JP2000251905A - Electrolyte film for solid high polymer fuel cell and its manufacture - Google Patents
Electrolyte film for solid high polymer fuel cell and its manufactureInfo
- Publication number
- JP2000251905A JP2000251905A JP11050579A JP5057999A JP2000251905A JP 2000251905 A JP2000251905 A JP 2000251905A JP 11050579 A JP11050579 A JP 11050579A JP 5057999 A JP5057999 A JP 5057999A JP 2000251905 A JP2000251905 A JP 2000251905A
- Authority
- JP
- Japan
- Prior art keywords
- exchange membrane
- cation exchange
- membrane
- heavy metal
- electrolyte membrane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、固体高分子型燃料
電池用の電解質膜およびその製造方法に関する。The present invention relates to an electrolyte membrane for a polymer electrolyte fuel cell and a method for producing the same.
【０００２】[0002]
【従来の技術】従来、この種の固体高分子型燃料電池用
の電解質膜としては、電解質膜の表面に表面粗化処理を
施してなるものが提案されている（特開平５−２５８７
５６号公報など）。この電解質膜では、表面に施した表
面粗化処理により形成される凹凸の凹部に触媒としての
金属を堆積させることにより、電解質膜と触媒とガスと
の三相界面で生じる電気化学反応の反応場を拡大させて
触媒の利用率を高め、電池特性の向上を図ることができ
るとされている。2. Description of the Related Art Heretofore, as an electrolyte membrane for a polymer electrolyte fuel cell of this type, a membrane obtained by subjecting the surface of an electrolyte membrane to a surface roughening treatment has been proposed (JP-A-5-2587).
No. 56). In this electrolyte membrane, a metal as a catalyst is deposited in concaves and convexes formed by surface roughening treatment performed on the surface, thereby forming a reaction field of an electrochemical reaction generated at a three-phase interface between the electrolyte membrane, the catalyst, and the gas. It is said that the efficiency of the catalyst can be increased by enlarging the catalyst and the battery characteristics can be improved.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、こうし
た電解質膜では、その凹部に堆積した触媒のうち膜表面
付近の触媒粒子が電気化学反応に寄与するだけで、その
凹部に堆積した多くの触媒粒子は反応に寄与しないとい
った問題があった。こうした問題は、触媒として貴金属
を用いる場合には、電解質膜を用いる燃料電池のコスト
を増大させるという問題を併発する。However, in such an electrolyte membrane, of the catalyst deposited in the recess, only the catalyst particles near the membrane surface contribute to the electrochemical reaction, and many catalyst particles deposited in the recess are There was a problem that it did not contribute to the reaction. Such a problem is accompanied by a problem that when a noble metal is used as a catalyst, the cost of a fuel cell using an electrolyte membrane increases.
【０００４】また、表面に粗化処理を施した電解質膜で
は、処理方法にもよるが膜の表面の構造が化学的に変質
されたり、物理的に破壊されるおそれがあり、電解質膜
として有効に機能しない部分を生じるという問題もあっ
た。通常、電解質膜としてイオン交換膜を用いるが、化
学的な表面処理や物理的な表面処理によりイオン交換に
寄与する官能基が破壊される場合があり、この場合、イ
オン交換の機能を失い、電解質膜としての性能を低下さ
せてしまう。Further, in the case of an electrolyte membrane whose surface has been subjected to a roughening treatment, the structure of the surface of the membrane may be chemically altered or physically destroyed depending on the treatment method. There was also a problem that some parts did not work. Normally, an ion exchange membrane is used as an electrolyte membrane, but a functional group contributing to ion exchange may be destroyed by chemical surface treatment or physical surface treatment.In this case, the ion exchange function is lost, The performance as a film is reduced.
【０００５】なお、こうした問題の一部を解決するもの
として、出願人は、電解質膜表面にプラズマスパッタエ
ッチング処理を施して膜表面に凹凸を形成し、その凹凸
に沿ってほぼ一様な厚さの触媒層を形成してなる電解質
膜を提案している（特願平６−３１５５０２号）。In order to solve some of these problems, the applicant has applied a plasma sputter etching process to the surface of the electrolyte film to form irregularities on the film surface, and has a substantially uniform thickness along the irregularities. (Japanese Patent Application No. 6-315502).
