Recent advances in polybenzimidazole/phosphoric acid membranes for high-temperature fuel cells

Proton exchange membrane fuel cells are one of the most promising technologies for sustainable power generation in the future. In particular, high-temperature proton exchange membrane fuel cells (HT-PEMFCs) offer several advantages such as increased kinetics, reduced catalyst poisoning and better heat management. One of the essential components of a HT-PEMFC is the proton exchange membrane, which has to possess good proton conductivity as well as stability and durability at the required operating temperatures. Amongst the various membrane candidates, phosphoric acid-impregnated polybenzimidazole-type polymer membranes (PBI/PA) are considered the most mature and some of the most promising, providing the necessary characteristics for good performance in HT-PEMFCs. This review aims to examine the recent advances made in the understanding and fabrication of PBI/PA membranes, and offers a perspective on the future and prospects of deployment of this technology in the fuel cell market. © 2014 Society of Chemical Industry

[1]  T. Lim,et al.  Synthesis and characterization of acid-doped polybenzimidazole membranes by sol–gel and post-membrane casting method , 2010 .

[2]  Ki-Hyun Kim,et al.  Highly durable polymer electrolyte membranes at elevated temperature: Cross-linked copolymer structure consisting of poly(benzoxazine) and poly(benzimidazole) , 2013 .

[3]  K. Scott,et al.  A H2SO4 Loaded Polybenzimidazole (PBI) Membrane for High Temperature PEMFC , 2012 .

[4]  S. Hsu,et al.  Synthesis and properties of a new fluorine‐containing polybenzimidazole for high‐temperature fuel‐cell applications , 2006 .

[5]  D. Wan,et al.  A facile crosslinking method of polybenzimidazole with sulfonyl azide groups for proton conducting membranes , 2012 .

[6]  Ronghuan He,et al.  Proton conductivity of phosphoric acid doped polybenzimidazole and its composites with inorganic proton conductors , 2003 .

[7]  T. Fujigaya,et al.  Remarkably Durable High Temperature Polymer Electrolyte Fuel Cell Based on Poly(vinylphosphonic acid)-doped Polybenzimidazole , 2013, Scientific Reports.

[8]  R. Savinell,et al.  #2#1 and #2#1 NMR Study of Phosphoric Acid–Doped Polybenzimidazole under Controlled Water Activity , 2009 .

[9]  N. Kim,et al.  A new self-cross-linked, net-structured, proton conducting polymer membrane for high temperature proton exchange membrane fuel cells , 2010 .

[10]  Deborah J. Jones,et al.  Role of post-sulfonation thermal treatment in conducting and thermal properties of sulfuric acid sulfonated poly(benzimidazole) membranes , 2002 .

[11]  H. Na,et al.  End-group cross-linked polybenzimidazole blend membranes for high temperature proton exchange membrane , 2012 .

[12]  Qingfeng Li,et al.  Membranes for High Temperature PEMFC Based on Acid‐Doped Polybenzimidazoles , 2008 .

[13]  Jian‐mei Lu,et al.  Polybenzimidazole/zwitterion-coated silica nanoparticle hybrid proton conducting membranes for anhydrous proton exchange membrane application , 2012 .

[14]  P. Gómez‐Romero,et al.  Enhanced conductivity in polyanion-containing polybenzimidazoles. Improved materials for proton-exchange membranes and PEM fuel cells , 2003 .

[15]  S. An,et al.  Synthesis of Poly(2,5‐benzimidazole) for Use as a Fuel‐Cell Membrane , 2004 .

[16]  Pedro Gómez-Romero,et al.  Proton-conducting membranes based on benzimidazole polymers for high-temperature PEM fuel cells. A chemical quest. , 2010, Chemical Society reviews.

[17]  Jong‐Chan Lee,et al.  Polybenzimidazole containing benzimidazole side groups for high-temperature fuel cell applications , 2009 .

[18]  Y. Oono,et al.  Influence of operating temperature on cell performance and endurance of high temperature proton exchange membrane fuel cells , 2010 .

[19]  K. Kinoshita,et al.  Determination of carbon surface oxides on platinum-catalyzed carbon , 1974 .

[20]  Brian C. Benicewicz,et al.  Synthesis and Properties of Segmented Block Copolymers of Functionalised Polybenzimidazoles for High‐Temperature PEM Fuel Cells , 2011 .

[21]  Mark E Tuckerman,et al.  The mechanism of proton conduction in phosphoric acid. , 2012, Nature chemistry.

[22]  N. Kim,et al.  Poly(2,5-benzimidazole)–silica nanocomposite membranes for high temperature proton exchange membrane fuel cell , 2012 .

[23]  F. Arnold,et al.  Para‐ordered polybenzimidazole , 1976 .

[24]  Jens Oluf Jensen,et al.  Properties, degradation and high temperature fuel cell test of different types of PBI and PBI blend membranes , 2010 .

