磺化杂萘联苯聚芳醚酮酮质子交换膜的研究
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摘要
本论文是以磺化聚芳醚酮在质子交换膜燃料电池中的应用为研究背景,从分子设计角度合成了几种不同结构的磺化杂萘联苯聚芳醚酮酮(SPPEKKs),并对其相关性能进行了研究,希望能够得到一种新的性能较好的质子交换膜材料。
采用发烟硫酸作为磺化试剂,通过亲电取代反应,分别在1,4-二(4-氯代苯甲酰基)苯(BCBB)和1,4-二(4-氟代苯甲酰基)苯(BFBB)上引入磺酸钠基团,成功合成了1,4-二(3-磺酸钠基-4-氯代苯甲酰基)苯(SBCBB)和1,4-二(3-磺酸钠基-4-氟代苯甲酰基)苯(SBFBB)两种磺化单体,利用FT-IR和~1H-NMR对磺化单体进行了结构表征。
通过亲核缩聚反应,调节SBCBB(SBFBB)与BFBB(BCBB)的比例与4-(4-羟基苯基)-2,3-二氮杂萘-1-酮(DHPZ)聚合,合成了不同磺化度的磺化聚芳醚酮酮(SPPEKK、SPPEKK-F);不同比例的SBFBB和BFBB与含二甲基双酚单体(DMDHPZ)进行聚合,得到了不同磺化度的高分子量含二甲基磺化杂萘联苯聚醚酮酮(SPPEKK-D);不同比例的SBFBB和DFBN与DMDHPZ进行聚合,得到了不同磺化度的高分子量磺化杂萘联苯聚醚腈酮酮(SPPENKK)。利用FT-IR和~1H-NMR对所合成的磺化杂萘联苯聚芳醚酮酮结构进行了表征。磺化杂萘联苯聚芳醚酮酮都溶于NMP、DMSO和DMAC等极性非质子性溶剂。
利用溶液浇铸法制备了磺化聚芳醚酮酮膜。所制备的磺化聚芳醚酮酮都具有好的机械性能,拉伸强度在46Mpa以上,杨氏模量在1.5Gpa以上。测试了膜的吸水率、溶胀率、耐氧化性、离子交换容量和质子传导率等性能。吸水率、溶胀率和质子传导率随温度和磺化度的增加而增加。耐氧化性随磺化度的增加而降低。
对不同结构磺化杂萘联苯聚芳醚酮酮的性能进行了比较。所制备磺化聚芳醚酮酮均具有良好的热稳定性,5%的热失重温度分别在448℃(盐型)和331℃(酸型)以上;由于甲基取代了酚氧原子邻位的活泼氢原子,SPPEKK-D具有最好的氧化稳定性。利用TEM对SPPEKKs膜的微观形态进行分析,同磺化度的SPPENKK由于氰基的引入,膜中的离子簇密度和尺寸变大,亲水相分布更为连续,表现出更好的相分离结构,具有更高的吸水率、离子交换容量和质子传导率。所有聚合物膜在磺化度大于0.8、温度高于80℃时,具有较高的质子传导率(＞10~(-2)S/cm),达到了质子交换膜燃料电池的使用要求。
In this thesis,several kinds of sulfonated poly(phthalazinone ether ketone ketone)s (SPPEKKs)have been synthesized based on the molecular design principle under the background of the application of sulfonated poly(arylene ether keton)s in proton exchange membrane fuel cells(PEMFC).Correlative performances of all polymers are studied in order to find a novel membrane material with good properties in PEMFC application.
Two sulfonated monomers 1,4-bis(3-sodium sulfonate-4-chlorobenzoyl)bezene(SBCBB) and 1,4-bis(3-sodium sulfonate-4-fluorobenzoyl)bezene(SBFBB)are successfully prepared by sulfonation of 1,4-bis(4-chlorobenzoyl)benzene(BCBB)and 1,4-bis(4-fluorobenzoyl) benzene(BFBB)respectively with fuming sulfuric acid via aromatic electrophilic substitution reaction.FT-IR and ~1H-NMR are used to characterize the structures of sulfonated monomers'.
Novel sulfonated poly(phthalazinone ether ketone ketone)(SPPEKK)with different sulfonation degree(SD)are synthesized via direct nucleophilic polycondensation from SBCBB(SBFBB),BFBB(BCBB)and 4-(4-hydroxyphenyl)-2,3-phthalazin-1-one(DHPZ); sulfonated poly(phthalazinone ether ketone ketone)(SPPEKK-D)containing dimethyl groups with different sulfonation degree and high molecular weight are prepared by direct aromatic nucleophilic polycondensation of SBFBB,BFBB and 4-(3,5-dimethyl-4-hydroxyphenyl)-2,3-phthalazin-1-one(DMDHPZ);sulfonated poly(phthalazinone ether nitrile ketone ketone) (SPPENKK)containing dimethyl groups with different sulfonation degree and high molecular weight are obtained by direct nucleophilic polycondensation of SBFBB,2,6-difluoro benzonitrile(DFBN)and DMDHPZ.Polymers' structures are characterized by FT-IR and ~1H-NMR.All polymers have good solubility in polar aprotic solvent such as NMP,DMAC and DMSO.
Sulfonated poly(phthalazinone ether ketone ketone)s films are prepared by solution casting method.Membranes' properties such as water uptake,swelling ratio,oxidative resistance,ion exchange capacity(IEC)and proton conductivities have been measured.Water uptake,swelling ratio,IEC and proton conductivity increased with the increasing SD. However,oxidative resistance decreased with SD increasing.The tensile test results show that tensile stress is above 46Mpa and Young's Modulus is above 1.5Gpa,which indicates sulfonated poly(phthalazinone ether ketone ketone)s films have good mechanical stability.
