JP2008204928A - Solid polymer electrolyte membrane, and fuel cell using it - Google Patents
Solid polymer electrolyte membrane, and fuel cell using it Download PDFInfo
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Abstract
Description
本発明は、固体高分子電解質膜及びそれを用いた燃料電池に関する。 The present invention relates to a solid polymer electrolyte membrane and a fuel cell using the same.
イオン交換膜を電解質膜として用いる固体高分子形燃料電池（ＰＥＦＣ）やダイレクトメタノール型燃料電池（ＤＭＦＣ）は、低温で作動し、出力密度が高く、小型化が可能であることから、近年、特に注目され、家庭用分散電源，業務用分散電源，自動車用電源，携帯用電源等に適用すべく、開発が急ピッチで進められている。 In recent years, polymer electrolyte fuel cells (PEFC) and direct methanol fuel cells (DMFC) that use ion exchange membranes as electrolyte membranes operate at low temperatures, have high output density, and can be miniaturized. Attention has been focused on, and development is proceeding at a rapid pace to be applied to household distributed power supplies, commercial distributed power supplies, automobile power supplies, portable power supplies and the like.
燃料電池用の電解質膜としては、一般にフッ素系のポリパーフロロカーボンスルホン酸電解質膜が市販されている。その代表的なものとして、ナフィオン（Nafion，登録商標：米国Dupont社製），アシプレックス（Aciplex 、登録商標：旭化成工業株式会社製），フレミオン（Flemion、登録商標：旭硝子株式会社製）等がある。 Generally as a fuel cell electrolyte membrane, a fluorine-based polyperfluorocarbonsulfonic acid electrolyte membrane is commercially available. Representative examples include Nafion (Nafion, registered trademark: manufactured by Dupont, USA), Aciplex (registered trademark: manufactured by Asahi Kasei Kogyo Co., Ltd.), Flemion (registered trademark: manufactured by Asahi Glass Co., Ltd.), and the like. .
ＤＭＦＣやＰＥＦＣの普及を図るためには、高効率化，高出力密度化等による性能向上及び低コスト化が必須である。 In order to popularize DMFC and PEFC, it is essential to improve performance and reduce costs by increasing efficiency and increasing output density.
このようなポリパーフロロカーボンスルホン酸電解質膜は、フッ素化学プロセスが必須であり、用途が食塩電解や燃料電池応用に限られたスーパーファインケミカル材料である。 Such a polyperfluorocarbon sulfonic acid electrolyte membrane is a super fine chemical material in which a fluorine chemical process is essential and its use is limited to salt electrolysis and fuel cell applications.
これに対して、芳香族炭化水素系電解質膜は、ポリパーフロロカーボンスルホン酸電解質膜に比べると低コストである。しかし、燃料電池の高効率化，高出力密度化等による性能向上を図るためには、固体高分子電解質膜のイオン伝導抵抗を減少させ、イオン伝導度を向上させる必要がある。 In contrast, aromatic hydrocarbon electrolyte membranes are less expensive than polyperfluorocarbon sulfonic acid electrolyte membranes. However, in order to improve the performance by increasing the efficiency and the output density of the fuel cell, it is necessary to reduce the ionic conduction resistance of the solid polymer electrolyte membrane and improve the ionic conductivity.
固体高分子電解質膜のイオン伝導抵抗を減少する方法として、膜厚の低減がある。膜厚の低減は、膜の機械強度の低下，加工性・取扱性の低下等の問題が生じる。 As a method for reducing the ionic conduction resistance of the solid polymer electrolyte membrane, there is a reduction in film thickness. The reduction of the film thickness causes problems such as a decrease in the mechanical strength of the film and a decrease in workability and handleability.
このような問題を解決するため、補強材により電解質膜を補強する試みが種々なされており、例えば、特許文献１には多孔質基材を用いた高分子電解質複合膜が開示されている。 In order to solve such problems, various attempts have been made to reinforce the electrolyte membrane with a reinforcing material. For example, Patent Document 1 discloses a polymer electrolyte composite membrane using a porous substrate.
しかしながら、補強材が単一である場合には、燃料電池として連続使用した際の耐久性が必ずしも満足できるものではなかった。 However, when a single reinforcing material is used, the durability when continuously used as a fuel cell is not always satisfactory.
本発明の目的は、耐久性に優れた固体高分子電解質膜及びそれを用いた燃料電池を提供することにある。 An object of the present invention is to provide a solid polymer electrolyte membrane excellent in durability and a fuel cell using the same.
