JP4720090B2 - Sulfonic acid group-containing polymer electrolyte membrane and article using the same - Google Patents
Sulfonic acid group-containing polymer electrolyte membrane and article using the same Download PDFInfo
- Publication number
- JP4720090B2 JP4720090B2 JP2004050750A JP2004050750A JP4720090B2 JP 4720090 B2 JP4720090 B2 JP 4720090B2 JP 2004050750 A JP2004050750 A JP 2004050750A JP 2004050750 A JP2004050750 A JP 2004050750A JP 4720090 B2 JP4720090 B2 JP 4720090B2
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- JP
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- Prior art keywords
- sulfonic acid
- polymer electrolyte
- electrolyte membrane
- acid group
- membrane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Fuel Cell (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Conductive Materials (AREA)
Description
本発明は、高分子電解質膜に関し、詳しくはスルホン酸基含有高分子電解質膜及びそれを用いた複合体、該複合体を用いた燃料電池などの物品に関するものである。 The present invention relates to a polymer electrolyte membrane, and more particularly to a sulfonic acid group-containing polymer electrolyte membrane, a composite using the same, and a product such as a fuel cell using the composite.
液体電解質のかわりに高分子固体電解質をイオン伝導体として用いる電気化学的装置の例として、水電解槽や燃料電池を上げることができる。これらに用いられる高分子膜は、カチオン交換膜としてプロトン伝導率とともに化学的、熱的、電気化学的および力学的に十分安定なものでなくてはならない。このため、長期にわたり使用できるものとしては、主に米デュポン社製の「ナフィオン（登録商標）」を代表例とするパーフルオロカーボンスルホン酸膜が使用されてきた。しかしながら、ナフィオン膜を１００℃を越える条件で運転しようとすると、膜の含水率が急激に落ちるほか、膜の軟化も顕著となる。また、メタノールを燃料とする燃料電池においては、ナフィオン膜中のメタノール透過速度が大きいために性能低下が顕著であり、十分な性能を発揮できないことが指摘されている。また、現在主に検討されている水素を燃料として８０℃付近で運転する燃料電池においても、膜のコストが高すぎることが燃料電池技術の確立の障害として指摘されている。 As an example of an electrochemical device using a polymer solid electrolyte as an ionic conductor instead of a liquid electrolyte, a water electrolyzer and a fuel cell can be raised. The polymer membrane used for these must be sufficiently stable chemically, thermally, electrochemically and mechanically with proton conductivity as a cation exchange membrane. For this reason, perfluorocarbon sulfonic acid membranes, typically “Nafion (registered trademark)” manufactured by DuPont, have been used as long-term usable products. However, if the Nafion membrane is operated under conditions exceeding 100 ° C., the moisture content of the membrane drops rapidly and the membrane softens significantly. In addition, it has been pointed out that in a fuel cell using methanol as a fuel, the methanol permeation rate in the Nafion membrane is large, so that the performance degradation is remarkable and sufficient performance cannot be exhibited. Further, even in a fuel cell that is currently studied mainly using hydrogen as a fuel and operated at around 80 ° C., it is pointed out that the cost of the membrane is too high as an obstacle to the establishment of fuel cell technology.
このような欠点を克服するため、非フッ素系芳香族環含有ポリマーにスルホン酸基を導入した高分子電解質膜が種々検討されている。ポリマー骨格としては、耐熱性や化学的安定性を考慮すると、芳香族ポリアリーレンエーテルケトン類や芳香族ポリアリーレンエーテルスルホン類などの、芳香族ポリアリーレンエーテル化合物を有望な構造としてとらえることができ、ポリアリールエーテルスルホンをスルホン化したもの（例えば、非特許文献１参照。）、ポリエーテルエーテルケトンをスルホン化したもの（例えば、特許文献１参照。）、スルホン化ポリスチレン等が報告されている。しかしながら、これらのポリマーのスルホン化反応により芳香環上に導入されたスルホン酸基は一般に熱により脱離しやすい傾向にあり、これを改善する方法として電子吸引性芳香環上にスルホン酸基を導入したモノマーを用いて重合することで、熱的に安定性の高いスルホン化ポリアリールエーテルスルホン系化合物が報告されている（例えば、特許文献２参照。）。この場合、モノマーの反応性が低いために、ポリマーを得るのに長時間の重合を必要とする問題が生じている（例えば、非特許文献２参照）。これらの非フッ素系高分子電解質はスルホン酸基の酸性度が低いこともあり、フッ素系高分子電解質膜と同レベルのプロトン伝導性を発現するためには、フッ素系高分子電解質の場合よりも多くのスルホン酸基を高分子鎖中に導入することが必要となる。しかし、スルホン酸基量を多くすると湿潤時の膜の膨潤が大きくなる傾向となり、特に高温側発電時の障害となる問題があり、より寸法安定性に優れ、かつ優れた力学特性を示す高分子電解質膜が求められている。
本発明の目的は、単一化合物系非フッ素芳香族高分子電解質でありながら、高いイオン伝導性を示すと共に、特に湿潤時において寸法安定性に優れ、かつ優れた力学特性を示す高分子電解質膜、更には該高分子電解質膜を用いた複合体、該複合体を用いた燃料電池などの物品を提供することにある。 An object of the present invention is to provide a polymer electrolyte membrane that is a single compound non-fluorine aromatic polymer electrolyte, exhibits high ionic conductivity, has excellent dimensional stability especially when wet, and has excellent mechanical properties Furthermore, another object is to provide a composite using the polymer electrolyte membrane and an article such as a fuel cell using the composite.
本発明者らは鋭意研究を重ねた結果、芳香環上にスルホン酸を導入した高分子電解質において、そのポリマー構造を工夫することにより、上記目的が達成されることを見いだすに至った。 As a result of intensive studies, the present inventors have found that the above object can be achieved by devising the polymer structure of a polymer electrolyte in which a sulfonic acid is introduced onto an aromatic ring.
すなわち、本発明は下記（１）〜（７）により達成される。 That is, the present invention is achieved by the following (1) to (7).
（１）実質的に単一化合物から構成される電解質膜であって、２０℃、相対湿度６５％の雰囲気下での引っ張り強度が４０ＭＰａ以上であるとともに、２５℃の水中で測定した引っ張り伸度が２５０％以下であることを特徴とするスルホン酸基含有高分子電解質膜。 (1) An electrolyte membrane substantially composed of a single compound, having a tensile strength in an atmosphere of 20 ° C. and a relative humidity of 65% of 40 MPa or more, and a tensile elongation measured in water at 25 ° C. Is a sulfonic acid group-containing polymer electrolyte membrane, characterized by being 250% or less.
（２）実質的に単一化合物から構成される高分子電解質膜であって、２０℃、相対湿度６５％の雰囲気下での引っ張り強度が４０ＭＰａ以上であるとともに、２５℃の水中で測定した引っ張り伸度と２０℃、相対湿度６５％の雰囲気下で測定した引っ張り伸度の差が１５０％以下の値であることを特徴とするスルホン酸基含有高分子電解質膜。 (2) A polymer electrolyte membrane substantially composed of a single compound, which has a tensile strength in an atmosphere of 20 ° C. and a relative humidity of 65% of 40 MPa or more and is measured in water at 25 ° C. A sulfonic acid group-containing polymer electrolyte membrane, wherein the difference between the elongation and the tensile elongation measured in an atmosphere at 20 ° C. and a relative humidity of 65% is a value of 150% or less.
（３）８０℃、９５％ＲＨの雰囲気下で測定したプロトン伝導率が０．０１Ｓ／ｃｍ以上であることを特徴とする第１の発明または第２の発明に記載のスルホン酸基含有高分子電解質膜。 (3) The sulfonic acid group-containing polymer according to the first or second invention, wherein the proton conductivity measured in an atmosphere of 80 ° C. and 95% RH is 0.01 S / cm or more. Electrolyte membrane.
（４）一般式（１）とともに一般式（２）で示される構造単位を有することを特徴とする第１の発明〜第３の発明のいずれかに記載のスルホン酸基含有高分子電解質膜。
（５）第１の発明から第４の発明のいずれかに記載の高分子電解質膜と電極とを含有することを特徴とする複合体。 (5) A composite comprising the polymer electrolyte membrane according to any one of the first to fourth inventions and an electrode.
（６）第５の発明に記載の複合体を含有することを特徴とする燃料電池。 (6) A fuel cell comprising the composite according to the fifth invention.
（７）メタノールを燃料として使用することを特徴とする第６の発明に記載の燃料電池。 (7) The fuel cell according to the sixth invention, wherein methanol is used as a fuel.
本発明の高分子電解質膜は、単一化合物系非フッ素芳香族高分子電解質でありながら、イオン伝導性だけでなく、力学特性、特に湿潤時の力学特性、寸法安定性に優れた、燃料電池などの高分子電解質として際立った性能を示すものである。また、本発明におけるスルホン酸基含有高分子化合物は、メタノール透過性が低いという特徴もあるため、ダイレクトメタノール型燃料電池用の高分子電解質膜としても有用である。 The polymer electrolyte membrane of the present invention is a single-cell non-fluorine aromatic polymer electrolyte, and has excellent mechanical properties, in particular, mechanical properties when wet, and dimensional stability, as well as ion conductivity. It shows outstanding performance as a polymer electrolyte. The sulfonic acid group-containing polymer compound in the present invention is also useful as a polymer electrolyte membrane for a direct methanol fuel cell because it has a feature of low methanol permeability.