Polymers with different structures have different performances,and performance details are given to make some comparison.The 5%weight loss temperature of these polymers is above 448℃(in sodium form)and above 331℃(in acid form),respectively,indicating they have good thermal stabilities.The SPPEKK-D membranes have the best oxidative stability, probably due to the introduction of dimethyl groups which substitute the active hydrogen atoms at the ortho position of phenolate oxygen atom.Transmission electron microscope (TEM)is used to study the membrane's micro-morphology.Compared with other polymers, SPPENKK membrane with a same SD has a much higher water uptake,IEC value and proton conductivities;the ionic-clusters' density in them is much higher and their average size becomes larger.Moreover,the hydrophilic phase becomes more continuous and the phase-separation becomes more obvious.This might because of the introduction of polar and hydrophilic cyano groups into SPPENKK's main chain.When temperature is above 80℃,all polymers with SD more than 0.8 show good proton conductivities(＞10~(-2)S·cm~(-1)),which meets the requirement in PEMFC application.
采用发烟硫酸作为磺化试剂,通过亲电取代反应,分别在1,4-二(4-氯代苯甲酰基)苯(BCBB)和1,4-二(4-氟代苯甲酰基)苯(BFBB)上引入磺酸钠基团,成功合成了1,4-二(3-磺酸钠基-4-氯代苯甲酰基)苯(SBCBB)和1,4-二(3-磺酸钠基-4-氟代苯甲酰基)苯(SBFBB)两种磺化单体,利用FT-IR和~1H-NMR对磺化单体进行了结构表征。
通过亲核缩聚反应,调节SBCBB(SBFBB)与BFBB(BCBB)的比例与4-(4-羟基苯基)-2,3-二氮杂萘-1-酮(DHPZ)聚合,合成了不同磺化度的磺化聚芳醚酮酮(SPPEKK、SPPEKK-F);不同比例的SBFBB和BFBB与含二甲基双酚单体(DMDHPZ)进行聚合,得到了不同磺化度的高分子量含二甲基磺化杂萘联苯聚醚酮酮(SPPEKK-D);不同比例的SBFBB和DFBN与DMDHPZ进行聚合,得到了不同磺化度的高分子量磺化杂萘联苯聚醚腈酮酮(SPPENKK)。利用FT-IR和~1H-NMR对所合成的磺化杂萘联苯聚芳醚酮酮结构进行了表征。磺化杂萘联苯聚芳醚酮酮都溶于NMP、DMSO和DMAC等极性非质子性溶剂。
利用溶液浇铸法制备了磺化聚芳醚酮酮膜。所制备的磺化聚芳醚酮酮都具有好的机械性能,拉伸强度在46Mpa以上,杨氏模量在1.5Gpa以上。测试了膜的吸水率、溶胀率、耐氧化性、离子交换容量和质子传导率等性能。吸水率、溶胀率和质子传导率随温度和磺化度的增加而增加。耐氧化性随磺化度的增加而降低。
对不同结构磺化杂萘联苯聚芳醚酮酮的性能进行了比较。所制备磺化聚芳醚酮酮均具有良好的热稳定性,5%的热失重温度分别在448℃(盐型)和331℃(酸型)以上;由于甲基取代了酚氧原子邻位的活泼氢原子,SPPEKK-D具有最好的氧化稳定性。利用TEM对SPPEKKs膜的微观形态进行分析,同磺化度的SPPENKK由于氰基的引入,膜中的离子簇密度和尺寸变大,亲水相分布更为连续,表现出更好的相分离结构,具有更高的吸水率、离子交换容量和质子传导率。所有聚合物膜在磺化度大于0.8、温度高于80℃时,具有较高的质子传导率(＞10~(-2)S/cm),达到了质子交换膜燃料电池的使用要求。
In this thesis,several kinds of sulfonated poly(phthalazinone ether ketone ketone)s (SPPEKKs)have been synthesized based on the molecular design principle under the background of the application of sulfonated poly(arylene ether keton)s in proton exchange membrane fuel cells(PEMFC).Correlative performances of all polymers are studied in order to find a novel membrane material with good properties in PEMFC application.
Two sulfonated monomers 1,4-bis(3-sodium sulfonate-4-chlorobenzoyl)bezene(SBCBB) and 1,4-bis(3-sodium sulfonate-4-fluorobenzoyl)bezene(SBFBB)are successfully prepared by sulfonation of 1,4-bis(4-chlorobenzoyl)benzene(BCBB)and 1,4-bis(4-fluorobenzoyl) benzene(BFBB)respectively with fuming sulfuric acid via aromatic electrophilic substitution reaction.FT-IR and ~1H-NMR are used to characterize the structures of sulfonated monomers'.
Novel sulfonated poly(phthalazinone ether ketone ketone)(SPPEKK)with different sulfonation degree(SD)are synthesized via direct nucleophilic polycondensation from SBCBB(SBFBB),BFBB(BCBB)and 4-(4-hydroxyphenyl)-2,3-phthalazin-1-one(DHPZ); sulfonated poly(phthalazinone ether ketone ketone)(SPPEKK-D)containing dimethyl groups with different sulfonation degree and high molecular weight are prepared by direct aromatic nucleophilic polycondensation of SBFBB,BFBB and 4-(3,5-dimethyl-4-hydroxyphenyl)-2,3-phthalazin-1-one(DMDHPZ);sulfonated poly(phthalazinone ether nitrile ketone ketone) (SPPENKK)containing dimethyl groups with different sulfonation degree and high molecular weight are obtained by direct nucleophilic polycondensation of SBFBB,2,6-difluoro benzonitrile(DFBN)and DMDHPZ.Polymers' structures are characterized by FT-IR and ~1H-NMR.All polymers have good solubility in polar aprotic solvent such as NMP,DMAC and DMSO.
