JP4470034B2 - Solid electrolyte membrane and polymer electrolyte fuel cell using zeolite - Google Patents
Solid electrolyte membrane and polymer electrolyte fuel cell using zeolite Download PDFInfo
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- JP4470034B2 JP4470034B2 JP2003055634A JP2003055634A JP4470034B2 JP 4470034 B2 JP4470034 B2 JP 4470034B2 JP 2003055634 A JP2003055634 A JP 2003055634A JP 2003055634 A JP2003055634 A JP 2003055634A JP 4470034 B2 JP4470034 B2 JP 4470034B2
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Description
【０００１】
【発明の属する技術分野】
固体電解質膜は、燃料電池、リチウム２次電池、イオンセンサー、ガスセンサーなどに利用されている。また、固体高分子型燃料電池は、水素やメタノールなどを燃料とし、アノード、カソード、セパレーター、固体電解質膜などから成り立ち、携帯機器用、家庭用、自動車用の新しいエネルギー源として期待されている。本発明は、固体電解質膜及びその固体電解質膜を使用する固体高分子型燃料電池に関するものである。
【０００２】
【従来の技術】
従来、水素やメタノールなどを燃料とする固体高分子型燃料電池用の固体電解質膜は、パーフルオロスルホン酸系のイオン交換膜が使われていた。しかしパーフルオロスルホン酸系のイオン交換膜は、高温で使用できないため電極の選択肢が少なくなること、高コストであること、メタノールを燃料とした場合においてメタノールの浸透性が大きいことなどの問題が指摘されていた。
【０００３】
ゼオライトを用いた固体電解質膜については、報告例がある（例えば、非特許文献１）。その中で、Ｈ−モルデナイトのみからなる膜が、プロトン導電性を有していることが報告されている。
【０００４】
また、ゼオライトと有機系高分子を混合し、成膜した固体電解質膜についても、幾つか報告例（例えば、特許文献１）がある。その中で、イオン交換樹脂を高分子マトリックスとする固体イオン導電体であって、吸湿性無機多孔質粒子の吸湿容量が、関係湿度２０％において２〜１５％であることなどを特徴とする固体イオン導電体が開示されている。吸湿性無機多孔質粒子の含量は、イオン交換樹脂１００重量部に対して０．５〜６０重量部、特に好ましくは１〜３０重量部、であることが好ましいと記載されている。ゼオライトを用いた実施例としては、合成ゼオライト（商品名：モレキュラーシーブ２３３６４−１、アルドリッチ社製）を５重量部配合したパーフルオロカーボンスルホン酸樹脂の１例のみである。合成ゼオライトは、導電性を有するパーフルオロカーボンスルホン酸樹脂に対して、水を保持することができる吸湿剤（添加剤）として利用されており、ゼオライトの導電性に関して特に記述はない。
【０００５】
またＨ−Ｙ型ゼオライト，Ｈ−モルデナイトなどのゼオライトと、パーフルオロスルホン酸（ナフィオン），ポリテトラフルオロエチレンなどの有機高分子を混合し、成膜した固体電解質膜について報告されている（例えば、非特許文献２）。その中で、膜の導電率は、１０-4Ｓ／ｃｍ以下の低いものであり、また膜の導電率は、ゼオライトのブロンステッド酸量に依存していると記載されている。
【０００６】
更にＮａ−Ｙ型ゼオライトとポリテトラフルオロエチレンを混合し、成膜した固体電解質膜が報告されている（例えば、非特許文献３）。その中で、膜の導電率は、１０-3Ｓ／ｃｍ以下と低い導電率しか報告されていない。
【０００７】
以上、ゼオライトと有機系高分子を混合し、成膜した固体電解質膜では、導電率などの性能面において、満足するものは得られていなかった。
【０００８】
【特許文献１】
特許第３０３５８８５号公報
【非特許文献１】
ヒビノ（Ｔ．Ｈｉｂｉｎｏ）、他２名、「ソリッド ステイト イオニックス（Ｓｏｌｉｄ Ｓｔａｔｅ Ｉｏｎｉｃｓ）」，（オランダ）、６７，１−２，ｐ７１−７６（１９９３）
