JP2004095553A - Transfer sheet, catalyst layer-electrolyte membrane laminate, electrode-electrolyte membrane junction body, and manufacturing method of the same - Google Patents
Transfer sheet, catalyst layer-electrolyte membrane laminate, electrode-electrolyte membrane junction body, and manufacturing method of the same Download PDFInfo
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Abstract
Description
本発明は、転写シート、触媒層−電解質膜積層体、電極−電解質膜接合体及びこれらの製造方法に関する。 The present invention relates to a transfer sheet, a catalyst layer-electrolyte membrane laminate, an electrode-electrolyte membrane assembly, and a method for producing these.
燃料電池は、電解質膜の両面に触媒層を配置し、水素と酸素の電気化学反応により発電する発電するシステムであり、発電時に発生するのは水のみである。燃料電池は、従来の内燃機関と異なり、二酸化炭素等の環境負荷ガスを発生しないために、次世代のクリーンエネルギーシステムとして注目されている。 (4) A fuel cell is a system in which catalyst layers are arranged on both sides of an electrolyte membrane and generates power by an electrochemical reaction between hydrogen and oxygen. Only water is generated during power generation. Fuel cells have attracted attention as next-generation clean energy systems because they do not generate environmentally harmful gases such as carbon dioxide, unlike conventional internal combustion engines.
固体高分子型燃料電池は、電解質膜層として水素イオン伝導性高分子電解質膜を用い、その両面に触媒層を配置し、次いでその両面に電極基材を配置し、更にこれをセパレータで挟んだ構造をしている。電解質膜層の両面に触媒層を配置し、次いでその両面に電極基材を配置したもの（即ち、電極基材／触媒層／電解質膜／触媒層／電極基材の層構成のもの）は、電極−電解質膜接合体と称されている。 The polymer electrolyte fuel cell uses a hydrogen ion conductive polymer electrolyte membrane as an electrolyte membrane layer, a catalyst layer is arranged on both sides thereof, and then an electrode substrate is arranged on both sides thereof, and this is sandwiched between separators. Has a structure. The catalyst layer is disposed on both sides of the electrolyte membrane layer, and then the electrode substrate is disposed on both sides (that is, the electrode substrate / catalyst layer / electrolyte membrane / catalyst layer / electrode substrate layer configuration) It is called an electrode-electrolyte membrane assembly.
従来、電極−電解質膜接合体の製造方法としては、例えば、白金を炭素粉に担持させた触媒粉のスラリー液又はペースト化した塗工液を、(1)電極基材の片面に印刷法又はスプレー法を適用して触媒層を形成した２個の電極基材を用い、該電極基材の触媒層面が電解質膜の両面に接するように配置し、熱プレスする方法（例えば、特許文献１、特許文献２等）、(2)電解質膜の両面に印刷法又はスプレー法を適用して触媒層を形成し、各々の触媒層面に電極基材が接するように配置し、熱プレスする方法（例えば、特許文献３等）、(3)基材上に印刷法を適用して形成した触媒層を高温高圧下に電解質膜に転写し、基材を剥離し、次いで電解質膜の両面に転写された触媒層面に電極基材が接するように配置し、熱プレスする方法（例えば、特許文献４等）等が知られている。 Conventionally, as a method of manufacturing an electrode-electrolyte membrane assembly, for example, a slurry solution or a coating solution of a catalyst powder in which platinum is supported on carbon powder, or a coating solution in the form of a paste, (1) printing method on one surface of the electrode substrate or A method in which two electrode substrates each having a catalyst layer formed by applying a spray method are arranged such that the catalyst layer surfaces of the electrode substrates are in contact with both surfaces of the electrolyte membrane, and hot pressing is performed (for example, Patent Document 1, Patent Document 2), (2) A method of applying a printing method or a spray method to both surfaces of an electrolyte membrane to form a catalyst layer, disposing an electrode substrate in contact with each catalyst layer surface, and hot pressing (for example, , Patent Document 3 etc.), (3) The catalyst layer formed by applying a printing method on the base material was transferred to the electrolyte membrane under high temperature and high pressure, the base material was peeled off, and then transferred to both sides of the electrolyte membrane A method of arranging the electrode substrate in contact with the catalyst layer surface and hot pressing (for example, see Patent 4, etc.), and the like are known.
しかしながら、これらの方法には種々の欠点がある。 However, these methods have various disadvantages.
(1)の方法は、印刷法又はスプレー法を適用して触媒層を電極基材上に形成する際に、触媒層が多孔質の電極基材の中に入り込むので、触媒層の膜厚調整が困難になったり、触媒層を電極基材上に均一に形成させることが困難になる。更に、(1)の方法は、電極基材表面乃至内部の孔を塞ぎ、ガスの通流性能を阻害する。その結果、(1)の方法で得られる電極−電解質膜接合体を使用した燃料電池は、その性能が低下するのが避けられない。 In the method (1), when the catalyst layer is formed on the electrode substrate by applying a printing method or a spray method, the catalyst layer enters the porous electrode substrate, so that the thickness of the catalyst layer is adjusted. And it becomes difficult to uniformly form the catalyst layer on the electrode substrate. Furthermore, the method (1) closes the pores on the surface or inside of the electrode substrate, and impedes the gas flow performance. As a result, the performance of the fuel cell using the electrode-electrolyte membrane assembly obtained by the method (1) is inevitably reduced.
(2)の方法は、触媒層構成成分を有機溶剤に溶解又は分散させた液を電解質膜の両面に印刷又はスプレーして触媒層を形成させるが、電解質膜が有機溶媒により膨潤し、変形して電解質膜の形状を維持することが困難になる。そのために、触媒層の膜厚調整が困難になったり、触媒層を電解質膜上に均一に形成させることが困難になる。その結果、(2)の方法で得られる電極−電解質膜接合体を使用した燃料電池は、その性能にバラツキが生じる。従って、(2)の方法で得られる電極−電解質膜接合体では、均一な性能を備えた燃料電池を製造できない。 In the method (2), a catalyst layer is formed by printing or spraying a solution obtained by dissolving or dispersing the components of the catalyst layer in an organic solvent on both sides of the electrolyte membrane, but the electrolyte membrane swells and deforms due to the organic solvent. Therefore, it becomes difficult to maintain the shape of the electrolyte membrane. Therefore, it becomes difficult to adjust the thickness of the catalyst layer, and it is difficult to uniformly form the catalyst layer on the electrolyte membrane. As a result, the performance of the fuel cell using the electrode-electrolyte membrane assembly obtained by the method (2) varies. Therefore, with the electrode-electrolyte membrane assembly obtained by the method (2), a fuel cell having uniform performance cannot be manufactured.
(3)の方法は、触媒層の電解質膜への転写を高温高圧下に行う必要があるが、高圧下での転写の際に電解質膜が過剰に圧縮される部分が生じ、電解質膜が局所的に破壊される危険がある。また、高温下での転写の際、電解質膜が溶融し、膜自体が変性する危険がある。その結果、(3)の方法で得られる電極−電解質膜接合体を使用した燃料電池は、所望の性能を備えた燃料電池にはなり得ない。
本発明は、上記欠点のない電極−電解質膜接合体の製造方法を提供することを課題とする。 。 It is an object of the present invention to provide a method for producing an electrode-electrolyte membrane assembly that does not have the above-mentioned disadvantages.
本発明は、上記欠点のない電極−電解質膜接合体を製造するための転写シートを提供することを課題とする。 。 It is an object of the present invention to provide a transfer sheet for producing an electrode-electrolyte membrane assembly without the above-mentioned disadvantages.
