JP2006059756A - Solid polyelectrolyte film and polymer electrolyte fuel cell using the same, and their manufacturing method - Google Patents

Solid polyelectrolyte film and polymer electrolyte fuel cell using the same, and their manufacturing method Download PDF

Info

Publication number
JP2006059756A
JP2006059756A JP2004242600A JP2004242600A JP2006059756A JP 2006059756 A JP2006059756 A JP 2006059756A JP 2004242600 A JP2004242600 A JP 2004242600A JP 2004242600 A JP2004242600 A JP 2004242600A JP 2006059756 A JP2006059756 A JP 2006059756A
Authority
JP
Japan
Prior art keywords
electrolyte membrane
fuel cell
strength thin
polymer electrolyte
solid polymer
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.)
Pending
Application number
JP2004242600A
Other languages
Japanese (ja)
Inventor
Masaki Ando
雅樹 安藤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toyota Motor Corp
Original Assignee
Toyota Motor Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Toyota Motor Corp filed Critical Toyota Motor Corp
Priority to JP2004242600A priority Critical patent/JP2006059756A/en
Publication of JP2006059756A publication Critical patent/JP2006059756A/en
Pending legal-status Critical Current

Links

Images

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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

<P>PROBLEM TO BE SOLVED: To provide a solid polyelectrolyte film excellent in durability and capable of exerting a stable performance from low-humidified condition to a high-humidified condition, and to provide a polymer electrolyte fuel cell using the same, and their manufacturing method. <P>SOLUTION: The solid polymer fuel cell 10 is provided with an electrolyte film 12 equipped with an electrolyte layer 30 with proton conductivity with an EW of 600 to 800 and a film thickness of 30 to 100 μm, and a first and a second high-intensity thin films 26A, 26B with proton conductivity arranged at either side of the solid electrolyte with a film thickness of 10 to 20 μm, and a hydrogen electrode 14 and an air electrode 16 arranged at either side of the electrolyte film 12 and containing metal catalyst. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

本発明は、固体高分子型燃料電池に用いられる固体高分子電解質膜、及び、これを用いた固体高分子型燃料電池、並びに、これらの製造方法に関する。   The present invention relates to a solid polymer electrolyte membrane used in a solid polymer fuel cell, a solid polymer fuel cell using the same, and a method for producing the same.

近年、化石燃料の埋蔵量が激減しており、その代替となる燃料の開発が求められている。化石燃焼の代替燃料としては、容易に生成することが可能であり、環境に対する負荷の少ない水素が着目されている。水素ガスを用いたエネルギー源としては、発電の際に二酸化炭素等を発生せず、クリーンなエネルギー源である燃料電池が注目されており、各種開発が盛んに行われている。   In recent years, reserves of fossil fuels have drastically decreased, and development of alternative fuels has been demanded. As an alternative fuel for fossil combustion, attention has been focused on hydrogen that can be easily generated and has a low environmental impact. As an energy source using hydrogen gas, a fuel cell which does not generate carbon dioxide during power generation and is a clean energy source has attracted attention, and various developments have been actively conducted.

燃料電池の一種である固体高分子型燃料電池は、水素などの燃料ガス又は空気などの酸化剤ガスが供給される一対の電極と、前記電極に挟持される電解質膜と、を備え、白金等の触媒上で電気化学的に反応させ、電気を発生させるものである。   A polymer electrolyte fuel cell, which is a type of fuel cell, includes a pair of electrodes supplied with a fuel gas such as hydrogen or an oxidant gas such as air, and an electrolyte membrane sandwiched between the electrodes, such as platinum. It is made to react electrochemically on this catalyst and generate electricity.

図７を用いて従来の固体高分子型燃料電池の発電機構について説明する。図７は、従来の固体高分子型燃料電池の構造を示す概略図である。図７に示すように従来の固体高分子型燃料電池１００は、プロトン伝導性を有し、選択的に水素イオンを移動させることが可能な電解質膜１０２と、燃料である水素ガスが供給される水素電極１０４（アノード）と、酸化剤として空気が供給される空気電極１０６（カソード）とで構成される。   A conventional power generation mechanism of a polymer electrolyte fuel cell will be described with reference to FIG. FIG. 7 is a schematic view showing the structure of a conventional polymer electrolyte fuel cell. As shown in FIG. 7, a conventional polymer electrolyte fuel cell 100 is supplied with an electrolyte membrane 102 having proton conductivity and capable of selectively transferring hydrogen ions, and hydrogen gas as a fuel. It is composed of a hydrogen electrode 104 (anode) and an air electrode 106 (cathode) to which air is supplied as an oxidant.

水素電極１０４は、白金系の金属触媒を担持したカーボン粉末を主成分とする触媒層１０４Ａと、気孔を有する多孔質部材で構成されるガス拡散層１０４Ｂとを有しており、電解質膜１０２の一方の面と触媒層１０４Ａとが密着するように配置される。同様に、空気電極１０６は、白金系の金属触媒を担持したカーボン粉末を主成分とする触媒層１０６Ａと、気孔を有する多孔質部材で構成されるガス拡散層１０６Ｂとから構成されており、電解質膜１０２の他方の面に触媒層１０６Ａが密着するように配置されている。また、水素電極１０４と空気電極１０６とは、外部回路１０８を通じて電気的に接続されており、水素電極１０４と空気電極１０６との外側には、各ガスの流通路を形成するセパレータ１１２がそれぞれ設置されている。   The hydrogen electrode 104 includes a catalyst layer 104A mainly composed of carbon powder supporting a platinum-based metal catalyst, and a gas diffusion layer 104B composed of a porous member having pores. One surface and the catalyst layer 104A are arranged so as to be in close contact with each other. Similarly, the air electrode 106 is composed of a catalyst layer 106A mainly composed of carbon powder carrying a platinum-based metal catalyst, and a gas diffusion layer 106B composed of a porous member having pores. The catalyst layer 106 </ b> A is disposed in close contact with the other surface of the membrane 102. Further, the hydrogen electrode 104 and the air electrode 106 are electrically connected through an external circuit 108, and a separator 112 that forms a flow passage for each gas is installed outside the hydrogen electrode 104 and the air electrode 106, respectively. Has been.

固体高分子型燃料電池１００は、水素電極１０４に供給された水素ガスと触媒層１０４Ａに担持された金属触媒との反応によって生じた水素イオンが電解質膜１０２を通過して空気電極１０６まで移動し、空気電極１０６に供給された空気中の酸素と触媒上で電気化学反応を起こすことで発電する。固体高分子型燃料電池１００で発生した電気は、外部回路１０８を介して外部装置１１０に供給される。   In the polymer electrolyte fuel cell 100, hydrogen ions generated by the reaction between the hydrogen gas supplied to the hydrogen electrode 104 and the metal catalyst supported on the catalyst layer 104A pass through the electrolyte membrane 102 and move to the air electrode 106. Electricity is generated by causing an electrochemical reaction on the catalyst with oxygen in the air supplied to the air electrode 106. Electricity generated in the polymer electrolyte fuel cell 100 is supplied to the external device 110 via the external circuit 108.

通常、水素電極１０４や空気電極１０６に供給され、反応に寄与しなかった水素ガスや空気は排出口を通じて排出される。また、近年では、水素ガスの全てを反応に用いることができるデッドエンド型の燃料電池も開発されてきている。   Normally, hydrogen gas or air that is supplied to the hydrogen electrode 104 or the air electrode 106 and does not contribute to the reaction is discharged through the discharge port. In recent years, dead-end fuel cells that can use all of hydrogen gas for the reaction have been developed.

電解質膜１０２は、プロトン伝導性を有し、水素イオンのみを選択的に透過させる膜である。電解質膜１０２は、プロトン導電体として機能するために膜中の水分量を一定以上に保つ必要がある。電解質膜中の水分量が減少してしまうと、セル抵抗が上昇し、プロトン伝導性が低下してしまう。このため、通常は各電極に供給されるガスに水分を含ませる等の手段により、電解質膜中の水分量を制御している。しかし、電解質膜１０２は、低電流運転時やドライガス運転時には電解質膜が乾燥しやすい（電解質膜中の単位体積当たりの水分量が低下しやすい）状態にあり、プロトン伝導性の低下によって電池性能が低下してしまうといった問題がある。また、上述の電気化学反応は発熱反応であることから、燃料電池を連続で稼働させていると固体高分子型燃料電池１００の温度（セル温度）の上昇に伴って電解質膜１０２中の水分が蒸発しやすくなる。このように、セル温度が高く電解質膜１０２中の水分が蒸発しやすい状態にあると、加湿により供給される水分よりも蒸発する水分の方が徐々に多くなり、膜中の単位体積当たりの含水量が少なくなってしまう。   The electrolyte membrane 102 has proton conductivity and selectively transmits only hydrogen ions. Since the electrolyte membrane 102 functions as a proton conductor, it is necessary to keep the water content in the membrane at a certain level or more. If the amount of water in the electrolyte membrane decreases, cell resistance increases and proton conductivity decreases. For this reason, normally, the amount of moisture in the electrolyte membrane is controlled by means such as adding moisture to the gas supplied to each electrode. However, the electrolyte membrane 102 is in a state where the electrolyte membrane is easily dried during low current operation or dry gas operation (the amount of water per unit volume in the electrolyte membrane is likely to be reduced), and the battery performance is reduced due to the decrease in proton conductivity. There is a problem that will decrease. In addition, since the above-described electrochemical reaction is an exothermic reaction, when the fuel cell is continuously operated, moisture in the electrolyte membrane 102 is increased as the temperature (cell temperature) of the polymer electrolyte fuel cell 100 increases. It tends to evaporate. Thus, when the cell temperature is high and the moisture in the electrolyte membrane 102 is in a state of being easily evaporated, the amount of moisture evaporated gradually increases compared to the moisture supplied by humidification, and the content per unit volume in the membrane is included. The amount of water will decrease.