Sulfonated poly(phthalazinone ether ketone ketone)s films are prepared by solution casting method.Membranes' properties such as water uptake,swelling ratio,oxidative resistance,ion exchange capacity(IEC)and proton conductivities have been measured.Water uptake,swelling ratio,IEC and proton conductivity increased with the increasing SD. However,oxidative resistance decreased with SD increasing.The tensile test results show that tensile stress is above 46Mpa and Young's Modulus is above 1.5Gpa,which indicates sulfonated poly(phthalazinone ether ketone ketone)s films have good mechanical stability.
Polymers with different structures have different performances,and performance details are given to make some comparison.The 5%weight loss temperature of these polymers is above 448℃(in sodium form)and above 331℃(in acid form),respectively,indicating they have good thermal stabilities.The SPPEKK-D membranes have the best oxidative stability, probably due to the introduction of dimethyl groups which substitute the active hydrogen atoms at the ortho position of phenolate oxygen atom.Transmission electron microscope (TEM)is used to study the membrane's micro-morphology.Compared with other polymers, SPPENKK membrane with a same SD has a much higher water uptake,IEC value and proton conductivities;the ionic-clusters' density in them is much higher and their average size becomes larger.Moreover,the hydrophilic phase becomes more continuous and the phase-separation becomes more obvious.This might because of the introduction of polar and hydrophilic cyano groups into SPPENKK's main chain.When temperature is above 80℃,all polymers with SD more than 0.8 show good proton conductivities(＞10~(-2)S·cm~(-1)),which meets the requirement in PEMFC application.
引文
[1]雷永泉,万群,石永康.新能源材料.天津:天津大学出版社,2000.
[2]衣宝廉.燃料电池.化学工业出版社,2000.
[3]Rikukawa M,Sanui K.Proton-conducting polymer electrolyte membranes based on hydrocarbon polymers.J Prog Polym Sci.2000,25:1463-1502.
[4]Sakai T,Yuasa A,Ishikawa H,et al.Nickel-metal hydride battery using microencapsulated alloys.J less-Common Met 1991,172-174:1194-1204
[5]Appleby A J,Foulkes F R.Fuel cell handbook.New York:Van Nostrand Reinhold,1989.
[6]林维明.燃料电池系统.北京:化学工业出版社,1996.
[7]查全性.燃料电池技术的发展与我国应有的对策.应用化学.1993,10(5):38-42.
[8]周运鸿.燃料电池,电源技术.1996,20(4):161-164.
[9]Raymond G,Klaus H.New Energy Generation.2001,2:24-26.
[10]Zalbowitz M,Thomas S.Fuel Cells,Green Power,Department of Energy.1999.
[11]Jun C,Huatang Y.Recent R&D of fuel cells in Japan.Chinese Journal of Power Sources.2002,26(1):39-42.
[12]衣宝廉.燃料电池-高效、环境友好的发电方式.北京:化学工业出版社,2000.
[13]钟家轮.质子交换膜燃料电池的发展及展望.电池工业.1999,4(1),23-25.
[14]张华民,明平文,邢丹敏.质子交换膜燃料电池的发展现状.当代化工.2001,30(1):7-11.
[15]Harrision W L,Hicker M A,Kim Y S,et al.Poly(arylene ether sulfone)copolymers and related systems from disulfonated monomer building blocks:Synthesis,Characterization,and Performance.Fuel Cells.2005,5:201-212.
[16]杜春慧,陈建勇.质子交换膜燃料电池的应用研究,能源研究与信息.2002,18(1):51-56
[17]李国欣.新型化学电源导论.上海:复旦大学出版社,1992.
[18]蔡年生.质子交换膜在燃料电池中的应用.膜科学与技术.1996,16(4):1-6.
[19]Rikukawa M,Sanui K.Proton-conducting polymer electrolyte membranes based on hydrocarbon polymers.Prog.Polym.Sci.,2000,25:1463-1502
[20]Houblod H G.Nano structure of NAFION:a SAXS study.J Electrochimica Acta,2001,46:1559-1563.
[21]Carla H W.Recent advances in perfluorinated ionomer membranes:structure,properties and applications.J Membr Sci.1996,120(1):1-33.
[22]Komoroski R A,Mauritz K Ah.A sodium-23 nuclear magnetic resonance study of ionic mobility and contact ion pairing in a perfluorosulfonate ionomer.J.Am.Chem.Soc.,1978,100:7487-7489.
[23]Hsu W Y,Girerke T D.Ion transport and clustering in nafion perfluorinated membranes.J Membr Sci.1983,13(3):307-326.
[24] Lee P C, Meisel D. Luminescence quenching in the cluster network of perfluorosulfonate membrane. J. Am. Chem. Soc., 1980, 102:5477-5481.
[25] Yeager H L, Steck A. Cation and water diffusion in Nafion ion exchange membranes. J. Electrochem. Soc., 1981, 128(9): 1880-1884.
[26] Makoto U, Yuko F, Yasushi S, et al. Improved Preparation Process of Very Low-Platinum-Loading Electrodes for Polymer Electrolyte Fuel Cells. J. Electrochem. Soc., 1998, 145: 3708-3713.
[27] Heinzel A, Barragan V M. A review of the state-of-the-art of the methanol crossover in direct methanol fuel cells. J. Power Sources, 1999, 84: 70-74.