【０００６】本発明の固体高分子型燃料電池用の電解質
膜は、電解質膜としての性能を低下させることなく触媒
との接触面積を多くして反応性を高めることを目的とす
る。本発明の固体高分子型燃料電池用の電解質膜の製造
方法は、電解質膜としての性能を低下させることなく触
媒との接触面積が多くとれる電解質膜の製造方法を提供
することを目的とする。An object of the present invention is to increase reactivity by increasing a contact area with a catalyst without deteriorating performance as an electrolyte membrane. An object of the present invention is to provide a method for producing an electrolyte membrane for a polymer electrolyte fuel cell, which can provide a large contact area with a catalyst without deteriorating the performance as an electrolyte membrane.
【０００７】[0007]
【課題を解決するための手段およびその作用・効果】本
発明の固体高分子型燃料電池用の電解質膜およびその製
造方法は、上述の目的の少なくとも一部を達成するため
に以下の手段を採った。Means for Solving the Problems and Actions and Effects Thereof The electrolyte membrane for a polymer electrolyte fuel cell and the method for producing the same according to the present invention employs the following means to at least partially achieve the above-mentioned object. Was.
【０００８】本発明の固体高分子型燃料電池用の電解質
膜の製造方法は、固体高分子型燃料電池に用いられる電
解質膜の製造方法であって、陽イオン交換膜のプロトン
を重金属で置換する重金属置換工程と、該置換された陽
イオン交換膜の少なくとも一方の面に放射線を照射して
該面に所定形状の窪みを複数形成する表面処理を行なう
表面処理工程と、該表面処理された陽イオン交換膜の前
記重金属をプロトンに置換するプロトン置換工程とを備
えることを要旨とする。The method for producing an electrolyte membrane for a polymer electrolyte fuel cell according to the present invention is a method for producing an electrolyte membrane used for a polymer electrolyte fuel cell, wherein protons of a cation exchange membrane are replaced with heavy metals. A heavy metal substitution step, a surface treatment step of irradiating at least one surface of the substituted cation exchange membrane with radiation to form a plurality of depressions of a predetermined shape on the surface, and a surface treatment step of performing the surface treatment. And a proton substitution step of replacing the heavy metal of the ion exchange membrane with protons.
【０００９】この本発明の固体高分子型燃料電池用の電
解質膜の製造方法では、陽イオン交換膜のプロトンを重
金属で置換することにより表面処理の際にイオン交換に
寄与する官能基を変質や破壊から防止することができ
る。この結果、表面処理により電解質膜の性能を低下さ
せることがない。また、表面処理により膜の表面に所定
形状の窪みを複数形成するから、触媒との接触面積を多
くすることができる。ここで、「放射線」には、プラズ
マや電子線，Ｘ線，γ線などが含まれる。また、「重金
属」には、鉛，亜鉛，アルミニウム，鉄，白金などが含
まれる。In the method for producing an electrolyte membrane for a polymer electrolyte fuel cell according to the present invention, the protons of the cation exchange membrane are replaced with heavy metals to alter the functional groups contributing to ion exchange during surface treatment. It can be prevented from destruction. As a result, the performance of the electrolyte membrane is not reduced by the surface treatment. Further, since a plurality of depressions of a predetermined shape are formed on the surface of the film by the surface treatment, the contact area with the catalyst can be increased. Here, “radiation” includes plasma, electron beam, X-ray, γ-ray, and the like. The “heavy metals” include lead, zinc, aluminum, iron, platinum and the like.
