氧化石墨烯在质子交换膜中的应用研究进展
作者:施奕磊1 杨腊文1 蒋仲庆1,  贾志舰1  蒋仲杰2
单位: 1.宁波工程学院 化学工程学院 宁波 315016; 2.华南理工大学 环境与能源学院 广州 510006
关键词: 氧化石墨烯 磺酸化氧化石墨烯 质子交换膜 燃料电池 复合膜
出版年,卷(期):页码: 2015,35(5):114-121

摘要:
  氧化石墨烯(graphene oxide, GO)和磺酸化氧化石墨烯(sulfonated graphene oxide, SGO)是石墨烯的衍生材料,具有两亲性能、超高的比表面积、良好的电子绝缘性和柔韧性,使其作为掺杂材料在燃料电池、电膜分离过程、扩散渗析、电化学分析和传感等领域具有广泛的应用前景。本文主要综述了GO和SGO在质子交换膜中的应用。质子交换膜是燃料电池的重要组成部分,在燃料电池中主要起传导质子和防止燃料渗透的作用。当前商用化的燃料电池电解质膜主要存在质子导电性低、燃料渗透率高、稳定性差等问题。GO和SGO的掺入可以提高膜的质子导电性和稳定性、降低膜的燃料渗透率,因此对提高膜的性质以及燃料电池的性能具有十分重要的作用。本文主要概括了近几年来GO及SGO在质子交换膜中的应用研究进展,并系统地介绍了GO及SGO对Nafion及新型的非氟类聚合物质子交换膜材料性能的影响。
 
  Graphene oxide (GO) and sulfonated graphene oxide (SGO) are the derivatives of graphene with amphiphilic properties. They are reported to have high specific surface area, good electrical insulation and high flexibility, which make them highly attractive as the doping material of polymer membranes for various applications in fuel cells, electro-membrane separation, diffusion dialysis, electrochemical analysis and sensing, etc. This paper mainly reviews the uses of GO and SGO in proton exchange membranes (PEM), which is an indispensable component, playing a bi-functional role of conducting proton and preventing fuel permeation from the anode to the cathode in PEM fuel cell (PEMFCs). Currently, the commercialized membranes used in PEMFCs suffer from several severe problems of low proton conductivity, high fuel permeability and poor stability. The doping of GO or SGO can greatly improve proton conductivity and stability of the membranes, but decrease their fuel permeability, which are therefor of great potential to improve the properties of PEMs and thereby the performance of the corresponding PEMFCs. The present work mainly summarizes recent progress on the applications of GO and SGO in PEMs. The effects of GO and SGO on the properties of Nafion (a commercialized PEM) and some newly developed non-fluorinated PEM are systematically discussed.
 
