A review on methanol crossover in direct methanol fuel cells: challenges and achievements

SUMMARY Direct methanol fuel cells have the potential to power future microelectronic and portable electronic devices because of their high energy density. One of the major obstacles that currently prevent the widespread applications of direct methanol fuel cells is the methanol crossover through the polymer-electrolyte membrane. Methanol crossover is closely related to several factors including membrane structure and morphology, membrane thickness, and fuel cell operating conditions such as temperature, pressure, and methanol feed concentration. This work presents a comprehensive overview of the state-of-the-art technology for the most important factors, affecting methanol crossover in direct methanol fuel cells. In addition, the current and future directions of the research and development activities, aiming to reduce the methanol crossover are reviewed and discussed in order to improve the performance of direct methanol fuel cells. Copyright © 2011 John Wiley & Sons, Ltd.

[1]  Dukjoon Kim,et al.  Enhanced transport performance of sulfonated mesoporous benzene-silica incorporated poly(ether ether ketone) composite membranes for fuel cell application , 2010 .

[2]  Xiangyang Zhou,et al.  High temperature transport properties of polyphosphazene membranes for direct methanol fuel cells , 2003 .

[3]  M. Bartolozzi,et al.  A Comparative Investigation of Proton and Methanol Transport in Fluorinated Ionomeric Membranes , 2000 .

[4]  Qiang Zhang,et al.  Novel side-chain-type cardo poly(aryl ether sulfone) bearing pendant sulfoalkyl groups for proton ex , 2011 .

[5]  Q. Liao,et al.  Two-dimensional two-phase mass transport model for methanol and water crossover in air-breathing direct methanol fuel cells , 2009 .

[6]  Jingtao Wang,et al.  Simultaneously enhanced methanol barrier and proton conductive properties of phosphorylated titanate nanotubes embedded nanocomposite membranes , 2010 .

[7]  Y. Lee,et al.  Crosslinked poly(vinyl alcohol) membranes containing sulfonic acid group: proton and methanol transport through membranes , 2004 .

[8]  Bokyung Kim,et al.  Transport of methanol and protons through partially sulfonated polymer blend membranes for direct methanol fuel cell , 2004 .

[9]  Darren J. Martin,et al.  Nafion-MPMDMS nanocomposite membranes with low methanol permeability , 2007 .

[10]  Xiaofeng Xie,et al.  Novel modification method to prepare crosslinked sulfonated poly(ether ether ketone)/silica hybrid membranes for fuel cells , 2010 .

[11]  Yan-Jie Wang,et al.  Proton conducting 9P2O5–6TiO2–85SiO2 glass-filled Nafion® composite membranes , 2011 .

[12]  S. Kwak,et al.  Nafion/sulfated β-cyclodextrin composite membranes for direct methanol fuel cells , 2008 .

[13]  T. Zhao,et al.  Pd and Pd-Cu Alloy Deposited Nafion Membranes for Reduction of Methanol Crossover in Direct Methanol Fuel Cells , 2005 .

[14]  Yushan Yan,et al.  Nanocomposite fuel cell membranes based on Nafion and acid functionalized zeolite beta nanocrystals , 2008 .

[15]  Mahendra Kumar,et al.  Organic-inorganic hybrid alkaline membranes by epoxide ring opening for direct methanol fuel cell applications , 2010 .

[16]  Tao Yang Poly(vinyl alcohol)/sulfated β-cyclodextrin for direct methanol fuel cell applications , 2009 .

[17]  S. Moon,et al.  Highly charged proton exchange membranes prepared by using water soluble polymer blends for fuel cells , 2005 .

[18]  Zhongyi Jiang,et al.  Proton conducting CS/P(AA-AMPS) membrane with reduced methanol permeability for DMFCs , 2008 .

[19]  In-Hwan Oh,et al.  Performance evaluation of passive DMFC single cells , 2006 .

[20]  Hoyoung Kim,et al.  Effect of morphology and pore size of sulfonated mesoporous benzene-silicas in the preparation of poly(vinyl alcohol)-based hybrid nanocomposite membranes for direct methanol fuel cell application. , 2009, The journal of physical chemistry. B.

[21]  H. Na,et al.  Composite membranes based on a novel benzimidazole grafted PEEK and SPEEK for fuel cells , 2010 .

