JP5119046B2 - POLYMER ELECTROLYTE MEMBRANE MANUFACTURING METHOD AND SOLID POLYMER TYPE FUEL CELL - Google Patents
POLYMER ELECTROLYTE MEMBRANE MANUFACTURING METHOD AND SOLID POLYMER TYPE FUEL CELL Download PDFInfo
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- 239000005518 polymer electrolyte Substances 0.000 title claims description 81
- 239000012528 membrane Substances 0.000 title claims description 56
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- 229920000642 polymer Polymers 0.000 title claims description 13
- 239000000446 fuel Substances 0.000 title description 11
- 239000007787 solid Substances 0.000 title description 5
- 239000002243 precursor Substances 0.000 claims description 40
- 239000003795 chemical substances by application Substances 0.000 claims description 31
- 238000006116 polymerization reaction Methods 0.000 claims description 26
- 239000003792 electrolyte Substances 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 9
- 238000002955 isolation Methods 0.000 claims description 7
- 238000010306 acid treatment Methods 0.000 claims description 6
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 230000001747 exhibiting effect Effects 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 238000000034 method Methods 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 150000001785 cerium compounds Chemical class 0.000 description 5
- 125000000542 sulfonic acid group Chemical group 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- -1 fluorine ions Chemical class 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920000557 Nafion® Polymers 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 230000002225 anti-radical effect Effects 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Description
本発明は、耐ラジカル性に優れた高分子電解質膜を簡素化した工程で製造する方法に関する。また、製造された高分子電解質膜を有する固体高分子型燃料電池に関する。 The present invention relates to a method for producing a polymer electrolyte membrane having excellent radical resistance in a simplified process. The present invention also relates to a polymer electrolyte fuel cell having the manufactured polymer electrolyte membrane.
固体高分子電解質型燃料電池は、電解質として固体高分子電解質膜を用い、この膜の両面に触媒電極層を接合した構造を有する。このような固体高分子電解質型燃料電池を構成する固体電解質膜や触媒電極層は、プロトン伝導性を有する高分子電解質材料を用いて形成されるのが一般的である。このような電解質材料としては、ナフィオン（商品名：Ｎａｆｉｏｎ、デュポン株式会社製）等のパーフルオロスルホン酸系樹脂が広く用いられてきた。 A solid polymer electrolyte fuel cell has a structure in which a solid polymer electrolyte membrane is used as an electrolyte and a catalyst electrode layer is bonded to both surfaces of the membrane. The solid electrolyte membrane and the catalyst electrode layer constituting such a solid polymer electrolyte fuel cell are generally formed using a polymer electrolyte material having proton conductivity. As such an electrolyte material, perfluorosulfonic acid resins such as Nafion (trade name: Nafion, manufactured by DuPont Co., Ltd.) have been widely used.
しかしながら、燃料電池のカソード側で起こる水を生成する反応の際に発生するラジカル等の影響により、高分子電解質膜及び電極触媒は劣化しやすく、従来から用いられている比較的耐ラジカル性に優れるパーフルオロスルホン酸系樹脂を用いて形成された高分子電解質膜及び電極触媒でも劣化等の問題があった。特に、上記ラジカル等の影響により上記電解質膜および触媒電極層から溶出したフッ素イオンが、燃料電池のガスの配管等の他部材に対して悪影響を及ぼす可能性があるため、燃料電池としての耐久性が低下するおそれが生じた。 However, the polymer electrolyte membrane and the electrode catalyst are likely to deteriorate due to the influence of radicals and the like generated during the reaction that generates water that occurs on the cathode side of the fuel cell, and are relatively excellent in radical resistance that has been conventionally used. Even polymer electrolyte membranes and electrode catalysts formed using perfluorosulfonic acid resins have problems such as deterioration. In particular, since the fluorine ions eluted from the electrolyte membrane and the catalyst electrode layer due to the influence of the radicals and the like may adversely affect other members such as gas piping of the fuel cell, durability as a fuel cell There was a risk that it would decrease.
