CN101629003B - 由pfsa和磺化pfcb聚合物的混合物组成的聚合电解质膜 - Google Patents

由pfsa和磺化pfcb聚合物的混合物组成的聚合电解质膜 Download PDF

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CN101629003B
CN101629003B CN200910149724.1A CN200910149724A CN101629003B CN 101629003 B CN101629003 B CN 101629003B CN 200910149724 A CN200910149724 A CN 200910149724A CN 101629003 B CN101629003 B CN 101629003B
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polymkeric substance
aryl
polymeric blends
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described polymeric
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CN101629003A (zh
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T·J·富勒
S·M·麦金农
M·R·舍内韦斯
C·S·吉特尔曼
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GM Global Technology Operations LLC
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2275—Heterogeneous membranes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2275—Heterogeneous membranes
    • C08J5/2281—Heterogeneous membranes fluorine containing heterogeneous membranes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2345/00—Characterised by the use of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Derivatives of such polymers
CN200910149724.1A 2008-05-09 2009-05-08 由pfsa和磺化pfcb聚合物的混合物组成的聚合电解质膜 Active CN101629003B (zh)

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US5214808P 2008-05-09 2008-05-09
US61/052148 2008-05-09
US12/434749 2009-05-04
US12/434,749 US7985805B2 (en) 2008-05-09 2009-05-04 Polyelectrolyte membranes comprised of blends of PFSA and sulfonated PFCB polymers

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CN101629003B true CN101629003B (zh) 2012-10-10