以下、本発明を詳細に説明する。
本発明は、スルホン酸基を含有する高分子電解質膜において、優れた力学特性、特に湿潤時の寸法安定性に優れたものを提供する。スルホン酸基を含有する高分子電解質膜は、含有するスルホン酸基のために親水性の高い構造となっており、水分を吸収することにより、弾性率、強度等の力学特性が低下すると共に、引っ張り伸度が大きくなる傾向を示す。 本発明者らは、引っ張り伸度が大きいことは、膜が水分を吸収、放出する際の膨潤、収縮挙動とも関連があることをとらえ、水分吸収時の引っ張り伸度が小さい物ほど特に燃料電池で使用されるような湿潤状態での膜の寸法安定性に優れるとの結論を得るに至った。すなわち、実質的に単一化合物から構成される高分子電解質であって、２０℃、相対湿度６５％の雰囲気下での引っ張り強度が４０ＭＰａ以上であるとともに、２５℃の水中で測定した引っ張り伸度が２５０％以下であることを特徴とするスルホン酸基含有高分子電解質膜により、本発明の目的を達成することができる。湿潤時の膜の寸法変化を抑える目的としては、高分子電解質とともに何らかの補強成分を使用する試みもなされているが、本発明の高分子電解質膜は、補強成分を必要としないことが特徴である。ここで、「実質的に単一化合物から構成される」とは、このような目的の補強成分を持たないことを言う。高分子電解質そのものの特性で寸法安定性を発現できるので、複雑な成形プロセスも必要としない。相対湿度６５％の雰囲気下での引っ張り強度が４０ＭＰａ以上である高分子電解質は通常の取扱いにおいて良好に使用できるものであるが、水中での引っ張り伸度が２５０％よりも大きくなると、燃料電池として発電を行った場合、膜のクリープによる問題が発生したり、起動停止に伴う膨潤収縮サイクルにおいて膜が損傷を受けやすくなってしまう。水中での引っ張り伸度を２５０％以下とすることで、これらの問題のない膜とすることができる。水中での引っ張り伸度は２００％以下であればさらに好ましい。仮に、伸度が２５０％以下のものでも、上記相対湿度下での強度特性を持っていないと、高分子電解質膜としての取扱い性が低下してくるため、両特性を兼ね備えていることが必要である。
Hereinafter, the present invention will be described in detail.
The present invention provides a polymer electrolyte membrane containing a sulfonic acid group having excellent mechanical properties, particularly excellent dimensional stability when wet. The polymer electrolyte membrane containing a sulfonic acid group has a highly hydrophilic structure because of the sulfonic acid group contained, and by absorbing moisture, mechanical properties such as elastic modulus and strength are reduced, It shows a tendency for tensile elongation to increase. The present inventors have understood that the fact that the tensile elongation is large is also related to the swelling and shrinkage behavior when the membrane absorbs and releases moisture. It was concluded that the film has excellent dimensional stability in the wet state as used in the above. That is, it is a polymer electrolyte substantially composed of a single compound, has a tensile strength in an atmosphere of 20 ° C. and a relative humidity of 65% of 40 MPa or more, and a tensile elongation measured in water at 25 ° C. The object of the present invention can be achieved by a sulfonic acid group-containing polymer electrolyte membrane characterized in that the sulfonic acid group content is 250% or less. In order to suppress the dimensional change of the membrane when wet, attempts have been made to use some reinforcing component together with the polymer electrolyte, but the polymer electrolyte membrane of the present invention is characterized by not requiring a reinforcing component. . Here, “substantially composed of a single compound” means having no reinforcing component for such purpose. Since the dimensional stability can be expressed by the characteristics of the polymer electrolyte itself, a complicated molding process is not required. A polymer electrolyte having a tensile strength of 40 MPa or more in an atmosphere with a relative humidity of 65% can be used well in normal handling. However, when the tensile elongation in water is greater than 250%, the polymer electrolyte When power generation is performed, a problem due to the creep of the film occurs, or the film is likely to be damaged in a swelling / shrinkage cycle accompanying start / stop. By setting the tensile elongation in water to 250% or less, a film free from these problems can be obtained. More preferably, the tensile elongation in water is 200% or less. Even if the elongation is 250% or less, if it does not have the strength characteristics under the above relative humidity, the handleability as a polymer electrolyte membrane is lowered, so both characteristics must be combined. It is.
本発明の高分子電解質膜は２５℃の水中で測定した引っ張り伸度が２５０％以下であればよいが、乾燥時の引っ張り強度との差があまり大きくないものが好ましい。すなわち、実質的に単一化合物から構成される電解質膜であって、２０℃、相対湿度６５％の雰囲気下での引っ張り強度が４０ＭＰａ以上であるとともに、２５℃の水中で測定した引っ張り伸度が２０℃、相対湿度６５％の雰囲気下で測定した引っ張り伸度の差が１５０％以下の値であることが好ましい。ここでの差とは、２５℃水中での引っ張り伸度値（％単位）から２０℃、相対湿度６５％の雰囲気下で測定した引っ張り伸度値（％単位）を引いた値のことを言う（％単位で表示する）。この吸湿時と乾燥時の引っ張り伸度の差が１５０％よりも大きいものは、膨潤収縮サイクルにおいて膜が損傷を受けやすくなる傾向にあるためである。差は１００％以内であることがさらに好ましい。２５℃の水中で測定した引っ張り伸度が２５０％以下であると共に、上記の差が１５０％以内であると燃料電池の起動停止サイクルでの安定性がより増す傾向となる。 The polymer electrolyte membrane of the present invention may have a tensile elongation measured in water at 25 ° C. of 250% or less, but is preferably not so different from the tensile strength during drying. That is, the electrolyte membrane is substantially composed of a single compound, has a tensile strength in an atmosphere of 20 ° C. and a relative humidity of 65% of 40 MPa or more, and a tensile elongation measured in water at 25 ° C. The difference in tensile elongation measured under an atmosphere of 20 ° C. and relative humidity of 65% is preferably a value of 150% or less. The difference here means a value obtained by subtracting a tensile elongation value (% unit) measured in an atmosphere of 20 ° C. and a relative humidity of 65% from a tensile elongation value (% unit) in 25 ° C. water. (Displayed in%). The reason why the difference in tensile elongation between moisture absorption and drying is greater than 150% is that the membrane tends to be easily damaged in the swelling shrinkage cycle. More preferably, the difference is within 100%. When the tensile elongation measured in water at 25 ° C. is 250% or less and the difference is within 150%, the stability of the fuel cell in the start / stop cycle tends to increase.
スルホン酸基含有高分子電解質膜は、一般にそのプロトン伝導率はポリマー中のスルホン酸基濃度が増すに従い大きな値を示す様になる。しかし、スルホン酸基含有率が増加すると、電解質の親水性が増すために湿潤時の寸法安定性は悪くなる傾向になってしまう。このため、高い伝導率を有すると共に、湿潤時の寸法安定性が良いことが好ましく、上記の力学特性を示すとともに、８０℃、９５％ＲＨの雰囲気下で測定したプロトン伝導率が１．０×１０-3Ｓ／ｃｍ以上であることが好ましい。イオン伝導率が１．０×１０-3Ｓ／ｃｍ以上である場合には、そのイオン伝導膜を用いた燃料電池において良好な出力が得られる傾向にあり、１．０×１０-3Ｓ／ｃｍ未満である場合には燃料電池の出力低下が起こる傾向にある。０．０１Ｓ／ｃｍ以上であるものがより好ましいものと言える。プロトン伝導率が０．１Ｓ／ｃｍ以上であればさらに好ましい。 In general, the proton conductivity of the sulfonic acid group-containing polymer electrolyte membrane becomes larger as the sulfonic acid group concentration in the polymer increases. However, when the sulfonic acid group content increases, the hydrophilicity of the electrolyte increases, so that the dimensional stability when wet tends to deteriorate. For this reason, it is preferable that it has high conductivity and good dimensional stability when wet, exhibits the above-mentioned mechanical characteristics, and has a proton conductivity of 1.0 × measured in an atmosphere of 80 ° C. and 95% RH. It is preferably 10 −3 S / cm or more. When the ion conductivity of 1.0 × 10 -3 S / cm or higher, tend to better output is obtained in the fuel cell using the ion conductive membrane, 1.0 × 10 -3 S / When it is less than cm, the output of the fuel cell tends to decrease. It can be said that what is 0.01 S / cm or more is more preferable. More preferably, the proton conductivity is 0.1 S / cm or more.
