JP3504021B2 - Electrode for electrochemical device and method for producing the same - Google Patents
Electrode for electrochemical device and method for producing the sameInfo
- Publication number
- JP3504021B2 JP3504021B2 JP12155695A JP12155695A JP3504021B2 JP 3504021 B2 JP3504021 B2 JP 3504021B2 JP 12155695 A JP12155695 A JP 12155695A JP 12155695 A JP12155695 A JP 12155695A JP 3504021 B2 JP3504021 B2 JP 3504021B2
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- film
- catalyst
- current collector
- electrochemical device
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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
Description
【０００１】[0001]
【産業上の利用分野】本発明は高分子固体電解質を用い
た電気化学装置、例えば、高分子固体電解質燃料電池、
水電解装置、オゾン発生器等に使用される電極と、その
製造方法に関わる。TECHNICAL FIELD The present invention relates to an electrochemical device using a polymer solid electrolyte, for example, a polymer solid electrolyte fuel cell,
The present invention relates to electrodes used in water electrolysis devices, ozone generators, and the like, and manufacturing methods thereof.
【０００２】[0002]
【従来の技術】従来高分子固体電解質を用いた電気化学
装置用電極として下記の方法で作成した電極が提案され
ている。
（１）ポリテトラフルオロエチレン（以下、ＰＴＦＥと
略す。）や高分子固体電解質をバインダーとして触媒物
質を高分子固体電解質膜上にホットプレスして電極を形
成する。2. Description of the Related Art Conventionally, an electrode prepared by the following method has been proposed as an electrode for an electrochemical device using a polymer solid electrolyte. (1) A catalyst material is hot-pressed on a polymer solid electrolyte membrane using polytetrafluoroethylene (hereinafter abbreviated as PTFE) or polymer solid electrolyte as a binder to form an electrode.
【０００３】（２）ＰＴＦＥディスパージョンと触媒物
質、あるいは、高分子固体電解質の溶液と触媒物質又は
その前駆物質とを混合したペースト状あるいはインク状
液を高分子固体電解質膜に塗布、乾燥、加熱して形成す
るか、ペースト状あるいはインク状液から溶媒を除去し
て膜状としこれを高分子固体電解質膜に転写、ホットプ
レスする。(2) A paste-like or ink-like liquid obtained by mixing a PTFE dispersion and a catalyst substance or a solution of a polymer solid electrolyte and a catalyst substance or a precursor thereof is applied to a polymer solid electrolyte membrane, dried and heated. Or a solvent is removed from the paste-like or ink-like liquid to form a film, which is transferred to the polymer solid electrolyte film and hot pressed.
【０００４】（３）集電体上に触媒層を形成しこれを高
分子固体電解質膜にホットプレスする。
（４）ＰＴＦＥと触媒物質からシート状の電極を形成し
これを高分子固体電解質膜にホットプレスするか、高分
子固体電解質溶液を表面に塗布した後、これをバインダ
ーとして高分子固体電解質膜にホットプレスする。(3) A catalyst layer is formed on the current collector and hot pressed onto the polymer solid electrolyte membrane. (4) A sheet-shaped electrode is formed from PTFE and a catalyst substance and hot-pressed onto the polymer solid electrolyte membrane, or a polymer solid electrolyte solution is applied to the surface, and then this is used as a binder to form the polymer solid electrolyte membrane. Hot press.
【０００５】[0005]
【発明が解決しようとする課題】上記の方法が提案され
ているが、しかしこれらの方法は反応界面が二次元的で
十分な反応の場が確保されなかったり、全体が親水性と
なり反応ガスの供給が確保できなかったり、触媒量が十
分確保できなかったりするという問題があった。また、
本出願人は特開平２−８５３８７号公報にて、フッ素含
有重合体バインダと電気化学的機能性材料粉末とからな
る連続多孔体の一表面から気孔内へ向ってイオン交換樹
脂又はそれと金属との混合物を分布させたイオン交換樹
脂含有シート状電極材料を提案したが、燃料電池用とし
ては性能が十分でない。The above methods have been proposed. However, these methods have a two-dimensional reaction interface and cannot secure a sufficient reaction field, or the whole becomes hydrophilic and the reaction gas becomes There was a problem that the supply could not be secured or the catalyst amount could not be secured sufficiently. Also,
The applicant of the present invention discloses in Japanese Patent Application Laid-Open No. 2-85387 that an ion exchange resin or a metal and an ion exchange resin are formed from one surface of a continuous porous body composed of a fluorine-containing polymer binder and an electrochemically functional material powder into pores Although a sheet-shaped electrode material containing an ion exchange resin in which a mixture is distributed has been proposed, its performance is not sufficient for a fuel cell.
【０００６】本発明はこれらの問題点を解決し、上記三
相界面反応帯を三次元的に十分確保し、また塗布基材が
例えばカーボンペーパーの様な表面の凹凸のあるもので
も再現性良く均一な触媒層を形成でき、かつ触媒層自体
が十分な機械的強度を有しながら空孔率も高くでき従っ
てガス拡散性がよく、生成イオンの移動も速やかに行わ
れる反応性の高い触媒層を形成できるとともに、この成
形と同時に集（給）電体との接着も同時に行うことので
きるものを提供することを目的とする。The present invention solves these problems, secures the three-phase interfacial reaction zone three-dimensionally, and has good reproducibility even when the coated substrate has surface irregularities such as carbon paper. A highly reactive catalyst layer capable of forming a uniform catalyst layer, having a sufficient mechanical strength of the catalyst layer itself, and having a high porosity, and thus having a good gas diffusibility and rapidly transferring generated ions. It is an object of the present invention to provide a material which can be formed at the same time and can be bonded to a current collector (electrical power supply) simultaneously with this molding.
