Nafion® based hybrid composite membrane containing GO and dihydrogen phosphate functionalized ionic liquid for high temperature polymer electrolyte membrane fuel cell

Abstract A new hybrid composite proton exchange membrane has been synthesized from dihydrogen phosphate functionalized imidazolium ionic liquid (IL-H2PO4), graphene oxide, and Nafion 117 solution. The chemical structure and thermal stability of the dihydrogen phosphate functionalized imidazolium ionic liquid (IL-H2PO4) have been analyzed by 1H nuclear magnetic resonance (NMR) spectroscopy, Fourier transform infrared (FTIR) spectroscopy, and thermogravimetric analysis (TGA). The structural, thermal, and surface properties of synthesized membranes have been confirmed by FTIR spectroscopy, X-ray diffraction, TGA, and scanning electron microscopy. The proton exchange membranes have been characterized by their ionic conductivity and unit cell performance. The incorporation of IL-H2PO4 and graphene oxide in the Nafion membrane increases its thermal stability. The ionic conductivity of the membranes increases with temperature and amount of IL-H2PO4. The highest ionic conductivity of 0.061 Scm−1 has been achieved at 110 °C under anhydrous conditions which is 1.3 times higher than that of commercial Nafion 117. The synthesized membrane, Nafion/IL/GO, shows the best unit cell performance with a power density of 0.02 W cm−2, which is 13 times higher than that of the commercial Nafion 117 membrane at 110 °C.

[1]  Steve Greenbaum,et al.  New membranes based on ionic liquids for PEM fuel cells at elevated temperatures , 2008 .

[2]  Xiaojun Yan,et al.  Preparation and characterization of nonaqueous proton-conducting membranes with protic ionic liquids. , 2013, ACS applied materials & interfaces.

[3]  Y. Yoon,et al.  Where do poly(vinyl alcohol) based membranes stand in relation to Nafion ® for direct methanol fuel cell applications? , 2012 .

[4]  Y. Yoon,et al.  An approach of balancing the ionic conductivity and mechanical properties of PVA based nanocomposite membrane for DMFC by various crosslinking agents with ionic liquid , 2015 .

[5]  G. He,et al.  Enhanced proton conductivity of Nafion hybrid membrane under different humidities by incorporating metal-organic frameworks with high phytic acid loading. , 2014, ACS applied materials & interfaces.

[6]  Dimitrios Gournis,et al.  Graphene-based nafion nanocomposite membranes: enhanced proton transport and water retention by novel organo-functionalized graphene oxide nanosheets. , 2012, Small.

[7]  Jiujun Zhang,et al.  A review of polymer electrolyte membranes for direct methanol fuel cells , 2007 .

[8]  Miaofang Chi,et al.  Direct exfoliation of natural graphite into micrometre size few layers graphene sheets using ionic liquids. , 2010, Chemical communications.

[9]  P. Gómez‐Romero,et al.  Incorporation of benzimidazolium ionic liquid in proton exchange membranes ABPBI-H3PO4 , 2013 .

[10]  Emmanuel P. Giannelis,et al.  Nafion® nanocomposite membranes with enhanced properties at high temperature and low humidity environments , 2016 .

[11]  Y. Yoon,et al.  Hollow Sodium Nickel Fluoride Nanocubes Deposited MWCNT as An Efficient Electrocatalyst for Urea Oxidation , 2017 .

[12]  Manabu Tanaka,et al.  Phosphoric acid-doped sulfonated polyimide and polybenzimidazole blend membranes: high proton transport at wide temperatures under low humidity conditions due to new proton transport pathways , 2012 .

[13]  M. Doyle,et al.  High‐Temperature Proton Conducting Membranes Based on Perfluorinated Ionomer Membrane‐Ionic Liquid Composites , 2000 .

[14]  A. Saccà,et al.  Composites Nafion-titania membranes for Polymer Electrolyte Fuel Cell (PEFC) applications at low relative humidity levels: Chemical physical properties and electrochemical performance , 2016 .

[15]  Yuyan Shao,et al.  Proton exchange membrane fuel cell from low temperature to high temperature: Material challenges , 2007 .

[16]  Roberto F. de Souza,et al.  Ionic liquids in proton exchange membrane fuel cells: Efficient systems for energy generation , 2010 .

[17]  D. Gournis,et al.  Composite polymer electrolyte membranes based on Mg–Al layered double hydroxide (LDH) platelets for H2/air-fed fuel cells , 2015 .

[18]  Enrico Negro,et al.  Structure-relaxation interplay of a new nanostructured membrane based on tetraethylammonium trifluoromethanesulfonate ionic liquid and neutralized nafion 117 for high-temperature fuel cells. , 2010, Journal of the American Chemical Society.

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

[20]  Y. Yoon,et al.  Anode catalysts for direct methanol fuel cells in acidic media: do we have any alternative for Pt or Pt-Ru? , 2014, Chemical reviews.

[21]  B. Boonchom.  Kinetics and Thermodynamic Properties of the Thermal Decomposition of Manganese Dihydrogenphosphate Dihydrate , 2008 .

[22]  B. Lalia,et al.  Polymer electrolytes containing ionic liquids with acidic counteranion (DMRImH2PO4, R = ethyl, butyl and octyl) , 2006 .

[23]  G. He,et al.  Enhanced proton conductivity of Nafion nanohybrid membrane incorporated with phosphonic acid functionalized graphene oxide at elevated temperature and low humidity , 2016 .

[24]  S. Sasikala,et al.  Block co-polymer templated mesoporous carbon–Nafion hybrid membranes for polymer electrolyte fuel cells under reduced relative humidity , 2016 .

[25]  Yan Li,et al.  More sustainable electricity generation in hot and dry fuel cells with a novel hybrid membrane of Nafion/nano-silica/hydroxyl ionic liquid , 2016 .

[26]  Y. Yoon,et al.  Imidazolium functionalized poly(vinyl chloride-co-vinyl acetate)-based anion exchange membrane , 2016 .

[27]  Jing Zhao,et al.  Functionalized carbon nanotube via distillation precipitation polymerization and its application in nafion-based composite membranes. , 2014, ACS applied materials & interfaces.

[28]  S. Subianto,et al.  Composite polymer electrolyte containing ionic liquid and functionalized polyhedral oligomeric silsesquioxanes for anhydrous PEM applications. , 2009, ACS applied materials & interfaces.

[29]  W. Kim,et al.  Nafion/graphene oxide composite membranes for low humidifying polymer electrolyte membrane fuel cell , 2014 .

[30]  J. Lai,et al.  Nanohybrids of graphene oxide chemically-bonded with Nafion: Preparation and application for proton exchange membrane fuel cells , 2016 .

[31]  Takeshi Matsui,et al.  Graphene oxide nanosheet with high proton conductivity. , 2013, Journal of the American Chemical Society.

[32]  H. N. Yang,et al.  Preparation of Nafion/Pt-containing TiO2/graphene oxide composite membranes for self-humidifying proton exchange membrane fuel cell , 2016 .