本発明の高分子電解質膜に使用できる材料としては、芳香族系のスルホン酸基含有ポリマーであることが好ましい。このようなポリマー骨格の例として、ポリスルホン、ポリエーテルスルホン、ポリフェニレンオキシド、ポリフェニレンスルフィド、ポリフェニレンスルフィドスルホン、ポリパラフェニレン、ポリアリーレン系ポリマー、ポリフェニルキノキサリン、ポリアリールケトン、ポリエーテルケトン、ポリベンズオキサゾール、ポリベンズチアゾール、ポリイミド等の構成成分の少なくとも１種を含むポリマーが挙げられる。なお、ここでいうポリスルホン、ポエーテルスルホン、ポリエーテルケトン等は、その分子鎖にスルホン結合、エーテル結合、ケトン結合を有しているポリマーの総称であり、ポリエーテルケトンケトン、ポリエーテルエーテルケトン、ポリエーテルエーテルケトンケトン、ポリエーテルケトンエーテルケトンケトン、ポリエーテルケトンスルホンなどを含むとともに、特定のポリマー構造を限定するものではない。 The material that can be used for the polymer electrolyte membrane of the present invention is preferably an aromatic sulfonic acid group-containing polymer. Examples of such polymer skeletons include polysulfone, polyethersulfone, polyphenylene oxide, polyphenylene sulfide, polyphenylene sulfide sulfone, polyparaphenylene, polyarylene polymer, polyphenylquinoxaline, polyaryl ketone, polyether ketone, polybenzoxazole, Examples thereof include polymers containing at least one component such as polybenzthiazole and polyimide. Polysulfone, polyethersulfone, polyetherketone, and the like referred to here are generic names for polymers having a sulfone bond, an ether bond, and a ketone bond in their molecular chains. Polyetherketoneketone, polyetheretherketone, It includes polyether ether ketone ketone, polyether ketone ether ketone ketone, polyether ketone sulfone and the like, and does not limit the specific polymer structure.
上記芳香族系ポリマーのうち、ポリスルホン、ポリエーテルスルホン、ポリフェニレンスルフィド、ポリフェニレンスルフィドスルホン、ポリエーテルケトン等のポリマーが加工性と安定性の面から好ましいものと言えるが、下記一般式（１）とともに下記一般式（２）で示される構造単位を有する芳香族系ポリマーであることが特に好ましい。 Among the aromatic polymers, polymers such as polysulfone, polyethersulfone, polyphenylene sulfide, polyphenylene sulfide sulfone, and polyether ketone are preferable from the viewpoint of processability and stability. An aromatic polymer having a structural unit represented by the general formula (2) is particularly preferable.
上記一般式（１）および一般式（２）で示される構造単位を有する芳香族ポリマーは、上記一般式（１）および一般式（２）で示される以外の構造単位が含まれていてもかまわないが、上記一般式（１）または一般式（２）で示される以外の構造単位はポリマー中の５０重量％以上であることが好ましく、７０重量％であることが特に好ましい。 The aromatic polymer having the structural units represented by the general formula (1) and the general formula (2) may contain structural units other than those represented by the general formula (1) and the general formula (2). However, the structural units other than those represented by the general formula (1) or (2) are preferably 50% by weight or more, and particularly preferably 70% by weight in the polymer.
本発明のスルホン酸基含有高分子電解質膜を構成する化合物において、スルホン酸基含有量は０．３〜３．５ｍｅｑ／ｇの範囲にあることが好ましい。０．３ｍｅｑ／ｇよりも少ない場合には、イオン伝導膜として使用したときに十分なイオン伝導性を示さない傾向があり、３．５ｍｅｑ／ｇよりも大きい場合にはイオン伝導膜を高温高湿条件においた場合に膜膨潤が大きくなりすぎて使用に適さなくなる傾向がある。なお、スルホン酸基含有量はポリマー組成より計算することができる。より好ましくは１．０〜３．０ｍｅｑ／ｇである。 In the compound constituting the sulfonic acid group-containing polymer electrolyte membrane of the present invention, the sulfonic acid group content is preferably in the range of 0.3 to 3.5 meq / g. When it is less than 0.3 meq / g, there is a tendency that sufficient ion conductivity is not exhibited when used as an ion conductive membrane, and when it is greater than 3.5 meq / g, the ion conductive membrane is not heated and humidified. When the conditions are met, membrane swelling tends to be too large to be suitable for use. The sulfonic acid group content can be calculated from the polymer composition. More preferably, it is 1.0-3.0 meq / g.
上記のスルホン酸基含有高分子電解質膜を構成する化合物は、下記一般式（３）とともに一般式（４）で示される構造単位を有するものが特に好ましい。ビフェニレン構造を有していることにより高温高湿条件での寸法安定性に優れるとともに、フィルムの強靱性もより高いものとなる。 As for the compound which comprises said sulfonic acid group containing polymer electrolyte membrane, what has a structural unit shown by General formula (4) with following General formula (3) is especially preferable. By having a biphenylene structure, the film has excellent dimensional stability under high-temperature and high-humidity conditions, and the film has higher toughness.
上記のスルホン酸基含有高分子電解質膜を構成する化合物は、下記一般式（５）および一般式（６）で表される化合物をモノマーとして含む芳香族求核置換反応により重合することができる。一般式（５）で表される化合物の具体例としては、３，３’−ジスルホ−４，４’−ジクロロジフェニルスルホン、３，３’−ジスルホ−４，４’−ジフルオロジフェニルスルホン、３，３’−ジスルホ−４，４’−ジクロロジフェニルケトン、３，３’−ジスルホ−４，４’−ジフルオロジフェニルスルホン、およびそれらのスルホン酸基が１価カチオン種との塩になったもの等が挙げられる。１価カチオン種としては、ナトリウム、カリウムや他の金属種や各種アミン類等でも良く、これらに制限される訳ではない。一般式（６）で表される化合物としては、２，６−ジクロロベンゾニトリル、２，６−ジフルオロベンゾニトリル、２，４−ジクロロベンゾニトリル、２，４−ジフルオロベンゾニトリル、等を挙げることができる。 The compound constituting the sulfonic acid group-containing polymer electrolyte membrane can be polymerized by an aromatic nucleophilic substitution reaction containing the compounds represented by the following general formulas (5) and (6) as monomers. Specific examples of the compound represented by the general formula (5) include 3,3′-disulfo-4,4′-dichlorodiphenyl sulfone, 3,3′-disulfo-4,4′-difluorodiphenyl sulfone, 3, 3'-disulfo-4,4'-dichlorodiphenyl ketone, 3,3'-disulfo-4,4'-difluorodiphenyl sulfone, and those whose sulfonic acid groups are converted to salts with monovalent cation species Can be mentioned. The monovalent cation species may be sodium, potassium, other metal species, various amines, or the like, but is not limited thereto. Examples of the compound represented by the general formula (6) include 2,6-dichlorobenzonitrile, 2,6-difluorobenzonitrile, 2,4-dichlorobenzonitrile, 2,4-difluorobenzonitrile, and the like. it can.
上述の芳香族求核置換反応において、上記一般式（５）、（６）で表される化合物とともに各種活性化ジフルオロ芳香族化合物やジクロロ芳香族化合物をモノマーとして併用することもできる。これらの化合物例としては、４，４’−ジクロロジフェニルスルホン、４，４’−ジフルオロジフェニルスルホン、４，４’−ジフルオロベンゾフェノン、４，４’−ジクロロベンゾフェノン、デカフルオロビフェニル等が挙げられるがこれらに制限されることなく、芳香族求核置換反応に活性のある他の芳香族ジハロゲン化合物、芳香族ジニトロ化合物、芳香族ジシアノ化合物なども使用することができる。 In the above aromatic nucleophilic substitution reaction, various activated difluoroaromatic compounds and dichloroaromatic compounds can be used in combination with the compounds represented by the general formulas (5) and (6) as monomers. Examples of these compounds include 4,4′-dichlorodiphenyl sulfone, 4,4′-difluorodiphenyl sulfone, 4,4′-difluorobenzophenone, 4,4′-dichlorobenzophenone, decafluorobiphenyl, and the like. However, other aromatic dihalogen compounds, aromatic dinitro compounds, aromatic dicyano compounds and the like that are active in aromatic nucleophilic substitution can also be used.
また、上述の一般式（１）で表される構造単位中のＡｒおよび上述の一般式（２）で表される構造単位中のＡｒ’は、一般には芳香族求核置換重合において上述の一般式（５）、（６）で表される化合物とともに使用される芳香族ジオール成分モノマーより導入される構造である。このような芳香族ジオールモノマーの例としては、４，４’−ビフェノール、ビス（４−ヒドロキシフェニル）スルホン、１，１−ビス（４−ヒドロキシフェニル）エタン、２，２−ビス（４−ヒドロキシフェニル）プロパン、ビス（４−ヒドロキシフェニル）メタン、２，２−ビス（４−ヒドロキシフェニル）ブタン、３，３−ビス（４−ヒドロキシフェニル）ペンタン、２，２−ビス（４−ヒドロキシ−３，５−ジメチルフェニル）プロパン、ビス（４−ヒドロキシ−３，５−ジメチルフェニル）メタン、ビス（４−ヒドロキシ−２，５−ジメチルフェニル）メタン、ビス（４−ヒドロキシフェニル）フェニルメタン、ビス（４−ヒドロキシフェニル）ジフェニルメタン、９，９−ビス（４−ヒドロキシフェニル）フルオレン、９，９−ビス（３−メチル−４−ヒドロキシフェニル）フルオレン、２，２−ビス（４−ヒドロキシフェニル）ヘキサフルオロプロパン、ハイドロキノン、レゾルシン、１，６−ナフタレンジオール、２，７−ナフタレンジオール、ビス（４−ヒドロキシフェニル）ケトン等があげられるが、この他にも芳香族求核置換反応によるポリアリーレンエーテル系化合物の重合に用いることができる各種芳香族ジオールを使用することもできる。これら芳香族ジオールは、単独で使用することができるが、複数の芳香族ジオールを併用することも可能である。また、例えば光反応性や熱反応性をもつモノマー成分を一部共重合しておき、製膜後に光照射処理や熱処理により、架橋構造を導入できるようにしておくことも可能である。 In addition, Ar in the structural unit represented by the general formula (1) and Ar ′ in the structural unit represented by the general formula (2) are generally the same as those described above in the aromatic nucleophilic substitution polymerization. It is a structure introduced from an aromatic diol component monomer used together with the compounds represented by formulas (5) and (6). Examples of such aromatic diol monomers include 4,4′-biphenol, bis (4-hydroxyphenyl) sulfone, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxy). Phenyl) propane, bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) butane, 3,3-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxy-3) , 5-dimethylphenyl) propane, bis (4-hydroxy-3,5-dimethylphenyl) methane, bis (4-hydroxy-2,5-dimethylphenyl) methane, bis (4-hydroxyphenyl) phenylmethane, bis ( 4-hydroxyphenyl) diphenylmethane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9- (3-methyl-4-hydroxyphenyl) fluorene, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, hydroquinone, resorcin, 1,6-naphthalenediol, 2,7-naphthalenediol, bis (4- Hydroxyphenyl) ketone and the like can be mentioned, but various aromatic diols that can be used for polymerization of polyarylene ether compounds by aromatic nucleophilic substitution reaction can also be used. These aromatic diols can be used alone, but a plurality of aromatic diols can be used in combination. Further, for example, it is possible to partially copolymerize monomer components having photoreactivity and heat reactivity so that a crosslinked structure can be introduced by light irradiation treatment or heat treatment after film formation.
