JP2010146794A - Manufacturing method of membrane-electrode assembly for fuel cell - Google Patents
Manufacturing method of membrane-electrode assembly for fuel cell Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 239000000446 fuel Substances 0.000 title claims description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 156
- 239000003792 electrolyte Substances 0.000 claims abstract description 66
- 238000009792 diffusion process Methods 0.000 claims abstract description 41
- 238000005520 cutting process Methods 0.000 claims abstract description 11
- 239000012528 membrane Substances 0.000 claims description 62
- 238000007654 immersion Methods 0.000 claims description 6
- 238000005304 joining Methods 0.000 claims description 3
- 210000004027 cell Anatomy 0.000 claims 2
- 210000000170 cell membrane Anatomy 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 24
- 238000000034 method Methods 0.000 abstract description 20
- 238000000576 coating method Methods 0.000 abstract description 12
- 239000011248 coating agent Substances 0.000 abstract description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical group Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 239000011737 fluorine Substances 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- 238000011144 upstream manufacturing Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
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
Landscapes
- Fuel Cell (AREA)
Abstract
Description
本発明は、固体高分子形の燃料電池に用いられる膜−電極接合体（ＭＥＡ：Membrane Electrode Assembly）の製造方法に関するものである。 The present invention relates to a method for producing a membrane-electrode assembly (MEA) used in a polymer electrolyte fuel cell.
従来、この種の技術としては特許文献１に記載のものがあった。
これは、電解質膜の両面に、所望の開口部が形成されたマスクフィルムを配置し、それらの外側に触媒層形成用フィルムを配置するように、電解質膜、マスクフィルム及び触媒層形成用フィルムを連続的に供給し、熱プレス転写を連続的に施し、連続的に供給されている電解質膜上に間欠的に触媒層を形成した後、切り出す（裁断する）ことにより、ＭＥＡを連続的に製造するというものである。
Conventionally, this type of technology has been described in Patent Document 1.
This is because the electrolyte film, the mask film, and the catalyst layer forming film are arranged so that the mask film in which a desired opening is formed is arranged on both surfaces of the electrolyte membrane, and the catalyst layer forming film is arranged outside of the mask film. Continuously supply, heat press transfer continuously, intermittently form catalyst layer on continuously supplied electrolyte membrane, then cut out (cut), continuously manufacture MEA It is to do.
しかしながら上記従来技術では、次のような課題があった。
すなわち、上記従来技術のように電解質膜上に間欠的に触媒層を形成する理由の一つは、個々のＭＥＡに裁断した後において、触媒層が電解質膜の端部まで達しないようにすることにある。触媒層が電解質膜の端部まで達すると、同端部において触媒が電解質膜表裏面に回り込み、燃料極と空気極を電子的に短絡させてしまう虞があることによる。
However, the above prior art has the following problems.
That is, one of the reasons why the catalyst layer is intermittently formed on the electrolyte membrane as in the prior art is that the catalyst layer does not reach the end of the electrolyte membrane after being cut into individual MEAs. It is in. This is because when the catalyst layer reaches the end of the electrolyte membrane, the catalyst may enter the front and back surfaces of the electrolyte membrane at the same end and electronically short-circuit the fuel electrode and the air electrode.
しかし、上記従来技術のような電解質膜上に間欠的に触媒層を形成するという間欠塗工法においては、塗工以降の工程において膜が膨潤・収縮するために、膜及び触媒層の寸法・形状にバラツキが生じやすく、ＭＥＡの性能や組付け上の問題が発生しやすかった。
例えば、ＭＥＡの性能上の問題としては、触媒層面積が小さすぎる場合には発電面積が小さくなるのでセル出カが低くなることが挙げられる。
ＭＥＡの組付け上の問題としては、ＭＥＡ裁断後に収縮した場合にはＭＥＡ端部とセルの端部シール部間に隙間が生じて内部リ−クを生じさせることが挙げられる。また、触媒層面積が大きすぎる場合には、触媒層がガス拡散層からはみ出したり、ＭＥＡの端部シール（シールのための接着やガスケット組付け等）の際に気密不良を起こして外部リ−クを生じさせることが挙げられる。
However, in the intermittent coating method in which the catalyst layer is intermittently formed on the electrolyte membrane as in the above prior art, since the membrane swells and contracts in the steps after coating, the dimensions and shape of the membrane and the catalyst layer As a result, MEA performance and assembly problems were likely to occur.
For example, as a performance problem of MEA, when the catalyst layer area is too small, the power generation area becomes small, so that the cell output becomes low.
