面向能源和环境应用的高分子膜制备基础研究
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摘要
伴随着科技和经济的发展,环境污染、全球变暖、化石燃料日益枯竭等资源与环境问题开始阻碍了人类社会的可持续发展。在这些问题的诸多解决方案中,膜技术由于其简单高效、无污染、节能等优点引起了人们的日益关注。
本论文立足于可使用于清洁生产的双极膜电渗析技术和替代化石能源的燃料电池技术,重点研究这两个过程中的的双极膜和质子交换膜的制备。在双极膜制备方面,由于双极膜的中间界面层对双极膜性能至关重要,所以本论文分别选取AgCl-明胶、超支化聚合物等作为催化层,制备新型多层结构双极膜,并对双极膜中间界面层物质对双极膜水解离能力的影响作了深入研究:在质子交换膜制备方面,引入酸碱离子对和有机无机杂化思想,制备出可使用于直接甲醇燃料电池的高性能质子交换膜,并对其燃料电池方面的特性进行了考察。主要研究结果表明:
(1)采用氯化银/明胶修饰双极膜中间层可以有效催化水解离,提高双极膜的应用性能。单独的银离子可以通过形成氯化银有效地催化双极膜的水解离,吸附的氯化银的量对所制备的双极膜的水解离性能有较大的影响。采用单独的明胶溶液修饰双极膜中间界面层时,其催化水解离效果取决于其亲水性和空间位阻效应之间的竞争。而硝酸银和明胶的复合溶液修饰双极膜中间界面层时,具有协同催化作用,其催化效果优于同浓度下单纯硝酸银溶液或者明胶溶液处理后的情况,并且该类双极膜在应用过程中由于明胶对银离子的固定作用而表现得更加稳定。
(2)具有大量的羟基官能团的Boltorn(?)系列超支化聚酯作为双极膜中间界面层也可以有效催化水解离。超支化聚酯浓度,代数对双极膜性能均具有很大影响,亲水性和空间位阻效应共同决定了水解离催化效果。除此以外,超支化聚合物的端基官能团也是影响双极膜水解离性能的重要因素,端基官能团的亲水性越高,越促进水解离,其中分子间氢键起到关键作用。
(3)壳聚糖和磺化聚醚醚酮(SPEEK)之间可以形成酸碱离子对交联,由这两者酸碱共混制备出的复合型质子交换膜的吸水率和溶胀性相对于单纯的磺化聚醚醚酮膜来说得到了很大改善,热稳定性也很好;磺化度为71.4%的SPEEK与壳聚糖以5:1摩尔比共混制备的质子交换膜,其与燃料电池有关的一些性质甚至可以与商品化的Nafion 117相媲美。
(4)利用3-氨丙基三乙氧基硅烷和磺化聚醚醚酮可以在质子交换膜制备过程中同时引入酸碱离子对交联以及有机无机杂化,改性后得到的杂化复合膜具有较高的质子传导率,较好的阻醇性,很好的热稳定性、尺寸稳定性以及机械稳定性。
随着高效稳定的双极膜和质子交换膜的研制成功,双极膜电渗析和燃料电池技术将获得更大规模的应用,为工业的可持续发展做出更大的贡献。
Along with the deveolpmemt in technology and economy,energy and environmental problems,such as environmental pollution,global warming,and depletion of fossil fuels,have been holding back the sustainble development in human society.To cope with this situation,many solutions have been proposed.Membrane technology,due to its simplicity,high efficiency,low energy consumption,and environmental benignity,attracts increasing attention from the academia and industry.
For cleaning production and alternative energy supply,bipolar membrane electrodialysis and fuel cells are two promising membrane techniques.Accordingly, the focus of this dissertaion falls on the preparation of multi-layer bipolar membranes and proton exchange membranes for application in the two processes mentioned above.With regard to bipolar membrane fabrication,since the intermediate layer plays a crucial role in bipolar membrane performance,AgCl-glutin,hyperbranched polyester and its derivatives were chosen as catalysts,and their catalytic effect on water splitting was investigated extensively.As for proton exchange membranes,two concepts - acid-base polymer blending and organic-inorganic hybridizaton - were incorporated into membrane preparation,and a series of high-performance proton exchange membranes for direct methanol fuel cells(DMFCs) were obtained.The main experimental results are listed below.
(1) The introduction of AgCl/Glutin into bipolar membrane intermediate layer can catalyze water splitting effectively and thus makes the bipolar membrane suitable for industiral applications.When silver ions are introduced alone into the intermediate layer,they exist in the form of AgCl and act as a catalyst for water splitting.The amount of absorbed AgCl affects water splitting significantly.If glutin is introduced alone into the intermediate layer,the catalytic effect on water splitting depends on the competition between hydrophilicity and steric effect.However,when silver ions and glutin are introduced into the intermediate layer together,they can have a synergic effect and catalyze water splitting better than silver ions alone or glutin alone; moreover,the bipolar membrane's performance is more stable due the immobilizaton of silver ions by glutin.
(2) Hyperbranched Boltorn(?) polyesters possess plentiful hydroxyl end groups and also can catalyze water splitting.Both the amount of absorbed hyperbranched polyester and the generation of the polyester play an important role in bipolar memnbrane performance,which is a result of the competition between hydrophilicity and steric effect.Furthermore,the end group of hyperbranched polymer is another important factor affecting water splitting,and the hyperbranched polymer with highlier hydrophilic end groups is the better catalyst,which is due to the formation of hydrogen bonding between hyperbranchend polyester and water moleculars.
(3) A series of SPEEK/chitosan composite membrane were prepared by acid-base blending.Compared to pure SPEEK membrane,the composite membrane exhibited reduced water uptake and membrane swelling,and excellent thermal stability.The performance of the composite membrane prepared at the molar ratio of SPEEK(71.4%of sulphonation degree) to chitosan 5:1 is even comparable to commercial Nafion 117.
(4) Novel proton-conducting membranes were prepared from sulfonated poly(ether ether ketone)(SPEEK) and 3-aminopropyltriethoxysilane(APTES) by acid-base blending and organic-inorganic hybridization.These acid-base hybrid membranes exhibited high proton condunctivity,low methanol permeability,and excellent thermal,dimensional,and mechanical stabilities.
Upon successful preparation of bipolar membranes and proton exchange membranes with good and stable performance,there will be more large-scale applications for bipolar membrane electrodialysis and fuel cells,which will make more contribution to industrial sustainable development.