上記のスルホン酸基含有高分子電解質膜を構成する化合物を芳香族求核置換反応により重合する場合、上記一般式（５）および一般式（６）で表せる化合物を含む活性化ジフルオロ芳香族化合物及び／またはジクロロ芳香族化合物と芳香族ジオール類を塩基性化合物の存在下で反応させることで重合体を得ることができる。重合は、０〜３５０℃の温度範囲で行うことができるが、５０〜２５０℃の温度であることが好ましい。０℃より低い場合には、十分に反応が進まない傾向にあり、３５０℃より高い場合には、ポリマーの分解も起こり始める傾向がある。反応は、無溶媒下で行うこともできるが、溶媒中で行うことが好ましい。使用できる溶媒としては、Ｎ−メチル−２−ピロリドン、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジメチルホルムアミド、ジメチルスルホキシド、ジフェニルスルホン、スルホランなどを挙げることができるが、これらに限定されることはなく、芳香族求核置換反応において安定な溶媒として使用できるものであればよい。これらの有機溶媒は、単独でも２種以上の混合物として使用されても良い。塩基性化合物としては、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カリウム等があげられるが、芳香族ジオール類を活性なフェノキシド構造にしうるものであれば、これらに限定されず使用することができる。芳香族求核置換反応においては、副生物として水が生成する場合がある。この際は、重合溶媒とは関係なく、トルエンなどを反応系に共存させて共沸物として水を系外に除去することもできる。水を系外に除去する方法としては、モレキュラーシーブなどの吸水材を使用することもできる。芳香族求核置換反応を溶媒中で行う場合、得られるポリマー濃度として５〜５０重量％となるようにモノマーを仕込むことが好ましい。５重量％よりも少ない場合は、重合度が上がりにくい傾向がある。一方、５０重量％よりも多い場合には、反応系の粘性が高くなりすぎ、反応物の後処理が困難になる傾向がある。重合反応終了後は、反応溶液より蒸発によって溶媒を除去し、必要に応じて残留物を洗浄することによって、所望のポリマーが得られる。また、反応溶液を、ポリマーの溶解度が低い溶媒中に加えることによって、ポリマーを固体として沈殿させ、沈殿物の濾取によりポリマーを得ることもできる。 When the compound constituting the sulfonic acid group-containing polymer electrolyte membrane is polymerized by an aromatic nucleophilic substitution reaction, an activated difluoroaromatic compound containing the compounds represented by the general formula (5) and the general formula (6), and A polymer can be obtained by reacting a dichloro aromatic compound and an aromatic diol in the presence of a basic compound. The polymerization can be carried out in the temperature range of 0 to 350 ° C., but is preferably 50 to 250 ° C. When the temperature is lower than 0 ° C., the reaction does not proceed sufficiently, and when the temperature is higher than 350 ° C., the polymer tends to be decomposed. The reaction can be carried out in the absence of a solvent, but is preferably carried out in a solvent. Examples of the solvent that can be used include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, diphenyl sulfone, sulfolane, and the like. And any solvent that can be used as a stable solvent in the aromatic nucleophilic substitution reaction. These organic solvents may be used alone or as a mixture of two or more. Examples of the basic compound include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, and the like, and those that can convert an aromatic diol into an active phenoxide structure may be used. It can use without being limited to. In the aromatic nucleophilic substitution reaction, water may be generated as a by-product. In this case, regardless of the polymerization solvent, water can be removed from the system as an azeotrope by coexisting toluene or the like in the reaction system. As a method for removing water out of the system, a water absorbing material such as molecular sieve can also be used. When the aromatic nucleophilic substitution reaction is carried out in a solvent, it is preferable to charge the monomer so that the resulting polymer concentration is 5 to 50% by weight. When the amount is less than 5% by weight, the degree of polymerization tends to be difficult to increase. On the other hand, when the amount is more than 50% by weight, the viscosity of the reaction system becomes too high, and the post-treatment of the reaction product tends to be difficult. After completion of the polymerization reaction, the solvent is removed from the reaction solution by evaporation, and the residue is washed as necessary to obtain the desired polymer. Further, the polymer can be obtained by precipitating the polymer as a solid by adding the reaction solution in a solvent having low polymer solubility, and collecting the precipitate by filtration.
また、本発明のスルホン酸基含有高分子電解質膜を構成する化合物は、後で述べる方法により測定したポリマー対数粘度が０．１以上であることが好ましい。対数粘度が０．１よりも小さいと、イオン伝導膜として成形したときに、膜が脆くなりやすくなる。還元比粘度は、０．３以上であることがさらに好ましい。一方、還元比粘度が５を超えると、ポリマーの溶解が困難になるなど、加工性での問題が出てくるので好ましくない。なお、対数粘度を測定する溶媒としては、一般にＮ−メチルピロリドン、Ｎ，Ｎ−ジメチルアセトアミドなどの極性有機溶媒を使用することができるが、これらに溶解性が低い場合には濃硫酸を用いて測定することもできる。 In addition, the compound constituting the sulfonic acid group-containing polymer electrolyte membrane of the present invention preferably has a polymer log viscosity measured by a method described later of 0.1 or more. When the logarithmic viscosity is less than 0.1, the membrane is likely to be brittle when formed as an ion conductive membrane. The reduced specific viscosity is more preferably 0.3 or more. On the other hand, if the reduced specific viscosity exceeds 5, problems in processability such as difficulty in dissolving the polymer occur, which is not preferable. As a solvent for measuring the logarithmic viscosity, polar organic solvents such as N-methylpyrrolidone and N, N-dimethylacetamide can be generally used. When the solubility in these is low, concentrated sulfuric acid is used. It can also be measured.