【非特許文献２】
タカミ マサヨシ（Ｍａｓａｙｏｓｉ Ｔａｋａｍｉ）、他２名、「エレクトロケミストリー（Ｅｌｅｃｔｒｏｃｈｅｍｉｓｔｒｙ）」，６９，２，ｐ９８−１０３（２００１）
【非特許文献３】
譽田祐樹、他３名、「第８８回触媒討論会（２００１）予稿集」、ｐ３２
【０００９】
【発明が解決しようとする課題】
本発明は、高温で使用できる安価な固体電解質膜を提供すること、及びその固体電解質膜を使用する固体高分子型燃料電池を提供することを目的とする。
【００１０】
【課題を解決するための手段】
本発明者等は、Ｌｉ−Ｙ型のゼオライトと有機系高分子を混合し、成膜した固体電解質膜を詳細に検討した結果、ゼオライト含有量が６５重量％以上９９重量％以下であり、膜の水分吸着量が１０ｍｍｏｌ／ｇ以上２０ｍｍｏｌ／ｇ以下である固体電解質膜が優れた導電率を有することを見出し、本発明を完成するに至ったものである。固体電解質膜の水分吸着量と導電率が相関する機構は明らかでないが、ゼオライトに吸着した水がＨ３Ｏ＋ホッピングの役割を担っていると考えられる。以下、本発明を詳細に説明する。
【００１１】
Ｌｉ−Ｙ型のゼオライトは、有機系高分子と混合・成膜した膜において、その含有量が６５重量％以上９９重量％以下、好ましくは７０重量％以上９５重量％以下である。含有量が６５重量％より少なすぎると成膜したときの導電率が低くなり好ましくない。また９９重量％より多すぎると膜の強度が低下するため好ましくない。
【００１２】
ゼオライトの構造は、ＦＡＵ構造のゼオライトである。またゼオライトのＳｉ／Ａｌも特に限定されないが、Ｓｉ／Ａｌが小さいほどゼオライトの水分吸着量が多くなるため、Ｓｉ／Ａｌが１０より小さい方が好ましい。更にゼオライトのイオン種もＬｉである。
【００１３】
ゼオライトの凝集粒子径は特に限定されず、例えば、０．１〜３００μｍが例示できる。またゼオライトの平均細孔径、細孔容量も特に限定されない。
【００１４】
ゼオライトの水分吸着量も、特に限定されないが、有機系高分子と混合・成膜した膜の水分吸着量を大きくするため、大きい方が好ましい。例えば、２５℃、相対湿度２０％において、２０％以上が例示できる。
【００１５】
本発明で使用される有機系高分子は、固体電解質膜として運転する温度において熱的に安定であれば良く、特に限定されないが、耐熱性高分子であることが好ましい。耐熱性高分子としては、ポリテトラフルオロエチレン、ポリアミド、アラミド、ポリイミド、ポリベンズイミダゾール、ポリエーテルイミド、ポリアミドイミド、ポリフェニレンスルフィド、ポリエーテルスルホン、ポリスルホン、ポリエーテルエーテルケトン、ポリメチルペンテン、ポリビニリデンフロライド、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、ポリアリレート、ポリアセタールおよびポリフェニレンエーテルが例示でき、これらのうち少なくとも一種を用いる。
【００１６】
本発明において、ゼオライトと有機系高分子を混合し、成膜した固体電解質膜の水分吸着量が、１０ｍｍｏｌ／ｇ以上２０ｍｍｏｌ／ｇ以下、好ましくは１５ｍｍｏｌ／ｇ以上２０ｍｍｏｌ／ｇ以下である。水分吸着量が、１０ｍｍｏｌ／ｇ未満では導電率が低く、固体電解質膜としての性能が低くなる。また、水分吸着量が２０ｍｍｏｌ／ｇを越えると、ゼオライトおよび／または有機系高分子が特殊なものでしか実現できず、高価になるため、好ましくない。水分吸着量と導電率が相関する機構は明らかでないが、ゼオライトに吸着した水がＨ3Ｏ+ホッピングの役割を担っていると考えられる。膜の水分吸着量は、膜をデシケーター中で飽和塩化アンモニウム水溶液と１２時間以上室温で保った後に、熱分析（２０℃から２５０℃までの重量減）することにより算出できる。
【００１７】
ゼオライトと有機系高分子を混合し、成膜する方法は、特に限定されない。例えば、予め合成したゼオライト粒子と有機系高分子を懸濁・凝集させて、ゼオライトと有機系高分子の均一混合物を得て、更にホットプレスなどを用いて成膜する方法が挙げられる。
【００１８】
膜の厚さは、特に限定されないが、例えば、１０〜１０００μｍが例示できる。また、膜中のゼオライトと有機系高分子の分散度も特に限定されないが、均一であることが好ましい。
【００１９】
本発明の固体電解質膜は、燃料電池、リチウム２次電池、イオンセンサー、ガスセンサーなどに利用できる。
【００２０】