As a problem in assembling the MEA, when contracted after the MEA cutting, there is a gap between the MEA end portion and the cell end seal portion to cause an internal leak. If the catalyst layer area is too large, the catalyst layer may protrude from the gas diffusion layer or cause an airtight defect when sealing the end of the MEA (adhesion for sealing, gasket assembly, etc.). This may be caused.
本発明は、触媒層の寸法・形状にバラツキが発生せず、したがってバラツキ発生に起因する膜−電極接合体（ＭＥＡ）の性能上や組付け上の問題を解消でき、しかも生産性の高い燃料電池用膜−電極接合体製造方法を提供することを課題とする。 The present invention does not generate variations in the size and shape of the catalyst layer, and therefore can solve the problems in the performance and assembly of the membrane-electrode assembly (MEA) due to the occurrence of variations, and has high productivity. It is an object to provide a method for producing a membrane-electrode assembly for a battery.
上記課題は、燃料電池用膜−電極接合体製造方法を下記各態様の構成とすることによって解決される。
各態様は、請求項と同様に、項に区分し、各項に番号を付し、必要に応じて他の項の番号を引用する形式で記載する。これは、あくまでも本発明の理解を容易にするためであり、本明細書に記載の技術的特徴及びそれらの組合わせが以下の各項に記載のものに限定されると解釈されるべきではない。また、１つの項に複数の事項が記載されている場合、それら複数の事項を常に一緒に採用しなければならないわけではなく、一部の事項のみを取り出して採用することも可能である。
The said subject is solved by making the membrane-electrode assembly manufacturing method for fuel cells into the structure of each following aspect.
As with the claims, each aspect is divided into sections, each section is numbered, and is described in a form that cites the numbers of other sections as necessary. This is merely for the purpose of facilitating the understanding of the present invention, and the technical features described in this specification and combinations thereof should not be construed as being limited to those described in the following sections. . In addition, when a plurality of items are described in one section, it is not always necessary to employ the plurality of items together, and it is also possible to take out only a part of the items and employ them.
以下の各項のうち、（１）項が請求項１に、（２）項が請求項２に、（３）項が請求項３に、各々対応する。（４）項及び（５）項は請求項に係る発明ではない。 Of the following items, (1) corresponds to claim 1, (2) corresponds to claim 2, and (3) corresponds to claim 3. Claims (4) and (5) are not claimed inventions.
（１） 一方向に搬送される帯状の電解質膜に触媒を連続塗工する第１工程と、前記触媒が塗工されてなる触媒層上に間隔をおいてガス拡散層を接合する第２工程と、隣接する前記ガス拡散層相互間の定位置で前記触媒が塗工済みの電解質膜を切断する第３工程と、前記切断により分離された、前記触媒が塗工済みでその触媒層上にガス拡散層が接合された電解質膜の少なくとも前記触媒層が露出する端部分を、その触媒層を電解質膜から除去可能な触媒除去液中に浸漬する第４工程とを、備えることを特徴とする燃料電池用膜−電極接合体製造方法。
拡散層としては、電極の形状を安定化させる役割を持たせるため、剛性の高い基材を持つものが好適である。
触媒層上へのガス拡散層の接合には圧着接合ないし熱圧接合が好適である。
触媒除去液としては、電解質膜に塗工された触媒を溶解等により除去可能な液体であればそのいずれでもよい。白金を含む触媒が用いられた場合における王水がその典型例である。また、一種類の触媒除去液で除去が困難である場合には、複数種類の触媒除去液を順に用いてもよい。
ガス拡散層は一般に撥水性を有するので、触媒層が露出する電解質膜端部分からガス拡散層に亘って触媒除去液中に浸漬されても、触媒除去液はガス拡散層中に浸透し難く、また触媒層除去後に触媒除去液中から引き上げれば、触媒除去液はガス拡散層から容易に滴下排出される。
（２） 前記第４工程における触媒除去液中への前記電解質膜の浸漬は、複数の前記電解質膜について一括して行うことを特徴とする（１）項に記載の燃料電池用膜−電極接合体製造方法。
（３） 前記第４工程における触媒除去液中への前記電解質膜の浸漬は、複数の前記電解質膜について一括して、かつその全体に対して行うことを特徴とする（１）項に記載の燃料電池用膜−電極接合体製造方法。
本項に記載の発明では、触媒が塗工済みでその触媒層上にガス拡散層が接合された電解質膜を複数一括して、かつその全体を触媒除去液中へ浸漬するので、ガス拡散層の撥水性を高くし、また浸漬時間を短時間にすることが望ましい。
（４） 前記触媒は白金を含む触媒であり、前記触媒除去液は王水であることを特徴とする（１）項、（２）項又は（３）項に記載の燃料電池用膜−電極接合体製造方法。
本項に記載の発明によれば、燃料電池用膜−電極接合体における触媒として一般的な白金を含む触媒について、その除去を可能とする。
（５） 前記電解質膜はフッ素系電解質膜であり、前記ガス拡散層はフッ素系樹脂による撥水性を有するガス拡散層であることを特徴とする（４）項に記載の燃料電池用膜−電極接合体製造方法。
フッ素系電解質膜は、炭化水素系電解質膜より耐王水性の観点から望ましい。また、ガス拡散層は一般に撥水性を有するが、フッ素系樹脂による撥水性は撥水効果が大きく、したがって、王水中への触媒塗工済み電解質膜の浸漬時において、ガス拡散層で覆われた触媒層への王水の影響を最小限にとどめることができる。すなわち、電解質膜及びガス拡散層で覆われた触媒層への王水の影響を最小限にとどめながら、（４）項に記載の燃料電池用膜−電極接合体製造方法を実施できる。