[22]  Tao Yang Composite membrane of sulfonated poly(ether ether ketone) and sulfated poly(vinyl alcohol) for use in direct methanol fuel cells , 2009 .

[23]  H. Na,et al.  Novel covalent-ionically cross-linked membranes with extremely low water swelling and methanol crossover for direct methanol fuel cell applications , 2010 .

[24]  B. Pivovar,et al.  Direct Methanol Fuel Cell Performance of Disulfonated Poly(arylene ether benzonitrile) Copolymers , 2004 .

[25]  C. W. Lin,et al.  Preparation and characterization of high selectivity organic–inorganic hybrid-laminated Nafion 115 membranes for DMFC , 2006 .

[26]  Siti Kartom Kamarudin,et al.  Overview of hybrid membranes for direct-methanol fuel-cell applications , 2010 .

[27]  Y. Elabd,et al.  Polymer electrolyte membranes for the direct methanol fuel cell: A review , 2006 .

[28]  Jinhwan Kim,et al.  Proton conductivities and methanol permeabilities of membranes made from partially sulfonated polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene copolymers , 2002 .

[29]  Yu-Jen Chiu An algebraic semi-empirical model for evaluating fuel crossover fluxes of a DMFC under various operating conditions , 2010 .

[30]  Yong Yang,et al.  A novel inorganic/organic composite membrane tailored by various organic silane coupling agents for use in direct methanol fuel cells , 2009 .

[31]  Zhongwei An,et al.  Crosslinked sulfonated poly(arylene ether ketone) membranes bearing quinoxaline and acid–base complex cross-linkages for fuel cell applications , 2011 .

[32]  Yuxin Wang,et al.  Sulfonated poly(ether ether ketone) membranes for direct methanol fuel cell , 2003 .

[33]  K. Friedrich,et al.  Transport properties of ionomer composite membranes for direct methanol fuel cells , 2002 .

[34]  H. Na,et al.  A facile approach to prepare self-cross-linkable sulfonated poly(ether ether ketone) membranes for direct methanol fuel cells , 2010 .

[35]  S. Zaidi,et al.  Proton and methanol transport behavior of SPEEK/TPA/MCM-41 composite membranes for fuel cell application , 2008 .

[36]  F. Picchioni,et al.  Ionomeric membranes based on partially sulfonated poly(styrene): synthesis, proton conduction and methanol permeation , 2000 .

[37]  Chien-Kung Lin,et al.  Preparation of nitrated sulfonated poly(ether ether ketone) membranes for reducing methanol permeability in direct methanol fuel cell applications , 2009 .

[38]  H. Munakata,et al.  Three-dimensionally ordered macroporous polyimide composite membrane with controlled pore size for direct methanol fuel cells , 2008 .

[39]  Chao-Yang Wang,et al.  Mathematical Modeling of Liquid-Feed Direct Methanol Fuel Cells , 2003 .

[40]  Y. Sung,et al.  A Pd-impregnated nanocomposite Nafion membrane for use in high-concentration methanol fuel in DMFC , 2003 .

[41]  Tongtao Wang,et al.  Suppression of methanol cross-over in novel composite membranes for direct methanol fuel cells , 2009 .

[42]  M. J. Cánovas,et al.  Preparation and characterization of hybrid membranes for fuel cell applications: EPDM filled with organophilized silicas , 2009 .

[43]  B. Pivovar,et al.  Sulfonated poly(arylene ether sulfone) copolymer proton exchange membranes: composition and morphology effects on the methanol permeability , 2004 .

[44]  Anil Verma,et al.  Synthesis and Ex‐situ Characterization of Nafion/TiO2 Composite Membranes for Direct Ethanol Fuel Cell , 2009 .

[45]  Mitsuru Higa,et al.  Sulfonated polyimides bearing benzimidazole groups for direct methanol fuel cell applications , 2010 .

[46]  P. Shen,et al.  Low methanol permeable sulfonated poly(phthalazinone ether sulfone) membranes for DMFCs , 2007 .

[47]  S. Chirachanchai,et al.  Sulfonated montmorillonite/sulfonated poly(ether ether ketone) (SMMT/SPEEK) nanocomposite membrane for direct methanol fuel cells (DMFCs) , 2008 .

