance technique is briefly discussed.     

Non-dimensional analysis of PEM fuel cell phenomena by means of AC impedance measurements

AC impedance or electrochemical impedance spectroscopy (EIS) is becoming a fundamental technique used by researchers and scientists in proton exchange membrane (PEM) fuel cell analysis and development. In this work, in situ impedance measurements are presented for a series of operating conditions in a 50 cm² fuel cell. The electrode charge transfer resistance was determined from the corresponding arcs of the Nyquist diagrams. The analyses were performed for H₂/O₂ and H₂/air operation at different stoichiometric factors and reactant gases humidification. Characteristic time scales of charge transfer processes at the different operating conditions were estimated from the corresponding Bode plots. These values were used for a non-dimensional analysis of the different fuel cell electrochemical and transport processes, namely electrochemical reaction versus GDL reactant transport. Fuel cell adapted Damkhöler numbers are thus presented, where the results indicate that the GDL diffusion transport is the limiting process for the cases under analysis, especially when air is used as oxidant. Additional analysis of channel convective mass transport versus GDL diffusive mass transport is also presented.     

Corrosion behavior of polyphenylene sulfide–carbon black–graphite composites for bipolar plates of polymer electrolyte membrane fuel cells

The aim of this work was to study the corrosion behavior of polyphenylene sulfide (PPS) – carbon black – graphite composites regarding their application as bipolar plates of polymer electrolyte membrane (PEM) fuel cells. Electrochemical impedance spectroscopy (EIS), potentiostatic and potentiodynamic polarization tests were used to characterize the electrochemical response of the composites in a simulated PEM fuel cell environment. Cross-sectional views of fractured specimens were observed by scanning electron microscopy (SEM). The results showed that the corrosion behavior depends on the carbon black content incorporated into the composite formulation. There was a trend of decreasing the corrosion resistance for higher carbon black contents. This behavior could be explained based on the porosity and electrical conductivity of the composites.     

Electrical test methods for on-line fuel cell ohmic resistance measurement

The principles and trade-offs of four electrical test methods suitable for on-line measurement of the ohmic resistance (R_Ω) of fuel cells is presented: current interrupt, AC resistance, high frequency resistance (HFR), and electrochemical impedance spectroscopy (EIS). The internal resistance of a proton exchange membrane (PEM) fuel cell determined with the current interrupt, HFR and EIS techniques is compared. The influence of the AC amplitude and frequency of the HFR measurement on the observed ohmic resistance is examined, as is the ohmic resistance extracted from the EIS data by modeling the spectra with a transmission line model for porous electrodes. The ohmic resistance of a H₂/O₂ PEM fuel cell determined via the three methods was within 10–30% of each other. The current interrupt technique consistently produced measured cell resistances that exceeded those of the other two techniques. For the HFR technique, the frequency at which the measurement was conducted influenced the measured resistance (i.e., higher frequency providing smaller R_Ω), whereas the AC amplitude did not effect the observed value. The difference in measured ohmic resistance between these techniques exceeds that reasonably accounted for by measurement error. The source of the discrepancy between current interrupt and impedance-based methods is attributed to the difference in the response of a non-uniformly polarized electrode, such as a porous electrode with non-negligible ohmic resistance, to a large perturbation (current interrupt event) as compared to a small perturbation (impedance measurement).     

An EIS alternative for impedance measurement of a high temperature PEM fuel cell stack based on current pulse injection

In this paper a method for estimating the fuel cell impedance is presented, namely the current pulse injection (CPI) method, which is well suited for online implementation. This method estimates the fuel cell impedance and unlike electrochemical impedance spectroscopy (EIS), it is simple to implement at a low cost. This makes it appealing as a characterization method for on-line diagnostic algorithms. In this work a parameter estimation method for estimation of equivalent electrical circuit (EEC) parameters, which is suited for on-line use is proposed. Tests on a 10 cell high temperature PEM fuel cell show that the method yields consistent results in estimating EEC parameters for different current pulse at different current loads, with a low variance. A comparison with EIS shows that despite its simplicity the response of CPI can reproduce well the impedance response of the high and intermediate frequencies.     