[28] Savadogo O J. New Materials fox Electrochemical Systems. 1998. 1, 47
[29] US, 5422411, 1995
[30] D A Boysen. Polymer Solid Acid Composite Membranes for Fuel-Cell Applications. J Electrochem Soc, 2000, 147, 3610-3613.
[31] Hickner M A, Ghassemi H, Kim Y S, et al. Altemative polymer Systems for proton exehange membranes(PEMs). Chem. Rev. 2004,104(10):4587-4612)
[32] Genies C, Mercier R, et al. Stability study of sulfonated phthalic and naphthalenic polyimide structures in aqueous medium. Polymer, 2001, 42:5097-5105.
[33] Genies C, Mercier R, et al. Soluble sulfonated naphthalenic polyimides as materials for proton exchange membranes. Polymer, 2001, 42:359-373.
[34] Gieselman M B, Reynolds J R. Water-soluble polybenzimidazole-based polyelectrolytes. Macromolecules, 1992, 25: 4832-4834.
[35] Gieselman M B, Reynolds J R. Aramid and imidazole based polyelectrolytes: physical properties and ternary phase behavior with poly(benzobisthiazole) in methanesulfonic acid. Macromolecules, 1993, 26: 5633-5642.
[36] Kawahara M, Rikukawa M, Sanui K, et al. Synthesis and proton conductivity of sulfo- propylated poly(benzimidazole) films. Solid State Ionics, 2000,136-137:1193-1196.
[37] Kawahara M, Rikukawa M, Sanui K. Polym. Adv. Technol., 2000, 11, 544.
[38] Glipa X, Haddad M E, Jones D J, et al. Synthesis and characterisation of sulfonated polybenzimidazole: a highly conducting proton exchange polymer. Solid State Ionics, 1997, 97:323-331.
[39] Manea C, Mulder M. New polymeric electrolyte membranes based on proton donor-proton acceptor properties for direct methanol fuel cells. Desalination, 2002, 147:179-182.
[40] Wang J T, Wainright J S, Savinell R F, et al. A direct methanol fuel cell using acid doped plybenzimi dazole as polymer electrolyte. J Appl. Electrochem., 1996, 26, 751-756.
[41] Savinell R F. Liu M H. US, Patent, 6025085, 2000, 2, 15.
[42] Wang J T, Savinell R F, Wainright J S, et al. A H_2/O_2 fuel cell using acid doped polybenzimidazole as polymer electrolyte.Electrochimica Acta,1996,41:193-197.
[43]Li Q F,Hjuler H A,Bjerrum N.Oxygen reduction on carbon supported platinum catalysts in high temperature polymer electrolytes.Electrocbimica Acta,2000,45:4219-4226.
[44]Savadogo O.Emerging of membranes for electrochemical systems:(1)solid polymer electrolyte membranes for fuel cell systems.J New Mat for Electrochem Systems,1998,1:47-66
[45]Nakajma H,Honma I,Proton-conductiong hybrid solid electrolytes for intermediate temperature fuel cell.Solid State Ionics.2002,148:607-610.
[46]Manea C,Mulder M.Desalination,2002,147,179.
[47]Faure S,Cornet N,Gebel G,et al.Proceeding of the Second International Symposium on New Materials for Fuel and Modern Battery Systems,Montreal,Canda,July 6-10,1997.
[48]Jacaid Zaidi S M.Preparation and characterization of composite membrane using blends of SPEEK/PBI with boron phosphate.Electrochimica Acta.2005,50(24):4771-4777.
[49]Li X F,Zhao C J,Lu H,et al.Preparation of a new type of ion-exehange membrane based on sulfonated Poly(ether ether ketone ketone).J.A.Polym.Sci.,2005,98(6):2481-2486.
[50]Li X F,Na H,Lu H.Novel sulfonated Poly(ether ether ketone ketone)derived from bisphenol S.J.Appl.Polym.Sci.,2004,94(4):1569-1574.
[51]Li X F,Zhao C J,Lu H,et al.Direct synthesis of sulfonated poly(ether ether ketone ketone)s(SPEEKKs)proton exchange membranes for fuel cell application.Polymer,2005,46:5820-5827.
[52]Lakshmi V V,Choudhary V,Varma I K.Macromol.Symp.,2004,210,21.
[53]Xing P X,Robertson G P,Guiver M D.Sulfonated poly(arylene ether ketone)s containing naphthalene moieties obtained by directed polymerization as novel polymers for Proton exchange membrane.J.Polym.Sci.,Part A:Polymer Chemistry,2004,42(12):2866-2876.
[54]Gao Y,Robertson G P,Guiver M D.Synthesis of Poly(arylene ether ether ketone ketone)Copolymers Containing Pendant Sulfonic Acid Groups Bonded to Naphthalene as Proton Exchange Membrane Materials.Macromolecules,2004,37:6748-6754.
[55]Liu S Z,Chen T L.Novel sodium sulfonate-functionalized poly(ether ether ketone)s derived from 4,4' -thiodiphenol.Polymer,2001,42(7):3293-3296.
[56]刘晨光,那辉,赵成吉等.一种新型磺化聚醚醚酮的合成、表征和性能.高等学校化学学报,2004,25(12):2359-2362.
[57]李先锋,那辉,陆辉.一种新型的用于质子交换膜燃料电池的磺化聚醚醚酮酮.高等学校化学学报,2004,25(8):1563-1566.
