直接甲醇燃料电池电催化机理及多孔电极传质过程研究

doi:10.61558/2993-074X.2956

摘要/Abstract

摘要： 直接甲醇燃料电池以其独特的优势被业界人士视为本世纪最有可能实现商业化的燃料电池. 因此，众多研究院所和公司展开了深入研究，取得了瞩目的成就. 本文分析了膜电极结构的电催化和多孔电极传质过程的机制，并结合制备工艺、有序多层结构以及电池内部传输过程，讨论了近年来膜电极在直接甲醇燃料电池相关的研究进展.

关键词:

直接甲醇燃料电池, 膜电极, 电催化, 传质

Abstract: Direct methanol fuel cell (DMFC) is considered to be a promising commercial energy conversion device for portable electronics due to its many advantages. In order to improve the performance of DMFC, many companies and research institutes have been launching the deep research and obtaining a lot of conspicuous achievements. In this paper, the electrocatalytic mechanism and porous electrode mass transfer process in membrane electrode assembly (MEA) are analyzed. In addition, combined with the preparation process of MEA, multilayer ordered structures and internal transfer process of the cell, recent progresses of MEA in DMFC are discussed.

Key words:

direct methanol fuel cell, membrane electrode assemble, electrocatalytic, mass transfer

中图分类号:

TM911.4

王新东, 王一拓, 刘桂成, 王萌, 田哲. 直接甲醇燃料电池电催化机理及多孔电极传质过程研究[J]. 电化学（中英文）, 2013, 19(3): 246-255.

WANG Xin-Dong, WANG Yi-Tuo, LIU Gui-Cheng, WANG Meng, TIAN Zhe. Electrocatalytic Mechanism and Porous Electrode Mass Transfer Process in Membrane Electrode Assembly for Direct Methanol Fuel Cells[J]. Journal of Electrochemistry, 2013, 19(3): 246-255.

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链接本文: https://electrochem.xmu.edu.cn/CN/10.61558/2993-074X.2956