上述のような低加湿条件下等においても電解質膜１０２中の単位体積当たりの含水量を確保するためには、電解質膜１０２を薄くすることで解決を図ることができる。しかし、電解質膜１０２を薄くすると、電解質膜１０２の耐久性が低くなるという問題を併発してしまう。また、電解質膜１０２は、各電極間の水素ガスの移動を遮る役割も果たしている。しかし、電解質膜１０２を薄くすると電解質膜１２の水素ガス透過量が増大し、電解質膜１０２を通過して他方の電極にガスが移動するクロスリークの問題も生じてしまう。   In order to ensure the water content per unit volume in the electrolyte membrane 102 even under the low humidification condition as described above, a solution can be achieved by making the electrolyte membrane 102 thin. However, when the electrolyte membrane 102 is made thin, the problem that the durability of the electrolyte membrane 102 is lowered is caused. The electrolyte membrane 102 also plays a role of blocking the movement of hydrogen gas between the electrodes. However, when the electrolyte membrane 102 is thinned, the hydrogen gas permeation amount of the electrolyte membrane 12 increases, and a problem of cross leakage in which gas moves through the electrolyte membrane 102 to the other electrode also occurs.

これに対し、電解質膜１０２の耐久性やガス遮断能を確保するためにある程度の膜厚を有したまま、低加湿条件下における高分子型燃料電池１００の性能向上を図るために、含水率の高い低ＥＷの電解質膜を用いることが検討されている。しかし、低ＥＷの電解質膜は、含水率が高いが故に高加湿条件下において膨潤し、形状が変化してしまう。更に、低ＥＷの電解質膜は、低ＥＷ化を可能とすべく、分子量の高いフッ素系高分子を用いたり、スルホン酸基等の官能基を有した側鎖が短いものを用いたりするため、触媒層との接合性が低下してしまう。このため、低ＥＷの電解質膜を用いても十分な性能や耐久性を得ることができず、その改良が求められていた。ここで、前記「ＥＷ」とは、プロトン伝導性を有する交換基の当量重量を意味する。また、「当量重量」とは、イオン交換基１当量当たりのイオン交換膜の乾燥質量を意味し、「ｇ／ｅｗ」の単位で表すことができる。   On the other hand, in order to improve the performance of the polymer fuel cell 100 under low humidification conditions while maintaining a certain film thickness in order to ensure the durability and gas barrier performance of the electrolyte membrane 102, The use of a high low EW electrolyte membrane has been studied. However, the low EW electrolyte membrane swells under high humidification conditions because of its high water content, and its shape changes. Furthermore, the low EW electrolyte membrane uses a high molecular weight fluoropolymer or a short side chain having a functional group such as a sulfonic acid group in order to enable low EW. Bondability with a catalyst layer will fall. For this reason, even if a low EW electrolyte membrane is used, sufficient performance and durability cannot be obtained, and improvement thereof has been demanded. Here, the “EW” means an equivalent weight of an exchange group having proton conductivity. The “equivalent weight” means the dry mass of the ion exchange membrane per equivalent of ion exchange group, and can be expressed in units of “g / ew”.

電解質膜のＥＷを規定した電解質膜としては、固体高分子膜と触媒層との間に、固体高分子膜とは異なるＥＷのプロトン伝導性ポリマー層を備えた膜・電極接合体が提案されている（例えば、特許文献１参照）。かかる膜は、固体高分子膜の両面にＥＷの異なるポリマー層を設けることで、水をカソードから排出しやすくし、低電流密度から高電流密度領域まで安定した電池電圧を得ることを目的としている。しかし、係る固体高分子膜に設けられるポリマー層は、実質１μｍ程度の膜であり、その目的も水の流動を図ることにあることから、高湿度条件下における膜の形状変化を防止することが出来ない。   As an electrolyte membrane that defines the EW of the electrolyte membrane, a membrane / electrode assembly having a proton conducting polymer layer of EW different from the solid polymer membrane between the solid polymer membrane and the catalyst layer has been proposed. (For example, refer to Patent Document 1). The purpose of such a membrane is to provide a stable battery voltage from a low current density to a high current density region by providing a polymer layer with different EW on both sides of the solid polymer membrane, thereby facilitating discharge of water from the cathode. . However, the polymer layer provided in such a solid polymer film is a film of about 1 μm substantially, and its purpose is to aim at the flow of water, so that the change in the shape of the film under high humidity conditions can be prevented. I can't.

特開平１０−３３４９２３JP-A-10-334923

上述の諸問題を解決すべく、本発明は、耐久性に優れ、低加湿条件から高加湿条件化において安定した性能を発揮することが可能な固体高分子型電解質膜及びこれを用いた固体高分子型燃料電池、並びに、これらの製造方法を提供することを目的とする。   In order to solve the above-mentioned problems, the present invention provides a solid polymer electrolyte membrane that is excellent in durability and capable of exhibiting stable performance from low humidification conditions to high humidification conditions, and a solid polymer electrolyte membrane using the same. It is an object of the present invention to provide molecular fuel cells and methods for producing them.

本発明の固体高分子電解質膜は、ＥＷが６００〜８００且つ膜厚が３０〜１００μｍであり、プロトン伝導性を有する電解質膜と、前記固体電解質膜の両面に配置され且つ膜厚が１０〜２０μｍであり、プロトン伝導性を有する一対の高強度薄膜と、を備える。   The solid polymer electrolyte membrane of the present invention has an EW of 600 to 800 and a thickness of 30 to 100 μm, and is disposed on both surfaces of the proton conductive electrolyte membrane and the solid electrolyte membrane and has a thickness of 10 to 20 μm. And a pair of high-strength thin films having proton conductivity.

本発明の固体高分子電解質膜によれば、低ＥＷの電解質膜を高強度薄膜で挟持することにより、低ＥＷの電解質膜により低加湿条件下におけるプロトン伝導性を確保しつつ、耐久性及び高加湿条件時における安定性を付与することができ、更に、膜の水素透過量が少ない。これにより、燃料電池の固体高分子膜として用いた場合に、各電極間におけるクロスリークを防止することができ、耐久性が高く、更に、低加湿条件から高加湿条件下において安定した電池性能を発揮することができる。   According to the solid polymer electrolyte membrane of the present invention, a low EW electrolyte membrane is sandwiched between high strength thin films, so that proton conductivity under low humidification conditions is ensured by the low EW electrolyte membrane, while durability and high durability are ensured. Stability during humidifying conditions can be imparted, and the hydrogen permeation amount of the membrane is small. As a result, when used as a solid polymer membrane of a fuel cell, cross leakage between each electrode can be prevented, durability is high, and stable battery performance from low humidification conditions to high humidification conditions is achieved. It can be demonstrated.

前記電解質膜のＥＷは６００〜８００である。この際、低加湿条件下における含水量を確保する観点からは、前記電解質膜のＥＷは６５０〜７５０が好ましく、７００程度が特に好ましい。また、前記電解質膜の膜厚は３０〜１００μｍである。この際、膜の耐久性及び水素透過抑制、並びに、低加湿条件下における膜の含水量を確保する観点からは、前記電解質膜の膜厚は、３０〜９０μｍが好ましく、４５〜８５μｍが更に好ましい。   The EW of the electrolyte membrane is 600 to 800. At this time, from the viewpoint of securing the water content under low humidification conditions, the EW of the electrolyte membrane is preferably 650 to 750, and particularly preferably about 700. The thickness of the electrolyte membrane is 30 to 100 μm. At this time, from the viewpoint of durability of the membrane, suppression of hydrogen permeation, and securing water content of the membrane under low humidification conditions, the thickness of the electrolyte membrane is preferably 30 to 90 μm, and more preferably 45 to 85 μm. .

また、前記高強度薄膜とは、プロトン伝導性を有し、機械強度特性に優れた薄膜を意味する。前記高強度薄膜の強度は、例えば、引っ張り破断強度又は破断弾性率等で表わすことができる。前記高強度薄膜の２５℃・相対湿度４０％における引っ張り破断強度としては、３００ｋｇ／ｃｍ2以上が好ましく、具体的には、３００〜７００ｋｇ／ｃｍ2が更に好ましく、４５０〜５５０ｋｇ／ｃｍ2が特に好ましい。また、前記高強度薄膜の２５℃・相対湿度４０％における破断弾性率としては、３０００ｋｇ／ｃｍ2以上が好ましく、具体的には、３０００〜８０００ｋｇ／ｃｍ2が更に好ましく、４０００〜５０００ｋｇ／ｃｍ2が特に好ましい。更に、８０℃・相対湿度９５％における前記高強度薄膜の引っ張り破断強度としては、１００〜４００ｋｇ／ｃｍ2が好ましく、２００〜３００ｋｇ／ｃｍ2が更に好ましい。また、８０℃・相対湿度９５％における破断弾性率としては３００〜１５００ｋｇ／ｃｍ2が好ましく、７００〜１２００ｋｇ／ｃｍ2が更に好ましい。 The high-strength thin film means a thin film having proton conductivity and excellent mechanical strength characteristics. The strength of the high-strength thin film can be expressed by, for example, tensile strength at break or elastic modulus at break. The breaking strength tensile at 25 ° C. · 40% relative humidity of the high strength thin, preferably 300 kg / cm 2 or more, specifically, more preferably 300~700kg / cm 2, 450~550kg / cm 2 is particularly preferable. Further, the high as the breaking modulus at 25 ° C. · 40% relative humidity strength thin, preferably 3000 kg / cm 2 or more, specifically, more preferably 3000~8000kg / cm 2, 4000~5000kg / cm 2 Is particularly preferred. Furthermore, as the tensile breaking strength of the high strength thin at 80 ° C. · 95% RH, preferably 100~400kg / cm 2, more preferably 200~300kg / cm 2. Further, preferably 300~1500kg / cm 2 as the breaking modulus at 80 ° C. · 95% RH, more preferably 700~1200kg / cm 2.