本発明者は、上記課題を解決するために鋭意研究を重ねてきた。その結果、基材の少なくとも片面に離型層を介して１個又は２個以上の触媒層が形成された電極−電解質膜接合体製造用転写シートを用い、該転写シートの離型層面が電解質膜面に対面するように転写シートを配置し、加圧した後、該転写シートの基材を剥離することにより、所望の電極−電解質膜接合体を製造できることを見い出した。本発明は、斯かる知見に基づき完成されたものである。
１．本発明は、基材の少なくとも片面に離型層を介して１個又は２個以上の触媒層が形成された、電極−電解質膜接合体製造用転写シートである。
２．本発明は、触媒層の他面に接着層が形成されている上記１に記載の転写シートである。
３．本発明は、離型層が融点６０〜１００℃のワックスからなる上記１又は２に記載の転写シートである。
４．本発明は、基材の少なくとも片面に離型層を形成し、次いで該離型層の上に１個又は２個以上の触媒層を形成させる、上記１に記載の電極−電解質膜接合体製造用転写シートの製造方法である。
５．本発明は、基材の少なくとも片面に離型層を形成し、次いで該離型層の上に１個又は２個以上の触媒層を形成させ、更に触媒層上に接着層を形成させる、上記２に記載の電極−電解質膜接合体製造用転写シートの製造方法である。
６．本発明は、上記１に記載の転写シートの触媒層面が電解質膜面に対面するように転写シートを配置し、加圧した後、該転写シートの基材を触媒層面から剥離することを特徴とする触媒層−電解質膜積層体の製造方法である。
７．本発明は、上記１に記載の転写シートの触媒層面が電解質膜の両面に対面するように転写シートを配置し、加圧した後、該転写シートの基材を触媒層面から剥離することを特徴とする触媒層−電解質膜積層体の製造方法である。
８．本発明は、上記２に記載の転写シートの接着層面が電解質膜面に対面するように転写シートを配置し、加圧した後、該転写シートの基材を触媒層面から剥離することを特徴とする触媒層−電解質膜積層体の製造方法である。
９．本発明は、上記２に記載の転写シートの接着層面が電解質膜の両面に対面するように転写シートを配置し、加圧した後、該転写シートの基材を触媒層面から剥離することを特徴とする触媒層−電解質膜積層体の製造方法である。
１０．本発明は、上記１〜３のいずれかに記載の転写シートを用いて製造される触媒層−電解質膜積層体である。
１１．本発明は、上記６〜９のいずれかの方法で製造される触媒層−電解質膜積層体である。
１２．本発明は、上記１０又は１１に記載の積層体の両面に電極基材を配置し、加圧することを特徴とする電極−電解質膜接合体の製造方法である。
１３．本発明は、上記１０又は１１に記載の積層体を用いて製造される電極−電解質膜接合体である。
１４．本発明は、上記１２に記載の方法により製造される電極−電解質膜接合体である。
１５．本発明は、
(1)基材の少なくとも片面に離型層を形成し、次いで該離型層の上に１個又は２個以上の触媒層を形成させて電極−電解質膜接合体製造用転写シートを得る工程、
(2)上記(1)工程で得られる転写シートの触媒層面が電解質膜面に対面するように転写シートを配置し、加圧した後、該転写シートの基材を触媒層面から剥離することにより触媒層−電解質膜積層体を得る工程、
(3)上記(2)工程で得られる触媒層−電解質膜積層体の両面に電極基材を配置し、加圧することにより電極−電解質膜接合体を得る工程、及び
(4)上記(3)工程で得られる電極−電解質膜接合体を用いて燃料電池を得る工程
を備えた燃料電池の製造方法である。
１６．本発明は、
(1)基材の少なくとも片面に離型層を形成し、次いで該離型層の上に１個又は２個以上の触媒層を形成させ、更に触媒層上に接着層を形成させて電極−電解質膜接合体製造用転写シートを得る工程、
(2)上記(1)工程で得られる転写シートの接着層面が電解質膜面に対面するように転写シートを配置し、加圧した後、該転写シートの基材を触媒層面から剥離することにより触媒層−電解質膜積層体を得る工程、
(3)上記(2)工程で得られる触媒層−電解質膜積層体の両面に電極基材を配置し、加圧することにより電極−電解質膜接合体を得る工程、及び
(4)上記(3)工程で得られる電極−電解質膜接合体を用いて燃料電池を得る工程
を備えた燃料電池の製造方法である。
１７．本発明は、上記１３又は１４に記載の電極−電解質膜接合体を組み込んだ燃料電池である。
１８．本発明は、上記１５又は１６に記載の方法で得られる燃料電池である。
The present inventor has made intensive studies to solve the above-mentioned problems. As a result, a transfer sheet for producing an electrode-electrolyte membrane assembly in which one or two or more catalyst layers are formed on at least one surface of a base material via a release layer, and the release layer surface of the transfer sheet is an electrolyte It has been found that a desired electrode-electrolyte membrane assembly can be produced by arranging a transfer sheet so as to face the membrane surface, applying pressure, and then peeling off the base material of the transfer sheet. The present invention has been completed based on such findings.
1. The present invention is a transfer sheet for producing an electrode-electrolyte membrane assembly, in which one or two or more catalyst layers are formed on at least one surface of a substrate via a release layer.
2. The present invention is the transfer sheet according to the above item 1, wherein an adhesive layer is formed on the other surface of the catalyst layer.
3. The present invention is the transfer sheet according to 1 or 2, wherein the release layer is made of wax having a melting point of 60 to 100 ° C.
4. The present invention provides the production of an electrode-electrolyte membrane assembly according to the above 1, wherein a release layer is formed on at least one surface of the substrate, and then one or more catalyst layers are formed on the release layer. This is a method for producing a transfer sheet for use.
5. The present invention comprises forming a release layer on at least one surface of a substrate, then forming one or more catalyst layers on the release layer, and further forming an adhesive layer on the catalyst layer. 3. The method for producing a transfer sheet for producing an electrode-electrolyte membrane assembly according to item 2.
6. The present invention is characterized in that the transfer sheet is arranged so that the catalyst layer surface of the transfer sheet according to the above 1 faces the electrolyte membrane surface, and after pressing, the base material of the transfer sheet is separated from the catalyst layer surface. This is a method for producing a catalyst layer-electrolyte membrane laminate.
7. The present invention is characterized in that the transfer sheet is arranged so that the catalyst layer surface of the transfer sheet according to the above 1 faces both surfaces of the electrolyte membrane, and after pressing, the base material of the transfer sheet is separated from the catalyst layer surface. The method for producing a catalyst layer-electrolyte membrane laminate described above.
8. The present invention is characterized in that the transfer sheet is arranged so that the adhesive layer surface of the transfer sheet according to the above item 2 faces the electrolyte membrane surface, and after pressing, the base material of the transfer sheet is peeled from the catalyst layer surface. This is a method for producing a catalyst layer-electrolyte membrane laminate.
9. The present invention is characterized in that the transfer sheet is arranged so that the adhesive layer surface of the transfer sheet according to the above 2 faces both surfaces of the electrolyte membrane, and after pressing, the base material of the transfer sheet is peeled off from the catalyst layer surface. The method for producing a catalyst layer-electrolyte membrane laminate described above.
10. The present invention is a catalyst layer-electrolyte membrane laminate manufactured using the transfer sheet according to any one of the above 1 to 3.
11. The present invention is a catalyst layer-electrolyte membrane laminate produced by any one of the above methods 6 to 9.
12. The present invention is a method for producing an electrode-electrolyte membrane assembly, wherein electrode base materials are arranged on both surfaces of the laminate according to the above item 10 or 11, and pressure is applied.
13. The present invention is an electrode-electrolyte membrane assembly manufactured using the laminate described in 10 or 11 above.
14． The present invention is an electrode-electrolyte membrane assembly manufactured by the method described in the above item 12.
15. The present invention
(1) A step of forming a release layer on at least one surface of a substrate, and then forming one or more catalyst layers on the release layer to obtain a transfer sheet for producing an electrode-electrolyte membrane assembly. ,
(2) By disposing the transfer sheet so that the catalyst layer surface of the transfer sheet obtained in the step (1) faces the electrolyte membrane surface, pressurizing, and then peeling the base material of the transfer sheet from the catalyst layer surface. Obtaining a catalyst layer-electrolyte membrane laminate,
(3) a step of obtaining an electrode-electrolyte membrane assembly by arranging electrode base materials on both surfaces of the catalyst layer-electrolyte membrane laminate obtained in the above (2) step, and applying pressure; and
(4) A method for manufacturing a fuel cell including a step of obtaining a fuel cell using the electrode-electrolyte membrane assembly obtained in the step (3).
16. The present invention
(1) forming a release layer on at least one side of the base material, then forming one or more catalyst layers on the release layer, and further forming an adhesive layer on the catalyst layer to form an electrode; A step of obtaining a transfer sheet for manufacturing an electrolyte membrane assembly,
(2) By disposing the transfer sheet so that the adhesive layer surface of the transfer sheet obtained in the step (1) faces the electrolyte membrane surface, pressurizing, and then peeling the base material of the transfer sheet from the catalyst layer surface. Obtaining a catalyst layer-electrolyte membrane laminate,
(3) a step of obtaining an electrode-electrolyte membrane assembly by arranging electrode base materials on both surfaces of the catalyst layer-electrolyte membrane laminate obtained in the above (2) step, and applying pressure; and
(4) A method for manufacturing a fuel cell including a step of obtaining a fuel cell using the electrode-electrolyte membrane assembly obtained in the step (3).
17. The present invention is a fuel cell incorporating the electrode-electrolyte membrane assembly according to 13 or 14 above.