【０００７】[0007]
【課題を解決するための手段】上記目的を達成するため
に、本発明によれば、延伸多孔質ポリテトラフルオロエ
チレン（以下、ＥＰＴＦＥと略す。）の空隙部に少なく
とも高分子固体電解質樹脂と触媒を含む成分を充填して
成る触媒層を有する電極、及び集（給）電体またはガス
拡散層材料面上にＥＰＴＦＥの空隙に少なくとも高分子
固体電解質樹脂（以下、ＳＰＥと略す。）と触媒を含む
成分が充填された触媒層が一体に成形されている電極を
提供する。In order to achieve the above object, according to the present invention, at least a polymer solid electrolyte resin and a catalyst are provided in the voids of expanded porous polytetrafluoroethylene (hereinafter abbreviated as EPTFE). An electrode having a catalyst layer filled with a component containing, and a polymer solid electrolyte resin (hereinafter abbreviated as SPE) and a catalyst in the voids of EPTFE on the surface of the material of the current collector (current collector) or the gas diffusion layer. Provided is an electrode in which a catalyst layer filled with a component including the component is integrally molded.
【０００８】また、このような電極を製造する好適な方
法として、ＥＰＴＦＥフィルムの空隙に、少なくとも高
分子固体電解質樹脂と触媒とを含むインク状溶液を含浸
した後、集（給）電体材料またはガス拡散層材料面上に
これを固定し、溶媒を除去することを特徴とする電気化
学装置用電極の製造方法、及び集（給）電体材料または
ガス拡散層材料面上にＥＰＴＦＥフィルムを固定した後
その表面に少なくとも高分子固体電解質樹脂と触媒を含
むインク状溶液を塗布することにより、ＥＰＴＦＥフィ
ルムの空隙部に該インク状成分を含浸し、引き続いて溶
媒成分を除去することにより、インク状成分をＥＰＴＦ
Ｅフィルム内部に固定すると共に集（給）電体材料また
はガス拡散層材料との接着を行い、一体に成形すること
を特徴とする電気化学装置用電極の製造方法を提供す
る。Further, as a preferred method for producing such an electrode, after impregnating the voids of the EPTFE film with an ink-like solution containing at least a polymer solid electrolyte resin and a catalyst, A method for manufacturing an electrode for an electrochemical device, which comprises fixing the gas diffusion layer on the material surface and removing the solvent, and fixing an EPTFE film on the current collector (supply) material or the gas diffusion layer material surface. After that, the ink-like solution containing at least the solid polymer electrolyte resin and the catalyst is applied to the surface of the EPTFE film to impregnate the ink-like component with the ink-like component, and subsequently the solvent component is removed to form the ink-like solution. Ingredients EPTF
Provided is a method for manufacturing an electrode for an electrochemical device, which comprises fixing the inside of an E film and adhering it to a current collector material or a gas diffusion layer material to integrally form the electrode.
【０００９】本発明で使用されるＥＰＴＦＥとは特公昭
５１−１８９９１号公報に記載されるようなものであ
り、無数のＰＴＦＥの微小結節とこれらを相互に連結す
るＰＴＦＥ微細繊維から成る三次元的網目構造物であ
る。その物性、構造は製造条件により制御可能である。
本発明に適したＥＰＴＦＥの物性、構造としては、膜厚
３〜２００μｍ、空隙率６０％以上、孔径がＥＢＰ値
（ＡＳＴＭ；Ｆ−３１６−８６に記載の方法であり、最
大孔径の目安となるが、ＥＰＴＦＥはフィブリル構造の
為最大孔径をそのまま算出するものではない。）で０．
５kg／cm2 以下である。最適な膜厚は必要な触媒量及び
要求特性により変化するが、３μｍ未満では必要な触媒
量を確保するのが困難でありまた十分な三次元的反応の
場を確保できない。２００μｍ超ではガス拡散性、イオ
ン伝導性に支障があり、触媒が十分機能しない。空孔率
が６０％未満では相対的にＰＴＦＥ量が多くなり、抵抗
値が十分低く成らず、また充填できる触媒量も少なくな
ってしまう。孔径がＥＢＰ値で０．５kg／cm2 超では孔
径が小さすぎて触媒粒子を膜内空隙部に充填することが
困難である。また、できるだけ微小結節部の小さい構
造、可能ならば微小繊維のみからなる構造が好ましいが
これに限定されない。この様なＥＰＴＦＥフィルムを使
用することによりはじめてその空隙部にＳＰＥ及び触媒
成分を含む材料を充填することが可能となるとともに必
要な触媒量、ガス拡散性、導電性（イオン及び電子）を
確保でき、したがって優れた電極として機能できるとと
もに、ＥＰＴＦＥフィブリルネットによる補強効果、及
びＥＰＴＦＥのマトリクス効果により、均一な触媒層を
再現性良く得ることができる。The EPTFE used in the present invention is as described in JP-B-51-18991, and it is a three-dimensional structure composed of innumerable PTFE micro-nodules and PTFE fine fibers interconnecting these micro-nodules. It is a mesh structure. Its physical properties and structure can be controlled by the manufacturing conditions.
As physical properties and structure of EPTFE suitable for the present invention, the film thickness is 3 to 200 μm, the porosity is 60% or more, and the pore diameter is a method described in EBP value (ASTM; F-316-86, which is a standard for the maximum pore diameter. However, EPTFE does not calculate the maximum pore size as it is because of the fibril structure.)
