Direct utilization of methanol in solid oxide fuel cells: An electrochemical and catalytic study

Abstract This study deals with an investigation of the direct methanol oxidation in Solid Oxide Fuel Cells (SOFCs). A new catalyst formulation characterized by mixed electronic – ionic conductivity was developed for the anodic process. A composite Ni-modified La0.6Sr0.4Fe0.8Co0.2O3–Ce0.9Gd0.1O2 electrocatalyst was prepared by incipient wetness and subsequent ball milling. The obtained composite material was calcined at 1100 °C for 2 h in static air. After thermal activation, Ni was mainly present as highly dispersed La2NiO4 particles on a La-depleted Sr(Fe0.5Co0.5)O2.88 perovskite. The subsequent thermal reduction at 800 °C in hydrogen caused the occurrence of highly dispersed metallic Ni on the electrocatalyst surface. The surface area of the composite material was determined by BET measurement. The reduced catalyst was used as anode in intermediate temperature Solid Oxide Fuel Cells (IT-SOFCs) directly fed with methanol. Ex-situ catalytic studies for the composite anode material under steam reforming, partial oxidation and autothermal reforming of methanol were carried out at 800 °C. A comparison of SOFC performance at 800 °C in the presence of syngas or methanol as fuels was carried out. The performance achieved for the direct utilization of methanol (350 mW cm−2) appears promising for SOFC application in remote and micro-distributed energy generation as well as for portable power sources.

[1]  S. Singhal Solid oxide fuel cells for stationary, mobile, and military applications , 2002 .

[2]  V. Antonucci,et al.  Propane-fed Solid Oxide Fuel Cell Based on a Composite Ni-La-CGO Anode Catalyst , 2010 .

[3]  Massimiliano Cimenti,et al.  Direct utilization of ethanol on ceria‐based anodes for solid oxide fuel cells , 2009 .

[4]  G. Marbán,et al.  Towards the hydrogen economy , 2007 .

[5]  Kevin Kendall,et al.  Formulating liquid hydrocarbon fuels for SOFCs , 2004 .

[6]  John B Goodenough,et al.  Double Perovskites as Anode Materials for Solid-Oxide Fuel Cells , 2006, Science.

[7]  Serguei N. Lvov,et al.  Direct oxidation of jet fuels and Pennsylvania crude oil in a solid oxide fuel cell , 2004 .

[8]  George A. Olah,et al.  After Oil and Gas: Methanol Economy , 2004 .

[9]  O. Yamamoto Solid oxide fuel cells: fundamental aspects and prospects , 2000 .

[10]  Zongping Shao,et al.  Coking-free direct-methanol-flame fuel cell with traditional nickel-cermet anode , 2010 .

[11]  J. Hill,et al.  Direct utilization of methanol on impregnated Ni/YSZ and Ni–Zr0.35Ce0.65O2/YSZ anodes for solid oxide fuel cells , 2010 .

[12]  Scott A. Barnett,et al.  Operation of anode-supported solid oxide fuel cells on propane–air fuel mixtures , 2004 .

[13]  S. Singhal,et al.  Polarization Effects in Intermediate Temperature, Anode‐Supported Solid Oxide Fuel Cells , 1999 .

[14]  S. Singhal Advances in solid oxide fuel cell technology , 2000 .

[15]  A. Muñoz,et al.  High pressure synthesis, crystal, magnetic structure and magnetotransport of SrFe0.5Co0.5O3−δ , 2006 .

[16]  V. Antonucci,et al.  Electrochemical investigation of a propane-fed solid oxide fuel cell based on a composite Ni-perovskite anode catalyst , 2009 .

[17]  P. Holtappels,et al.  Solid oxide fuel cells (SOFC) , 2010 .

[18]  Hubert A. Gasteiger,et al.  Handbook of Fuel Cells , 2010 .

[19]  V. Antonucci,et al.  Technology up date and new strategies on fuel cells , 2001 .

[20]  Frank A. Coutelieris,et al.  Fuel options for solid oxide fuel cells: A thermodynamic analysis , 2003 .

[21]  Kevin Kendall,et al.  Formulating liquid ethers for microtubular SOFCs , 2006 .