18. The present invention is a fuel cell obtained by the method described in 15 or 16 above.
電極−電解質膜接合体製造用転写シート
本発明の電極−電解質膜接合体製造用転写シートは、基材の少なくとも片面に離型層を介して１個又は２個以上の触媒層が形成されてなるものである。
The transfer sheet for producing an electrode-electrolyte membrane assembly The transfer sheet for producing an electrode-electrolyte membrane assembly of the present invention has one or two or more catalyst layers formed on at least one surface of a substrate via a release layer. It becomes.
本発明の電極−電解質膜接合体製造用転写シートの一例を図１に示す。図１に示す転写シートは、基材の片面に離型層が形成され、更に該離型層の上に触媒層が形成されている。 FIG. 1 shows an example of the transfer sheet for producing an electrode-electrolyte membrane assembly of the present invention. The transfer sheet shown in FIG. 1 has a release layer formed on one side of a substrate, and a catalyst layer formed on the release layer.
本発明の電極−電解質膜接合体製造用転写シートの他の一例を図２に示す。図２に示す転写シートは、基材の片面に離型層が形成され、該離型層の上に触媒層が形成され、更に該触媒層の上に接着層が形成されている。 FIG. 2 shows another example of the transfer sheet for producing an electrode-electrolyte membrane assembly of the present invention. The transfer sheet shown in FIG. 2 has a release layer formed on one surface of a substrate, a catalyst layer formed on the release layer, and an adhesive layer formed on the catalyst layer.
本発明の電極−電解質膜接合体製造用転写シートの他の一例を図３及び図４に示す。図３は本発明の電極−電解質膜接合体製造用転写シートの断面図であり、図４は該転写シートの平面図である。図３及び図４に示す転写シートは、基材の片面に離型層が形成され、更に該離型層の上に複数個の触媒層が形成されている。 FIGS. 3 and 4 show another example of the transfer sheet for producing an electrode-electrolyte membrane assembly of the present invention. FIG. 3 is a sectional view of a transfer sheet for producing an electrode-electrolyte membrane assembly according to the present invention, and FIG. 4 is a plan view of the transfer sheet. The transfer sheet shown in FIGS. 3 and 4 has a release layer formed on one surface of a base material, and a plurality of catalyst layers formed on the release layer.
基材としては、例えば、ポリイミド、ポリエチレンテレフタレート、ポリパルバン酸アラミド、ポリアミド（ナイロン）、ポリサルホン、ポリエーテルサルホン、ポリフェニレンサルファイド、ポリエーテル・エーテルケトン、ポリエーテルイミド、ポリアリレート、ポリエチレンナフタレート等の高分子フィルムを挙げることができる。 As the base material, for example, polyimide, polyethylene terephthalate, polypalvanic acid aramid, polyamide (nylon), polysulfone, polyethersulfone, polyphenylene sulfide, polyether ether ketone, polyetherimide, polyarylate, polyethylene naphthalate, etc. Molecular films can be mentioned.
また、エチレンテトラフルオロエチレン共重合体（ETFE）、テトラフルオロエチレン−ヘキサフルオロプロピレン共重合体（FEP）、テトラフルオロパーフルオロアルキルビニルエーテル共重合体（PFA）、ポリテトラフルオロエチレン（PTFE）等の耐熱性フッ素樹脂を用いることもできる。 In addition, heat resistance of ethylene tetrafluoroethylene copolymer (ETFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroperfluoroalkylvinyl ether copolymer (PFA), polytetrafluoroethylene (PTFE), etc. A fluorocarbon resin can also be used.
更に、基材は、高分子フィルム以外に、アート紙、コート紙、軽量コート紙等の塗工紙、ノート用紙、コピー用紙等の非塗工紙等の紙であってもよい。 Further, the base material may be paper such as coated paper such as art paper, coated paper and lightweight coated paper, uncoated paper such as notebook paper and copy paper, in addition to the polymer film.
基材の厚さは、取り扱い性及び経済性の観点から、通常６〜１００μｍ程度、好ましくは６〜３０μｍ程度、より好ましくは６〜１５μｍ程度とするのがよい。 (4) The thickness of the substrate is usually about 6 to 100 μm, preferably about 6 to 30 μm, and more preferably about 6 to 15 μm, from the viewpoint of handleability and economy.
従って、基材としては、安価で入手が容易な高分子フィルムが好ましく、ポリエチレンテレフタレート等がより好ましい。 Therefore, as the substrate, a polymer film that is inexpensive and easily available is preferable, and polyethylene terephthalate and the like are more preferable.
本発明において、離型層は、ワックスから構成される。ワックスとしては、例えば、石油系ワックス、植物系ワックス、動物系ワックス、鉱物系ワックス、合成系ワックス等を挙げることができる。本発明で用いられるワックスには、例えば、Ｃ16〜Ｃ32の脂肪酸とアルコールとのエステルが包含される。本発明において、これらワックスは、１種単独で又は２種以上混合して使用される。 In the present invention, the release layer is made of wax. Examples of the wax include petroleum wax, vegetable wax, animal wax, mineral wax, and synthetic wax. The wax used in the present invention are, for example, esters of fatty acids with alcohols of C 16 -C 32 are included. In the present invention, these waxes are used alone or as a mixture of two or more.
本発明で用いられるワックスは、好ましくは融点が４０〜１４０℃、より好ましくは融点が６０〜１００℃の範囲にあるのがよい。 ワ ッ ク ス The wax used in the present invention preferably has a melting point of 40 to 140 ° C, more preferably 60 to 100 ° C.
本発明において、好ましいワックスは植物系ワックスであり、より好ましいワックスはカルナウバワックス、カンデリラワックス等である。 に お い て In the present invention, preferred waxes are vegetable waxes, and more preferred waxes are carnauba wax, candelilla wax and the like.
離型層の厚さは、通常０．１〜３μｍ程度、好ましくは０．５〜１μｍ程度がよい。 厚 The thickness of the release layer is usually about 0.1 to 3 µm, preferably about 0.5 to 1 µm.
基材上に離型層を形成させるに当たっては、所望の厚さになるように、上記ワックスを公知の方法に従い塗布するのがよい。また、塗布作業を容易にするために、ワックスを適当な溶剤に溶解又は分散して溶液又はエマルジョン液の形態で使用してもよい。塗布方法としては、特に限定されるものではなく、例えば、ナイフコーター、バーコーター、スプレー、ディップコーター、スピンコーター、ロールコーター、ダイコーター、カーテンコーター、スクリーン印刷等の一般的な方法を適用できる。 (4) In forming a release layer on a substrate, the wax is preferably applied according to a known method so as to have a desired thickness. In order to facilitate the coating operation, the wax may be dissolved or dispersed in a suitable solvent and used in the form of a solution or an emulsion. The coating method is not particularly limited, and for example, a general method such as a knife coater, a bar coater, a spray, a dip coater, a spin coater, a roll coater, a die coater, a curtain coater, and screen printing can be applied.
触媒層は、公知のものである。 The catalyst layer is a known one.
触媒層は、触媒粒子を担持させた炭素粒子及び水素イオン伝導性高分子電解質を含有する。 The catalyst layer contains carbon particles carrying catalyst particles and a hydrogen ion conductive polymer electrolyte.
触媒粒子としては、例えば白金、白金化合物等が挙げられる。白金化合物としては、例えば、ルテニウム、パラジウム、ニッケル、モリブデン、イリジウム、鉄等からなる群から選ばれる少なくとも１種の金属と白金との合金等が挙げられる。 Examples of the catalyst particles include platinum and a platinum compound. Examples of the platinum compound include an alloy of platinum with at least one metal selected from the group consisting of ruthenium, palladium, nickel, molybdenum, iridium, iron and the like.
水素イオン伝導性高分子電解質としては、例えばパーフルオロスルホン酸系のフッ素イオン交換樹脂等が挙げられる。 Examples of the hydrogen ion conductive polymer electrolyte include perfluorosulfonic acid-based fluorine ion exchange resins.
離型層上に触媒層を形成させるに当たっては、触媒粒子を担持させた炭素粒子及び水素イオン伝導性高分子電解質を適当な溶剤に混合、分散してペースト状にしておき、形成される触媒層が所望の厚さになるように、このペーストを公知の方法に従い離型層上に塗布するのがよい。 In forming the catalyst layer on the release layer, the carbon particles supporting the catalyst particles and the hydrogen ion conductive polymer electrolyte are mixed and dispersed in an appropriate solvent to form a paste, and the formed catalyst layer is formed. This paste is preferably applied on a release layer according to a known method so that the thickness of the paste becomes a desired thickness.
溶剤としては、例えば、各種アルコール類、各種エーテル類、各種ジアルキルスルホキシド類、水又はこれらの混合物等が挙げられる。 Examples of the solvent include various alcohols, various ethers, various dialkyl sulfoxides, water, and mixtures thereof.