(1) A first step in which a catalyst is continuously applied to a strip-shaped electrolyte membrane conveyed in one direction, and a second step in which a gas diffusion layer is joined at an interval on the catalyst layer on which the catalyst is applied. And a third step of cutting the electrolyte membrane coated with the catalyst at a fixed position between the adjacent gas diffusion layers, and the catalyst separated by the cutting and coated on the catalyst layer. And a fourth step of immersing at least an end portion of the electrolyte membrane to which the gas diffusion layer is bonded, in which the catalyst layer is exposed in a catalyst removing solution capable of removing the catalyst layer from the electrolyte membrane. A method for producing a membrane-electrode assembly for a fuel cell.
As the diffusion layer, a layer having a highly rigid base material is preferable in order to have a role of stabilizing the shape of the electrode.
For bonding of the gas diffusion layer on the catalyst layer, pressure bonding or hot pressure bonding is suitable.
The catalyst removing liquid may be any liquid that can remove the catalyst applied to the electrolyte membrane by dissolution or the like. A typical example is aqua regia when a platinum-containing catalyst is used. Further, when it is difficult to remove with one type of catalyst removal solution, a plurality of types of catalyst removal solutions may be used in order.
Since the gas diffusion layer generally has water repellency, even if the catalyst removal solution is immersed in the catalyst removal solution over the gas diffusion layer from the end portion of the electrolyte membrane where the catalyst layer is exposed, the catalyst removal solution is difficult to penetrate into the gas diffusion layer. Further, if the catalyst is removed from the catalyst removal solution after removal of the catalyst layer, the catalyst removal solution is easily dropped and discharged from the gas diffusion layer.
(2) The membrane-electrode bonding for a fuel cell according to (1), wherein the immersion of the electrolyte membrane in the catalyst removal solution in the fourth step is performed collectively for the plurality of electrolyte membranes. Body manufacturing method.
(3) The immersion of the electrolyte membrane in the catalyst removal solution in the fourth step is performed on the whole of the plurality of electrolyte membranes and the entirety thereof, as described in (1) A method for producing a membrane-electrode assembly for a fuel cell.
In the invention described in this section, a plurality of electrolyte membranes in which the catalyst has been applied and the gas diffusion layer is bonded onto the catalyst layer are collectively and immersed in the catalyst removal solution. It is desirable to increase the water repellency and to shorten the dipping time.
(4) The membrane-electrode for a fuel cell according to (1), (2) or (3), wherein the catalyst is a catalyst containing platinum and the catalyst removal solution is aqua regia. Bonded body manufacturing method.
According to the invention described in this section, it is possible to remove a catalyst containing general platinum as a catalyst in a membrane-electrode assembly for a fuel cell.
(5) The membrane-electrode for a fuel cell according to (4), wherein the electrolyte membrane is a fluorine-based electrolyte membrane, and the gas diffusion layer is a gas diffusion layer having water repellency by a fluorine-based resin. Bonded body manufacturing method.
The fluorine-based electrolyte membrane is more desirable than the hydrocarbon-based electrolyte membrane from the viewpoint of water resistance. In addition, the gas diffusion layer generally has water repellency, but the water repellency due to the fluorine-based resin has a large water repellency effect, and therefore, the catalyst-coated electrolyte membrane was covered with the gas diffusion layer when immersed in aqua regia. The influence of aqua regia on the catalyst layer can be minimized. That is, the method for producing a membrane-electrode assembly for a fuel cell according to the item (4) can be carried out while minimizing the influence of aqua regia on the catalyst layer covered with the electrolyte membrane and the gas diffusion layer.