Validation of a methodology for determining the PEM fuel cell complex impedance modelling parameters

In this paper, we present a new methodology for determining the complex impedance parameters for a Proton Exchange Membrane (PEM) Fuel Cell in order to have a general model for embedded diagnosis. The modelling of Fuel Cells is a very important phase because it contributes to a better understanding and representation of the internal phenomena in this type of generator. After obtaining the experimental results of the complex impedance using a realized test bench for Proton Exchange Membrane (PEM) Fuel Cell using an electrochemical method which is the electrochemical impedance spectroscopy (EIS), we treat these results with an identification algorithm based on least squares method in the objective to determine the variations laws of the complex impedance parameters then implement in a PEM Fuel Cell model with Matlab/Simulink software. The established model of the complex impedance is based on electrical components and takes into account the mathematical equations of the different elements. The simulation results of this implemented model inform us about the state of the PEM Fuel Cell and validate the choice of the parameters. The validation of this choice is done by a comparative study using residual analysis method between the experimental and the simulation results. The general model is obtained from the superposition of the measured and theoretical results.     

Hierarchy carbon paper for the gas diffusion layer of proton exchange membrane fuel cells

This communication described the fabrication of a hierarchy carbon paper, and its application to the gas diffusion layer (GDL) of proton exchange membrane (PEM) fuel cells. The carbon paper was fabricated by growing carbon nanotubes (CNTs) on carbon fibers via covalently assembling metal nanocatalysts. Surface morphology observation revealed a highly uniform distribution of hydrophobic materials within the carbon paper. The contact angle to water of this carbon paper was not only very large but also particularly even. Polarization measurements verified that the hierarchy carbon paper facilitated the self-humidifying of PEM fuel cells, which could be mainly attributed to its higher hydrophobic property as diagnosed by electrochemical impedance spectroscopy (EIS).     

Design and manufacturing of end plates of a 5 kW PEM fuel cell

End plate is one of the main components of the proton exchange membrane (PEM) fuel cells. The major role of the end plate is providing uniform pressure distribution between various components of the fuel cell (bipolar plates, etc.) and consequently reducing contact resistance between them. In this study a procedure for design of end plate has been developed. At first a suitable material was selected using various criteria. Then a finite element (FE) analysis was accomplished to analyze end plate deflections and get its optimized thickness. After fabricating the end plates, a single cell was assembled and electrochemical impedance spectroscopy (EIS) tests were carried out to ensure their good operation. A 5 kW fuel cell assembled with these end plates was tested at different operating conditions. The test results show an appropriate assembly pressure distribution inside the stack which indicates good performance of the designed end plates.     

AC impedance diagnosis of a 500 W PEM fuel cell stack: Part II: Individual cell impedance

AC impedance or electrochemical impedance spectroscopy (EIS) has been demonstrated to be a powerful technique for characterizing and evaluating fuel cells. In this work, as an extension of our previous study on the stack impedance of a 500 W PEM fuel cell, we report the AC impedance studies on individual cells of the same fuel cell stack. The EIS of the stack with an active area of 280 cm² was measured at currents from 10 to 210 A in steps of 20 A using the combination of a FuelCon test station, a TDI loadbank and a Solartron 1260 Frequency Response Analyzer. Measurement of the individual cell EIS was carried out with the help of a rotary switch unit made in our lab. Two methods (floating mode and grounded mode) were utilized for measuring the impedance spectroscopy of the individual cells. The results show that both methods are applicable to individual cells. The results also indicate a good agreement between the total Ohmic loss in the stack and the combined Ohmic losses of the individual cells.     

Characterisation of a PEM electrolyser using the current interrupt method

A method is proposed to model the electrochemical characteristics of a Proton Exchange Membrane (PEM) electrolyser. The electrochemical characteristics, which include the Ohmic, activation and concentration losses, are modelled by means of an equivalent electric circuit impedance. The equivalent electric circuit impedance under consideration is the Randles–Warburg (RW) cell and the parameters are obtained through the current interrupt (CI) method. The CI method consists of two parts, 1) the natural voltage response (NVR) method to model the Ohmic losses, and 2) the current switching (CS) method to model the activation and concentration losses. A simulation model of the RW cell is used to verify and validate the CI method. Thereafter, the CI method is practically implemented and the results presented. Results show that the Ohmic losses correlates well with existing literature. The paper furthermore illustrates the capability of the CI method to visually illustrate the RW impedance through Nyquist diagrams. Nyquist diagrams are used to illustrate the concentration losses and indicate the degradation state of the PEM at specific operating conditions. Results show that the concentration losses decrease with an increase in the operating current density and temperature.     