ペーストの塗布方法としては、特に限定されるものではなく、例えば、ナイフコーター、バーコーター、スプレー、ディップコーター、スピンコーター、ロールコーター、ダイコーター、カーテンコーター、スクリーン印刷等の一般的な方法を適用できる。 The method for applying the paste is not particularly limited. For example, a general method such as a knife coater, a bar coater, a spray, a dip coater, a spin coater, a roll coater, a die coater, a curtain coater, and screen printing is applied. it can.
斯かるペーストを塗布した後、乾燥することにより、触媒層が形成される。乾燥温度は、ワックスの融点以下であることが望ましく、通常４０〜１００℃程度、好ましくは６０〜８０℃程度である。乾燥時間は、乾燥温度にもよるが、通常５分〜２時間程度、好ましくは３０分〜１時間程度である。 After the paste is applied and dried, a catalyst layer is formed. The drying temperature is desirably equal to or lower than the melting point of the wax, and is usually about 40 to 100C, preferably about 60 to 80C. The drying time depends on the drying temperature, but is usually about 5 minutes to 2 hours, preferably about 30 minutes to 1 hour.
触媒層の厚さは、通常１０〜５０μｍ程度、好ましくは１５〜３０μｍ程度がよい。 The thickness of the catalyst layer is usually about 10 to 50 µm, preferably about 15 to 30 µm.
本発明においては、上記で形成された触媒層の上に更に接着層が形成されているのが好ましい。 に お い て In the present invention, it is preferable that an adhesive layer is further formed on the catalyst layer formed above.
接着層は、触媒層に含まれる水素イオン伝導性高分子電解質膜と異種の高分子材料からなるものでもよいが、触媒層に含まれる水素イオン伝導性高分子電解質膜と同種の高分子材料、例えばパーフルオロスルホン酸系のフッ素イオン交換樹脂等からなるものが好ましい。 The adhesive layer may be made of a polymer material different from the hydrogen ion conductive polymer electrolyte membrane contained in the catalyst layer, but may be the same type of polymer material as the hydrogen ion conductive polymer electrolyte membrane contained in the catalyst layer, For example, a resin made of a perfluorosulfonic acid-based fluorine ion exchange resin or the like is preferable.
接着層の厚さは、通常１〜１５μｍ程度、好ましくは３〜１０μｍ程度がよい。 The thickness of the adhesive layer is usually about 1 to 15 μm, preferably about 3 to 10 μm.
触媒層上に接着層を形成させるに当たっては、上記高分子材料を適当な溶剤に混合、分散してペースト状にしておき、形成される接着層が所望の層厚になるように、このペーストを公知の方法に従い触媒層上に塗布するのがよい。 In forming the adhesive layer on the catalyst layer, the polymer material is mixed and dispersed in an appropriate solvent to form a paste, and the paste is formed so that the formed adhesive layer has a desired thickness. It is preferable to apply on the catalyst layer according to a known method.
溶剤としては、例えば、各種アルコール類、各種エーテル類、各種ジアルキルスルホキシド類、水又はこれらの混合物等が挙げられる。 Examples of the solvent include various alcohols, various ethers, various dialkyl sulfoxides, water, and mixtures thereof.
ペーストの塗布方法としては、特に限定されるものではなく、例えば、ナイフコーター、バーコーター、スプレー、ディップコーター、スピンコーター、ロールコーター、ダイコーター、カーテンコーター、スクリーン印刷等の一般的な方法を適用できる。 The method for applying the paste is not particularly limited. For example, a general method such as a knife coater, a bar coater, a spray, a dip coater, a spin coater, a roll coater, a die coater, a curtain coater, and screen printing is applied. it can.
斯かるペーストを塗布した後、乾燥することにより、接着層が形成される。乾燥温度は、通常４０〜１００℃程度、好ましくは６０〜８０℃程度である。乾燥時間は、乾燥温度にもよるが、通常５分〜２時間程度、好ましくは３０分〜１時間程度である。 After the paste is applied and dried, an adhesive layer is formed. The drying temperature is usually about 40 to 100 ° C, preferably about 60 to 80 ° C. The drying time depends on the drying temperature, but is usually about 5 minutes to 2 hours, preferably about 30 minutes to 1 hour.
本発明の電極−電解質膜接合体製造用転写シートは、基材の両面に離型層が形成され、次いでこれら離型層の上に１個又は２個以上の触媒層が形成され、更にこれら触媒層の上に接着層が形成されていてもよい。 In the transfer sheet for producing an electrode-electrolyte membrane assembly of the present invention, a release layer is formed on both surfaces of a substrate, and then one or two or more catalyst layers are formed on these release layers. An adhesive layer may be formed on the catalyst layer.
触媒層−電解質膜積層体
本発明の触媒層が積層された電解質膜（触媒層−電解質膜積層体）は、例えば本発明転写シートの触媒層面が電解質膜面に対面するように転写シートを配置し、加圧した後、該転写シートの基材を剥離することにより製造される。この操作を２回繰り返すことにより、触媒層面が電解質膜の両面に積層された触媒層−電解質膜積層体が製造される。
Catalyst Layer-Electrolyte Membrane Stack The electrolyte membrane (catalyst layer-electrolyte membrane laminate) on which the catalyst layer of the present invention is laminated is arranged, for example, such that the catalyst layer surface of the transfer sheet of the present invention faces the electrolyte membrane surface. Then, after pressing, the base material of the transfer sheet is peeled off to manufacture the transfer sheet. By repeating this operation twice, a catalyst layer-electrolyte membrane laminate in which the catalyst layer surface is laminated on both sides of the electrolyte membrane is manufactured.
作業性を考慮すると、触媒層面を電解質膜の両面に同時に積層するのがよい。この場合には、例えば、本発明転写シートの触媒層面が電解質膜の両面に対面するように転写シートを配置し、加圧した後、該転写シートの基材を剥離すればよい。 と Considering the workability, it is preferable that the catalyst layer surface is simultaneously laminated on both surfaces of the electrolyte membrane. In this case, for example, the transfer sheet may be arranged so that the catalyst layer surface of the transfer sheet of the present invention faces both surfaces of the electrolyte membrane, and after pressing, the base material of the transfer sheet may be peeled off.
使用される電解質膜は、公知のものである。電解質膜の膜厚は、通常２０〜２５０μｍ程度、好ましくは２０〜８０μｍ程度である。電解質膜の具体例としては、デュポン社製の「Nafion」膜、旭硝子（株）製の「Flemion」膜、旭化成（株）製の「Aciplex」膜、ゴア（Gore）社製の「Gore Select」膜等が挙げられる。 電解 The electrolyte membrane used is a known one. The thickness of the electrolyte membrane is usually about 20 to 250 μm, preferably about 20 to 80 μm. Specific examples of the electrolyte membrane include “Nafion” membrane manufactured by DuPont, “Flemion” membrane manufactured by Asahi Glass Co., Ltd., “Aciplex” membrane manufactured by Asahi Kasei Corporation, and “Gore Select” manufactured by Gore. And the like.
本発明において、電解質膜の一方面又は両面は、表面粗さ（Ｒａ）が１〜１０μｍ程度、好ましくは１〜３μｍ程度に粗面化されていてもよい。 In the present invention, one or both surfaces of the electrolyte membrane may have a surface roughness (Ra) of about 1 to 10 μm, preferably about 1 to 3 μm.
本発明では、後の工程で触媒層が配置されるべき固体電解質の表面のみを粗面化処理しておくのが好ましいが、触媒層が配置されるべき固体電解質の表面だけでなく、その周辺部まで粗面化しても本発明の効果を損なわない限り何ら差し支えない。 In the present invention, it is preferable to roughen only the surface of the solid electrolyte on which the catalyst layer is to be disposed in a later step, but not only the surface of the solid electrolyte on which the catalyst layer is to be disposed, but also the periphery thereof. Even if the part is roughened, there is no problem as long as the effect of the present invention is not impaired.
電解質膜の一方面又は両面を粗面化しておくことにより、触媒層との密着性が向上でき、また、最終製品となる燃料電池に優れた電池性能を与えることができる。 (4) By roughening one or both surfaces of the electrolyte membrane, adhesion to the catalyst layer can be improved, and excellent cell performance can be given to a fuel cell as a final product.
電解質膜の粗面化には公知の技術を利用できる。公知の技術としては、例えば、エッチング処理、大気圧コロナ放電処理、大気圧プラズマによる処理、サンドブラスト処理等が挙げられる。これらの中でも、サンドブラスト処理は、電解質膜が、有機溶媒による膨潤変形、熱変形等の虞れがないので、好適である。 に は A known technique can be used for roughening the electrolyte membrane. Known techniques include, for example, an etching process, an atmospheric pressure corona discharge process, a process using atmospheric pressure plasma, a sandblasting process, and the like. Among these, sandblasting is preferable because the electrolyte membrane does not have a risk of swelling deformation or thermal deformation due to an organic solvent.