It is 5 kg / cm 2 or less. The optimum film thickness varies depending on the required amount of catalyst and the required characteristics, but if it is less than 3 μm, it is difficult to secure the required amount of catalyst, and a sufficient three-dimensional reaction field cannot be secured. If it exceeds 200 μm, gas diffusivity and ionic conductivity are impaired, and the catalyst does not function sufficiently. If the porosity is less than 60%, the amount of PTFE will be relatively large, the resistance value will not be sufficiently low, and the amount of catalyst that can be filled will also be small. If the pore size is more than 0.5 kg / cm 2 in terms of EBP value, the pore size is too small and it is difficult to fill the catalyst particles into the intramembrane space. Further, a structure having as small a micro-nodule portion as possible, if possible, a structure consisting of only fine fibers is preferable, but the structure is not limited to this. Only by using such an EPTFE film, it becomes possible to fill the voids with a material containing SPE and a catalyst component and to secure the required amount of catalyst, gas diffusivity, and conductivity (ions and electrons). Therefore, it can function as an excellent electrode, and a uniform catalyst layer can be obtained with good reproducibility due to the reinforcing effect of EPTFE fibril net and the matrix effect of EPTFE.
【００１０】またこのＥＰＴＦＥとして、その材料肉質
に導電性材料、例えばカーボンブラック、黒鉛粉末、白
金をコートしたチタン粉末、等を含んでいても良い。も
ちろんこの粉末が触媒そのもの、または触媒を担持した
ものでも良い。この様に材料肉質にこれらの微粉末を含
むＥＰＴＦＥを作成するには、ＰＴＦＥのディスパージ
ョンにこれら粉末を分散させた分散液を混合後、共凝集
させた後水分を除去し、粉砕して粉末状にした材料を用
意し、これをＰＴＦＥの材料と同様に特公昭５１−１８
９９１号公報に開示の方法に準じて加工して得ることが
できる。The EPTFE may contain a conductive material such as carbon black, graphite powder, platinum-coated titanium powder, etc. in its material quality. Of course, this powder may be the catalyst itself, or the one carrying the catalyst. In this way, in order to prepare EPTFE containing these fine powders in the material meat, a dispersion liquid in which these powders are dispersed is mixed with PTFE, co-aggregated, water is removed, and the powder is pulverized. Prepared in the form of a sheet, which is prepared in the same manner as the PTFE material.
It can be obtained by processing according to the method disclosed in Japanese Patent Publication No. 991.
【００１１】ＥＰＴＦＥの空隙部への少なくとも高分子
固体電解質樹脂と触媒を含む成分の充填は、これら成分
を含む混合溶液をＥＰＴＦＥ空隙部に含浸した後、溶媒
を除去することにより行われる。この溶液の溶媒として
は、水＋界面活性剤、有機溶剤等またはこれらの混合溶
剤が使用されるが、高分子固体電解質樹脂が溶解できる
かまたは安定して分散していられるものである必要があ
る。The filling of the components containing at least the polymer solid electrolyte resin and the catalyst into the voids of EPTFE is carried out by impregnating the EPTFE voids with a mixed solution containing these components and then removing the solvent. As the solvent of this solution, water + surfactant, organic solvent or the like or a mixed solvent thereof is used, but it is necessary that the solid polymer electrolyte resin can be dissolved or stably dispersed. .
【００１２】高分子固体電解質樹脂としては、炭化水素
系またはフッ素系のイオン交換樹脂が任意に使用し得る
が、最適にはパーフロロカーボン系のイオン交換樹脂、
特にパーフロロスルフォン酸樹脂が好ましい。この樹脂
は例えば米国デュポン社より「ナフィオン」の商標で入
手できる。またこの樹脂の溶液の溶媒は各種アルコール
類を中心とする有機溶剤またはこれと水との混合溶媒が
使用される。As the polymer solid electrolyte resin, a hydrocarbon type or fluorine type ion exchange resin can be optionally used, but the most preferable is a perfluorocarbon type ion exchange resin,
Perfluorosulphonic acid resin is particularly preferable. This resin is available, for example, from DuPont, USA under the trademark "Nafion". Further, as a solvent for the resin solution, an organic solvent mainly containing various alcohols or a mixed solvent of this and water is used.
【００１３】触媒は、電極触媒として作用する任意の粉
末が用途に合わせて使用し得る。例えばオゾン発生電極
では二酸化鉛、水電解電極では白金または白金属金属合
金、燃料電池では白金または白金合金担持カーボンブラ
ック等である。この触媒粉末と高分子固体電解質樹脂と
の混合溶液は、上記溶媒に触媒粉末を分散させた後、高
分子固体電解質樹脂溶液を加えることにより作製でき
る、さらに場合によっては、ＰＴＦＥディスパージョン
またはＦＥＰディスパージョン等を加えることにより撥
水性を強化したり、重炭酸アンモニウム、食塩、炭酸カ
ルシウム等の造孔剤を加え成形後に除去することにより
孔を作り、ガス拡散性をさらに高めるようにしても良
い。As the catalyst, any powder that acts as an electrocatalyst can be used depending on the application. For example, the ozone generating electrode is lead dioxide, the water electrolysis electrode is platinum or a platinum metal alloy, and the fuel cell is platinum or a platinum alloy-carrying carbon black. The mixed solution of the catalyst powder and the polymer solid electrolyte resin can be prepared by dispersing the catalyst powder in the above solvent and then adding the polymer solid electrolyte resin solution. In some cases, the PTFE dispersion or the FEP dispersion is used. The water repellency may be enhanced by adding John or the like, or pores may be formed by adding a pore-forming agent such as ammonium bicarbonate, sodium chloride, calcium carbonate or the like after molding to further enhance the gas diffusibility.
【００１４】この溶液をＥＰＴＦＥに含浸するには、こ
の溶液中に単にＥＰＴＦＥフィルムを浸漬することによ
り行ってもよく、またはさらに超音波を作用させたり、
機械的にもみ込むような力を作用させることにより行っ
てもよい。また単にフィルム表面に塗布することにより
行うこともできる。またこれをさらにロール等に通すこ
とにより機械的にＥＰＴＦＥフィルム中に押し込むよう
にしてもよい。The impregnation of EPTFE with this solution may be carried out by simply dipping the EPTFE film in this solution, or by further applying ultrasonic waves,
It may be performed by applying a force that mechanically entraps it. It can also be carried out by simply coating the film surface. Further, it may be mechanically pushed into the EPTFE film by further passing it through a roll or the like.