【００１０】こうした本発明の固体高分子型燃料電池用
の電解質膜の製造方法において、前記陽イオン交換膜と
して強酸性陽イオン交換膜を用いるものとすることもで
きる。また、本発明の固体高分子型燃料電池用の電解質
膜の製造方法において、前記重金属置換工程は、前記重
金属の弱酸塩水溶液を用いて置換する工程であるものと
することもできる。ここで、「重金属の弱酸塩水溶液」
には、酢酸による重金属塩の水溶液（例えば、酢酸鉛や
酢酸亜鉛などの水溶液）などが含まれる。In the method for producing an electrolyte membrane for a polymer electrolyte fuel cell according to the present invention, a strongly acidic cation exchange membrane may be used as the cation exchange membrane. Further, in the method for producing an electrolyte membrane for a polymer electrolyte fuel cell according to the present invention, the heavy metal replacement step may be a step of replacement using a weak salt aqueous solution of the heavy metal. Here, "aqueous salt solution of heavy metal"
Include aqueous solutions of heavy metal salts with acetic acid (eg, aqueous solutions of lead acetate, zinc acetate, etc.).
【００１１】本発明の固体高分子型燃料電池用の電解質
膜の製造方法において、前記表面処理工程は、前記放射
線として電子線を用いて行なう工程であるものとするこ
ともできる。電子線は制御しやすいから、膜の表面に所
定形状の窪みを容易に形成することができる。また、電
子線はプラズマやＸ線，γ線に比して安価に得られるか
ら、電解質膜の製造コストを低減することができる。In the method for producing an electrolyte membrane for a polymer electrolyte fuel cell according to the present invention, the surface treatment step may be a step using an electron beam as the radiation. Since the electron beam is easily controlled, a depression having a predetermined shape can be easily formed on the surface of the film. In addition, since the electron beam can be obtained at a lower cost than plasma, X-ray, and γ-ray, the manufacturing cost of the electrolyte membrane can be reduced.
【００１２】本発明の第１の固体高分子型燃料電池用の
電解質膜は、固体高分子型燃料電池に用いられる電解質
膜であって、陽イオン交換膜のプロトンを重金属で置換
し、該置換された陽イオン交換膜の少なくとも一方の面
に放射線を照射して該面に所定の形状の窪みを複数形成
し、該所定形状の窪みが複数形成された陽イオン交換膜
の前記重金属をプロトンに置換してなることを要旨とす
る。The first electrolyte membrane for a polymer electrolyte fuel cell according to the present invention is an electrolyte membrane used for a polymer electrolyte fuel cell, wherein protons of a cation exchange membrane are substituted with heavy metals, and the substitution is performed. Irradiation is performed on at least one surface of the cation exchange membrane thus formed to form a plurality of depressions of a predetermined shape on the surface, and the heavy metal of the cation exchange membrane having the plurality of depressions of the predetermined shape formed as protons. The gist is that it is replaced.
【００１３】本発明の第１の固体高分子型燃料電池用の
電解質膜では、陽イオン交換膜のプロトンを重金属で置
換して表面処理し、表面処理された膜の表面にイオン交
換に寄与する官能基を備えているから、電解質膜として
の性能を十分に発揮することができる。また、表面処理
により膜の表面に所定形状の窪みが複数形成されている
から、触媒との接触面積を多くすることができる。In the first electrolyte membrane for a polymer electrolyte fuel cell of the present invention, the protons of the cation exchange membrane are replaced with heavy metals for surface treatment, and the surface of the surface-treated membrane contributes to ion exchange. Since it has a functional group, the performance as an electrolyte membrane can be sufficiently exhibited. Further, since a plurality of depressions having a predetermined shape are formed on the surface of the film by the surface treatment, the contact area with the catalyst can be increased.
【００１４】本発明の第２の固体高分子型燃料電池用の
電解質膜は、固体高分子型燃料電池に用いられる電解質
膜であって、強酸性陽イオン交換膜により形成され、該
強酸性陽イオン交換膜の少なくとも一方の面に１０-6ｍ
のオーダーの所定形状の窪みを複数備えることを要旨と
する。The second electrolyte membrane for a polymer electrolyte fuel cell according to the present invention is an electrolyte membrane used for a polymer electrolyte fuel cell, which is formed by a strongly acidic cation exchange membrane. 10 -6 m on at least one side of the ion exchange membrane
And a plurality of depressions of a predetermined shape of the order
【００１５】この本発明の第２の固体高分子型燃料電池
用の電解質膜では、膜の表面に所定形状の窪みが複数形
成されているから、触媒との接触面積を多くすることが
できる。In the electrolyte membrane for a polymer electrolyte fuel cell according to the second aspect of the present invention, since a plurality of recesses having a predetermined shape are formed on the surface of the membrane, the contact area with the catalyst can be increased.
