In this work, the effect of chloride as a catalyst contaminant was studied on the performance and durability of a low power open-cathode fuel cell, intended for passive management of water. In an ex-situ study, cyclic voltammetry was used to assess the redox behaviour of platinum in chloride contaminated solutions at room temperature.The cell was operated integrating a range of relative humidity (RH) from ~30 to 80% and temperatures from 5 to 55 ºC. Results indicated that 60% RH is 
associated to maximum fuel cell performance over the studied temperature range. An examination of the fuel cell components after 100 h of operation revealed that chloride contamination has produced cathode failure associated to catalyst migration favored by operation conditions that allowed platinum particles to break free from their carbon backing and migrate toward the polymer electrolyte. Migration resulted in precipitation with larger mean particle size distribution within the solid electrolyte 
when compared to the original catalyst layer, rendering a very significant loss of thickness in the cathode material

Hashimoto, T.

Paiva, T. I.

Plancha, Maria João

Rangel, C. M.

Thompson, G. E.

Laboratório Nacional de Energia e Geologia Repository

The effect of chloride as catalyst layer contaminant on the degradation of PEMFCs

Paiva Luís, Teresa

Repositório do LNEG

IV Iberian Symposium on Hydrogen, Fuel Cells and Advanced Batteries. Estoril, Portugal, June 26-28 2013 The effect of chloride as catalyst layer contaminant on the       degradation of PEMFCs  T.I.Paiva1, T. Hashimoto2, M. J.Plancha1, G.E.Thompson2, C.M. Rangel*1  1Laboratório Nacional de Energia e Geologia, Paço do Lumiar 22, 1649-038 Lisboa, Portugal  2The University of Manchester, Corrosion and Protection Centre, Manchester M13 9PL UK  (*) e-mail: carmen.rangel@lneg.pt ______________________________________________________________________________________  Abstract In this work, the effect of chloride as a catalyst contaminant was studied on the performance and durability of a low pow-er open-cathode fuel cell, intended for passive management of water. In an ex-situ study, cyclic voltammetry was used to assess the redox behaviour of platinum in chloride contaminated solutions at room temperature.The cell was operated in-tegrating a range of relative humidity (RH) from ~30 to 80% and temperatures from 5 to 55 ºC. Results indicated that 60% RH is associated to maximum fuel cell performance over the studied temperature range. An examination of the fuel cell components after 100 h of operation revealed that chloride contamination has produced cathode failure associated to catalyst migration favored by operation conditions that allowed platinum particles to break free from their carbon backing and migrate toward the polymer electrolyte. Migration resulted in precipitation with larger mean particle size distribution within the solid electrolyte when compared to the original catalyst layer, rendering a very significant loss of thickness in the cathode material.  ______________________________________________________________________________________  Keywords: PEM fuel cell, chloride, degradation, platinum instability, aglomeration  1 Introduction  A great deal of attention has been given, in the last few years, to materials ageing mechanisms and degradation in proton exchange membrane fuel cells (PEMFC) and their impact on performance. This is mainly due to the maturity reached by the technology, demonstrated in the various viable options for applications and the advent of the first markets. Membrane-electrode assembly (MEA) ageing and degradation mechanisms are not well under-stood, being affected by the unavoidable degrada-tion of materials in the context of load cycling and/or the influence of operating conditions such as temperature and humidity.  Common degrada-tion mechanisms concerning the membrane in-clude conductivity loss and chemical attack due to poor water management or by internally generated species as a result of the redox reactions and also due to thermal or mechanical stress [1-2]. The catalytic layer durability is a key issue in view of meeting requirements for long-term perfor-mance. Fuel cell voltage at any given current de-pends largely on the available catalyst surface ar-ea. Chemical deactivation or poisoning, sintering of the catalyst nanoparticles, carbon corrosion, are among other factors that lead to the reduction in electrochemical surface area [3-9].  In this work, platinum agglomeration and particle growth, Pt loss and migration occurring in normal operating conditions in a low power 4-cell PEM fuel cells is induced by contamination with chloride ions possibly coming from two different sources: the cathode feed-stream of air in the fuel cell and from the high-surface area catalysts synthesized from halide-containing compounds. 