ECN-RX--05-073 CARBON DIOXIDE POISONING ON PROTON-EXCANGE-MEMBRANE FUEL CELL ANODES G.J.M. Janssen N.P. Lebedeva Presented at the Conference: Fuel Cells Science and Technology 2004, 6-7 October 2004, Munich, Germany. MARC 2005
Carbon dioxide poisoning on proton-exchange-membrane fuel cell anodes G.J.M. Janssen*, N.P. Lebedeva Energy research Centre of the Netherlands ECN, Fuel Cell Technology, The Netherlands janssen@ecn.nl Carbon dioxide, which is present in reformate fuels in concentrations up 25%, can have a detrimental effect on the fuel cell performance that goes beyond dilution effects associated with an inert gas. The origin of these poisoning effects is the reverse water gas shift reaction, i.e in a fuel cell CO 2 can be reduced by hydrogen adsorbed on the catalyst. This reaction results in an adsorbate on the anode catalyst. Fuel cell tests involving various based catalysts have shown that anode poisoning depends on the composition of the catalyst. The carbon dioxide reduction on -based carbon supported catalysts as a function of the electrode potential was studied using cyclic voltammetry and chronocoulometry. The results indicate the formation of adsorbed species (most likely, carbon monoxide) on the surface of all these catalysts. Closer inspection also revealed differences between the samples. From the kinetic data analysis it is clear that, unlike /C, some bimetallic (M/C) catalysts also catalyse the oxidation of the adsorbed species to carbon dioxide at low overpotentials. This ensures a higher equilibrium concentration of the free sites on the surface of this type of catalysts compared to that on /C. Studies with a kinetic model have shown that main effect of CO 2 reduction is that a large part of the catalytic surface area becomes inactive for 2 dissociation. Subsequent desorption of CO from the catalyst surface, transport down the gas channel, and subsequent re-adsorption of CO plays a minor role. The main reason for this is that a large blockage of the surface area inhibits further formation of CO in the reduction reaction. It was found that a high rate constant of this reaction increases the anode polarisation losses, as does a reduced rate constant of the hydrogen dissociation reaction. The effects are mitigated by a high ratio of the CO desorption and adsorption rate constants, as well as by a high CO electro-oxidation rate constant. Keywords: PEM fuel cell, reformate gas, carbon dioxide reduction, electrocatalysis
Carbon dioxide poisoning on PEM fuel cell anodes Gaby J.M. Janssen and Natalia P. Lebedeva ECN-Fuel Cell Technology Petten, The Netherlands Fuel Cells Science & Technology, München, 2004 Poisoning by reformate gas: Reformate gas contains large amounts of CO 2 (order 25%) and small amounts of 10-50 ppm CO. Carbon monoxide poisoning: - very severe on ( > 1ppm) - Ru, Mo much more CO (tolerant 20-50 ppm) Carbon dioxide poisoning: - much smaller poisoning effect - tolerance also dependent on catalyst (Me) Are CO tolerant materials also CO 2 tolerant?