加圧レベルは、転写不良を避けるために、通常０．５〜２０Ｍｐａ程度、好ましくは１〜１０Ｍｐａ程度がよい。また、この加圧操作の際に、転写不良を避けるために、加圧面を加熱するのが好ましい。加熱温度は、電解質膜の破損、変性等を避けるために、通常２００℃以下、好ましくは１５０℃以下がよい。 (4) The pressure level is usually about 0.5 to 20 Mpa, preferably about 1 to 10 Mpa, in order to avoid poor transfer. In this pressing operation, it is preferable to heat the pressing surface in order to avoid transfer failure. The heating temperature is usually 200 ° C. or lower, preferably 150 ° C. or lower, in order to avoid damage, denaturation, etc. of the electrolyte membrane.
また、本発明の触媒層が積層された電解質膜は、本発明転写シートの接着層面が電解質膜の両面に対面するように転写シートを配置し、加圧した後、該転写シートの基材を接着層面から剥離することにより製造することができる。 Further, the electrolyte membrane on which the catalyst layer of the present invention is laminated, the transfer sheet is disposed such that the adhesive layer surface of the transfer sheet of the present invention faces both surfaces of the electrolyte membrane, and after pressing, the base material of the transfer sheet is removed. It can be manufactured by peeling from the surface of the adhesive layer.
離型層は、基本的には転移せず、基材側に残る。しかし、離型層の一部が転移しても、(i)電極基材との接合をワックスの融点よりも高い温度で行うためにワックスが蒸発する、(ii)初期の電池反応時にワックスが電気分解を受けて分解される、等のために、離型層転移による問題は生じない。 The release layer basically does not transfer and remains on the substrate side. However, even if a part of the release layer is transferred, (i) the wax evaporates because the bonding with the electrode substrate is performed at a temperature higher than the melting point of the wax, and (ii) the wax is removed during the initial battery reaction. No problem is caused by the release layer transition because of being decomposed by electrolysis.
本発明の触媒層−電解質膜積層体の一例を図５に示す。また、本発明の触媒層−電解質膜積層体の他の一例を図６に示す。 FIG. 5 shows an example of the catalyst layer-electrolyte membrane laminate of the present invention. FIG. 6 shows another example of the catalyst layer-electrolyte membrane laminate of the present invention.
電極−電解質膜接合体
本発明の電極−電解質膜接合体は、触媒層−電解質膜積層体の両面に電極基材を配置し、加圧することにより製造される。
Electrode-electrolyte membrane assembly The electrode-electrolyte membrane assembly of the present invention is manufactured by arranging electrode bases on both surfaces of the catalyst layer-electrolyte membrane laminate and applying pressure.
電極基材は、公知であり、燃料極、空気極を構成する各種の電極基材を使用できる。 The electrode substrate is known, and various electrode substrates constituting the fuel electrode and the air electrode can be used.
加圧レベルは、通常０．１〜１００Ｍｐａ程度、好ましくは５〜１５Ｍｐａ程度がよい。この加圧操作の際に加熱するのが好ましく、加熱温度は通常１２０〜１５０℃程度でよい。 The pressure level is usually about 0.1 to 100 Mpa, preferably about 5 to 15 Mpa. It is preferable to heat at the time of this pressing operation, and the heating temperature may be usually about 120 to 150 ° C.
本発明の電極−電解質膜接合体の一例を図７に示す。 FIG. 7 shows an example of the electrode-electrolyte membrane assembly of the present invention.
燃料電池
本発明の燃料電池は、例えば、次のようにして製造される。
Fuel Cell The fuel cell of the present invention is manufactured, for example, as follows.
例えば、本発明の燃料電池は、
(1)基材の少なくとも片面に離型層を形成し、次いで該離型層の上に１個又は２個以上の触媒層を形成させて電極−電解質膜接合体製造用転写シートを得る工程、
(2)上記(1)工程で得られる転写シートの触媒層面が電解質膜の片面又は両面に対面するように転写シートを配置し、加圧した後、該転写シートの基材を触媒層面から剥離することにより触媒層−電解質膜積層体を得る工程、
(3)上記(2)工程で得られる触媒層−電解質膜積層体の両面に電極基材を配置し、加圧することにより電極−電解質膜接合体を得る工程、及び
(4)上記(3)工程で得られる電極−電解質膜接合体を用いて燃料電池を得る工程
を経て製造される。
For example, the fuel cell of the present invention
(1) A step of forming a release layer on at least one surface of a substrate, and then forming one or more catalyst layers on the release layer to obtain a transfer sheet for producing an electrode-electrolyte membrane assembly. ,
(2) The transfer sheet is arranged so that the catalyst layer surface of the transfer sheet obtained in the step (1) faces one or both surfaces of the electrolyte membrane, and after pressing, the base material of the transfer sheet is peeled from the catalyst layer surface. Step of obtaining a catalyst layer-electrolyte membrane laminate by doing
(3) placing the electrode substrate on both sides of the catalyst layer obtained in the step (2) -electrolyte membrane laminate, a step of obtaining an electrode-electrolyte membrane assembly by pressing, and
(4) It is manufactured through a step of obtaining a fuel cell using the electrode-electrolyte membrane assembly obtained in the step (3).
また、本発明の燃料電池は、
(1)基材の少なくとも片面に離型層を形成し、次いで該離型層の上に１個又は２個以上の触媒層を形成させ、更に触媒層上に接着層を形成させて電極−電解質膜接合体製造用転写シートを得る工程、
(2)上記(1)工程で得られる転写シートの接着層面が電解質膜の片面又は両面に対面するように転写シートを配置し、加圧した後、該転写シートの基材を触媒層面から剥離することにより触媒層−電解質膜積層体を得る工程、
(3)上記(2)工程で得られる触媒層−電解質膜積層体の両面に電極基材を配置し、加圧することにより電極−電解質膜接合体を得る工程、及び
(4)上記(3)工程で得られる電極−電解質膜接合体を用いて燃料電池を得る工程
を経て製造される。
Further, the fuel cell of the present invention,
(1) forming a release layer on at least one side of the substrate, forming one or more catalyst layers on the release layer, and further forming an adhesive layer on the catalyst layer to form an electrode; A step of obtaining a transfer sheet for manufacturing an electrolyte membrane assembly,
(2) The transfer sheet is arranged so that the adhesive layer surface of the transfer sheet obtained in the step (1) faces one or both surfaces of the electrolyte membrane, and after pressing, the base material of the transfer sheet is separated from the catalyst layer surface. Step of obtaining a catalyst layer-electrolyte membrane laminate by doing
(3) placing the electrode substrate on both sides of the catalyst layer obtained in the step (2) -electrolyte membrane laminate, a step of obtaining an electrode-electrolyte membrane assembly by pressing, and
(4) It is manufactured through a step of obtaining a fuel cell using the electrode-electrolyte membrane assembly obtained in the step (3).
本発明は、上記電極−電解質膜接合体を組み込んだ燃料電池を提供する。 The present invention provides a fuel cell incorporating the above-mentioned electrode-electrolyte membrane assembly.
本発明転写シートを使用すれば、触媒層が多孔質の電極基材の中に入り込む虞れがないので、触媒層の膜厚調整が容易となり、また均一な触媒層を電極基材上に容易に形成させることができる。 When the transfer sheet of the present invention is used, there is no possibility that the catalyst layer enters into the porous electrode substrate, so that the thickness of the catalyst layer can be easily adjusted and a uniform catalyst layer can be easily formed on the electrode substrate. Can be formed.
また、本発明転写シートを使用すれば、電極基材表面乃至内部の孔を塞ぐことはないので、ガスの通流性能を阻害する虞れがない。 れ ば Further, when the transfer sheet of the present invention is used, the pores on the surface or inside of the electrode base material are not blocked, so that there is no fear that the gas flow performance is hindered.
本発明の方法では、触媒層の電解質膜への転写を、従来のように高温高圧下に行う必要がないので、電解質膜が溶融することがなく、膜自体が変性する危険が少ない。 According to the method of the present invention, since the transfer of the catalyst layer to the electrolyte membrane does not need to be performed at a high temperature and a high pressure as in the prior art, the electrolyte membrane does not melt, and there is little risk of the membrane itself being denatured.
従って、本発明の電極−電解質膜接合体を使用すれば、優れた電池性能を備えた高品質の燃料電池を製造することができる。 Therefore, by using the electrode-electrolyte membrane assembly of the present invention, a high-quality fuel cell having excellent cell performance can be manufactured.