2 Experimental The effect of the concentration of chloride ions on the redox characteristics of a carbon supported platinum catalyst was examined by cyclic voltam-metry (CV) in a 0.5 M H2SO4 solution. Other solu-tions were prepared with added chloride to concen-trations of 0.001 M, 0.01 M, 0.1 M and 0.6 M NaCl.  A Pt catalyst ink was painted on a glassy car-bon plate with ~ 0.5 x 2 cm, the catalyst occupying an area of 0.25 cm2.Cyclic voltammograms (CV) were run in all solutions in a Greene electrochemi-cal cell, using a Lugging-Harber capillary as a bridge to an external Ag/AgCl KCl saturated elec-trode. A platinum wire was used as a counter elec-trode. The CVs were conducted using an EG&G Potentiostat /Galvanostat, Model 273A.  A low power fuel cell, intended for passive management of water, was operated integrating a range of relative humidity (RH) from 30 up to 80% and temperatures from 5 to 55 ºC. The stack used in this work was composed by 4 cells connected in series, operating with pure hydrogen and air with a cathode designed to contribute to easy water re-moval and stack cooling. An air fan located at the edge of the cathode manifolds was used to provide an excess air stoichiometry condition.The stack uses own design flow field drawn on graphite plates from Schunk. The MEA is a catalyst coated membrane from 3M and a gas diffusion layer (GDL/GDE) with carbon supported catalyst, con-IV Iberian Symposium on Hydrogen, Fuel Cells and Advanced Batteries. Estoril, Portugal, June 26-28 2013  taining 0.3 mgcm-2 Pt. The geometrical active area was 3.8 cm2. Polarization curves were registered for a full stack characterization using a purpose-built test station which allows control over gas flow, pressure, temperature and relative humidity. The fuel cell was subjected to several experimental conditions, during approximately 100 h operation, including periods at the open circuit potential. After fuel cell failure, a post mortem analysis of materials and components was undertaken. The fuel cell was dismantled and the MEAs embedded in a resin for cross section morphological and ele-mental analysis using a Phillips Scanning Electron Microscope, Model XL 30 FEG, coupled to an En-ergy Dispersive Spectrometer, EDS, which also allowed elemental mapping. Transmission electron microscopy (TEM) of individual cells of the stack was undertaken using a Tecnai F30 field emission gun instrument operated at an accelerating voltage of 300 kV. Cross sections were prepared by ultramicrotomy using a Leica Ultracut UCT appa-ratus. Elemental analysis was performed with an Energy Dispersive X-Ray spectroscopy system attached to the microscope. 3 Results and discussion 3.1 Electrochemical activity Fig.1a) shows typical cyclic voltammograms for Pt/C catalyst in acid medium. An increase in the electrochemical surface area (ECSA) with cycling was evident and associated to the increase in the charge in the hydrogen adsorption-desorption re-gion showing the activating effect of cycling which is also evident in the Pt oxide formation region. The voltammogram in 0.5 M H2SO4 can be di-vided into three regions: the region of hydrogen adsorption-desorption (from -0.2 to 0.1 V); the dou-ble layer region (from 0.1 to 0.5 V) and the surface oxidation of Pt region (from 0.5 to 1.25 V). The effect of the concentration of chloride ions on the Pt/C catalyst was also examined, see Fig. 1b). The effect of the chloride concentration is evidenced in the extension of the double layer charging region, more noticeable in the positive-going scan. This is thought to be caused by a strong retardation effect caused by adsorbed Cl−, which suppressed oxide formation and is associated to the reduction in the charge of the Pt oxide reduction peak, noticeable in the negative-going scan (at 0.5 V). Some authors had attributed this to the dissolution of Pt [1-3]  by the formation of the soluble chloride complexes as shown in Eqs. (1) and (2).  Pt + 4Cl- = [PtCl4]2- + 2e- Eº=0.758V (vs. SHE)   (1) Pt + 6Cl- = [PtCl6]2- + 4e- Eº=0.742V (vs. SHE)   (2)  Moreover, the region of hydrogen adsorption-desorption is narrowed in the presence of Cl− and also changes its shape apparently affecting Pt (100), probably due to strong adsorption of Cl−. From the region of H2 adsorption-desorption, ESCA has been determined. Results indicate reductions of 44%, 56%, 58% and 53% for the respective chloride concentrations of 0.001M, 0.01M, 0.1M and 0.6M.   (a)  (b) Fig. 1. Cyclic voltammograms of Pt catalyst ink deposit-ed on glassy carbon at 50 mVs-1 in a 0.5 M H2SO4 solu-tion(consecutive cycles in a number of 30 were conduct-ed) (a), 0.5 M H2SO4 solution + added chloride ions (b).  3.2 Fuel cell testing The stack was activated before use. The fuel cell was subjected to experimental conditions schematically shown in Fig. 2, including periods at the open circuit potential. Results indicated that 60% relative humidity is associated to maximum performance on the fuel cell under study, see figure 3. A loss in perfor-mance is found with temperature increase, related to an increase in the membrane resistance which may correspond to loss of water on the anode side. Performances at temperatures lower that room temperature showed only slight decrease in power (not shown).   