[25]  H. Zhang,et al.  Properties of Polymer Electrolyte Membranes Based on Poly(Aryl Ether Benzimidazole) and Sulphonated Poly(Aryl Ether Benzimidazole) for High Temperature PEMFCs , 2010 .

[26]  Jong‐Chan Lee,et al.  Synthesis and properties of poly(aryl ether benzimidazole) copolymers for high-temperature fuel cell membranes , 2008 .

[27]  E. Choe Catalysts for the preparation of polybenzimidazoles , 1994 .

[28]  H. Na,et al.  Silane-cross-linked polybenzimidazole with improved conductivity for high temperature proton exchange membrane fuel cells , 2013 .

[29]  Hyuk Chang,et al.  Cross-Linked Benzoxazine–Benzimidazole Copolymer Electrolyte Membranes for Fuel Cells at Elevated Temperature , 2012 .

[30]  D. Wan,et al.  Preparation and Characterisation of Proton Exchange Membranes Based on Crosslinked Polybenzimidazole and Phosphoric Acid , 2010 .

[31]  B. Benicewicz,et al.  Synthesis and Properties of Random Copolymers of Functionalised Polybenzimidazoles for High Temperature Fuel Cells , 2011 .

[32]  Hongwei Zhang,et al.  Advances in the high performance polymer electrolyte membranes for fuel cells. , 2012, Chemical Society reviews.

[33]  S. Hsu,et al.  Synthesis of novel cross-linked polybenzimidazole membranes for high temperature proton exchange membrane fuel cells , 2013 .

[34]  Brian C. Benicewicz,et al.  High-Temperature Polybenzimidazole Fuel Cell Membranes via a Sol-Gel Process , 2005 .

[35]  Werner Lehnert,et al.  Membrane electrode assemblies for high-temperature polymer electrolyte fuel cells based on poly(2,5-benzimidazole) membranes with phosphoric acid impregnation via the catalyst layers , 2009 .

[36]  E. Quartarone,et al.  Novel aryloxy-polybenzimidazoles as proton conducting membranes for high temperature PEMFCs , 2011 .

[37]  D. Wan,et al.  Synthesis and Characterization of Fluorine-Containing Polybenzimidazole for Proton Conducting Membranes in Fuel Cells , 2010 .

[38]  Waldemar Bujalski,et al.  High temperature (HT) polymer electrolyte membrane fuel cells (PEMFC) – A review , 2013 .

[39]  Frederik C. Krebs,et al.  Roll-to-roll coated PBI membranes for high temperature PEM fuel cells , 2012 .

[40]  Deborah J. Jones,et al.  Solution sulfonation of a novel polybenzimidazole: a proton electrolyte for fuel cell application , 2008 .

[41]  Agglomeration of Platinum Particles Supported on Carbon in Phosphoric Acid , 1988 .

[42]  Brian C. Benicewicz,et al.  Polybenzimidazole/Acid Complexes as High-Temperature Membranes , 2008 .

[43]  Brian C. Benicewicz,et al.  Synthesis and Characterization of Pyridine‐Based Polybenzimidazoles for High Temperature Polymer Electrolyte Membrane Fuel Cell Applications , 2005 .

[44]  Zhongfang Li,et al.  Proton-conducting membrane preparation based on SiO2-riveted phosphotungstic acid and poly (2,5-benzimidazole) via direct casting method and its durability , 2012, Journal of Materials Science.

[45]  Jie Yin,et al.  Synthesis of novel polybenzimidazoles with pendant amino groups and the formation of their crosslinked membranes for medium temperature fuel cell applications , 2009 .

[46]  P. Cañizares,et al.  Scale-up of a high temperature polymer electrolyte membrane fuel cell based on polybenzimidazole , 2011 .

[47]  Gang Zhang,et al.  Cross-linked polybenzimidazole with enhanced stability for high temperature proton exchange membrane fuel cells , 2011 .

[48]  K. Kreuer Proton Conductivity: Materials and Applications , 1996 .

[49]  Huamin Zhang,et al.  A novel H3PO4/Nafion–PBI composite membrane for enhanced durability of high temperature PEM fuel cells , 2007 .

[50]  A. Asiri,et al.  Fuel cell based on novel hyper-branched polybenzimidazole membrane , 2012, Macromolecular Research.

[51]  U. Kharul,et al.  Enhancement of gas permeation properties of polybenzimidazoles by systematic structure architecture , 2006 .

[52]  Y. Oono,et al.  Influence of the phosphoric acid-doping level in a polybenzimidazole membrane on the cell performance of high-temperature proton exchange membrane fuel cells , 2009 .

[53]  T. Jana,et al.  Polybenzimidazole/silica nanocomposites: Organic-inorganic hybrid membranes for PEM fuel cell , 2011 .