https://electrochem.xmu.edu.cn/CN/Y2013/V19/I3/246

参考文献

[1] Liu G C(刘桂成), Zhang H(张浩), Wang Y T(王一拓), et al. Matching and optimization of working condition of liquid feed direct methanol fuel cell[J]. Battery Bimonthly(电池), 2012, 42(1): 7-10.
[2] Li J J, Ye F, Chen L, et al. A study on novel pulse preparation and electrocatalytic activities of Pt/C-Nafion electrodes for proton exchange membrane fuel cell[J]. Journal of Power Sources, 2009, 186(2): 320-327.
[3] Liu G C, Xu J Y, Wang T T, et al. The performance and mechanism of multi-step activation of MEA for DMFC[J]. International Journal of Hydrogen Energy, 2010, 35 (22): 12341-12345.
[4] Fang Y, Wang T T, Miao R Y, et al. Modification of Nafion membranes with ternary composite materials for direct methanol fuel cells[J]. Electrochimica Acta, 2010, 55(7): 2404-2408.
[5] Matsui T, Fujiwara K, Okanishi T, et al. Electrochemical oxidation of CO over tin oxide supported platinum catalysts[J]. Journal of power sources, 2006, 155(2): 152-156.
[6] Waki K, Matsubara K, Ke K, et al. Self-organized Pt/SnO₂electrocatalysts on mutiwalled caborn nanotubes[J]. Electrochemistry Solid-State Letters, 2005, 10(8): A489-A491.
[7] Justin P, Rao G R. Enhanced activity of methanol electro-oxidation on Pt-V₂O₅/C catalysts[J]. Catalysis Today, 2009, 141(1/2): 138-143.
[8] Zhao T T(赵婷婷). Study on tin dioxide nanoparicles as co-catalysts of direct methanol fuel cell[D]. University of Science & Technology Beijing( 北京科技大学), 2011: 25-80.
[9] Shukla A K, Raman R K, Choudhury N A, et al. Carbon-supported Pt-Fe alloy as a methanol-resistant oxygen-reduction catalyst for direct methanol fuel cells[J]. Journal of Electroanalytical Chemistry, 2004, 563(2): 181-190.
[10] Shukla A K, Neergat M, Bera P, et al. An XPS study on binary and ternary alloys of transition metals with platinized carbon and its bearing upon oxygen electroreduction in direct methanol fuel cells[J]. Journal of Electroanalytical Chemistry, 2001, 504(1): 111-119.
[11] Li J J(李晶晶). Study on electrodeposition of Pt based electrocatalysts for fuel cell[D]. University of Science & Technology Beijing(北京科技大学), 2008: 20-80.
[12] Wei Y S, Matar S, Shen L B, et al. A novel membrane for DMFC-Na₂Ti₃O₇ Nanotubes/ Nafion® composite membrane: Performances studies [J]. International Journal of Hydrogen Energy, 2012, 37(2): 1857-1864.
[13] Shroti N, Barbora L, Verma A. Neodymium triflate modified nafion composite membrane for reduced alcohol permeability in direct alcohol fuel cell[J]. International Journal of Hydrogen Energy, 2011, 36(22): 14907-14913.
[14] Tang L(唐玲). Study on the nafion-based composite proton exchange membrane for DMFC[D]. University of Science & Technology Beijing ( 北京科技大学), 2010: 13-90.
[15] Lin H L, Wang S H, Chiu C K, et al. Preparation of Nafion/poly(vinyl alcohol) electro-spun fiber composite membranes for direct methanol fuel cells[J]. Journal of Membrane Science, 2010, 365(1/2): 114-122.
[16] Xiang Y, Yang M, Zhang J, et al. Phosphotungstic acid (HPW) molecules anchored in the bulk of Nafion as methanol-blocking membrane for direct methanol fuel cells[J]. Journal of Membrane Science, 2011, 368(1/2): 241-245.
[17] Wu J(吴珺). Study on the chitosan modified proton exchange membrane for DMFC[D]. University of Science & Technology Beijing(北京科技大学), 2011: 23-56.
[18] Xiong L, Manthiram A. High performance membraneelectrode assemblies with ultra-low Pt loading for proton exchange membrane fuel cells[J]. Electrochimica Acta, 2005, 50(16): 3200-3204.
[19] Wilson M S, Gottesfeld S. Thin-film catalyst layers for polymer electrolyte fuel cell electrodes[J]. Journal of Applied Electrochemistry, 1992, 22(1): 1-7.
[20] Lin C S(林才顺). Study of direct methanol fuel cells for portable and mobile power system[D]. University of Science & Technology Beijing ( 北京科技大学), 2007: 94-117.
[21] Liu G C, Wang M, Wang Y T, et al. Anode catalyst layer with novel microstructure for a direct methanol fuel cell[J]. International Journal of Hydrogen Energy, 2012, 37(10): 8659-8663.
[22] Zhang J, Yin G P, Wang Z B, et al. Effects of hot pressing conditions on the performances of MEAs for direct methanol fuel cells[J]. Journal of power sources, 2007, 165(1): 73-81.
[23] Uchida M, Fukuoka Y, Sugawara Y, et al. Improved Preparation process of very-low-platinum-loading electrodes for polymer electrolyte fuel cells[J]. Journal of the Electrochemical Society, 1998, 145(11): 3708-3713.
[24] Wei Z B, Wang S L, Yi B L, et al. Influence of electrode structure on the performance of a direct methanol fuel cell[J]. Journal of Power Sources, 2002, 106(1/2): 364-369.