また、前記高強度薄膜の膜厚は１０〜２０μｍである。この際、膜の耐久性及び高加湿条件下における形状安定性を向上させる観点から、前記電解質膜の膜厚は、１２〜１８μｍが好ましく、１５μｍ程度が更に好ましい。   The high-strength thin film has a thickness of 10 to 20 μm. At this time, from the viewpoint of improving the durability of the membrane and the shape stability under highly humidified conditions, the thickness of the electrolyte membrane is preferably 12 to 18 μm, and more preferably about 15 μm.

本発明の固体高分子電解質膜は、前記高強度薄膜が補強材を含むように構成することができる。前記補強材を含む高強度薄膜は耐久性に優れることから、本発明の固体高分子電解質膜の耐久性及び形状安定性を更に向上させることができる。また、前記補強材を含む高強度薄膜としては、多孔質構造を有するものを好ましく挙げることができる。このような、多孔質構造を有する高強度薄膜としては、例えば、ＰＴＦＥ多孔質材料等を挙げることができる。   The solid polymer electrolyte membrane of the present invention can be configured such that the high-strength thin film includes a reinforcing material. Since the high-strength thin film containing the reinforcing material is excellent in durability, the durability and shape stability of the solid polymer electrolyte membrane of the present invention can be further improved. Moreover, as a high intensity | strength thin film containing the said reinforcing material, what has a porous structure can be mentioned preferably. Examples of such a high-strength thin film having a porous structure include a PTFE porous material.

また、本発明の固体高分子電解質膜は、前記高強度薄膜のＥＷと前記電解質膜のＥＷとが異なるものを用いるのが好ましく、前記高強度薄膜のＥＷが前記電解質膜のＥＷよりも大きいことが更に好ましい。このように、前記電解質膜のＥＷと異なるＥＷを有する高強度薄膜を用いることで、高加湿条件化における形状安定性を高めることができる。前記高強度薄膜のＥＷと前記電解質膜のＥＷとの差は、２００以上であることが好ましく、３００〜４５０程度であることが更に好ましい。前記高強度薄膜のＥＷとしては、９００〜１３００が好ましく、１０００〜１１００が更に好ましい。   Moreover, it is preferable to use a polymer electrolyte membrane of the present invention in which the EW of the high-strength thin film is different from the EW of the electrolyte membrane, and the EW of the high-strength thin film is larger than the EW of the electrolyte membrane. Is more preferable. Thus, by using a high-strength thin film having an EW different from the EW of the electrolyte membrane, the shape stability under high humidification conditions can be enhanced. The difference between the EW of the high-strength thin film and the EW of the electrolyte membrane is preferably 200 or more, and more preferably about 300 to 450. The EW of the high-strength thin film is preferably 900-1300, more preferably 1000-1100.

本発明の固体高分子電解質膜は、膜厚が１０〜２０μｍのプロトン伝導性を有する一対の高強度薄膜と、前記一対の高強度薄膜に挟持され、ＥＷが６００〜８００且つ膜厚が３０〜１００μｍのプロトン伝導性を有する電解質膜と、をホットプレスによって積層化する工程を含む本発明の固体高分子電解質膜の製造方法によって好適に製造することができる。   The solid polymer electrolyte membrane of the present invention is sandwiched between a pair of high-strength thin films having proton conductivity of 10 to 20 μm and a pair of high-strength thin films, and has an EW of 600 to 800 and a thickness of 30 to 30. It can be suitably produced by the method for producing a solid polymer electrolyte membrane of the present invention comprising a step of laminating an electrolyte membrane having proton conductivity of 100 μm by hot pressing.

また、本発明の固体高分子電解質膜は、固体高分子型燃料電池に用いられる電解質膜として優れた性能を有する。本発明の固体高分子型燃料電池は、上述の本発明の固体高分子電解質膜と、前記固体高分子電解質膜の両面に配置され、且つ、金属触媒を含有する一対の触媒層とで構成することができる。   Moreover, the solid polymer electrolyte membrane of the present invention has excellent performance as an electrolyte membrane used in a solid polymer fuel cell. The solid polymer fuel cell of the present invention comprises the above-described solid polymer electrolyte membrane of the present invention and a pair of catalyst layers disposed on both sides of the solid polymer electrolyte membrane and containing a metal catalyst. be able to.

本発明の固体高分子型燃料電池は、電解質膜として本発明の固体高分子電解質膜を採用するため、耐久性に優れるとともに、低〜高加湿条件化において広く安定した性能を発揮することができる。   Since the polymer electrolyte fuel cell of the present invention employs the polymer electrolyte membrane of the present invention as an electrolyte membrane, it is excellent in durability and can exhibit wide and stable performance under low to high humidification conditions. .

本発明の固体高分子型燃料電池は、一方の面に金属触媒を含有する触媒層が設けられ且つ膜厚が１０〜２０μｍのプロトン伝導性を有する一対の高強度薄膜と、前記一対の高強度薄膜の前記触媒層が設けられていない側の面に挟持され、ＥＷが６００〜８００且つ膜厚が３０〜１００μｍのプロトン伝導性を有する電解質膜と、をホットプレスによって積層化する工程を含む本発明の固体高分子型燃料電池の製造方法によって好適に製造することができる。   The solid polymer fuel cell of the present invention comprises a pair of high strength thin films having a catalyst layer containing a metal catalyst on one surface and a proton conductivity of 10 to 20 μm, and the pair of high strength A book comprising a step of laminating a thin electrolyte membrane with a proton conductivity sandwiched between the surfaces of the thin film where the catalyst layer is not provided and having an EW of 600 to 800 and a thickness of 30 to 100 μm by hot pressing. It can be suitably manufactured by the method for manufacturing a polymer electrolyte fuel cell of the invention.

本発明によれば、耐久性に優れ、低加湿条件から高加湿条件化において安定した性能を発揮することが可能な固体高分子型電解質膜及びこれを用いた固体高分子型燃料電池、並びに、これらの製造方法を提供することができる。   According to the present invention, a solid polymer electrolyte membrane that is excellent in durability and capable of exhibiting stable performance from low humidification conditions to high humidification conditions, a solid polymer fuel cell using the same, and These manufacturing methods can be provided.

以下、本発明の固体高分子電解質膜（以下、「本発明の電解質膜」と称する。）及び本発明の固体高分子型燃料電池（以下、「本発明の燃料電池」と称する。）の実施形態について図を用いて詳細に説明する。   Hereinafter, the solid polymer electrolyte membrane of the present invention (hereinafter referred to as “the electrolyte membrane of the present invention”) and the solid polymer fuel cell of the present invention (hereinafter referred to as “the fuel cell of the present invention”) are implemented. A form is demonstrated in detail using figures.

図１は、本発明の電解質膜を備えた固体高分子型燃料電池の構成を示す概略図である。図１に示すように本発明の燃料電池１０は、本発明の電解質膜１２と、燃料である水素ガスが供給される水素電極１４（アノード）と、酸化剤として空気が供給される空気電極１６（カソード）と、セパレータ１８，２０と、から構成されており、水素電極１４及び空気電極１６とに接続された外部回路２２を通じて外部装置２４に電力を供給できるように構成されている。本発明の燃料電池１０は、燃料として供給された水素ガスが水素電極１４において水素イオンと電子とを放出し、放出された電子（ｅ-）が外部回路２２を介して空気電極１６まで移動することで発電する。 FIG. 1 is a schematic diagram showing the configuration of a polymer electrolyte fuel cell provided with the electrolyte membrane of the present invention. As shown in FIG. 1, a fuel cell 10 of the present invention includes an electrolyte membrane 12 of the present invention, a hydrogen electrode 14 (anode) to which hydrogen gas as a fuel is supplied, and an air electrode 16 to which air is supplied as an oxidant. (Cathode) and separators 18 and 20 are configured so that power can be supplied to the external device 24 through the external circuit 22 connected to the hydrogen electrode 14 and the air electrode 16. In the fuel cell 10 of the present invention, hydrogen gas supplied as fuel releases hydrogen ions and electrons at the hydrogen electrode 14, and the emitted electrons (e − ) move to the air electrode 16 via the external circuit 22. To generate electricity.

まず、本発明の電解質膜である電解質膜１２について説明する。本発明の電解質膜１２は、第１の高強度薄膜２６Ａと第２の高強度薄膜２６Ｂとで電解質層３０を挟んだ積層体として構成される。第１の高強度薄膜２６Ａ、第２の高強度薄膜２６Ｂ及び電解質層３０で構成される電解質膜１２は、水素電極１４で発生した電子と水素イオンとのうち、水素イオンのみを選択的に空気電極１６に通過させる膜である。   First, the electrolyte membrane 12 that is the electrolyte membrane of the present invention will be described. The electrolyte membrane 12 of the present invention is configured as a laminate in which the electrolyte layer 30 is sandwiched between the first high-strength thin film 26A and the second high-strength thin film 26B. The electrolyte membrane 12 including the first high-strength thin film 26A, the second high-strength thin film 26B, and the electrolyte layer 30 selectively air out only hydrogen ions out of electrons and hydrogen ions generated at the hydrogen electrode 14. It is a film that passes through the electrode 16.

第１の高強度薄膜２６Ａ及び第２の高強度薄膜２６Ｂ（以下、これらを総じて「高強度薄膜２６」と称する場合がある。）は、電解質層３０を挟持して電解質膜１２の強度を補強する役割を担っている。高強度薄膜２６は、プロトン伝導性を有し、機械強度を保つためにカーボンにテトラフルオロエチレンをコーティングして形成されている。本実施の形態において高強度薄膜２６の厚みは、それぞれ１５μｍ程度であり、ＥＷは１１００程度である。   The first high-strength thin film 26A and the second high-strength thin film 26B (hereinafter sometimes collectively referred to as “high-strength thin film 26”) sandwich the electrolyte layer 30 and reinforce the strength of the electrolyte membrane 12. Have a role to play. The high-strength thin film 26 has proton conductivity and is formed by coating carbon with tetrafluoroethylene in order to maintain mechanical strength. In the present embodiment, the high-strength thin film 26 has a thickness of about 15 μm and an EW of about 1100.