本论文立足于可使用于清洁生产的双极膜电渗析技术和替代化石能源的燃料电池技术,重点研究这两个过程中的的双极膜和质子交换膜的制备。在双极膜制备方面,由于双极膜的中间界面层对双极膜性能至关重要,所以本论文分别选取AgCl-明胶、超支化聚合物等作为催化层,制备新型多层结构双极膜,并对双极膜中间界面层物质对双极膜水解离能力的影响作了深入研究:在质子交换膜制备方面,引入酸碱离子对和有机无机杂化思想,制备出可使用于直接甲醇燃料电池的高性能质子交换膜,并对其燃料电池方面的特性进行了考察。主要研究结果表明:
(1)采用氯化银/明胶修饰双极膜中间层可以有效催化水解离,提高双极膜的应用性能。单独的银离子可以通过形成氯化银有效地催化双极膜的水解离,吸附的氯化银的量对所制备的双极膜的水解离性能有较大的影响。采用单独的明胶溶液修饰双极膜中间界面层时,其催化水解离效果取决于其亲水性和空间位阻效应之间的竞争。而硝酸银和明胶的复合溶液修饰双极膜中间界面层时,具有协同催化作用,其催化效果优于同浓度下单纯硝酸银溶液或者明胶溶液处理后的情况,并且该类双极膜在应用过程中由于明胶对银离子的固定作用而表现得更加稳定。
(2)具有大量的羟基官能团的Boltorn(?)系列超支化聚酯作为双极膜中间界面层也可以有效催化水解离。超支化聚酯浓度,代数对双极膜性能均具有很大影响,亲水性和空间位阻效应共同决定了水解离催化效果。除此以外,超支化聚合物的端基官能团也是影响双极膜水解离性能的重要因素,端基官能团的亲水性越高,越促进水解离,其中分子间氢键起到关键作用。
(3)壳聚糖和磺化聚醚醚酮(SPEEK)之间可以形成酸碱离子对交联,由这两者酸碱共混制备出的复合型质子交换膜的吸水率和溶胀性相对于单纯的磺化聚醚醚酮膜来说得到了很大改善,热稳定性也很好;磺化度为71.4%的SPEEK与壳聚糖以5:1摩尔比共混制备的质子交换膜,其与燃料电池有关的一些性质甚至可以与商品化的Nafion 117相媲美。
(4)利用3-氨丙基三乙氧基硅烷和磺化聚醚醚酮可以在质子交换膜制备过程中同时引入酸碱离子对交联以及有机无机杂化,改性后得到的杂化复合膜具有较高的质子传导率,较好的阻醇性,很好的热稳定性、尺寸稳定性以及机械稳定性。
随着高效稳定的双极膜和质子交换膜的研制成功,双极膜电渗析和燃料电池技术将获得更大规模的应用,为工业的可持续发展做出更大的贡献。
Along with the deveolpmemt in technology and economy,energy and environmental problems,such as environmental pollution,global warming,and depletion of fossil fuels,have been holding back the sustainble development in human society.To cope with this situation,many solutions have been proposed.Membrane technology,due to its simplicity,high efficiency,low energy consumption,and environmental benignity,attracts increasing attention from the academia and industry.
For cleaning production and alternative energy supply,bipolar membrane electrodialysis and fuel cells are two promising membrane techniques.Accordingly, the focus of this dissertaion falls on the preparation of multi-layer bipolar membranes and proton exchange membranes for application in the two processes mentioned above.With regard to bipolar membrane fabrication,since the intermediate layer plays a crucial role in bipolar membrane performance,AgCl-glutin,hyperbranched polyester and its derivatives were chosen as catalysts,and their catalytic effect on water splitting was investigated extensively.As for proton exchange membranes,two concepts - acid-base polymer blending and organic-inorganic hybridizaton - were incorporated into membrane preparation,and a series of high-performance proton exchange membranes for direct methanol fuel cells(DMFCs) were obtained.The main experimental results are listed below.
(1) The introduction of AgCl/Glutin into bipolar membrane intermediate layer can catalyze water splitting effectively and thus makes the bipolar membrane suitable for industiral applications.When silver ions are introduced alone into the intermediate layer,they exist in the form of AgCl and act as a catalyst for water splitting.The amount of absorbed AgCl affects water splitting significantly.If glutin is introduced alone into the intermediate layer,the catalytic effect on water splitting depends on the competition between hydrophilicity and steric effect.However,when silver ions and glutin are introduced into the intermediate layer together,they can have a synergic effect and catalyze water splitting better than silver ions alone or glutin alone; moreover,the bipolar membrane's performance is more stable due the immobilizaton of silver ions by glutin.
(2) Hyperbranched Boltorn(?) polyesters possess plentiful hydroxyl end groups and also can catalyze water splitting.Both the amount of absorbed hyperbranched polyester and the generation of the polyester play an important role in bipolar memnbrane performance,which is a result of the competition between hydrophilicity and steric effect.Furthermore,the end group of hyperbranched polymer is another important factor affecting water splitting,and the hyperbranched polymer with highlier hydrophilic end groups is the better catalyst,which is due to the formation of hydrogen bonding between hyperbranchend polyester and water moleculars.
(3) A series of SPEEK/chitosan composite membrane were prepared by acid-base blending.Compared to pure SPEEK membrane,the composite membrane exhibited reduced water uptake and membrane swelling,and excellent thermal stability.The performance of the composite membrane prepared at the molar ratio of SPEEK(71.4%of sulphonation degree) to chitosan 5:1 is even comparable to commercial Nafion 117.
(4) Novel proton-conducting membranes were prepared from sulfonated poly(ether ether ketone)(SPEEK) and 3-aminopropyltriethoxysilane(APTES) by acid-base blending and organic-inorganic hybridization.These acid-base hybrid membranes exhibited high proton condunctivity,low methanol permeability,and excellent thermal,dimensional,and mechanical stabilities.
Upon successful preparation of bipolar membranes and proton exchange membranes with good and stable performance,there will be more large-scale applications for bipolar membrane electrodialysis and fuel cells,which will make more contribution to industrial sustainable development.
引文
A.J.B.Kemperman.(2000)[M]Handbook on bipolar membrane technology.Twente University Press,Enschede.
Alcaraz A,Ramirez,P,Mafe,S,et al.(1996)A simple model for ac impedance spectra in bipolar membranes.[J]Journal of Physical Chemistry 100(38),15555-15561.
