全氟磺酸离子交换膜的制备
|
摘要
全氟磺酸酸离子交换膜(PFSIEM)是离子膜氯碱工业和质子交换膜燃料电池的核心材料，其工业化技术为挤出压延法，且仅为杜邦公司和日本Asahi等国外公司所掌握，国内用膜完全依赖进口。本工作研究了PFSIEM挤出加工技术：熔融挤出法和凝胶挤出法。所用树脂为东岳集团的全氟磺酸树脂(氟型：PFSR，氢型：PFSA)。
利用DSC和TG对PFSR的热性能进行了分析，对PFSR的熔融指数和毛细管流变性能进行了测定，结果表明：PFSR热稳定性优异，在190℃下MI值为3.3g/10min，熔体属假塑性流体、有切力变稀的流动特性。PFSR适于熔融挤出法成型，通过在一定范围内调整挤出机挤出速度和三辊上光机的牵引速度可得到厚度不同、表观平整密实的薄膜。
通过XRD分析了薄膜的结晶性，测定了PFSIEM的含水率、吸水率、溶解度、IEC值以及水化后膜的尺寸变化率，研究了工艺对PFSIEM力学性能的影响，结果表明：挤出PFSIEM具有良好的结晶度；膜的水合性、耐溶解性、IEC值受工艺影响不明显，纵向尺寸变化率小于横向；随着牵伸作用的增加，膜的横向最大拉伸强度无明显变化(17MPa)，纵向逐渐增大(达22MPa)；170℃下对膜热处理使拉伸强度有一定提高。
以GBL作增塑剂熔融挤出得到增塑型薄膜，表观较未增塑薄膜下降，结晶度有所改善，拉伸强度、水化后尺寸变化率略有变化，增塑对薄膜的水合性、耐溶解性、IEC值没有影响。
以GBL为潜溶剂配置PFSA凝胶体系，体系PH值为4，因此凝胶挤出法所用设备需具有很好的耐酸腐蚀性。凝胶法成型的薄膜的表观质量和结晶度较熔融挤出法的下降。
Perfluorosulfonated ion-exchanged membrane (PFSIEM) is the core material for alkali-chloride industry and proton-exchanged membrane fuel cell (PEMFC). The manufacture technology of PFSIEMs is extrusion-calendering, which is mastered by Dupont and Asahi, therefore domestic need has being depending on importation. In this work, we researched extrusion processing technology of PFSIEMs, including melt-extrusion and gel-extrusion. Resin used is made in Dongyue Company, one is Perfluorosulfonyl fluoride resin(PFSR), the other is perfluorosulfonic acid resin(PFSA).
DSC, TG, and capillarity rheometer were used to study the thermal stability and melt rheology of the PFSR. The results showed that PFSR has outstanding thermal stability, furthermore, the MI is 3.3g/10min at 190℃, and PFSR melt was a pseudoplastic fluid had a characteristic of shear thinning. So, PFSR is fit to melt-extrusion processing, and different thickness membranes with good appearance can be prepared by adjusting the extrusion speed and the linear speed of grazer.
XRD were used to study the crystallinity of PFSIEMs, the results showed PFSIEMs have good crystallinity. Water content, water absorption, solubility, and IEC were tested, the results showed that these parameters were little affected by art of processing. Dimension change of PFSIEMs were tested, results showed that dimension change in machine direction (MD) were less than that in transverse direction (TD). The effect on mechanical property of PFSIEMs of processing art have been studied, results showed that along with the extension increasing the max. tensile strength didn't change obviously in TD (17MPa) but increased gradually in MD(reached 22MPa). Moreover, the tension strength of PFSIEMs can be improved by hot treating at 170℃.
The PFSIEMs plasticized by GBL got inferior surface, but crystallinity is improved. Tension strength and dimension change are slightly changed after plasticizing. IEC and hydration property did not affected by plasticization.
Prepared PFSA gel system by using GBL as the latent solvent, and the PH of gel system reached 4. Thus, it is demand that all the machines and equipments used during gel-extrusion procedure with excellent acid resistance. Gel-extruded membranes have worse surface and crystallinity than melt-extruded ones.
