车用质子交换膜燃料电池膜电极组件综述An Review of Membrane Electrode Assemblies for Proton Exchange Membrane Fuel Cell Vehicles
金守一,盛夏,潘兴龙,赵洪辉,赵子亮
摘要(Abstract):
膜电极是质子交换膜燃料电池的核心部件,为多相物质传输和电化学反应提供场所。质子交换膜、催化剂和气体扩散层是影响膜电极性能、寿命和成本的决定性因素。梳理了质子交换膜和催化剂的种类和特性,并介绍了气体扩散层的基层和微孔层。其中,质子交换膜包括全氟磺酸膜、非氟质子交换膜和复合质子交换膜等;催化剂包括铂基催化剂和无铂催化剂;气体扩散层包括碳纤维纸、碳纤维布和多孔金属材料基层以及微孔层。目前,膜电极组件的研发和生产已经取得了很大的成果,但为了降低成本,提高膜电极性能,简化制备工艺,仍有大量技术需要突破:1)制备高强度、高稳定性、低透气性的超薄质子交换膜;2)研制高活性、高耐久性、低成本的非贵金属催化剂;3)开发机械强度高、排水性优异、厚度薄的气体扩散层。
关键词(KeyWords): 燃料电池;膜电极;质子交换膜;催化剂;气体扩散层
基金项目(Foundation):
作者(Author): 金守一,盛夏,潘兴龙,赵洪辉,赵子亮
参考文献(References):
- [1]Debe,Mark K.Electrocatalyst approaches and challenges for automotive fuel cells[J].Nature,2012,486(7401):43-51.
- [2]Li Q,Jensen J O,Savinell R F,et al.High temperature proton exchange membranes based on polybenzimidazoles for fuel cells[J].Progress in Polymer Science,2009,34(5):449-477.
- [3]Jeong G,Kim M,Han J,et al.High-performance membrane-electrode assembly with an optimal polytetrafluoroethylene content for high-temperature polymer electrolyte membrane fuel cells[J].Journal of Power Sources,2016,323:142-146.
- [4]Thomas S,Zalbowitz M.Fuel cells-green power[M].Los Alamos National Laboratory,2002
- [5]Gil M,Ji X,Li X,et al.Direct synthesis of sulfonated aromatic poly(ether ether ketone)proton exchange membranes for fuel cell applications[J].Journal of Membrane Science,2004,234(1):75-81.
- [6]Xiao L,Zhang H,Scanlon E,et al.High-temperature polybenzimidazole fuel cell membranes via a sol-gel process[J].Chemistry of Materials,2005,17(21):5328-5333.
- [7]Sannigrahi A,Arunbabu D,Jana T.Thermoreversible gelation of polybenzimidazole in phosphoric acid[J].Macromolecular Rapid Communications,2006,27(22):1962-1967.
- [8]Yang J,He R.Preparation and characterization of polybenzimidazole membranes prepared by gelation in phosphoric acid[J].Polymers for Advanced Technologies,2010,21(12):874-880.
- [9]朱晓兵.高性能多孔聚四氟乙烯增强复合质子交换膜合成及燃料电池性能研究[D].大连:中国科学院研究生院(大连化学物理研究所),2006.
- [10]James,Brian D,Kalinoski,et al.Mass Production Cost Estimation For Direct H2 PEM Fuel Cell Systesm for Automotive Applications.2010 Update[J].2008.
- [11]赵丹.燃料电池质子交换膜降解机理研究及新型质子交换膜的制备[D].大连:中国科学院大连化学物理研究所,2011.
- [12]Honma I,Takeda Y,Bae J M.Protonic Conducting Properties of Sol-Gel derived Organic/Inorganic Nanocomposites Membrane doped with Acidic Functional Molecules[J].MRS Proceedings,1999,576:257.
- [13]Dimitrios Papageorgopoulos,Bahman Habibzadeh.Opening Remarks and Workshop[R].Overview Bipolar Plate Workshop Report,2017.
- [14]Fang B,Wanjala B N,Yin J,et al.Electrocatalytic performance of Pt-based trimetallic alloy nanoparticle catalysts in proton exchange membrane fuel cells[J].International Journal of Hydrogen Energy,2012,37(5):4627-4632.
- [15]Wang K C,Huang H C,Wang C H.Synthesis of Pd@Pt 3Co/C core-shell structure as catalyst for oxygen reduction reaction in proton exchange membrane fuel cell[J].International Journal of Hydrogen Energy,2017,42(16):11771-11778.