本発明の固体電解質膜は、アノード、カソードの間に配置し、さらにアノードとカソードの外側にセパレーターを配置して固体高分子型燃料電池を構成することができる。燃料電池の燃料として、水素、メタノールが例示できる。本発明の固体電解質膜を用いた固体高分子型燃料電池の運転温度は、限定されないが、７０℃以上、特に１００℃以上のときに、ゼオライトと有機系高分子を混合し、成膜した膜以外の膜と比べて優位性が発揮できる。
【００２１】
【実施例】
以下本発明を実施例により更に詳細に説明するが、本発明は、これらの実施例に何ら限定されるものではない。
【００２２】
実施例１ （Ｌｉ−Ｙ型ゼオライト（８０重量％）とポリテトラフルオロエチレンを混合・成膜した固体電解質膜）
（膜の調製）
東ソー株式会社製のＮａ−Ｙ型ゼオライト（商品名３２０ＮＡＡ）を硝酸リチウム水溶液でリチウム交換を行ない、Ｌｉ−Ｙ型ゼオライトを得た。Ｌｉ−Ｙ型ゼオライトの一部をフッ酸水溶液で溶解し、ＩＣＰ発光分光分析でＬｉ交換率を求めたところ、７４％であった。またＬｉ−Ｙ型ゼオライトのＳｉ／Ａｌは２．８、凝集粒子径は６μｍ、水分吸着量（２５℃、相対湿度２０％）は３１％であった。次に、Ｌｉ−Ｙ型ゼオライトとポリテトラフルオロエチレン（３５重量％，アルドリッチ製）の混合懸濁液を、Ｌｉ−Ｙ型ゼオライトがポリテトラフルオロエチレンとの混合物として８０重量％になるように調製した。調製した混合懸濁液を５０℃で５０分間、強攪拌し、室温まで冷却した後に、凝集剤としてイソプロピルアルコールを加えた。得られた沈殿物をろ過し、７０℃で１２時間乾燥した。得られた乾燥物を３５０℃で加熱し、４．９ＭＰａの圧力で加圧して、Ｌｉ−Ｙ型ゼオライト（８０重量％）とポリテトラフルオロエチレンを混合・成膜した固体電解質膜を得た。
【００２３】
（膜の水分吸着量）
Ｌｉ−Ｙ型ゼオライト（８０重量％）とポリテトラフルオロエチレンを混合・成膜した固体電解質膜をデシケーター中で飽和塩化アンモニウム水溶液と１２時間以上室温で保った後に、島津製作所製ＤＴＧ−６０熱分析装置を用いて、２０℃から２５０℃までの重量減で評価した。膜の水分吸着量は、１０．５ｍｍｏｌ／ｇと大きな値であった。
【００２４】
（導電率の測定）
固体電解質膜の導電率を測定する装置を図１に示す。固体電解質膜を金のプレートで挟み、ＬＣＲメーター（安藤電機製；ＡＧ−４３１１）に金線でつないだ。測定雰囲気として、水（８０体積％）＋窒素（バランス）のガスを１２５ｃｍ3／ｍｉｎの流量で測定セルに流通させ、温度を７５〜１５０℃の間の一定温度で制御した。導電率は、０．１〜１００ｋＨｚの周波数で測定した。得られた導電率を図２および図３に示す。７５℃における導電率は、２．０×１０-3Ｓ／ｃｍと大きな値となった。
【００２５】
比較例１ （Ｎａ−Ｙ型ゼオライト（８０重量％）とポリテトラフルオロエチレンを混合・成膜した固体電解質膜）
（膜の調製）
東ソー株式会社製のＮａ−Ｙ型ゼオライト（商品名３２０ＮＡＡ）を用いて、実施例１と同様にＮａ−Ｙ型ゼオライト（８０重量％）とポリテトラフルオロエチレンを混合・成膜した固体電解質膜を得た。なお用いたＮａ−Ｙ型ゼオライトのＳｉ／Ａｌは２．８、凝集粒子径は６μｍ、水分吸着量（２５℃、相対湿度２０％）は３０％であった。
【００２６】
（膜の水分吸着量）
実施例１と同様に測定を行なった。図３に示したように、Ｌｉ−Ｙ型ゼオライト（８０重量％）とポリテトラフルオロエチレンを混合・成膜した固体電解質膜に比べて、水分吸着量は小さかった。
【００２７】
（導電率の測定）
実施例１と同様に測定を行なった。図２，３に示したように。Ｌｉ−Ｙ型ゼオライト（８０重量％）とポリテトラフルオロエチレンを混合・成膜した固体電解質膜に比べて、導伝率は小さかった。
【００２８】
比較例２ （Ｎａ−Ｙ型ゼオライト（５０重量％）とポリテトラフルオロエチレンを混合・成膜した固体電解質膜）
（膜の調製）
東ソー株式会社製のＮａ−Ｙ型ゼオライト（商品名３２０ＮＡＡ）を用いて、実施例１と同様にＮａ−Ｙ型ゼオライト（５０重量％）とポリテトラフルオロエチレンを混合・成膜した固体電解質膜を得た。
【００２９】
（膜の水分吸着量）
実施例１と同様に測定を行なった。図３に示したように、Ｌｉ−Ｙ型ゼオライト（８０重量％）とポリテトラフルオロエチレンを混合・成膜した固体電解質膜に比べて、水分吸着量は小さかった。
【００３０】
（導電率の測定）
実施例１と同様に測定を行なった。図３に示したように。Ｌｉ−Ｙ型ゼオライト（８０重量％）とポリテトラフルオロエチレンを混合・成膜した固体電解質膜に比べて、導伝率は小さかった。
【００３１】