そこで、高分子電解質膜の耐ラジカル性を向上させる方法として、
（１）難溶性セリウム化合物を−ＳＯ３Ｈ型電解質ポリマ分散液に分散させてキャスト製膜する方法
（２）−ＳＯ３Ｈ型電解質膜の−ＳＯ３Ｈの一部をセリウムカチオンで置換したものを、試薬処理にて膜内に難溶性セリウム化合物を発生させる方法
が考えられている。
Therefore, as a method of improving the radical resistance of the polymer electrolyte membrane,
(1) and the part of the -SO 3 H of a poorly soluble cerium compound dispersed in -SO 3 H type electrolyte polymer dispersions to cast film production method (2) -SO 3 H type electrolyte membrane was replaced with cerium cations A method is considered in which a hardly soluble cerium compound is generated in a film by reagent treatment.
例えば、下記特許文献１には、スルホン酸基を有する高分子化合物と難溶性セリウム化合物とからなる高分子電解質膜が開示されている。そこで開示された製造方法は、スルホン酸基を有する高分子化合物からなる陽イオン交換膜を、セリウムイオンを含む溶液中に浸漬してスルホン酸基の一部をセリウムイオンによりイオン交換した後、セリウムイオンと反応することにより難溶性セリウム化合物を形成する物質を含む溶液に浸漬して、膜中に難溶性セリウム化合物を形成するものである。 For example, Patent Document 1 below discloses a polymer electrolyte membrane comprising a polymer compound having a sulfonic acid group and a hardly soluble cerium compound. In the production method disclosed therein, a cation exchange membrane made of a polymer compound having a sulfonic acid group is immersed in a solution containing cerium ions, and a portion of the sulfonic acid groups are ion-exchanged with cerium ions. It is immersed in a solution containing a substance that forms a hardly soluble cerium compound by reacting with ions to form a hardly soluble cerium compound in the film.
しかし、イオン交換による添加では、電解質膜表面に添加物が局在し、触媒層の定着に不利である。 However, in the addition by ion exchange, the additive is localized on the surface of the electrolyte membrane, which is disadvantageous for fixing the catalyst layer.
一方、電解質分散液への添加は溶液キャスト製膜に限定されるので、溶融製膜も含めた汎用性のある工程としてはふさわしくない。 On the other hand, the addition to the electrolyte dispersion is limited to solution cast film formation, so it is not suitable as a versatile process including melt film formation.
又、高分子電解質前駆体との分散混合／溶融製膜と言う方法も考えられるが、（１）乾式混合の場合、高分子電解質前駆体の粘着性が高く微細化が困難であるので均一分散が困難である
（２）湿式混合の場合、高分子電解質前駆体が微分散した分散液に添加剤を混ぜることで可能である。湿式混合に適した分散系として乳化重合ディスバージョンがあげられるが、これは水系重合を経るために、微量の−ＳＯ３Ｈが生成して溶融成形不良の原因となる懸念がある。また、乳化剤に起因するＰＦＯＡ問題、重合前乳化や乳化剤洗浄除去などの煩雑なプロセスが必要となり課題が多い。
Although a method of dispersion mixing / melt film formation with a polymer electrolyte precursor is also conceivable, (1) in the case of dry mixing, since the polymer electrolyte precursor is highly adhesive and difficult to refine, uniform dispersion is possible. (2) In the case of wet mixing, it is possible to mix an additive with a dispersion in which the polymer electrolyte precursor is finely dispersed. As a dispersion system suitable for wet mixing, there is an emulsion polymerization dispersion. However, since it undergoes aqueous polymerization, there is a concern that a trace amount of —SO 3 H is generated and causes melt molding failure. Moreover, complicated processes such as PFOA problems caused by emulsifiers, pre-polymerization emulsification and emulsifier washing removal are necessary, and there are many problems.