利用DSC和TG对PFSR的热性能进行了分析，对PFSR的熔融指数和毛细管流变性能进行了测定，结果表明：PFSR热稳定性优异，在190℃下MI值为3.3g/10min，熔体属假塑性流体、有切力变稀的流动特性。PFSR适于熔融挤出法成型，通过在一定范围内调整挤出机挤出速度和三辊上光机的牵引速度可得到厚度不同、表观平整密实的薄膜。
通过XRD分析了薄膜的结晶性，测定了PFSIEM的含水率、吸水率、溶解度、IEC值以及水化后膜的尺寸变化率，研究了工艺对PFSIEM力学性能的影响，结果表明：挤出PFSIEM具有良好的结晶度；膜的水合性、耐溶解性、IEC值受工艺影响不明显，纵向尺寸变化率小于横向；随着牵伸作用的增加，膜的横向最大拉伸强度无明显变化(17MPa)，纵向逐渐增大(达22MPa)；170℃下对膜热处理使拉伸强度有一定提高。
以GBL作增塑剂熔融挤出得到增塑型薄膜，表观较未增塑薄膜下降，结晶度有所改善，拉伸强度、水化后尺寸变化率略有变化，增塑对薄膜的水合性、耐溶解性、IEC值没有影响。
以GBL为潜溶剂配置PFSA凝胶体系，体系PH值为4，因此凝胶挤出法所用设备需具有很好的耐酸腐蚀性。凝胶法成型的薄膜的表观质量和结晶度较熔融挤出法的下降。
Perfluorosulfonated ion-exchanged membrane (PFSIEM) is the core material for alkali-chloride industry and proton-exchanged membrane fuel cell (PEMFC). The manufacture technology of PFSIEMs is extrusion-calendering, which is mastered by Dupont and Asahi, therefore domestic need has being depending on importation. In this work, we researched extrusion processing technology of PFSIEMs, including melt-extrusion and gel-extrusion. Resin used is made in Dongyue Company, one is Perfluorosulfonyl fluoride resin(PFSR), the other is perfluorosulfonic acid resin(PFSA).
DSC, TG, and capillarity rheometer were used to study the thermal stability and melt rheology of the PFSR. The results showed that PFSR has outstanding thermal stability, furthermore, the MI is 3.3g/10min at 190℃, and PFSR melt was a pseudoplastic fluid had a characteristic of shear thinning. So, PFSR is fit to melt-extrusion processing, and different thickness membranes with good appearance can be prepared by adjusting the extrusion speed and the linear speed of grazer.
XRD were used to study the crystallinity of PFSIEMs, the results showed PFSIEMs have good crystallinity. Water content, water absorption, solubility, and IEC were tested, the results showed that these parameters were little affected by art of processing. Dimension change of PFSIEMs were tested, results showed that dimension change in machine direction (MD) were less than that in transverse direction (TD). The effect on mechanical property of PFSIEMs of processing art have been studied, results showed that along with the extension increasing the max. tensile strength didn't change obviously in TD (17MPa) but increased gradually in MD(reached 22MPa). Moreover, the tension strength of PFSIEMs can be improved by hot treating at 170℃.
The PFSIEMs plasticized by GBL got inferior surface, but crystallinity is improved. Tension strength and dimension change are slightly changed after plasticizing. IEC and hydration property did not affected by plasticization.
Prepared PFSA gel system by using GBL as the latent solvent, and the PH of gel system reached 4. Thus, it is demand that all the machines and equipments used during gel-extrusion procedure with excellent acid resistance. Gel-extruded membranes have worse surface and crystallinity than melt-extruded ones.
引文
[1] 安树林．膜科学技术实用教程{M]．北京：化学工业出版社，2005．5-58
[2] 徐麟．废旧全氟磺酸离子交换膜的回收和利用[D]．大连：大连交通大学，2003
[3] 任建新．膜分离技术及其应用[M]．北京：化学工业出版社，2003．8-10
[4] 刘凤岭，王贫清，曾蓉．全氟离子聚合物的特性及其应用[J]．化工新型材料，2002，30：19-22
[5] 刘凤岭．全氟离子交换膜的超选择性研究[D]．天津：天津大学，1991
[6] Ren X, Wilson M S, Gottesfeld S, et al. PEM fuel cells for transportation and stationary power generation applications [J]. International Journal of Hydrogen Energy,1997, 22(12): 1137-1144