【００１６】こうした本発明の第２の固体高分子型燃料
電池用の電解質膜において、前記強酸性陽イオン交換膜
の前記所定形状の窪みが形成された近傍表面にイオン交
換に寄与する官能基が配置されてなるものとすることも
できる。こうすれば、電解質膜の性能を十分に発揮させ
ることができる。In the electrolyte membrane for a polymer electrolyte fuel cell according to the second aspect of the present invention, a functional group contributing to ion exchange is formed on the surface of the strongly acidic cation exchange membrane in which the depression having the predetermined shape is formed. They may be arranged. In this case, the performance of the electrolyte membrane can be sufficiently exhibited.
【００１７】[0017]
【発明の実施の形態】次に、本発明の実施の形態を実施
例を用いて説明する。図１は本発明の一実施例である固
体高分子型燃料電池用の電解質膜３０の製造の様子を例
示する製造工程図であり、図２は実施例の電解質膜３０
の製造の様子を模式的に示す製造模式図である。Next, embodiments of the present invention will be described with reference to examples. FIG. 1 is a manufacturing process diagram illustrating the manufacturing process of an electrolyte membrane 30 for a polymer electrolyte fuel cell according to one embodiment of the present invention, and FIG.
FIG. 4 is a manufacturing schematic diagram schematically showing the state of manufacturing.
【００１８】図示するように電解質膜３０の製造は、ま
ず、強酸性陽イオン交換膜２２のプロトンを重金属に置
換する工程から始まる（工程Ｓ１０）。実施例では、イ
オン交換膜としてスルホン基を交換基とする強酸性陽イ
オン交換膜（ＤｕＰｏｎｔ社製のＮａｆｉｏｎ１２２）
を用い、電子染色技術により次式（１）に示すイオン交
換反応によりスルホン基のプロトンを重金属（例えば、
鉛や亜鉛，アルミニウム，鉄，白金など）で置換して、
重金属で置換されたイオン交換膜２４とした。なお、こ
の置換は弱酸塩水溶液（例えば、酢酸鉛や酢酸亜鉛など
の水溶液）に強酸性陽イオン交換膜２２を浸漬すること
により行なった。As shown in the figure, the production of the electrolyte membrane 30 starts with the step of replacing protons of the strongly acidic cation exchange membrane 22 with heavy metals (step S10). In the examples, a strongly acidic cation exchange membrane having a sulfone group as an exchange group (Nafion 122 manufactured by DuPont) is used as an ion exchange membrane.
And the proton of the sulfone group is converted to a heavy metal (for example,
Lead, zinc, aluminum, iron, platinum, etc.)
The ion exchange membrane 24 was replaced with a heavy metal. This substitution was performed by immersing the strongly acidic cation exchange membrane 22 in a weak acid salt aqueous solution (for example, an aqueous solution of lead acetate or zinc acetate).
【００１９】 イオン交換反応： ｎＲＨ+＋Ｍn+ ⇔ ＲnＭn+＋ｎＨ+ （１）Ion exchange reaction: nRH + + M n + ⇔R n M n + + nH + (1)
【００２０】図３は強酸性陽イオン交換膜２２を飽和酢
酸亜鉛水溶液に浸漬してプロトンを亜鉛で置換したとき
の亜鉛とスルホン基とのクラスタ推定構造を示す説明図
であり、図４は強酸性陽イオン交換膜２２を飽和酢酸鉛
水溶液に浸漬してプロトンを鉛で置換したときの鉛とス
ルホン基とのクラスタ推定構造を示す説明図である。図
示するように、スルホン基にはプロトンに代わって重金
属としての亜鉛や鉛が置換されている。FIG. 3 is an explanatory view showing the estimated structure of clusters of zinc and sulfone groups when the proton is replaced by zinc by immersing the strongly acidic cation exchange membrane 22 in a saturated zinc acetate aqueous solution. FIG. 3 is an explanatory diagram showing a cluster estimation structure of lead and a sulfone group when a proton is replaced with lead by immersing a cation exchange membrane 22 in a saturated lead acetate aqueous solution. As shown in the figure, zinc and lead as heavy metals are substituted for the sulfone groups instead of protons.
