JP5173262B2 - 固体高分子電解質膜の製造方法、固体高分子電解質膜、固体高分子形燃料電池用膜電極組立体および固体高分子形燃料電池 - Google Patents
固体高分子電解質膜の製造方法、固体高分子電解質膜、固体高分子形燃料電池用膜電極組立体および固体高分子形燃料電池 Download PDFInfo
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- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical group FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 description 2
- 238000010257 thawing Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
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- 239000004745 nonwoven fabric Substances 0.000 description 1
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Classifications
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- H—ELECTRICITY
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- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
- H01M8/106—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties characterised by the chemical composition of the porous support
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- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
- C08G65/326—Polymers modified by chemical after-treatment with inorganic compounds containing sulfur
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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
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- H—ELECTRICITY
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- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1023—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
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- H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
- H01M8/1062—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties characterised by the physical properties of the porous support, e.g. its porosity or thickness
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1067—Polymeric electrolyte materials characterised by their physical properties, e.g. porosity, ionic conductivity or thickness
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
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- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Sustainable Development (AREA)
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- Crystallography & Structural Chemistry (AREA)
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- Fuel Cell (AREA)
Description
(1)シート状多孔質補強材と高分子電解質前駆体とを用意する工程、
該高分子電解質前駆体を、溶媒不存在下、該シート状多孔質補強材の融点より高いがその熱分解温度より低い温度において該シート状多孔質補強材に含浸させることにより、該高分子電解質前駆体の少なくとも一部が該シート状多孔質補強材に含浸複合化された複合膜を得る工程、および
該高分子電解質前駆体を加水分解することにより高分子電解質へ転化する工程
を含んでなる、補強された固体高分子電解質膜の製造方法;
(2)シート状多孔質補強材と高分子電解質前駆体とを用意する工程、
該高分子電解質前駆体を、溶媒不存在下、該シート状多孔質補強材の融点より低い第1の温度において該シート状多孔質補強材に含浸させることにより、該高分子電解質前駆体の少なくとも一部が該シート状多孔質補強材に含浸複合化された複合膜を得る工程、
該複合膜を、該シート状多孔質補強材の融点より高いがその熱分解温度より低い第2の温度において熱処理する工程、および
該高分子電解質前駆体を加水分解することにより高分子電解質へ転化する工程
を含んでなる、補強された固体高分子電解質膜の製造方法;
(3)該補強された固体高分子電解質膜における該シート状多孔質補強材と該高分子電解質との間の剥離強度が2N/cm以上である、(1)または(2)に記載の方法;
(4)該熱分解温度より低い温度または該第2の温度が300℃以上である、(1)〜(3)のいずれか1項に記載の方法;
(5)該高分子電解質前駆体が、下記一般式(1)で表される重合体を含む、(1)〜(4)のいずれか1項に記載の方法;
(7)該シート状多孔質補強材が延伸多孔質ポリテトラフルオロエチレンである、(1)〜(6)のいずれか1項に記載の方法;
(8)(1)〜(7)のいずれか1項に記載の方法により製造された、固体高分子電解質膜;
(9)(8)に記載の固体高分子電解質膜の両面に電極層を組み合わせてなる、固体高分子形燃料電池用膜電極組立体;ならびに
(10)(9)に記載の膜電極組立体を含む、固体高分子形燃料電池
が提供される。
特に好ましい高分子電解質前駆体として、下記一般式(1)で表される重合体を含むものが挙げられる。
1)引っ張り試験
引張試験機(SHIMADZU製AUTOGRAPH AG−I)を用いて、引張速度50mm/秒ではく離強度を計測した。
2)凍結/解凍サイクル試験
水1Lを含有する1L容のポリプロピレン製瓶に試料片(15cm×15cm)を入れて密閉し、ESPEC製恒温恒湿槽SH−220において−30℃と100℃を各1時間ずつ保持することを1サイクルとし、25サイクル毎に試料を取り出してはく離の有無を目視で確認した。
イオン交換容量IECが0.9meq/gの高分子電解質前駆体(デュポン株式会社製Nafion(登録商標)ResinR−1100)をホットプレス法により180℃で厚さ300μmに成膜した。得られた高分子電解質前駆体膜をロール押出し機により90℃で押し出して厚さ40μmに加工した。この高分子電解質前駆体膜を、厚さ8.5μm、空孔率80%、平均孔径0.5μm、引張強さ45MPa、目付量4.0g/m2の延伸多孔質PTFE膜(融点327℃)の上に重ねて200℃で30分加熱して、高分子電解質前駆体膜の一部を延伸多孔質PTFE膜に含浸させた。次いで、この膜を裏返し、別の上記延伸多孔質PTFE膜の上に重ねて200℃で30分加熱して、高分子電解質前駆体膜の反対側の一部を延伸多孔質PTFE膜に含浸させた。熱処理時の膜収縮を防止するため、両面を延伸多孔質PTFE膜に含浸させた高分子電解質前駆体膜の4辺をピンフレームで固定し、オーブン内で340℃、10分の熱処理を施した。熱処理後、高分子電解質前駆体膜を、15質量%の水酸化カリウムおよび30質量%のジメチルスルホキシドを溶解した水溶液に浸漬し、温度60℃で4時間撹拌することによりアルカリ加水分解処理した。引き続いて、膜を2モル/L塩酸に浸漬し、温度60℃で3時間撹拌した。その後膜をイオン交換水で水洗し、そして温度85℃で4時間乾燥することにより固体高分子電解質膜を得た。
実施例1で用いた延伸多孔質PTFE膜(融点327℃)を2枚重ねて、その上に、実施例1で製作した厚さ40μmの高分子電解質前駆体膜を重ねて200℃で30分加熱して、高分子電解質前駆体膜の片側の一部を2枚の延伸多孔質PTFE膜に含浸させた。熱処理時の膜収縮を防止するため、片面を延伸多孔質PTFE膜に含浸させた高分子電解質前駆体膜の4辺をピンフレームで固定し、オーブン内で340℃、10分の熱処理を施した。熱処理後、高分子電解質前駆体膜を、15質量%の水酸化カリウムおよび30質量%のジメチルスルホキシドを溶解した水溶液に浸漬し、温度60℃で4時間撹拌することによりアルカリ加水分解処理した。引き続いて、膜を2モル/L塩酸に浸漬し、温度60℃で3時間撹拌した。その後膜をイオン交換水で水洗し、そして温度85℃で4時間乾燥することにより固体高分子電解質膜を得た。
厚さ16μm、空孔率80%、平均孔径0.1μm、引張強さ32MPa、目付量5.9g/m2の延伸多孔質PTFE膜(融点327℃)を2枚重ねて、その上に、実施例1で製作した厚さ40μmの高分子電解質前駆体膜を重ねて200℃で30分加熱して、高分子電解質前駆体膜の片側の一部を2枚の延伸多孔質PTFE膜に含浸させた。熱処理時の膜収縮を防止するため、片面を延伸多孔質PTFE膜に含浸させた高分子電解質前駆体膜の4辺をピンフレームで固定し、オーブン内で340℃、10分の熱処理を施した。熱処理後、高分子電解質前駆体膜を、15質量%の水酸化カリウムおよび30質量%のジメチルスルホキシドを溶解した水溶液に浸漬し、温度60℃で4時間撹拌することによりアルカリ加水分解処理した。引き続いて、膜を2モル/L塩酸に浸漬し、温度60℃で3時間撹拌した。その後膜をイオン交換水で水洗し、そして温度85℃で4時間乾燥することにより固体高分子電解質膜を得た。