比較例３ （Ｎａ−Ｙ型ゼオライト（２０重量％）とポリテトラフルオロエチレンを混合・成膜した固体電解質膜）
（膜の調製）
東ソー株式会社製のＮａ−Ｙ型ゼオライト（商品名３２０ＮＡＡ）を用いて、実施例１と同様にＮａ−Ｙ型ゼオライト（２０重量％）とポリテトラフルオロエチレンを混合・成膜した固体電解質膜を得た。
【００３２】
（膜の水分吸着量）
実施例１と同様に測定を行なった。図３に示したように、Ｌｉ−Ｙ型ゼオライト（８０重量％）とポリテトラフルオロエチレンを混合・成膜した固体電解質膜に比べて、水分吸着量は小さかった。
【００３３】
（導電率の測定）
実施例１と同様に測定を行なった。図３に示したように。Ｌｉ−Ｙ型ゼオライト（８０重量％）とポリテトラフルオロエチレンを混合・成膜した固体電解質膜に比べて、導伝率は小さかった。
【００３４】
比較例４ （Ｋ−Ｙ型ゼオライト（８０重量％）とポリテトラフルオロエチレンを混合・成膜した固体電解質膜）
（膜の調製）
東ソー株式会社製のＮａ−Ｙ型ゼオライト（商品名３２０ＮＡＡ）を用いて、Ｋ−Ｙ型ゼオライト（Ｋ交換率９２％）を調製し、実施例１と同様にＫ−Ｙ型ゼオライト（８０重量％）とポリテトラフルオロエチレンを混合・成膜した固体電解質膜を得た。なお用いたＫ−Ｙ型ゼオライトのＳｉ／Ａｌは２．８、凝集粒子径は６μｍであった。
【００３５】
（膜の水分吸着量）
実施例１と同様に測定を行なった。図３に示したように、Ｌｉ−Ｙ型ゼオライト（８０重量％）とポリテトラフルオロエチレンを混合・成膜した固体電解質膜に比べて、水分吸着量は小さかった。
【００３６】
（導電率の測定）
実施例１と同様に測定を行なった。図２，３に示したように。Ｌｉ−Ｙ型ゼオライト（８０重量％）とポリテトラフルオロエチレンを混合・成膜した固体電解質膜に比べて、導伝率は小さかった。
【００３７】
比較例５ （Ｈ−Ｙ型ゼオライト（８０重量％）とポリテトラフルオロエチレンを混合・成膜した固体電解質膜）
（膜の調製）
東ソー株式会社製のＮａ−Ｙ型ゼオライト（商品名３２０ＮＡＡ）を用いて、Ｈ−Ｙを調製し、実施例１と同様にＨ−Ｙ型ゼオライト（８０重量％）とポリテトラフルオロエチレンを混合・成膜した固体電解質膜を得た。なお用いたＨ−Ｙ型ゼオライトのＳｉ／Ａｌは２．８、凝集粒子径は６μｍ、水分吸着量（２５℃、相対湿度２０％）は２４％であった。
【００３８】
（膜の水分吸着量）
実施例１と同様に測定を行なった。図３に示したように、Ｌｉ−Ｙ型ゼオライト（８０重量％）とポリテトラフルオロエチレンを混合・成膜した固体電解質膜に比べて、水分吸着量は小さかった。
【００３９】
（導電率の測定）
実施例１と同様に測定を行なった。図２，３に示したように。Ｌｉ−Ｙ型ゼオライト（８０重量％）とポリテトラフルオロエチレンを混合・成膜した固体電解質膜に比べて、導伝率は小さかった。
【００４０】
【発明の効果】
本発明の固体電解質膜は、安価で且つ高温においても高い導電率を有する。また、その固体電解質膜を使用する固体高分子型燃料電池は、高温で使用できるため電極の選択肢が広がる等の効果がある。
【００４１】
【図面の簡単な説明】
【図１】導電率測定装置の概略図
【図２】導電率測定結果の温度依存性
【図３】導電率測定結果の水分吸着量依存性[0001]
BACKGROUND OF THE INVENTION
Solid electrolyte membranes are used in fuel cells, lithium secondary batteries, ion sensors, gas sensors, and the like. A polymer electrolyte fuel cell uses hydrogen, methanol, or the like as a fuel, and is composed of an anode, a cathode, a separator, a solid electrolyte membrane, and the like, and is expected as a new energy source for portable devices, home use, and automobiles. The present invention relates to a solid electrolyte membrane and a polymer electrolyte fuel cell using the solid electrolyte membrane.