【００１５】この触媒と高分子固体電解質樹脂溶液を混
合し含浸、溶媒除去による固化の操作により、触媒を高
分子固体電解質樹脂で被覆するとともに、高分子固体電
解質樹脂が触媒粒子同士を結着させ、またＥＰＴＦＥフ
ィルムの内部網目構造上に触媒を固定するバインダーの
役を果たし、更に触媒粒子上で生成されるイオンを速や
かに高分子固体電解質膜まで移動させる通路を形成す
る。The catalyst and the solid polymer electrolyte resin solution are mixed, impregnated, and solidified by removing the solvent to coat the catalyst with the solid polymer electrolyte resin, and the solid polymer electrolyte resin binds the catalyst particles together. Also, it serves as a binder for fixing the catalyst on the internal network structure of the EPTFE film, and further forms a path for rapidly moving the ions generated on the catalyst particles to the polymer solid electrolyte membrane.
【００１６】本発明によれば、触媒層の機械的強度はＥ
ＰＴＦＥフィルムマトリクスによるため、必要最小限の
高分子固体電解質樹脂により、機械的に安定した触媒層
を形成でき、そのため過剰な高分子固体電解質樹脂によ
るガス拡散性の阻害を防止できる。さらにこの混合溶液
から溶媒が除去される際には、固形成分が凝集し、体積
が小さくなるが、本発明によれば、ＥＰＴＦＥのフィブ
リルマトリクスにより凝集力が分散されるため、凝集収
縮時に、体積収縮、または溶媒容積分が、そのまま微細
空隙を形成することになりガス拡散性の良い構造とな
る。また高分子固体電解質樹脂そのものは連続している
ため、イオンの移動はスムースに行われ、結果として優
れた電極性能を提供する。According to the present invention, the mechanical strength of the catalyst layer is E
Since it is based on the PTFE film matrix, a mechanically stable catalyst layer can be formed with the minimum necessary amount of the polymer solid electrolyte resin, so that the gas diffusion property can be prevented from being hindered by the excess polymer solid electrolyte resin. Furthermore, when the solvent is removed from this mixed solution, the solid component aggregates and the volume becomes smaller. However, according to the present invention, the cohesive force is dispersed by the fibril matrix of EPTFE. The contraction or the volume of the solvent forms fine voids as it is, and the structure has good gas diffusibility. Further, since the solid polymer electrolyte resin itself is continuous, ions are smoothly transferred, and as a result, excellent electrode performance is provided.
【００１７】以上の説明でわかる通り本発明によれば電
極触媒層のみを得ることができるが、本発明ではさらに
集（給）電体との接合も同時に行ってもよい。この集
（給）電体と一体に成形する場合、上記の含浸を行った
後、まだ溶媒を除去しないうちに後述するような集
（給）電体またはガス拡散層材料面上に固定した後、溶
媒を風乾等により除去することにより、溶媒及び高分子
固体電解質樹脂の凝集力により、高分子固体電解質樹脂
をバインダーとして、接合、一体化する。別の一体化成
形方法としては、集（給）電体またはガス拡散層材料面
上にＥＰＴＦＥフィルムを固定した後、前述の混合溶液
を塗布するか、またはさらにこれをロール等に通すこと
によりＥＰＴＦＥの空隙中に溶液を含浸した後風乾等に
より溶媒を除去し、接合、一体化することもできる。As can be seen from the above description, according to the present invention, only the electrode catalyst layer can be obtained, but according to the present invention, the electrode catalyst layer may be further joined to the current collector. In the case of integrally molding with this current collector, after performing the above-mentioned impregnation, after fixing the solvent (current collector) or the gas diffusion layer material surface as described below before removing the solvent. By removing the solvent by air-drying or the like, the solid polymer electrolyte resin is used as a binder for bonding and integration due to the cohesive force of the solvent and the polymer solid electrolyte resin. As another integral molding method, after fixing the EPTFE film on the material surface of the current collector or the gas diffusion layer, the above-mentioned mixed solution is applied, or the EPTFE film is passed through a roll etc. After the solution is impregnated into the voids, the solvent can be removed by air-drying or the like to join and integrate them.
【００１８】以上の何れの方法においても、高分子固体
電解質樹脂の種類によって、最終的に加熱等の手段によ
り、樹脂を安定化する必要のある場合もある。一般に、
本発明の電極の用途では、触媒層のみで電極として機能
させることは少なく、多くの場合集電体または給電体と
ともに用いられ、特に燃料電池の場合、さらに、その間
に導電性の撥水性ガス拡散層が設けられることも多い。In any of the above methods, it may be necessary to finally stabilize the resin by means such as heating depending on the type of the polymer solid electrolyte resin. In general,
In the use of the electrode of the present invention, the catalyst layer alone rarely functions as an electrode and is often used in combination with a current collector or a power supply. Layers are often provided.
【００１９】集（給）電体としては、ニッケル、チタ
ン、銅、ステンレス等のメッシュまたはエクスパンドメ
ッシュ、あるいはこれらメタルメッシュに金や白金族の
メッキまたはコーティングしたもの、ポーラスカーボン
またはグラファイト、カーボンペーパー等が使用され
る。また、撥水性ガス拡散層としては上記集（給）電体
の材料と同様のものをＰＴＦＥで撥水処理したものや、
ＰＴＦＥとカーボンブラックまたは黒鉛等の導電性粉末
を混ぜ合わせて上記集（給）電体にプレス等により一体
に成形したもの、ペースト状にして塗布し、乾燥焼成し
て成形したもの、混練してシート状に成形したもの、さ
らにこれを延伸してより多孔度を上げたもの等がある。As the current collector, a mesh or expanded mesh of nickel, titanium, copper, stainless steel or the like, or a metal mesh of which gold or platinum group is plated or coated, porous carbon or graphite, carbon paper, etc. Is used. Further, as the water-repellent gas diffusion layer, the same material as the material of the above-mentioned current collector (power supply) treated with PTFE for water repellency,
A mixture of PTFE and a conductive powder such as carbon black or graphite, which is integrally formed on the above-mentioned current collector by pressing or the like, a paste which is applied and dried and fired, and kneaded There are a sheet-shaped product and a product obtained by stretching this to further increase the porosity.