本発明のスルホン酸基含有高分子電解質膜を構成する化合物は、実質的に体一化合物として使用されるが、力学特性に影響を及ぼさない程度であれば他の樹脂化合物が一部混合されていても構わない。これらのポリマーとしては、例えばポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレートなどのポリエステル類、ナイロン６、ナイロン６６、ナイロン６１０、ナイロン１２などのポリアミド類、ポリメチルメタクリレート、ポリメタクリル酸エステル類、ポリメチルアクリレート、ポリアクリル酸エステル類などのアクリレート系樹脂、ポリアクリル酸系樹脂、ポリメタクリル酸系樹脂、ポリエチレン、ポリプロピレン、ポリスチレンやジエン系ポリマーを含む各種ポリオレフィン、ポリウレタン系樹脂、酢酸セルロース、エチルセルロースなどのセルロース系樹脂、ポリアリレート、アラミド、ポリカーボネート、ポリフェニレンスルフィド、ポリフェニレンオキシド、ポリスルホン、ポリエーテルスルホン、ポリエーテルエーテルケトン、ポリエーテルイミド、ポリイミド、ポリアミドイミド、ポリベンズイミダゾール、ポリベンズオキサゾール、ポリベンズチアゾールなどの芳香族系ポリマー、エポキシ樹脂、フェノール樹脂、ノボラック樹脂、ベンゾオキサジン樹脂などの熱硬化性樹脂等、特に制限はない。ポリベンズイミダゾールやポリビニルピリジンなどの塩基性ポリマーとの樹脂組成物は、ポリマー寸法性の向上のために好ましい組み合わせと言える、これらの塩基性ポリマー中に、さらにスルホン酸基を導入しておくと、組成物の加工性がより好ましいものとなる。これら樹脂組成物として使用する場合には、本発明の高分子電解質に使用できる化合物は、樹脂組成物全体の８０質量％以上１００質量％未満含まれていることが好ましい。より好ましくは９０質量％以上１００質量％未満である。本発明の高分子電解質に使用できる化合物の含有量が樹脂組成物全体の８０重量％未満の場合には、この樹脂組成物を含むイオン伝導膜のスルホン酸基濃度が低くなり良好なイオン伝導性が得られない傾向にあり、また、スルホン酸基を含有するユニットが非連続相となり伝導するイオンの移動度が低下する傾向にある。なお、本発明の電解質膜は、必要に応じて、例えば酸化防止剤、熱安定剤、滑剤、粘着付与剤、可塑剤、架橋剤、粘度調整剤、静電気防止剤、抗菌剤、消泡剤、分散剤、重合禁止剤、などの各種添加剤を含んでいても良い。 The compound constituting the sulfonic acid group-containing polymer electrolyte membrane of the present invention is substantially used as a single compound, but other resin compounds are partially mixed as long as they do not affect the mechanical properties. It doesn't matter. Examples of these polymers include polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, polyamides such as nylon 6, nylon 66, nylon 610, and nylon 12, polymethyl methacrylate, polymethacrylates, and polymethyl. Acrylate resins such as acrylates and polyacrylates, polyacrylic acid resins, polymethacrylic acid resins, polyethylene, polypropylene, various polyolefins including polystyrene and diene polymers, polyurethane resins, cellulose acetate, cellulose such as ethyl cellulose Resin, polyarylate, aramid, polycarbonate, polyphenylene sulfide, polyphenylene oxide, polysulfone, polyethers Thermal curing of aromatic polymers such as phon, polyetheretherketone, polyetherimide, polyimide, polyamideimide, polybenzimidazole, polybenzoxazole, polybenzthiazole, epoxy resin, phenol resin, novolac resin, benzoxazine resin There are no particular restrictions on the conductive resin. A resin composition with a basic polymer such as polybenzimidazole or polyvinylpyridine can be said to be a preferable combination for improving the polymer dimensionality, and when a sulfonic acid group is further introduced into these basic polymers, The processability of the composition becomes more preferable. When using as these resin compositions, it is preferable that the compound which can be used for the polymer electrolyte of this invention is contained 80 mass% or more and less than 100 mass% of the whole resin composition. More preferably, it is 90 mass% or more and less than 100 mass%. When the content of the compound that can be used in the polymer electrolyte of the present invention is less than 80% by weight of the entire resin composition, the sulfonic acid group concentration of the ion conductive membrane containing this resin composition is lowered and good ion conductivity is obtained. The unit containing a sulfonic acid group tends to be a discontinuous phase and the mobility of ions to be conducted tends to decrease. In addition, the electrolyte membrane of the present invention, if necessary, for example, an antioxidant, a heat stabilizer, a lubricant, a tackifier, a plasticizer, a crosslinking agent, a viscosity modifier, an antistatic agent, an antibacterial agent, an antifoaming agent, Various additives such as a dispersant and a polymerization inhibitor may be included.
本発明のスルホン酸基含有高分子電解質膜を構成する化合物およびその組成物は、押し出し、紡糸、圧延またはキャストなど任意の方法で繊維やフィルムなどの成形体とすることができる。中でも適当な溶媒に溶解した溶液から成形することが好ましい。この溶媒としては、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、ジメチルスルホキシド、Ｎ−メチル−２−ピロリドン、ヘキサメチルホスホンアミドなどの非プロトン性極性溶媒や、メタノール、エタノール等のアルコール類から適切なものを選ぶことができるがこれらに限定されるものではない。これらの溶媒は、可能な範囲で複数を混合して使用してもよい。溶液中の化合物濃度は０．１〜５０重量％の範囲であることが好ましい。溶液中の化合物濃度が０．１重量％未満であると良好な成形物を得るのが困難となる傾向にあり、５０重量％を超えると加工性が悪化する傾向にある。溶液から成形体を得る方法は従来から公知の方法を用いて行うことができる。たとえば、加熱、減圧乾燥、化合物を溶解する溶媒とは相溶するが化合物自体は溶解しない溶媒への浸漬等によって、溶媒を除去し成形体を得ることができる。溶媒が、有機溶媒の場合には、加熱又は減圧乾燥によって溶媒を留去させることが好ましい。この際、必要に応じて他の化合物と混合された形で繊維状、フィルム状、ペレット状、プレート状、ロッド状、パイプ状、ボール状、ブロック状などの様々な形状に成形することもできる。溶解挙動が類似する化合物と組み合わせた場合には、良好な成形ができる点で好ましい。このようにして得られた成形体中のスルホン酸基はカチオン種と塩を形成したものを含んでいても良いが、必要に応じて酸処理することによりフリーのスルホン酸基に変換することもできる。 The compound constituting the sulfonic acid group-containing polymer electrolyte membrane of the present invention and the composition thereof can be formed into a molded body such as a fiber or a film by any method such as extrusion, spinning, rolling or casting. Among these, it is preferable to mold from a solution dissolved in an appropriate solvent. Examples of the solvent include aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone and hexamethylphosphonamide, and alcohols such as methanol and ethanol. An appropriate one can be selected, but is not limited thereto. A plurality of these solvents may be used as a mixture within a possible range. The compound concentration in the solution is preferably in the range of 0.1 to 50% by weight. If the concentration of the compound in the solution is less than 0.1% by weight, it tends to be difficult to obtain a good molded product, and if it exceeds 50% by weight, the workability tends to deteriorate. A method of obtaining a molded body from a solution can be performed using a conventionally known method. For example, the molded product can be obtained by removing the solvent by heating, drying under reduced pressure, immersion in a solvent that is compatible with the solvent that dissolves the compound but not the compound itself, and the like. When the solvent is an organic solvent, the solvent is preferably distilled off by heating or drying under reduced pressure. At this time, it can be formed into various shapes such as a fiber shape, a film shape, a pellet shape, a plate shape, a rod shape, a pipe shape, a ball shape, and a block shape by mixing with other compounds as necessary. . When combined with a compound having a similar dissolution behavior, it is preferable in that good molding is possible. The sulfonic acid group in the molded body thus obtained may contain a salt formed with a cationic species, but may be converted to a free sulfonic acid group by acid treatment as necessary. it can.
本発明のスルホン酸基含有高分子電解質膜を構成する化合物およびその樹脂組成物からイオン伝導膜を作製することができる。イオン伝導膜を成形する手法として最も好ましいのは、溶液からのキャストであり、キャストした溶液から上記のように溶媒を除去してイオン伝導膜を得ることができる。当該溶液としてはＮ−メチルピロリドン、Ｎ，Ｎ−ジメチルホルムアミド、ジメチルスルホキシド等の有機溶媒を用いた溶液や、場合によってはアルコール系溶媒等も挙げることができる。溶媒の除去は、乾燥によることがイオン伝導膜の均一性からは好ましい。また、化合物や溶媒の分解や変質を避けるため、減圧下でできるだけ低い温度で乾燥することもできる。また、溶液の粘度が高い場合には、基板や溶液を加熱して高温でキャストすると溶液の粘度が低下して容易にキャストすることができる。キャストする際の溶液の厚みは特に制限されないが、１０〜１５００μｍであることが好ましい。より好ましくは５０〜５００μｍである。溶液の厚みが１０μｍよりも薄いとイオン伝導膜としての形態を保てなくなる傾向にあり、１５００μｍよりも厚いと不均一な高分子電解質膜ができやすくなる傾向にある。溶液のキャスト厚を制御する方法は公知の方法を用いることができる。例えば、アプリケーター、ドクターブレードなどを用いて一定の厚みで塗布し、ガラスシャーレなどを用いてキャスト面積を一定にして溶液の量や濃度で厚みを制御することができる。キャストした溶液は、溶媒の除去速度を調整することでより均一な膜を得ることができる。例えば、加熱する場合には最初の段階では低温にして蒸発速度を下げたりすることができる。また、水などの非溶媒に浸漬する場合には、溶液を空気中や不活性ガス中に適当な時間放置しておくなどして化合物の凝固速度を調整することができる。本発明のイオン伝導膜は目的に応じて任意の膜厚にすることができるが、イオン伝導性の面からはできるだけ薄いことが好ましい。具体的には５〜２５０μｍであることが好ましく、５〜５０μｍであることがさらに好ましく、５〜２０μｍであることが最も好ましい。イオン伝導膜の厚みが５μｍより薄いとイオン伝導膜の取扱が困難となり燃料電池を作製した場合に短絡等が起こる傾向にあり、２５０μｍよりも厚いとイオン伝導膜の電気抵抗値が高くなり燃料電池の発電性能が低下する傾向にある。得られた膜は、必要に応じて熱処理や光照射等の後処理を施して膜構造を固定することもできる。イオン伝導膜として使用する場合、膜中のスルホン酸基は金属塩になっているものを含んでいても良いが、適当な酸処理によりフリーのスルホン酸に変換することもできる。この場合、硫酸、塩酸、等の水溶液中に加熱下あるいは加熱せずに膜を浸漬処理することで行うことも効果的である。 An ion conductive membrane can be produced from the compound constituting the sulfonic acid group-containing polymer electrolyte membrane of the present invention and the resin composition thereof. The most preferable method for forming the ion conductive membrane is casting from a solution, and the ion conductive membrane can be obtained by removing the solvent from the cast solution as described above. Examples of the solution include a solution using an organic solvent such as N-methylpyrrolidone, N, N-dimethylformamide, and dimethyl sulfoxide, and in some cases, an alcohol solvent. The removal of the solvent is preferably by drying from the uniformity of the ion conductive membrane. Moreover, in order to avoid decomposition | disassembly and alteration of a compound or a solvent, it can also dry at the lowest temperature possible under reduced pressure. Further, when the viscosity of the solution is high, when the substrate or the solution is heated and cast at a high temperature, the viscosity of the solution is lowered and the casting can be easily performed. The thickness of the solution at the time of casting is not particularly limited, but is preferably 10 to 1500 μm. More preferably, it is 50-500 micrometers. If the thickness of the solution is thinner than 10 μm, the form as an ion conductive membrane tends to be not maintained, and if it is thicker than 1500 μm, a non-uniform polymer electrolyte membrane tends to be easily formed. As a method for controlling the cast thickness of the solution, a known method can be used. For example, application can be performed with a constant thickness using an applicator, doctor blade, etc., and the thickness can be controlled by the amount and concentration of the solution with a cast area constant using a glass petri dish or the like. The cast solution can obtain a more uniform film by adjusting the solvent removal rate. For example, in the case of heating, the evaporation rate can be reduced by lowering the temperature in the first stage. In addition, when immersed in a non-solvent such as water, the coagulation rate of the compound can be adjusted by leaving the solution in air or an inert gas for an appropriate time. The ion conductive film of the present invention can have any film thickness depending on the purpose, but it is preferably as thin as possible from the viewpoint of ion conductivity. Specifically, it is preferably 5 to 250 μm, more preferably 5 to 50 μm, and most preferably 5 to 20 μm. If the thickness of the ion conductive membrane is less than 5 μm, handling of the ion conductive membrane becomes difficult and a short circuit or the like tends to occur when a fuel cell is produced. If the thickness of the ion conductive membrane is greater than 250 μm, the electric resistance value of the ion conductive membrane increases. The power generation performance tends to decrease. The obtained film may be subjected to post-treatment such as heat treatment or light irradiation as necessary to fix the film structure. When used as an ion conductive membrane, the sulfonic acid group in the membrane may contain a metal salt, but it can be converted to free sulfonic acid by an appropriate acid treatment. In this case, it is also effective to immerse the membrane in an aqueous solution of sulfuric acid, hydrochloric acid, etc. with or without heating.