Alcaraz A,Ramirez P,ManzanaresJA,.et al.(2001)Conductive and capacitive properties of the bipolar membrane junction studied by AC impedance spectroscopy.[J]Journal of Physical Chemistry B 105(47),11669-11677.
Aparicio M,Duran A.(2004)Hybrid organic/inorganic sol-gel materials for proton conducting membranes.[J]Journal of Sol-Gel Science and Technology,31(1-3),103-107
Arico AS,Creti P,GiordanoN,et al..(2003)Influence of the acid-base characteristics of inorganic fillers on the high temperature performance of composite membranes in direct methanol fuel cells.[J]Solid State Ionics 161(3-4),251-265.
Asif A,Shi WF.(2003a)Synthesis and properties of UV curable waterborne hyperbranched aliphatic polyester.[J]European Polymer Journal 39(5),933-938.
Asif A,Shi WF.(2003b)Synthesis and properties of UV curable waterborne hyperbranched aliphatic polyester.[J]European Polymer Journal 39(5),933-938.
Asif,A,Shi WF,Shen,XF.et al.(2005)Physical and thermal properties of UV curable waterborne polyurethane dispersions incorporating hyperbranched aliphatic polyester of varying generation number.[J]Polymer 46(24),11066-11078.
Bakker HJ,Gilijamse JJ,Lock,AJ.(2005)Energy transfer in single hydrogen-bonded water molecules.[J]Chemphyschem 6(6),1146-1156.
Bauer B.(1992)Bipolare mehrschichtmembranen(Bipolar multilayer membranes),.DE Pat.4026154.
Choi WC,Kim JD,Woo SI.(2001)Modification of proton conducting membrane for reducing methanol crossover in a direct-methanol fuel cell.[J]Journal of Power Sources 96(2),411-414.
Dougherty RC(1998)Temperature and pressure dependence of hydrogen bond strength:A perturbation molecular orbital approach.[J]Journal of Chemical Physics 109(17),7372-7378.
Eaves JD,Loparo JJ,Fecko CJ.et al.(2005)Hydrogen bonds in liquid water are broken only fleetingly.[J]Proceedings of the National Academy of Sciences of the United States of America 102(37),13019-13022.
Chlanda FP,Lee LT,Liu KJ.(1978)Bipolar membranes and method of making same.[P]U.S.Pat.4116889.
Fu RQ,Xu TW,Cheng YY.et al.(2004)Fundamental studies on the intermediate layer of a bipolar membrane:Part Ⅲ.Effect of starburst dendrimer PAMAM on water dissociation at the interface of a bipolar membrane.[J]Journal of Membrane Science 240(1-2),141-147.
Fu RQ,Xu TW,Wang G et al.(2003a)PEG-catalytic water splitting in the interface of a bipolar membrane.[J]Journal of Colloid and Interface Science 263(2),386-390.
Fu RQ,Cheng YY,Xu TW.et al.(2006)Fundamental studies on the intermediate layer of a bipolar membrane.Part VI.Effect of the coordinated complex between starburst dendrimer PAMAM and chromium(Ⅲ)on water dissociation at the interface of a bipolar membrane.[J]Desalination 196(1-3),260-265.
Fu RQ,Julius D,Hong L.et al.(2008)PPO-based acid-base polymer blend membranes for direct methanol fuel cells.[J]Journal of Membrane Science 322(2),331-338.
Fu RQ,Xu TW,Yang WH.et al.(2003b)Preparation of a mono-sheet bipolar membrane by simultaneous irradiation grafting polymerization of acrylic acid and chloromethylstyrene.[J]Journal of Applied Polymer Science 90(2),572-576.
Fu RQ,Xu TW,Yang WH et al.(2004)Fundamental studies on the intermediate layer of a bipolar membrane-Part Ⅱ.Effect of bovine serum albumin(BSA)on water dissociation at the interface of a bipolar membrane.[J]Journal of Colloid and Interface Science 278(2),318-324.
Fu RQ,Xue YH,Xu TW.et al.(2005)Fundamental studies on the intermediate layer of a bipolar membrane-Part Ⅳ.Effect of polyvinyl alcohol(PVA)on water dissociation at the interface of a bipolar membrane.[J]Journal of Colloid and Interface Science 285(1),281-287.
Gao Y,Robertson GP,Guiver MD.et al.(2005)Proton exchange membranes based on sulfonated poly(phthalazinone ether ketone)s/aminated polymer blends.[J]Solid State Ionics 176(3-4),409-415.
Grot WG(1994)Perfluorinated Ion-Exchange Polymers and Their Use in Research and Industry.[J]Macromolecular Symposia 82,161-172.
Hanada F,Hirayama K,Ohmura N,et al.(1993)Bipolar membrane and method for its production.[P]U.S.Pat.5221455.
Herring AM.(2006)Inorganic-polymer composite membranes for proton exchange membrane fuel cells.[J]Polymer Reviews 46(3),245-296.
Hobson LJ,Ozu H,Yamaguchi M.et al.(2001)Modified Nafion 117 as an improved polymer electrolyte membrane for direct methanol fuel cells.[J]Journal of the Electrochemical Society 148(10),A1185-A1190.
Hodgdon RB(1989)Novel bipolar membranes and process of manufacture.[P]U S Patent:4851100,.
Huang CH,Xu TW.(2006)Electrodialysis with bipolar membranes for sustainable development. [J]Environmental Science & Technology 40(17),5233-5243.
Huang CH,Xu TW,Zhang YP.et al.(2007)Application of electrodialysis to the production of organic acids:State-of-the-art and recent developments.[J]Journal of Membrane Science 288(1-2),1-12.
Moussaoui RE,Hurwitz H(1998)Single-film membrane,process for obtaining it and use thereof.[P]U.S.Pat.5840192
Jang W,Sundar S,Choi,S.et al.(2006)Acid-base polyimide blends for the application as electrolyte membranes for fuel cells.[J]Journal of Membrane Science 280(1-2),321-329.
Jorissen L,Gogel V,Kerres,J..et al.(2000)New membranes for direct methanol fuel cells.[J]In 7th Meeting on Ulmer Elektrochemische Tage,pp.267-273.Ulm,Germany.
Jung DH,Cho SY,Peck DH.et al.(2002)Performance evaluation of a Nafion/silicon oxide hybrid membrane for direct methanol fuel cell.[J]Journal of Power Sources 106(1-2),173-177.