[58]Daoust D,Devaux J,Godard P.Polym Int 2001,50:917-924
[59]Xiao G Y,Sun G M,Yan D Y.Poly electrolytes for fuel cells made of sulfonated(poly pathalazinone ether ketone).Macromol Rapid Commun,2002,23(8):488-492
[60]Ueda M,Toyota H,Ouchi T.J Poiym Sci Part A:Polymer chemistry,1993,31:853-858
[61]李磊,许莉,王宇新.磺化酚酞型聚醚砜膜的制备及其阻醇和质子导电性能.高分子学报,2003,4:465-467
[62]Xing P X,Robertson G P,Guiver M D,et al.Synthesis and characterization of sulfonate poly(ether ether ketone)for Proton exchang emembrane.Journal of Membrane Science 2004,229:95-106
[63]Xing P X,Robertson G P,Guiver M D,et al.Sulfonated Poly(aryl ether ketone)Containing the Hexafluoroisopropylidene Diphenyl Moiety Prepared by Direc Copolymerization as Proton Exchange Membranes for Fuel Cell Application.Macromolecules.2004,37:7960-7967.
[64]蹇锡高,陈平,廖功雄,等.含二氮杂荼酮结构新型聚芳醚系列高性能聚合物的合成与性能.高分子学报.2003,4:469-475.
[65]王国庆,朱秀玲,张守海等.一种杂环磺化聚芳醚腈酮质子交换膜材料的合成及表征.高分子学报.2006,2:209-212.
[66]Fang J,Guo X,Harada S,et al.Novel Sulfonated Polyimides as Polyelectrolytes for Fuel Cell Application.1.Synthesis,Proton Conductivity,and Water Stability of Polyimides from 4,4'-Diaminodiphenyl Ether-2,2'-disulfonic Acid.Macromolecules.2002,35:9022-9028
[67]March J.Advanced Organic Chemistry,3rd ed.,John Wiley and Sons:New York,1985.
[68]Jeffrey B M.Doctoral dissertation,2001.
[69]Miller J A.Aromatic Nucleophilic Substitution.American Elsevier:New York,1968.
[70]Bunnett J F,Zahler R E.Aromatic Nucleophilic Substitution Reactions.Chem.Rev..1951,49:273-412.
[71]Gao Y,Gilles P R,Michael D G,et al.Synthesis and characterization of sulfonated Poly(Phthalazinone ether ketone)for Proton exchange membrane material.J of Polymer Science,Part A:Polymer Chemistry,2003,41:2731-2742
[72]Liu B,Robertson G P,Kim D S,et al.Aromatic Poly(ether ketone)s with Pendant Sulfonic Acid Phenyl Groups Prepared by a Mild Sulfonation Method for Proton Exchange Membranes.Macromolecules.2007,40:1934-1944.
[73]卢婷利.燃料电池质子交换膜的研究.(硕士论文).西安:西安工业大学.2001.
[74]Kreuer K D.On the complexity of proton conduction phenomena.Solid State Ionics.2000,136-137:149-160.
[75]Gao Y,Robertson G P,Guiver M D,et al.Synthesis.of Copoly(aryl ether ether nitrile)s Containing Sulfonic Acid Groups for PEM Application.Macromolecules.2005,38:3237-3245.
[76]Gao Y,Robertson G P,Guiver M D,et al.Low-swelling proton-conducting copoly(aryl ether nitrile)s containing naphthalene structure with sulfonic acid groups meta to the ether linkage.Polymer.2006,47:808-816.
[77]Bai Z,Durstock M F,Dang T D.Proton conductivity and properties of sulfonated polyarylenethioether sulfones as proton exchange membranes in fuel cells.J Membr Sci.2006,281(1-2):508-516.
[78]Miyataka,K.;Oyaizu,K.;Tsuchida,E.;Hay,A.S.Synthesis and Properties of Nove1Sulfonated Arylene Ether/Fluorinated Alkane Copolymers.Macromolecules 2001,34,2065-2071.
[79]Zhao C J,Li X F,Lin H D,et al.J.Applied Polymer Science..2008,108,671-680.
[80]Wang L,Meng Y Z,Wang S J,et al.Synthesis and Sulfonation of Poly(arylene ether)s Containing Tetraphenyl Methane Moieties.Journal of Polymer Science:Part A:Polymer Chemistry,Col.42,1779- 1788(2004)
[81]张军,蹇锡高,朱秀玲等.大连理工大学学报.1999,39(3):405-409
[82]Jian X G,Dai Y,Zeng L,et al.Application of poly(phthalazinone ether sulfone ketone)s to gas membrane separation.J.Applied Polymer Science.1999,71:2385-2390
[83]张守海,杨大令,蹇锡高.含磺酸钠基的杂萘联苯聚芳醚砜酮的合成与表征.高等学校化学学报.2002,12:2382-2385
[84]刘彦军,蹇锡高,刘胜军等.高分子学报.1999,1:37-41
[85]Zhao C J,Li X F,Lin H,et al.Sulfonated poly(arylene ether ketone)s prepared by direct copolymerization as proton exchange membranes:Synthesis and comparative investigation on transport properties.Journal of Applied Polymer Science,2008,108:671-680.
[86]Sivaramakrishnan K P,Marvel C S.J.Polym.Sci.,Polym.Chem.Ed.1974,12,651.
[87]Sumner M J,Harrison W L,Weyers R M,et al.Novel proton conducting sulfonated poly(arylene ether)copolymers containing aromatic nitriles.J.Membr.Sci.2004,239(2):199-211.
[88]Li X F,Wang Z,Lu H,et al.Electrochemical properties of sulfonated PEEK used for ion exchange membranes Journal of Membrane Science.2005,254(1-2):147-155
[89]陈勇,王拴紧,孟跃中等.新型的含芳香二腈基磺化聚芳醚腈酮的合成与表征.2007,2:365-365
[90]Chikashige Y,Chikyu Y,Miyatake K,et al.Poly(arylene ether)ionomers containing sulfofluorenyl groups for fuel cell applications.Macromolecules,2005,38(16):7121-7126
[91]Eisenberg A.Clustering of Ions in Organic Polymers.A Theoretical Approach.Macromolecules.1970,3:147-154.