更に、一般的な手法として高分子電解質前駆体を溶媒に分散させて添加物を混合することが考えられるが、高分子電解質前駆体を単離してから行うと、粉砕や溶媒分散などの余分な工程が必要となる。
本発明は、上記従来技術の問題点に鑑みて発明されたものであり、耐ラジカル性に優れた高分子電解質膜を簡素化した工程で製造する方法を提供することを目的とする。また、これにより、固体高分子型燃料電池の耐久性の向上を図ることを目的とする。 The present invention has been invented in view of the above-described problems of the prior art, and an object thereof is to provide a method for producing a polymer electrolyte membrane excellent in radical resistance in a simplified process. Another object of the present invention is to improve the durability of the polymer electrolyte fuel cell.
本発明者は、特定の手段により、高分子電解質前駆体に耐ラジカル剤を添加・分散させる方法を見出し、本発明に到達した。 The present inventor has found a method of adding and dispersing a radical-resistant agent to the polymer electrolyte precursor by specific means, and has reached the present invention.
即ち、第１に、本発明は、アルカリ加水分解及び酸処理によりプロトン伝導性を発揮する高分子電解質前駆体を合成し、該高分子電解質前駆体を製膜し、該高分子電解質前駆体膜に対するアルカリ加水分解及び酸処理する高分子電解質膜の製造方法の発明であって、重合性原料仕込み時から重合し合成した該高分子電解質前駆体を単離するに至る重合工程中のいずれかに耐ラジカル剤を存在させることを特徴とする。 That is, first, the present invention synthesizes a polymer electrolyte precursor exhibiting proton conductivity by alkali hydrolysis and acid treatment, forms the polymer electrolyte precursor, and forms the polymer electrolyte precursor film. An invention of a method for producing a polymer electrolyte membrane subjected to alkali hydrolysis and acid treatment with respect to the polymer electrolyte membrane, and any one of the polymerization steps leading to isolation of the polymer electrolyte precursor polymerized and synthesized from the preparation of the polymerizable raw material It is characterized by the presence of a radical-proofing agent.
重合工程中のいずれかに耐ラジカル剤を存在させることによって、耐ラジカル剤の分散性が向上するとともに、高分子電解質前駆体中に耐ラジカル剤を添加・混合する工程が不要となる。 The presence of the radical-resistant agent in any of the polymerization steps improves the dispersibility of the radical-resistant agent and eliminates the need for adding and mixing the radical-resistant agent into the polymer electrolyte precursor.
本発明でいう『重合性原料仕込み時から重合し合成した該高分子電解質前駆体を単離するに至る重合工程中のいずれか』の中で、合成する原料仕込み時、重合反応中、及び重合反応直後が好ましく例示される。 In the present invention, “any one of the polymerization steps leading to isolation of the polymer electrolyte precursor polymerized and synthesized from the time when the polymerizable raw material is charged”, the raw material to be synthesized, the polymerization reaction, and the polymerization An example immediately after the reaction is preferred.
前記耐ラジカル剤量が、高分子電解質膜全量に対して、０．１〜２０ｗｔ％であることが好ましい。耐ラジカル剤量が０．１ｗｔ％未満であると耐ラジカル性が十分に発揮されず、耐ラジカル剤の量が２０ｗｔ％を越えると本来の高分子電解質膜の物性に悪影響をもたらす。 The amount of the radical-resistant agent is preferably 0.1 to 20 wt% with respect to the total amount of the polymer electrolyte membrane. If the amount of the radical-resistant agent is less than 0.1 wt%, the radical resistance is not sufficiently exhibited, and if the amount of the radical-resistant agent exceeds 20 wt%, the physical properties of the original polymer electrolyte membrane are adversely affected.