[7] 方度，杨维驿．全氟离子交换膜制法、性能和应用[M]．北京：化学工业出版社，1993．15-28
[8] Zawodzinski T A, Neeman M, Sillerud L O, etal. Determination of water diffusion coefficients in perfluorosulfonate ionomerie membranes[J]. Phys Chem,1991,95(15): 6040
[9] 邢岳．全氟磺酸质子交换膜的研究[D]．北京：北京化工大学，2003
[10] Handlin D L, Macknight J, Thomas E L. Critical evaluation of electron microscopy of ionomers[J]. Macromolecueles,1981,14:795
[11] Shahinpoor M, Kim K J. Ionic polymer-metal composites: Ⅰ. Fundamentals [J]. Smart Mater Struct,2001,10:819
[12] Arico A S, Creti P, Antonucci P L, etal. Optimization of operating parameters of a direct methanol fuel cell and physico-chemical investigation of catalyst-electrolyte interface [J]. Electrochimica Acta,1998,43(24): 3719-3729
[13] 胡霞，何小瑜，李志永．全氟磺酸树脂的性能和应用[J]．氟化工，2004，11(4)：12-13
[14] 卢婷利，梁国正，辛文利，等．燃料电池质子交换膜的研究进展[J]．化工新型材料，2002，30(4)：9-12
[15] Grot W G. Production of a liquid composition containing a perfluorinated ion exchange (?)er, and the use of this polymer [P]. Euro Patent, EP066369B 1. 1985-05-22
[16] 程殿彬．离子膜渗漏的原因及预防[J]．中国氯碱，1993，(12)：14
[17] 程殿彬．离子膜在我国氯碱工业中的使用情况[J]．氯碱工业，1996，(2)：11
[18] 程殿彬．离子膜法制碱生产技术[M]．4．北京：化学工业出版社，2004．95-162
[19] 韩百胜．氯碱生产工艺简介[J]．氯碱工业，2001，(4)：5-9
[20] 衣宝廉．燃料电池-原理·技术·应用[M]．北京：化学工业出版社，2003．145-200
[21] Heitner W C. Recent advances in perfluorinated ionomer membranes: structure, properties and applications[J]. Journal of Membrane Science,1996,120:1-33
[22] 张华民，刑丹敏，衣宝廉．燃料电池用质子交换膜的研究开发[J]．功能材料，2004，35：1782-1787
[23] Komoroski, R A and Mauritz, K A. A sodium-23 nuclear magnetic resonance study of ionic mobility and contact ion pairing in a perfluorosulfonate ionome[J]. Am. Chem. Soc., 1978, 100:7487-7489
[24] Lee P C, Meisel D. Luminescence quenching in the cluster network of perfluorosulforate membrane[J]. Am.Chem. Soc., 1980, 102:5477-5481
[25] Hsu W Y, Girerke T D. Ion transport and clustering in Nation perfluorinated membranes[J]. Membrane Sci., 1983, 13:307-326
[26] Gierke T D, Hsu W S. The cluster-network model of ion clustering in perfluorosulfonated membranes[A]. In: Eisenberg, Yeager H L, et al. Perfluorinated ionomer Membranes[C]. Washington DC:ACS Symp. Ser., American Chemical Society, 1982,180
[27] Komoroski R A, Mauritz K A. NMR studies and the theory ion pairing in perfluorosulfonate ionomers [A]. In: Eisenberg, Yeager H L, et al. Perfluorinated ionomer Membranes[C]. Washington DC:ACS Symp. Ser., American Chemical Society, 1982, 113-138
[28] Lowry S R, Mauritz K A. An investigation of ionic hydration effects in perfluorosulfonate ionomers by FTIR spectroscopy[J]. Am.Chem.Soc., 1980,102:4665
[29] Zawodznski T A, Neeman J M., Sillerud L O, et al. Determination of water diffusion coefficient in perfluorosulfonate ionomeric membranes[J].Phys,Chem., 1991,95:6040
[30] Schlick S, Gebel G., Pined M, et al. ~(19)F NMR spectroscopy of acid Nation membranes and solutions[J]. Macromolecules, 1991,24:3517
[31] 杜世勇．全氟离子交换膜的结构模型[J]．水处理技术，1990，16(1)：47-49
[32] Ogumi Z, Nishio K, Yoshiza Wa. Application of the SPE method to organic electrochemistry-Electrochemical hydrogenation of olefin double bonds[J]. Electrochem. Acta.,1981,26:1779-1782
[33] Ogumi Z, Yamashita H, Nishio K. Application of the solid polymer electrolyte (SPE) to organic[J]. Electro chem. Acta.,1983,28:1687-1693