【００２０】以上の如き本発明の電気化学装置用電極を
各種の電気化学装置に使用する仕方は、本発明の電極を
用いる以外従来と同様であることができる。図２に燃料
電池の例を示す。図２中、２１は高分子固体電解質、２
２，２３は電極、２４，２５は集（給）電体、２６，２
７はセパレータ板、２８，２９はガス供給溝である。必
要に応じて本発明の電極は集（給）電体との接合体、あ
るいは高分子固体電解質２１／電極２２の接合体又は電
極２２／高分子固体電解質２１／電極２３の接合体とし
て使用することができる。The method of using the electrode for electrochemical device of the present invention as described above in various electrochemical devices can be the same as the conventional method except that the electrode of the present invention is used. FIG. 2 shows an example of the fuel cell. In FIG. 2, 21 is a polymer solid electrolyte, 2
2 and 23 are electrodes, 24 and 25 are current collectors, 26 and 2
7 is a separator plate, and 28 and 29 are gas supply grooves. If necessary, the electrode of the present invention is used as a joint body with a current collector, a polymer solid electrolyte 21 / electrode 22 joint body, or an electrode 22 / polymer solid electrolyte 21 / electrode 23 joint body. be able to.
【００２１】こうして構成された高分子固体電解質燃料
電池では、図２を参照すると、ガス供給溝２８にＯ2 を
溝２９にＨ2 を供給すると、電極２２内でＯ2 ＋４Ｈ+
＋４ｅ- →２Ｈ2 Ｏ、電極２３内で２Ｈ2 →４Ｈ+ ＋４
ｅ- の反応が起こり、４Ｈ+は高分子固体電解質２１を
通って電極２３から電極２２へ流れ、４ｅ- は外部負荷
を通ることにより電気エネルギーとなる。作動温度は６
０℃から１００℃程度、好ましくは８０℃程度である。In the solid polymer electrolyte fuel cell thus constructed, referring to FIG. 2, when O 2 is supplied to the gas supply groove 28 and H 2 is supplied to the groove 29, O 2 + 4H + is generated in the electrode 22.
+ 4e − → 2H 2 O, 2H 2 → 4H + +4 in the electrode 23
The reaction of e − occurs, 4H + flows from the electrode 23 to the electrode 22 through the solid polymer electrolyte 21, and 4e − becomes electric energy by passing through an external load. Operating temperature is 6
It is about 0 ° C to 100 ° C, preferably about 80 ° C.
【００２２】なお、本発明の電極は高分子固体電解質燃
料電池のほか、水電解装置やオゾン発生器などにも使用
できる。The electrode of the present invention can be used not only in a polymer electrolyte fuel cell but also in a water electrolysis device, an ozone generator, and the like.
【００２３】[0023]
実施例１
膜厚１２μｍ、空隙率９３％、ＥＢＰ０．０８kg／cm2
のＥＰＴＦＥフィルムを用意した。これとは別に、二酸
化鉛微粉末をイソプロピルアルコール（ＩＰＡ）に分散
させた後これにパーフロロスルフォン酸樹脂溶液を二酸
化鉛８５％に対し樹脂分が１５％の割合となるように加
え、よく混合して混合液を得た。次に、図１の様に、２
本の金属ロール１１，１２間に支持フィルム１３上に前
記ＥＰＴＦＥフィルム１４を重ねて通し、上記の混合液
１５を供給することにより、ＥＰＴＦＥフィルム空隙に
この混合液を含浸した後風乾により溶媒を除去しさらに
支持フィルム１３を除去して本発明の電極１を得た。図
中、１６はドクターブレードである。Example 1 Film thickness 12 μm, porosity 93%, EBP 0.08 kg / cm 2
EPTFE film was prepared. Separately from this, fine powder of lead dioxide was dispersed in isopropyl alcohol (IPA), and then a solution of perfluorosulphonic acid resin was added to 85% of lead dioxide at a resin content of 15% and mixed well. A mixed solution was obtained. Next, as shown in Fig. 1, 2
The EPTFE film 14 is superposed on the support film 13 between the metal rolls 11 and 12 of the book, and the mixed solution 15 is supplied to impregnate the EPTFE film voids with the mixed solution and remove the solvent by air drying. Then, the supporting film 13 was removed to obtain the electrode 1 of the present invention. In the figure, 16 is a doctor blade.
【００２４】また厚さ２００μｍのカーボンペーパーの
表面に前記のＥＰＴＦＥフィルムと同じフィルムを固定
した後、その表面に、白金２０wt％担持したカーボンブ
ラックをＩＰＡに分散させた後これにパーフロロスルフ
ォン酸樹脂溶液を、白金担持カーボンブラック６０％に
対し樹脂分４０％となるように混合した後さらに超音波
を作用させてよく分散させた混合液を塗布することによ
り、ＥＰＴＦＥフィルム空隙中にこの混合液を含浸さ
せ、その後溶媒を除去して本発明の電極２を得た。Further, after fixing the same film as the above-mentioned EPTFE film on the surface of carbon paper having a thickness of 200 μm, carbon black carrying 20 wt% of platinum was dispersed in IPA on the surface, and then perfluorosulphonic acid resin was added thereto. The solution was mixed so that the resin content was 40% with respect to 60% of platinum-carrying carbon black, and then the mixed solution that was well dispersed by applying ultrasonic waves was applied to the mixed solution in the EPTFE film voids. After impregnation, the solvent was removed to obtain the electrode 2 of the present invention.