電解質層３０は、そのＥＷが７００程度と低い低ＥＷのフッ素系電解質膜である。このため、低加湿条件下においても電解質層３０中の含水量が多く、ドライ運転等の低加湿運転時においても安定した電力を供給することができる。また、本実施の形態において電解質層３０の厚みは７０μｍである。このため、高強度薄膜２６による補強と併せて電解質膜１２の強度を高くすることができるとともに、ある程度の膜厚を確保できることから電極間におけるガスの移動を遮断し、クロスリークの発生を抑制することができる。   The electrolyte layer 30 is a low EW fluorine-based electrolyte membrane having an EW as low as about 700. For this reason, even under low humidification conditions, the water content in the electrolyte layer 30 is large, and stable power can be supplied even during low humidification operations such as dry operation. In the present embodiment, the thickness of the electrolyte layer 30 is 70 μm. For this reason, the strength of the electrolyte membrane 12 can be increased together with the reinforcement by the high-strength thin film 26, and a certain amount of film thickness can be secured, so that the movement of gas between the electrodes is blocked and the occurrence of cross leak is suppressed. be able to.

また、電解質層３０は、第１の高強度薄膜２６Ａと第２の高強度薄膜２６Ｂとに挟持されていることから、高加湿条件下において電解質層３０の電解質成分が膨張して変形するのを抑制することができる。これにより、高加湿運転時においても安定した電力を供給することができる。更に、本実施の形態において電解質成分はフッ素系の材料であることから、炭化水素系電解質膜に比して過酸化水素やそのラジカルに対する耐性が高い。   Further, since the electrolyte layer 30 is sandwiched between the first high-strength thin film 26A and the second high-strength thin film 26B, the electrolyte component of the electrolyte layer 30 is expanded and deformed under high humidification conditions. Can be suppressed. Thereby, stable electric power can be supplied even during high humidification operation. Furthermore, in the present embodiment, since the electrolyte component is a fluorine-based material, it has higher resistance to hydrogen peroxide and its radicals than the hydrocarbon-based electrolyte membrane.

電解質層３０は、ＥＷが６００〜８００となるようにプロトン伝導性のポリマーで構成されている。プロトン伝導性のポリマーとしては、含フッ素高分子を骨格とし、少なくともスルホン酸基、カルボン酸基、ホスホン酸基及びリン酸基から選ばれる少なくとも１種を有するものが好ましい。また、ポリオレフィンのような炭化水素を骨格とするポリマーも使用することができる。   The electrolyte layer 30 is made of a proton-conductive polymer so that the EW is 600 to 800. The proton conductive polymer is preferably a polymer having a fluorinated polymer as a skeleton and at least one selected from a sulfonic acid group, a carboxylic acid group, a phosphonic acid group and a phosphoric acid group. A polymer having a hydrocarbon skeleton such as polyolefin can also be used.

前記含フッ素高分子としては、下記一般式（１）で表される第１のモノマーと、例えば、トリフルオロモノクロロエチレン、トリフルオロエチレン、テトラフルオロエチレン、フッ化ビニリデン、ヘキサフルオロプロピレン、１，１−ジフルオロ−２，２−ジクロロエチレン、１，１−ジフルオロ−２−クロロエチレン、１，１，１，３，３−ペンタフルオロプロピレン、オクタフルオロイソブチレン、エチレン、塩化ビニル、及び、アルキルビニルエステル等から選ばれる第２のモノマーと、から構成される２種若しくは３種以上のモノマーの共重合体、或いは、前記第１のモノマー１種以上で構成される重合体などが挙げられる。前記フッ素高分子としては、特に、スルホン酸基を有するパーフルオロカーボン重合体であることが好ましい。   Examples of the fluorine-containing polymer include a first monomer represented by the following general formula (1) and, for example, trifluoromonochloroethylene, trifluoroethylene, tetrafluoroethylene, vinylidene fluoride, hexafluoropropylene, 1,1. -From difluoro-2,2-dichloroethylene, 1,1-difluoro-2-chloroethylene, 1,1,1,3,3-pentafluoropropylene, octafluoroisobutylene, ethylene, vinyl chloride, alkyl vinyl ester, etc. Examples thereof include a copolymer of two or three or more monomers composed of the second monomer selected, or a polymer composed of one or more of the first monomers. The fluoropolymer is particularly preferably a perfluorocarbon polymer having a sulfonic acid group.

一般式（１）：Ｙ−（ＣＦ2）ａ−（ＣＦＲf）ｂ−（ＣＦＲf’）ｃ−Ｏ−〔ＣＦ（ＣＦ2Ｘ）−ＣＦ2−Ｏ〕n−ＣＦ＝ＣＦ2 Formula (1): Y- (CF 2 ) a- (CFR f) b- (CFR f ') c-O- [CF (CF 2 X) -CF 2 -O ] n -CF = CF 2

〔式中、Ｙは−ＳＯ2Ｆ、−ＳＯ3ＮＨ、−ＣＯＯＨ、−ＣＮ、−ＣＯＦ、−ＣＯＯＲ（Ｒは炭素数１〜１０のアルキル基）、−ＰＯ3Ｈ2又は−ＰＯ3 Ｈを表わす。ａは０〜６の整数、ｂは０〜６の整数、ｃは０又は１を表わす。但しａ＋ｂ＋ｃは０に等しくはならない。ｎは０〜６の整数を表わし、Ｘはｎ＞１の時、Ｃｌ、Ｂｒ、Ｆ又はそれらの混合物を表わす。Ｒf及びＲf’はそれぞれ独立して、Ｆ、Ｃｌ、約１〜１０個の炭素原子を有するパーフルオロアルキル基及び１〜１０個の炭素原子を有するフルオロクロロアルキル基からなる群から選択される。） Wherein, Y is -SO 2 F, -SO 3 NH, -COOH, -CN, -COF, -COOR (R is an alkyl group having 1 to 10 carbon atoms), - PO 3 H 2 or -PO 3 H Represents. a represents an integer of 0 to 6, b represents an integer of 0 to 6, and c represents 0 or 1. However, a + b + c is not equal to 0. n represents an integer of 0 to 6, and X represents Cl, Br, F or a mixture thereof when n> 1. R f and R f ′ are each independently selected from the group consisting of F, Cl, a perfluoroalkyl group having about 1-10 carbon atoms and a fluorochloroalkyl group having 1-10 carbon atoms. The )

プロトン伝導性のポリマーは、モノマーが２分子以上結合しているものであればよいが、耐久性の観点からその体積平均分子量が５０００以上であることが好ましい。また、ポリマーと低分子量化合物とを混合して用いることにより、電解質層３０のＥＷを適宜調節することも可能である。上述のプロトン伝導性のポリマーは成膜等の際に、例えば、メタノール、エタノール、プロパノール、ブタノール等のアルコール類；Ｎ，Ｎ’−ジメチルアセドアミド、Ｎ，Ｎ’−ジメチルホルムアミド、ジメチルスルホキシド、スルホラン等の極性溶媒；テトラヒドロフラン等の環状エーテル類；及び、前記溶媒群から選ばれた２種類以上の混合物；さらには前記溶媒群と水との混合物などに溶解させて用いることができる。前記溶媒としては、特に、エタノール、１−プロパノール、２−プロパノール等の低級アルコールの単独若しくは２種以上の溶媒と水との混合物が好ましい。さらに、前記溶媒群の少なくとも１種と、フルオロカーボンや含フッ素アルコール等の含フッ素化合物との混合溶媒も使用することができる。   The proton-conducting polymer may be one in which two or more monomers are bonded, but the volume average molecular weight is preferably 5000 or more from the viewpoint of durability. Further, the EW of the electrolyte layer 30 can be appropriately adjusted by using a mixture of a polymer and a low molecular weight compound. The above proton-conducting polymer is used for film formation or the like, for example, alcohols such as methanol, ethanol, propanol and butanol; N, N′-dimethylacetamide, N, N′-dimethylformamide, dimethylsulfoxide, It can be used by dissolving in a polar solvent such as sulfolane; a cyclic ether such as tetrahydrofuran; and a mixture of two or more selected from the solvent group; and a mixture of the solvent group and water. As the solvent, in particular, a lower alcohol such as ethanol, 1-propanol, or 2-propanol alone or a mixture of two or more solvents and water is preferable. Furthermore, a mixed solvent of at least one kind of the solvent group and a fluorine-containing compound such as a fluorocarbon or a fluorine-containing alcohol can also be used.

次に、本発明の燃料電池１０を構成する他の部材について説明する。図１に示すように本発明の燃料電池１０は、水素電極１４と空気電極１６とが電解質膜１２の両面と密着するように備えられている。また、水素電極１４と空気電極１６との外側には、水素ガス及び空気の流通路を形成するセパレータ１８及び２０がそれぞれ設置されている。   Next, other members constituting the fuel cell 10 of the present invention will be described. As shown in FIG. 1, the fuel cell 10 of the present invention is provided such that the hydrogen electrode 14 and the air electrode 16 are in close contact with both surfaces of the electrolyte membrane 12. In addition, separators 18 and 20 that form a flow path for hydrogen gas and air are installed outside the hydrogen electrode 14 and the air electrode 16, respectively.

図１に示すように水素電極１４は、白金系の金属触媒を担持したカーボン粉末等を主成分とする触媒層１４Ａと、気孔を有する多孔質部材で形成されたガス拡散層１４Ｂと、から構成されており、触媒層１４Ａが電解質膜１２の一方の面に密着するように配置されている。セパレータ１８によって形成される流通路を通じて供給された水素ガスは、ガス拡散層１４Ｂを通じて触媒層１４Ａに到達するようになっている。   As shown in FIG. 1, the hydrogen electrode 14 is composed of a catalyst layer 14A mainly composed of carbon powder or the like carrying a platinum-based metal catalyst, and a gas diffusion layer 14B formed of a porous member having pores. The catalyst layer 14 </ b> A is disposed so as to be in close contact with one surface of the electrolyte membrane 12. The hydrogen gas supplied through the flow path formed by the separator 18 reaches the catalyst layer 14A through the gas diffusion layer 14B.