本発明者らは鋭意検討の結果、固体高分子電解質と複数の多孔質膜からなる固体高分子電解質膜（固体高分子電解質複合膜）の新規な構造を発明するに至った。 As a result of intensive studies, the present inventors have invented a novel structure of a solid polymer electrolyte membrane (solid polymer electrolyte composite membrane) comprising a solid polymer electrolyte and a plurality of porous membranes.
本発明の代表的な実施態様は以下の通りである。 Exemplary embodiments of the present invention are as follows.
本発明の一実施態様である燃料電池用の固体高分子電解質膜は、燃料極と空気極との間に形成されるのものであって、この固体高分子電解質膜が、固体高分子電解質層と固体高分子電解質層とによって挟まれた、多孔内に固体高分子電解質が充填された、少なくとも２層以上の多孔質基材を有し、多孔質基材は、燃料極側の厚さが空気極側の厚さよりも厚いことを特徴とする。 A solid polymer electrolyte membrane for a fuel cell according to an embodiment of the present invention is formed between a fuel electrode and an air electrode, and the solid polymer electrolyte membrane is a solid polymer electrolyte layer. And at least two layers of porous substrates filled with a solid polymer electrolyte in the pores, and the porous substrate has a thickness on the fuel electrode side. It is characterized by being thicker than the thickness on the air electrode side.
そして、好ましくは、少なくとも２層以上の多孔質基材の間に、固体高分子電解質層が形成される。 Preferably, a solid polymer electrolyte layer is formed between at least two porous substrates.
また、燃料極と空気極との間に形成される燃料電池用の固体高分子電解質膜が、固体高分子電解質層，多孔質基材，固体高分子電解質層，多孔質基材，固体高分子電解質層の層構造を有し、多孔質基材は、多孔内に固体高分子電解質が充填され、燃料極側に形成される多孔質基材の厚さが空気極側に形成される多孔質基材の厚さよりも厚いことを特徴としてもよい。 In addition, a solid polymer electrolyte membrane for a fuel cell formed between a fuel electrode and an air electrode includes a solid polymer electrolyte layer, a porous substrate, a solid polymer electrolyte layer, a porous substrate, and a solid polymer. The porous substrate has a layer structure of an electrolyte layer, and the porous substrate is filled with a solid polymer electrolyte in the pores, and the porous substrate formed on the fuel electrode side has a thickness formed on the air electrode side It may be characterized by being thicker than the thickness of the substrate.
本発明によって、耐久性に優れた固体高分子電解質膜及びそれを用いた燃料電池を提供することができる。 According to the present invention, a solid polymer electrolyte membrane excellent in durability and a fuel cell using the same can be provided.
以下、実施例により本発明をさらに詳しく説明するが、本発明はこれらに限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.
本実施例で説明する燃料極と空気極との間に形成される燃料電池用の固体高分子電解質膜は、固体高分子電解質層，多孔質基材，固体高分子電解質層，多孔質基材，固体高分子電解質層の層構造を有し、多孔質基材は、多孔内に固体高分子電解質が充填され、燃料極側に形成される多孔質基材の厚さが空気極側に形成される多孔質基材の厚さよりも厚いことを特徴としている。 The solid polymer electrolyte membrane for a fuel cell formed between the fuel electrode and the air electrode described in this example is a solid polymer electrolyte layer, a porous substrate, a solid polymer electrolyte layer, and a porous substrate. , It has a layer structure of a solid polymer electrolyte layer, and the porous substrate is filled with a solid polymer electrolyte in the pores, and the thickness of the porous substrate formed on the fuel electrode side is formed on the air electrode side It is characterized by being thicker than the thickness of the porous substrate.
また、固体高分子電解質及び固体高分子電解質層は、ポリエーテルスルホンのスルホアルキル化物またはポリエーテルスルホンのスルホン化物であることが好ましい。 The solid polymer electrolyte and the solid polymer electrolyte layer are preferably polyethersulfone sulfoalkylates or polyethersulfone sulfonates.
また、こうした複合化された固体高分子電解質膜に、燃料極触媒層及び空気極触媒層を形成し、膜電極接合体を形成することも可能であり、更には、こうした膜電極接合体を搭載した燃料電池とすることも可能である。なお、燃料としてメタノール水溶液を用いた
ＤＭＦＣとすることが好ましい。
It is also possible to form a membrane electrode assembly by forming a fuel electrode catalyst layer and an air electrode catalyst layer on such a composite solid polymer electrolyte membrane, and furthermore, mounting such a membrane electrode assembly. It is also possible to make a fuel cell. In addition, it is preferable to set it as DMFC using methanol aqueous solution as a fuel.
多孔質基材としては、ポリオレフィン多孔質膜であることが好ましい。 The porous substrate is preferably a polyolefin porous membrane.