【００２５】つぎに、本発明の電極１／パーフロロスル
フォン酸樹脂膜（米デュポン社製：ナフィオン＃１１
７）／本発明の電極２、の順に重ねて１４０℃でヒート
プレスして一体化することにより膜−電極接合体を作製
した。この接合体の電極１の面に白金メッキチタンメッ
シュを当てた後、両面をリブつきの白金メッキステンレ
ス製のセルプレートではさみ、リブ部に純水を供給し、
電極１を陽極、電極２を陰極として、ＳＰＥ水電解によ
るオゾン発生器として作動させたところ、陽極よりオゾ
ン、陰極より水素の発生するのが確認できた。Next, the electrode 1 / perfluorosulphonic acid resin film of the present invention (manufactured by DuPont, USA: Nafion # 11)
7) / The electrode 2 of the present invention was laminated in this order and heat-pressed at 140 ° C. to integrate the membrane-electrode assembly. After applying a platinum-plated titanium mesh to the surface of the electrode 1 of this joined body, sandwich both sides with a cell plate made of platinum-plated stainless steel with ribs, and supply pure water to the ribs.
When the electrode 1 was used as an anode and the electrode 2 was used as a cathode and operated as an ozone generator by SPE water electrolysis, it was confirmed that ozone was generated from the anode and hydrogen was generated from the cathode.
【００２６】実施例２
白金２５wt％担持カーボンブラックをＩＰＡに分散させ
た後、パーフロロスルフォン酸樹脂溶液を、白金担持カ
ーボンブラック７５％、樹脂２５％の比率で加えて混合
した後、さらに超音波を作用させて、よく分散させて混
合溶液Ｃを用意した。Example 2 Platinum 25 wt% supported carbon black was dispersed in IPA, and then a perfluororosulphonic acid resin solution was added and mixed at a ratio of 75% platinum supported carbon black and 25% resin, and further ultrasonic waves were added. And mixed well to prepare a mixed solution C.
【００２７】次に、ＰＴＦＥにより撥水処理した膜厚２
３０μｍのカーボンペーパー面上に膜厚１６μｍ、空隙
率９４％、ＥＢＰ０．１２kg／cm2 のＥＰＴＦＥフィル
ムを固定した後、上記混合溶液Ｃを塗布することにより
ＥＰＴＦＥフィルム空隙中に含浸し、溶媒を風乾した後
１２０℃２４時間加熱して本発明の電極３を得た。続い
て、さらにこの表面にＥＰＴＦＥフィルムを固定した
後、パーフロロスルフォン酸樹脂溶液をその表面に塗布
し、風乾した。この塗布−風乾を３回繰り返して、膜／
電極接合体３′を得た。Next, the film thickness 2 which was made water repellent by PTFE
After fixing an EPTFE film having a film thickness of 16 μm, a porosity of 94% and an EBP of 0.12 kg / cm 2 on a carbon paper of 30 μm, the mixed solution C is applied to impregnate the EPTFE film into the voids and air-dry the solvent. After that, the electrode 3 of the present invention was obtained by heating at 120 ° C. for 24 hours. Then, after further fixing the EPTFE film on this surface, a perfluorosulphonic acid resin solution was applied to the surface and air-dried. This application-air drying was repeated 3 times to obtain a film /
An electrode assembly 3'was obtained.
【００２８】これとは別に、カーボンブラック６０％、
ＰＴＦＥ４０％からなり、膜厚６０μｍ、密度０．５１
ｇ／cm3 の、一軸延伸ＥＰＴＦＥフィルムを圧縮して得
た、撥水性導電性多孔質フィルムを用意した。このフィ
ルムを、やはりＰＴＦＥにより撥水処理したカーボンペ
ーパーにプレスすることにより一体化した後、３５０℃
に加熱して接合させた。この接合物の撥水導電性多孔質
フィルムの表面に、膜厚２０μｍ、空隙率９３％、ＥＢ
Ｐ０．１５kg／cm2 のＥＰＴＦＥフィルムを固定した
後、混合溶液Ｃをその表面に塗布して、このＥＰＴＦＥ
フィルム空隙中に含浸し引き続いて乾燥することにより
溶媒を除去して、本発明の電極４を得た。さらに、膜電
極接合体３′を得たのと同じようにして、膜／電極接合
体４′を得た。Apart from this, carbon black 60%,
Consisting of 40% PTFE, film thickness 60 μm, density 0.51
A water-repellent conductive porous film obtained by compressing a g / cm 3 uniaxially stretched EPTFE film was prepared. After this film was integrated by pressing it on carbon paper which was also treated with PTFE to make it water-repellent, 350 ° C
It was heated to bond. On the surface of the water-repellent conductive porous film of this bonded product, the film thickness was 20 μm, the porosity was 93%, and the EB was formed.
After fixing the EPTFE film of P0.15 kg / cm 2 , the mixed solution C was applied to the surface of the EPTFE film,
The solvent was removed by impregnating into the voids of the film, followed by drying to obtain the electrode 4 of the present invention. Further, a membrane / electrode assembly 4'was obtained in the same manner as the membrane electrode assembly 3'was obtained.