本発明のイオン伝導膜は、メタノールを燃料とするダイレクトメタノール型燃料電池にも有用であることが特徴である。平均厚さ５０μｍの膜を作製し、５Ｍメタノール水溶液を用いて２５℃で測定したメタノール透過速度が７ｍｍｏｌ／ｍ2・ｓｅｃ以下の値を示すイオン伝導膜が好ましい（測定法については後述する）。メタノール透過速度は４ｍｍｏｌ／ｍ2・ｓｅｃ以下であればさらに好ましく、１ｍｍｏｌ／ｍ2・ｓｅｃ以下であればより好ましい。このようなメタノール透過性を示すときに特に優れた発電特性を示すためである。メタノール透過性評価は平均厚み５０μｍの試料を作成して評価しているが、実際に燃料電池用イオン伝導膜として使用する際には、特に膜厚を限定しているわけではない。平均厚み５０μｍの膜とは、実質上は平均厚み４８μｍから平均厚み５２μｍの範囲に入っているものを示すものとする。 The ion conductive membrane of the present invention is also useful for direct methanol fuel cells using methanol as fuel. An ion conductive membrane in which a membrane having an average thickness of 50 μm is prepared and the methanol permeation rate measured at 25 ° C. using a 5 M aqueous methanol solution is 7 mmol / m 2 · sec or less is preferable (the measurement method will be described later). The methanol permeation rate is more preferably 4 mmol / m 2 · sec or less, and more preferably 1 mmol / m 2 · sec or less. This is because power generation characteristics particularly excellent when such methanol permeability is exhibited. Methanol permeability evaluation is performed by preparing a sample having an average thickness of 50 μm, but when actually used as an ion conductive membrane for a fuel cell, the thickness is not particularly limited. The film having an average thickness of 50 μm substantially indicates a film having an average thickness in the range of 48 μm to 52 μm.
また、上述した本発明のイオン伝導膜またはフィルム等に電極を設置することによって、本発明のイオン伝導膜またはフィルム等と電極との接合体を得ることができる。この接合体の作製方法としては、従来から公知の方法を用いて行うことができ、例えば、電極表面に接着剤を塗布しイオン伝導膜と電極とを接着する方法またはイオン伝導膜と電極とを加熱加圧する方法等がある。この中でも本発明のスルホン酸基含有高分子化合物およびその樹脂組成物を主成分とした接着剤を電極表面に塗布して接着する方法が好ましい。イオン伝導膜と電極との接着性が向上し、また、イオン伝導膜のイオン伝導性を損なうことが少なくなると考えられるためである。 Moreover, by installing an electrode on the above-described ion conductive membrane or film of the present invention, a joined body of the ion conductive membrane or film of the present invention and the electrode can be obtained. As a method for producing this joined body, a conventionally known method can be used. For example, an adhesive is applied to the electrode surface and the ion conductive film and the electrode are bonded, or the ion conductive film and the electrode are bonded. There is a method of heating and pressurizing. Among these, a method of applying and bonding an adhesive mainly composed of the sulfonic acid group-containing polymer compound of the present invention and the resin composition thereof to the electrode surface is preferable. This is because it is considered that the adhesion between the ion conductive film and the electrode is improved, and that the ion conductivity of the ion conductive film is less impaired.
上述したイオン伝導膜またはフィルム等と電極との接合体を用いて、燃料電池を作製することもできる。本発明のイオン伝導膜またはフィルム等は、耐熱性、加工性、イオン伝導性および寸法安定性に優れているため、高温での運転にも耐えることができ、作製が容易で、良好な出力を有する燃料電池を提供することができる。また、メタノールを直接燃料とする燃料電池として使用することも好ましい。 A fuel cell can also be produced using the above-described joined body of an ion conductive membrane or film and an electrode. Since the ion conductive membrane or film of the present invention is excellent in heat resistance, processability, ion conductivity and dimensional stability, it can withstand operation at high temperatures, is easy to produce, and has good output. A fuel cell can be provided. It is also preferable to use it as a fuel cell using methanol as a direct fuel.
以下本発明を実施例を用いて具体的に説明するが、本発明はこれらの実施例に限定されることはない。なお、各種測定は次のように行った。
・溶液粘度：ポリマー粉末を０．５ｇ／ｄｌの濃度でＮ−メチルピロリドンに溶解し、３０℃の恒温槽中でウベローデ型粘度計を用いて粘度測定を行い、対数粘度ｌｎ[ｔａ／ｔｂ]／ｃ）で評価した（ｔａは試料溶液の落下秒数、ｔｂは溶媒のみの落下秒数、ｃはポリマー濃度）。
・イオン伝導性測定：自作測定用プローブ（テフロン（Ｒ）製）上で短冊状膜試料の表面に白金線（直径：０．２ｍｍ）を押しあて、８０℃９５％ＲＨの恒温・恒湿オーブン（株式会社ナガノ科学機械製作所、ＬＨ−２０−０１）中に試料を保持し、白金線間のインピーダンスをＳＯＬＡＲＴＲＯＮ社１２５０ＦＲＥＱＵＥＮＣＹ ＲＥＳＰＯＮＳＥ ＡＮＡＬＹＳＥＲにより測定した。極間距離を変化させて測定し、極間距離とＣ−Ｃプロットから見積もられる抵抗測定値をプロットした勾配から以下の式により膜と白金線間の接触抵抗をキャンセルした導電率を算出した。
EXAMPLES Hereinafter, although this invention is demonstrated concretely using an Example, this invention is not limited to these Examples. Various measurements were performed as follows.
Solution viscosity: The polymer powder was dissolved in N-methylpyrrolidone at a concentration of 0.5 g / dl, the viscosity was measured using an Ubbelohde viscometer in a constant temperature bath at 30 ° C., and the logarithmic viscosity ln [ta / tb] / C) (ta is the drop time of the sample solution, tb is the drop time of the solvent only, and c is the polymer concentration).
・ Ion conductivity measurement: Constant temperature / humidity oven at 80 ° C. and 95% RH by pressing a platinum wire (diameter: 0.2 mm) on the surface of a strip-shaped membrane sample on a self-made measurement probe (Teflon (R)) The sample was held in (Nagano Scientific Machinery Co., Ltd., LH-20-01), and the impedance between the platinum wires was measured by SOLARTRON 1250 FREQUENCY RESPONSE ANALYSER. The measurement was performed while changing the distance between the electrodes, and the conductivity obtained by canceling the contact resistance between the film and the platinum wire was calculated from the gradient obtained by plotting the distance measured between the electrodes and the resistance measurement value estimated from the CC plot.