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Families Citing this family (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7897693B2 (en) * 2008-05-09 2011-03-01 Gm Global Technology Operations, Inc. Proton conductive polymer electrolytes and fuel cells
US7985805B2 (en) 2008-05-09 2011-07-26 GM Global Technology Operations LLC Polyelectrolyte membranes comprised of blends of PFSA and sulfonated PFCB polymers
US8030405B2 (en) * 2008-05-09 2011-10-04 GM Global Technology Operations LLC Blended PEM's with elastomers for improved mechanical durability
US7888433B2 (en) * 2008-05-09 2011-02-15 Gm Global Technology Operations, Inc. Sulfonated-polyperfluoro-cyclobutane-polyphenylene polymers for PEM fuel cell applications
US7897692B2 (en) * 2008-05-09 2011-03-01 Gm Global Technology Operations, Inc. Sulfonated perfluorocyclobutane block copolymers and proton conductive polymer membranes
US7897691B2 (en) * 2008-05-09 2011-03-01 Gm Global Technology Operations, Inc. Proton exchange membranes for fuel cell applications
US8008404B2 (en) * 2008-05-09 2011-08-30 GM Global Technology Operations LLC Composite membrane
US8003732B2 (en) * 2008-08-25 2011-08-23 GM Global Technology Operations LLC Gradient reinforced proton exchange membrane
US7976730B2 (en) * 2008-08-25 2011-07-12 GM Global Technology Operations LLC Blends of low equivalent molecular weight PFSA ionomers with Kynar 2751
US20110045381A1 (en) * 2009-08-18 2011-02-24 Gm Global Technology Operations, Inc. Hydrocarbon PEM Membranes with Perfluorosulfonic Acid Groups for Automotive Fuel Cells
US8852823B2 (en) * 2009-08-26 2014-10-07 GM Global Technology Operations LLC Sodium stannate additive to improve the durability of PEMS for H2/air fuel cells
US8053530B2 (en) * 2009-08-26 2011-11-08 GM Global Technology Operations LLC Polyelectrolyte membranes made of poly(perfluorocyclobutanes) with pendant perfluorosulfonic acid groups and blends with poly(vinylidene fluoride)
US8354201B2 (en) * 2009-08-28 2013-01-15 GM Global Technology Operations LLC Fuel cell with spatially non-homogeneous ionic membrane
US20110053009A1 (en) * 2009-08-28 2011-03-03 Gm Global Technology Operations, Inc. Customized water vapor transfer membrane layered structure
US20110053008A1 (en) * 2009-08-28 2011-03-03 Gm Global Technology Operations, Inc. Water vapor transfer membrane and paper integrated assembly
US7972732B2 (en) * 2009-08-28 2011-07-05 GM Global Technology Operations LLC Perfluorocyclobutane based water vapor transfer membranes with side chain perfluorosulfonic acid moieties
US8058352B2 (en) * 2009-08-28 2011-11-15 GM Global Technology Operations LLC Perfluorocyclobutane based water vapor transfer membranes
US8409765B2 (en) * 2009-08-31 2013-04-02 GM Global Technology Operations LLC Co(II)tetramethoxyphenylporphyrin additive to PFSA PEMS for improved fuel cell durability
US8048963B2 (en) * 2009-08-31 2011-11-01 GM Global Technology Operations LLC Ion exchange membrane having lamellar morphology and process of making the same
US8252712B2 (en) * 2009-11-13 2012-08-28 GM Global Technology Operations LLC Polymer dispersant addition to fuel cell electrode inks for improved manufacturability
US20110159404A1 (en) * 2009-12-29 2011-06-30 Gm Global Technology Operations, Inc. Polyolefin Support to Prevent Dielectric Breakdown in PEMS
US20110159405A1 (en) * 2009-12-30 2011-06-30 Gm Global Technology Operations, Inc. Hydrophilic Polyelectrolyte Membranes Containing Poly(Vinyl Acetate) and Poly(Vinyl Alcohol)
US20110165497A1 (en) * 2010-01-06 2011-07-07 Gm Global Technology Operations, Inc. Method for Mitigating Fuel Cell Chemical Degradation
US7989512B1 (en) 2010-03-17 2011-08-02 GM Global Technology Operations LLC Polyelectrolyte membranes derived from soluble perfluorocyclobutane polymers with sulfonyl chloride groups
US8044146B1 (en) 2010-04-16 2011-10-25 GM Global Technology Operations LLC Combination of main-chain and side-chain sulfonation of PFCB-6F high-temperature fuel cell membranes
US8735021B2 (en) 2010-04-16 2014-05-27 GM Global Technology Operations LLC Cobalt(II) tetramethoxyphenylporphyrin (CoTMPP) ionomer stabilization to prevent electrode degradation
US9172099B2 (en) * 2010-11-15 2015-10-27 GM Global Technology Operations LLC Nano-fibers for electrical power generation
US8609739B2 (en) 2011-02-17 2013-12-17 GM Global Technology Operations LLC Poly(perfluorocyclobutane) ionomer with phosphonic acid groups for high temperature fuel cells
US8609775B2 (en) * 2011-12-06 2013-12-17 GM Global Technology Operations LLC Electrode with reduced mud cracking via mixed equivalent weight ionomers
US9040209B2 (en) * 2012-02-02 2015-05-26 GM Global Technology Operations LLC Multi-layer polyelectrolyte membranes
US9782767B2 (en) * 2013-06-14 2017-10-10 Lg Chem, Ltd. Sulfonate-based compound and polymer electrolyte membrane using same
CN103819316B (zh) * 2014-03-13 2015-11-18 中国科学院上海有机化学研究所 可固化的聚芴及其作为耐热材料的应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5006408A (en) * 1989-01-03 1991-04-09 Allied-Signal Inc. Stain-resistant polymers derived from itaconic acid useful as coatings for fibers
CN1703761A (zh) * 2002-10-03 2005-11-30 大金工业株式会社 含有含氟醚链的含氟聚合物固体电解质
CN101016374A (zh) * 2005-11-01 2007-08-15 通用汽车环球科技运作公司 用于燃料电池的磺化全氟环丁烷聚合电解质膜
CN101130604A (zh) * 2006-07-28 2008-02-27 通用汽车环球科技运作公司 用于质子交换膜的氟化聚合物嵌段