[34] Yasuzawa M, Kan K, Kunugi A, et al. Electro oxidation of benzyl alcohol[J]. Electro chem. Acta.,1995,40:1785-1787
[35] Jorissen J. Ion exchange electro-organic membranes as solid polymer electrolytes (SPE) in without supporting electrolytes[J]. Electro chem. Acta.,1996,41:553-562
[36] 汉默 M A，孙群．由溶胶-凝胶法得到的用于烯烃异构化的全氟化离子交换型聚合物和金属氧化物的多孔复合物微粒[P]．中国专利，1170373，1998-01-14
[37] 刘平，孙亚平．Nafion薄膜中单分散TiO_2纳米晶体的合成[J]．无机化学学报，2003，19(4)：350-354
[38] Takeo Y, Carl A K, Richard D N, et al. Transport mechanism of carbon dioxide through perfluorosulfonate ionomer membranes containing an amine carder[J]. Chem Eng Sci,1996,51(21):4781-4789
[39] Way J D, Noble R D. Competitive facilitated transport of acid gases in perfluorosulfonic acid membrane[J]. J Membr Sci,1989,46:309-324
[40] Scott S K, Dovglas W J, Chen W J, et al. The dehydration of nitric acid using pervaporation and a nation perfluorosulfonate/perfluorocarboxylate bilayer membrane[J]. J Membr Sci,2002,203:155-166
[41] Ray S K, Sawant S B, Joshi J B, et al. Dehydration of acetic acid by pervaporation[J].J Membr Sci,1998,138:1-17
[42] Samuel P, Kusumocahyo, Masao S. Dehydration of acetic acid by pervaporation with charged membrane[J]. J Membr Sci,1999,161:77-83
[43] Thomas F, Florkiewicz J S. Factors for Successful Membrane Cell Chlor-alkali Operation [M]. Arlington: Chlorine Institute Ins,1985.15-18
[44] 龙荣．杜邦膜的技术与应用[J]．氯碱工业，2000，(1)：18-20
[45] 刘忠平．简述全氟磺酸离子交换膜在氯碱工业中的应用[J]．氯碱工业，1997(12)：13
[46] 方度，蒋兰荪．氯碱生产技术上册[M]．北京：化工部化工司，1985．158-159
[47] 李邦民．根据膜的结构及作用机理论工艺控制的重要性[J]．中国氯碱，2001(12)：10-12
[48] 毛宗强．燃料电池[M]．北京：化学工业出版社，2005．2-17
[49] 衣宝廉．燃料电池—原理、技术、应用[M]．2．北京：化学工业出版社，2004．3-14
[50] 毛宗强．氢能—21世纪的绿色能源[M]．北京：化学工业出版社，2005．251
[51] Yi B L, Yu H M, Hou Z J, et al. Electrocatalysts for Proton Exchange Membrane Fuel Cells in Dalian Institute of Chemical Physics[J]. Chinese Academy of Science,2002,23(3): 1-7
[52] Han K L, Jong H P, Do Y K, et al. A study on the characteristics of the diffusion layer thickness and porosity of PEMFC[J]. Journal of Power Sources,2004,131:200
[53] Hwang J J, Wang D Y, Shin N C. Development of a lightweight fuel cell vehicle[J]. Journal of Power Source,2005,141:108-115
[54] 兰泽全，曹欣玉，周俊虎，等．质子交换膜燃料电池及其在电动车上应用的现状[J]．能源工程，2002(3)：17-20
[55] 朗万中，许振良．全氟磺酸离子膜的结构与应用研究进展[J]．膜科学与技术,2005,25(6)：69-73
[56] Silva F R, Francesco M De, Pozio A. Solution-cast Nation membranes: preparation and characterization[J].Electrochimica Acta, 2004,49:3211-3216
[57] Seko M. Cation exchange membrane and use thereof in the electrolysis of sodium chloride[P].US Patent,4178218,1979-12-11
[58] Andreola C, Chlanda F P, Huang J P. Process for producing ion exchange membranes, and the ion exchange membranes produced thereby[P]. US Patent,5643968,1997-07-01
[59] Grot W G. Laminates of support material and fluorinated polymer containing pendant side chains containing sulfonyl groups[P].US Patent,3849243,1974-11-19
[60] 张永明，张建宏，刘传奇，等．全氟离子交换溶合增强膜及其制备方法[P]．中国专利，1624202,2003-12-05
[61] Seko N, Yamakoshi Y, Miyauchi H, et al. Cation exchange membrane preparation and use thereof[P]. US Patent,4151053, 1979-4-24
[62] 沈春晖，杨新胜，潘牧，等．燃料电池用全氟磺酸型复合质子交换膜的研究[J]．化工新型材料,2002,(8)：10-12
[63] Liu F Q, Yi B L, Xing D M, et al. Nation/PTFE composite membranes for fuel cell applications[J]. Journal of Membrane Science,2003,212:213-223