・導電率［Ｓ／ｃｍ］＝１／膜幅［ｃｍ］×膜厚［ｃｍ］×抵抗極間勾配［Ω/ｃｍ］
メタノール透過速度：イオン交換膜の液体燃料透過速度はメタノールの透過速度として、以下の方法で測定した。２５℃に調整した５Ｍ（モル／リットル）のメタノール水溶液に２４時間浸漬した平均厚み５０μｍのイオン交換膜（平均厚みが４８μｍから５２μｍの範囲に入っているものを平均厚み５０μｍの膜とする）をＨ型セルに挟み込み、セルの片側に１００ｍｌの５Ｍメタノール水溶液を、他方のセルに１００ｍｌの超純水（１８ＭΩ・ｃｍ）を注入し、２５℃で両側のセルを撹拌しながら、イオン交換膜を通って超純水中に拡散してくるメタノール量をガスクロマトグラフを用いて測定することで算出した（イオン交換膜の面積は、２．０ｃｍ2）。
・引張試験：２０℃相対湿度６５％での引張試験は東洋ボールドウィン製テンシロンＵＴＭＩＩを、２５℃水中での引張試験は東洋ボールドウィン製テンシロンＵＴＭＩＩＩを用いて、大きさを揃えて切り出したフィルム片を用いて測定した。
Conductivity [S / cm] = 1 / film width [cm] × film thickness [cm] × resistance interelectrode gradient [Ω / cm]
Methanol permeation rate: The liquid fuel permeation rate of the ion exchange membrane was measured as the permeation rate of methanol by the following method. An ion-exchange membrane having an average thickness of 50 μm (24 μm average thickness in the range of 48 μm to 52 μm as an average thickness of 50 μm) immersed in a 5M (mol / liter) methanol aqueous solution adjusted to 25 ° C. for 24 hours. Placed in an H-type cell, 100 ml of 5M aqueous methanol solution was poured into one side of the cell, 100 ml of ultrapure water (18 MΩ · cm) was poured into the other side, and the ion-exchange membrane was placed while stirring the cells on both sides at 25 ° C. It was calculated by measuring the amount of methanol diffusing through the ultrapure water using a gas chromatograph (the area of the ion exchange membrane was 2.0 cm 2 ).
・ Tensile test: Tensilon UTMII manufactured by Toyo Baldwin is used for tensile tests at 20 ° C and 65% relative humidity, and Tensilon UTMIII manufactured by Toyo Baldwin is used for tensile tests in water at 25 ° C. Measured.
・発電評価：Ｐｔ／Ｒｕ触媒担持カーボン（田中貴金属工業株式会社ＴＥＣ６１Ｅ５４）に少量の超純水およびイソプロピルアルコールを加えて湿らせた後、デュポン社製２０％ナフィオン溶液（品番：ＳＥ−２０１９２）を、Ｐｔ／Ｒｕ触媒担持カーボンとナフィオンの重量比が２．５：１になるように加えた。次いで撹拌してアノード用触媒ペーストを調製した。この触媒ペーストを、ガス拡散層となる東レ社製カーボンペーパーＴＧＰＨ−０６０に白金の付着量が２ｍｇ／ｃｍ2になるようにスクリーン印刷により塗布乾燥して、アノード用電極触媒層付きカーボンペーパーを作製した。また、Ｐｔ触媒担持カーボン（田中貴金属工業株式会社ＴＥＣ１０Ｖ４０Ｅ）に少量の超純水およびイソプロピルアルコールを加えて湿らせた後、デュポン社製２０％ナフィオン溶液（品番：ＳＥ−２０１９２）を、Ｐｔ触媒担持カーボンとナフィオンの重量比が２．５：１となるように加え、撹拌してカソード用触媒ペーストを調製した。この触媒ペーストを、撥水加工を施した東レ製カーボンペーパーＴＧＰＨ−０６０に白金の付着量が１ｍｇ／ｃｍ2となるように塗布・乾燥して、カソード用電極触媒層付きカーボンペーパーを作製した。上記２種類の電極触媒層付きカーボンペーパーの間に、膜試料を、電極触媒層が膜試料に接するように挟み、ホットプレス法により１３０℃、８ＭＰａにて３分間加圧、加熱することにより、膜−電極接合体とした。この接合体をＥｌｅｃｔｒｏｃｈｅｍ社製評価用燃料電池セルＦＣ２５−０２ＳＰに組み込み、燃料電池発電試験機（株式会社東陽テクニカ製）を用いて発電試験を行った。発電は、セル温度4０℃で、アノードおよびカソードにそれぞれ４０℃に調整した２ｍｏｌ／ｌのメタノール水溶液（１．５ｍｌ／ｍｉｎ）および高純度酸素ガス（８０ｍｌ／ｍｉｎ）を供給しながら行った。
スルホン酸基含有量：窒素雰囲気下で一晩乾燥した試料の重量をはかり、水酸化ナトリウム水溶液と撹拌処理した後、塩酸水溶液による逆滴定でイオン交換容量（ＩＥＣ）を求めた。
Power generation evaluation: After adding a small amount of ultrapure water and isopropyl alcohol to a Pt / Ru catalyst-supporting carbon (TEC61E54) and moistening it, a 20% Nafion solution (product number: SE-20192) manufactured by DuPont is used. The Pt / Ru catalyst-carrying carbon and Nafion were added at a weight ratio of 2.5: 1. Next, stirring was performed to prepare an anode catalyst paste. The catalyst paste is applied and dried by screen printing on carbon paper TGPH-060 manufactured by Toray Industries, Inc. as a gas diffusion layer so that the amount of platinum deposited is 2 mg / cm 2, and carbon paper with an electrode catalyst layer for anode is produced. did. Further, after adding a small amount of ultrapure water and isopropyl alcohol to a Pt catalyst-supporting carbon (Tanaka Kikinzoku Kogyo Co., Ltd. TEC10V40E) and moistening it, a 20% Nafion solution (product number: SE-20192) manufactured by DuPont was added to the Pt catalyst-supporting carbon. A cathode catalyst paste was prepared by adding carbon and Nafion at a weight ratio of 2.5: 1 and stirring. This catalyst paste was applied and dried on a carbon paper TGPH-060 manufactured by Toray made with a water-repellent finish so that the amount of platinum deposited was 1 mg / cm 2 , thereby producing a carbon paper with an electrode catalyst layer for cathode. By sandwiching the membrane sample between the two types of carbon paper with the electrode catalyst layer so that the electrode catalyst layer is in contact with the membrane sample, by pressurizing and heating at 130 ° C. and 8 MPa for 3 minutes by a hot press method, A membrane-electrode assembly was obtained. This joined body was incorporated into an evaluation fuel cell FC25-02SP manufactured by Electrochem, and a power generation test was performed using a fuel cell power generation tester (manufactured by Toyo Corporation). Power generation was performed at a cell temperature of 40 ° C. while supplying a 2 mol / l aqueous methanol solution (1.5 ml / min) and high-purity oxygen gas (80 ml / min) adjusted to 40 ° C. to the anode and cathode, respectively.
Sulfonic acid group content: A sample dried overnight under a nitrogen atmosphere was weighed, stirred with an aqueous sodium hydroxide solution, and then ion exchange capacity (IEC) was determined by back titration with an aqueous hydrochloric acid solution.
実施例１
３，３’−ジスルホ−４，４’−ジクロロジフェニルスルホン２ナトリウム塩（略号：Ｓ−ＤＣＤＰＳ４．５１９ｇ（０．００９２０ｍｏｌ）、２，６−ジクロロベンゾニトリル（略号：ＤＣＢＮ）２．５８１７ｇ（０．０１５０１ｍｏｌ）、４，４’−ビフェノール４．５０７７ｇ（０．０２４２１ｍｏｌ）、炭酸カリウム３．８４８４ｇ（０．０２７８４ｍｏｌ）、モレキュラーシーブ２．６１ｇを１００ｍｌ四つ口フラスコに計り取り、窒素を流した。３５ｍｌのＮＭＰを入れて、１５０℃で一時間撹拌した後、反応温度を１９５−２００℃に上昇させて系の粘性が十分上がるのを目安に反応を続けた（約５時間）。放冷の後、沈降しているモレキュラーシーブを除いて水中にストランド状に沈殿させた。得られたポリマーは、沸騰水中で１時間洗浄した後、乾燥した。ポリマーの対数粘度は１．０３を示した。
ポリマー１ｇをＮＭＰ５ｍｌに溶解し、ホットプレート上ガラス板に約２００μｍ厚にキャストし、フィルム状になるまでＮＭＰを留去した後、水中に一晩以上浸漬した。得られたフィルムは、希硫酸（濃硫酸６ｍｌ、水３００ｍｌ）中で１時間沸騰水処理して塩をはずした後、純水でさらに１時間煮沸することで酸成分を除去した。本フィルムのイオン伝導性を測定したところ、０．２２Ｓ／ｃｍの値を示した。滴定で求めたＩＥＣは１．８５を示した。本フィルムの引張試験結果を表１に示す。本フィルムは、熱水への浸漬、取りだしを繰り返しても形態に変化が見られない良好な寸法安定性を示した。
Example 1
3,3′-disulfo-4,4′-dichlorodiphenylsulfone disodium salt (abbreviation: S-DCDPS 4.519 g (0.00920 mol), 2,6-dichlorobenzonitrile (abbreviation: DCBN) 2.5817 g (0. 01501 mol), 4,4'-biphenol 4.5077 g (0.02421 mol), potassium carbonate 3.8484 g (0.02784 mol), and molecular sieve 2.61 g were weighed into a 100 ml four-necked flask and flushed with nitrogen. The NMP was added and stirred at 150 ° C. for 1 hour, and then the reaction was continued by raising the reaction temperature to 195-200 ° C. to sufficiently increase the viscosity of the system (about 5 hours). The polymer obtained in the form of a strand was precipitated in water except for the molecular sieve that had settled. After washing time, the logarithmic viscosity of the dried. The polymer showed 1.03.