触媒層１４Ａに備えられる触媒としては、公知の脱水素触媒を用いることができ、例えば、Ｐｔ、Ｐｔ−Ｒｈ、Ｐｔ−Ｉｒ、Ｐｔ−Ｒｅ、Ｐｔ−Ｗ等の貴金属系の金属を用いた炭素担持Ｐｔ触媒、炭素担持Ｐｔ−Ｉｒ複合金属触媒、炭素担持Ｐｔ−Ｒｅ複合金属触媒、炭素担持Ｐｔ−Ｗ複合金属触媒、又はニッケル系金属を使用した触媒等を用いることができる。触媒層１４Ａは、カーボン粉末等に担持した触媒と、高強度薄膜２６に用いられる高分子（電解質）の溶液と、結合剤等とを混合することで形成することができる。   As the catalyst provided in the catalyst layer 14A, a known dehydrogenation catalyst can be used. For example, carbon using a noble metal-based metal such as Pt, Pt—Rh, Pt—Ir, Pt—Re, and Pt—W. A supported Pt catalyst, a carbon supported Pt—Ir composite metal catalyst, a carbon supported Pt—Re composite metal catalyst, a carbon supported Pt—W composite metal catalyst, a catalyst using a nickel-based metal, or the like can be used. The catalyst layer 14A can be formed by mixing a catalyst supported on carbon powder or the like, a polymer (electrolyte) solution used for the high-strength thin film 26, and a binder.

触媒層１４Ａの外側（電解質膜１２と密着していない側）に配置されるガス拡散層１４Ｂは、気孔を有する多孔性部材で構成される。ガス拡散層１４Ｂを構成する多孔性部材としては、カーボンペーパー、カーボン不織布、又は、カーボンクロス等が挙げられる。   The gas diffusion layer 14B disposed outside the catalyst layer 14A (the side not in close contact with the electrolyte membrane 12) is composed of a porous member having pores. Examples of the porous member constituting the gas diffusion layer 14B include carbon paper, carbon nonwoven fabric, or carbon cloth.

同様に、空気電極１６は、白金系の金属触媒を担持したカーボン粉末等を主成分とする触媒層１６Ａと、気孔を有する多孔質部材で形成されたガス拡散層１６Ｂと、から構成されており、触媒層１６Ａが電解質膜１２の一方の面に密着するように配置されている。また、後述するセパレータ２０によって形成される流通路を通じて供給された空気は、ガス拡散層１６Ｂを通じて触媒層１６Ａに到達するようになっている。   Similarly, the air electrode 16 is composed of a catalyst layer 16A mainly composed of carbon powder or the like carrying a platinum-based metal catalyst, and a gas diffusion layer 16B formed of a porous member having pores. The catalyst layer 16A is disposed so as to be in close contact with one surface of the electrolyte membrane 12. In addition, air supplied through a flow passage formed by a separator 20 described later reaches the catalyst layer 16A through the gas diffusion layer 16B.

触媒層１６Ａに備えられる触媒としては、上述の触媒と同様のものを挙げることができる。また、触媒層１６Ａは、カーボン粉末等に担持した触媒と、高強度薄膜２６に用いられる高分子（電解質）の溶液と、結合剤等とを混合することで形成することができる。   Examples of the catalyst provided in the catalyst layer 16A include the same catalysts as those described above. The catalyst layer 16A can be formed by mixing a catalyst supported on carbon powder or the like, a polymer (electrolyte) solution used for the high-strength thin film 26, and a binder.

更に、触媒層１６Ａの外側（電解質膜１２と密着していない側）に配置されるガス拡散層１６Ｂは、上述と同様の気孔を有する多孔性部材で構成することができる。   Furthermore, the gas diffusion layer 16B disposed outside the catalyst layer 16A (side not in close contact with the electrolyte membrane 12) can be formed of a porous member having pores similar to those described above.

セパレータ１８によって形成される流通路から水素電極１４に供給された水素ガスは、ガス拡散層１４Ｂを介して触媒層１４Ａに到達し、触媒層１４Ａに備えられた触媒の作用により、水素イオンと電子とを生成する。触媒層１４Ａにおいて発生した水素イオンは、電解質膜１２を通過して、空気電極１６にまで移動する。一方、電解質膜１２を通過できない電子は、外部回路２２を介して空気電極１６まで移動する。本発明の燃料電池１０は、この電子の移動により外部装置２４に電力を供給することができる。   The hydrogen gas supplied from the flow path formed by the separator 18 to the hydrogen electrode 14 reaches the catalyst layer 14A via the gas diffusion layer 14B, and the action of the catalyst provided in the catalyst layer 14A causes hydrogen ions and electrons to be supplied. And generate Hydrogen ions generated in the catalyst layer 14 </ b> A pass through the electrolyte membrane 12 and move to the air electrode 16. On the other hand, electrons that cannot pass through the electrolyte membrane 12 move to the air electrode 16 via the external circuit 22. The fuel cell 10 of the present invention can supply electric power to the external device 24 by this movement of electrons.

この際、反応に寄与しなかった余剰水素ガス等の一部が、電解質膜１２を透過する場合があるが、電解質膜１２が十分な厚さを有することからその移動が遮られ、水素ガスが空気電極１６にまで達するのを防止することができる。   At this time, a part of surplus hydrogen gas or the like that has not contributed to the reaction may permeate the electrolyte membrane 12, but the movement of the electrolyte membrane 12 is blocked because the electrolyte membrane 12 has a sufficient thickness. Reaching the air electrode 16 can be prevented.

空気電極１６にまで移動した水素イオンは、セパレータ２０によって形成された流通路を介して供給される空気中の酸素と触媒層１６Ａにおいて反応し、外部回路２２を介して移動してきた電子を受け取って水を生成する。水素イオンと酸素との反応によって生じた水は、図示を省略する排出口により装置外に排出される。   The hydrogen ions that have moved to the air electrode 16 react with oxygen in the air supplied through the flow path formed by the separator 20 in the catalyst layer 16A, and receive the electrons that have moved through the external circuit 22. Produce water. Water generated by the reaction between hydrogen ions and oxygen is discharged out of the apparatus through a discharge port (not shown).

また、水素電極１４と同様に、空気電極１６において反応に寄与しなかった余剰空気等の一部が、電解質膜１２を透過する場合があるが、電解質膜１２が十分な厚さを有することからその移動が遮られ、空気が水素電極１４にまで達するのを防止することができる。   Similarly to the hydrogen electrode 14, some of the excess air that did not contribute to the reaction in the air electrode 16 may permeate the electrolyte membrane 12, but the electrolyte membrane 12 has a sufficient thickness. The movement is blocked and air can be prevented from reaching the hydrogen electrode 14.

次に、図２を用いて、本発明の電解質膜を用いた燃料電池の作製方法の一例について説明する。図２は、本発明の燃料電池の作製方法を説明するための概略図である。   Next, an example of a method for manufacturing a fuel cell using the electrolyte membrane of the present invention will be described with reference to FIG. FIG. 2 is a schematic view for explaining a method for producing a fuel cell of the present invention.

本発明の燃料電池は、図２（ａ）に示すように、まず、セパレータ１８上に水素電極１４と第１の高強度薄膜２６Ａとをこの順で積層して積層体（積層体Ａ）を形成し、更に、第１の高強度薄膜２６Ａ上に電解質層３０を形成する低ＥＷの電解質膜３０Ａを配置する。   In the fuel cell of the present invention, as shown in FIG. 2 (a), first, a hydrogen electrode 14 and a first high-strength thin film 26A are laminated in this order on a separator 18 to form a laminate (laminate A). Further, a low EW electrolyte membrane 30A for forming the electrolyte layer 30 is disposed on the first high-strength thin film 26A.

次いで、図２（ｂ）に示すように、別途セパレータ２０上に空気電極１６と高強度薄膜２６Ｂとを積層した積層体（積層体Ｂ）を用意し、積層体Ａの電解質膜３０Ａと積層体の高強度薄膜２６Ｂとが密着するように矢印方向に圧力をかけ、ホットプレスによって圧着することで、図２（ｃ）に示すような本発明の電解質膜１２を有する燃料電池１０を作製することができる。この際、高強度薄膜２６の強度の異方性（ＭＤ、ＴＤ）を利用（積層体Ａ及びＢの異方性がクロスするように積層）することで更なる耐久性の向上を図ることができる。   Next, as shown in FIG. 2B, a laminate (laminate B) in which the air electrode 16 and the high-strength thin film 26B are separately laminated on the separator 20 is prepared, and the electrolyte membrane 30A of the laminate A and the laminate are prepared. The fuel cell 10 having the electrolyte membrane 12 of the present invention as shown in FIG. 2 (c) is manufactured by applying pressure in the direction of the arrow so that the high-strength thin film 26B is in close contact with the high-strength thin film 26B. Can do. At this time, the durability can be further improved by utilizing the strength anisotropy (MD, TD) of the high-strength thin film 26 (lamination so that the anisotropies of the laminates A and B cross). it can.