本発明で用いられる耐ラジカル剤としては特に限定されないが、具体的には、酸化セリウム、酸化ジルコニウムから選択される１種以上が好ましく例示される。 Although it does not specifically limit as a radical-proof agent used by this invention, Specifically, 1 or more types selected from a cerium oxide and a zirconium oxide are illustrated preferably.
本発明で合成される該高分子電解質前駆体としては、後工程で加水分解されプロトン伝導性を発揮する官能基を有する公知の高分子化合物が用いられる。これらの高分子電解質前駆体の中で官能基としてＳＯ２Ｆを有するフッ素系高分子化合物が好ましく例示される。該高分子電解質前駆体は、２７０℃、荷重２．１６ｋｇにおけるメルトフローレート（ＭＲＦ）＝５〜１００ｇ／１０分、イオン化後ＥＷ＝５００〜１０００ｇ／ｅｑ、−ＳＯ２Ｘ基濃度＝１５〜４０ｍｏｌ％（Ｘ：ハロゲン）であることが好ましい。 As the polymer electrolyte precursor synthesized in the present invention, a known polymer compound having a functional group that is hydrolyzed in a later step and exhibits proton conductivity is used. Of these polymer electrolyte precursors, preferred are fluorine-based polymer compounds having SO 2 F as a functional group. The polymer electrolyte precursor has a melt flow rate (MRF) at 270 ° C. and a load of 2.16 kg = 5 to 100 g / 10 minutes, EW after ionization = 500 to 1000 g / eq, —SO 2 X group concentration = 15 to 40 mol % (X: halogen) is preferred.
第２に、本発明は、上記の方法で製造された高分子電解質膜を有する固体高分子型燃料電池である。 Second, the present invention is a polymer electrolyte fuel cell having a polymer electrolyte membrane produced by the above method.
本発明では、重合性原料仕込み時から重合し合成した該高分子電解質前駆体を単離するに至る重合工程中のいずれかに耐ラジカル剤を存在させることによって、耐ラジカル剤の分散性が向上するとともに、高分子電解質前駆体中に耐ラジカル剤を添加・混合する工程が不要となる。又、重合工程中に耐ラジカル剤を存在させて製膜するので、膜表面に耐ラジカル剤が局在せず、ＭＥＡ化の段階で触媒層の定着を良好に維持することが可能である。 In the present invention, the dispersibility of the radical resistant agent is improved by the presence of the radical resistant agent in any of the polymerization steps leading to the isolation of the polymer electrolyte precursor that has been polymerized and synthesized from the time when the polymerizable raw material is charged. In addition, the step of adding and mixing the radical-resistant agent to the polymer electrolyte precursor is not necessary. In addition, since the film is formed in the presence of a radical-resistant agent during the polymerization process, the radical-resistant agent is not localized on the film surface, and the catalyst layer can be well fixed at the stage of MEA conversion.
図１に、従来の電解質膜製造プロセスを示す。高分子電解質合成後に耐ラジカル剤を添加し、その後に、製膜している。 FIG. 1 shows a conventional electrolyte membrane manufacturing process. A radical-resistant agent is added after the polymer electrolyte synthesis, and then a film is formed.
図２に、本発明の電解質膜製造プロセスを示す。重合工程で耐ラジカル剤を添加し、その後の工程で製膜している。 FIG. 2 shows an electrolyte membrane manufacturing process of the present invention. A radical-proofing agent is added in the polymerization process, and a film is formed in the subsequent process.