[48]  O. Diat,et al.  Structural Study of Zirconium Phosphate−Nafion Hybrid Membranes for High-Temperature Proton Exchange Membrane Fuel Cell Applications , 2007 .

[49]  Y. Hudiono,et al.  Porous layered oxide/Nafion® nanocomposite membranes for direct methanol fuel cell applications , 2009 .

[50]  Suzhen Ren,et al.  Casting Nafion-sulfonated organosilica nano-composite membranes used in direct methanol fuel cells , 2006 .

[51]  H. Na,et al.  Layer-by-layer self-assembly of polyaniline on sulfonated poly(arylene ether ketone) membrane with high proton conductivity and low methanol crossover , 2010 .

[52]  Mohammad Mahdi Hasani-Sadrabadi,et al.  Novel nanocomposite proton exchange membranes based on Nafion and AMPS-modified montmorillonite fo , 2010 .

[53]  G. Robertson,et al.  Comb-Shaped Poly(arylene ether sulfone)s as Proton Exchange Membranes† , 2008 .

[54]  Lei Li,et al.  Novel proton conducting composite membranes for direct methanol fuel cell , 2003 .

[55]  R. Savinell,et al.  Evaluation of a Sol-Gel Derived Nafion/Silica Hybrid Membrane for Polymer Electrolyte Membrane Fuel Cell Applications: II. Methanol Uptake and Methanol Permeability , 2001 .

[56]  S. Woo,et al.  Proton conductivity and methanol permeation in Nafion™/ORMOSIL prepared with various organic silanes , 2004 .

[57]  B. Pivovar,et al.  Sulfonated naphthalene dianhydride based polyimide copolymers for proton-exchange-membrane fuel cells , 2005 .

[58]  Wenpeng Liu,et al.  Three-Dimensional Simulations of Liquid Feed Direct Methanol Fuel Cells , 2007 .

[59]  Soo-Bok Lee,et al.  Sulfonated polystyrene/PTFE composite membranes , 2005 .

[60]  Jung-Ki Park,et al.  Proton conducting semi-IPN based on Nafion and crosslinked poly(AMPS) for direct methanol fuel cell , 2004 .

[61]  Xin Wang,et al.  Multifunctional composite membrane based on a highly porous polyimide matrix for direct methanol fuel cells , 2010 .

[62]  Suli Wang,et al.  Nafion® and nano-size TiO2–SO42− solid superacid composite membrane for direct methanol fuel cell , 2008 .

[63]  Zhongyi Jiang,et al.  Zeolite beta-filled chitosan membrane with low methanol permeability for direct methanol fuel cell , 2008 .

[64]  Xu Fei,et al.  Preparation and properties of epoxy-based cross-linked sulfonated poly(arylene ether ketone) proton exchange membrane for direct methanol fuel cell applications , 2010 .

[65]  Y. Lee,et al.  Sulfonated poly(arylene ether sulfone)-silica nanocomposite membrane for direct methanol fuel cell (DMFC) , 2007 .

[66]  Rong Chen,et al.  Mass transport phenomena in direct methanol fuel cells , 2009 .

[67]  Y. Yamazaki,et al.  Novel Nafion/Hydroxyapatite composite membrane with high crystallinity and low methanol crossover for DMFCs , 2005 .

[68]  Q. Xin,et al.  Use of in situ polymerized phenol-formaldehyde resin to modify a Nafion® membrane for the direct methanol fuel cell , 2007 .

[69]  H. Na,et al.  Novel hybrid polymer electrolyte membranes with high proton conductivity prepared by a silane-crosslinking technique for direct methanol fuel cells , 2011 .

[70]  H. Na,et al.  Layer-by-layer self-assembly of in situ polymerized polypyrrole on sulfonated poly(arylene ether ketone) membrane with extremely low methanol crossover , 2009 .

[71]  H. R. Kunz,et al.  Preparation via supercritical fluid route of Pd-impregnated nafion membranes which exhibit reduced methanol crossover for DMFC , 2005 .

[72]  Chih-Chia Cheng,et al.  Preparation and characterization of high-durability zwitterionic crosslinked proton exchange membranes , 2010 .