施奕磊 ( 1991-11-10 ) , 男, 硕士生, 从事质子交换膜燃料电池的研究

参考文献:
 [1] Lim Y, Lee S, Jang H, et al. Sulfonated poly(ether sulfone) electrolytes structured with mesonaphthobifluorene graphene moiety for PEMFC[J]. Int J Hydrogen Energ, 2014, 39: 1532-1538.
[2] Mauritz K A, Moore R B. State of understanding of Nafion[J]. Chem Rev, 2004, 104: 4535-4585.
[3] Yang T. Preliminary study of SPEEK/PVA blend membranes for DMFC applications[J]. Int J Hydrogen Energ, 2008, 33: 6772-6779.
[4] Lin C K, Tsai J C. The effect of the side-chain ratio on main-chain-type and side-chain-type sulfonated poly(ether ether ketone) for direct methanol fuel cell applications[J]. J Mater Chem, 2012, 22: 9244-9252.
[5] Han M M, Zhang G, Li M Y, et al. Sulfonated poly(ether ether ketone)/polybenzimidazole oligomer/epoxy resin composite membranes in situ polymerization for direct methanol fuel cell usages[J]. J Power Sources, 2011, 196: 9916-9923.
[6] Mohtar S S, Ismail A F, Matsuura T. Preparation and characterization of SPEEK/MMT-STA composite membrane for DMFC application[J]. J Membrane Sci, 2011, 371: 10-19.
[7] Fu T, Cui Z, Zhong S, et al. Sulfonated poly(ether ether ketone)/clay-SO3H hybrid proton exchange membranes for direct methanol fuel cells[J]. J Power Sources, 2008, 185: 32-39.
[8] Si Y, Samulski E T. Synthesis of Water Soluble Graphene[J]. Nano Lett, 2008, 8: 1679-1682.
[9] Liu L-H, Lerner M M, Yan M. Derivitization of pristine graphene with well-defined chemical functionalities[J]. Nano Lett, 2010, 10: 3754-3756.
[10] Xu C X, Cao Y C, Kumar R, et al. A polybenzimidazole/sulfonated graphite oxide composite membrane for high temperature polymer electrolyte membrane fuel cells[J]. J Mater Chem, 2011, 21: 11359-11364.
[11] Chien H-C, Tsai L-D, Huang C-P, et al. Sulfonated graphene oxide/Nafion composite membranes for high-performance direct methanol fuel cells[J]. Int J Hydrogen Energ, 2013, 38: 13792-13801.
[12] Dai W, Yu L, Li Z, et al. Sulfonated Poly(Ether Ether Ketone)/Graphene composite membrane for vanadium redox flow battery[J]. Electrochim Acta, 2014, 132: 200-207.
[13] Kumar R, Mamlouk M, Scott K. Sulfonated polyether ether ketone-sulfonated graphene oxide composite membranes for polymer electrolyte fuel cells[J]. RSC Adv, 2014, 4: 617-623.
[14] Tseng C-Y, Ye Y-S, Cheng M-Y, et al. Sulfonated polyimide proton exchange membranes with graphene oxide show improved proton conductivity, methanol crossover impedance, and mechanical properties[J]. Adv Energy Mater, 2011, 1: 1220-1224.
[15] Jiang Z-J, Jiang Z, Chen W. The role of holes in improving the performance of nitrogen-doped holey graphene as an active electrode material for supercapacitor and oxygen reduction reaction[J]. J Power Sources, 2014, 251: 55-65.
[16] Jiang Z, Shi Y, Jiang Z-J, et al. High performance of a free-standing sulfonic acid functionalized holey graphene oxide paper as a proton conducting polymer electrolyte for air-breathing direct methanol fuel cells[J]. J Mater Chem A, 2014, 2: 6494-6503.
[17] Jiang Z, Jiang Z-J, Tian X, et al. Amine-functionalized holey graphene as a highly active metal-free catalyst for oxygen reduction reaction[J]. J Mater Chem A, 2014, 2: 441-450.
[18] Jiang Z-J, Jiang Z. Reduction of the oxygen reduction reaction overpotential of nitrogen-doped graphene by designing it to a microspherical hollow shape [J]. J Mater Chem A, 2014, 2: 14071-14081.
[19] Hummers W S, Offeman R E. Preparation of graphitic oxide[J]. J Am Chem Soc, 1958, 80: 1339-1339.
[20] Choi B G, Huh Y S, Park Y C, et al. Enhanced transport properties in polymer electrolyte composite membranes with graphene oxide sheets[J]. Carbon, 2012, 50: 5395-5402.