[92]李先锋.磺化聚芳醚酮类质子交换膜材料的结构与性能研究.(博士学位论文).吉林:吉林大学,2006.
[93]王哲.用于燃料电池质子交换膜材料的系列磺化聚芳醚砜的合成与性能研究.(博士学位论文). 吉林:吉林大学,2006.
[94]Kreuer K D.J.Membr.Sci.On the development of proton conducting polymer membranes for hydrogen and methanol fuel cells.2001,185(1):29-39.
[95]刘晨光.用于质子交换膜的磺化聚醚醚酮的合成与性能研究.(博士学位论文).吉林:吉林大学,2005.
[2]衣宝廉.燃料电池.化学工业出版社,2000.
[3]Rikukawa M,Sanui K.Proton-conducting polymer electrolyte membranes based on hydrocarbon polymers.J Prog Polym Sci.2000,25:1463-1502.
[4]Sakai T,Yuasa A,Ishikawa H,et al.Nickel-metal hydride battery using microencapsulated alloys.J less-Common Met 1991,172-174:1194-1204
[5]Appleby A J,Foulkes F R.Fuel cell handbook.New York:Van Nostrand Reinhold,1989.
[6]林维明.燃料电池系统.北京:化学工业出版社,1996.
[7]查全性.燃料电池技术的发展与我国应有的对策.应用化学.1993,10(5):38-42.
[8]周运鸿.燃料电池,电源技术.1996,20(4):161-164.
[9]Raymond G,Klaus H.New Energy Generation.2001,2:24-26.
[10]Zalbowitz M,Thomas S.Fuel Cells,Green Power,Department of Energy.1999.
[11]Jun C,Huatang Y.Recent R&D of fuel cells in Japan.Chinese Journal of Power Sources.2002,26(1):39-42.
[12]衣宝廉.燃料电池-高效、环境友好的发电方式.北京:化学工业出版社,2000.
[13]钟家轮.质子交换膜燃料电池的发展及展望.电池工业.1999,4(1),23-25.
[14]张华民,明平文,邢丹敏.质子交换膜燃料电池的发展现状.当代化工.2001,30(1):7-11.
[15]Harrision W L,Hicker M A,Kim Y S,et al.Poly(arylene ether sulfone)copolymers and related systems from disulfonated monomer building blocks:Synthesis,Characterization,and Performance.Fuel Cells.2005,5:201-212.
[16]杜春慧,陈建勇.质子交换膜燃料电池的应用研究,能源研究与信息.2002,18(1):51-56
[17]李国欣.新型化学电源导论.上海:复旦大学出版社,1992.
[18]蔡年生.质子交换膜在燃料电池中的应用.膜科学与技术.1996,16(4):1-6.
[19]Rikukawa M,Sanui K.Proton-conducting polymer electrolyte membranes based on hydrocarbon polymers.Prog.Polym.Sci.,2000,25:1463-1502
[20]Houblod H G.Nano structure of NAFION:a SAXS study.J Electrochimica Acta,2001,46:1559-1563.
[21]Carla H W.Recent advances in perfluorinated ionomer membranes:structure,properties and applications.J Membr Sci.1996,120(1):1-33.
[22]Komoroski R A,Mauritz K Ah.A sodium-23 nuclear magnetic resonance study of ionic mobility and contact ion pairing in a perfluorosulfonate ionomer.J.Am.Chem.Soc.,1978,100:7487-7489.
[23]Hsu W Y,Girerke T D.Ion transport and clustering in nafion perfluorinated membranes.J Membr Sci.1983,13(3):307-326.
[24] Lee P C, Meisel D. Luminescence quenching in the cluster network of perfluorosulfonate membrane. J. Am. Chem. Soc., 1980, 102:5477-5481.
[25] Yeager H L, Steck A. Cation and water diffusion in Nafion ion exchange membranes. J. Electrochem. Soc., 1981, 128(9): 1880-1884.
[26] Makoto U, Yuko F, Yasushi S, et al. Improved Preparation Process of Very Low-Platinum-Loading Electrodes for Polymer Electrolyte Fuel Cells. J. Electrochem. Soc., 1998, 145: 3708-3713.
[27] Heinzel A, Barragan V M. A review of the state-of-the-art of the methanol crossover in direct methanol fuel cells. J. Power Sources, 1999, 84: 70-74.
[28] Savadogo O J. New Materials fox Electrochemical Systems. 1998. 1, 47
[29] US, 5422411, 1995
[30] D A Boysen. Polymer Solid Acid Composite Membranes for Fuel-Cell Applications. J Electrochem Soc, 2000, 147, 3610-3613.
[31] Hickner M A, Ghassemi H, Kim Y S, et al. Altemative polymer Systems for proton exehange membranes(PEMs). Chem. Rev. 2004,104(10):4587-4612)
[32] Genies C, Mercier R, et al. Stability study of sulfonated phthalic and naphthalenic polyimide structures in aqueous medium. Polymer, 2001, 42:5097-5105.
[33] Genies C, Mercier R, et al. Soluble sulfonated naphthalenic polyimides as materials for proton exchange membranes. Polymer, 2001, 42:359-373.
[34] Gieselman M B, Reynolds J R. Water-soluble polybenzimidazole-based polyelectrolytes. Macromolecules, 1992, 25: 4832-4834.