[64] Yoshitake M, Tamura M, Yoshid N, et al. Studies of perfluorinated ion exchange membrane for electrolyte fuel cells[J]. Denki Kagaku,1996,64:727-736
[65] Verbrugge M W, Hill R F, Schneider E W. Composite of membranes for fuel cells applications[J]. AIChE Journal,1992,38(1):93-100
[66] Stek Alfred E, Stone Charles. Substituted a,b,b-trifluorostyrenene-based composite membranes[P]. US Patent, 5834523,1998-11-29
[67] Spethmann Jeffrey E, Keating James T. Composite ion exchange membranes containing highly crystallilne porous fluorinate polymer supports and electrochemical cell therefor[P]. PCT Patent,WO 9850457 A1.1998-11-12
[68] Bahar B, Hobson A R, Kolde J, et al. Ultra-thin integral composite membrane[P], US Patent,5547551,1996-08-20
[69] Banerjee Shoibal, Summers John Donald. Process for making composite ion exchange membranes[P].PCT Patent, WO 9851733 A1,1998-11-19
[70] Penner R M, Martin C R. Ion-transporting composite membranes, Ⅰ. Nation-impregnated Gore-Tex[J]. Electrochem. Soc.;1985,132:514
[71] Liu Chao, Martin C R. Ion-transporting composite membranes, Ⅱ. Ion transport mechanism in Nation-impregnated Gore-Tex membranes[J]. Electrochem.Soc.,1990,137(2):510
[72] Liu Chao, Martin C R. Ion-transporting composite membranes,Ⅲ.Selectivity and rate of ion transport in Nation-impregnated Gore-Tex membranes prepared by a high temperature solution -casting method[J]. Electrochem.Soc.,1990,137(10):314
[73] Karine M N, Peter S F. Nation based composite polymer electrolyte membranes[J]. Electrochemica Acta,43(16-17):2381
[74] 邬志良．全氟离子交换膜的加工技术[J]．含氟材料,1988,(1)：21-25
[75] 邬志刚．国外全氟离子交换膜的增强和复合技术[J]．有机氟工业,1991，(4)：9-11
[76] 刘富强，邢丹敏，于景荣，等．质子交换膜燃料电池Nafion ／PTFE复合膜的研究[J]．电化学,2002,8(1)：86-90
[77] Martin C R, Moore R B. Method for the preparation of ionomer films[P].US Patent,4731263,1988-03-15
[78] Gebel G, Aldebert P, Pined M. Structure and related properties of solution-cast perfluorosulfonated ionomer films [J]. Macromolecules,1987, 20:1425-1428
[79] Moore R B, Martin C R. Chemical and morphological properties of solution-cast perfluorosulfonate ionomers[J]. Macromolecules,1988, 21:1334-1338
[80] 周贵恩．聚合物X射线衍射[M]．合肥：中国科学技术大学出版社，1989：133
[81] 殷敬华，莫志深．现代高分子物理学(下)[M]．北京：科学出版社，2003(4)：622
[82] 卞晓锴，陆晓峰，施柳青．原子力显微镜及在膜科学技术研究中的应用[J]．膜科学与技术，2002，22(5)：36-40
[83] Bowen W R, Hilal N, Lovitt R W, et al. Atomic force microscope studies of membranes: Force measurement and imaging in electrolyte solutions[J]. J Membr Sci, 1997,126:77-89
[84] Bowen W R, Doneva T A. Artefacts in AFM studies of membranes: Correcting pore images using fact fourier transform filtering[J]. J Membr Sci, 2000,171:141-147
[85] Marc D, Mark E L, Mark G R, et al. Ionic conductivity of nonaqueous solvent-swollent ionomer membranes based on fluorosulfonate, fluorocarboxylate, and sulfonate fixed ion groups[J]. J.Phys.Chem.B2001,105:9392-9393
[86] Kolde J A, Bahar B, Wilson M S, et al. Advanced composite polymer electrolyte[J]. Fuel cell membrane,1995, 23:193-201
[87] 金日光，华幼卿．高分子物理[M]．2．北京：化学工业出版社，2000．45-128
[2] 徐麟．废旧全氟磺酸离子交换膜的回收和利用[D]．大连：大连交通大学，2003
[3] 任建新．膜分离技术及其应用[M]．北京：化学工业出版社，2003．8-10
[4] 刘凤岭，王贫清，曾蓉．全氟离子聚合物的特性及其应用[J]．化工新型材料，2002，30：19-22
[5] 刘凤岭．全氟离子交换膜的超选择性研究[D]．天津：天津大学，1991