012345Imax/At/minHR=45%F=0.2L/minF=0.3lL/minF=0.4lL/minF=0.5lL/minHR=45%T=25ºCActivationT=35ºCT=45ºCT=55ºCHR=60%T=25ºCT=45ºCT=35ºCT=55ºCHR=80%T=25ºCT=35ºCT=45ºCT=55ºC Fig. 2. Cycling of a low power 4 cell open cathode PEM stack vs time indicating polarization conditions and open circuit periods. OC: open circuit. IV Iberian Symposium on Hydrogen, Fuel Cells and Advanced Batteries. Estoril, Portugal, June 26-28 2013   Fig. 3. Polarization and power curves for a 4 cell PEM stack. 60% RH and temperatures between 25 and 55 ºC.   Open circuit potential values did not change significantly during the life span of the fuel cell as shown in fig 4. Even though a cell potential decay with time is measurable, it is found to be reversible when the system is purged indicating that potential decay is probably related to water accumulation.    Fig. 4. Open circuit potential as a function of time for a 4 cell PEM stack. In the inset short term data show decay of the potential values at 1 A, reversible upon purging for 25 and 35ºC.   3.3 Post mortem analysis After 100 hour operation the dominant degrada-tion mode found after examination by SEM was Pt precipitation as a Pt band on the membrane near to the cathode, which was found in every single cell (see figure 5). As a consequence of the loss of catalyst, the cathode thickness has been greatly reduced. Fig. 5b) shows that the cathode catalyst layer thickness decreases comparatively with the unused MEA. The decrease is more evident for the cathode than the anode for all the cells, which is also represented in the figure. A common degrada-tion among all of the analyzed MEAs was also the cracking of the catalyst layer, as can be observed in figure 5a). Delamination describes a MEA failure feature whereby the catalyst layer has been sepa-rated from the polymer membrane electrolyte.  This can be considered a defect which may result from MEA manufacturing procedure or from the disman-tling of cell for posterior analysis, but it can also be induced by the degradation of the catalytic layer. It forces the current to flow away from delaminated zones, through neighboring regions in which heat is locally produced. As these neighboring zones are prone to water accumulation they may degrade faster than other parts of the catalytic layers.         (a)                               (b) Fig. 5. SEM cross section of MEA showing Pt band  near cathode interface, electrode delamination and thickness variation (a); thickness of catalyst layers showing marked reduction of the cathode, values obtained by SEM obser-vations of 4 diferent cells of the PEM stack (b).  The Pt band was more clearly observed in the cross section TEM image. It is located at about 3 µm from the interface between the cathode catalyst layer and the membrane. Platinum is thought to be reduced by action of hydrogen supply via gas crossover from the anode. In this way the position of the band depends on the relative partial pres-sures of hydrogen and oxygen and their relative permeability through the membrane. Nafion 111 type membrane was used. Both SEM and TEM suggests that chloride con-tamination has produced cathode failure associat-ed to catalyst migration anomalies favored by con-ditions that allowed platinum particles to break free from their carbon backing and migrate toward the polymer electrolyte membrane. It is suggested that the presence of chloride has induced Pt dissolution [1-3] producing Pt ions [PtCl4]2- or [PtCl6]2-. Dissolu-tion and migration of platinum resulted in precipita-tion with larger mean particle size distribution within the solid electrolyte when compared to the original catalyst layer, rendering a very significant loss of thickness in the cathode material. Coarsening of platinum particles occurs at nano and micro-scale, as demonstrated by TEM analysis. TEM view of metallic Pt particles deposited  within the membrane can be seen in figure 6.         (a)  (b) Fig. 6. TEM cross section image of the fuel cell mem-brane, showing platinum in the platinum band identified by X-Ray diffraction (a) and distribuition of chloride in the neighbourhood of the platinum band (b).  1,522,533,544,50 10 20 30 40 50 60E/Vt /minT=25ºC T=35ºCI=0AI=1A5 nmPt 110 2 nm2nPt band IV Iberian Symposium on Hydrogen, Fuel Cells and Advanced Batteries. Estoril, Portugal, June 26-28 2013  Chloride ions concentrations up to 1.41 wt% were found between the cathode interface with the membrane and the platinum band. The amount of chloride in the catalyst layer diminished regarding the initial amount of chloride present. This was indicated by analysis of the fresh MEA.The amount of chloride that may come from the cathode feed-stream of air in the fuel cell could amount to 0.4 ppm according to measurements of chloride in the environmental chamber, where the cell was condi-tioned during testing. Loss of fluor is also indicated.  