【００２９】次に、膜／電極接合体４′の表面にさらに
パーフロロスルフォン酸樹脂溶液を塗布した後、膜／電
極接合体４′と膜／電極接合体３′とを膜面が向かい合
うようにして、間に気泡が入らない様、注意しながら圧
着し、溶媒を風乾により除去した後、１３０℃２４時間
加熱して、樹脂を安定化させて、高分子固体電解質タイ
プ燃料電池の電極／膜／電極接合体を作製した。Next, after perfluorosulphonic acid resin solution is applied to the surface of the membrane / electrode assembly 4 ', the membrane / electrode assembly 4'and the membrane / electrode assembly 3'are made to face each other. Then, pressure-bonding should be done carefully so that air bubbles do not enter between them, and after removing the solvent by air-drying, heating at 130 ° C for 24 hours stabilizes the resin, and the solid polymer electrolyte type fuel cell electrode / A membrane / electrode assembly was prepared.
【００３０】この接合体の、電極３側に加湿した水素、
電極４側に酸素を供給して、燃料電池として作動させた
ところ、１Ａ／cm2 の電流密度で０．７１Ｖの出力が得
られた。
比較例
実施例２において一軸延伸ＥＰＴＦＥフィルムを圧縮し
て得た、撥水性導電性多孔質フィルムをカーボンペーパ
ーに接合させて電極材料を得た。Moistened hydrogen on the electrode 3 side of this bonded body,
When oxygen was supplied to the electrode 4 side to operate as a fuel cell, an output of 0.71 V was obtained at a current density of 1 A / cm 2 . Comparative Example A water-repellent conductive porous film obtained by compressing the uniaxially stretched EPTFE film in Example 2 was bonded to carbon paper to obtain an electrode material.
【００３１】この電極基材に直接混合溶液を塗布したと
ころ多数のひび割れが発生し、その一部は基材から剥離
していた。またこれを使用して、実施例２と同様にし
て、燃料電池として作動させたところ１Ａ／cm2 の電流
密度で０．６７Ｖの出力であった。When the mixed solution was directly applied to this electrode base material, a large number of cracks were generated, and some of them were peeled off from the base material. When this was used and operated as a fuel cell in the same manner as in Example 2, the output was 0.67 V at a current density of 1 A / cm 2 .
【００３２】[0032]
【発明の効果】本発明によれば、高分子固体電解質を用
いた電気化学的装置用の電極において、三相界面反応帯
を三次元的に十分確保し、触媒層自体が十分な機械的強
度を有しながら空孔率を高くでき、従ってガス拡散性が
よく、生成イオンの移動も速やかに行なわれる反応性の
高い触媒層を形成でき、その成形と同時に集（給）電体
との接着も同時に行なうことができる電極が提供され
る。According to the present invention, in an electrode for an electrochemical device using a polymer solid electrolyte, a three-phase interfacial reaction zone is sufficiently secured three-dimensionally, and the catalyst layer itself has a sufficient mechanical strength. It is possible to form a highly reactive catalyst layer that has a high porosity, and therefore has good gas diffusibility and moves the generated ions quickly, while adhering to the current collector at the same time as molding. An electrode is provided that can be performed simultaneously.
【図１】実施例１におけるＥＰＰＴＦＥフィルムへの高
分子固体電解質樹脂及び触媒の混合液の含浸を示す図で
ある。FIG. 1 is a diagram showing impregnation of an EPPTFE film with a mixed liquid of a polymer solid electrolyte resin and a catalyst in Example 1.
【図２】本発明の電極の燃料電池への応用例を示す図で
ある。FIG. 2 is a diagram showing an application example of the electrode of the present invention to a fuel cell.
１１，１２…ローラ
１３…ＥＰＴＦＥフィルム
１４…支持フィルム
１５…二酸化鉛微粉末＋パーフルオロスルフォン酸樹脂
溶液
１６…ドクターブレード
２１…高分子固体電解質
２２，２３…電極
２４，２５…集（給）電体
２６，２７…セパレータ板
２８，２９…ガス供給口11, 12 ... Roller 13 ... EPTFE film 14 ... Support film 15 ... Lead dioxide fine powder + perfluorosulfonic acid resin solution 16 ... Doctor blade 21 ... Polymer solid electrolyte 22, 23 ... Electrodes 24, 25 ... Body 26, 27 ... Separator plate 28, 29 ... Gas supply port
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 4/86 H01M 4/88 C25B 11/03 C25B 11/20 C01B 13/10 ─────────────────────────────────────────────────── ─── Continuation of front page (58) Fields surveyed (Int.Cl. 7 , DB name) H01M 4/86 H01M 4/88 C25B 11/03 C25B 11/20 C01B 13/10
Claims (5)
以上、孔径がＥＢＰ値で０．５ｋｇ／ｃｍ２以下の延伸
多孔質ポリテトラフルオロエチレンフィルムの空隙に、
少なくとも高分子電解質樹脂と電子導電性を付与するに
十分な量の触媒とを含む成分を充填してなる触媒層を有
することを特徴とする電気化学装置用電極。1. A film thickness of 3 to 200 μm and a porosity of 60%
As described above, in the voids of the stretched porous polytetrafluoroethylene film having a pore diameter of 0.5 kg / cm 2 or less in EBP value,
An electrode for an electrochemical device comprising a catalyst layer filled with a component containing at least a polymer electrolyte resin and a catalyst in an amount sufficient to impart electronic conductivity.
ボンブラックであり、前記電気化学装置が燃料電池であ
る請求項１に記載の電気化学装置用電極。2. The electrode for an electrochemical device according to claim 1, wherein the catalyst is platinum or platinum alloy-supporting carbon black, and the electrochemical device is a fuel cell.
面上に、請求項１に記載の触媒層が一体に成形されてい
ることを特徴とする請求項１または２に記載の電気化学
装置用電極。3. The electricity according to claim 1, wherein the catalyst layer according to claim 1 is integrally formed on the surface of the current collector material or the gas diffusion layer material. Electrodes for chemical equipment.