[0002]
[Prior art]
Conventionally, perfluorosulfonic acid ion exchange membranes have been used as solid electrolyte membranes for polymer electrolyte fuel cells using hydrogen or methanol as fuel. However, perfluorosulfonic acid ion exchange membranes cannot be used at high temperatures, so there are fewer electrode options, high costs, and high methanol permeability when methanol is used as fuel. It had been.
[0003]
There are reported examples of solid electrolyte membranes using zeolite (for example, Non-Patent Document 1). Among them, it has been reported that a film composed only of H-mordenite has proton conductivity.
[0004]
Moreover, there are some report examples (for example, patent document 1) about the solid electrolyte membrane formed by mixing zeolite and organic polymer. Among them, a solid ionic conductor having an ion exchange resin as a polymer matrix, wherein the hygroscopic inorganic porous particles have a moisture absorption capacity of 2 to 15% at a relative humidity of 20%. An ionic conductor is disclosed. It is described that the content of the hygroscopic inorganic porous particles is preferably 0.5 to 60 parts by weight, particularly preferably 1 to 30 parts by weight with respect to 100 parts by weight of the ion exchange resin. As an example using zeolite, there is only one example of perfluorocarbon sulfonic acid resin containing 5 parts by weight of synthetic zeolite (trade name: Molecular Sieve 23364-1, manufactured by Aldrich). Synthetic zeolite is used as a hygroscopic agent (additive) capable of retaining water with respect to conductive perfluorocarbon sulfonic acid resin, and there is no particular description regarding the conductivity of zeolite.
[0005]
In addition, solid electrolyte membranes have been reported in which zeolites such as HY zeolite and H-mordenite are mixed with organic polymers such as perfluorosulfonic acid (Nafion) and polytetrafluoroethylene (for example, Non-patent document 2). Among them, it is described that the conductivity of the membrane is as low as 10 −4 S / cm or less, and that the conductivity of the membrane depends on the amount of Bronsted acid of the zeolite.
[0006]
Furthermore, a solid electrolyte membrane formed by mixing Na-Y zeolite and polytetrafluoroethylene to form a film has been reported (for example, Non-Patent Document 3). Among them, only a low conductivity of 10 −3 S / cm or less has been reported.
[0007]
As described above, a solid electrolyte membrane formed by mixing zeolite and an organic polymer to form a film has not been satisfactory in terms of performance such as conductivity.
[0008]
[Patent Document 1]
Japanese Patent No. 3035885 [Non-Patent Document 1]
T. Hibino, two others, "Solid State Ionics", (Netherlands), 67, 1-2, p71-76 (1993)
[Non-Patent Document 2]
Masayoshi Takami, two others, "Electrochemistry", 69, 2, p98-103 (2001)
[Non-Patent Document 3]
Yuki Hamada and 3 others, “88th Catalysis Conference (2001) Proceedings”, p. 32
[0009]
[Problems to be solved by the invention]
An object of the present invention is to provide an inexpensive solid electrolyte membrane that can be used at a high temperature, and to provide a polymer electrolyte fuel cell using the solid electrolyte membrane.
[0010]
[Means for Solving the Problems]
As a result of examining the solid electrolyte membrane formed by mixing Li-Y type zeolite and organic polymer in detail, the inventors have found that the zeolite content is 65 wt% or more and 99 wt% or less. It has been found that a solid electrolyte membrane having a moisture adsorption amount of 10 mmol / g or more and 20 mmol / g or less has excellent conductivity, and has completed the present invention. Although the mechanism by which the moisture adsorption amount of the solid electrolyte membrane correlates with the conductivity is not clear, it is considered that the water adsorbed on the zeolite plays a role of H 3 O + hopping. Hereinafter, the present invention will be described in detail.