Jung HY,Cho KY,Sung KA.et al.(2006)The effect of sulfonated poly(ether ether ketone)as an electrode binder for direct methanol fuel cell(DMFC).[J]Journal of Power Sources 163(1),56-59.
Jung HY,Park JK.(2007)Blend membranes based on sulfonated poly(ether ether ketone)and poly(vinylidene fluoride)for high performance direct methanol fuel cell.[J]Electrochimica Acta 52(26),7464-7468.
Umemura K,Naganuma T,Miyake H(1995)Bipolar membrane.[P]U.S.Pat.5401408.
Kemperman A JB.(2000)[M]Handbook on bipolar membrane technology 88-95.
Kerres JA.(2001)Development of ionomer membranes for fuel cells.[J]Journal of Membrane Science 185(1),3-27.
Kerres JA.(2005)Blended and cross-linked ionomer membranes for application in membrane fuel cells.[J]Fuel Cells 5(2),230-247.
Kim YM,Choi SH,Lee HC.et al.(2004)Organic-inorganic composite membranes as addition of Si02 for high temperature-operation in polymer electrolyte membrane fuel cells(PEMFCs).[J]Electrochimica Acta 49(26),4787-4796.
Kim YM,Park KW,Choi JH.et al.(2003a)A Pd-impregnated nanocomposite Nafion membrane for use in high-concentration methanol fuel in DMFC.[J]Electrochemistry Communications 5(7),571-574.
Kim YS,Dong LM,Hickner MA,et al.(2003b)State of water in disulfonated poly(arylene ether sulfone)copolymers and a perfluorosulfonic acid copolymer(nafion)and its effect on physical and electrochemical properties.[J]Macromolecules 36(17),6281-6285.
Kreuer KD(1996)Proton Conductivity:Materials and Applications.[J]Chemistry of materials.8. 610-641.
Kreuer KD(2001)On the development of proton conducting polymer membranes for hydrogen and methanol fuel cells.[J]Journal of Membrane Science 185(1),29-39.
Lee CH,Min KA,Park HB.et al.(2007)Sulfonated poly(arylene ether sulfone)-silica nanocomposite membrane for direct methanol fuel cell(DMFC).[J]Journal of Membrane Science 303(1-2),258-266.
Li L,Wang YX.(2006)Proton conducting composite membranes from sulfonated polyethersulfone Cardo and phosphotungstic acid for fuel cell application.[J]Journal of Power Sources 162(1),541-546.
Li QF,He RH,Jensen JO..et al.(2003)Approaches and recent development of polymer electrolyte membranes for fuel cells operating above 100 degrees C.[J]Chemistry of Materials 15(26),4896-4915.
Lobato J,Canizares P,Rodrigo MA.et al.(2008)Performance of a vapor-fed polybenzimidazole(PBI)-based direct methanol fuel cell.[J]Energy & Fuels 22(5),3335-3345.
Ma ZQ,Cheng P,Zhao TS(2003)A palladium-alloy deposited Nafion membrane for direct methanol fuel cells.[J]Journal of Membrane Science 215(1-2),327-336.
Mader J,Xiao L,Schmidt TJ.et al.(2008)Polybenzimidazole/Acid Complexes as High-Temperature Membranes.[J]Fuel Cells li.216,pp.63-124.
Mahreni A,Mohamad AB,Kadhum AA.et al.(2009)Nafion/silicon oxide/phosphotungstic acid nanocomposite membrane with enhanced proton conductivity.[J]Journal of Membrane Science 327(1-2),32-40.
Mauritz KA,Moore RB.(2004)State of understanding of Nafion.[J]Chemical Reviews 104(10),4535-4585.
Mecheri B,D'Epifanio A,Traversa E,et al.(2007)Sulfonated polyether ether ketone and hydrated tin oxide proton conducting composites for direct methanol fuel cell applications.[J]In 3rd International Conference on Polymer Batteries and Fuel Cells,pp.554-560.Rome,ITALY.
Muthu L,Choudhary V,Varma IK.(2005)Sulphonated poly(ether ether ketone):Synthesis and characterisation.[J]Journal of Materials Science 40(3),629-636.
Nagarale RK,Gohil GS,Shahi VK(2006)Sulfonated poly(ether ether ketone)/polyaniline composite proton-exchange membrane.[J]Journal of Membrane Science 280(1-2),389-396.
Park JS,Krishnan P,Park SH.et al.(2008a)A study on fabrication of sulfonated poly(ether ether ketone)-based membrane-electrode assemblies for polymer electrolyte membrane fuel cells.[J]Journal of Power Sources 178(2),642-650.
Park KT,Jung UH,Choi DW.et al.(2008b)Zr02-Si02/Nafion(R)composite membrane for polymer electrolyte membrane fuel cells operation at high temperature and low humidity.[J]Journal of Power Sources 177(2),247-253.
Park YS,Yamazaki Y(2005a)Low methanol permeable and high proton-conducting Nafion/calcium phosphate composite membrane for DMFC.[J]Solid State Ionics 176(11-12),1079-1089.
Park YS,Yamazaki Y.(2005b)Novel nafion/hydroxyapatite composite membrane with high crystallinity and low methanol crossover for DMFCs.[J]Polymer Bulletin 53(3),181-192.
Pei HQ,Hong L,Lee JY(2006)Polymer electrolyte membrane based on 2-acrylamido-2-methyl propanesulfonic acid fabricated by embedded polymerization.[J]Journal of Power Sources 160(2),949-956.
Ralph CD.(1998)Temperature and pressure dependence of hydrogen bond strength:A
perturbation molecular orbital approach.[J]Journal of Chemistry Physics.109.7372-7378.AIP.
Francesco P,Mauro R(1995)Process for the manufacture of a bipolar membrane and process for the manufacture of an aqueous alkali metal hydroxide solution.[P]U.S.Pat.5380413.
Sashiwa H,Shigemasa Y,Roy R.(2000)Dissolution of chitosan in dimethyl sulfoxide by salt formation.[J]Chemistry Letters(6),596-597.
Sheldeshov NV,Zabolotskii VI,Pismenskaya ND.et al.(1986)Catalysis of Water Dissociation by the Phosphoric-Acid Groups of an Mb-3 Bipolar Membrane.Soviet[J]Electrochemistry 22(6),742-746.
Simons R.(1979)Strong electric field effects on proton transfer between membrane-bound amines and water.[J]Nature 280(5725),824-826.