本発明の電解質膜１２は、低ＥＷの電解質層３０（電解質膜３０Ａ）と、水素電極１４の触媒層１４Ａや空気電極１６の触媒層１６Ａと、がそれぞれ高強度薄膜２６を介して接着されるので、低ＥＷの電解質膜をそのまま用いた場合のように触媒層と電解質膜との接着性が低下する問題が生じたり、フッ素系電解質膜と触媒層とが直接接することによって生じる界面によってプロトン導電性が低下する問題がない。尚、積層体Ａと積層体Ｂとの圧着条件は、通常、圧力１〜５０ＭＰａ（好ましくは、５〜２０ＭＰａ）、温度８０〜２００℃（好ましくは、１００〜１４０℃）、時間１〜６０分（好ましくは、１〜２０分）である。   In the electrolyte membrane 12 of the present invention, the low EW electrolyte layer 30 (electrolyte membrane 30A) and the catalyst layer 14A of the hydrogen electrode 14 and the catalyst layer 16A of the air electrode 16 are bonded via a high-strength thin film 26, respectively. Therefore, there is a problem that the adhesion between the catalyst layer and the electrolyte membrane is lowered as in the case of using the low EW electrolyte membrane as it is, or the proton conductivity is caused by the interface caused by the direct contact between the fluorine-based electrolyte membrane and the catalyst layer. There is no problem that the performance decreases. The pressure bonding conditions between the laminate A and the laminate B are usually a pressure of 1 to 50 MPa (preferably 5 to 20 MPa), a temperature of 80 to 200 ° C. (preferably 100 to 140 ° C.), and a time of 1 to 60 minutes. (Preferably 1 to 20 minutes).

上述の通り、本発明の電解質膜は特定の膜厚の低ＥＷの電解質膜を特定の膜厚の高強度薄膜で挟み込むように構成されているため、低加湿条件下においては低ＥＷの電解質膜の作用により膜中の含水量を確保することができると共に、高加湿条件下においては低ＥＷの電解質の膨潤による変形を高強度薄膜で抑えることができる。これにより、耐久性が高く、低〜高加湿条件にかけて広く安定した電力を供給することができる固体高分子型燃料電池を構成することができる。また、本発明の電解質膜はある程度の厚さを有しながら低加湿条件下での電力安定性を実現することができることから、電極間におけるガスの移動を抑制し、クロスリークの発生を防止することができる。   As described above, the electrolyte membrane of the present invention is configured such that a low EW electrolyte membrane having a specific thickness is sandwiched between high strength thin films having a specific thickness, so that the low EW electrolyte membrane under low humidification conditions. As a result, the water content in the film can be secured, and deformation due to swelling of the low EW electrolyte can be suppressed by the high strength thin film under high humidification conditions. Thereby, a polymer electrolyte fuel cell having high durability and capable of supplying wide and stable power over low to high humidification conditions can be configured. In addition, since the electrolyte membrane of the present invention can achieve power stability under low humidification conditions while having a certain thickness, it suppresses the movement of gas between electrodes and prevents the occurrence of cross leaks. be able to.

このため、本発明の燃料電池を車両に搭載される燃料電池として使用すると、低電流運転時やドライガス運転時のように空気電極（カソード）における水の生成が少なく電解質膜が乾燥しやすい状況下であっても、電解質膜中の水分量をある程度以上確保でき、プロトン伝導性の低下による燃料電池性能の低下を抑制し、広く安定した電力を供給することができる。   For this reason, when the fuel cell of the present invention is used as a fuel cell mounted on a vehicle, the situation where the electrolyte membrane is easy to dry is less generated at the air electrode (cathode) as in low current operation or dry gas operation. Even under such conditions, it is possible to secure a certain amount of moisture in the electrolyte membrane, to suppress a decrease in fuel cell performance due to a decrease in proton conductivity, and to supply a wide and stable power.

また、本実施形態においては単セル構造の燃料電池を例に説明したが、本発明はこれに限定されるものではなく、複数のセルを積層した燃料電池として構成することも可能である。   In the present embodiment, the fuel cell having a single cell structure has been described as an example. However, the present invention is not limited to this, and can be configured as a fuel cell in which a plurality of cells are stacked.

以下、実施例において本発明を具体的に説明する。但し、本発明は以下の実施例に限定されるものではない。   Hereinafter, the present invention will be specifically described in Examples. However, the present invention is not limited to the following examples.

［実施例１］
カーボンで形成されたセパレータ上に、拡散層（厚さ２００μｍ、サイズ３．５ｃｍ×３．５ｃｍ）、触媒層（厚さ１５μｍ、サイズ３．５ｃｍ×３．５ｃｍ）、ＰＴＦＥ多孔剤補強膜（厚さ１５μｍ、サイズ６ｃｍ×６ｃｍ、ＥＷ１１００）をこの順で積層して積層体Ａ及びＢを形成した。 [Example 1]
On a separator made of carbon, a diffusion layer (thickness 200 μm, size 3.5 cm × 3.5 cm), a catalyst layer (thickness 15 μm, size 3.5 cm × 3.5 cm), a PTFE porous agent reinforced membrane (thickness) 15 μm, size 6 cm × 6 cm, EW1100) were laminated in this order to form laminates A and B.

この際、拡散層は、細孔径約３０μｍ、厚み２００μｍのカーボンペーパーに、撥水ペーストを塗布し、３００℃で焼成して作製した。   At this time, the diffusion layer was prepared by applying a water-repellent paste to carbon paper having a pore diameter of about 30 μm and a thickness of 200 μm and firing at 300 ° C.

また、触媒層は、白金を担持したカーボン粉末と、パーフルオロスルホン酸溶液（商品名：Ｎａｆｉｏｎ（Ｒ）１１２、５質量％、アルドリッチ社製）と、水とを混合して触媒層用塗布液を調製し、これを拡散層上に塗布し、８０℃で乾燥することによって形成した。   The catalyst layer is a catalyst layer coating solution prepared by mixing platinum-supported carbon powder, a perfluorosulfonic acid solution (trade name: Nafion® 112, 5% by mass, manufactured by Aldrich) and water. This was prepared by coating on the diffusion layer and drying at 80 ° C.

さらに、積層体ＡのＰＴＦＥ多孔剤補強膜上に電解質層として、低ＥＷのフッ素系電解質膜（厚さ５０μｍ、サイズ６ｃｍ×６ｃｍ、ＥＷ７００）を設置した。   Further, on the PTFE porous agent reinforced membrane of the laminate A, a low EW fluorine-based electrolyte membrane (thickness 50 μm, size 6 cm × 6 cm, EW700) was installed as an electrolyte layer.

続いて、積層体Ａにおける電解質層と積層体ＢのＰＴＦＥ多孔剤補強膜とが密着するように、圧力１０ＭＰａ、温度１２０℃の条件で２分間圧着（ホットプレス）し、電解質膜が８０μｍの単一セルからなる本発明の燃料電池を作製した。   Subsequently, the electrolyte layer in the laminate A and the PTFE porous agent reinforcing membrane in the laminate B were pressed (hot pressed) for 2 minutes under conditions of a pressure of 10 MPa and a temperature of 120 ° C., and the electrolyte membrane was 80 μm in size. A fuel cell of the present invention consisting of one cell was produced.

［比較例１］
カーボンで形成されたセパレータ上に、拡散層（厚さ２００μｍ、サイズ３．５ｃｍ×３．５ｃｍ）、触媒層（厚さ１５μｍ、サイズ３．５ｃｍ×３．５ｃｍ）、電解質層としては、パーフルオロスルホン酸膜（商品名：Ｎａｆｉｏｎ（Ｒ）１１２、デュポン社製、厚さ５０μｍ、サイズ６ｃｍ×６ｃｍ、ＥＷ１１００）をこの順で積層した積層体を形成した。この積層体に、更に、セパレータ上に前記拡散層及び触媒層が積層された積層体を実施例１と同じ条件で圧着（ホットプレス）して、電解質膜が５０μｍの比較用の単一セルからなる燃料電池を作製した。 [Comparative Example 1]
On a separator formed of carbon, a diffusion layer (thickness 200 μm, size 3.5 cm × 3.5 cm), a catalyst layer (thickness 15 μm, size 3.5 cm × 3.5 cm), and an electrolyte layer include perfluoro A laminate in which a sulfonic acid film (trade name: Nafion® 112, manufactured by DuPont, thickness 50 μm, size 6 cm × 6 cm, EW1100) was laminated in this order was formed. Further, the laminate in which the diffusion layer and the catalyst layer are laminated on the separator is pressure-bonded (hot-pressed) under the same conditions as in Example 1 so that the electrolyte membrane is from a single cell for comparison having a thickness of 50 μm. A fuel cell was produced.

［比較例２］
カーボンで形成されたセパレータ上に、拡散層（厚さ２００μｍ、サイズ３．５ｃｍ×３．５ｃｍ）、触媒層（厚さ１５μｍ、サイズ３．５ｃｍ×３．５ｃｍ）、低ＥＷのフッ素系電解質膜（厚さ５０μｍ、サイズ６ｃｍ×６ｃｍ、ＥＷ７００）をこの順で積層し積層体を形成した。この積層体に、更に、これとセパレータ上に前記拡散層及び触媒層が積層された積層体を実施例１と同じ条件で圧着（ホットプレス）し、電解質膜が５０μｍの比較用の単一セルからなる燃料電池を作製した。 [Comparative Example 2]
On a separator made of carbon, a diffusion layer (thickness 200 μm, size 3.5 cm × 3.5 cm), a catalyst layer (thickness 15 μm, size 3.5 cm × 3.5 cm), a low EW fluorine-based electrolyte membrane (Thickness 50 μm, size 6 cm × 6 cm, EW700) was laminated in this order to form a laminate. Further, this laminate and the laminate in which the diffusion layer and the catalyst layer are laminated on the separator are pressure-bonded (hot pressed) under the same conditions as in Example 1, and a single cell for comparison having an electrolyte membrane of 50 μm. A fuel cell comprising:

＜評価＞
上述から得られた燃料電池について、寸法変化、電流密度に対するセル電圧、水素透過量、セル温度に対するセル電圧について測定した。 <Evaluation>
The fuel cell obtained from the above was measured for dimensional change, cell voltage against current density, hydrogen permeation, and cell voltage against cell temperature.