[73]  B. Smitha,et al.  Synthesis and characterization of poly(vinyl alcohol)‐based membranes for direct methanol fuel cell , 2005 .

[74]  H. Na,et al.  Novel cross-linked sulfonated poly (arylene ether ketone) membranes for direct methanol fuel cell , 2010 .

[75]  P. P. Chu,et al.  A polyvinyl alcohol/p-sulfonate phenolic resin composite proton conducting membrane , 2006 .

[76]  Ho Seok Park,et al.  Physical and electrochemical properties of Nafion/polypyrrole composite membrane for DMFC , 2006 .

[77]  Jingli Luo,et al.  Methanol permeability and proton conductivity of Nafion membranes modified electrochemically with polyaniline , 2008 .

[78]  Otoo Yamada,et al.  Methanol permeability and proton conductivity of sulfonated co-polyimide membranes , 2005 .

[79]  Zhongyi Jiang,et al.  A facile surface modification of Nafion membrane by the formation of self-polymerized dopamine nano-layer to enhance the methanol barrier property , 2009 .

[80]  L. Gubler,et al.  Celtec-V A Polybenzimidazole-Based Membrane for the Direct Methanol Fuel Cell , 2007 .

[81]  H. Ha,et al.  Nano-silica layered composite membranes prepared by PECVD for direct methanol fuel cells , 2004 .

[82]  M. Guiver,et al.  Sulfonated naphthalenic polyimides containing ether and ketone linkages as polymer electrolyte membr , 2011 .

[83]  H. Na,et al.  Sulphonated Tetramethyl Poly(ether ether ketone)/Epoxy/Sulphonated Phenol Novolac Semi‐IPN Membranes for Direct Methanol Fuel Cells , 2009 .

[84]  H. Na,et al.  Preparation and properties of novel cross-linked sulfonated poly(arylene ether ketone) for direct methanol fuel cell application , 2010 .

[85]  Jingtao Wang,et al.  Chitosan/titanate Nanotube Hybrid Membrane with Low Methanol Crossover for Direct Methanol Fuel Cells , 2010 .

[86]  S. S. Murthy,et al.  Synthesis and characterization of composite membranes based on α-zirconium phosphate and silicotungstic acid , 2007 .

[87]  C. W. Lin,et al.  DBSA-doped PEG/SiO2 proton-conducting hybrid membranes for low-temperature fuel cell applications , 2005 .

[88]  H. Kita,et al.  Synthesis, proton conductivity and methanol permeability of a novel sulfonated polyimide from 3-(2′,4′-diaminophenoxy)propane sulfonic acid , 2003 .

[89]  Ih. Oh,et al.  Modification of polymer electrolyte membranes for DMFCs using Pd films formed by sputtering , 2002 .

[90]  Fuqiang Liu,et al.  Low Crossover of Methanol and Water Through Thin Membranes in Direct Methanol Fuel Cells , 2006 .

[91]  Tien Hoa Nguyen,et al.  Pore-filling membrane for direct methanol fuel cells based on sulfonated poly(styrene-ran-ethylene) and porous polyimide matrix , 2009 .

[92]  Zhongqing Jiang,et al.  Preparation of Proton Exchange Membranes by a Plasma Polymerization Method and Application in Direct Methanol Fuel Cells (DMFCs) , 2010 .

[93]  Suli Wang,et al.  Nano-sized Fe2O3–SO42− solid superacid composite Nafion® membranes for direct methanol fuel cells , 2010 .

[94]  T. Yamaguchi,et al.  Low methanol crossover and high performance of DMFCs achieved with a pore-filling polymer electrolyte membrane , 2007 .

[95]  H. Ha,et al.  Zirconium meta-sulfonphenyl phosphonic acid-incorporated Nafion® membranes for reduction of methanol permeability , 2008 .

[96]  B. Pivovar,et al.  Pervaporation membranes in direct methanol fuel cells , 1999 .

[97]  Tao Yang,et al.  Primary study on double-layer membranes for direct methanol fuel cell , 2008 .

[98]  Siti Kartom Kamarudin,et al.  Overview on the challenges and developments of micro-direct methanol fuel cells (DMFC) , 2007 .

[99]  Hongtan Liu,et al.  Real time measurements of methanol crossover in a DMFC , 2007 .