以上、孔径がＥＢＰ値で０．５ｋｇ／ｃｍ２以下の延伸
多孔質ポリテトラフルオロエチレンフィルムの空隙に、
少なくとも高分子電解質樹脂と電子導電性を付与するに
十分な量の触媒とを含むインク状溶液を含浸した後、集
（給）電体材料またはガス拡散層材料面上に該フィルム
を固定し、溶媒を除去することを特徴とする電気化学装
置用電極の製造方法。4. The film thickness is 3 to 200 μm, and the porosity is 60%.
As described above, in the voids of the stretched porous polytetrafluoroethylene film having a pore diameter of 0.5 kg / cm 2 or less in EBP value,
After impregnating an ink-like solution containing at least a polymer electrolyte resin and a catalyst in an amount sufficient to impart electronic conductivity, the film is fixed on a current collector (supply) current collector material or gas diffusion layer material surface, A method for producing an electrode for an electrochemical device, which comprises removing a solvent.
面上に膜厚が３〜２００μm、空隙率が６０％以上、孔
径がＥＢＰ値で０．５ｋｇ／ｃｍ２以下の延伸多孔質ポ
リテトラフルオロエチレンフィルムを固定した後その表
面に少なくとも高分子電解質樹脂と電子導電性を付与す
るに十分な量の触媒とを含むインク状溶液を塗布するこ
とにより、該フィルムの空隙部に該インク状成分を含浸
し、引き続いて溶媒成分を除去することにより、該イン
ク状成分を該フィルム内部に固定すると共に集（給）電
体材料またはガス拡散層材料との接着を行い、一体に成
形することを特徴とする電気化学装置用電極の製造方
法。5. A stretched porous material having a film thickness of 3 to 200 μm, a porosity of 60% or more, and a pore diameter of 0.5 kg / cm 2 or less as an EBP value on the surface of a current collector (material) or gas diffusion layer material. After fixing the polytetrafluoroethylene film, an ink-like solution containing at least a polymer electrolyte resin and a catalyst in an amount sufficient to impart electronic conductivity is applied to the surface of the polytetrafluoroethylene film to apply the ink to the voids of the film. The ink-like component is fixed to the inside of the film by being impregnated with the liquid component and then the solvent component is removed, and the ink-like component is adhered to the current collector material or the gas diffusion layer material to be integrally molded. A method for manufacturing an electrode for an electrochemical device, comprising:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12155695A JP3504021B2 (en) | 1994-12-08 | 1995-05-19 | Electrode for electrochemical device and method for producing the same |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6-304991 | 1994-12-08 | ||
| JP30499194 | 1994-12-08 | ||
| JP12155695A JP3504021B2 (en) | 1994-12-08 | 1995-05-19 | Electrode for electrochemical device and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08213027A JPH08213027A (en) | 1996-08-20 |
| JP3504021B2 true JP3504021B2 (en) | 2004-03-08 |
Family
ID=26458892
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12155695A Expired - Lifetime JP3504021B2 (en) | 1994-12-08 | 1995-05-19 | Electrode for electrochemical device and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3504021B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007072098A2 (en) | 2005-12-23 | 2007-06-28 | ThalesNano Nanotechnológiai Zrt. | Ozone generating electrolysis cell |
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| JP2001181876A (en) | 1999-12-22 | 2001-07-03 | Teeiku Wan Sogo Jimusho:Kk | Ozone generating electrolytic cell and its manufacturing method |
| DE60331406D1 (en) | 2002-10-10 | 2010-04-08 | Asahi Glass Co Ltd | Fuel cell and manufacturing process |
| JP4811992B2 (en) * | 2005-08-22 | 2011-11-09 | 日産自動車株式会社 | Conductive porous film |
| CN100452509C (en) * | 2007-04-27 | 2009-01-14 | 新源动力股份有限公司 | Compound film electrode of catalytic layer supported proton exchange film fuel cells and method for making same |
| JP2010170892A (en) * | 2009-01-23 | 2010-08-05 | Panasonic Corp | Fuel cell |
| GB0921996D0 (en) | 2009-12-17 | 2010-02-03 | Johnson Matthey Plc | Catayst layer assembley |
| JP5873071B2 (en) * | 2011-02-25 | 2016-03-01 | デノラ・ペルメレック株式会社 | Method for producing anode catalyst body and method for producing electrolytic cell for ozone generation |
| JP6278932B2 (en) * | 2014-08-04 | 2018-02-14 | 本田技研工業株式会社 | Membrane-electrode assembly for fuel cell and polymer electrolyte fuel cell |
| JP6743483B2 (en) * | 2016-05-24 | 2020-08-19 | 東洋インキＳｃホールディングス株式会社 | Composition for forming catalyst layer used in water electrolysis apparatus, catalyst layer and water electrolysis apparatus |
| EP3453785A1 (en) * | 2017-09-07 | 2019-03-13 | Kabushiki Kaisha Toshiba | Membrane electrode assembly, electrochemical cell, and electrochemical device |
| JP7209221B2 (en) | 2018-07-23 | 2023-01-20 | パナソニックＩｐマネジメント株式会社 | electrochemical hydrogen pump |
| WO2020080201A1 (en) * | 2018-10-19 | 2020-04-23 | 国立研究開発法人理化学研究所 | Electrochemical cell and cell stack |
| JP7213537B2 (en) * | 2018-10-19 | 2023-01-27 | 国立研究開発法人理化学研究所 | Electrochemical cells and cell stacks |
| WO2023095201A1 (en) * | 2021-11-24 | 2023-06-01 | 日本電信電話株式会社 | Porous electrode-supporting electrolyte membrane and production method for porous electrode-supporting electrolyte membrane |
-
1995
- 1995-05-19 JP JP12155695A patent/JP3504021B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007072098A2 (en) | 2005-12-23 | 2007-06-28 | ThalesNano Nanotechnológiai Zrt. | Ozone generating electrolysis cell |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08213027A (en) | 1996-08-20 |
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