Simons R.(1984)Electric field effects on proton transfer between ionizable groups and water in ion exchange membranes.[J]Electrochimica Acta 29(2),151-158.
Simons,R.(1985)Water splitting in ion exchange membranes.[J]Electrochimica Acta 30(3),275-282.
Simons R.(1986)A novel method for preparing bipolar membranes.[J]Electrochimica Acta 31(9),1175-1177.
Simons R.(1993)Preparation of a high performance bipolar membrane.[J]Journal of Membrane Science 78(1-2),13-23.
Smitha B,Sridhar S,Khan AA.(2004)Polyelectrolyte Complexes of Chitosan and Poly(acrylic acid)As Proton Exchange Membranes for Fuel Cells.[J]Macromoleculars.37.2233-2239.
Smitha B,Sridhar S,Khan AA.(2005)Solid polymer electrolyte membranes for fuel cell applications-a review.[J]Journal of Membrane Science 259(1-2),10-26.
Spendelow JS,Wieckowski A.(2004)Noble metal decoration of single crystal platinum surfaces to create well-defined bimetallic electrocatalysts.[J]Physical Chemistry Chemical Physics 6(22),5094-5118.
Thanpitcha T,Sirivat A,Jamieson AM.et al.(2006)Preparation and characterization of polyaniline/chitosan blend film.[J]Carbohydrate Polymers 64(4),560-568.
Tian H,Savadogo O.(2006)Silicotungstic Acid Nafion Composite membrane for proton-exchange membrane fuel cell operation at high temperature.[J]Journal of New Materials for Electrochemical Systems 9(1),61-71.
Tricoli V.(1998)Proton and methanol transport in poly(perfluorosulfonote)membranes containing Cs+and H+cations.[J]Journal of the Electrochemical Society 145(11),3798-3801.
Woo Y,Oh SY,Kang YS.et al.(2003)Synthesis and characterization of sulfonated polyimide membranes for direct methanol fuel cell.[J]Journal of Membrane Science 220(1-2),31-45.
Wu HL,Ma CCM,Li CH.et al.(2006)Sulfonated poly(ether ether ketone)/poly(amide imide)polymer blends for proton conducting membrane.[J]Journal of Membrane Science 280(1-2),501-508.
Xing PX,Robertson GP,Guiver MD.et al.(2004)Synthesis and characterization of sulfonated poly(ether ether ketone)for proton exchange membranes.[J]Journal of Membrane Science 229(1-2),95-106.
Xu TW,Huang CH.(2008)Electrodialysis-Based Separation Technologies:A Critical Review.[J]Aiche Journal 54(12),3147-3159.
Xu TW,Wu D,Wu L.(2008)Poly(2,6-dimethyl-l,4-phenylene oxide)(PPO)-A versatile starting polymer for proton conductive membranes(PCMs).[J]Progress in Polymer Science 33(9),894-915.
Xue S,Yin GP(2006)Methanol permeability in sulfonated poly(etheretherketone)membranes:A comparison with Nafion membranes.[J]European Polymer Journal 42(4),776-785.
Xue YH,Xu TW,Fu RQ.et al.(2007)Catalytic water dissociation using hyperbranched aliphatic polyester(Boltorn?series)as the interface of a bipolar membrane.[J]Journal of Colloid and Interface Science 316(2),604-611.
Yamaguchi T,Miyata F,Nakao S.(2003)Pore-filling type polymer electrolyte membranes for a direct methanol fuel cell.[J]Journal of Membrane Science 214(2),283-292.
Yoon SR,Hwang GH,Cho WI.et al.(2001)Modification of polymer electrolyte membranes for DMFCs using Pd films formed by sputtering.[J]In 7th Grov Fuel Cell Symposium,pp.215-223.London,England.
Zagar E,Huskic M,Zigon M.(2006)Structure-to-properties relationship of aliphatic hyperbranched polyesters.[J]In Symposium on Polymer Architecture - From Structure to Functional Control held at the 1st European Chemistry Congress,pp.1379-1387.Budapest,HUNGARY.
Zhang HQ,Li XF,Zhao CJ.et al.(2008) Composite membranes based on highly sulfonated PEEK and PBI:Morphology characteristics and performance.[J]Journal of Membrane Science 308(1-2),66-74.
Zhang SL,Xu TW,Wu CM.(2006) Synthesis and characterizations of novel,positively charged hybrid membranes from poly(2,6-dimethyl-1,4-phenylene oxide).[J]Journal of Membrane Science 269(1-2),142-151.
Zhang ST,Fu RW,Wu DC.et al.(2004) Preparation and characterization of antibacterial silver-dispersed activated carbon aerogels.[J]Carbon 42(15),3209-3216.
Zou JH,Shi WF,Wang J.et al.(2005) Encapsulation and controlled release ofa hydrophobic drug using a novel nanoparticle-forming hyperbranched polyester.[J]Macromolecular Bioscience 5(7),662-668.
傅荣强(2005)[D]多层结构双极膜催化层的筛选及催化水解离机理的研究.博士学位论文,6-14.
衣宝廉(2000)[M]燃料电池-高效环境友好的发电方式,1-99.
衣宝廉(2003a)[M]燃料电池--原理.技术.应用.5-15.
衣宝廉(2003b)[M]燃料电池--原理.技术.应用.336-382.
傅献彩,沈文霞,姚天扬(2004)[M]物理化学(下册).918-934.
柳茉娥,陈欢林,柴红(2001)[M]膜分离技术应用手册,1-480.
徐铜文(2003a)[M]膜化学与技术教程,213-216.
徐铜文,傅荣强,杨伟华(2003b)食品工业中的双极膜技术.[J]膜科学与技术23(4),80-87.
徐铜文,何炳林(2000)双极膜-新的工业革命.[J]世界科技研究与发展22(3),19-27.
傅荣强,徐.,杨伟华(2003)双极膜的制各技术进展.[J]水处理技术29(2)。67-69.
褚良银,陈文梅(2003)膜技术与可持续发展.[J]膜科学与技术23(6),49-53.
时钧,袁权,高从增.(2001)[M]膜技术手册,247-766.
汪国雄,孙公权,辛勤,衣宝廉.(2004)直接甲醇燃料电池.[J]物理学与新能源材料专题33(3),165-169.
许振良.(2001)[M]膜法水处理技术.1-325.