さらに好ましくは、超高分子量ポリオレフィン樹脂を含有することである。超高分子量ポリオレフィン樹脂としては、エチレン，プロピレン，１−ブテン，４−メチル−１−ペンテン，１−ヘキセン等のオレフィンの単独重合体，共重合体、およびこれらの混合物等が挙げられ、これらの中では、得られる多孔質膜の高強度化の観点から、重量平均分子量１×１０6以上の超高分子量ポリエチレン樹脂が好ましく用いられる。 More preferably, it contains an ultrahigh molecular weight polyolefin resin. Examples of the ultrahigh molecular weight polyolefin resin include homopolymers and copolymers of olefins such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, and 1-hexene, and mixtures thereof. Among them, an ultrahigh molecular weight polyethylene resin having a weight average molecular weight of 1 × 10 6 or more is preferably used from the viewpoint of increasing the strength of the resulting porous membrane.
他にも芳香族系高分子の多孔質膜を用いることもでき、例えば、ポリイミド，ポリスルホン等が挙げられ、単独またはポリオレフィン多孔質膜との併用が可能である。 In addition, a porous membrane of an aromatic polymer can be used, and examples thereof include polyimide, polysulfone, and the like, which can be used alone or in combination with a polyolefin porous membrane.
さらに、これらは予め公知の方法でスルホン化した多孔質膜を使用することも可能である。 Furthermore, it is possible to use a porous membrane sulfonated in advance by a known method.
本実施例で説明するポリオレフィン多孔質膜は、膜厚が３〜３５μｍであることが好ましい。 The polyolefin porous membrane described in this example preferably has a thickness of 3 to 35 μm.
膜厚が３μｍより小さいと寸法変化を押さえることが難しくなり、複合化したことによる高強度化の効果が得にくくなる。 When the film thickness is smaller than 3 μm, it is difficult to suppress the dimensional change, and it becomes difficult to obtain the effect of increasing the strength due to the composite.
膜厚が３５μｍより大きいと固体高分子電解質膜の抵抗が大きくなり、燃料電池の性能が悪くなる。 When the film thickness is larger than 35 μm, the resistance of the solid polymer electrolyte membrane increases and the performance of the fuel cell deteriorates.
本実施例で説明するポリオレフィン多孔質膜は、空孔率が４０〜９０％であることが好ましい。 The polyolefin porous membrane described in this example preferably has a porosity of 40 to 90%.
空孔率が４０％より小さいと固体高分子電解質膜の抵抗が大きくなり、燃料電池の性能が悪くなる。 When the porosity is less than 40%, the resistance of the solid polymer electrolyte membrane is increased, and the performance of the fuel cell is deteriorated.
空孔率が９０％より大きいと寸法変化を押さえることが難しくなり、複合化したことによる高強度化の効果が得にくくなる。 When the porosity is larger than 90%, it is difficult to suppress the dimensional change, and it is difficult to obtain the effect of increasing the strength due to the composite.
ポリオレフィン多孔質膜の多孔質基材の多孔内に、固体高分子電解質を充填する方法やポリオレフィン多孔質膜と固体高分子電解質層とを複合化する方法としては、固体高分子電解質となる材料の溶液又は分散液を、ポリオレフィン多孔質膜に含浸させた後、乾燥し成膜を行う方法や、固体高分子電解質となる材料の溶液をポリオレフィン多孔質膜に塗布し、乾燥，成膜を行う方法や、ポリオレフィン多孔質膜に減圧下で固体高分子電解質となる材料の溶液を接触させ、その後常圧に戻して含浸させ、乾燥，成膜を行う方法等が挙げられる。 As a method for filling a solid polymer electrolyte in the pores of a porous substrate of a polyolefin porous membrane or a method for compounding a polyolefin porous membrane and a solid polymer electrolyte layer, the material used as the solid polymer electrolyte A method in which a polyolefin porous membrane is impregnated with a solution or dispersion and then dried to form a film, or a solution of a material to be a solid polymer electrolyte is applied to a polyolefin porous membrane, and then dried and formed into a film Alternatively, a method of bringing a polyolefin porous membrane into contact with a solution of a material that becomes a solid polymer electrolyte under reduced pressure, and then impregnating it by returning to normal pressure, followed by drying and film formation, and the like.
燃料極側に用いられるポリオレフィン多孔質膜の厚さ（ｔA ）は、固体高分子電解質膜の厚さ（ｔC ）に対して、１５％〜９５％であることが好ましい。この割合が１５％より小さいと、ハンドリングが難しくなり、また、９５％より大きいと、燃料極側の膨潤が大きくなるため、耐久性が必ずしも満足できるものではなくなる。なお、特に、好ましくは２０％〜８０％である。 The thickness (t A ) of the polyolefin porous membrane used on the fuel electrode side is preferably 15% to 95% with respect to the thickness (t C ) of the solid polymer electrolyte membrane. If this ratio is less than 15%, handling becomes difficult, and if it is more than 95%, the swelling on the fuel electrode side increases, so that the durability is not always satisfactory. In particular, it is preferably 20% to 80%.