プロトン伝導性を有する高分子電解質（以下、Ｈ型高分子電解質という）とはスルホン酸基等有し、特に後工程で変性させなくてもそれ自体がプロトン伝導性を有するものであるのに対し、本発明で用いる、アルカリ加水分解及び酸処理によりプロトン伝導性を発揮する高分子電解質前駆体（以下、単に高分子電解質前駆体やＦ型高分子電解質という）とは、後工程で加水分解処理や酸型化処理を行うことによってスルホン酸基等のプロトン伝導性基に変性される前駆体基、例えば−ＳＯ２Ｆ基、−ＳＯ２Ｃｌ基など、を有するものである。 A polymer electrolyte having proton conductivity (hereinafter referred to as “H-type polymer electrolyte”) has a sulfonic acid group and the like, and in particular has proton conductivity even if it is not modified in a subsequent process. The polymer electrolyte precursor used in the present invention and exhibiting proton conductivity by alkali hydrolysis and acid treatment (hereinafter simply referred to as polymer electrolyte precursor or F-type polymer electrolyte) is a hydrolysis treatment in a later step. Or a precursor group that is modified to a proton conductive group such as a sulfonic acid group by performing an acidification treatment, such as a —SO 2 F group or a —SO 2 Cl group.
本発明で合成される高分子電解質前駆体の重合方法としては、例えば非水溶媒系の溶液重合や懸濁重合が上げられる。生成ポリマー構造としては、ＭＦＲ＝５〜１００、ＥＷ＝５００〜１０００、−ＳＯ２Ｆ基濃度＝１５〜４０ｍｏｌ％が好ましい。耐ラジカル剤としては、ＣｅＯ２、ＺｒＯ２などが好ましく例示され、その粒径は１０ｎｍ〜１μｍ程度が好ましい。耐ラジカル剤の混合比としては、０．１〜２０ｗｔ％が好ましい。耐ラジカル剤を添加するタイミングとしては、（１）重合原料仕込み時、（２）重合反応終了後〜溶媒洗浄開始の間が好ましい。目的物の単離方法としては、例えば、液成分を減圧除去後、適宜別溶媒にて洗浄する方法が採用される。 Examples of the polymerization method of the polymer electrolyte precursor synthesized in the present invention include non-aqueous solvent type solution polymerization and suspension polymerization. The resulting polymer structure, MFR = 5~100, EW = 500~1000 , -SO 2 F group concentration = 15~40mol% is preferred. Preferred examples of the radical-proofing agent include CeO 2 and ZrO 2 , and the particle size is preferably about 10 nm to 1 μm. The mixing ratio of the anti-radical agent is preferably 0.1 to 20 wt%. The timing of adding the radical-proofing agent is preferably (1) when the polymerization raw material is charged, and (2) after the completion of the polymerization reaction to the start of solvent washing. As a method for isolating the target product, for example, a method in which the liquid component is removed under reduced pressure and then appropriately washed with another solvent is employed.
本発明では、ＣＦ２＝ＣＦＯＣＦ２ＣＦ（ＣＦ３）Ｏ（ＣＦ２ＣＦ２）ＳＯ２Ｆと重合生成ポリマーが共存することで分散性が良好である。特に、−ＳＯ２Ｆ濃度を１８ｍｏｌ％以上とすることで分散性が良好となる。又、ポリマーの単離（＝モノマー及び溶媒、副生成物除去）を耐ラジカル剤分散より後回しにすることで余分な工程を増やす必要がない。 In the present invention, CF 2 ═CFOCF 2 CF (CF 3 ) O (CF 2 CF 2 ) SO 2 F and a polymerization product polymer coexist so that the dispersibility is good. In particular, the dispersibility is improved by setting the —SO 2 F concentration to 18 mol% or more. Moreover, it is not necessary to increase the number of extra steps by postponing the isolation of the polymer (= removal of monomer, solvent and by-products) after the dispersion of the radical-resistant agent.
本発明では、前記高分子電解質前駆体は単膜として用いても良く、強度と耐久性の観点から、多孔性膜と高分子電解質前駆体とを複合させた複合高分子電解質膜前駆体として用いても良い。多孔性膜と高分子電解質前駆体とを複合させて複合高分子電解質膜前駆体とする方法については特に限定されず、各種公知の方法を採用することができる。この複合高分子電解質膜前駆体をアルカリ加水分解及び酸処理することで複合高分子電解質膜が得られる。 In the present invention, the polymer electrolyte precursor may be used as a single membrane, and is used as a composite polymer electrolyte membrane precursor in which a porous membrane and a polymer electrolyte precursor are combined from the viewpoint of strength and durability. May be. The method of combining the porous membrane and the polymer electrolyte precursor to form the composite polymer electrolyte membrane precursor is not particularly limited, and various known methods can be employed. The composite polymer electrolyte membrane is obtained by subjecting the composite polymer electrolyte membrane precursor to alkaline hydrolysis and acid treatment.