（１）項に記載の発明によれば、触媒層の寸法・形状は拡散層の形状により規定されるため、にバラツキが発生せず、したがってバラツキ発生に起因する膜−電極接合体の性能上や組付け上の問題を解消でき、しかも生産性の高い燃料電池用膜−電極接合体製造方法を提供できる。
（２）項に記載の発明によれば、（１）項に記載の発明よりも生産性の高い膜−電極接合体製造方法を提供できる。
（３）項に記載の発明によれば、更に生産性の高い膜−電極接合体製造方法を提供できる。
なお、（４）項及び（５）項に記載の発明は、本発明（特許請求の範囲に記載した発明）ではないので、上記課題を解決するための手段の欄に、その効果を述べた。
According to the invention described in item (1), since the size and shape of the catalyst layer are defined by the shape of the diffusion layer, there is no variation. Therefore, in terms of performance of the membrane-electrode assembly due to the occurrence of variation. In addition, it is possible to provide a method for producing a fuel cell membrane-electrode assembly, which can solve the problems in assembly and high productivity.
According to the invention described in the item (2), a method for producing a membrane-electrode assembly having higher productivity than the invention described in the item (1) can be provided.
According to the invention described in item (3), it is possible to provide a membrane-electrode assembly manufacturing method with higher productivity.
Since the inventions described in the items (4) and (5) are not the present invention (the invention described in the claims), the effect is described in the column of means for solving the above problems. .
以下、本発明の実施の形態を図面に基づき説明する。なお、各図間において、同一符号は同一又は相当部分を示す。
図１は、本発明による燃料電池用膜−電極接合体製造方法の一実施形態の説明図で、同膜−電極接合体を連続的に製造する工程の一例を側方から示している。図２は、図１中の一点鎖線で囲んだ部分アの拡大図である。
図１に示すように、本実施形態に係る燃料電池用膜−電極接合体製造方法は、第１工程Ｉ〜第４工程IＶを備える。
Hereinafter, embodiments of the present invention will be described with reference to the drawings. In addition, the same code | symbol shows the same or an equivalent part between each figure.
FIG. 1 is an explanatory view of an embodiment of a method for producing a membrane-electrode assembly for a fuel cell according to the present invention, and shows an example of a process for continuously producing the membrane-electrode assembly from the side. FIG. 2 is an enlarged view of a portion a surrounded by a one-dot chain line in FIG.
As shown in FIG. 1, the fuel cell membrane-electrode assembly manufacturing method according to the present embodiment includes a first step I to a fourth step IV.
第１工程Ｉは、例えばロール状に巻いた状態から繰り出され、一方向イ、図示例では右方向に搬送される帯状の電解質膜１１に触媒１２を連続塗工（べた塗り）する工程である。
ここでは、電解質膜１１としてフッ素系電解質膜が、触媒１２として白金を含む触媒、具体的にはカーボン粒子に白金を担持させてなる触媒が、各々用いられている。電解質膜１１、触媒１２の材質はこれらのみに限定されない。
触媒１２の塗工は、帯状の電解質膜１１の表裏各面の全領域（全面）に対して連続して行う。この際、塗工厚が一様にされることは勿論である。このような塗工が可能ならばどのような塗工手段でもよいが、ここではダイコータ１３が好例として用いられている。ダイコータ１３は帯状の電解質膜１１の表裏各面側に各々配置されるが、図示例では帯状の電解質膜１１の搬送方向に適宜間隔置いて配置されている。
The first step I is a step in which the catalyst 12 is continuously applied (solid coating) to the strip-shaped electrolyte membrane 11 which is fed out from a state wound, for example, in a roll shape and conveyed in one direction i, in the illustrated example, in the right direction. .
Here, a fluorine-based electrolyte membrane is used as the electrolyte membrane 11, and a catalyst containing platinum as the catalyst 12, specifically, a catalyst in which platinum is supported on carbon particles, is used. The materials of the electrolyte membrane 11 and the catalyst 12 are not limited to these.
The application of the catalyst 12 is continuously performed on the entire area (entire surface) of each surface of the belt-shaped electrolyte membrane 11. In this case, it is a matter of course that the coating thickness is made uniform. Any coating means may be used as long as such coating is possible, but here the die coater 13 is used as a good example. The die coater 13 is disposed on each side of the front and back surfaces of the strip-shaped electrolyte membrane 11. In the illustrated example, the die coater 13 is disposed at an appropriate interval in the transport direction of the strip-shaped electrolyte membrane 11.
第２工程IIは、第１工程Ｉによって帯状の電解質膜１１の表裏両面に触媒１２が塗工されてなる触媒層１４上に間隔をおいてガス拡散層１５を接合、ここでは熱圧接合する工程である。
上記ガス拡散層１５は、カーボン材からなり撥水性を有するが、ここではフッ素系樹脂、例えばポリテトラフルオロエチレン（ＰＴＦＥ）等によって更なる撥水性と耐王水性が付与されている。
In the second step II, the gas diffusion layer 15 is joined with a gap on the catalyst layer 14 formed by coating the catalyst 12 on both the front and back surfaces of the strip-shaped electrolyte membrane 11 in the first step I. It is a process.