以下に実施例及び比較例を掲げて、本発明をより一層明らかにする。 (4) The present invention will be further clarified with reference to Examples and Comparative Examples below.
実施例１
白金担持触媒１０ｇ（Ｐｔ：２０ｗｔ％、田中貴金属工業製のＴＥＣ１０シリーズ）及びバインダーとして５ｗｔ％ナフィオン（Nafion）溶液（デュポン社製、溶剤：ｎ−プロパノール）４０ｇを分散機にて攪拌混合することでペーストを調製した。
Example 1
10 g of a platinum-supported catalyst (Pt: 20 wt%, TEC10 series manufactured by Tanaka Kikinzoku Kogyo) and 40 g of a 5 wt% Nafion solution (manufactured by DuPont, solvent: n-propanol) as a binder are stirred and mixed by a disperser. A paste was prepared.
一方、ＰＥＴフィルム（Ｅ３１２０、東洋紡績（株）製、厚さ１３μｍ）上に、カルナウバワックスのエマルジョン液（ＥＭＵＳＴＡＲ−０１９９、日本精鑞製、液の濃度：２０重量％）を０．５〜１μｍ程度の厚さに片面塗工し、エマルジョン液を乾燥させた。次に、カルナウバワックスの上に、上記で調製したペーストを、ドクターブレードにより厚さ５０μｍとなるように塗布し、これを大気雰囲気中５０℃で１２時間乾燥させ、触媒層を形成した。 On the other hand, on a PET film (E3120, manufactured by Toyobo Co., Ltd., 13 μm in thickness), an emulsion liquid of carnauba wax (EMUSTAR-0199, manufactured by Nippon Seiro, concentration of the liquid: 20% by weight) was added to 0.5 to 0.5%. One-side coating was performed to a thickness of about 1 μm, and the emulsion was dried. Next, the paste prepared above was applied on carnauba wax with a doctor blade so as to have a thickness of 50 μm, and dried at 50 ° C. for 12 hours in an air atmosphere to form a catalyst layer.
触媒層の転写は、一対のプレス型の間に転写シートの触媒層面が、水素イオン伝導性高分子電解質膜（Nafion112、デュポン社製）と接触するようにして１３０℃、３Ｍｐａの条件で挟持した後、ＰＥＴフィルムを剥離することにより行なった。このようにして、本発明の触媒層−電解質膜積層体を製造した。 The transfer of the catalyst layer was performed between a pair of press dies so that the catalyst layer surface of the transfer sheet was in contact with a hydrogen ion conductive polymer electrolyte membrane (Nafion112, manufactured by DuPont) at 130 ° C. and 3 MPa. Thereafter, the peeling was performed by peeling off the PET film. Thus, the catalyst layer-electrolyte membrane laminate of the present invention was manufactured.
以上のような方法により触媒層の転写を１０回試み、各サンプルについて転写触媒層の転写状態を目視により観察した。触媒層の転写が完全に行われた状態である場合に○、ＰＥＴフィルム上に触媒層が一部でも残った状態である場合に×として評価した。結果を表１に示す。 触媒 The transfer of the catalyst layer was attempted 10 times by the method described above, and the transfer state of the transfer catalyst layer was visually observed for each sample. The case where the transfer of the catalyst layer was completely performed was evaluated as ○, and the case where the catalyst layer was partially left on the PET film was evaluated as x. Table 1 shows the results.
実施例２
白金担持触媒１０ｇ（Ｐｔ：２０ｗｔ％、田中貴金属工業製のＴＥＣ１０シリーズ）及びバインダーとして５ｗｔ％ナフィオン（Nafion）溶液（デュポン社製、溶剤：ｎ−プロパノール）４０ｇを分散機にて攪拌混合することでペーストを調製した。
Example 2
10 g of a platinum-supported catalyst (Pt: 20 wt%, TEC10 series manufactured by Tanaka Kikinzoku Kogyo) and 40 g of a 5 wt% Nafion solution (manufactured by DuPont, solvent: n-propanol) as a binder are stirred and mixed by a disperser. A paste was prepared.
一方、ＰＥＴフィルム（Ｅ３１２０、東洋紡績（株）製、厚さ１３μｍ）上に、カルナウバワックスのエマルジョン液（ＥＭＵＳＴＡＲ−０１９９、日本精鑞製、液の濃度：２０重量％）を０．５〜１μｍ程度の厚さに片面塗工し、エマルジョン液を乾燥させた。次に、カルナウバワックスの上に、上記で調製したペーストを、ドクターブレードにより厚さ５０μｍとなるように塗布し、これを大気雰囲気中５０℃で１２時間乾燥させ、触媒層を形成した。 On the other hand, on a PET film (E3120, manufactured by Toyobo Co., Ltd., 13 μm in thickness), an emulsion liquid of carnauba wax (EMUSTAR-0199, manufactured by Nippon Seiro, concentration of the liquid: 20% by weight) was added to 0.5 to 0.5%. One-side coating was performed to a thickness of about 1 μm, and the emulsion was dried. Next, the paste prepared above was applied on carnauba wax with a doctor blade so as to have a thickness of 50 μm, and dried at 50 ° C. for 12 hours in an air atmosphere to form a catalyst layer.
上記で形成した触媒層上に、２０ｗｔ％ナフィオン（Nafion）溶液（デュポン社製、溶剤：ｎ−プロパノール）を塗布、含浸させ、接着層（厚さ３μｍ）を形成した。 ２０ A 20 wt% Nafion solution (manufactured by DuPont, solvent: n-propanol) was applied and impregnated on the catalyst layer formed above to form an adhesive layer (thickness: 3 μm).
触媒層の転写は、一対のプレス型の間に転写シートの接着層面が、水素イオン伝導性高分子電解質膜（Nafion112、デュポン社製）と接触するようにして１３０℃、３Ｍｐａの条件で挟持した後、ＰＥＴフィルムを剥離することにより行なった。このようにして、本発明の触媒層−電解質膜積層体を製造した。 The transfer of the catalyst layer was carried out between a pair of press dies so that the adhesive layer surface of the transfer sheet was in contact with a hydrogen ion conductive polymer electrolyte membrane (Nafion112, manufactured by DuPont) at 130 ° C. and 3 MPa. Thereafter, the peeling was performed by peeling off the PET film. Thus, the catalyst layer-electrolyte membrane laminate of the present invention was manufactured.
以上のような方法により触媒層の転写を１０回試み、各サンプルについて転写触媒層の転写状態を目視により観察し、実施例１と同様に評価した。結果を表１に示す。 The transfer of the catalyst layer was attempted 10 times by the method described above, and the transfer state of the transfer catalyst layer was visually observed for each sample, and evaluated in the same manner as in Example 1. Table 1 shows the results.
実施例３
白金担持触媒１０ｇ（Ｐｔ：２０ｗｔ％、田中貴金属工業製のＴＥＣ１０シリーズ）及びバインダーとして５ｗｔ％ナフィオン（Nafion）溶液（デュポン社製、溶剤：ｎ−プロパノール）４０ｇを分散機にて攪拌混合することでペーストを調製した。
Example 3
10 g of a platinum-supported catalyst (Pt: 20 wt%, TEC10 series manufactured by Tanaka Kikinzoku Kogyo) and 40 g of a 5 wt% Nafion solution (manufactured by DuPont, solvent: n-propanol) as a binder are stirred and mixed by a disperser. A paste was prepared.
一方、ＰＥＴフィルム（Ｅ３１２０、東洋紡績（株）製、厚さ１３μｍ）上に、カルナウバワックスのエマルジョン液（ＥＭＵＳＴＡＲ−０１９９、日本精鑞製、液の濃度：２０重量％）を０．５〜１μｍ程度の厚さに片面塗工し、エマルジョン液を乾燥させて、ＰＥＴフィルム上に離型層を形成した。 On the other hand, on a PET film (E3120, manufactured by Toyobo Co., Ltd., 13 μm in thickness), an emulsion liquid of carnauba wax (EMUSTAR-0199, manufactured by Nippon Seiro, concentration of the liquid: 20% by weight) was added to 0.5 to 0.5%. One-side coating was performed to a thickness of about 1 μm, and the emulsion was dried to form a release layer on the PET film.
次に、ステンレス版（１８０ｍｍ×１８０ｍｍ、厚さ０．３ｍｍ）を用い、スクリーン印刷機にて、ＰＥＴフィルム上に形成した離型層上に同一形状の５０ｍｍ×５０ｍｍの触媒層が一定間隔で複数個形成できるように印刷を行った。これを大気雰囲気中５０℃で１２時間乾燥させ、触媒層（厚さ２０μｍ）を形成した。 Next, using a stainless steel plate (180 mm × 180 mm, thickness 0.3 mm), a screen printer was used to form a plurality of 50 mm × 50 mm catalyst layers of the same shape at regular intervals on the release layer formed on the PET film. Printing was performed so that individual pieces could be formed. This was dried in an air atmosphere at 50 ° C. for 12 hours to form a catalyst layer (thickness: 20 μm).