ポリオレフィン多孔質膜については、例えば、２枚使用する場合、それぞれの空孔率は、異なっていても良い。この場合には、燃料極側に空気極側に比較して、空孔率の小さいポリオレフィン多孔質膜を配置し、燃料の透過を抑制することが好ましい。 For example, when two polyolefin porous membranes are used, the porosity of each may be different. In this case, it is preferable to dispose a polyolefin porous membrane having a lower porosity than the air electrode side on the fuel electrode side to suppress fuel permeation.
同様に、孔径の異なるものを使用しても良く、その場合には、燃料極側に空気極側に比較して、孔径の小さいポリオレフィン多孔質膜を配置し、燃料の透過を抑制することが好ましい。 Similarly, ones having different pore diameters may be used. In that case, a polyolefin porous membrane having a smaller pore diameter than that on the air electrode side may be disposed on the fuel electrode side to suppress fuel permeation. preferable.
また、固体高分子電解質及び固体高分子電解質層には、ポリエーテルスルホンのスルホアルキル化物またはポリエーテルスルホンのスルホン化物であることが好ましい。 The solid polymer electrolyte and the solid polymer electrolyte layer are preferably a polyethersulfone sulfoalkylated product or a polyethersulfone sulfonated product.
スルホアルキル化ポリエーテルスルホンとして、スルホメチル化ポリエーテルスルホン，スルホプロピル化ポリエーテルスルホン，スルホン化物として、スルホン化ポリエーテルスルホンなどが耐久性の点から好ましい。 As the sulfoalkylated polyethersulfone, sulfomethylated polyethersulfone, sulfopropylated polyethersulfone, and sulfonated product such as sulfonated polyethersulfone are preferable from the viewpoint of durability.
他の電解質及び電解質層としては、スルホン化ポリエーテルエーテルケトン，スルホン化ポリエーテルエーテルスルホン，スルホン化ポリスルホン，スルホン化ポリスルフィッド，スルホン化ポリフェニレン等のスルホン化エンジニアプラスチック系電解質材料，スルホアルキル化ポリエーテルエーテルケトン，スルホアルキル化ポリエーテルエーテルスルホン，スルホアルキル化ポリスルホン，スルホアルキル化ポリスルフィッド，スルホアルキル化ポリフェニレン等のスルホアルキル化エンジニアプラスチック系電解質材料等が用いられる。 Other electrolytes and electrolyte layers include sulfonated polyether ether ketone, sulfonated polyether ether sulfone, sulfonated polysulfone, sulfonated polysulfide, sulfonated polyphenylene and other sulfonated engineered plastic materials, sulfoalkylated polyether ethers Examples include sulfoalkylated engineered plastic electrolyte materials such as ketones, sulfoalkylated polyetherethersulfones, sulfoalkylated polysulfones, sulfoalkylated polysulfides, and sulfoalkylated polyphenylenes.
固体高分子電解質及び固体高分子電解質層のイオン交換容量としては、０.５〜２.０ミリ当量／ｇ乾燥樹脂、更には０.７〜１.６ミリ当量／ｇ乾燥樹脂の範囲が好ましい。スルホン酸当量がこの範囲より、低い場合にはイオン伝導抵抗が大きくなり、高い場合には水に溶解し易くなり好ましくない。 The ion exchange capacity of the solid polymer electrolyte and the solid polymer electrolyte layer is preferably in the range of 0.5 to 2.0 meq / g dry resin, more preferably 0.7 to 1.6 meq / g dry resin. . When the sulfonic acid equivalent is lower than this range, the ionic conduction resistance becomes large, and when it is high, the sulfonic acid equivalent is easily dissolved in water.
固体高分子電解質膜の厚みは、特に制限はないが、１０〜２００μｍが好ましい。特に２０〜１００μｍが好ましい。実用に耐える膜の強度を得るには１０μｍより厚い方が好ましく、膜抵抗の低減、つまり発電性能向上のためには２００μｍより薄い方が好ましい。最も好ましい厚さは３０〜８０μｍである。 Although there is no restriction | limiting in particular in the thickness of a solid polymer electrolyte membrane, 10-200 micrometers is preferable. 20-100 micrometers is especially preferable. A thickness of more than 10 μm is preferable to obtain a membrane strength that can withstand practical use, and a thickness of less than 200 μm is preferable to reduce membrane resistance, that is, to improve power generation performance. The most preferred thickness is 30 to 80 μm.