The gas diffusion layer 15 is made of a carbon material and has water repellency. Here, further water repellency and water resistance are imparted by a fluorine-based resin such as polytetrafluoroethylene (PTFE).
第３工程IIIは、第２工程IIによって触媒層１４上にガス拡散層１５が接合された、触媒１２（触媒層１４）塗工済みの帯状の電解質膜１１を切断、詳しくは隣接するガス拡散層１５，１５相互間の中央位置で裁断する工程である。図１中の１６は、この際用いられる裁断刃を示し、一点鎖線矢印ハは次工程（第４工程IＶ）への繋がりを示す。 In the third step III, the strip-shaped electrolyte membrane 11 coated with the catalyst 12 (catalyst layer 14), in which the gas diffusion layer 15 is joined on the catalyst layer 14 in the second step II, is cut. This is a step of cutting at the center position between the layers 15 and 15. 1 in FIG. 1 indicates a cutting blade used at this time, and a one-dot chain line arrow C indicates a connection to the next process (fourth process IV).
第４工程IＶは、第３工程IIIにおける裁断によって分離された、触媒塗工済みでその触媒層１４上にガス拡散層１５が接合された電解質膜１１の少なくとも触媒層１４が露出する端部分を、その触媒層１４を電解質膜１１から除去可能な触媒除去液１６中に浸漬する工程である。
触媒除去液１６は、電解質膜１１に塗工された触媒１２（触媒層１４）を溶解等により除去可能な液体であればそのいずれでもよい。本実施形態では、触媒１２として白金を含む触媒が用いられているので、触媒除去液１６には王水、つまり濃塩酸と濃硝酸とを３：１の体積比で混合した液体が用いられている。図中１７は、触媒除去液１６を収容した槽（触媒除去液槽）である。
なお、上記裁断によって分離された、触媒塗工済みでその触媒層１４上にガス拡散層１５が接合された電解質膜１１は、概ね膜−電極−ガス拡散層接合体（ＭＥＧＡ：Membrane Electrode Gas diffusion layer Assembly）を構成する接合体であり、以下、これをＭＥＧＡ素体１８と記す。このＭＥＧＡ素体１８からガス拡散層１５を除いた構成部分が概ね膜−電極接合体（ＭＥＡ）を構成する接合体であり、以下、これをＭＥＡ素体１９と記す。
In the fourth step IV, an end portion of the electrolyte membrane 11 separated by cutting in the third step III and coated with the catalyst and having the gas diffusion layer 15 bonded on the catalyst layer 14 is exposed. In this step, the catalyst layer 14 is immersed in a catalyst removal solution 16 that can be removed from the electrolyte membrane 11.
The catalyst removal liquid 16 may be any liquid as long as it can remove the catalyst 12 (catalyst layer 14) applied to the electrolyte membrane 11 by dissolution or the like. In this embodiment, since a catalyst containing platinum is used as the catalyst 12, the catalyst removal liquid 16 is aqua regia, that is, a liquid in which concentrated hydrochloric acid and concentrated nitric acid are mixed at a volume ratio of 3: 1. Yes. In the figure, reference numeral 17 denotes a tank (catalyst removal liquid tank) containing the catalyst removal liquid 16.
The electrolyte membrane 11 separated by the above-described cutting and coated with the catalyst and having the gas diffusion layer 15 bonded onto the catalyst layer 14 is generally a membrane-electrode-gas diffusion layer assembly (MEGA). layer assembly), which is hereinafter referred to as MEGA element body 18. A component obtained by removing the gas diffusion layer 15 from the MEGA body 18 is a joined body that generally constitutes a membrane-electrode assembly (MEA), which is hereinafter referred to as a MEA body 19.
この第４工程IＶでは、図２に拡大して示すように、上記ＭＥＡ素体１９（全体としてはＭＥＧＡ素体１８）の触媒層１４が露出する部分を含む端部分を触媒除去液１６中に浸漬して同ＭＥＡ素体１９端部分に露出する触媒層１４部分を溶解し、電解質膜１１から除去するもので、これによりＭＥＡ２０が製造（全体としてはＭＥＧＡ２１が製造）される。 In the fourth step IV, as shown in an enlarged view in FIG. 2, the end portion including the portion where the catalyst layer 14 of the MEA element body 19 (the MEGA element body 18 as a whole) is exposed is placed in the catalyst removal liquid 16. The portion of the catalyst layer 14 that is immersed and exposed at the end portion of the MEA element body 19 is dissolved and removed from the electrolyte membrane 11, whereby the MEA 20 is manufactured (the MEGA 21 is manufactured as a whole).