In situ diagnostic techniques for characterisation of polymer electrolyte membrane water electrolysers – Flow visualisation and electrochemical impedance spectroscopy

An optically transparent polymer electrolyte membrane (PEM) water electrolysis cell was studied using a high-speed camera, thermal imaging and electrochemical impedance spectroscopy to examine the relationship between flow and electrochemical performance. The flow regime spans bubble and slug flow, depending on the rate of gas formation (current density) and water feed rate. Electrochemical impedance spectroscopy (EIS) shows that there is a reduction in mass transport limitation associated with the transition to slug flow.     

An integrated system development including PEM fuel cell/biogas purification during acidogenic biohydrogen production from dairy wastewater

Biohydrogen production from dairy wastewater with subsequent biogas purification by hollow fiber membrane module was investigated in this study. The purified and not purified (raw) biohydrogen were used as fuel in polymer electrolyte membrane (PEM) fuel cell. Furthermore, the effect of CO₂ on the performance of PEM fuel cell was evaluated considering cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and polarization curves. The maximum H₂ production rate was 0.015 mmol H₂/mol glucose and the biohydrogen concentration in biogas was ranged 33%–60% (v/v). CO₂/H₂ selectivity decreased with increasing pressure and maximum selectivity was obtained as 4.4 at feed pressure of 1.5 bar. The electrochemical active surface (EASA) areas were decreased with increasing CO₂ ratio. The maximum power densities were 0.2, 0.08 and 0.045 W cm⁻² for 100%, 80% and 60% (v/v) H₂, respectively. The results indicated that integrated PEM fuel cell/biogas purification system can be used as a potential clean energy sources during acidogenic biohydrogen production from dairy wastewater.     

Application of electrochemical impedance spectroscopy in bio-fuel cell characterization: A review

Fuel cell is an efficient energy conversion device converting chemical energy directly into electrical energy. It is a fact that, to boost the fuel cell performance, resistance (charge transfer resistance, mass transfer resistance and electrolyte resistance) should be decreased. For this, many techniques have been used for cell testing such as: cyclic voltammetry, current interruption measurement, chronoamperometry, chronopotentiometry, polarization curve and electrochemical impedance spectroscopy (EIS). Among these techniques, EIS is a well-established, non-intrusive, non-destructive, semi-quantitative, and an efficient technique for identification of each circuit element. In this review article, application of electrochemical impedance spectroscopy in identification of individual components of total resistance and their dependence on different factors in biofuel cell along with some recent advancement in this technique have been discussed.     

Assessing cell polarity reversal degradation phenomena in PEM fuel cells by electrochemical impedance spectroscopy

Electrochemical impedance spectroscopy (EIS) is identified as one of the most promising in-situ diagnostics tools available for assessing fuel cell ageing and degradation. In this work, the degradation phenomena caused by cell polarity reversal due to fuel starvation of an open cathode 16 membrane electrode assembly (MEA) – low power (PEM) fuel cell (15 W nominal power) – is reported using EIS as a base technique. Measuring the potential of individual cells, while the fuel cell is on load, was found instrumental in assessing the “state of health” of cells at fixed current. Location of affected cells, those farthest away from hydrogen entry in the stack, was revealed by very low or even negative potential values. EIS spectra were taken at selected break-in periods during fuel cell functioning. The analysis of impedance data was made using an a priori equivalent circuit describing the transfer function of the system in question – equivalent circuit elements were evaluated by a complex non-linear least square (CNLS) fitting algorithm, and by calculating and analyzing the corresponding distribution of relaxation times (DRT). Results and interpretation of cell polarity reversal due to hydrogen starvation were complemented with ex-situ MEA cross section analysis, using scanning electron microscopy. Electrode thickness reduction and delamination of catalyst layers were observed as a result of reactions taking place during hydrogen starvation. Carbon corrosion and membrane degradation by fluoride depletion are discussed.     