[54]  Qingfeng Li,et al.  Cross-linked polybenzimidazole membranes for high temperature proton exchange membrane fuel cells with dichloromethyl phosphinic acid as a cross-linker , 2008 .

[55]  K. Scott,et al.  A PBI‐Sb0.2Sn0.8P2O7‐H3PO4 Composite Membrane for Intermediate Temperature Fuel Cells , 2011 .

[56]  S. Hsu,et al.  Phosphoric acid-doped cross-linked porous polybenzimidazole membranes for proton exchange membrane fuel cells , 2011 .

[57]  W. Yoon,et al.  Preparation of MEA with the Polybenzimidazole Membrane for High Temperature PEM Fuel Cell , 2011 .

[58]  R. Marschall,et al.  Proton conductivity of imidazole functionalized ordered mesoporous silica: Influence of type of anchorage, chain length and humidity , 2009 .

[59]  Hsieh-Yu Li,et al.  Polyelectrolyte composite membranes of polybenzimidazole and crosslinked polybenzimidazole-polybenzoxazine electrospun nanofibers for proton exchange membrane fuel cells , 2013 .

[60]  Nam Hoon Kim,et al.  Polymer membranes for high temperature proton exchange membrane fuel cell : recent advances and challenges , 2011 .

[61]  P. Cañizares,et al.  Promising TiOSO₄ composite polybenzimidazole-based membranes for high temperature PEMFCs. , 2011, ChemSusChem.

[62]  B. Benicewicz,et al.  A new sequence isomer of AB‐polybenzimidazole for high‐temperature PEM fuel cells , 2012 .

[63]  H. Pu,et al.  Proton Conducting Membranes Based on Poly(2,2′‐imidazole‐5,5′‐bibenzimidazole) , 2012 .

[64]  K. Müllen,et al.  Functionalized poly(benzimidazole)s as membrane materials for fuel cells , 2007 .

[65]  B. Steele,et al.  Materials for fuel-cell technologies , 2001, Nature.

[66]  Unal Sen,et al.  Proton conducting membranes based on Poly(2,5-benzimidazole) (ABPBI)–Poly(vinylphosphonic acid) blends for fuel cells , 2009 .

[67]  Jong‐Chan Lee,et al.  Cross-linked poly(2,5-benzimidazole) consisting of wholly aromatic groups for high-temperature PEM f , 2011 .

[68]  D. Plackett,et al.  High-temperature proton exchange membranes based on polybenzimidazole and clay composites for fuel cells , 2011 .

[69]  Shuai-Shuai Han,et al.  Enhancing the high-temperature proton conductivity of phosphoric acid doped poly(2,5-benzimidazole) by preblending boron phosphate nanoparticles to the raw materials , 2012 .

[70]  D. Aili,et al.  Covalently cross-linked sulfone polybenzimidazole membranes with poly(vinylbenzyl chloride) for fuel cell applications. , 2013, ChemSusChem.

[71]  P. Cañizares,et al.  Titanium composite PBI-based membranes for high temperature polymer electrolyte membrane fuel cells. Effect on titanium dioxide amount , 2012 .

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

[73]  D. Aili,et al.  Thermal curing of PBI membranes for high temperature PEM fuel cells , 2012 .

[74]  Brian C. Benicewicz,et al.  Synthesis and Properties of Functionalized Polybenzimidazoles for High-Temperature PEMFCs , 2009 .

[75]  Piercarlo Mustarelli,et al.  Polymer fuel cells based on polybenzimidazole/H3PO4 , 2012 .

[76]  R. Graf,et al.  Anhydrous Poly(2,5-benzimidazole)–Poly(vinylphosphonic Acid) Acid–Base Polymer Blends: a Detailed Solid-State NMR Investigation , 2009 .

[77]  E. Quartarone,et al.  Increasing the permanent conductivity of PBI membranes for HT-PEMs , 2012 .

[78]  J. K. Gillham,et al.  Polymer Structure: Cross-Linking of a Polybenzimidazole , 1963, Science.

[79]  H. Penchev,et al.  Polybenzimidazole‐graft‐polyvinylphosphonic acid—proton conducting fuel cell membranes , 2013 .

[80]  P. Eaton,et al.  Phosphorus pentoxide-methanesulfonic acid. Convenient alternative to polyphosphoric acid , 1973 .

[81]  Robert F. Savinell,et al.  High temperature proton exchange membranes based on polybenzimidazoles for fuel cells , 2009 .

[82]  C. Tomasi,et al.  Developments of new proton conducting membranes based on different polybenzimidazole structures for fuel cells applications , 2006 .

[83]  G. Jung,et al.  Membrane electrode assemblies doped with H3PO4 for high temperature proton exchange membrane fuel cells , 2012 .

[84]  T. Murahashi,et al.  Change of Pt Distribution in the Active Components of Phosphoric Acid Fuel Cell , 1988 .