[0011]
The content of the Li-Y type zeolite in the film mixed and formed with the organic polymer is 65% by weight to 99% by weight, preferably 70% by weight to 95% by weight. If the content is less than 65% by weight, the conductivity when the film is formed is lowered, which is not preferable. On the other hand, if it is more than 99% by weight, the strength of the film is lowered, which is not preferable.
[0012]
The zeolite has a FAU structure . Also, the Si / Al of the zeolite is not particularly limited, but the smaller the Si / Al, the greater the amount of moisture adsorption of the zeolite. Therefore, the Si / Al is preferably smaller than 10. Further, the ionic species of zeolite is also Li .
[0013]
The agglomerated particle diameter of zeolite is not particularly limited, and examples thereof include 0.1 to 300 μm. Further, the average pore diameter and pore volume of zeolite are not particularly limited.
[0014]
The amount of moisture adsorption of zeolite is not particularly limited, but a larger amount is preferable in order to increase the amount of moisture adsorption of the film mixed and formed with an organic polymer. For example, 20% or more can be exemplified at 25 ° C. and a relative humidity of 20%.
[0015]
The organic polymer used in the present invention is not particularly limited as long as it is thermally stable at the temperature at which it operates as a solid electrolyte membrane, but is preferably a heat resistant polymer. Examples of heat-resistant polymers include polytetrafluoroethylene, polyamide, aramid, polyimide, polybenzimidazole, polyetherimide, polyamideimide, polyphenylene sulfide, polyethersulfone, polysulfone, polyetheretherketone, polymethylpentene, and polyvinylidene fluoride. Ride, polyethylene terephthalate, polybutylene terephthalate, polyarylate, polyacetal, and polyphenylene ether can be exemplified, and at least one of them is used.
[0016]
In the present invention, the moisture adsorption amount of the solid electrolyte membrane formed by mixing zeolite and an organic polymer is 10 mmol / g or more and 20 mmol / g or less, preferably 15 mmol / g or more and 20 mmol / g or less. When the moisture adsorption amount is less than 10 mmol / g, the electrical conductivity is low, and the performance as a solid electrolyte membrane is low. On the other hand, if the amount of moisture adsorption exceeds 20 mmol / g, the zeolite and / or the organic polymer can be realized only with special ones and is expensive. Although the mechanism that correlates the moisture adsorption amount and the conductivity is not clear, it is considered that the water adsorbed on the zeolite plays a role of H 3 O + hopping. The moisture adsorption amount of the membrane can be calculated by thermal analysis (weight loss from 20 ° C. to 250 ° C.) after keeping the membrane in a desiccator with a saturated aqueous ammonium chloride solution for 12 hours or more at room temperature.
[0017]
A method for forming a film by mixing zeolite and an organic polymer is not particularly limited. For example, a method of suspending and aggregating previously synthesized zeolite particles and organic polymer to obtain a uniform mixture of zeolite and organic polymer, and further forming a film using a hot press or the like can be mentioned.
[0018]
Although the thickness of a film | membrane is not specifically limited, For example, 10-1000 micrometers can be illustrated. Further, the degree of dispersion of the zeolite and the organic polymer in the membrane is not particularly limited, but is preferably uniform.
[0019]
The solid electrolyte membrane of the present invention can be used for fuel cells, lithium secondary batteries, ion sensors, gas sensors and the like.
[0020]
The solid electrolyte membrane of the present invention can be disposed between an anode and a cathode, and further a separator can be disposed outside the anode and the cathode to constitute a solid polymer fuel cell. Examples of the fuel for the fuel cell include hydrogen and methanol. The operating temperature of the polymer electrolyte fuel cell using the solid electrolyte membrane of the present invention is not limited, but a membrane formed by mixing zeolite and an organic polymer when the temperature is 70 ° C. or higher, particularly 100 ° C. or higher. Advantages can be demonstrated compared to other films.
[0021]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples at all.