この第４工程IＶを加えた理由を以下に述べる。
第３工程III、すなわちＭＥＡ素体１９（ＭＥＧＡ素体１８）の裁断工程を経ただけでは、図３に示すようにＭＥＡ素体１９の端部分には触媒層１４が露出している。この触媒層１４は、厚さｔ１＝数μｍ〜数十μｍ程度という極薄い電解質膜１１の両面に接合形成されている。このため、ＭＥＡ素体１９の端部分に触媒層１４が露出していると、両触媒層１４，１４間、換言すれば燃料極と空気極間が至近距離Ｌ１で近接することになり、触媒１２の回り込みによって両極間に短絡を生じさせる虞がある。
第４工程IＶにより、ＭＥＡ素体１９の端部分に露出する触媒層１４を除去すれば、図４に示すように両触媒層１４，１４（燃料極及び空気極）間の距離は上記Ｌ１より長いＬ２（Ｌ２＞Ｌ１）となって、上記触媒１２の回り込みによる両極間の短絡を防止できる。
The reason why the fourth step IV is added will be described below.
As shown in FIG. 3, the catalyst layer 14 is exposed at the end portion of the MEA element body 19 only after the third process III, that is, the cutting process of the MEA element body 19 (MEGA element body 18). The catalyst layer 14 is formed on both surfaces of an extremely thin electrolyte membrane 11 having a thickness t1 of about several μm to several tens of μm. For this reason, when the catalyst layer 14 is exposed at the end portion of the MEA element body 19, the catalyst layers 14 and 14, in other words, the fuel electrode and the air electrode are close to each other at a close distance L1, and the catalyst There is a risk that a short circuit will occur between the two poles due to the wrap around 12.
If the catalyst layer 14 exposed at the end portion of the MEA element body 19 is removed by the fourth step IV, the distance between the catalyst layers 14 and 14 (the fuel electrode and the air electrode) as shown in FIG. It becomes long L2 (L2> L1), and the short circuit between both electrodes by the wraparound of the catalyst 12 can be prevented.
ＭＥＡ２０（ＭＥＧＡ２１）は、通常、触媒層１４とガス拡散層１５は同寸法・形状、同位置に設定されるので、図５に例示するように四角形のＭＥＡ素体１９（ＭＥＧＡ素体１８）の４辺５１〜５４の全てについて第４工程が実施される。
したがって、第３工程で裁断された後の触媒層塗工済みの電解質膜１１（ＭＥＡ素体１９）の、第４工程における触媒除去液１６中への浸漬を、触媒層１４が露出する端部分のみならず、図６に示すようにＭＥＡ素体１９の全体に対して行ってもよく、これによれば生産性を高めることができる。なお図６では、複数のＭＥＡ素体１９について一括して触媒除去液槽１７内の触媒除去液１６中へ浸漬する例を示しており、更に生産性を高めることができる。
裁断された後の触媒層塗工済みの電解質膜１１（ＭＥＡ素体１９）の全体ではなく、各辺別の触媒除去液１６中への浸漬ではあるが、複数のＭＥＡ素体１９を一括して触媒除去液１６中に浸漬するようにしてもよい。
触媒除去液１６中への浸漬時に、ガス拡散層１５が触媒層１４から剥がれないように支持するようにしてもよい。
In the MEA 20 (MEGA 21), the catalyst layer 14 and the gas diffusion layer 15 are usually set to the same size, shape, and position, so that the rectangular MEA element 19 (MEGA element 18) is formed as illustrated in FIG. A 4th process is implemented about all the 4 sides 51-54.
Therefore, the end portion where the catalyst layer 14 is exposed is the immersion of the electrolyte membrane 11 (MEA element body 19) coated with the catalyst layer after being cut in the third step into the catalyst removal liquid 16 in the fourth step. In addition, as shown in FIG. 6, the entire MEA element 19 may be performed, and according to this, productivity can be improved. FIG. 6 shows an example in which a plurality of MEA bodies 19 are immersed in the catalyst removal liquid 16 in the catalyst removal liquid tank 17 at a time, and productivity can be further increased.
It is not the entire electrolyte membrane 11 (MEA element body 19) that has been coated with the catalyst layer after being cut, but is immersed in the catalyst removal liquid 16 for each side, but a plurality of MEA element bodies 19 are collected together. Then, it may be immersed in the catalyst removal liquid 16.
You may make it support so that the gas diffusion layer 15 may not peel from the catalyst layer 14 at the time of immersion in the catalyst removal liquid 16. FIG.