[25] Volfkovich Y M, Sosenkin V E, Bagotsky V S. Structural and wetting properties of fuel cell components[J]. Journal of Power Sources, 2010, 195(17): 5429-5441.
[26] Fischer A, Jindra J, Wendt H. Porosity and catalyst utilization of thin layer cathodes in air operated PEM-fuel cells[J]. Journal of Applied Electrochemistry, 1998, 28(3): 277-282.
[27] Prabhuram J, Krishnan N N, Choi B, et al. Long-term durability test for direct methanol fuel cell made of hydrocarbon membrane[J]. International Journal of Hydrogen Energy, 2010, 35(13): 6924-6933.
[28] Matar S, Liu H. Effect of cathode catalyst layer thickness on methanol cross-over in a DMFC[J]. Electrochimica Acta, 2010, 56(1): 600-606.
[29] Wang T T, Lin C S, Ye F, et al. MEA with double-layered catalyst cathode to mitigate methanol crossover in DMFC[J]. Electrochemistry Communications, 2008, 10(9): 1261-1263.
[30] Nordlund J, Roessler A, Lindbergh G. The influence of electrode morphology on the performance of a DMFC anode[J]. Journal of Applied Electrochemistry, 2002, 32(3): 259-265.
[31] Shaffer C E, Wang C Y. High concentration methanol fuel cells: Design and theory[J]. Journal of Power Sources, 2010, 195(13): 4185-4195.
[32] Liang J S, Liu C, Chen L, et al. In situ visual investigation of CO₂ bubbles clogging phenomena in mDMFC anode micro flow field[C]//Proceedings of the 1st IEEE International Conference on Nano/Micro Engineered and Molecular Systems, January 18-21, Zhuhai, China, 2006: 1374-1378.
[33] Wang G X, Sun G Q, Wang Q, et al. Effect of carbon black additive in Pt black cathode catalyst layer on direct methanol fuel cell performance[J]. International Journal of Hydrogen Energy, 2010, 35(20): 11245-11253.
[34] Cao J Y, Chen M, Chen J, et al. Double microporous layer cathode for membrane electrode assembly of passive direct methanol fuel cells[J]. International Journal of Hydrogen Energy, 2010, 35(10): 4622-4629.
[35] Xu C, Faghri A. Water transport characteristics in a passive liquid-feed DMFC[J]. International Journal of Heat and Mass Transfer, 2010, 53(9/10): 1951-1966.
[36] Xiao B, Bahrami H, Faghri A. Analysis of heat and mass transport in a miniature passive and semi passive liquid-feed direct methanol fuel cell[J]. Journal of Power Sources, 2010, 195(8): 2248-2259.
[1] Liu G C(刘桂成), Zhang H(张浩), Wang Y T(王一拓), et al. Matching and optimization of working condition of liquid feed direct methanol fuel cell[J]. Battery Bimonthly(电池), 2012, 42(1): 7-10.
[2] Li J J, Ye F, Chen L, et al. A study on novel pulse preparation and electrocatalytic activities of Pt/C-Nafion electrodes for proton exchange membrane fuel cell[J]. Journal of Power Sources, 2009, 186(2): 320-327.
[3] Liu G C, Xu J Y, Wang T T, et al. The performance and mechanism of multi-step activation of MEA for DMFC[J]. International Journal of Hydrogen Energy, 2010, 35 (22): 12341-12345.
[4] Fang Y, Wang T T, Miao R Y, et al. Modification of Nafion membranes with ternary composite materials for direct methanol fuel cells[J]. Electrochimica Acta, 2010, 55(7): 2404-2408.
[5] Matsui T, Fujiwara K, Okanishi T, et al. Electrochemical oxidation of CO over tin oxide supported platinum catalysts[J]. Journal of power sources, 2006, 155(2): 152-156.
[6] Waki K, Matsubara K, Ke K, et al. Self-organized Pt/SnO₂electrocatalysts on mutiwalled caborn nanotubes[J]. Electrochemistry Solid-State Letters, 2005, 10(8): A489-A491.
[7] Justin P, Rao G R. Enhanced activity of methanol electro-oxidation on Pt-V₂O₅/C catalysts[J]. Catalysis Today, 2009, 141(1/2): 138-143.
[8] Zhao T T(赵婷婷). Study on tin dioxide nanoparicles as co-catalysts of direct methanol fuel cell[D]. University of Science & Technology Beijing( 北京科技大学), 2011: 25-80.
[9] Shukla A K, Raman R K, Choudhury N A, et al. Carbon-supported Pt-Fe alloy as a methanol-resistant oxygen-reduction catalyst for direct methanol fuel cells[J]. Journal of Electroanalytical Chemistry, 2004, 563(2): 181-190.
[10] Shukla A K, Neergat M, Bera P, et al. An XPS study on binary and ternary alloys of transition metals with platinized carbon and its bearing upon oxygen electroreduction in direct methanol fuel cells[J]. Journal of Electroanalytical Chemistry, 2001, 504(1): 111-119.
[11] Li J J(李晶晶). Study on electrodeposition of Pt based electrocatalysts for fuel cell[D]. University of Science & Technology Beijing(北京科技大学), 2008: 20-80.
[12] Wei Y S, Matar S, Shen L B, et al. A novel membrane for DMFC-Na₂Ti₃O₇ Nanotubes/ Nafion® composite membrane: Performances studies [J]. International Journal of Hydrogen Energy, 2012, 37(2): 1857-1864.