1 g of the polymer was dissolved in 5 ml of NMP, cast on a glass plate on a hot plate to a thickness of about 200 μm, NMP was distilled off until it became a film, and then immersed in water overnight. The obtained film was treated with boiling water in dilute sulfuric acid (concentrated sulfuric acid 6 ml, water 300 ml) for 1 hour to remove the salt, and then boiled with pure water for 1 hour to remove the acid component. When the ionic conductivity of this film was measured, it was 0.22 S / cm. The IEC determined by titration was 1.85. Table 1 shows the tensile test results of this film. This film showed good dimensional stability with no change in form even after repeated immersion and extraction in hot water.
実施例２〜８
Ｓ−ＤＣＤＰＳとＤＣＢＮの混合比を変える以外は実施例１と同様にして、組成の異なるポリマーを合成し、評価を行った。引張試験結果を表１に示す。いずれのフィルムも熱水への浸漬、取りだしを繰り返しても形態に変化が見られない良好な寸法安定性を示した。
Examples 2-8
Polymers having different compositions were synthesized and evaluated in the same manner as in Example 1 except that the mixing ratio of S-DCDPS and DCBN was changed. Table 1 shows the tensile test results. All films showed good dimensional stability with no change in form even after repeated immersion and extraction in hot water.
比較例１
Ｓ−ＤＣＤＰＳとＤＣＢＮの混合比をかえる以外は実施例１と同様にして、組成の異なるポリマーを合成し、評価を行った。引張試験結果を表２に示す。得られたフィルムは熱水への浸漬、取りだしを繰り返すと形態に崩れが認められた。
Comparative Example 1
Polymers having different compositions were synthesized and evaluated in the same manner as in Example 1 except that the mixing ratio of S-DCDPS and DCBN was changed. Table 2 shows the tensile test results. When the obtained film was repeatedly immersed in hot water and taken out, it was confirmed that the form was broken.
比較例２及び３
実施例２において、ＤＣＢＮのかわりに４，４’−ジクロロジフェニルスルホン（ＤＣＤＰＳ）を用いて組成の異なるポリマーを合成し、評価を行った。引張試験結果を表３に示す。いずれのフィルムも熱水への浸漬、取りだしを繰り返すと変形や皺の発生などが認められた。
Comparative Examples 2 and 3
In Example 2, polymers having different compositions were synthesized using 4,4′-dichlorodiphenylsulfone (DCDPS) instead of DCBN, and evaluated. Table 3 shows the tensile test results. Both films were deformed and wrinkled when they were repeatedly immersed in hot water and removed.
実施例９
実施例１において、モノマーとして４，４’−ジフルオロベンゾフェノン０．１４１０ｇ（０．０００６４ｍｏｌ）とビス（２，５−ジメチル−４−ヒドロキシフェニル）メタン０．１６５７ｇ（０．０００６４ｍｏｌ）を追加して、同様に重合を行った。得られたリマーの対数粘度は１．１３を示した。ポリマー１ｇをＮＭＰ５ｍｌに溶解し、ホットプレート上ガラス板に約２００μｍ厚にキャストし、フィルム状になるまでＮＭＰを留去した後、水中に一晩以上浸漬し、さらに紫外線ランプ照射１時間処理した。得られたフィルムは、希硫酸（濃硫酸６ｍｌ、水３００ｍｌ）中で１時間沸騰水処理して塩をはずした後、純水でさらに１時間煮沸することで酸成分を除去した。本フィルムのイオン伝導性を測定したところ、０．２０Ｓ／ｃｍの値を示した。滴定で求めたＩＥＣは１．８０を示した。本フィルムの引張試験結果を表４に示す。本フィルムは、熱水への浸漬、取りだしを繰り返しても形態に変化が見られない良好な寸法安定性を示した。
Example 9
In Example 1, 0.1410 g (0.00064 mol) of 4,4′-difluorobenzophenone and 0.1657 g (0.00064 mol) of bis (2,5-dimethyl-4-hydroxyphenyl) methane were added as monomers, Polymerization was carried out in the same manner. The logarithmic viscosity of the obtained limer was 1.13. 1 g of the polymer was dissolved in 5 ml of NMP, cast on a glass plate on a hot plate to a thickness of about 200 μm, NMP was distilled off until a film was formed, and then immersed in water overnight or more and further treated with ultraviolet lamp irradiation for 1 hour. The obtained film was treated with boiling water in dilute sulfuric acid (concentrated sulfuric acid 6 ml, water 300 ml) for 1 hour to remove the salt, and then boiled with pure water for 1 hour to remove the acid component. When the ionic conductivity of this film was measured, it showed a value of 0.20 S / cm. The IEC determined by titration was 1.80. Table 4 shows the tensile test results of this film. This film showed good dimensional stability with no change in form even after repeated immersion and extraction in hot water.
実施例１０
実施例１で得られたフィルムのメタノール透過速度は、６．２１ｍｍｏｌ／ｍ2・ｓｅｃを示した。このフィルムを用いて発電評価を実施したところ、１００ｍＡの電流密度において０．３５Ｖと、良好な発電特性が得られた。
Example 10
The methanol permeation rate of the film obtained in Example 1 was 6.21 mmol / m 2 · sec. When this film was used for power generation evaluation, good power generation characteristics of 0.35 V at a current density of 100 mA were obtained.
本発明のスルホン酸基含有高分子化合物による高分子電解質膜は、イオン伝導性に優れるとともに、特に湿潤時の力学特性、寸法安定性に優れる。このため、イオン伝導膜として、水素やメタノールを原料として使用する燃料電池や水電解槽に使うこと可能であり、各種電池用電解質、表示素子、センサー、バインダー類、添加剤などとしても利用することが期待できる。 The polymer electrolyte membrane made of the sulfonic acid group-containing polymer compound of the present invention is excellent in ionic conductivity, and is particularly excellent in mechanical properties and dimensional stability when wet. Therefore, it can be used as an ion conductive membrane in fuel cells and water electrolyzers that use hydrogen or methanol as a raw material, and it can also be used as various battery electrolytes, display elements, sensors, binders, additives, etc. Can be expected.
Claims (5)
The fuel cell according to claim 4 , wherein methanol is used as a fuel.
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| JP2004050750A JP4720090B2 (en) | 2004-02-26 | 2004-02-26 | Sulfonic acid group-containing polymer electrolyte membrane and article using the same |
| AT04771020T ATE509383T1 (en) | 2003-07-31 | 2004-07-29 | ELECTROLYTE MEMBRANE ELECTRODE ASSEMBLY, FUEL CELL THEREFROM AND METHOD FOR PRODUCING AN ELECTROLYTE MEMBRANE ELECTRODE ASSEMBLY |
| PCT/JP2004/010807 WO2005013399A1 (en) | 2003-07-31 | 2004-07-29 | Electrolyte membrane-electrode assembly, fuel cell using same, and method for producing electrolyte membrane-electrode assembly |
| CN2004800223292A CN1833330B (en) | 2003-07-31 | 2004-07-29 | Electrolyte membrane-electrode assembly, fuel cell using same, and method for producing electrolyte membrane-electrode assembly |
| EP04771020A EP1653541B1 (en) | 2003-07-31 | 2004-07-29 | Electrolyte membrane-electrode assembly, fuel cell using same, and method for producing electrolyte membrane-electrode assembly |
| US10/566,218 US20080063917A1 (en) | 2003-07-31 | 2004-07-29 | Electrolyte Membrane-Electrode Assembly, Fuel Cell Using The Same, And Method For Producing Electrolyte Membrane-Electrode Assembly |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09199144A (en) * | 1996-01-12 | 1997-07-31 | Toyota Central Res & Dev Lab Inc | Manufacture of electrolyte membrane |
| JPH1021943A (en) * | 1996-06-28 | 1998-01-23 | Sumitomo Chem Co Ltd | Polymer electrolytic substance for fuel cell, and fuel cell |
| JPH1045913A (en) * | 1996-04-18 | 1998-02-17 | Sumitomo Chem Co Ltd | High-molecular electrolyte, its production and fuel cell made by using the same |
| JPH1167224A (en) * | 1997-08-22 | 1999-03-09 | Asahi Chem Ind Co Ltd | Membrane-electrode bonding body for solid polymer fuel cell |
| JP2002298870A (en) * | 2001-03-30 | 2002-10-11 | Toyobo Co Ltd | Solid polymer electrolytic film/electrode joint body for fuel cell, and manufacturing method therefor |
| JP2004149779A (en) * | 2002-10-08 | 2004-05-27 | Toyobo Co Ltd | Poly(arylene ether) compound, composition containing the same and method for producing them |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09199144A (en) * | 1996-01-12 | 1997-07-31 | Toyota Central Res & Dev Lab Inc | Manufacture of electrolyte membrane |
| JPH1045913A (en) * | 1996-04-18 | 1998-02-17 | Sumitomo Chem Co Ltd | High-molecular electrolyte, its production and fuel cell made by using the same |
| JPH1021943A (en) * | 1996-06-28 | 1998-01-23 | Sumitomo Chem Co Ltd | Polymer electrolytic substance for fuel cell, and fuel cell |
| JPH1167224A (en) * | 1997-08-22 | 1999-03-09 | Asahi Chem Ind Co Ltd | Membrane-electrode bonding body for solid polymer fuel cell |
| JP2002298870A (en) * | 2001-03-30 | 2002-10-11 | Toyobo Co Ltd | Solid polymer electrolytic film/electrode joint body for fuel cell, and manufacturing method therefor |
| JP2004149779A (en) * | 2002-10-08 | 2004-05-27 | Toyobo Co Ltd | Poly(arylene ether) compound, composition containing the same and method for producing them |
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