複合高分子電解質膜を用いることにより、固体高分子電解質膜の厚さを薄くすることが可能であり、また、高分子フィルム又は高分子シート基材を電解質膜の支持体として用いるため、電解質膜の強度を補強することができるので、複合高分子電解質膜を備えた燃料電池は、高耐久性であるとともに、燃料ガスのクロスリーク量が少なく、電流−電圧特性を向上することができる。
以下、本発明の実施例を示す。
By using the composite polymer electrolyte membrane, it is possible to reduce the thickness of the solid polymer electrolyte membrane, and since the polymer film or the polymer sheet substrate is used as a support for the electrolyte membrane, the electrolyte membrane Therefore, the fuel cell provided with the composite polymer electrolyte membrane is highly durable, has a small amount of fuel gas cross-leakage, and can improve current-voltage characteristics.
Examples of the present invention will be described below.
［実施例１：重合生成物へのＣｅ化合物添加］
（高分子電解質前駆体合成）
３ＬのＳＵＳ製耐圧容器内を真空置換後減圧し、ついで重合溶媒Ｃ６Ｆ１４を１０８０ｇ、ＣＦ２＝ＣＦＯＣＦ２ＣＦ（ＣＦ３）Ｏ（ＣＦ２ＣＦ２）ＳＯ２Ｆ液１３２０ｇを吸引した後、ＴＦＥガス１４０ｇで加圧し、さらに温度２５℃に調整・攪拌した。重合開始剤（（Ｃ３Ｆ７ＣＯＯ）２）を対ＳＯ２Ｆモノマー比０．０３ｍｏｌ％投入して反応開始し、常に圧力一定（０．３０ＭＰａ）となるようにＴＦＥガスを追加供給した。テトラフルオロエチレンガス４３ｇを追加した段階で圧力を開放し、反応を終了させた。
（生成ポリマー洗浄／Ｃｅ化合物添加）
反応終了後の容器内に酸化セリウム（粒径約１μｍ）１ｇを投入し、所定時間攪拌した。これを取り出してエバポレータで濃縮し、さらにアセトンで数回洗浄して残モノマー液をのぞいた。これを乾燥機で１２０℃、８時間乾燥し、目的物である高分子電解質膜前駆体を得た。得られた目的物は１０５ｇ、ＭＦＲ＝７６ｇ／１０分、ＥＷ＝８８５であった。
（製膜／イオン化）
上記生成物をポリイミドフィルムにはさんで２３０℃でプレスし約１００μｍ厚の高分子電解質膜前駆体膜を得た。
[Example 1: Addition of Ce compound to polymerization product]
(Polymer electrolyte precursor synthesis)
After the inside of the 3 L pressure vessel made of SUS was vacuum-reduced, the pressure was reduced, and then 1080 g of the polymerization solvent C 6 F 14 and 1320 g of CF 2 = CFOCF 2 CF (CF 3 ) O (CF 2 CF 2 ) SO 2 F solution were sucked. The mixture was pressurized with 140 g of TFE gas, and further adjusted and stirred at a temperature of 25 ° C. A polymerization initiator ((C 3 F 7 COO) 2 ) was added to the SO 2 F monomer ratio of 0.03 mol% to start the reaction, and TFE gas was additionally supplied so that the pressure was always constant (0.30 MPa). The pressure was released when 43 g of tetrafluoroethylene gas was added, and the reaction was terminated.