[35] Gieselman M B, Reynolds J R. Aramid and imidazole based polyelectrolytes: physical properties and ternary phase behavior with poly(benzobisthiazole) in methanesulfonic acid. Macromolecules, 1993, 26: 5633-5642.
[36] Kawahara M, Rikukawa M, Sanui K, et al. Synthesis and proton conductivity of sulfo- propylated poly(benzimidazole) films. Solid State Ionics, 2000,136-137:1193-1196.
[37] Kawahara M, Rikukawa M, Sanui K. Polym. Adv. Technol., 2000, 11, 544.
[38] Glipa X, Haddad M E, Jones D J, et al. Synthesis and characterisation of sulfonated polybenzimidazole: a highly conducting proton exchange polymer. Solid State Ionics, 1997, 97:323-331.
[39] Manea C, Mulder M. New polymeric electrolyte membranes based on proton donor-proton acceptor properties for direct methanol fuel cells. Desalination, 2002, 147:179-182.
[40] Wang J T, Wainright J S, Savinell R F, et al. A direct methanol fuel cell using acid doped plybenzimi dazole as polymer electrolyte. J Appl. Electrochem., 1996, 26, 751-756.
[41] Savinell R F. Liu M H. US, Patent, 6025085, 2000, 2, 15.
[42] Wang J T, Savinell R F, Wainright J S, et al. A H_2/O_2 fuel cell using acid doped polybenzimidazole as polymer electrolyte.Electrochimica Acta,1996,41:193-197.
[43]Li Q F,Hjuler H A,Bjerrum N.Oxygen reduction on carbon supported platinum catalysts in high temperature polymer electrolytes.Electrocbimica Acta,2000,45:4219-4226.
[44]Savadogo O.Emerging of membranes for electrochemical systems:(1)solid polymer electrolyte membranes for fuel cell systems.J New Mat for Electrochem Systems,1998,1:47-66
[45]Nakajma H,Honma I,Proton-conductiong hybrid solid electrolytes for intermediate temperature fuel cell.Solid State Ionics.2002,148:607-610.
[46]Manea C,Mulder M.Desalination,2002,147,179.
[47]Faure S,Cornet N,Gebel G,et al.Proceeding of the Second International Symposium on New Materials for Fuel and Modern Battery Systems,Montreal,Canda,July 6-10,1997.
[48]Jacaid Zaidi S M.Preparation and characterization of composite membrane using blends of SPEEK/PBI with boron phosphate.Electrochimica Acta.2005,50(24):4771-4777.
[49]Li X F,Zhao C J,Lu H,et al.Preparation of a new type of ion-exehange membrane based on sulfonated Poly(ether ether ketone ketone).J.A.Polym.Sci.,2005,98(6):2481-2486.
[50]Li X F,Na H,Lu H.Novel sulfonated Poly(ether ether ketone ketone)derived from bisphenol S.J.Appl.Polym.Sci.,2004,94(4):1569-1574.
[51]Li X F,Zhao C J,Lu H,et al.Direct synthesis of sulfonated poly(ether ether ketone ketone)s(SPEEKKs)proton exchange membranes for fuel cell application.Polymer,2005,46:5820-5827.
[52]Lakshmi V V,Choudhary V,Varma I K.Macromol.Symp.,2004,210,21.
[53]Xing P X,Robertson G P,Guiver M D.Sulfonated poly(arylene ether ketone)s containing naphthalene moieties obtained by directed polymerization as novel polymers for Proton exchange membrane.J.Polym.Sci.,Part A:Polymer Chemistry,2004,42(12):2866-2876.
[54]Gao Y,Robertson G P,Guiver M D.Synthesis of Poly(arylene ether ether ketone ketone)Copolymers Containing Pendant Sulfonic Acid Groups Bonded to Naphthalene as Proton Exchange Membrane Materials.Macromolecules,2004,37:6748-6754.
[55]Liu S Z,Chen T L.Novel sodium sulfonate-functionalized poly(ether ether ketone)s derived from 4,4' -thiodiphenol.Polymer,2001,42(7):3293-3296.
[56]刘晨光,那辉,赵成吉等.一种新型磺化聚醚醚酮的合成、表征和性能.高等学校化学学报,2004,25(12):2359-2362.
[57]李先锋,那辉,陆辉.一种新型的用于质子交换膜燃料电池的磺化聚醚醚酮酮.高等学校化学学报,2004,25(8):1563-1566.
[58]Daoust D,Devaux J,Godard P.Polym Int 2001,50:917-924
[59]Xiao G Y,Sun G M,Yan D Y.Poly electrolytes for fuel cells made of sulfonated(poly pathalazinone ether ketone).Macromol Rapid Commun,2002,23(8):488-492
[60]Ueda M,Toyota H,Ouchi T.J Poiym Sci Part A:Polymer chemistry,1993,31:853-858
[61]李磊,许莉,王宇新.磺化酚酞型聚醚砜膜的制备及其阻醇和质子导电性能.高分子学报,2003,4:465-467
[62]Xing P X,Robertson G P,Guiver M D,et al.Synthesis and characterization of sulfonate poly(ether ether ketone)for Proton exchang emembrane.Journal of Membrane Science 2004,229:95-106
[63]Xing P X,Robertson G P,Guiver M D,et al.Sulfonated Poly(aryl ether ketone)Containing the Hexafluoroisopropylidene Diphenyl Moiety Prepared by Direc Copolymerization as Proton Exchange Membranes for Fuel Cell Application.Macromolecules.2004,37:7960-7967.
[64]蹇锡高,陈平,廖功雄,等.含二氮杂荼酮结构新型聚芳醚系列高性能聚合物的合成与性能.高分子学报.2003,4:469-475.