[0022]
Example 1 (Li-Y type zeolite (80 wt%) and polytetrafluoroethylene mixed / film-formed solid electrolyte membrane)
(Preparation of membrane)
Lithium exchange was performed on Na-Y zeolite (trade name 320NAA) manufactured by Tosoh Corporation with a lithium nitrate aqueous solution to obtain Li-Y zeolite. A part of the Li-Y type zeolite was dissolved in a hydrofluoric acid aqueous solution, and the Li exchange rate was determined by ICP emission spectroscopic analysis. As a result, it was 74%. Moreover, Si / Al of the Li—Y type zeolite was 2.8, the agglomerated particle diameter was 6 μm, and the moisture adsorption amount (25 ° C., relative humidity 20%) was 31%. Next, a mixed suspension of Li-Y type zeolite and polytetrafluoroethylene (35% by weight, manufactured by Aldrich) is prepared so that the Li-Y type zeolite becomes 80% by weight as a mixture with polytetrafluoroethylene. did. The prepared mixed suspension was vigorously stirred at 50 ° C. for 50 minutes and cooled to room temperature, and then isopropyl alcohol was added as a flocculant. The resulting precipitate was filtered and dried at 70 ° C. for 12 hours. The obtained dried product was heated at 350 ° C. and pressurized at a pressure of 4.9 MPa to obtain a solid electrolyte membrane in which Li-Y zeolite (80 wt%) and polytetrafluoroethylene were mixed and formed.
[0023]
(Moisture adsorption amount of membrane)
A solid electrolyte membrane formed by mixing and forming a Li-Y zeolite (80% by weight) and polytetrafluoroethylene was kept in a desiccator with a saturated aqueous ammonium chloride solution at room temperature for 12 hours or more, and then DTG-60 thermal analysis manufactured by Shimadzu Corporation. Using the apparatus, the weight loss from 20 ° C. to 250 ° C. was evaluated. The moisture adsorption amount of the film was a large value of 10.5 mmol / g.
[0024]
(Measurement of conductivity)
An apparatus for measuring the conductivity of the solid electrolyte membrane is shown in FIG. The solid electrolyte membrane was sandwiched between gold plates and connected to an LCR meter (manufactured by Ando Electric Co., AG-4311) with a gold wire. As a measurement atmosphere, a gas of water (80% by volume) + nitrogen (balance) was passed through the measurement cell at a flow rate of 125 cm 3 / min, and the temperature was controlled at a constant temperature between 75 ° C. and 150 ° C. The conductivity was measured at a frequency of 0.1 to 100 kHz. The obtained conductivity is shown in FIG. 2 and FIG. The conductivity at 75 ° C. was a large value of 2.0 × 10 −3 S / cm.
[0025]
Comparative Example 1 (Solid electrolyte membrane in which Na-Y zeolite (80% by weight) and polytetrafluoroethylene are mixed and formed)
(Preparation of membrane)
Using a Na-Y zeolite (trade name 320NAA) manufactured by Tosoh Corporation, a solid electrolyte membrane in which Na-Y zeolite (80% by weight) and polytetrafluoroethylene were mixed and formed in the same manner as in Example 1 Obtained. The Na—Y zeolite used had an Si / Al ratio of 2.8, an aggregated particle size of 6 μm, and a moisture adsorption amount (25 ° C., relative humidity 20%) of 30%.
[0026]
(Moisture adsorption amount of membrane)
Measurements were performed in the same manner as in Example 1. As shown in FIG. 3, the moisture adsorption amount was smaller than that of the solid electrolyte membrane in which Li-Y type zeolite (80 wt%) and polytetrafluoroethylene were mixed and formed.
[0027]
(Measurement of conductivity)
Measurements were performed in the same manner as in Example 1. As shown in Figs. Compared with the solid electrolyte membrane in which Li-Y type zeolite (80% by weight) and polytetrafluoroethylene were mixed and formed, the conductivity was small.
[0028]
Comparative Example 2 (Solid electrolyte membrane in which Na-Y zeolite (50% by weight) and polytetrafluoroethylene are mixed and formed)
(Preparation of membrane)
Using a Na-Y zeolite (trade name 320NAA) manufactured by Tosoh Corporation, a solid electrolyte membrane in which Na-Y zeolite (50 wt%) and polytetrafluoroethylene were mixed and formed in the same manner as in Example 1 was prepared. Obtained.
[0029]
(Moisture adsorption amount of membrane)
Measurements were performed in the same manner as in Example 1. As shown in FIG. 3, the moisture adsorption amount was smaller than that of the solid electrolyte membrane in which Li-Y type zeolite (80 wt%) and polytetrafluoroethylene were mixed and formed.
[0030]
(Measurement of conductivity)
Measurements were performed in the same manner as in Example 1. As shown in FIG. Compared with the solid electrolyte membrane in which Li-Y type zeolite (80% by weight) and polytetrafluoroethylene were mixed and formed, the conductivity was small.
[0031]
Comparative Example 3 (Solid electrolyte membrane in which Na-Y zeolite (20% by weight) and polytetrafluoroethylene are mixed and formed)
(Preparation of membrane)
Using a Na-Y zeolite (trade name 320NAA) manufactured by Tosoh Corporation, a solid electrolyte membrane in which Na-Y zeolite (20% by weight) and polytetrafluoroethylene were mixed and formed in the same manner as in Example 1. Obtained.