(Production polymer washing / Ce compound addition)
1 g of cerium oxide (particle size: about 1 μm) was put into the container after completion of the reaction and stirred for a predetermined time. This was taken out, concentrated with an evaporator, and further washed several times with acetone to remove the residual monomer solution. This was dried with a drier at 120 ° C. for 8 hours to obtain a target polymer electrolyte membrane precursor. The obtained object was 105g, MFR = 76g / 10min, EW = 885.
(Film / Ionization)
The product was pressed at 230 ° C. between polyimide films to obtain a polymer electrolyte membrane precursor membrane having a thickness of about 100 μm.
これを□５ｃｍにカットし、１Ｎ‐ＮａＯＨ／ＤＭＳＯ＝６：４混合液中８０℃、２時間処理後、水洗して０．５Ｎ‐Ｈ２ＳＯ４中８０℃、１時間処理し、さらにイオン交換水中９０℃、２時間処理後１２０℃乾燥して高分子電解質膜とした。
（フェントン試験）
下記条件でフェントン試験を行った結果、溶出Ｆイオンは４．４ｐｐｍであった。
Ｆｅ２＋：１０ｐｐｍ／Ｈ２Ｏ２：１％／１００℃、８時間
This is cut to 5 cm, treated in a 1N-NaOH / DMSO = 6: 4 mixture at 80 ° C. for 2 hours, washed with water, treated in 0.5N—H 2 SO 4 at 80 ° C. for 1 hour, and further ionized. The polymer electrolyte membrane was obtained by treating at 90 ° C. in exchanged water for 2 hours and then drying at 120 ° C.
(Fenton test)
As a result of conducting a Fenton test under the following conditions, the eluted F ion was 4.4 ppm.
Fe 2+ : 10 ppm / H 2 O 2 : 1% / 100 ° C., 8 hours
［実施例２：重合仕込み段階でのＣｅ化合物添加］
（高分子電解質前駆体合成／Ｃｅ化合物添加）
３ＬのＳＵＳ製耐圧容器内に酸化セリウム（粒径約１μｍ）１ｇを入れておき、真空置換後減圧し、ついで重合溶媒Ｃ６Ｆ１４を１０８０ｇ、ＳＯ２Ｆモノマー液１３２０ｇを吸引した後、ＴＦＥガス１４０ｇで加圧し、さらに温度２５℃に調整・攪拌した。重合開始剤（（Ｃ３Ｆ７ＣＯＯ）２）を対ＳＯ２Ｆモノマー比０．０３ｍｏｌ％投入して反応開始し、常に圧力一定（０．３０ＭＰａ）となるようにＴＦＥガスを追加供給した。ＴＦＥガス４２ｇを追加した段階で圧力を開放し、反応を終了させた。
（生成ポリマー洗浄）
内容物を容器から取り出し、エバポレータで濃縮し、さらにアセトンで数回洗浄して残モノマー液を除いた。これを乾燥機で１２０℃、８時間乾燥し、目的物をえた。得られた目的物は１０５ｇ、ＭＦＲ＝８２、ＥＷ＝８８３であった。
（製膜／イオン化）
上記生成物をポリイミドフィルムに挟んで２３０℃でプレスし約１００μｍ厚の高分子電解質膜前駆体膜（Ｆ型高分子電解質膜）を得た。
[Example 2: Ce compound addition at the stage of polymerization preparation]
(Polymer electrolyte precursor synthesis / Ce compound addition)
1 g of cerium oxide (particle size: about 1 μm) was placed in a 3 L SUS pressure vessel, and the pressure was reduced after vacuum substitution. Then, 1080 g of the polymerization solvent C 6 F 14 and 1320 g of the SO 2 F monomer solution were sucked, and then TFE. The gas was pressurized with 140 g, and further adjusted and stirred at a temperature of 25 ° C. A polymerization initiator ((C3F 7 COO) 2 ) was added to the SO 2 F monomer ratio of 0.03 mol% to start the reaction, and TFE gas was additionally supplied so that the pressure was always constant (0.30 MPa). When 42 g of TFE gas was added, the pressure was released and the reaction was terminated.