【００２１】次に、重金属で置換されたイオン交換膜２
４に対して放射線を照射して膜の表面に所定形状の窪み
２６をパターン形成する（工程Ｓ１２）。イオン交換膜
に放射線を照射すると、イオン交換膜は架橋して硬化す
るか、分解することが多い。強酸性陽イオン交換膜では
放射線の照射は分解を促進するが、プロトンを重金属で
置換すると、その強度が高くなり放射線によるイオン交
換膜の劣化（分解）が抑制されるから、放射線を照射し
てもイオン交換膜の構造に変化は生じない。放射線とし
てはプラズマや電子線，Ｘ線，γ線などが含まれ、その
いずれでもパターン形成することができる。実施例で
は、強度などの制御が容易な電子線を用い、電子線リソ
グラフィーによりパターン形成を行なった。なお、パタ
ーン形成に電子線リソグラフィーを用いれば、膜の表面
に１０-6ｍオーダーの所望の形状の窪みを形成すること
ができる。Next, an ion-exchange membrane 2 substituted with a heavy metal
4 is irradiated with radiation to form a pattern of recesses 26 of a predetermined shape on the surface of the film (step S12). When the ion exchange membrane is irradiated with radiation, the ion exchange membrane is often crosslinked and hardened or decomposed. Irradiation promotes decomposition in strongly acidic cation exchange membranes, but replacing protons with heavy metals increases the strength and suppresses the degradation (decomposition) of ion exchange membranes due to radiation. Also, no change occurs in the structure of the ion exchange membrane. The radiation includes plasma, electron beam, X-ray, γ-ray and the like, and any of them can be used for pattern formation. In the example, the pattern was formed by electron beam lithography using an electron beam whose intensity and the like were easily controlled. If electron beam lithography is used for pattern formation, a depression having a desired shape on the order of 10 −6 m can be formed on the surface of the film.
【００２２】そして、重金属で置換されたイオン交換膜
２４に対して上述の式（１）のイオン交換反応の逆反応
を用いて重金属をプロトンで置換して（工程Ｓ１４）、
電解質膜３０を完成する。実施例では、重金属で置換さ
れたイオン交換膜２４を希硫酸に浸漬して重金属をプロ
トンに置換した。Then, the heavy metal is replaced with protons in the ion exchange membrane 24 replaced with the heavy metal by using the reverse reaction of the ion exchange reaction of the above formula (1) (step S14).
The electrolyte membrane 30 is completed. In the example, the heavy metal was replaced with protons by immersing the ion-exchange membrane 24 replaced with heavy metals in dilute sulfuric acid.
【００２３】完成した電解質膜３０は、その表面に１０
-6ｍオーダーの所定形状の窪み３２を備えており、この
所定形状の窪み３２の形成された面の表面にはイオン交
換基としてのスルホン基が変質や破壊されることなく存
在する。なお、所定形状の窪み３２は、断面が矩形や三
角その他の多角形，円形，楕円形など如何なる形状であ
ってもよい。The completed electrolyte membrane 30 has 10
A depression 32 having a predetermined shape on the order of -6 m is provided, and a sulfone group serving as an ion exchange group is present on the surface of the surface where the depression 32 having the predetermined shape is formed without being altered or destroyed. The recess 32 of a predetermined shape may have a cross section of any shape such as a rectangle, a triangle, other polygons, a circle, and an ellipse.
【００２４】以上説明した実施例の電解質膜３０によれ
ば、その表面に１０-6ｍオーダーの所定形状の窪み３２
を備えるから、触媒との接触面積を大きく持つことがで
き、反応性の高い電解質膜とすることができる。また、
実施例の電解質膜３０によれば、所定形状の窪み３２の
形成された面の表面にはイオン交換基としてのスルホン
基が変質や破壊されることなく存在するから、所定形状
の窪み３２の形成による膜表面の変質がなく、電解質膜
の性能を十分に発揮することができる。According to the electrolyte membrane 30 of the embodiment described above, the depression 32 having a predetermined shape on the order of 10 -6 m is formed on the surface thereof.