触媒層の転写は、一対のプレス型の間に転写シートの触媒層面が、水素イオン伝導性高分子電解質膜（Nafion112、デュポン社製）と接触するようにして１３０℃、３Ｍｐａの条件で挟持した後、ＰＥＴフィルムを剥離することにより行なった。このようにして、本発明の触媒層−電解質膜積層体を製造した。 The transfer of the catalyst layer was performed between a pair of press dies so that the catalyst layer surface of the transfer sheet was in contact with a hydrogen ion conductive polymer electrolyte membrane (Nafion112, manufactured by DuPont) at 130 ° C. and 3 MPa. Thereafter, the peeling was performed by peeling off the PET film. Thus, the catalyst layer-electrolyte membrane laminate of the present invention was manufactured.
以上のような方法により触媒層の転写を１０回試み、各サンプルについて転写触媒層の転写状態を目視により観察し、実施例１と同様に評価した。結果を表１に示す。 The transfer of the catalyst layer was attempted 10 times by the method described above, and the transfer state of the transfer catalyst layer was visually observed for each sample, and evaluated in the same manner as in Example 1. Table 1 shows the results.
実施例４
白金担持触媒１０ｇ（Ｐｔ：２０ｗｔ％、田中貴金属工業製のＴＥＣ１０シリーズ）及びバインダーとして５ｗｔ％ナフィオン（Nafion）溶液（デュポン社製、溶剤：ｎ−プロパノール）４０ｇを分散機にて攪拌混合することでペーストを調製した。
Example 4
10 g of a platinum-supported catalyst (Pt: 20 wt%, TEC10 series manufactured by Tanaka Kikinzoku Kogyo) and 40 g of a 5 wt% Nafion solution (manufactured by DuPont, solvent: n-propanol) as a binder are stirred and mixed by a disperser. A paste was prepared.
一方、ＰＥＴフィルム（Ｅ３１２０、東洋紡績（株）製、厚さ１３μｍ）上に、カルナウバワックスのエマルジョン液（ＥＭＵＳＴＡＲ−０１９９、日本精鑞製、液の濃度：２０重量％）を０．５〜１μｍ程度の厚さに片面塗工し、エマルジョン液を乾燥させて、ＰＥＴフィルム上に離型層を形成した。 On the other hand, on a PET film (E3120, manufactured by Toyobo Co., Ltd., 13 μm in thickness), an emulsion liquid of carnauba wax (EMUSTAR-0199, manufactured by Nippon Seiro, concentration of the liquid: 20% by weight) was added to 0.5 to 0.5%. One-side coating was performed to a thickness of about 1 μm, and the emulsion was dried to form a release layer on the PET film.
次に、ステンレス版（１８０ｍｍ×１８０ｍｍ、厚さ０．３ｍｍ）を用い、スクリーン印刷機にて、ＰＥＴフィルム上に形成した離型層上に同一形状の５０ｍｍ×５０ｍｍの触媒層が一定間隔で複数個形成できるように印刷を行った。これを大気雰囲気中５０℃で１２時間乾燥させ、触媒層（厚さ２０μｍ）を形成した。 Next, using a stainless steel plate (180 mm × 180 mm, thickness 0.3 mm), a screen printer was used to form a plurality of 50 mm × 50 mm catalyst layers of the same shape at regular intervals on the release layer formed on the PET film. Printing was performed so that individual pieces could be formed. This was dried in an air atmosphere at 50 ° C. for 12 hours to form a catalyst layer (thickness: 20 μm).
上記で形成した各々の触媒層上に、２０ｗｔ％ナフィオン（Nafion）溶液（デュポン社製、溶剤：ｎ−プロパノール）を塗布、含浸させ、接着層（厚さ３μｍ）を形成した。 ２０ A 20 wt% Nafion solution (manufactured by DuPont, solvent: n-propanol) was applied and impregnated on each of the catalyst layers formed above to form an adhesive layer (thickness: 3 μm).
触媒層の転写は、一対のプレス型の間に転写シートの接着層面が、水素イオン伝導性高分子電解質膜（Nafion112、デュポン社製）と接触するようにして１３０℃、３Ｍｐａの条件で挟持した後、ＰＥＴフィルムを剥離することにより行なった。このようにして、本発明の触媒層−電解質膜積層体を製造した。 The transfer of the catalyst layer was carried out between a pair of press dies so that the adhesive layer surface of the transfer sheet was in contact with a hydrogen ion conductive polymer electrolyte membrane (Nafion112, manufactured by DuPont) at 130 ° C. and 3 MPa. Thereafter, the peeling was performed by peeling off the PET film. Thus, the catalyst layer-electrolyte membrane laminate of the present invention was manufactured.
以上のような方法により触媒層の転写を１０回試み、各サンプルについて転写触媒層の転写状態を目視により観察し、実施例１と同様に評価した。結果を表１に示す。 The transfer of the catalyst layer was attempted 10 times by the method described above, and the transfer state of the transfer catalyst layer was visually observed for each sample, and evaluated in the same manner as in Example 1. Table 1 shows the results.
比較例１
白金担持触媒１０ｇ（Ｐｔ：２０ｗｔ％、田中貴金属工業製のＴＥＣ１０シリーズ）及びバインダーとして５ｗｔ％ナフィオン（Nafion）溶液（デュポン社製、溶剤：ｎ−プロパノール）４０ｇを分散機にて攪拌混合することでペーストを調製した。
Comparative Example 1
10 g of a platinum-supported catalyst (Pt: 20 wt%, TEC10 series manufactured by Tanaka Kikinzoku Kogyo) and 40 g of a 5 wt% Nafion solution (manufactured by DuPont, solvent: n-propanol) as a binder are stirred and mixed by a disperser. A paste was prepared.
一方、ＰＥＴフィルム（Ｅ３１２０、東洋紡績（株）製、厚さ１３μｍ）上に、上記で調製したペーストを、ドクターブレードにより厚さ５０μｍとなるように塗布し、これを大気雰囲気中５０℃で１２時間乾燥させ、触媒層を形成した。 On the other hand, the paste prepared above was applied on a PET film (E3120, manufactured by Toyobo Co., Ltd., 13 μm in thickness) so as to have a thickness of 50 μm by a doctor blade. After drying for a time, a catalyst layer was formed.
触媒層の転写は、一対のプレス型の間に転写シートの触媒層面が、水素イオン伝導性高分子電解質膜（Nafion112、デュポン社製）と接触するようにして１３０℃、３Ｍｐａの条件で挟持した後、ＰＥＴフィルムを剥離することにより行なった。 The transfer of the catalyst layer was performed between a pair of press dies so that the catalyst layer surface of the transfer sheet was in contact with a hydrogen ion conductive polymer electrolyte membrane (Nafion112, manufactured by DuPont) at 130 ° C. and 3 MPa. Thereafter, the peeling was performed by peeling off the PET film.
以上のような方法により触媒層の転写を１０回試み、各サンプルについて転写触媒層の転写状態を目視により観察し、実施例１と同様に評価した。結果を表１に示す。 The transfer of the catalyst layer was attempted 10 times by the method described above, and the transfer state of the transfer catalyst layer was visually observed for each sample, and evaluated in the same manner as in Example 1. Table 1 shows the results.
比較例２
白金担持触媒１０ｇ（Ｐｔ：２０ｗｔ％、田中貴金属工業製のＴＥＣ１０シリーズ）及びバインダーとして５ｗｔ％ナフィオン（Nafion）溶液（デュポン社製、溶剤：ｎ−プロパノール）４０ｇを分散機にて攪拌混合することでペーストを調製した。
Comparative Example 2
10 g of a platinum-supported catalyst (Pt: 20 wt%, TEC10 series manufactured by Tanaka Kikinzoku Kogyo) and 40 g of a 5 wt% Nafion solution (manufactured by DuPont, solvent: n-propanol) as a binder are stirred and mixed by a disperser. A paste was prepared.
一方、ＰＥＴフィルム（Ｅ３１２０、東洋紡績（株）製、厚さ１３μｍ）上に、シリコーン（ＫＦ９６、信越シリコーン社製を０．５〜１μｍ程度の厚さに片面塗工した。次に、シリコーンの上に、上記で調製したペーストを、ドクターブレードにより厚さ５０μｍとなるように塗布し、これを大気雰囲気中５０℃で１２時間乾燥させ、触媒層を形成した。 On the other hand, silicone (KF96, Shin-Etsu Silicone Co., Ltd.) was coated on a PET film (E3120, manufactured by Toyobo Co., Ltd., 13 μm in thickness) to a thickness of about 0.5 to 1 μm on one side. The paste prepared above was applied to a thickness of 50 μm using a doctor blade, and dried in an air atmosphere at 50 ° C. for 12 hours to form a catalyst layer.