ポリオレフィン多孔質膜、及び、固体高分子電解質や固体高分子電解質層の電解質材料には、必要に応じて酸化防止剤等の添加物を、目的を損なわない範囲で、添加することができる。 Additives such as antioxidants can be added to the polyolefin porous membrane and the electrolyte material of the solid polymer electrolyte or the solid polymer electrolyte layer as necessary within a range that does not impair the purpose.
なお、このような固体高分子電解質膜は、ＰＥＦＣに用いた場合には、低加湿運転の場合などに用いることが可能である。 Such a solid polymer electrolyte membrane can be used in a low humidification operation when used in PEFC.
本形態によれば、メタノール燃料電池における燃料極側での電解質膜の膨潤を抑制することができるため、連続発電を行った場合においても耐久性の良好な固体高分子電解質膜を提供することができる。 According to this embodiment, since the swelling of the electrolyte membrane on the fuel electrode side in the methanol fuel cell can be suppressed, it is possible to provide a solid polymer electrolyte membrane having good durability even when continuous power generation is performed. it can.
更に、燃料極側から空気極側へのメタノール透過量を抑制できるため、発電電圧が高く、安定した発電が可能な固体高分子電解質膜を提供することができる。 Furthermore, since the amount of methanol permeation from the fuel electrode side to the air electrode side can be suppressed, it is possible to provide a solid polymer electrolyte membrane having a high power generation voltage and capable of stable power generation.
また、燃料極側の電極触媒層の厚さが空気極側に比べて極端に厚い場合においても、燃料極側の膨潤が抑制されていることから、電極層の剥離が生じにくい膜電極接合体を提供することができる。 In addition, even when the electrode catalyst layer on the fuel electrode side is extremely thicker than the air electrode side, the membrane electrode assembly is less prone to peeling of the electrode layer because swelling on the fuel electrode side is suppressed. Can be provided.
（固体高分子電解質膜の作製）
固体高分子電解質膜（電解質膜）の作製に先立って、スルホメチル化ポリエーテルスルホンＳＭ−ＰＥＳ（１.５ ミリ当量／ｇ）をＮ，Ｎ−ジメチルアセトアミドに溶解して
２３重量％の電解質溶液を作製した。
(Preparation of solid polymer electrolyte membrane)
Prior to the production of the solid polymer electrolyte membrane (electrolyte membrane), sulfomethylated polyethersulfone SM-PES (1.5 meq / g) was dissolved in N, N-dimethylacetamide to prepare a 23 wt% electrolyte solution. Produced.
ガラス基板上でこの電解質溶液を流延塗布後、厚さ１０μｍのポリオレフィン多孔質膜をのせて含浸させた。 The electrolyte solution was cast on a glass substrate, and then impregnated with a polyolefin porous film having a thickness of 10 μm.
次に、この上に電解質溶液を流延塗布後、厚さ１６μｍのポリオレフィン多孔質膜をのせて含浸し、更にこの上に電解質溶液を流延塗布した。 Next, the electrolyte solution was cast on this, and then impregnated with a polyolefin porous film having a thickness of 16 μm. Further, the electrolyte solution was cast on this.
その後、９０℃で３０分間、次いで、１２０℃で３０分間、加熱乾燥して溶液中の溶媒を除去して電解質膜を作製した。 Then, the electrolyte membrane was produced by removing the solvent in the solution by heating and drying at 90 ° C. for 30 minutes and then at 120 ° C. for 30 minutes.
得られた電解質膜の膜厚は、４５μｍであった。図１に、この電解質膜の断面構造図を示す。１は固体高分子電解質膜、２は電解質層、３は電解質が含浸された多孔質基材である。 The thickness of the obtained electrolyte membrane was 45 μm. FIG. 1 shows a cross-sectional structure diagram of the electrolyte membrane. Reference numeral 1 denotes a solid polymer electrolyte membrane, 2 denotes an electrolyte layer, and 3 denotes a porous substrate impregnated with an electrolyte.
（膜電極接合体の作製）
燃料極としてカーボンブラックにＰｔとＲｕとをそれぞれ２５ｗｔ％担持した電極触媒を用い、空気極としてＰｔを５０ｗｔ％担持した電極触媒を用いた。
(Production of membrane electrode assembly)
An electrode catalyst supporting 25 wt% of Pt and Ru on carbon black was used as the fuel electrode, and an electrode catalyst supporting 50 wt% of Pt was used as the air electrode.