[6] Ren X, Wilson M S, Gottesfeld S, et al. PEM fuel cells for transportation and stationary power generation applications [J]. International Journal of Hydrogen Energy,1997, 22(12): 1137-1144
[7] 方度，杨维驿．全氟离子交换膜制法、性能和应用[M]．北京：化学工业出版社，1993．15-28
[8] Zawodzinski T A, Neeman M, Sillerud L O, etal. Determination of water diffusion coefficients in perfluorosulfonate ionomerie membranes[J]. Phys Chem,1991,95(15): 6040
[9] 邢岳．全氟磺酸质子交换膜的研究[D]．北京：北京化工大学，2003
[10] Handlin D L, Macknight J, Thomas E L. Critical evaluation of electron microscopy of ionomers[J]. Macromolecueles,1981,14:795
[11] Shahinpoor M, Kim K J. Ionic polymer-metal composites: Ⅰ. Fundamentals [J]. Smart Mater Struct,2001,10:819
[12] Arico A S, Creti P, Antonucci P L, etal. Optimization of operating parameters of a direct methanol fuel cell and physico-chemical investigation of catalyst-electrolyte interface [J]. Electrochimica Acta,1998,43(24): 3719-3729
[13] 胡霞，何小瑜，李志永．全氟磺酸树脂的性能和应用[J]．氟化工，2004，11(4)：12-13
[14] 卢婷利，梁国正，辛文利，等．燃料电池质子交换膜的研究进展[J]．化工新型材料，2002，30(4)：9-12
[15] Grot W G. Production of a liquid composition containing a perfluorinated ion exchange (?)er, and the use of this polymer [P]. Euro Patent, EP066369B 1. 1985-05-22
[16] 程殿彬．离子膜渗漏的原因及预防[J]．中国氯碱，1993，(12)：14
[17] 程殿彬．离子膜在我国氯碱工业中的使用情况[J]．氯碱工业，1996，(2)：11
[18] 程殿彬．离子膜法制碱生产技术[M]．4．北京：化学工业出版社，2004．95-162
[19] 韩百胜．氯碱生产工艺简介[J]．氯碱工业，2001，(4)：5-9
[20] 衣宝廉．燃料电池-原理·技术·应用[M]．北京：化学工业出版社，2003．145-200
[21] Heitner W C. Recent advances in perfluorinated ionomer membranes: structure, properties and applications[J]. Journal of Membrane Science,1996,120:1-33
[22] 张华民，刑丹敏，衣宝廉．燃料电池用质子交换膜的研究开发[J]．功能材料，2004，35：1782-1787
[23] Komoroski, R A and Mauritz, K A. A sodium-23 nuclear magnetic resonance study of ionic mobility and contact ion pairing in a perfluorosulfonate ionome[J]. Am. Chem. Soc., 1978, 100:7487-7489
[24] Lee P C, Meisel D. Luminescence quenching in the cluster network of perfluorosulforate membrane[J]. Am.Chem. Soc., 1980, 102:5477-5481
[25] Hsu W Y, Girerke T D. Ion transport and clustering in Nation perfluorinated membranes[J]. Membrane Sci., 1983, 13:307-326
[26] Gierke T D, Hsu W S. The cluster-network model of ion clustering in perfluorosulfonated membranes[A]. In: Eisenberg, Yeager H L, et al. Perfluorinated ionomer Membranes[C]. Washington DC:ACS Symp. Ser., American Chemical Society, 1982,180
[27] Komoroski R A, Mauritz K A. NMR studies and the theory ion pairing in perfluorosulfonate ionomers [A]. In: Eisenberg, Yeager H L, et al. Perfluorinated ionomer Membranes[C]. Washington DC:ACS Symp. Ser., American Chemical Society, 1982, 113-138
[28] Lowry S R, Mauritz K A. An investigation of ionic hydration effects in perfluorosulfonate ionomers by FTIR spectroscopy[J]. Am.Chem.Soc., 1980,102:4665
[29] Zawodznski T A, Neeman J M., Sillerud L O, et al. Determination of water diffusion coefficient in perfluorosulfonate ionomeric membranes[J].Phys,Chem., 1991,95:6040
[30] Schlick S, Gebel G., Pined M, et al. ~(19)F NMR spectroscopy of acid Nation membranes and solutions[J]. Macromolecules, 1991,24:3517
[31] 杜世勇．全氟离子交换膜的结构模型[J]．水处理技术，1990，16(1)：47-49
[32] Ogumi Z, Nishio K, Yoshiza Wa. Application of the SPE method to organic electrochemistry-Electrochemical hydrogenation of olefin double bonds[J]. Electrochem. Acta.,1981,26:1779-1782