[0032]
(Moisture adsorption amount of membrane)
Measurements were performed in the same manner as in Example 1. As shown in FIG. 3, the moisture adsorption amount was smaller than that of the solid electrolyte membrane in which Li-Y type zeolite (80 wt%) and polytetrafluoroethylene were mixed and formed.
[0033]
(Measurement of conductivity)
Measurements were performed in the same manner as in Example 1. As shown in FIG. Compared with the solid electrolyte membrane in which Li-Y type zeolite (80% by weight) and polytetrafluoroethylene were mixed and formed, the conductivity was small.
[0034]
Comparative Example 4 (Solid electrolyte membrane in which KY type zeolite (80% by weight) and polytetrafluoroethylene were mixed and formed)
(Preparation of membrane)
Using Na-Y type zeolite (trade name 320NAA) manufactured by Tosoh Corporation, KY type zeolite (K exchange rate 92%) was prepared, and KY type zeolite (80% by weight) was prepared in the same manner as in Example 1. ) And polytetrafluoroethylene were mixed to form a solid electrolyte membrane. The KY type zeolite used had a Si / Al ratio of 2.8 and an agglomerated particle diameter of 6 μm.
[0035]
(Moisture adsorption amount of membrane)
Measurements were performed in the same manner as in Example 1. As shown in FIG. 3, the moisture adsorption amount was smaller than that of the solid electrolyte membrane in which Li-Y type zeolite (80 wt%) and polytetrafluoroethylene were mixed and formed.
[0036]
(Measurement of conductivity)
Measurements were performed in the same manner as in Example 1. As shown in Figs. Compared with the solid electrolyte membrane in which Li-Y zeolite (80% by weight) and polytetrafluoroethylene were mixed and formed, the conductivity was small.
[0037]
Comparative Example 5 (Solid electrolyte membrane in which H-Y zeolite (80% by weight) and polytetrafluoroethylene are mixed and formed)
(Preparation of membrane)
H-Y was prepared using Na-Y zeolite (trade name 320NAA) manufactured by Tosoh Corporation, and H-Y zeolite (80 wt%) and polytetrafluoroethylene were mixed in the same manner as in Example 1. A formed solid electrolyte membrane was obtained. The H—Y type zeolite used had a Si / Al ratio of 2.8, an agglomerated particle size of 6 μm, and a moisture adsorption amount (25 ° C., relative humidity 20%) of 24%.
[0038]
(Moisture adsorption amount of membrane)
Measurements were performed in the same manner as in Example 1. As shown in FIG. 3, the moisture adsorption amount was smaller than that of the solid electrolyte membrane in which Li-Y type zeolite (80 wt%) and polytetrafluoroethylene were mixed and formed.
[0039]
(Measurement of conductivity)
Measurements were performed in the same manner as in Example 1. As shown in Figs. Compared with the solid electrolyte membrane in which Li-Y zeolite (80% by weight) and polytetrafluoroethylene were mixed and formed, the conductivity was small.
[0040]
【The invention's effect】
The solid electrolyte membrane of the present invention is inexpensive and has high conductivity even at high temperatures. In addition, since the polymer electrolyte fuel cell using the solid electrolyte membrane can be used at a high temperature, there are effects such as widening the choice of electrodes.
[0041]
[Brief description of the drawings]
[Fig. 1] Schematic diagram of conductivity measuring device [Fig. 2] Temperature dependence of conductivity measurement results [Fig. 3] Moisture adsorption dependence of conductivity measurement results
Claims (4)
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| WO2012045335A1 (en) | 2010-10-05 | 2012-04-12 | Universiteit Twente | Proton exchange membrane |
| KR101710233B1 (en) * | 2014-09-17 | 2017-02-24 | 주식회사 엘지화학 | Composition for electrode protective film, electrode protective film comprising the same, electrode comprising the same, battery comprising the same and preparation method thereof |
| KR101845126B1 (en) * | 2014-09-17 | 2018-04-03 | 주식회사 엘지화학 | Composition for solide electrolyte, solide electrolyte comprising the same, battery comprising the same and preparation method thereof |
| JP6437307B2 (en) * | 2014-12-26 | 2018-12-12 | 旭化成株式会社 | Solid electrolyte |
| JP2016219134A (en) * | 2015-05-15 | 2016-12-22 | 旭化成株式会社 | Solid electrolyte |
| JP6889607B2 (en) * | 2017-05-23 | 2021-06-18 | 旭化成株式会社 | Solid electrolyte membrane |
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