触媒層の転写は、一対のプレス型の間に転写シートの触媒層面が、水素イオン伝導性高分子電解質膜（Nafion112、デュポン社製）と接触するようにして１３０℃、３Ｍｐａの条件で挟持した後、ＰＥＴフィルムを剥離することにより行なった。 The transfer of the catalyst layer was performed between a pair of press dies so that the catalyst layer surface of the transfer sheet was in contact with a hydrogen ion conductive polymer electrolyte membrane (Nafion112, manufactured by DuPont) at 130 ° C. and 3 MPa. Thereafter, the peeling was performed by peeling off the PET film.
以上のような方法により触媒層の転写を１０回試み、各サンプルについて転写触媒層の転写状態を目視により観察し、実施例１と同様に評価した。結果を表１に示す。 The transfer of the catalyst layer was attempted 10 times by the method described above, and the transfer state of the transfer catalyst layer was visually observed for each sample, and evaluated in the same manner as in Example 1. Table 1 shows the results.
実施例１と同様にして、電解質膜の両面に触媒層を転写し、本発明の触媒層−電解質膜積層体を製造した。
In the same manner as in Example 1, the catalyst layers were transferred to both surfaces of the electrolyte membrane to produce a catalyst layer-electrolyte membrane laminate of the present invention.
実施例６
実施例２と同様にして、電解質膜の両面に触媒層を転写し、本発明の触媒層−電解質膜積層体を製造した。
Example 6
In the same manner as in Example 2, the catalyst layers were transferred to both surfaces of the electrolyte membrane to produce a catalyst layer-electrolyte membrane laminate of the present invention.
実施例７
実施例３と同様にして、電解質膜の両面に触媒層を転写し、本発明の触媒層−電解質膜積層体を製造した。
Example 7
In the same manner as in Example 3, the catalyst layers were transferred to both surfaces of the electrolyte membrane to produce a catalyst layer-electrolyte membrane laminate of the present invention.
実施例８
実施例４と同様にして、電解質膜の両面に触媒層を転写し、本発明の触媒層−電解質膜積層体を製造した。
Example 8
In the same manner as in Example 4, the catalyst layers were transferred to both surfaces of the electrolyte membrane to produce a catalyst layer-electrolyte membrane laminate of the present invention.
実施例９
実施例５で製造した触媒層−電解質膜積層体の両側に、電極基材（炭素繊維からなるカーボンペーパー、ＴＧＰ−Ｈ−９０、厚さ０．２８ｍｍ、東レ（株）製）を配置し、１５０℃、５ＭＰａの条件にて熱プレスを行い、本発明の電極−電解質膜接合体を製造した。
Example 9
An electrode substrate (carbon paper made of carbon fiber, TGP-H-90, thickness 0.28 mm, manufactured by Toray Industries, Inc.) was placed on both sides of the catalyst layer-electrolyte membrane laminate produced in Example 5, Hot pressing was performed at 150 ° C. and 5 MPa to produce an electrode-electrolyte membrane assembly of the present invention.
実施例１０
実施例６で製造した触媒層−電解質膜積層体の両側に、電極基材（炭素繊維からなるカーボンペーパー、ＴＧＰ−Ｈ−９０、東レ（株）製）を配置し、１５０℃、５ＭＰａの条件にて熱プレスを行い、本発明の電極−電解質膜接合体を製造した。
Example 10
An electrode substrate (carbon paper made of carbon fiber, TGP-H-90, manufactured by Toray Industries, Inc.) was placed on both sides of the catalyst layer-electrolyte membrane laminate produced in Example 6, and the conditions were 150 ° C. and 5 MPa. Was subjected to hot pressing to produce an electrode-electrolyte membrane assembly of the present invention.
実施例１１
実施例７で製造した触媒層−電解質膜積層体の電解質膜が露出している部分から、所定の大きさに裁断し、次に裁断した触媒層−電解質膜積層体の両側に、電極基材（炭素繊維からなるカーボンペーパー、ＴＧＰ−Ｈ−９０、東レ（株）製）を配置し、１５０℃、５ＭＰａの条件にて熱プレスを行い、本発明の電極−電解質膜接合体を製造した。
Example 11
The catalyst layer-electrolyte membrane laminate manufactured in Example 7 was cut into a predetermined size from a portion where the electrolyte membrane was exposed, and then the electrode base material was placed on both sides of the cut catalyst layer-electrolyte membrane stack. (Carbon paper made of carbon fiber, TGP-H-90, manufactured by Toray Industries, Inc.) was placed and hot-pressed at 150 ° C. and 5 MPa to produce an electrode-electrolyte membrane assembly of the present invention.
実施例１２
実施例８で製造した触媒層−電解質膜積層体の電解質膜が露出している部分から、所定の大きさに裁断し、次に裁断した触媒層−電解質膜積層体の両側に、電極基材（炭素繊維からなるカーボンペーパー、ＴＧＰ−Ｈ−９０、東レ（株）製）を配置し、１５０℃、５ＭＰａの条件にて熱プレスを行い、本発明の電極−電解質膜接合体を製造した。
Example 12
The catalyst layer-electrolyte layer laminate manufactured in Example 8 was cut into a predetermined size from a portion where the electrolyte membrane was exposed, and then the electrode base material was placed on both sides of the cut catalyst layer-electrolyte layer stack. (Carbon paper made of carbon fiber, TGP-H-90, manufactured by Toray Industries, Inc.) was placed and hot-pressed at 150 ° C. and 5 MPa to produce an electrode-electrolyte membrane assembly of the present invention.
Claims (18)
(2)上記(1)工程で得られる転写シートの触媒層面が電解質膜面に対面するように転写シートを配置し、加圧した後、該転写シートの基材を触媒層面から剥離することにより触媒層−電解質膜積層体を得る工程、
(3)上記(2)工程で得られる触媒層−電解質膜積層体の両面に電極基材を配置し、加圧することにより電極−電解質膜接合体を得る工程、及び
(4)上記(3)工程で得られる電極−電解質膜接合体を用いて燃料電池を得る工程
を備えた燃料電池の製造方法。 (1) A step of forming a release layer on at least one surface of a substrate, and then forming one or more catalyst layers on the release layer to obtain a transfer sheet for producing an electrode-electrolyte membrane assembly. ,
(2) By disposing the transfer sheet so that the catalyst layer surface of the transfer sheet obtained in the step (1) faces the electrolyte membrane surface, pressurizing, by peeling the base material of the transfer sheet from the catalyst layer surface Obtaining a catalyst layer-electrolyte membrane laminate,
(3) placing the electrode substrate on both sides of the catalyst layer obtained in the step (2) -electrolyte membrane laminate, a step of obtaining an electrode-electrolyte membrane assembly by pressing, and
(4) A method for manufacturing a fuel cell, comprising a step of obtaining a fuel cell using the electrode-electrolyte membrane assembly obtained in the step (3).
(2)上記(1)工程で得られる転写シートの接着層面が電解質膜面に対面するように転写シートを配置し、加圧した後、該転写シートの基材を触媒層面から剥離することにより触媒層−電解質膜積層体を得る工程、
(3)上記(2)工程で得られる触媒層−電解質膜積層体の両面に電極基材を配置し、加圧することにより電極−電解質膜接合体を得る工程、及び
(4)上記(3)工程で得られる電極−電解質膜接合体を用いて燃料電池を得る工程
を備えた燃料電池の製造方法。 (1) forming a release layer on at least one side of the substrate, forming one or more catalyst layers on the release layer, and further forming an adhesive layer on the catalyst layer to form an electrode; A step of obtaining a transfer sheet for manufacturing an electrolyte membrane assembly,
(2) By disposing the transfer sheet so that the adhesive layer surface of the transfer sheet obtained in the step (1) faces the electrolyte membrane surface, pressurizing, by peeling the base material of the transfer sheet from the catalyst layer surface Obtaining a catalyst layer-electrolyte membrane laminate,
(3) placing the electrode substrate on both sides of the catalyst layer obtained in the step (2) -electrolyte membrane laminate, a step of obtaining an electrode-electrolyte membrane assembly by pressing, and
(4) A method for manufacturing a fuel cell, comprising a step of obtaining a fuel cell using the electrode-electrolyte membrane assembly obtained in the step (3).
A fuel cell obtained by the method according to claim 15.
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