Therefore, a contact area with the catalyst can be increased, and an electrolyte membrane having high reactivity can be obtained. Also,
According to the electrolyte membrane 30 of the embodiment, since the sulfone group as the ion exchange group is present on the surface of the surface where the recesses 32 of the predetermined shape are formed without being altered or destroyed, the formation of the recesses 32 of the predetermined shape is formed. And the performance of the electrolyte membrane can be sufficiently exhibited.
【００２５】以上説明した実施例の電解質膜３０の製造
方法によれば、触媒との接触面積が大きく、イオン交換
性能を十分に発揮できる電解質膜を製造することができ
る。また、実施例の電解質膜３０の製造方法によれば、
強酸性陽イオン交換膜２２のプロトンを重金属で置換し
た後に膜に放射線を照射してその表面に所定形状の窪み
２６を形成するから、放射線の照射によりイオン交換膜
の分解やイオン交換基の変質，破壊を防止することがで
きる。さらに、実施例の電解質膜３０の製造方法によれ
ば、放射線としてその強度などの制御が容易な電子線を
用いたので、膜の表面に所望の形状の窪み２６をパター
ン形成することができる。According to the method of manufacturing the electrolyte membrane 30 of the embodiment described above, it is possible to manufacture an electrolyte membrane having a large contact area with the catalyst and sufficiently exhibiting ion exchange performance. Further, according to the manufacturing method of the electrolyte membrane 30 of the embodiment,
After the protons of the strongly acidic cation exchange membrane 22 are replaced with heavy metals, the membrane is irradiated with radiation to form dents 26 of a predetermined shape on the surface thereof. ， Destruction can be prevented. Furthermore, according to the method of manufacturing the electrolyte membrane 30 of the embodiment, since the electron beam whose intensity and the like can be easily controlled is used as the radiation, the depression 26 having a desired shape can be pattern-formed on the surface of the membrane.
【００２６】実施例の電解質膜３０では、イオン交換膜
として強酸性陽イオン交換膜２２を用いたが、電解質膜
として機能すれば弱酸性陽イオン交換膜などを用いても
よい。In the electrolyte membrane 30 of the embodiment, the strongly acidic cation exchange membrane 22 is used as an ion exchange membrane, but a weakly acidic cation exchange membrane or the like may be used as long as it functions as an electrolyte membrane.
【００２７】以上、本発明の実施の形態について実施例
を用いて説明したが、本発明はこうした実施例に何等限
定されるものではなく、本発明の要旨を逸脱しない範囲
内において、種々なる形態で実施し得ることは勿論であ
る。The embodiments of the present invention have been described with reference to the embodiments. However, the present invention is not limited to these embodiments, and various embodiments may be made without departing from the scope of the present invention. Of course, it can be carried out.
【図１】 本発明の一実施例である固体高分子型燃料電
池用の電解質膜３０の製造の様子を例示する製造工程図
である。FIG. 1 is a manufacturing process diagram illustrating a state of manufacturing an electrolyte membrane 30 for a polymer electrolyte fuel cell according to one embodiment of the present invention.
【図２】 実施例の電解質膜３０の製造の様子を模式的
に示す製造模式図である。FIG. 2 is a schematic production view schematically showing a state of production of an electrolyte membrane 30 of an example.
【図３】 強酸性陽イオン交換膜２２を飽和酢酸亜鉛水
溶液に浸漬してプロトンを亜鉛で置換したときの亜鉛と
スルホン基とのクラスタ推定構造を示す説明図である。FIG. 3 is an explanatory diagram showing a presumed structure of a cluster of zinc and a sulfone group when a strongly acidic cation exchange membrane 22 is immersed in a saturated zinc acetate aqueous solution to replace protons with zinc.