[33] Ogumi Z, Yamashita H, Nishio K. Application of the solid polymer electrolyte (SPE) to organic[J]. Electro chem. Acta.,1983,28:1687-1693
[34] Yasuzawa M, Kan K, Kunugi A, et al. Electro oxidation of benzyl alcohol[J]. Electro chem. Acta.,1995,40:1785-1787
[35] Jorissen J. Ion exchange electro-organic membranes as solid polymer electrolytes (SPE) in without supporting electrolytes[J]. Electro chem. Acta.,1996,41:553-562
[36] 汉默 M A，孙群．由溶胶-凝胶法得到的用于烯烃异构化的全氟化离子交换型聚合物和金属氧化物的多孔复合物微粒[P]．中国专利，1170373，1998-01-14
[37] 刘平，孙亚平．Nafion薄膜中单分散TiO_2纳米晶体的合成[J]．无机化学学报，2003，19(4)：350-354
[38] Takeo Y, Carl A K, Richard D N, et al. Transport mechanism of carbon dioxide through perfluorosulfonate ionomer membranes containing an amine carder[J]. Chem Eng Sci,1996,51(21):4781-4789
[39] Way J D, Noble R D. Competitive facilitated transport of acid gases in perfluorosulfonic acid membrane[J]. J Membr Sci,1989,46:309-324
[40] Scott S K, Dovglas W J, Chen W J, et al. The dehydration of nitric acid using pervaporation and a nation perfluorosulfonate/perfluorocarboxylate bilayer membrane[J]. J Membr Sci,2002,203:155-166
[41] Ray S K, Sawant S B, Joshi J B, et al. Dehydration of acetic acid by pervaporation[J].J Membr Sci,1998,138:1-17
[42] Samuel P, Kusumocahyo, Masao S. Dehydration of acetic acid by pervaporation with charged membrane[J]. J Membr Sci,1999,161:77-83
[43] Thomas F, Florkiewicz J S. Factors for Successful Membrane Cell Chlor-alkali Operation [M]. Arlington: Chlorine Institute Ins,1985.15-18
[44] 龙荣．杜邦膜的技术与应用[J]．氯碱工业，2000，(1)：18-20
[45] 刘忠平．简述全氟磺酸离子交换膜在氯碱工业中的应用[J]．氯碱工业，1997(12)：13
[46] 方度，蒋兰荪．氯碱生产技术上册[M]．北京：化工部化工司，1985．158-159
[47] 李邦民．根据膜的结构及作用机理论工艺控制的重要性[J]．中国氯碱，2001(12)：10-12
[48] 毛宗强．燃料电池[M]．北京：化学工业出版社，2005．2-17
[49] 衣宝廉．燃料电池—原理、技术、应用[M]．2．北京：化学工业出版社，2004．3-14
[50] 毛宗强．氢能—21世纪的绿色能源[M]．北京：化学工业出版社，2005．251
[51] Yi B L, Yu H M, Hou Z J, et al. Electrocatalysts for Proton Exchange Membrane Fuel Cells in Dalian Institute of Chemical Physics[J]. Chinese Academy of Science,2002,23(3): 1-7
[52] Han K L, Jong H P, Do Y K, et al. A study on the characteristics of the diffusion layer thickness and porosity of PEMFC[J]. Journal of Power Sources,2004,131:200
[53] Hwang J J, Wang D Y, Shin N C. Development of a lightweight fuel cell vehicle[J]. Journal of Power Source,2005,141:108-115
[54] 兰泽全，曹欣玉，周俊虎，等．质子交换膜燃料电池及其在电动车上应用的现状[J]．能源工程，2002(3)：17-20
[55] 朗万中，许振良．全氟磺酸离子膜的结构与应用研究进展[J]．膜科学与技术,2005,25(6)：69-73
[56] Silva F R, Francesco M De, Pozio A. Solution-cast Nation membranes: preparation and characterization[J].Electrochimica Acta, 2004,49:3211-3216
[57] Seko M. Cation exchange membrane and use thereof in the electrolysis of sodium chloride[P].US Patent,4178218,1979-12-11
[58] Andreola C, Chlanda F P, Huang J P. Process for producing ion exchange membranes, and the ion exchange membranes produced thereby[P]. US Patent,5643968,1997-07-01
[59] Grot W G. Laminates of support material and fluorinated polymer containing pendant side chains containing sulfonyl groups[P].US Patent,3849243,1974-11-19
[60] 张永明，张建宏，刘传奇，等．全氟离子交换溶合增强膜及其制备方法[P]．中国专利，1624202,2003-12-05
[61] Seko N, Yamakoshi Y, Miyauchi H, et al. Cation exchange membrane preparation and use thereof[P]. US Patent,4151053, 1979-4-24