- [16]Liang H P,Zhang H M,Hu J S,et al.Pt hollow nanospheres:facile synthesis and enhanced electrocatalysts.[J].Angewandte Chemie,2004,43(12):1540-1543.
- [17]Chen Z,Higgins D,Chen Z.Nitrogen doped carbon nanotubes and their impact on the oxygen reduction reaction in fuel cells.Carbon 48:3057[J].Carbon,2010,48(11):3057-3065.
- [18]Liu R,Wu D,Feng X,et al.Nitrogen-Doped Ordered Mesoporous Graphitic Arrays with High Electrocatalytic Activity for Oxygen Reduction[J].Angewandte Chemie International Edition,2010,49(14):2565-2569.
- [19]Maldonado S.,Stevenson K.J..Influence of Nitrogen Doping on Oxygen Reduction Electrocatalysis at Carbon Nanofiber Electrodes[J].The Journal of Physical Chemistry B,2005,109(10):4707-4716.
- [20]Yang L.J,Jiang S.J,Zhao Y.,et al.Boron-Doped Carbon Nanotubes as Metal-Free Electrocatalysts for the Oxygen Reduction Reaction[J].Angewandte Chemie International Edition,2011,50(31):7132-7135.
- [21]Yang Z,Yao Z,Li G,et al.Sulfur-Doped Graphene as an Efficient Metal-free Cathode Catalyst for Oxygen Reduction[J].ACS NANO,2012,6(1):205-211.
- [22]Charreteur F,Frédéric Jaouen,Stéphane Ruggeri,et al.Fe/N/C non-precious catalysts for PEM fuel cells:Influence of the structural parameters of pristine commercial carbon blacks on their activity for oxygen reduction[J].Electrochimica Acta,2008,53(6):2925-2938
- [23]Si Y J,Chen C G,Wei Y,et al.The synthesis and characterization of a Co-N/C composite catalyst for the oxygen reduction reaction in acidic solution[J].Chinese Science Bulletin,2011,56(11):1086-1091.
- [24]Youn D H,Bae G,Han S,et al.A highly efficient transition metal nitride-based electrocatalyst for oxygen reduction reaction:Ti N on a CNT-graphene hybrid support[J].Journal of Materials Chemistry A,2013,1(27):8007-8015.
- [25]Chen S.,Duan J.,Tang Y.,et al.Molybdenum sulfide clusters-nitrogen-doped graphene hybrid hydrogel film as an efficient three-dimensional hydrogen evolution electrocatalyst[J].Nano Energy,2015,11:11-18.
- [26]Park S,Lee J W,Popov B N.Effect of carbon loading in microporous layer on PEM fuel cell performance[J].Journal of Power Sources,2006,163(1):357-363.
- [27]周书助,尹绍峰,黄启忠,等.PVB改性酚醛树脂对PEMFC碳纸的影响[J].高科技纤维与应用,2017(2).
- [28]吕金艳,张学军,沈曾民.中间相沥青粒子对PEMFC用碳纤维纸性能的影响[J].电源技术,2006,30(10).
- [29]Zhang X J,Pei H,Shen Z M.Carbon Fiber Paper Modified with Carbon Nanotube for Proton Exchange Membrane Fuel Cell[J].Advanced Materials Research,2010,139-141:76-79.
- [30]Liao Y K,Ko T H,Liu C H.Performance of a Polymer Electrolyte Membrane Fuel Cell with Fabricated Carbon Fiber Cloth Electrode[J].Energy&Fuels,2008,22(5):3351-3354.
- [31]Hussain N,Van Steen E,Tanaka S,et al.Metal based gas diffusion layers for enhanced fuel cell performance at high current densities[J].Journal of Power Sources,2017,337:18-24.
- [32]Zhang F Y,Advani S G,Prasad A K.Performance of a metallic gas diffusion layer for PEM fuel cells[J].Journal of Power Sources,2008,176(1):293-298.
- [33]冷小辉.质子交换膜燃料电池微孔层和催化层的研究[D].天津:天津大学,2014.
- [34]Wang X L,Zhang H M,Zhang J L,et al.Micro-porous layer with composite carbon black for PEM fuel cells[J].Electrochimica Acta,2006,51(23):4909-4915.
- [35]Chun J H,Park K T,Jo D H,et al.Development of a novel hydrophobic/hydrophilic double micro porous layer for use in a cathode gas diffusion layer in PEMFC[J].International Journal of Hydrogen Energy,2011,36(14):8422-8428.
- [36]Weng F B,Hsu C Y,Su M C.Experimental study of microporous layers for PEMFC with gradient hydrophobicity under various humidity conditions[J].International Journal of Hydrogen Energy,2011,36(21):13708-13714.