[21] Lin C W, Lu Y S. Highly ordered graphene oxide paper laminated with a Nafion membrane for direct methanol fuel cells[J]. J Power Sources, 2013, 237: 187-194.
[22] Yuan T, Pu L, Huang Q, et al. An effective methanol-blocking membrane modified with graphene oxide nanosheets for passive direct methanol fuel cells[J]. Electrochim Acta, 2014, 117: 393-397.
[23] Lee S, Choi B G, Choi D, et al. Nanoindentation of annealed Nafion/sulfonated graphene oxide nanocomposite membranes for the measurement of mechanical properties[J]. J Membrane Sci, 2014, 451: 40-45.
[24] Choi B G, Hong J, Park Y C, et al. Innovative polymer nanocomposite electrolytes: nanoscale manipulation of ion channels by functionalized graphenes[J]. ACS Nano, 2011, 5: 5167-5174.
[25] Zarrin H, Higgins D, Jun Y, et al. Functionalized graphene oxide nanocomposite membrane for low humidity and high temperature proton exchange membrane fuel cells[J]. J Phys Chem C, 2011, 115: 20774-20781.
[26] Jiang Z, Zhao X, Fu Y, et al. Composite membranes based on sulfonated poly(ether ether ketone) and SDBS-adsorbed graphene oxide for direct methanol fuel cells[J]. J Mater Chem, 2012, 22: 24862–24869.
[27] Ravikumar, Scott K. Freestanding sulfonated graphene oxide paper: a new polymer electrolyte for polymer electrolyte fuel cells[J]. Chem Commun, 2012, 48: 5584.
[28] Shirdast A, Sharif A, Abdollahi M. Prediction of proton conductivity of graphene oxide-containing polymeric membranes[J]. Int J Hydrogen Energ, 2014, 39: 1760-1768.
[29] Fu Y, Manthiram A, Guiver M D. Blend membranes based on sulfonated poly(ether ether ketone) and polysulfone bearing benzimidazole side groups for proton exchange membrane fuel cells[J]. Electrochem Commun, 2006, 8: 1386-1390.
[30] Fu Y Z, Manthiram A, Guiver M D. Acid-base blend membranes based on 2-amino-benzimidazole and sulfonated poly(ether ether ketone) for direct methanol fuel cells[J]. Electrochem Commun, 2007, 9: 905-910.
[31] Jaafar J, Ismail A F, Matsuura T, et al. Performance of SPEEK based polymer–nanoclay inorganic membrane for DMFC[J]. J Membrane Sci, 2011, 382: 202-211.
[32] Jiang Z, Zhao X, Manthiram A. Sulfonated Poly(Ether Ether Ketone) Membranes with sulfonated graphene oxide fillers for direct methanol fuel cells [J]. Int J Hydrogen Energy, 2013, 38: 5875-5884.
[33] Heo Y, Im H, Kim J. The effect of sulfonated graphene oxide on Sulfonated Poly (Ether Ether Ketone) membrane for direct methanol fuel cells[J]. J Membrane Sci, 2013, 425-426: 11-22.
[34] 徐帆, 范晨亮, 徐宏杰, 等. 聚苯并咪唑在高温质子交换膜燃料电池中的应用研究进展[J]. 化工新型材料, 2012, 40:4-6+18.
[35] He R, Li Q, Xiao G, et al. Proton conductivity of phosphoric acid doped polybenzimidazole and its composites with inorganic proton conductors[J]. J Membrane Sci, 2003, 226: 169-184.
[36] Li Q, Pan C, Jensen J O, et al. Cross-linked polybenzimidazole membranes for fuel cells[J]. Chem Mater, 2007, 19: 350-352.
[37] Xue C, Zou J, Sun Z, et al. Graphite oxide/functionalized graphene oxide and polybenzimidazole composite membranes for high temperature proton exchange membrane fuel cells[J]. Int J Hydrogen Energ, 2014, 39: 7931-7939.
[38] Xu C, Cao Y, Kumar R, et al. A polybenzimidazole/sulfonated graphite oxide composite membrane for high temperature polymer electrolyte membrane fuel cells[J]. J Mater Chem, 2011, 21: 11359-1136.
[39] Cao Y-C, Xu C, Wu X, et al. A poly (ethylene oxide)/graphene oxide electrolyte membrane for low temperature polymer fuel cells[J]. J Power Sources, 2011, 196: 8377-8382.
[40] Ye Y-S, Cheng M-Y, Xie X-L, et al. Alkali doped polyvinyl alcohol/graphene electrolyte for direct methanol alkaline fuel cells[J]. J Power Sources, 2013, 239: 424-432.
 

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