[62] 沈春晖，杨新胜，潘牧，等．燃料电池用全氟磺酸型复合质子交换膜的研究[J]．化工新型材料,2002,(8)：10-12
[63] Liu F Q, Yi B L, Xing D M, et al. Nation/PTFE composite membranes for fuel cell applications[J]. Journal of Membrane Science,2003,212:213-223
[64] Yoshitake M, Tamura M, Yoshid N, et al. Studies of perfluorinated ion exchange membrane for electrolyte fuel cells[J]. Denki Kagaku,1996,64:727-736
[65] Verbrugge M W, Hill R F, Schneider E W. Composite of membranes for fuel cells applications[J]. AIChE Journal,1992,38(1):93-100
[66] Stek Alfred E, Stone Charles. Substituted a,b,b-trifluorostyrenene-based composite membranes[P]. US Patent, 5834523,1998-11-29
[67] Spethmann Jeffrey E, Keating James T. Composite ion exchange membranes containing highly crystallilne porous fluorinate polymer supports and electrochemical cell therefor[P]. PCT Patent,WO 9850457 A1.1998-11-12
[68] Bahar B, Hobson A R, Kolde J, et al. Ultra-thin integral composite membrane[P], US Patent,5547551,1996-08-20
[69] Banerjee Shoibal, Summers John Donald. Process for making composite ion exchange membranes[P].PCT Patent, WO 9851733 A1,1998-11-19
[70] Penner R M, Martin C R. Ion-transporting composite membranes, Ⅰ. Nation-impregnated Gore-Tex[J]. Electrochem. Soc.;1985,132:514
[71] Liu Chao, Martin C R. Ion-transporting composite membranes, Ⅱ. Ion transport mechanism in Nation-impregnated Gore-Tex membranes[J]. Electrochem.Soc.,1990,137(2):510
[72] Liu Chao, Martin C R. Ion-transporting composite membranes,Ⅲ.Selectivity and rate of ion transport in Nation-impregnated Gore-Tex membranes prepared by a high temperature solution -casting method[J]. Electrochem.Soc.,1990,137(10):314
[73] Karine M N, Peter S F. Nation based composite polymer electrolyte membranes[J]. Electrochemica Acta,43(16-17):2381
[74] 邬志良．全氟离子交换膜的加工技术[J]．含氟材料,1988,(1)：21-25
[75] 邬志刚．国外全氟离子交换膜的增强和复合技术[J]．有机氟工业,1991，(4)：9-11
[76] 刘富强，邢丹敏，于景荣，等．质子交换膜燃料电池Nafion ／PTFE复合膜的研究[J]．电化学,2002,8(1)：86-90
[77] Martin C R, Moore R B. Method for the preparation of ionomer films[P].US Patent,4731263,1988-03-15
[78] Gebel G, Aldebert P, Pined M. Structure and related properties of solution-cast perfluorosulfonated ionomer films [J]. Macromolecules,1987, 20:1425-1428
[79] Moore R B, Martin C R. Chemical and morphological properties of solution-cast perfluorosulfonate ionomers[J]. Macromolecules,1988, 21:1334-1338
[80] 周贵恩．聚合物X射线衍射[M]．合肥：中国科学技术大学出版社，1989：133
[81] 殷敬华，莫志深．现代高分子物理学(下)[M]．北京：科学出版社，2003(4)：622
[82] 卞晓锴，陆晓峰，施柳青．原子力显微镜及在膜科学技术研究中的应用[J]．膜科学与技术，2002，22(5)：36-40
[83] Bowen W R, Hilal N, Lovitt R W, et al. Atomic force microscope studies of membranes: Force measurement and imaging in electrolyte solutions[J]. J Membr Sci, 1997,126:77-89
[84] Bowen W R, Doneva T A. Artefacts in AFM studies of membranes: Correcting pore images using fact fourier transform filtering[J]. J Membr Sci, 2000,171:141-147
[85] Marc D, Mark E L, Mark G R, et al. Ionic conductivity of nonaqueous solvent-swollent ionomer membranes based on fluorosulfonate, fluorocarboxylate, and sulfonate fixed ion groups[J]. J.Phys.Chem.B2001,105:9392-9393
[86] Kolde J A, Bahar B, Wilson M S, et al. Advanced composite polymer electrolyte[J]. Fuel cell membrane,1995, 23:193-201
[87] 金日光，华幼卿．高分子物理[M]．2．北京：化学工业出版社，2000．45-128