この電極触媒に、ナフィオン溶液を電極触媒対ナフィオン溶液の重量比が１対９となる割合で秤量し、混合して電極触媒ペーストを作製した。この電極触媒ペーストを電解質膜にスプレー塗布後、加熱プレスして電極触媒層を形成した。その際、厚みが大きいポリオレフィン多孔質層に燃料極触媒層を形成し、厚みが小さいポリオレフィン多孔質層に空気極触媒層を形成した。 The electrode catalyst was weighed with a Nafion solution at a ratio of 1: 9 to the weight ratio of the electrode catalyst to the Nafion solution, and mixed to prepare an electrode catalyst paste. After spraying this electrode catalyst paste on the electrolyte membrane, it was heated and pressed to form an electrode catalyst layer. At that time, a fuel electrode catalyst layer was formed on the polyolefin porous layer having a large thickness, and an air electrode catalyst layer was formed on the polyolefin porous layer having a small thickness.
図２は、燃料電池発電装置単セルの断面図である。セパレータ７とセパレータ７との間に、燃料極側の拡散層６，燃料極電極４，固体高分子電解質膜１，空気極電極５，空気極側の拡散層６が形成されている。
FIG. 2 is a cross-sectional view of a single cell of a fuel cell power generator. Between the
この際、燃料極電極４と空気極電極５との間に形成される燃料電池用の固体高分子電解質膜１は、固体高分子電解質層２，多孔質基材３，固体高分子電解質層２，多孔質基材３，固体高分子電解質層２の層構造を有している。
Under the present circumstances, the solid polymer electrolyte membrane 1 for fuel cells formed between the fuel electrode 4 and the air electrode 5 is the solid
そして、多孔質基材３は、燃料極電極４側に形成される多孔質基材３の厚さが空気極電極５側に形成される多孔質基材３の厚さよりも厚い。
In the
（固体高分子電解質膜の作製）
実施例１において厚さ１１μｍのポリオレフィン多孔質膜をのせて含浸させた。次に、この上に電解質溶液を流延塗布後、厚さ１６μｍのポリオレフィン多孔質膜をのせて含浸し、更に、この上に電解質溶液を流延塗布した。
(Preparation of solid polymer electrolyte membrane)
In Example 1, a polyolefin porous membrane having a thickness of 11 μm was placed and impregnated. Next, the electrolyte solution was cast on this, and then impregnated with a polyolefin porous film having a thickness of 16 μm. Further, the electrolyte solution was cast on this.
（膜電極接合体の作製）
実施例１と同様の方法により作製した。その際、厚みが大きいポリオレフィン多孔質層側に燃料極触媒層を形成し、厚みが小さいポリオレフィン多孔質層側に空気極触媒層を形成した。
(Production of membrane electrode assembly)
It was produced by the same method as in Example 1. At that time, a fuel electrode catalyst layer was formed on the polyolefin porous layer side having a large thickness, and an air electrode catalyst layer was formed on the polyolefin porous layer side having a small thickness.
（固体高分子電解質膜の作製）
実施例１において厚さ１０μｍのポリオレフィン多孔質膜をのせて含浸させた。次に、この上に電解質溶液を流延塗布後、厚さ２５μｍのポリオレフィン多孔質膜をのせて含浸し、更に、この上に電解質溶液を流延塗布した。
(Preparation of solid polymer electrolyte membrane)
In Example 1, a polyolefin porous membrane having a thickness of 10 μm was placed and impregnated. Next, the electrolyte solution was cast on this, and then impregnated with a 25 μm-thick polyolefin porous membrane. Further, the electrolyte solution was cast on this.
（膜電極接合体の作製）
実施例１と同様の方法により作製した。その際、厚みが大きいポリオレフィン多孔質層側に燃料極触媒層を形成し、厚みが小さいポリオレフィン多孔質層側に空気極触媒層を形成した。
(Production of membrane electrode assembly)
It was produced by the same method as in Example 1. At that time, a fuel electrode catalyst layer was formed on the polyolefin porous layer side having a large thickness, and an air electrode catalyst layer was formed on the polyolefin porous layer side having a small thickness.
（固体高分子電解質膜の作製）
実施例１において電解質としてスルホン化ポリエーテルスルホンＳ−ＰＥＳ（１.３ミリ当量／ｇ）を用いた以外は、実施例１と同様に固体高分子電解質膜を作製した。
(Preparation of solid polymer electrolyte membrane)
A solid polymer electrolyte membrane was prepared in the same manner as in Example 1 except that sulfonated polyethersulfone S-PES (1.3 meq / g) was used as the electrolyte in Example 1.