Family Cites Families (58)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5159037A (en) 1989-06-09 1992-10-27 The Dow Chemical Company Perfluorocyclobutane ring-containing polymers
US5066746A (en) 1989-06-09 1991-11-19 The Dow Chemical Company Perfluorocyclobutane ring-containing polymers
US5037917A (en) 1989-06-09 1991-08-06 The Dow Chemical Company Perfluorocyclobutane ring-containing polymers
US5021602A (en) 1989-06-09 1991-06-04 The Dow Chemical Company Reactive compounds containing perfluorocyclobutane rings
US5159038A (en) 1989-06-09 1992-10-27 Dow Chemical Company Perfluorocyclobutane ring-containing polymers
US6444343B1 (en) 1996-11-18 2002-09-03 University Of Southern California Polymer electrolyte membranes for use in fuel cells
US5910378A (en) 1997-10-10 1999-06-08 Minnesota Mining And Manufacturing Company Membrane electrode assemblies
US6124060A (en) 1998-05-20 2000-09-26 Honda Giken Kogyo Kabushiki Kaisha Solid polymer electrolytes
US6620899B1 (en) 1998-10-15 2003-09-16 E. I. Du Pont De Nemours And Company Polymers, containing a fluorocyclobutyl ring and their preparation
US6277512B1 (en) 1999-06-18 2001-08-21 3M Innovative Properties Company Polymer electrolyte membranes from mixed dispersions
US6523699B1 (en) 1999-09-20 2003-02-25 Honda Giken Kogyo Kabushiki Kaisha Sulfonic acid group-containing polyvinyl alcohol, solid polymer electrolyte, composite polymer membrane, method for producing the same and electrode
DE60143635D1 (de) 2000-02-15 2011-01-27 Asahi Glass Co Ltd Blockpolymer, Verfahren zur Herstellung von Polymer und Festpolymerelektrolytbrennstoffzelle
EP1268619A2 (en) * 2000-03-22 2003-01-02 Victrex Manufacturing Limited Composite ion exchange material
US6268532B1 (en) 2000-06-05 2001-07-31 3M Innovative Properties Company Sulfonated perfluorovinyl functional monomers
US6559237B1 (en) 2000-06-05 2003-05-06 3M Innovative Properties Company Sulfonated perfluorocyclobutane ion-conducting membranes
IT1318593B1 (it) 2000-06-23 2003-08-27 Ausimont Spa Ionomeri fluorurati.
JP3411897B2 (ja) 2000-10-12 2003-06-03 本田技研工業株式会社 固体高分子型燃料電池の活性固体高分子電解質膜
DE10201691A1 (de) 2001-01-19 2002-09-05 Honda Motor Co Ltd Polymerelektrolytmembran, Verfahren zu deren Herstellung und Membranelektrodenanordnung und Polymerelektrolytbrennstoffzelle, die diese umfasst
DE10201886B4 (de) 2001-01-19 2014-01-23 Honda Giken Kogyo K.K. Polymerelektrolytmembran sowie Verfahren zur Herstellung dieser und Festpolymerelektrolytbrennstoffzelle, welche diese verwendet
US7541308B2 (en) 2001-04-11 2009-06-02 Cabot Corporation Fuel cells and other products containing modified carbon products
JP2003017074A (ja) 2001-07-02 2003-01-17 Honda Motor Co Ltd 燃料電池
US6953653B2 (en) 2001-08-30 2005-10-11 Clemson University Fluoropolymer compositions, optical devices, and methods for fabricating optical devices
JP3634304B2 (ja) 2001-12-12 2005-03-30 本田技研工業株式会社 固体高分子型燃料電池用電極構造体
JP3621078B2 (ja) 2002-06-20 2005-02-16 田中貴金属工業株式会社 高分子固体電解質形燃料電池の燃料極
JP4037698B2 (ja) 2002-06-26 2008-01-23 本田技研工業株式会社 固体高分子型セルアセンブリ
JP3878520B2 (ja) 2002-07-18 2007-02-07 本田技研工業株式会社 プロトン伝導性高分子固体電解質およびその製造方法
JP3867029B2 (ja) 2002-08-20 2007-01-10 Ｊｓｒ株式会社 プロトン伝導膜の製造方法
WO2004051776A1 (ja) 2002-12-02 2004-06-17 Sanyo Electric Co.,Ltd. 固体高分子電解質膜、当該膜を用いた固体高分子型燃料電池、およびその製造方法
JP2004186050A (ja) 2002-12-04 2004-07-02 Honda Motor Co Ltd 固体高分子型燃料電池用電極構造体
EP1465277A1 (en) 2003-03-19 2004-10-06 HONDA MOTOR CO., Ltd. Solid polymer electrolyte and protonconducting membrane