Alcaraz A,Ramirez,P,Mafe,S,et al.(1996)A simple model for ac impedance spectra in bipolar membranes.[J]Journal of Physical Chemistry 100(38),15555-15561.
Alcaraz A,Ramirez P,ManzanaresJA,.et al.(2001)Conductive and capacitive properties of the bipolar membrane junction studied by AC impedance spectroscopy.[J]Journal of Physical Chemistry B 105(47),11669-11677.
Aparicio M,Duran A.(2004)Hybrid organic/inorganic sol-gel materials for proton conducting membranes.[J]Journal of Sol-Gel Science and Technology,31(1-3),103-107
Arico AS,Creti P,GiordanoN,et al..(2003)Influence of the acid-base characteristics of inorganic fillers on the high temperature performance of composite membranes in direct methanol fuel cells.[J]Solid State Ionics 161(3-4),251-265.
Asif A,Shi WF.(2003a)Synthesis and properties of UV curable waterborne hyperbranched aliphatic polyester.[J]European Polymer Journal 39(5),933-938.
Asif A,Shi WF.(2003b)Synthesis and properties of UV curable waterborne hyperbranched aliphatic polyester.[J]European Polymer Journal 39(5),933-938.
Asif,A,Shi WF,Shen,XF.et al.(2005)Physical and thermal properties of UV curable waterborne polyurethane dispersions incorporating hyperbranched aliphatic polyester of varying generation number.[J]Polymer 46(24),11066-11078.
Bakker HJ,Gilijamse JJ,Lock,AJ.(2005)Energy transfer in single hydrogen-bonded water molecules.[J]Chemphyschem 6(6),1146-1156.
Bauer B.(1992)Bipolare mehrschichtmembranen(Bipolar multilayer membranes),.DE Pat.4026154.
Choi WC,Kim JD,Woo SI.(2001)Modification of proton conducting membrane for reducing methanol crossover in a direct-methanol fuel cell.[J]Journal of Power Sources 96(2),411-414.
Dougherty RC(1998)Temperature and pressure dependence of hydrogen bond strength:A perturbation molecular orbital approach.[J]Journal of Chemical Physics 109(17),7372-7378.
Eaves JD,Loparo JJ,Fecko CJ.et al.(2005)Hydrogen bonds in liquid water are broken only fleetingly.[J]Proceedings of the National Academy of Sciences of the United States of America 102(37),13019-13022.
Chlanda FP,Lee LT,Liu KJ.(1978)Bipolar membranes and method of making same.[P]U.S.Pat.4116889.
Fu RQ,Xu TW,Cheng YY.et al.(2004)Fundamental studies on the intermediate layer of a bipolar membrane:Part Ⅲ.Effect of starburst dendrimer PAMAM on water dissociation at the interface of a bipolar membrane.[J]Journal of Membrane Science 240(1-2),141-147.
Fu RQ,Xu TW,Wang G et al.(2003a)PEG-catalytic water splitting in the interface of a bipolar membrane.[J]Journal of Colloid and Interface Science 263(2),386-390.
Fu RQ,Cheng YY,Xu TW.et al.(2006)Fundamental studies on the intermediate layer of a bipolar membrane.Part VI.Effect of the coordinated complex between starburst dendrimer PAMAM and chromium(Ⅲ)on water dissociation at the interface of a bipolar membrane.[J]Desalination 196(1-3),260-265.
Fu RQ,Julius D,Hong L.et al.(2008)PPO-based acid-base polymer blend membranes for direct methanol fuel cells.[J]Journal of Membrane Science 322(2),331-338.
Fu RQ,Xu TW,Yang WH.et al.(2003b)Preparation of a mono-sheet bipolar membrane by simultaneous irradiation grafting polymerization of acrylic acid and chloromethylstyrene.[J]Journal of Applied Polymer Science 90(2),572-576.
Fu RQ,Xu TW,Yang WH et al.(2004)Fundamental studies on the intermediate layer of a bipolar membrane-Part Ⅱ.Effect of bovine serum albumin(BSA)on water dissociation at the interface of a bipolar membrane.[J]Journal of Colloid and Interface Science 278(2),318-324.
Fu RQ,Xue YH,Xu TW.et al.(2005)Fundamental studies on the intermediate layer of a bipolar membrane-Part Ⅳ.Effect of polyvinyl alcohol(PVA)on water dissociation at the interface of a bipolar membrane.[J]Journal of Colloid and Interface Science 285(1),281-287.
Gao Y,Robertson GP,Guiver MD.et al.(2005)Proton exchange membranes based on sulfonated poly(phthalazinone ether ketone)s/aminated polymer blends.[J]Solid State Ionics 176(3-4),409-415.
Grot WG(1994)Perfluorinated Ion-Exchange Polymers and Their Use in Research and Industry.[J]Macromolecular Symposia 82,161-172.
Hanada F,Hirayama K,Ohmura N,et al.(1993)Bipolar membrane and method for its production.[P]U.S.Pat.5221455.
Herring AM.(2006)Inorganic-polymer composite membranes for proton exchange membrane fuel cells.[J]Polymer Reviews 46(3),245-296.
Hobson LJ,Ozu H,Yamaguchi M.et al.(2001)Modified Nafion 117 as an improved polymer electrolyte membrane for direct methanol fuel cells.[J]Journal of the Electrochemical Society 148(10),A1185-A1190.
Hodgdon RB(1989)Novel bipolar membranes and process of manufacture.[P]U S Patent:4851100,.
Huang CH,Xu TW.(2006)Electrodialysis with bipolar membranes for sustainable development. [J]Environmental Science & Technology 40(17),5233-5243.
Huang CH,Xu TW,Zhang YP.et al.(2007)Application of electrodialysis to the production of organic acids:State-of-the-art and recent developments.[J]Journal of Membrane Science 288(1-2),1-12.
Moussaoui RE,Hurwitz H(1998)Single-film membrane,process for obtaining it and use thereof.[P]U.S.Pat.5840192
Jang W,Sundar S,Choi,S.et al.(2006)Acid-base polyimide blends for the application as electrolyte membranes for fuel cells.[J]Journal of Membrane Science 280(1-2),321-329.
Jorissen L,Gogel V,Kerres,J..et al.(2000)New membranes for direct methanol fuel cells.[J]In 7th Meeting on Ulmer Elektrochemische Tage,pp.267-273.Ulm,Germany.
Jung DH,Cho SY,Peck DH.et al.(2002)Performance evaluation of a Nafion/silicon oxide hybrid membrane for direct methanol fuel cell.[J]Journal of Power Sources 106(1-2),173-177.