-based catalysts for CO tolerance - - CO + * CO- * ligand effect - Me Me CO 2 Me 2O + * M O- * M + + + e CO- * + O- * M CO2 + + + e bifunctional mechanism - O Me O Me O Me Reverse water gas shift equilibrium: CO 2 + 2 CO + 2 O 80 ppm CO in equilibrium 60 40 20 0 0 10 20 30 40 50 60 % CO 2 in 2 80oC, 1.5 bar, water saturated
CO tolerance: < Ru < Mo -0.10 Anode losses (V) 0.00 0.10 0.20 0.30 Mo Ru 0 50 100 150 200 250 300 ppm CO j= 350 ma/cm2,t=80oc, ppm CO in 2 (1.5 bar) metal loading anode 0.4 mg/cm2 CO 2 tolerance: Mo < < Ru -0.05 Anode losses (V) 0.00 Ru 0.05 0.10 Mo 0.15 0% 10% 20% 30% 40% 50% 60% % CO 2 in 2 j= 350 ma/cm2,t=80oc, % CO 2 in 2 (1.5 bar) metal loading anode 0.4 mg/cm2
8 6 CO 2 poisoning on /C: cyclic voltammogram 18 mv 168 mv w 368 mv clean s I (ma) 4 2 0-2 -4-6 -8 0 0.2 0.4 0.6 0.8 1 1.2 E / V vs RE F.A. de Bruijn et al. J. Power Sources 110 (2002) 117 Mechanism in electrochemical cell: /C + + e ad CO 2 + 2 ad CO ad + 2 O dθ dt dθ dt CO CO θ 2 θ = k( η)(1 θ = f ( η) CO ) 2
Kinetics of CO 2 reduction on /C θco 1 0.8 0.6 0.4 0, 58, 108 mv 158 mv 183 mv 208 mv 0.2 0 0 1000 2000 3000 time / s CO 2 reduction on /C in CO 2 -saturated 0.5 M 2 SO 4 Kinetics of CO 2 reduction on Mo/C 1 0.8 θco 0.6 0.4 0.2 58 mv 108 mv 208 mv 58 mv 108 mv 208 mv 0 0 500 1000 1500 2000 2500 3000 t / s CO 2 reduction on /C in CO 2 -saturated 0.5 M 2 SO 4
Mechanism in electrochemical cell: /C + + e ad CO 2 + 2 ad CO ad + 2 O CO 2 reduction occurs : steady-state θ CO = 1& θ free = 0 Mo/ C + + e ad CO 2 + 2 ad CO ad + 2 O CO ad + 2 O CO 2 + 2 + + 2e CO oxidation as well: steady-state θ CO < 1 & θ free > 0 No evidence for faster CO 2 reduction Fuel Cell Anode Reactions/ Reformate Gas 2 2 ad ad + + e k a CO CO ad k dc /k ac CO ad + 2 O CO 2 + 2 + + 2e kec CO 2 + 2 ad CO ad + 2 O k rs G.J.M. Janssen J. Power Sources 136 (2004) 45
θ CO Model results: CO coverage 0.8 2 / 0.2 CO 2 1.0 0.8 k rs =0.02 A/cm 2 bar 0.6 0.4 k rs =0.002 0.2 k rs =0.0 0.0 0.0 0.2 0.4 0.6 0.8 1.0 Current Density (A/cm 2 ) θ CO = k dc k + k rs ec pco exp 2 ( η / b ) c θ 2 Model results: CO coverage (0.8 2 /0.2 CO 2 /CO) 1.0 θ CO 0.9 0.8 0.7 50 ppm 20 ppm 10 ppm 0.6 0.5 0.0 0.3 0.6 0.9 1.2 1.5 1.8 Current Density (A/cm 2 ) Dotted: 2 /CO Drawn: 80% 2 / 20% CO 2 / CO
Polarisation curves 0.15 0.12 50 ppm 20 ppm 10 ppm η (V) 0.09 0.06 0.03 0 0.0 0.3 0.6 0.9 1.2 1.5 1.8 Current Density (A/cm 2 ) Model results: 2 /CO 2 feed V cell (V) 0.75 +CO oxid 0.70 kdc/kac*2 0.65 base ka*0.1 0.60 krs*100 0% 20% 40% 60% % CO 2
Comparison with experiment -0.05 Vlossesl(V) 0.00 0.05 0.10 +CO oxid Ru kdc/kac*2 ka*0.1 Mo krs*100 0.15 0% 10% 20% 30% 40% 50% 60% % CO 2 Model results: CO in outlet (fixed 2 stoichiometry) 75 ppm CO in outlet 50 kdc/kac*2 krs*100 25 +CO oxid base ka*0.1 0 0% 20% 40% 60% % CO 2
Mechanism: CO 2 poisoning: conclusions - CO 2 reduction product poisons catalyst - non-electrochemical reaction with ad Modelling results: - CO 2 poisoning important at low CO content, decreases with current density - 2 / CO 2 : no relation poisoning effect and resulting CO content in flow CO tolerant catalysts not always more CO 2 tolerant - Ru more CO 2 tolerant than due to ligand effect - Mo less tolerant: reduced 2 dissociation rate suspected