【図４】 強酸性陽イオン交換膜２２を飽和酢酸鉛水溶
液に浸漬してプロトンを鉛で置換したときの鉛とスルホ
ン基とのクラスタ推定構造を示す説明図である。FIG. 4 is an explanatory diagram showing a cluster estimated structure of lead and a sulfone group when a strongly acidic cation exchange membrane 22 is immersed in a saturated aqueous lead acetate solution to replace protons with lead.
２２ 強酸性陽イオン交換膜、２４ 重金属で置換され
たイオン交換膜、２６所定形状の窪み、３０ 電解質
膜、３２ 所定形状の窪み。22 Strongly acidic cation exchange membrane, 24 Ion exchange membrane substituted with heavy metal, 26 Predetermined shape depression, 30 Electrolyte membrane, 32 Predetermined shape depression.
Claims (8)
質膜の製造方法であって、 陽イオン交換膜のプロトンを重金属で置換する重金属置
換工程と、 該置換された陽イオン交換膜の少なくとも一方の面に放
射線を照射して該面に所定形状の窪みを複数形成する表
面処理を行なう表面処理工程と、 該表面処理された陽イオン交換膜の前記重金属をプロト
ンに置換するプロトン置換工程とを備える電解質膜の製
造方法。1. A method for producing an electrolyte membrane used in a polymer electrolyte fuel cell, comprising: a heavy metal substitution step of replacing protons of a cation exchange membrane with heavy metals; and at least one of the substituted cation exchange membranes. A surface treatment step of irradiating the surface with radiation to form a plurality of depressions of a predetermined shape on the surface, and a proton substitution step of replacing the heavy metal of the surface-treated cation exchange membrane with protons. The manufacturing method of the provided electrolyte membrane.
ン交換膜を用いる請求項１記載の電解質膜の製造方法。2. The method according to claim 1, wherein a strongly acidic cation exchange membrane is used as the cation exchange membrane.
ム，鉄，白金のいずれかである請求項１または２記載の
電解質膜の製造方法。3. The method according to claim 1, wherein the heavy metal is one of lead, zinc, aluminum, iron, and platinum.
酸塩水溶液を用いて置換する工程である請求項１ないし
３いずれか記載の電解質膜の製造方法。4. The method for producing an electrolyte membrane according to claim 1, wherein said heavy metal replacement step is a step of replacement using an aqueous solution of a weak salt of said heavy metal.
電子線を用いて行なう工程である請求項１ないし４いず
れか記載の電解質膜の製造方法。5. The method for producing an electrolyte membrane according to claim 1, wherein said surface treatment step is a step performed using an electron beam as said radiation.
質膜であって、 陽イオン交換膜のプロトンを重金属で置換し、該置換さ
れた陽イオン交換膜の少なくとも一方の面に放射線を照
射して該面に所定形状の窪みを複数形成し、該所定形状
の窪みが複数形成された陽イオン交換膜の前記重金属を
プロトンに置換してなる電解質膜。6. An electrolyte membrane used in a polymer electrolyte fuel cell, wherein protons of a cation exchange membrane are replaced with heavy metals, and at least one surface of the substituted cation exchange membrane is irradiated with radiation. An electrolyte membrane formed by forming a plurality of recesses of a predetermined shape on the surface, and replacing the heavy metal of the cation exchange membrane having the plurality of recesses of the predetermined shape with protons.
質膜であって、 強酸性陽イオン交換膜により形成され、 該強酸性陽イオン交換膜の少なくとも一方の面に１０-6
ｍのオーダーの所定形状の窪みを複数備える電解質膜。7. An electrolyte membrane used for a polymer electrolyte fuel cell, which is formed by a strongly acidic cation exchange membrane, wherein at least one surface of the strongly acidic cation exchange membrane is 10 -6.
An electrolyte membrane having a plurality of depressions of a predetermined shape on the order of m.