前記寸法変化については、実施例及び比較例の燃料電池に用いられる電解質膜に対し１時間毎に２５℃による乾燥と８０℃の水への浸漬とを繰り返した。寸法変化については、最初の２５℃による乾燥状態のものを基準としてその変換率を求めた。結果を図３に示す。図３からわかるように、低ＥＷのみで構成された比較例２の電解質膜は８０℃の水中において膨潤し寸法の変化が著しく大きいのに対し、実施例の電解質膜は寸法の変化が抑制されているのがわかる。尚、実施例１の電解質膜は従来から用いられているＮａｆｉｏｎ（Ｒ）１１２のみで構成された比較例１の電解質膜よりも寸法安定性が良好であった。   About the said dimensional change, the drying by 25 degreeC and the immersion to 80 degreeC water were repeated every hour with respect to the electrolyte membrane used for the fuel cell of an Example and a comparative example. About the dimensional change, the conversion rate was calculated | required on the basis of the thing of the dry state by the first 25 degreeC. The results are shown in FIG. As can be seen from FIG. 3, the electrolyte membrane of Comparative Example 2 composed only of low EW swells in water at 80 ° C. and the change in size is remarkably large, whereas the electrolyte membrane of the example suppresses the change in size. I can see that In addition, the electrolyte membrane of Example 1 had better dimensional stability than the electrolyte membrane of Comparative Example 1 composed only of the conventionally used Nafion® 112.

前記電流密度に対するセル電圧の測定は、セル温度を８０℃に保ち８０％の加湿条件でおこなった。結果を図４に示す。図４からわかるように、高加湿条件下で運転をおこなうと、低ＥＷのみで構成された比較例２の燃料電池は電解質膜の寸法変化のため、電流密度の上昇に伴ってセル電圧が低下していた。これに対し、実施例１及び比較例１の燃料電池は、セル電圧の低下がゆるやかであった。尚、前記セル電圧は電圧測定器として、８９０Ｃ−１００Ｗ／５０Ａ（スクリブナー社製）を用いた。   The measurement of the cell voltage with respect to the current density was performed under a humidified condition of 80% while keeping the cell temperature at 80 ° C. The results are shown in FIG. As can be seen from FIG. 4, when operated under high humidification conditions, the fuel cell of Comparative Example 2 configured only with low EW decreases in cell voltage as the current density increases due to the dimensional change of the electrolyte membrane. Was. On the other hand, in the fuel cells of Example 1 and Comparative Example 1, the decrease in cell voltage was gradual. The cell voltage was 890C-100W / 50A (manufactured by Scribner) as a voltage measuring device.

前記水素透過量の測定は、燃料電池のアノードに水素ガスを、また、カソードに窒素ガスをガス流量５００ｍｌ／ｍｉｎの条件で１時間供給し、その後カソードにおける水素ガスの量を測定することでおこなった。結果を図５に示す。図５からわかるように実施例１の燃料電池は、比較例１及び２に対して顕著に水素透過量が少ないことがわかる。このことから、実施例１の燃料電池はクロスリークの発生が効果的に抑制されているのがわかる。   The hydrogen permeation is measured by supplying hydrogen gas to the anode of the fuel cell and nitrogen gas to the cathode at a gas flow rate of 500 ml / min for 1 hour, and then measuring the amount of hydrogen gas at the cathode. It was. The results are shown in FIG. As can be seen from FIG. 5, the fuel cell of Example 1 has significantly less hydrogen permeation than Comparative Examples 1 and 2. From this, it can be seen that the fuel cell of Example 1 effectively suppresses the occurrence of cross leak.

前記セル温度に対するセル電圧の測定は、加湿運転でアノード及びカソードの電極を５０℃に設定し、電流密度０．５Ａ／ｃｍ2、ガス利用率５０％の条件でおこなった。結果を図６に示す。図６から、従来から用いられているＮａｆｉｏｎ（Ｒ）１１２のみで構成された電解質膜を有する比較例１の燃料電池は、セル温度に対するセル電圧の降下が著しいのに比して、実施例１の燃料電池のセル電圧の低下はゆるやかであった。尚、前記セル電圧は電圧測定器として、８９０Ｃ−１００Ｗ／５０Ａ（スクリブナー社製）を用いた。 The measurement of the cell voltage with respect to the cell temperature was performed under the conditions of a current density of 0.5 A / cm 2 and a gas utilization rate of 50%, with the anode and cathode electrodes set to 50 ° C. in a humidifying operation. The results are shown in FIG. As shown in FIG. 6, the fuel cell of Comparative Example 1 having an electrolyte membrane composed only of Nafion® 112 that has been used in the related art has a lower drop in cell voltage with respect to the cell temperature. The decrease in the cell voltage of the fuel cell was moderate. The cell voltage was 890C-100W / 50A (manufactured by Scribner) as a voltage measuring device.

また、実施例１及び各比較例の燃料電池の強度を比較したところ、実施例１の燃料電池の強度は、比較例１及び２の燃料電池の強度よりも優れていた。   Moreover, when the strength of the fuel cell of Example 1 and each comparative example was compared, the strength of the fuel cell of Example 1 was superior to the strength of the fuel cells of Comparative Examples 1 and 2.

本発明の電解質膜を備えた固体高分子型燃料電池の構成を示す概略図である。It is the schematic which shows the structure of the polymer electrolyte fuel cell provided with the electrolyte membrane of this invention. 本発明の燃料電池の作製方法を説明するための概略図である。It is the schematic for demonstrating the manufacturing method of the fuel cell of this invention. 実施例における寸法変化の度合いを示すグラフである。It is a graph which shows the degree of the dimensional change in an Example. 実施例における電流密度に対するセル電圧の測定値を示すグラフである。It is a graph which shows the measured value of the cell voltage with respect to the current density in an Example. 実施例における水素透過量の測定値を示すグラフである。It is a graph which shows the measured value of the hydrogen permeation amount in an Example. 実施例におけるセル温度に対するセル電圧の測定値を示すグラフである。It is a graph which shows the measured value of the cell voltage with respect to the cell temperature in an Example. 従来の固体高分子型燃料電池の構造を示す概略図である。It is the schematic which shows the structure of the conventional polymer electrolyte fuel cell.

符号の説明Explanation of symbols

１０ 燃料電池
１２ 電解質膜
１４ 水素電極
１４Ａ 触媒層
１４Ｂ ガス拡散層
１６ 空気電極
１６Ａ 触媒層
１６Ｂ ガス拡散層
１８，２０ セパレータ
２２ 外部回路
２４ 外部装置
２６Ａ 第１の高強度薄膜
２６Ｂ 第２の高強度薄膜
３０ 電解質層 10 Fuel Cell 12 Electrolyte Membrane 14 Hydrogen Electrode 14A Catalyst Layer 14B Gas Diffusion Layer 16 Air Electrode 16A Catalyst Layer 16B Gas Diffusion Layers 18, 20 Separator 22 External Circuit 24 External Device 26A First High Strength Thin Film 26B Second High Strength Thin Film 30 Electrolyte layer

Claims (9)

ＥＷが６００〜８００且つ膜厚が３０〜１００μｍであり、プロトン伝導性を有する電解質膜と、
前記電解質膜の両面に配置され且つ膜厚が１０〜２０μｍであり、プロトン伝導性を有する一対の高強度薄膜と、
を備えた固体高分子電解質膜。 An electrolyte membrane having an EW of 600 to 800 and a film thickness of 30 to 100 μm and having proton conductivity;
A pair of high-strength thin films disposed on both surfaces of the electrolyte membrane and having a thickness of 10 to 20 μm and having proton conductivity;
A solid polymer electrolyte membrane. 前記高強度薄膜が補強材を含む請求項１に記載の固体高分子電解質膜。   The solid polymer electrolyte membrane according to claim 1, wherein the high-strength thin film contains a reinforcing material. 前記高強度薄膜が多孔質構造を有する請求項１又は２に記載の固体高分子電解質膜。   The solid polymer electrolyte membrane according to claim 1 or 2, wherein the high-strength thin film has a porous structure. 前記高強度薄膜のＥＷと前記電解質膜のＥＷとが異なる請求項１〜３のいずれか１項に記載の固体高分子電解質膜。   The solid polymer electrolyte membrane according to any one of claims 1 to 3, wherein the EW of the high-strength thin film and the EW of the electrolyte membrane are different. 前記高強度薄膜のＥＷが前記電解質膜のＥＷよりも大きい請求項１〜４のいずれか１項に記載の固体高分子電解質膜。   The solid polymer electrolyte membrane according to any one of claims 1 to 4, wherein an EW of the high-strength thin film is larger than an EW of the electrolyte membrane. 前記高強度薄膜のＥＷが９００〜１３００である請求項１〜５のいずれか１項に記載の固体高分子電解質膜。   The solid polymer electrolyte membrane according to any one of claims 1 to 5, wherein the high-strength thin film has an EW of 900 to 1300. 請求項１〜６のいずれか１項に記載された固体高分子電解質膜と、前記固体高分子電解質膜の両面に配置され、且つ、金属触媒を含有する一対の触媒層と、を備えた固体高分子型燃料電池。   A solid comprising the solid polymer electrolyte membrane according to any one of claims 1 to 6 and a pair of catalyst layers disposed on both sides of the solid polymer electrolyte membrane and containing a metal catalyst. Polymer fuel cell. 膜厚が１０〜２０μｍのプロトン伝導性を有する一対の高強度薄膜と、前記一対の高強度薄膜に挟持され、ＥＷが６００〜８００且つ膜厚が３０〜１００μｍのプロトン伝導性を有する電解質膜と、をホットプレスによって積層化する工程を含む固体高分子電解質膜の製造方法。   A pair of high-strength thin films having proton conductivity of 10 to 20 μm, and an electrolyte membrane having proton conductivity sandwiched between the pair of high-strength thin films and having an EW of 600 to 800 and a thickness of 30 to 100 μm The manufacturing method of the solid polymer electrolyte membrane including the process of laminating | stacking by hot press. 一方の面に金属触媒を含有する触媒層が設けられ且つ膜厚が１０〜２０μｍのプロトン伝導性を有する一対の高強度薄膜と、前記一対の高強度薄膜の前記触媒層が設けられていない側の面に挟持され、ＥＷが６００〜８００且つ膜厚が３０〜１００μｍのプロトン伝導性を有する電解質膜と、をホットプレスによって積層化する工程を含む固体高分子型燃料電池の製造方法。   A pair of high-strength thin films having a catalyst layer containing a metal catalyst on one side and a proton conductivity of 10 to 20 μm, and a side of the pair of high-strength thin films on which the catalyst layer is not provided A method for producing a polymer electrolyte fuel cell comprising a step of laminating a proton conductive electrolyte membrane having an EW of 600 to 800 and a film thickness of 30 to 100 μm by hot pressing.
JP2004242600A 2004-08-23 2004-08-23 Solid polyelectrolyte film and polymer electrolyte fuel cell using the same, and their manufacturing method Pending JP2006059756A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2004242600A JP2006059756A (en) 2004-08-23 2004-08-23 Solid polyelectrolyte film and polymer electrolyte fuel cell using the same, and their manufacturing method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2004242600A JP2006059756A (en) 2004-08-23 2004-08-23 Solid polyelectrolyte film and polymer electrolyte fuel cell using the same, and their manufacturing method