JP4384485B2 (ja) 2003-07-09 2009-12-16 本田技研工業株式会社 燃料電池
JP2005036113A (ja) 2003-07-16 2005-02-10 Honda Motor Co Ltd スルホン化ポリフォスファゼン誘導体及びその製造方法
JP2007503098A (ja) 2003-08-19 2007-02-15 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー 電気化学電池のための、非イオノマーフルオロポリマーとブレンドされたフッ素化イオノマーの膜
JP5000073B2 (ja) 2003-09-08 2012-08-15 本田技研工業株式会社 燃料電池スタックの氷点下起動方法、燃料電池スタックの氷点下起動システム、および燃料電池スタックの設計方法
US6974648B2 (en) 2003-09-12 2005-12-13 General Motors Corporation Nested bipolar plate for fuel cell and method
EP1517390A3 (en) 2003-09-19 2009-12-16 HONDA MOTOR CO., Ltd. Membrane-electrode structure for solid polymer fuel cell
JP4486341B2 (ja) 2003-10-22 2010-06-23 本田技研工業株式会社 燃料電池用電解質膜の製造方法および燃料電池用電解質膜の製造装置
JP4486340B2 (ja) 2003-10-22 2010-06-23 本田技研工業株式会社 燃料電池用電極−膜接合体の製造方法
US7601447B2 (en) 2003-11-12 2009-10-13 Honda Motor Co., Ltd. Electrolyte-electrode assembly comprising an isotropic layer
US20050106440A1 (en) 2003-11-19 2005-05-19 Honda Motor Co., Ltd. Proton conductor and method for producing the same
JP2005162772A (ja) 2003-11-28 2005-06-23 Jsr Corp プロトン伝導体組成物およびプロトン伝導膜
JP2005166557A (ja) 2003-12-04 2005-06-23 Jsr Corp 高分子電解質複合膜およびその製造法、ならびにそれを用いた固体高分子型燃料電池
JP4294457B2 (ja) 2003-12-10 2009-07-15 Ｊｓｒ株式会社 プロトン伝導体組成物およびプロトン伝導膜
JP4431650B2 (ja) 2003-12-15 2010-03-17 サンノプコ株式会社 蛍光増白増強剤
JP4304101B2 (ja) 2003-12-24 2009-07-29 本田技研工業株式会社 電解質膜・電極構造体及び燃料電池
JP4109623B2 (ja) 2003-12-25 2008-07-02 本田技研工業株式会社 プロトン伝導体及びその製造方法
JP4351557B2 (ja) 2004-03-03 2009-10-28 本田技研工業株式会社 プロトン伝導体
JP4116585B2 (ja) 2004-04-07 2008-07-09 本田技研工業株式会社 固体高分子型燃料電池
JP2006054165A (ja) 2004-07-15 2006-02-23 Honda Motor Co Ltd 固体高分子型燃料電池及び固体高分子型燃料電池の製造方法
US20060127728A1 (en) 2004-12-15 2006-06-15 JSR CORPORATION; and Membrane-electrode assembly for fuel cell
US8178224B2 (en) 2005-02-08 2012-05-15 GM Global Technology Operations LLC Sulfonated polyelectrolyte membranes containing perfluorosulfonate ionomers
KR100756457B1 (ko) 2005-11-01 2007-09-07 주식회사 엘지화학 퍼플루오로싸이클로부탄기를 포함하는 블록 공중합체 및이를 이용한 전해질막
JP5358115B2 (ja) 2008-04-04 2013-12-04 出光興産株式会社 脂環式構造及びペルフルオロシクロブチルエーテル構造を有するポリマー
US7897693B2 (en) 2008-05-09 2011-03-01 Gm Global Technology Operations, Inc. Proton conductive polymer electrolytes and fuel cells
US7888433B2 (en) 2008-05-09 2011-02-15 Gm Global Technology Operations, Inc. Sulfonated-polyperfluoro-cyclobutane-polyphenylene polymers for PEM fuel cell applications
US7897691B2 (en) 2008-05-09 2011-03-01 Gm Global Technology Operations, Inc. Proton exchange membranes for fuel cell applications
US7985805B2 (en) 2008-05-09 2011-07-26 GM Global Technology Operations LLC Polyelectrolyte membranes comprised of blends of PFSA and sulfonated PFCB polymers
US7897692B2 (en) 2008-05-09 2011-03-01 Gm Global Technology Operations, Inc. Sulfonated perfluorocyclobutane block copolymers and proton conductive polymer membranes

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5006408A (en) * 1989-01-03 1991-04-09 Allied-Signal Inc. Stain-resistant polymers derived from itaconic acid useful as coatings for fibers
CN1703761A (zh) * 2002-10-03 2005-11-30 大金工业株式会社 含有含氟醚链的含氟聚合物固体电解质
CN101016374A (zh) * 2005-11-01 2007-08-15 通用汽车环球科技运作公司 用于燃料电池的磺化全氟环丁烷聚合电解质膜
CN101130604A (zh) * 2006-07-28 2008-02-27 通用汽车环球科技运作公司 用于质子交换膜的氟化聚合物嵌段

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US7985805B2 (en) 2011-07-26
DE102009020175B4 (de) 2015-12-17
US20090278083A1 (en) 2009-11-12
CN101629003A (zh) 2010-01-20

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