(Production polymer washing)
The contents were taken out from the container, concentrated with an evaporator, and further washed with acetone several times to remove the residual monomer solution. This was dried with a dryer at 120 ° C. for 8 hours to obtain the desired product. The obtained object was 105 g, MFR = 82, EW = 883.
(Film / Ionization)
The product was sandwiched between polyimide films and pressed at 230 ° C. to obtain a polymer electrolyte membrane precursor membrane (F type polymer electrolyte membrane) having a thickness of about 100 μm.
これを□５ｃｍにカットし、１Ｎ−ＮａＯＨ／ＤＭＳＯ＝６：４混合液中、８０℃、２時間処理後、水洗して０．５Ｎ‐Ｈ２ＳＯ４中、８０℃、１時間処理し、さらにイオン交換水中９０℃、２時間処理後、１２０℃で乾燥して高分子電解質膜（Ｈ型高分子電解質膜）とした。
（フェントン試験）
上記と同様の条件でフェントン試験を行った結果、溶出Ｆイオンは４．８ｐｐｍであった。
This was cut into 5 cm, treated in 1N-NaOH / DMSO = 6: 4 mixture at 80 ° C. for 2 hours, washed with water and treated in 0.5N—H 2 SO 4 at 80 ° C. for 1 hour. Further, after treatment at 90 ° C. for 2 hours in ion-exchanged water, the polymer electrolyte membrane (H-type polymer electrolyte membrane) was obtained by drying at 120 ° C.
(Fenton test)
As a result of conducting a Fenton test under the same conditions as described above, the eluted F ion was 4.8 ppm.
［比較例］
酸化セリウムを重合工程で添加しないこと以外は、実施例２と同様の手順で高分子電解質膜を調製した。フェントン試験の結果、溶出Ｆイオンは６０ｐｐｍであった。
[Comparative example]
A polymer electrolyte membrane was prepared in the same procedure as in Example 2 except that cerium oxide was not added in the polymerization step. As a result of the Fenton test, the eluted F ion was 60 ppm.
実施例１及び２の結果より、重合性原料仕込み時から重合し合成した高分子電解質前駆体を単離するに至る重合工程中のいずれかに耐ラジカル剤である酸化セリウムを存在させることによって、耐ラジカル剤の分散性が向上する。これにより、製造された高分子電解質膜の耐久性が向上することが分かる。 From the results of Examples 1 and 2, the presence of cerium oxide, which is a radical-resistant agent, in any of the polymerization steps leading to isolation of the polymer electrolyte precursor polymerized and synthesized from when the polymerizable raw material was charged, Dispersibility of the radical resistant agent is improved. Thereby, it turns out that durability of the manufactured polymer electrolyte membrane improves.
本発明により、高分子電解質膜中の耐ラジカル剤の分散性が向上するとともに、高分子電解質前駆体（Ｆ型高分子電解質）中に耐ラジカル剤を添加・混合する工程が不要となる。又、重合工程中に耐ラジカル剤を存在させて製膜するので、膜表面に耐ラジカル剤が局在せず、ＭＥＡ化の段階で触媒層の定着を良好に維持することが可能である。これにより、燃料電池の耐久性の向上に貢献する。 According to the present invention, the dispersibility of the radical-resistant agent in the polymer electrolyte membrane is improved, and the step of adding and mixing the radical-resistant agent into the polymer electrolyte precursor (F-type polymer electrolyte) becomes unnecessary. In addition, since the film is formed in the presence of a radical-resistant agent during the polymerization process, the radical-resistant agent is not localized on the film surface, and the catalyst layer can be well fixed at the stage of MEA conversion. This contributes to improving the durability of the fuel cell.
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