Publications (1)

Publication Number Publication Date
JP2006059756A true JP2006059756A (en) 2006-03-02

Family

ID=36107036

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2004242600A Pending JP2006059756A (en) 2004-08-23 2004-08-23 Solid polyelectrolyte film and polymer electrolyte fuel cell using the same, and their manufacturing method

Country Status (1)

Country Link
JP (1) JP2006059756A (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008226646A (en) * 2007-03-13 2008-09-25 Sanyo Electric Co Ltd Fuel cell
WO2009107273A1 (en) * 2008-02-26 2009-09-03 トヨタ自動車株式会社 Reinforced electrolyte membrane for fuel cell, fuel cell membrane-electrode assembly, and solid polymer electrolyte fuel cell comprising the fuel cell membrane-electrode assembly
JP2009283364A (en) * 2008-05-23 2009-12-03 Toshiba Corp Polymer electrolyte membrane type fuel cell
WO2010087556A1 (en) * 2009-01-30 2010-08-05 전북대학교산학협력단 Method for pulse plating carbon black sheet with metallic nano particle thin film layer, and carbon black sheet & fuel cell polymer electrolyte membrane / electrode assembly prepared using sheet
US8795923B2 (en) 2007-04-19 2014-08-05 Toyota Jidosha Kabushiki Kaisha Reinforced electrolyte membrane for fuel cell, fuel cell membrane-electrode assembly, and solid polymer electrolyte fuel cell comprising the fuel cell membrane-electrode assembly
US8802314B2 (en) 2008-10-17 2014-08-12 Toyota Jidosha Kabushiki Kaisha Reinforced electrolyte membrane for fuel cell, membrane-electrode assembly for fuel cell, and polymer electrolyte fuel cell comprising the same
CN110741499A (en) * 2018-05-17 2020-01-31 株式会社Lg化学 Ion exchange membrane and flow battery comprising same

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07296818A (en) * 1994-04-22 1995-11-10 Japan Gore Tex Inc Polymer solid electrolyte fuel cell electrode and joint of same with polymer solid electrolyte
JPH1079257A (en) * 1996-09-03 1998-03-24 Mitsubishi Heavy Ind Ltd Ion exchange membrane
JPH10334923A (en) * 1997-04-04 1998-12-18 Asahi Chem Ind Co Ltd Solid high polymer fuel cell film/electrode connecting body
JP2001243964A (en) * 2000-02-28 2001-09-07 Asahi Glass Co Ltd Solid polymer electrolyte fuel cell

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07296818A (en) * 1994-04-22 1995-11-10 Japan Gore Tex Inc Polymer solid electrolyte fuel cell electrode and joint of same with polymer solid electrolyte
JPH1079257A (en) * 1996-09-03 1998-03-24 Mitsubishi Heavy Ind Ltd Ion exchange membrane
JPH10334923A (en) * 1997-04-04 1998-12-18 Asahi Chem Ind Co Ltd Solid high polymer fuel cell film/electrode connecting body
JP2001243964A (en) * 2000-02-28 2001-09-07 Asahi Glass Co Ltd Solid polymer electrolyte fuel cell

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008226646A (en) * 2007-03-13 2008-09-25 Sanyo Electric Co Ltd Fuel cell
US8795923B2 (en) 2007-04-19 2014-08-05 Toyota Jidosha Kabushiki Kaisha Reinforced electrolyte membrane for fuel cell, fuel cell membrane-electrode assembly, and solid polymer electrolyte fuel cell comprising the fuel cell membrane-electrode assembly
WO2009107273A1 (en) * 2008-02-26 2009-09-03 トヨタ自動車株式会社 Reinforced electrolyte membrane for fuel cell, fuel cell membrane-electrode assembly, and solid polymer electrolyte fuel cell comprising the fuel cell membrane-electrode assembly
CN101960658A (en) * 2008-02-26 2011-01-26 丰田自动车株式会社 Reinforced electrolyte membrane for fuel cell, fuel cell membrane-electrode assembly, and solid polymer electrolyte fuel cell comprising the fuel cell membrane-electrode assembly
JP2009283364A (en) * 2008-05-23 2009-12-03 Toshiba Corp Polymer electrolyte membrane type fuel cell
US8802314B2 (en) 2008-10-17 2014-08-12 Toyota Jidosha Kabushiki Kaisha Reinforced electrolyte membrane for fuel cell, membrane-electrode assembly for fuel cell, and polymer electrolyte fuel cell comprising the same
WO2010087556A1 (en) * 2009-01-30 2010-08-05 전북대학교산학협력단 Method for pulse plating carbon black sheet with metallic nano particle thin film layer, and carbon black sheet & fuel cell polymer electrolyte membrane / electrode assembly prepared using sheet
US8927177B2 (en) 2009-01-30 2015-01-06 Industrial Cooperation Foundation Chonbuk National University Methods for preparing carbon black sheet with metallic nanoparticle thin layer by electrophoresis deposition and membrane electrode assembly (MEA) for proton exchange membrane fuel cell
CN110741499A (en) * 2018-05-17 2020-01-31 株式会社Lg化学 Ion exchange membrane and flow battery comprising same
JP2020524386A (en) * 2018-05-17 2020-08-13 エルジー・ケム・リミテッド Ion exchange separation membrane and flow battery including the same
US11309567B2 (en) * 2018-05-17 2022-04-19 Lg Chem, Ltd. Ion exchange membrane and flow battery including same
JP7069224B2 (en) 2018-05-17 2022-05-17 エルジー・ケム・リミテッド Ion exchange separation membrane and flow battery containing it
CN110741499B (en) * 2018-05-17 2022-11-29 株式会社Lg化学 Ion exchange membrane and flow battery comprising same

Similar Documents

Publication Publication Date Title
JP3760895B2 (en) LIQUID FUEL SUPPLY FUEL CELL, FUEL CELL ELECTRODE, AND METHOD FOR PRODUCING THEM
US7803495B2 (en) Polymer electrolyte membrane for fuel cell, method for preparing the same, and fuel cell system comprising the same
JP6312666B2 (en) Ion conductive membrane
JP4410156B2 (en) ELECTROLYTE MEMBRANE FOR FUEL CELL AND FUEL CELL INCLUDING THE SAME
JPH11288727A (en) Solid high polymer fuel cell film/electrode junction body
JP2006114502A (en) Polymer electrolyte film for direct oxidation type fuel cell, its manufacturing method, and direct oxidation type fuel cell system including this
JP5532630B2 (en) Membrane electrode assembly, method for producing the same, and polymer electrolyte fuel cell
JP5260009B2 (en) Membrane electrode assembly and fuel cell
JP4090108B2 (en) Membrane / electrode assembly for polymer electrolyte fuel cells
JP2009016074A (en) Electrolyte membrane, and fuel cell using the same
JP2003109604A (en) Gas diffusion electrode for fuel cell and method of manufacturing the same
Song et al. Investigation of direct methanol fuel cell performance of sulfonated polyimide membrane
JP2007287663A (en) Direct oxidation type fuel cell and its manufacturing method
JP2007234359A (en) Membrane electrode assembly for solid polymer fuel cell
JP2007265898A (en) Electrolyte membrane for polymer electrolyte fuel cell, and polymer electrolyte fuel cell equipped with it
JP2006059756A (en) Solid polyelectrolyte film and polymer electrolyte fuel cell using the same, and their manufacturing method
KR101312971B1 (en) Hydrocarbon based polyelectrolyte separation membrane surface-treated with fluorinated ionomer, membrane electrode assembly, and fuel cell
JP2004273257A (en) Electrode catalyst layer for fuel cell
JP2011171301A (en) Direct oxidation fuel cell
Kinoshita et al. (Plenary) Development of PFSA Ionomers and Their Use in Fuel Cells
JP6105215B2 (en) Membrane electrode assembly for polymer electrolyte fuel cell
KR20170131025A (en) polymer electrolytic membrane having low hydrogen permeablility, and membrane electrode assembly using the same
JP7272319B2 (en) Laminates for fuel cells
US11302946B2 (en) Manufacturing method for membrane electrode assembly, and stacked body
JP5313569B2 (en) Solid polymer electrolyte membrane and method for producing solid polymer electrolyte membrane

Legal Events

Date Code Title Description
A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20070611

A977 Report on retrieval

Free format text: JAPANESE INTERMEDIATE CODE: A971007

Effective date: 20100422

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20100427

A02 Decision of refusal

Free format text: JAPANESE INTERMEDIATE CODE: A02

Effective date: 20101005