本実施形態によれば、図３及び図４を参照して述べたように、ＭＥＡ素体１９の端部分において触媒１２の回り込みによる両触媒層１４，１４（燃料極と空気極）間の短絡を、電解質膜上に間欠的に触媒層を形成するという従来の間欠塗工法におけると同様に防止できる。
その一方で、従来の間欠塗工法における、触媒層の寸法・形状のバラツキは生じない。本実施形態では、ＭＥＡ２０は、帯状の電解質膜１１に触媒１２を連続塗工（べた塗り）した後に、無用部分であるＭＥＡ素体１９の端部分の触媒層１４を除去して、触媒層１４の寸法・形状を揃えるようにしたからである。
したがって本実施形態によれば、触媒層１４の寸法・形状のバラツキ発生に起因するＭＥＡ２０の性能上や組付け上の問題を解消できる。すなわち、ＭＥＡ２０の性能上の問題としては、触媒層１４面積が小さすぎる場合の発電面積の縮小によるセル出カの低下を防止できる。また、ＭＥＡ２０の組付け上の問題としては、前述したような、触媒層１４の面積が小さすぎる場合の内部リ−クや大きすぎる場合の外部リ−クの発生を防止できる。 しかも、このような効果を有するＭＥＡ２０を、第１工程Ｉ〜第４工程IＶと連続する工程により連続して製造できるので、生産性を高めることができる。
According to the present embodiment, as described with reference to FIGS. 3 and 4, the short circuit between the catalyst layers 14 and 14 (the fuel electrode and the air electrode) due to the wraparound of the catalyst 12 at the end portion of the MEA element body 19. Can be prevented as in the conventional intermittent coating method in which the catalyst layer is intermittently formed on the electrolyte membrane.
On the other hand, there is no variation in the size and shape of the catalyst layer in the conventional intermittent coating method. In this embodiment, the MEA 20 removes the catalyst layer 14 at the end portion of the MEA element body 19 which is a useless portion after continuously applying (solid coating) the catalyst 12 to the belt-shaped electrolyte membrane 11, thereby removing the catalyst layer 14. This is because the size and shape of the are made uniform.
Therefore, according to the present embodiment, problems in performance and assembly of the MEA 20 due to occurrence of variations in the size and shape of the catalyst layer 14 can be solved. That is, as a performance problem of the MEA 20, it is possible to prevent a decrease in cell output due to a reduction in the power generation area when the area of the catalyst layer 14 is too small. Further, as a problem in assembling the MEA 20, it is possible to prevent the occurrence of an internal leak when the area of the catalyst layer 14 is too small or an external leak when it is too large as described above. And since MEA20 which has such an effect can be continuously manufactured by the process which is continuous with the 1st process I-the 4th process IV, productivity can be raised.
本実施形態においては、ガス拡散層１５の撥水性が高められているので、上記のように触媒層１４が露出する電解質膜１１の端部分を触媒除去液１６中に浸漬しても、触媒除去液１６はガス拡散層１５中に浸透し難く、また触媒層１４除去後に触媒除去液１６中から引き上げれば触媒除去液１６はガス拡散層１５から容易に滴下排出される。
したがって、触媒除去液１６中への触媒塗工済み電解質膜１１の浸漬時において、ガス拡散層１５で覆われた触媒層１４への触媒除去液１６の影響を最小限にとどめることができる。つまり、電解質膜１１及びガス拡散層１５で覆われた触媒層１４への触媒除去液１６、本実施形態では王水の影響を最小限にとどめながらＭＥＡ素体１９（全体としてはＭＥＧＡ素体１８）を製造できる。
In the present embodiment, since the water repellency of the gas diffusion layer 15 is enhanced, even if the end portion of the electrolyte membrane 11 where the catalyst layer 14 is exposed is immersed in the catalyst removal liquid 16 as described above, the catalyst removal is performed. The liquid 16 hardly penetrates into the gas diffusion layer 15, and if the catalyst removal liquid 16 is pulled up from the catalyst removal liquid 16 after the catalyst layer 14 is removed, the catalyst removal liquid 16 is easily dropped from the gas diffusion layer 15.
Therefore, the influence of the catalyst removing liquid 16 on the catalyst layer 14 covered with the gas diffusion layer 15 can be minimized when the catalyst-coated electrolyte membrane 11 is immersed in the catalyst removing liquid 16. That is, the catalyst removal liquid 16 to the catalyst layer 14 covered with the electrolyte membrane 11 and the gas diffusion layer 15, in this embodiment, the MEA element body 19 (the MEGA element body 18 as a whole while minimizing the influence of aqua regia). ) Can be manufactured.