（膜電極接合体の作製）
実施例１と同様の方法により作製した。その際、厚みが大きいポリオレフィン多孔質層側に燃料極触媒層を形成し、厚みが小さいポリオレフィン多孔質層側に空気極触媒層を形成した。
(Production of membrane electrode assembly)
It was produced by the same method as in Example 1. At that time, a fuel electrode catalyst layer was formed on the polyolefin porous layer side having a large thickness, and an air electrode catalyst layer was formed on the polyolefin porous layer side having a small thickness.
〔比較例１〕
（固体高分子電解質膜の作製）
実施例１で作製した電解質溶液をガラス基板上に流延塗布し、その上に厚さ２５μｍのポリオレフィン多孔質膜をのせて含浸させた。次に、この上に電解質溶液を流延塗布した。その後、９０℃で３０分間、次いで、１２０℃で３０分間、加熱乾燥して溶液中の溶媒を除去して電解質複合膜を作製した。得られた電解質複合膜の膜厚は４９μｍであった。
[Comparative Example 1]
(Preparation of solid polymer electrolyte membrane)
The electrolyte solution prepared in Example 1 was cast on a glass substrate, and a polyolefin porous film having a thickness of 25 μm was placed on the glass substrate and impregnated. Next, the electrolyte solution was cast and applied thereon. Then, the electrolyte composite membrane was produced by removing the solvent in the solution by heating and drying at 90 ° C. for 30 minutes and then at 120 ° C. for 30 minutes. The film thickness of the obtained electrolyte composite membrane was 49 μm.
（膜電極接合体の作製）
燃料極としてカーボンブラックにＰｔとＲｕとをそれぞれ２５ｗｔ％担持した電極触媒を用い、空気極としてＰｔを５０ｗｔ％担持した電極触媒を用いた。この電極触媒に、ナフィオン溶液を電極触媒対ナフィオン溶液の重量比が１対９となる割合で秤量し、混合して電極触媒ペーストを作製した。この電極触媒ペーストを電解質膜にスプレー塗布後、加熱プレスして電極触媒層を形成した。
(Production of membrane electrode assembly)
An electrode catalyst supporting 25 wt% of Pt and Ru on carbon black was used as the fuel electrode, and an electrode catalyst supporting 50 wt% of Pt was used as the air electrode. The electrode catalyst was weighed with a Nafion solution at a ratio of 1: 9 to the weight ratio of the electrode catalyst to the Nafion solution, and mixed to prepare an electrode catalyst paste. After spraying this electrode catalyst paste on the electrolyte membrane, the electrode catalyst layer was formed by heating and pressing.
〔比較例２〕
（固体高分子電解質膜の作製）
比較例１において厚さ１６μｍのポリオレフィン多孔質膜を用いた以外は比較例１と同様に電解質膜を作製した。電解質膜全体の厚さは５１μｍであった。
[Comparative Example 2]
(Preparation of solid polymer electrolyte membrane)
An electrolyte membrane was prepared in the same manner as in Comparative Example 1 except that a polyolefin porous membrane having a thickness of 16 μm was used in Comparative Example 1. The total thickness of the electrolyte membrane was 51 μm.
（膜電極接合体の作製）
比較例１と同様に電極触媒層を形成した。
(Production of membrane electrode assembly)
An electrode catalyst layer was formed in the same manner as in Comparative Example 1.
（ＤＭＦＣ電池性能評価）
実施例および比較例の電解質膜を用いた膜電極接合体をＤＭＦＣ発電装置単セルに組み込んで電池性能を測定した。燃料として燃料極側に１０ｗｔ％のメタノール水溶液を循環させ、空気極側に自然呼気形式で空気を供給した。電流密度５０ｍＡ／cm2 の負荷をかけながら３５℃で連続運転した。
(DMFC battery performance evaluation)
Membrane / electrode assemblies using the electrolyte membranes of Examples and Comparative Examples were incorporated into a single cell of a DMFC power generator and the battery performance was measured. As a fuel, a 10 wt% aqueous methanol solution was circulated on the fuel electrode side, and air was supplied to the air electrode side in a natural exhalation format. Continuous operation was performed at 35 ° C. while applying a load with a current density of 50 mA / cm 2 .
表１に実施例１〜４および比較例１〜２で作製した膜電極接合体を用いてＤＭＦＣ連続発電試験を行った結果を示す。 Table 1 shows the results of a DMFC continuous power generation test using the membrane electrode assemblies produced in Examples 1-4 and Comparative Examples 1-2.
表１から明らかなように、実施例による固体高分子電解質膜を用いたＤＭＦＣは比較例による高分子電解質膜を用いたＤＭＦＣに比べて、連続発電後の電圧低下が少なく、優れた耐久性を示すことが明らかである。 As is clear from Table 1, the DMFC using the solid polymer electrolyte membrane according to the example has less voltage drop after continuous power generation and superior durability compared to the DMFC using the polymer electrolyte membrane according to the comparative example. It is clear to show.