Figure 7 shows particle size analysis with a broad distribution for the cathode catalyst. Coars-ening of particles is evident when compared to data obtained with a fresh MEA.   Fig. 7. Catalyst particle size distribution of new and de-graded MEA (cathode).  4 Discussion Traces of chloride ions can change the activity and stability of Pt as a catalyst when acting as a cathode in fuel cell environment. This is mainly due to the structure sensitive kinetics for the oxygen reduction reaction (ORR), which arises from a structure sensitive adsorption of anions. Single crystal studies show two main effects refered in the case of chloride adsorption on supported platinum: a blocking effect by Cl_ads of the adsorption of O2, reducing active sites, which has been suggested to be associated with (111) facets; an enhancement in peroxide production related to the adsorption of chloride ion on (100) facets and (110) corner/edge sites, which effect the breaking of the O-O bond. Moreover, based on HRTEM analysis the effect of Cl_ads can be explained by the single crystal results by the relationship between particle size and differ-ent surface sites in supported Pt [10].  Although these results were obtained in liquid media, they are expected to apply to electrodes in fuel cell environment and have implications regard-ing both blocking effects and stability of the Nafion membrane and ionomers present in the catalyst layer since results indicate loss of fluor. This will be further discussed. 5 Conclusions Chloride presence in the catalyst layers has in-duced Pt dissolution. The effect was examined using cyclic voltammetry in aqueous media. ECSA losses of 44%, 56%, 58% and 53% in the presence of 0.001M, 0.01M, 0.1M and 0.6M NaCl were at-tributed. An examination of the fuel cell components after 100 h of operation revealed cathode failure associ-ated to the presence of chloride up to 1.4 wt% al-lowing platinum dissolution as platinum chloride complexes and migration to the polymer electro-lyte.  Precipitation of platinum, with larger mean par-ticle size distribution, within the solid electrolyte rendered a very significant loss of thickness in the cathode material.  Coarsening of platinum particles occurs at nano and micro-scale.   The mechanism for the lost of catalyst by disso-lution and growth is discussed on the basis of a joint electrochemical and SEM/TEM study.  Acknowledgements To FCT and FEDER (QREN-COMPETE) for provi-sion of funding (PTDC/CTM-CER/109843/2009).  6 References   [1] Kundu, S., Fowler, M.W., Simon, L. C., Grot, S. Grot., Morphological Features (defects) in Fuel Cell Mem-brane Electrode Assemblies. J. Power Sources, 157, pp. 650-656, 2006. [2] Wu, J., Yuan, X., Martin, J., Wang, J., Haijiang, Zhang J., Shen, J., Wu, Shaohong, M., Walter. A Review of PEM Fuel Cell Durability: Degradation Mechanisms and Mitigation Strategies. J. Power Sources, 184, pp.104-119, 2008. [3] Ferreira, P.J., LaO, G.J, Shao-Horn, Y., Morgan, D., Makharia, R., Kocha, S., Gasteiger, H. A., Instability of Pt/C Electrocatalyst in Proton Exchange Mem-brane Fuel Cell, J. Electrochem. Soc., 152, pp. A2256-2271, 2005. [4] Steinback, A. J., Hamilton, Jr. C.V., Debe, M.K., Im-pact of Micromolar Concentration of Externally Pro-vided Chloride and Sulphide Contaminants on PEM Reversible Stability, ESC Transactions, 11 (2007), 889-902. [5] Matsuaka, K., Sakamoto, S., Nakato, K., Hamada, A., Itoh, Y., Degradation of Polymer Electrolyte Fuell Cells under the Existence of Anion Species. J. Pow-er Sources, 179, 560-565, 2008.  [6] Péron, J., Nedellec, Y., Jones, D.J., Roziére, J., The Effect of Dissolution, Migration and Precipitation of Platinum in Nafion-based Membrane Electrode As-semblies During Fuell Cell Operation at High Poten-tial. J. Power Sources, 185, pp. 1209-1217, 2008.  [7] Zhang, S., Yuan, X., Hin, J. N.C., Wang, H., Frie-drich, K. A., Schulze, M., A Review of Platinum-Based Catalyt Layer Degradation in Proton Ex-change Membrane Fuel Fells. J. Power Sources, 194, pp. 588-600, 2009. [8] Lam, A., Li, H., Zhang, S., Wang, H., Wilkinson, D. P., Wessel, S., Cheng, T. T. H., Ex Situ Study of Chloride Contamination on Carbon Supported Pt Catalyst, J. Power Sources 205, pp. 235-238, 2012. [9] Guétaz, L., Escribano, S., Sicardy, O., Study by Elec-tron Microscopy of Proton Exchange Membrane Fuel Cell Membrane-Electrode Assembly Degradation Mechanisms: Influence of Local Conditions, J. Power Sources, 212, pp. 169-178, 2012.  [10]Markovic, Schmidt T.J., Stamenkovic V. and Ross P.N., Oxygen Reduction Reaction on Pt and Pt Bi-metallic Surfaces: A Selective Review, Fuel Cells, 1, pp. 105-116, 2001. (b) 

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The effect of chloride as catalyst layer contaminant on the degradation of PEMFCs

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