Electric circuit modeling of fuel cell system including compressor effect and current ripples

This study aims to investigate the development of an Electrical Circuit Model (ECM) that represents the behavior of a PEM fuel cell system. The ECM parameters are identified based on sets of impedance data obtained by using a characterization process known as Electrochemical Impedance Spectroscopy (EIS). In this process, a small magnitude of alternating current sweeping a broad spectrum of frequencies is superimposed on a DC current drawn from the fuel cell while measuring the resulting voltage response. The measured impedance is fitted to an ECM using a nonlinear least-square fitting method. The proposed ECM is able to reflect the voltage response of the system to current ripples and represent the effect of the compressor. The proposed model is validated using a commercial fuel cell power module. In general, such model representation is useful for analyzing the effects of the operating conditions on the fuel cell performance, efficiency and durability. It also helps in comprehending the effects of current ripple on the fuel cell while operating with power-conditioning units     

Dynamic fuel cell gas humidification system

Water management is one of the crucial factors regarding the performance and durability of low temperature PEM fuel cells. Amongst other factors, the water balance in an operating fuel cell can be influenced by the humidification of the reaction gases. For transient response investigations of the fuel cell behavior under fast humidification changes a system is needed which is able to humidify the supplied gases in a highly dynamic and reproducible way. Exact knowledge of the water content of the supplied gases is of utmost importance to study humidification effects. In this contribution, a dynamic fuel cell humidification system is presented. Reliability of the concept is proven by using three different methods: straightforward dew point measurements, electrochemical impedance spectroscopy (EIS) and in situ neutron radiography. The test setup is able to provide dew point temperatures with a tolerance range of 1–3 K leading to a highly reproducible fuel cell performance and water content of the complete cell.     

Impact of clamping pressure and stress relaxation on the performance of different polymer electrolyte membrane water electrolysis cell designs

One promising option for storing surplus electricity from renewable energy sources is the conversion of electricity to hydrogen by polymer electrolyte membrane (PEM) electrolysis and the subsequent storage of the hydrogen produced. In order to obtain good contact, the components of an electrolysis cell are compressed at a certain clamping pressure. However, too high of a pressure can have a negative effect on cell performance. This work discusses how clamping pressure affects the cell performance of different PEM electrolysis cell designs. A special test cell is designed that makes it possible to apply pressure directly onto the active area of the cell. Polarization curves are measured at different clamping pressures, while electrochemical impedance spectroscopy (EIS) is used to show the effect of pressure on performance losses. Above a critical clamping pressure of 2.5 MPa ohmic losses are found to rise. In addition, it is tested as to whether the clamping pressure remains constant over time. The results show that stress relaxation of the catalyst coated membrane (CCM) leads to a pressure loss and thus to a decline in performance. Therefore, not only is it shown that pressure is crucial for cell performance but also, for the first time, a mechanical effect is described as an element of the cell's degradation.     

Identifying in operando changes in membrane hydration in polymer electrolyte membrane fuel cells using synchrotron X-ray radiography

The cost of the polymer electrolyte membrane (PEM) fuel cell must undergo significant reductions before the widespread adoption of PEM fuel cell powered automotive drivetrains can be achieved. Eliminating the need for active anode humidification is one strategy for reducing the cost and system size of the PEM fuel cell. In this study, we investigated the impact of anode gas inlet relative humidity (RH) on membrane hydration and the associated electrochemical performance of the PEM fuel cell. The anode gas inlet RH was varied to study the impact on fuel cell potential, during which simultaneous in operando visualizations were performed using synchrotron X-ray radiography, and electrochemical impedance spectroscopy was used to gain an understanding of the membrane hydration and water dynamics. The thickness of a Nafion^® N115 membrane expanded by up to 26 μm (20% of nominal thickness) compared to the manufacturer specification, as a result of changes in membrane hydration. Through this work, we present the utility of synchrotron X-ray radiography for tracking changes in membrane hydration of an operating PEM fuel cell.