Jung HY,Cho KY,Sung KA.et al.(2006)The effect of sulfonated poly(ether ether ketone)as an electrode binder for direct methanol fuel cell(DMFC).[J]Journal of Power Sources 163(1),56-59.
Jung HY,Park JK.(2007)Blend membranes based on sulfonated poly(ether ether ketone)and poly(vinylidene fluoride)for high performance direct methanol fuel cell.[J]Electrochimica Acta 52(26),7464-7468.
Umemura K,Naganuma T,Miyake H(1995)Bipolar membrane.[P]U.S.Pat.5401408.
Kemperman A JB.(2000)[M]Handbook on bipolar membrane technology 88-95.
Kerres JA.(2001)Development of ionomer membranes for fuel cells.[J]Journal of Membrane Science 185(1),3-27.
Kerres JA.(2005)Blended and cross-linked ionomer membranes for application in membrane fuel cells.[J]Fuel Cells 5(2),230-247.
Kim YM,Choi SH,Lee HC.et al.(2004)Organic-inorganic composite membranes as addition of Si02 for high temperature-operation in polymer electrolyte membrane fuel cells(PEMFCs).[J]Electrochimica Acta 49(26),4787-4796.
Kim YM,Park KW,Choi JH.et al.(2003a)A Pd-impregnated nanocomposite Nafion membrane for use in high-concentration methanol fuel in DMFC.[J]Electrochemistry Communications 5(7),571-574.
Kim YS,Dong LM,Hickner MA,et al.(2003b)State of water in disulfonated poly(arylene ether sulfone)copolymers and a perfluorosulfonic acid copolymer(nafion)and its effect on physical and electrochemical properties.[J]Macromolecules 36(17),6281-6285.
Kreuer KD(1996)Proton Conductivity:Materials and Applications.[J]Chemistry of materials.8. 610-641.
Kreuer KD(2001)On the development of proton conducting polymer membranes for hydrogen and methanol fuel cells.[J]Journal of Membrane Science 185(1),29-39.
Lee CH,Min KA,Park HB.et al.(2007)Sulfonated poly(arylene ether sulfone)-silica nanocomposite membrane for direct methanol fuel cell(DMFC).[J]Journal of Membrane Science 303(1-2),258-266.
Li L,Wang YX.(2006)Proton conducting composite membranes from sulfonated polyethersulfone Cardo and phosphotungstic acid for fuel cell application.[J]Journal of Power Sources 162(1),541-546.
Li QF,He RH,Jensen JO..et al.(2003)Approaches and recent development of polymer electrolyte membranes for fuel cells operating above 100 degrees C.[J]Chemistry of Materials 15(26),4896-4915.
Lobato J,Canizares P,Rodrigo MA.et al.(2008)Performance of a vapor-fed polybenzimidazole(PBI)-based direct methanol fuel cell.[J]Energy & Fuels 22(5),3335-3345.
Ma ZQ,Cheng P,Zhao TS(2003)A palladium-alloy deposited Nafion membrane for direct methanol fuel cells.[J]Journal of Membrane Science 215(1-2),327-336.
Mader J,Xiao L,Schmidt TJ.et al.(2008)Polybenzimidazole/Acid Complexes as High-Temperature Membranes.[J]Fuel Cells li.216,pp.63-124.
Mahreni A,Mohamad AB,Kadhum AA.et al.(2009)Nafion/silicon oxide/phosphotungstic acid nanocomposite membrane with enhanced proton conductivity.[J]Journal of Membrane Science 327(1-2),32-40.
Mauritz KA,Moore RB.(2004)State of understanding of Nafion.[J]Chemical Reviews 104(10),4535-4585.
Mecheri B,D'Epifanio A,Traversa E,et al.(2007)Sulfonated polyether ether ketone and hydrated tin oxide proton conducting composites for direct methanol fuel cell applications.[J]In 3rd International Conference on Polymer Batteries and Fuel Cells,pp.554-560.Rome,ITALY.
Muthu L,Choudhary V,Varma IK.(2005)Sulphonated poly(ether ether ketone):Synthesis and characterisation.[J]Journal of Materials Science 40(3),629-636.
Nagarale RK,Gohil GS,Shahi VK(2006)Sulfonated poly(ether ether ketone)/polyaniline composite proton-exchange membrane.[J]Journal of Membrane Science 280(1-2),389-396.
Park JS,Krishnan P,Park SH.et al.(2008a)A study on fabrication of sulfonated poly(ether ether ketone)-based membrane-electrode assemblies for polymer electrolyte membrane fuel cells.[J]Journal of Power Sources 178(2),642-650.
Park KT,Jung UH,Choi DW.et al.(2008b)Zr02-Si02/Nafion(R)composite membrane for polymer electrolyte membrane fuel cells operation at high temperature and low humidity.[J]Journal of Power Sources 177(2),247-253.
Park YS,Yamazaki Y(2005a)Low methanol permeable and high proton-conducting Nafion/calcium phosphate composite membrane for DMFC.[J]Solid State Ionics 176(11-12),1079-1089.
Park YS,Yamazaki Y.(2005b)Novel nafion/hydroxyapatite composite membrane with high crystallinity and low methanol crossover for DMFCs.[J]Polymer Bulletin 53(3),181-192.
Pei HQ,Hong L,Lee JY(2006)Polymer electrolyte membrane based on 2-acrylamido-2-methyl propanesulfonic acid fabricated by embedded polymerization.[J]Journal of Power Sources 160(2),949-956.
Ralph CD.(1998)Temperature and pressure dependence of hydrogen bond strength:A
perturbation molecular orbital approach.[J]Journal of Chemistry Physics.109.7372-7378.AIP.
Francesco P,Mauro R(1995)Process for the manufacture of a bipolar membrane and process for the manufacture of an aqueous alkali metal hydroxide solution.[P]U.S.Pat.5380413.
Sashiwa H,Shigemasa Y,Roy R.(2000)Dissolution of chitosan in dimethyl sulfoxide by salt formation.[J]Chemistry Letters(6),596-597.
Sheldeshov NV,Zabolotskii VI,Pismenskaya ND.et al.(1986)Catalysis of Water Dissociation by the Phosphoric-Acid Groups of an Mb-3 Bipolar Membrane.Soviet[J]Electrochemistry 22(6),742-746.