なお上述実施形態において、電解質膜は剛性が低いので、図７に示すように、帯状の電解質膜１１を挟んでダイコータ１３と対向する位置に支持ローラ７１を各々配置すれば、電解質膜１１を支えながら触媒１２を塗工できる。
この場合、搬送方向イの下流側（図中、右側）に位置するダイコータ１３に対応する支持ローラ７１は上流側（図中、左側）に位置するダイコータ１３によって塗工された触媒１２を介して電解質膜１１を支えることになる。したがって、上流側に位置するダイコータ１３によって触媒１２が塗工された電解質膜１１部分が、下流側に位置するダイコータ１３（支持ローラ７１）に達するまでに、上流側に位置するダイコータ１３によって塗工された触媒１２が乾くようになされる。例えば、上下流側のダイコータ１３，１３相互間の距離を離したり、上下流側のダイコータ１３，１３相互間に上流側に位置するダイコータ１３によって塗工された触媒１２の乾燥を促進させる手段を配置する。
塗工された触媒１２が乾ききると、第２工程II（図１参照）における触媒層１４へのガス拡散層１５の接合がされにくくなるので、この場合は、触媒層１４又はガス拡散層１５の、ガス拡散層１５又は触媒層１４との接合面に接着剤を塗布する等、両層１４，１５の接合を容易にする処理が施される。
In the above-described embodiment, since the electrolyte membrane has low rigidity, as shown in FIG. 7, if the support rollers 71 are respectively disposed at positions facing the die coater 13 with the strip-shaped electrolyte membrane 11 interposed therebetween, the electrolyte membrane 11 is supported. However, the catalyst 12 can be applied.
In this case, the support roller 71 corresponding to the die coater 13 located on the downstream side (right side in the drawing) of the conveying direction (b) passes through the catalyst 12 coated by the die coater 13 located on the upstream side (left side in the drawing). The electrolyte membrane 11 is supported. Therefore, the portion of the electrolyte membrane 11 coated with the catalyst 12 by the die coater 13 located on the upstream side is coated by the die coater 13 located on the upstream side until reaching the die coater 13 (support roller 71) located on the downstream side. The prepared catalyst 12 is dried. For example, means for increasing the distance between the upstream and downstream die coaters 13 and 13 and promoting the drying of the catalyst 12 coated by the upstream die coater 13 between the upstream and downstream die coaters 13 and 13 is provided. Deploy.
When the coated catalyst 12 is dried, it becomes difficult to join the gas diffusion layer 15 to the catalyst layer 14 in the second step II (see FIG. 1). In this case, the catalyst layer 14 or the gas diffusion layer 15 Then, a treatment for facilitating the joining of the two layers 14 and 15 is performed, such as applying an adhesive to the joining surface with the gas diffusion layer 15 or the catalyst layer 14.
Ｉ：第１工程、II：第２工程、III：第３工程、IＶ：第４工程、１１：帯状の電解質膜、１２：触媒、１３：ダイコータ、１４：触媒層、１５：ガス拡散層、１６：触媒除去液（王水）、１８：ＭＥＧＡ素体、１９：ＭＥＡ素体、２０：ＭＥＡ、２１：ＭＥＧＡ。 I: 1st process, II: 2nd process, III: 3rd process, IV: 4th process, 11: Strip-shaped electrolyte membrane, 12: Catalyst, 13: Die coater, 14: Catalyst layer, 15: Gas diffusion layer, 16: Catalyst removal solution (Aqua regia), 18: MEGA element, 19: MEA element, 20: MEA, 21: MEGA.
Claims (3)
前記触媒が塗工されてなる触媒層上に間隔をおいてガス拡散層を接合する第２工程と、
隣接する前記ガス拡散層相互間の定位置で前記触媒が塗工済みの電解質膜を切断する第３工程と、
前記切断により分離された、前記触媒が塗工済みでその触媒層上にガス拡散層が接合された電解質膜の少なくとも前記触媒層が露出する端部分を、その触媒層を電解質膜から除去可能な触媒除去液中に浸漬する第４工程とを、
備えることを特徴とする燃料電池用膜−電極接合体製造方法。 A first step of continuously applying a catalyst to a strip-shaped electrolyte membrane conveyed in one direction;
A second step of joining the gas diffusion layer at an interval on the catalyst layer coated with the catalyst;
A third step of cutting the electrolyte membrane coated with the catalyst at a fixed position between the adjacent gas diffusion layers;
The catalyst layer can be removed from the electrolyte membrane at least an end portion of the electrolyte membrane separated by the cutting and coated with the catalyst and having a gas diffusion layer bonded onto the catalyst layer. A fourth step of immersing in the catalyst removal solution,
A method for producing a membrane-electrode assembly for a fuel cell, comprising:
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