本発明は、固体高分子電解質膜及びそれを用いた燃料電池に関するものであり、特に、イオン交換膜を電解質膜として用いる固体高分子形燃料電池（ＰＥＦＣ）やダイレクトメタノール型燃料電池（ＤＭＦＣ）に利用可能である。 The present invention relates to a solid polymer electrolyte membrane and a fuel cell using the same, and particularly to a polymer electrolyte fuel cell (PEFC) or a direct methanol fuel cell (DMFC) using an ion exchange membrane as an electrolyte membrane. Is available.
１ 固体高分子電解質膜
２ 電解質層
３ 多孔質基材
４ 燃料極電極
５ 空気極電極
６ 拡散層
７ セパレータ
DESCRIPTION OF SYMBOLS 1 Solid
Claims (9)
前記固体高分子電解質膜が、固体高分子電解質層と固体高分子電解質層とによって挟まれた、多孔内に固体高分子電解質が充填された、少なくとも２層以上の多孔質基材を有し、
前記多孔質基材は、前記燃料極側の厚さが前記空気極側の厚さよりも厚いことを特徴とする固体高分子電解質膜。 A solid polymer electrolyte membrane for a fuel cell formed between a fuel electrode and an air electrode,
The solid polymer electrolyte membrane has at least two layers of porous base materials sandwiched between a solid polymer electrolyte layer and a solid polymer electrolyte layer, and filled with a solid polymer electrolyte in a pore;
The porous base material has a thickness on the fuel electrode side larger than a thickness on the air electrode side.
前記固体高分子電解質膜が、固体高分子電解質層，多孔質基材，固体高分子電解質層，多孔質基材，固体高分子電解質層の層構造を有し、
前記多孔質基材は、多孔内に固体高分子電解質が充填され、前記燃料極側に形成される多孔質基材の厚さが前記空気極側に形成される多孔質基材の厚さよりも厚いことを特徴とする固体高分子電解質膜。 A solid polymer electrolyte membrane for a fuel cell formed between a fuel electrode and an air electrode,
The solid polymer electrolyte membrane has a layer structure of a solid polymer electrolyte layer, a porous substrate, a solid polymer electrolyte layer, a porous substrate, and a solid polymer electrolyte layer,
The porous substrate is filled with a solid polymer electrolyte in the pores, and the thickness of the porous substrate formed on the fuel electrode side is larger than the thickness of the porous substrate formed on the air electrode side. A solid polymer electrolyte membrane characterized by being thick.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009022728A1 (en) * | 2007-08-10 | 2009-02-19 | Japan Gore-Tex Inc. | Reinforced solid polymer electrolyte composite membrane, membrane electrode assembly for solid polymer fuel cell, and solid polymer fuel cell |
| JP2014099412A (en) * | 2014-01-31 | 2014-05-29 | Toyota Motor Corp | Fuel cell |
| KR20150020712A (en) * | 2013-04-22 | 2015-02-26 | 도오꾜오까고오교 가부시끼가이샤 | Method for producing porous polyimide film, porous polyimide film and separator using same |
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2007
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009022728A1 (en) * | 2007-08-10 | 2009-02-19 | Japan Gore-Tex Inc. | Reinforced solid polymer electrolyte composite membrane, membrane electrode assembly for solid polymer fuel cell, and solid polymer fuel cell |
| US8906573B2 (en) | 2007-08-10 | 2014-12-09 | W. L. Gore & Associates, Co., Ltd. | Reinforced solid polymer electrolyte composite membrane, membrane electrode assembly for solid polymer fuel cell, and solid polymer fuel cell |
| KR20150020712A (en) * | 2013-04-22 | 2015-02-26 | 도오꾜오까고오교 가부시끼가이샤 | Method for producing porous polyimide film, porous polyimide film and separator using same |
| KR101670617B1 (en) * | 2013-04-22 | 2016-10-28 | 도오꾜오까고오교 가부시끼가이샤 | Method for producing porous polyimide film, porous polyimide film and separator using same |
| US9601739B2 (en) | 2013-04-22 | 2017-03-21 | Tokyo Ohka Kogyo Co., Ltd. | Method for producing porous polyimide film, porous polyimide film and separator using same |
| US9911955B2 (en) | 2013-04-22 | 2018-03-06 | Tokyo Ohka Kogyo Co., Ltd. | Method for producing porous polyimide film, porous polyimide film and separator using same |
| JP2014099412A (en) * | 2014-01-31 | 2014-05-29 | Toyota Motor Corp | Fuel cell |
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