[100]  Young Jin Kim,et al.  Fixation of nanosized proton transport channels in membranes , 2003 .

[101]  Young Moo Lee,et al.  Preparation and characterization of crosslinked PVA/SiO2 hybrid membranes containing sulfonic acid groups for direct methanol fuel cell applications , 2004 .

[102]  H. Na,et al.  Synthesis and characterization of novel sulfonated poly(arylene ether ketone) copolymers with pendant carboxylic acid groups for proton exchange membranes , 2009 .

[103]  Jinhwan Kim,et al.  Morphology and transport properties of protons and methanol through partially sulfonated block copolymers , 2005 .

[104]  Yuyan Shao,et al.  Permeabilities of methanol, ethanol and dimethyl ether in new composite membranes: A comparison with Nafion membranes , 2007 .

[105]  James M. Fenton,et al.  Composite silica/Nafion® membranes prepared by tetraethylorthosilicate sol-gel reaction and solution casting for direct methanol fuel cells , 2006 .

[106]  Lei Li,et al.  Sulfonated polyethersulfone Cardo membranes for direct methanol fuel cell , 2005 .

[107]  Hwayong Kim,et al.  Composite Nafion/polyphenylene oxide (PPO) membranes with phosphomolybdic acid (PMA) for direct methanol fuel cells , 2005 .

[108]  Se Young Oh,et al.  Synthesis and characterization of sulfonated polyimide membranes for direct methanol fuel cell , 2003 .

[109]  Jingtao Wang,et al.  Fabrication and performances of solid superacid embedded chitosan hybrid membranes for direct methanol fuel cell , 2010 .

[110]  W. Liang,et al.  Inorganic–organic hybrid polymer electrolyte based on polysiloxane/poly(maleic imide-co-styrene) network , 2010 .

[111]  K. S. Dhathathreyan,et al.  Methanol crossover studies on heat-treated Nafion® membranes , 2008 .

[112]  Chaoyang Wang,et al.  Development of high-power electrodes for a liquid-feed direct methanol fuel cell , 2003 .

[113]  Zhongyi Jiang,et al.  Tuning the performance of direct methanol fuel cell membranes by embedding multifunctional inorganic submicrospheres into polymer matrix , 2009 .

[114]  Mats Danielson Sensitivity Analyses in Interval Decision Modelling , 2009, Eng. Lett..

[115]  L. Tang,et al.  Modification of Nafion membranes with ternary composite materials for direct methanol fuel cells , 2010 .

[116]  H. Na,et al.  A novel sulfonated poly(ether ether ketone) and cross-linked membranes for fuel cells , 2010 .

[117]  Norman N. Li Advanced membrane technology and applications , 2008 .

[118]  X. Yan,et al.  Design of an effective methanol-blocking membrane with purple membrane for direct methanol fuel cell , 2011 .

[119]  M. Guiver,et al.  Comparative effect of phthalazinone units in sulfonated poly(arylene ether ether ketone ketone) copolymers as proton exchange membrane materials , 2008 .

[120]  Dawn M. Crawford,et al.  Triblock copolymer ionomer membranes: Part I. Methanol and proton transport , 2003 .

[121]  Xiaofeng Xie,et al.  Synthesis and characterization of crosslinked sulfonated poly(arylene ether sulfone) membranes for DMFC applications , 2009 .

[122]  D. Seung,et al.  Functionalized carbon nanotube-poly(arylene sulfone) composite membranes for direct methanol fuel cells with enhanced performance , 2008 .

[123]  L. Hong,et al.  PPO-based acid–base polymer blend membranes for direct methanol fuel cells , 2008 .

[124]  P. Kuo,et al.  Preparation, characterization and methanol permeability of proton conducting membranes based on sulfonated ethylene-vinyl alcohol copolymer , 2010 .

[125]  Chuh‐Yung Chen,et al.  Blended Nafion®/SPEEK direct methanol fuel cell membranes for reduced methanol permeability , 2009 .

[126]  J. Weidner,et al.  Experimental validation of a methanol crossover model in DMFC applications , 2008 .

[127]  Tao Yang Preliminary study of SPEEK/PVA blend membranes for DMFC applications , 2008 .