状の窪みが形成された近傍表面にイオン交換に寄与する
官能基が配置されてなる請求項７記載の電解質膜。8. The electrolyte membrane according to claim 7, wherein a functional group contributing to ion exchange is arranged on a surface of the strongly acidic cation exchange membrane where the depression of the predetermined shape is formed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05057999A JP4337162B2 (en) | 1999-02-26 | 1999-02-26 | Method for producing electrolyte membrane for polymer electrolyte fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05057999A JP4337162B2 (en) | 1999-02-26 | 1999-02-26 | Method for producing electrolyte membrane for polymer electrolyte fuel cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000251905A true JP2000251905A (en) | 2000-09-14 |
| JP4337162B2 JP4337162B2 (en) | 2009-09-30 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP05057999A Expired - Fee Related JP4337162B2 (en) | 1999-02-26 | 1999-02-26 | Method for producing electrolyte membrane for polymer electrolyte fuel cell |
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| Country | Link |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003068327A (en) * | 2001-08-28 | 2003-03-07 | Kanegafuchi Chem Ind Co Ltd | Film for fuel cell |
| JP2005085544A (en) * | 2003-09-05 | 2005-03-31 | Toyota Central Res & Dev Lab Inc | Polyelectrolyte membrane and membrane electrode assembly |
| JP2005174565A (en) * | 2003-12-08 | 2005-06-30 | Hitachi Ltd | Polymer electrolyte membrane for fuel cell, membrane/electrode joint body, its manufacturing method, and fuel cell using it |
| WO2007083229A2 (en) * | 2006-01-20 | 2007-07-26 | Toyota Jidosha Kabushiki Kaisha | Membrane electrode assembly and polymer electrolyte membrane fuel cell containing the same |
| WO2009145568A2 (en) | 2008-05-28 | 2009-12-03 | 주식회사 엘지화학 | Method for manufacturing a polymer electrolyte membrane for fuel cell, membrane electrode assembly, and polymer electrolyte membrane type fuel cell |
| JP2018098190A (en) * | 2016-12-13 | 2018-06-21 | 現代自動車株式会社Ｈｙｕｎｄａｉ Ｍｏｔｏｒ Ｃｏｍｐａｎｙ | Membrane-electrode assembly for fuel battery and method for manufacturing the same |
-
1999
- 1999-02-26 JP JP05057999A patent/JP4337162B2/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003068327A (en) * | 2001-08-28 | 2003-03-07 | Kanegafuchi Chem Ind Co Ltd | Film for fuel cell |
| JP2005085544A (en) * | 2003-09-05 | 2005-03-31 | Toyota Central Res & Dev Lab Inc | Polyelectrolyte membrane and membrane electrode assembly |
| JP4576813B2 (en) * | 2003-09-05 | 2010-11-10 | 株式会社豊田中央研究所 | Polymer electrolyte membrane and membrane electrode assembly |
| JP2005174565A (en) * | 2003-12-08 | 2005-06-30 | Hitachi Ltd | Polymer electrolyte membrane for fuel cell, membrane/electrode joint body, its manufacturing method, and fuel cell using it |
| WO2007083229A2 (en) * | 2006-01-20 | 2007-07-26 | Toyota Jidosha Kabushiki Kaisha | Membrane electrode assembly and polymer electrolyte membrane fuel cell containing the same |
| WO2007083229A3 (en) * | 2006-01-20 | 2008-01-17 | Toyota Motor Co Ltd | Membrane electrode assembly and polymer electrolyte membrane fuel cell containing the same |
| US8187765B2 (en) | 2006-01-20 | 2012-05-29 | Toyota Jidosha Kabushiki Kaisha | Membrane electrode assembly and polymer electrolyte membrane fuel cell |
| WO2009145568A2 (en) | 2008-05-28 | 2009-12-03 | 주식회사 엘지화학 | Method for manufacturing a polymer electrolyte membrane for fuel cell, membrane electrode assembly, and polymer electrolyte membrane type fuel cell |
| JP2018098190A (en) * | 2016-12-13 | 2018-06-21 | 現代自動車株式会社Ｈｙｕｎｄａｉ Ｍｏｔｏｒ Ｃｏｍｐａｎｙ | Membrane-electrode assembly for fuel battery and method for manufacturing the same |
| JP7122816B2 (en) | 2016-12-13 | 2022-08-22 | 現代自動車株式会社 | MEMBRANE ELECTRODE ASSEMBLY FOR FUEL CELL AND MANUFACTURING METHOD THEREOF |
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| Publication number | Publication date |
|---|---|
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