[65]王国庆,朱秀玲,张守海等.一种杂环磺化聚芳醚腈酮质子交换膜材料的合成及表征.高分子学报.2006,2:209-212.
[66]Fang J,Guo X,Harada S,et al.Novel Sulfonated Polyimides as Polyelectrolytes for Fuel Cell Application.1.Synthesis,Proton Conductivity,and Water Stability of Polyimides from 4,4'-Diaminodiphenyl Ether-2,2'-disulfonic Acid.Macromolecules.2002,35:9022-9028
[67]March J.Advanced Organic Chemistry,3rd ed.,John Wiley and Sons:New York,1985.
[68]Jeffrey B M.Doctoral dissertation,2001.
[69]Miller J A.Aromatic Nucleophilic Substitution.American Elsevier:New York,1968.
[70]Bunnett J F,Zahler R E.Aromatic Nucleophilic Substitution Reactions.Chem.Rev..1951,49:273-412.
[71]Gao Y,Gilles P R,Michael D G,et al.Synthesis and characterization of sulfonated Poly(Phthalazinone ether ketone)for Proton exchange membrane material.J of Polymer Science,Part A:Polymer Chemistry,2003,41:2731-2742
[72]Liu B,Robertson G P,Kim D S,et al.Aromatic Poly(ether ketone)s with Pendant Sulfonic Acid Phenyl Groups Prepared by a Mild Sulfonation Method for Proton Exchange Membranes.Macromolecules.2007,40:1934-1944.
[73]卢婷利.燃料电池质子交换膜的研究.(硕士论文).西安:西安工业大学.2001.
[74]Kreuer K D.On the complexity of proton conduction phenomena.Solid State Ionics.2000,136-137:149-160.
[75]Gao Y,Robertson G P,Guiver M D,et al.Synthesis.of Copoly(aryl ether ether nitrile)s Containing Sulfonic Acid Groups for PEM Application.Macromolecules.2005,38:3237-3245.
[76]Gao Y,Robertson G P,Guiver M D,et al.Low-swelling proton-conducting copoly(aryl ether nitrile)s containing naphthalene structure with sulfonic acid groups meta to the ether linkage.Polymer.2006,47:808-816.
[77]Bai Z,Durstock M F,Dang T D.Proton conductivity and properties of sulfonated polyarylenethioether sulfones as proton exchange membranes in fuel cells.J Membr Sci.2006,281(1-2):508-516.
[78]Miyataka,K.;Oyaizu,K.;Tsuchida,E.;Hay,A.S.Synthesis and Properties of Nove1Sulfonated Arylene Ether/Fluorinated Alkane Copolymers.Macromolecules 2001,34,2065-2071.
[79]Zhao C J,Li X F,Lin H D,et al.J.Applied Polymer Science..2008,108,671-680.
[80]Wang L,Meng Y Z,Wang S J,et al.Synthesis and Sulfonation of Poly(arylene ether)s Containing Tetraphenyl Methane Moieties.Journal of Polymer Science:Part A:Polymer Chemistry,Col.42,1779- 1788(2004)
[81]张军,蹇锡高,朱秀玲等.大连理工大学学报.1999,39(3):405-409
[82]Jian X G,Dai Y,Zeng L,et al.Application of poly(phthalazinone ether sulfone ketone)s to gas membrane separation.J.Applied Polymer Science.1999,71:2385-2390
[83]张守海,杨大令,蹇锡高.含磺酸钠基的杂萘联苯聚芳醚砜酮的合成与表征.高等学校化学学报.2002,12:2382-2385
[84]刘彦军,蹇锡高,刘胜军等.高分子学报.1999,1:37-41
[85]Zhao C J,Li X F,Lin H,et al.Sulfonated poly(arylene ether ketone)s prepared by direct copolymerization as proton exchange membranes:Synthesis and comparative investigation on transport properties.Journal of Applied Polymer Science,2008,108:671-680.
[86]Sivaramakrishnan K P,Marvel C S.J.Polym.Sci.,Polym.Chem.Ed.1974,12,651.
[87]Sumner M J,Harrison W L,Weyers R M,et al.Novel proton conducting sulfonated poly(arylene ether)copolymers containing aromatic nitriles.J.Membr.Sci.2004,239(2):199-211.
[88]Li X F,Wang Z,Lu H,et al.Electrochemical properties of sulfonated PEEK used for ion exchange membranes Journal of Membrane Science.2005,254(1-2):147-155
[89]陈勇,王拴紧,孟跃中等.新型的含芳香二腈基磺化聚芳醚腈酮的合成与表征.2007,2:365-365
[90]Chikashige Y,Chikyu Y,Miyatake K,et al.Poly(arylene ether)ionomers containing sulfofluorenyl groups for fuel cell applications.Macromolecules,2005,38(16):7121-7126
[91]Eisenberg A.Clustering of Ions in Organic Polymers.A Theoretical Approach.Macromolecules.1970,3:147-154.
[92]李先锋.磺化聚芳醚酮类质子交换膜材料的结构与性能研究.(博士学位论文).吉林:吉林大学,2006.
[93]王哲.用于燃料电池质子交换膜材料的系列磺化聚芳醚砜的合成与性能研究.(博士学位论文). 吉林:吉林大学,2006.
[94]Kreuer K D.J.Membr.Sci.On the development of proton conducting polymer membranes for hydrogen and methanol fuel cells.2001,185(1):29-39.
[95]刘晨光.用于质子交换膜的磺化聚醚醚酮的合成与性能研究.(博士学位论文).吉林:吉林大学,2005.