Simons R.(1979)Strong electric field effects on proton transfer between membrane-bound amines and water.[J]Nature 280(5725),824-826.
Simons R.(1984)Electric field effects on proton transfer between ionizable groups and water in ion exchange membranes.[J]Electrochimica Acta 29(2),151-158.
Simons,R.(1985)Water splitting in ion exchange membranes.[J]Electrochimica Acta 30(3),275-282.
Simons R.(1986)A novel method for preparing bipolar membranes.[J]Electrochimica Acta 31(9),1175-1177.
Simons R.(1993)Preparation of a high performance bipolar membrane.[J]Journal of Membrane Science 78(1-2),13-23.
Smitha B,Sridhar S,Khan AA.(2004)Polyelectrolyte Complexes of Chitosan and Poly(acrylic acid)As Proton Exchange Membranes for Fuel Cells.[J]Macromoleculars.37.2233-2239.
Smitha B,Sridhar S,Khan AA.(2005)Solid polymer electrolyte membranes for fuel cell applications-a review.[J]Journal of Membrane Science 259(1-2),10-26.
Spendelow JS,Wieckowski A.(2004)Noble metal decoration of single crystal platinum surfaces to create well-defined bimetallic electrocatalysts.[J]Physical Chemistry Chemical Physics 6(22),5094-5118.
Thanpitcha T,Sirivat A,Jamieson AM.et al.(2006)Preparation and characterization of polyaniline/chitosan blend film.[J]Carbohydrate Polymers 64(4),560-568.
Tian H,Savadogo O.(2006)Silicotungstic Acid Nafion Composite membrane for proton-exchange membrane fuel cell operation at high temperature.[J]Journal of New Materials for Electrochemical Systems 9(1),61-71.
Tricoli V.(1998)Proton and methanol transport in poly(perfluorosulfonote)membranes containing Cs+and H+cations.[J]Journal of the Electrochemical Society 145(11),3798-3801.
Woo Y,Oh SY,Kang YS.et al.(2003)Synthesis and characterization of sulfonated polyimide membranes for direct methanol fuel cell.[J]Journal of Membrane Science 220(1-2),31-45.
Wu HL,Ma CCM,Li CH.et al.(2006)Sulfonated poly(ether ether ketone)/poly(amide imide)polymer blends for proton conducting membrane.[J]Journal of Membrane Science 280(1-2),501-508.
Xing PX,Robertson GP,Guiver MD.et al.(2004)Synthesis and characterization of sulfonated poly(ether ether ketone)for proton exchange membranes.[J]Journal of Membrane Science 229(1-2),95-106.
Xu TW,Huang CH.(2008)Electrodialysis-Based Separation Technologies:A Critical Review.[J]Aiche Journal 54(12),3147-3159.
Xu TW,Wu D,Wu L.(2008)Poly(2,6-dimethyl-l,4-phenylene oxide)(PPO)-A versatile starting polymer for proton conductive membranes(PCMs).[J]Progress in Polymer Science 33(9),894-915.
Xue S,Yin GP(2006)Methanol permeability in sulfonated poly(etheretherketone)membranes:A comparison with Nafion membranes.[J]European Polymer Journal 42(4),776-785.
Xue YH,Xu TW,Fu RQ.et al.(2007)Catalytic water dissociation using hyperbranched aliphatic polyester(Boltorn?series)as the interface of a bipolar membrane.[J]Journal of Colloid and Interface Science 316(2),604-611.
Yamaguchi T,Miyata F,Nakao S.(2003)Pore-filling type polymer electrolyte membranes for a direct methanol fuel cell.[J]Journal of Membrane Science 214(2),283-292.
Yoon SR,Hwang GH,Cho WI.et al.(2001)Modification of polymer electrolyte membranes for DMFCs using Pd films formed by sputtering.[J]In 7th Grov Fuel Cell Symposium,pp.215-223.London,England.
Zagar E,Huskic M,Zigon M.(2006)Structure-to-properties relationship of aliphatic hyperbranched polyesters.[J]In Symposium on Polymer Architecture - From Structure to Functional Control held at the 1st European Chemistry Congress,pp.1379-1387.Budapest,HUNGARY.
Zhang HQ,Li XF,Zhao CJ.et al.(2008) Composite membranes based on highly sulfonated PEEK and PBI:Morphology characteristics and performance.[J]Journal of Membrane Science 308(1-2),66-74.
Zhang SL,Xu TW,Wu CM.(2006) Synthesis and characterizations of novel,positively charged hybrid membranes from poly(2,6-dimethyl-1,4-phenylene oxide).[J]Journal of Membrane Science 269(1-2),142-151.
Zhang ST,Fu RW,Wu DC.et al.(2004) Preparation and characterization of antibacterial silver-dispersed activated carbon aerogels.[J]Carbon 42(15),3209-3216.
Zou JH,Shi WF,Wang J.et al.(2005) Encapsulation and controlled release ofa hydrophobic drug using a novel nanoparticle-forming hyperbranched polyester.[J]Macromolecular Bioscience 5(7),662-668.
傅荣强(2005)[D]多层结构双极膜催化层的筛选及催化水解离机理的研究.博士学位论文,6-14.
衣宝廉(2000)[M]燃料电池-高效环境友好的发电方式,1-99.
衣宝廉(2003a)[M]燃料电池--原理.技术.应用.5-15.
衣宝廉(2003b)[M]燃料电池--原理.技术.应用.336-382.
傅献彩,沈文霞,姚天扬(2004)[M]物理化学(下册).918-934.
柳茉娥,陈欢林,柴红(2001)[M]膜分离技术应用手册,1-480.
徐铜文(2003a)[M]膜化学与技术教程,213-216.
徐铜文,傅荣强,杨伟华(2003b)食品工业中的双极膜技术.[J]膜科学与技术23(4),80-87.
徐铜文,何炳林(2000)双极膜-新的工业革命.[J]世界科技研究与发展22(3),19-27.
傅荣强,徐.,杨伟华(2003)双极膜的制各技术进展.[J]水处理技术29(2)。67-69.
褚良银,陈文梅(2003)膜技术与可持续发展.[J]膜科学与技术23(6),49-53.
时钧,袁权,高从增.(2001)[M]膜技术手册,247-766.
汪国雄,孙公权,辛勤,衣宝廉.(2004)直接甲醇燃料电池.[J]物理学与新能源材料专题33(3),165-169.
许振良.(2001)[M]膜法水处理技术.1-325.