[13] Shroti N, Barbora L, Verma A. Neodymium triflate modified nafion composite membrane for reduced alcohol permeability in direct alcohol fuel cell[J]. International Journal of Hydrogen Energy, 2011, 36(22): 14907-14913.
[14] Tang L(唐玲). Study on the nafion-based composite proton exchange membrane for DMFC[D]. University of Science & Technology Beijing ( 北京科技大学), 2010: 13-90.
[15] Lin H L, Wang S H, Chiu C K, et al. Preparation of Nafion/poly(vinyl alcohol) electro-spun fiber composite membranes for direct methanol fuel cells[J]. Journal of Membrane Science, 2010, 365(1/2): 114-122.
[16] Xiang Y, Yang M, Zhang J, et al. Phosphotungstic acid (HPW) molecules anchored in the bulk of Nafion as methanol-blocking membrane for direct methanol fuel cells[J]. Journal of Membrane Science, 2011, 368(1/2): 241-245.
[17] Wu J(吴珺). Study on the chitosan modified proton exchange membrane for DMFC[D]. University of Science & Technology Beijing(北京科技大学), 2011: 23-56.
[18] Xiong L, Manthiram A. High performance membraneelectrode assemblies with ultra-low Pt loading for proton exchange membrane fuel cells[J]. Electrochimica Acta, 2005, 50(16): 3200-3204.
[19] Wilson M S, Gottesfeld S. Thin-film catalyst layers for polymer electrolyte fuel cell electrodes[J]. Journal of Applied Electrochemistry, 1992, 22(1): 1-7.
[20] Lin C S(林才顺). Study of direct methanol fuel cells for portable and mobile power system[D]. University of Science & Technology Beijing ( 北京科技大学), 2007: 94-117.
[21] Liu G C, Wang M, Wang Y T, et al. Anode catalyst layer with novel microstructure for a direct methanol fuel cell[J]. International Journal of Hydrogen Energy, 2012, 37(10): 8659-8663.
[22] Zhang J, Yin G P, Wang Z B, et al. Effects of hot pressing conditions on the performances of MEAs for direct methanol fuel cells[J]. Journal of power sources, 2007, 165(1): 73-81.
[23] Uchida M, Fukuoka Y, Sugawara Y, et al. Improved Preparation process of very-low-platinum-loading electrodes for polymer electrolyte fuel cells[J]. Journal of the Electrochemical Society, 1998, 145(11): 3708-3713.
[24] Wei Z B, Wang S L, Yi B L, et al. Influence of electrode structure on the performance of a direct methanol fuel cell[J]. Journal of Power Sources, 2002, 106(1/2): 364-369.
[25] Volfkovich Y M, Sosenkin V E, Bagotsky V S. Structural and wetting properties of fuel cell components[J]. Journal of Power Sources, 2010, 195(17): 5429-5441.
[26] Fischer A, Jindra J, Wendt H. Porosity and catalyst utilization of thin layer cathodes in air operated PEM-fuel cells[J]. Journal of Applied Electrochemistry, 1998, 28(3): 277-282.
[27] Prabhuram J, Krishnan N N, Choi B, et al. Long-term durability test for direct methanol fuel cell made of hydrocarbon membrane[J]. International Journal of Hydrogen Energy, 2010, 35(13): 6924-6933.
[28] Matar S, Liu H. Effect of cathode catalyst layer thickness on methanol cross-over in a DMFC[J]. Electrochimica Acta, 2010, 56(1): 600-606.
[29] Wang T T, Lin C S, Ye F, et al. MEA with double-layered catalyst cathode to mitigate methanol crossover in DMFC[J]. Electrochemistry Communications, 2008, 10(9): 1261-1263.
[30] Nordlund J, Roessler A, Lindbergh G. The influence of electrode morphology on the performance of a DMFC anode[J]. Journal of Applied Electrochemistry, 2002, 32(3): 259-265.
[31] Shaffer C E, Wang C Y. High concentration methanol fuel cells: Design and theory[J]. Journal of Power Sources, 2010, 195(13): 4185-4195.
[32] Liang J S, Liu C, Chen L, et al. In situ visual investigation of CO₂ bubbles clogging phenomena in mDMFC anode micro flow field[C]//Proceedings of the 1st IEEE International Conference on Nano/Micro Engineered and Molecular Systems, January 18-21, Zhuhai, China, 2006: 1374-1378.
[33] Wang G X, Sun G Q, Wang Q, et al. Effect of carbon black additive in Pt black cathode catalyst layer on direct methanol fuel cell performance[J]. International Journal of Hydrogen Energy, 2010, 35(20): 11245-11253.
[34] Cao J Y, Chen M, Chen J, et al. Double microporous layer cathode for membrane electrode assembly of passive direct methanol fuel cells[J]. International Journal of Hydrogen Energy, 2010, 35(10): 4622-4629.
[35] Xu C, Faghri A. Water transport characteristics in a passive liquid-feed DMFC[J]. International Journal of Heat and Mass Transfer, 2010, 53(9/10): 1951-1966.
[36] Xiao B, Bahrami H, Faghri A. Analysis of heat and mass transport in a miniature passive and semi passive liquid-feed direct methanol fuel cell[J]. Journal of Power Sources, 2010, 195(8): 2248-2259.