熱処理(340℃、10分)を施さないことを除き、実施例1と同じ手順で固体高分子電解質膜を得た。得られた固体高分子電解質膜を、幅1cm、長さ10cmになるように切断し、固体高分子電解質膜と延伸多孔質PTFE膜の間のはく離強度を上記引張試験機により計測したところ、1.3N/cmであった。また、上記凍結/解凍サイクル試験による破断までのサイクル数は750回であった。
イオン交換容量IECが0.9meq/gの高分子電解質樹脂溶液(デュポン株式会社製Nafion(登録商標)SE−20192)を、エチレン−テトラフルオロエチレン共重合体(ETFE)フィルム上に厚さ300μmになるように塗工した。次いで、その塗膜の上に、厚さ10μm、空孔率70%、平均孔径0.2μm、引張強さ45MPa、目付量4.0g/m2の延伸多孔質PTFE膜(融点327℃)2枚を接触させ、含浸膜を製作した。次いで、得られた含浸膜を恒温槽において140℃で5分間乾燥し、延伸多孔質PTFE膜で補強された膜厚40μmの固体高分子電解質膜を得た。得られた固体高分子電解質膜を、幅1cm、長さ10cmになるように切断し、固体高分子電解質膜と延伸多孔質PTFE膜の間のはく離強度を上記引張試験機により計測したところ、1.1N/cmであった。また、上記凍結/解凍サイクル試験による破断までのサイクル数は250回であった。
Claims (9)
- シート状多孔質補強材と高分子電解質前駆体とを用意する工程、
該高分子電解質前駆体を、溶媒不存在下、該シート状多孔質補強材の融点より低い第1の温度において該シート状多孔質補強材に含浸させることにより、該高分子電解質前駆体の少なくとも一部が該シート状多孔質補強材に含浸複合化された複合膜を得る工程、
該複合膜を、該シート状多孔質補強材の融点より高いがその熱分解温度より低い第2の温度において熱処理する工程、および
該高分子電解質前駆体を加水分解することにより高分子電解質へ転化する工程
を含んでなり、
該高分子電解質前駆体が、下記一般式(1)で表される重合体を含む、補強された固体高分子電解質膜の製造方法。
- 該補強された固体高分子電解質膜における該シート状多孔質補強材と該高分子電解質との間の剥離強度が2N/cm以上である、請求項1または2に記載の方法。
- 該熱分解温度より低い温度または該第2の温度が300℃以上である、請求項1〜3のいずれか1項に記載の方法。
- 前記一般式(1)において、m=2である、請求項1〜4のいずれか1項に記載の方法。
- 該シート状多孔質補強材が延伸多孔質ポリテトラフルオロエチレンである、請求項1〜5のいずれか1項に記載の方法。
- 請求項1〜6のいずれか1項に記載の方法により製造された、固体高分子電解質膜。
- 請求項7に記載の固体高分子電解質膜の両面に電極層を組み合わせてなる、固体高分子形燃料電池用膜電極組立体。
- 請求項8に記載の膜電極組立体を含む、固体高分子形燃料電池。
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KR1020097027192A KR101597835B1 (ko) | 2007-05-29 | 2008-05-20 | 고체 고분자 전해질막의 제조 방법 및 고체 고분자 전해질막 |
PCT/JP2008/059611 WO2008146766A1 (ja) | 2007-05-29 | 2008-05-20 | 固体高分子電解質膜の製造方法、固体高分子電解質膜 |
EP08753118A EP2154744B1 (en) | 2007-05-29 | 2008-05-20 | Process for producing solid polymer electrolyte membrane, and solid polymer electrolyte membrane |
CN200880023420A CN101730954A (zh) | 2007-05-29 | 2008-05-20 | 固体高分子电解质膜的制造方法、固体高分子电解质膜 |
CA002688021A CA2688021A1 (en) | 2007-05-29 | 2008-05-20 | Method of fabricating solid polymer electrolyte membrane, solid polymer electrolyte membrane, membrane electrode assembly for solid polymer fuel cell, and solid polymer fuel cell |
US12/600,889 US20100203419A1 (en) | 2007-05-29 | 2008-05-20 | Process For Producing Solid Polymer Electrolyte Membrane, and Solid Polymer Electrolyte Membrane |
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EP2154744B1 (en) | 2013-01-09 |
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