[22]  Antonino S. Aricò,et al.  DMFCs: From Fundamental Aspects to Technology Development , 2001 .

[23]  S. Barnett,et al.  Direct operation of solid oxide fuel cells with methane fuel , 2005 .

[24]  Raymond J. Gorte,et al.  Direct oxidation of hydrocarbons in a solid-oxide fuel cell , 2000, Nature.

[25]  B. Lundqvist,et al.  Quantum origin of the oxygen storage capability of ceria. , 2002, Physical review letters.

[26]  B. Zhu,et al.  Catalysts and Performances for Direct Methanol Low-Temperature ( 300 to 600 ° C ) Solid Oxide Fuel Cells , 2006 .

[27]  Suttichai Assabumrungrat,et al.  Catalytic steam reforming of methane, methanol, and ethanol over Ni/YSZ : The possible use of these fuels in internal reforming SOFC , 2007 .

[28]  Antonino S. Aricò,et al.  Investigation of passive DMFC mini-stacks at ambient temperature , 2009 .

[29]  Antonino S. Aricò,et al.  Mitigation of carbon deposits formation in intermediate temperature solid oxide fuel cells fed with dry methane by anode doping with barium , 2009 .

[30]  Rizwan Raza,et al.  Development of methanol‐fueled low‐temperature solid oxide fuel cells , 2011 .

[31]  R. Gorte,et al.  Direct hydrocarbon solid oxide fuel cells. , 2004, Chemical reviews.

[32]  Massimiliano Cimenti,et al.  Importance of pyrolysis and catalytic decomposition for the direct utilization of methanol in solid oxide fuel cells , 2010 .

[33]  Andrzej Cybulski,et al.  Liquid-Phase Methanol Synthesis: Catalysts, Mechanism, Kinetics, Chemical Equilibria, Vapor-Liquid Equilibria, and Modeling—A Review , 1994 .

[34]  V. Antonucci,et al.  Effect of PtRu alloy composition on high-temperature methanol electro-oxidation , 2002 .

[35]  A. Boudghene Stambouli,et al.  Solid oxide fuel cells (SOFCs): a review of an environmentally clean and efficient source of energy , 2002 .

[36]  E. Ivers-Tiffée,et al.  Coke Formation and Degradation in SOFC Operation with a Model Reformate from Liquid Hydrocarbons , 2008 .

[37]  Ryan Clemmer,et al.  Effect of hydrogen on carbon formation on Ni/YSZ composites exposed to methane , 2008 .

[38]  L. Bedel,et al.  Co0 from partial reduction of La(Co,Fe)O3 perovskites for Fischer–Tropsch synthesis , 2003 .

[39]  Daniel Knapp,et al.  Density functional theory studies of methane dissociation on anode catalysts in solid-oxide fuel cells: Suggestions for coke reduction , 2007 .

[40]  Massimiliano Cimenti,et al.  Thermodynamic analysis of solid oxide fuel cells operated with methanol and ethanol under direct utilization, steam reforming, dry reforming or partial oxidation conditions , 2009 .

[41]  Frank A. Coutelieris,et al.  Electricity from ethanol fed SOFCs: the expectations for sustainable development and technological benefits , 2004 .

[42]  K. Sing Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity (Recommendations 1984) , 1985 .

[43]  V. Antonucci,et al.  Propane conversion over a Ru/CGO catalyst and its application in intermediate temperature solid oxide fuel cells , 2007 .

[44]  Anil V. Virkar,et al.  A High Performance, Anode-Supported Solid Oxide Fuel Cell Operating on Direct Alcohol , 2001 .

[45]  Raymond J. Gorte,et al.  Anodes for Direct Oxidation of Dry Hydrocarbons in a Solid‐Oxide Fuel Cell , 2000 .

[46]  Masayuki Dokiya,et al.  SOFC system and technology , 2002 .

[47]  A. Tenconi,et al.  Technical considerations of SOFCs for mixed DG/backup power applications , 2008 .

[48]  Anne Griboval-Constant,et al.  Combined methane reforming in presence of CO2 and O2 over LaFe1−xCoxO3 mixed-oxide perovskites as catalysts precursors , 2005 .