JP2019114463A - Method for manufacturing membrane-electrode assembly - Google Patents
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 96
- 229920000554 ionomer Polymers 0.000 claims abstract description 40
- 239000005518 polymer electrolyte Substances 0.000 claims abstract description 39
- 239000007787 solid Substances 0.000 claims abstract description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 30
- 238000012546 transfer Methods 0.000 claims abstract description 26
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 18
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 18
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 13
- 238000005342 ion exchange Methods 0.000 claims abstract description 7
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 6
- 239000012528 membrane Substances 0.000 claims description 48
- 239000000758 substrate Substances 0.000 claims description 17
- 239000011248 coating agent Substances 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 239000000446 fuel Substances 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 6
- 239000000976 ink Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000003411 electrode reaction Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 229920003937 Aquivion® Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- CLBRCZAHAHECKY-UHFFFAOYSA-N [Co].[Pt] Chemical compound [Co].[Pt] CLBRCZAHAHECKY-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
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- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
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- Fuel Cell (AREA)
- Inert Electrodes (AREA)
Abstract
Description
本発明は、膜電極接合体の製造方法に関する。 The present invention relates to a method of manufacturing a membrane electrode assembly.
燃料ガスと酸化剤ガスとの電気化学反応によって発電する燃料電池として固体高分子型燃料電池がエネルギー源として注目されている。固体高分子型燃料電池は、室温作動が可能であり、出力密度も高いため、自動車用途などに適した形態として、活発に研究されている。 A polymer electrolyte fuel cell attracts attention as an energy source as a fuel cell which generates electric power by an electrochemical reaction between a fuel gas and an oxidant gas. Since polymer electrolyte fuel cells can be operated at room temperature and have a high power density, they are being actively studied as a form suitable for automotive applications and the like.
固体高分子型燃料電池では、一般に、電解質膜である固体高分子電解質膜の両面に、それぞれ、触媒層からなる電極（空気極及び燃料極）を接合してなる膜電極接合体（「燃料極−固体高分子電解質膜−空気極」）（以下、「ＭＥＡ」ともいう）が使用される。 In a polymer electrolyte fuel cell, in general, a membrane electrode assembly ("fuel electrode") is formed by bonding electrodes (air electrode and fuel electrode) each comprising a catalyst layer on both sides of a solid polymer electrolyte film which is an electrolyte film. -Solid polymer electrolyte membrane-air electrode "(hereinafter also referred to as" MEA ") is used.
各電極は、触媒層から形成され、触媒層は、触媒層中に含まれる電極触媒によって電極反応をおこなわせるための層である。電極反応を進行させるためには、電解質、触媒及び反応ガスの三相が共存する三相界面が必要であることから、触媒層は、一般に、触媒と、電解質とを含む層からなっている。 Each electrode is formed of a catalyst layer, and the catalyst layer is a layer for causing an electrode reaction by an electrode catalyst contained in the catalyst layer. The catalyst layer is generally composed of a layer containing a catalyst and an electrolyte because a three-phase interface in which three phases of an electrolyte, a catalyst, and a reaction gas coexist is necessary for the electrode reaction to proceed.
例えば、特許文献１は、電解質膜と、その両側に配され、導電性担体に触媒が担持されてなる触媒担持担体と高分子電解質とからなる、アノード側触媒層及びカソード側触媒層と、から形成された膜電極接合体について開示しており、前記アノード側触媒層は、Ｉ／Ｃ（導電性担体の質量（Ｃ）に対する高分子電解質の質量（Ｉ）の比）が１．０〜２．０の範囲であり、ＥＷ（スルホン酸等量重量）が７５０〜１１００の範囲にあり、さらに高分子電解質の厚みが１０ｎｍ〜２４ｎｍの範囲にある。 For example, Patent Document 1 is composed of an electrolyte membrane and an anode-side catalyst layer and a cathode-side catalyst layer, each of which comprises a catalyst-supporting carrier disposed on both sides thereof and having a catalyst supported on a conductive carrier and a polymer electrolyte. It is disclosed about the formed membrane electrode assembly, and the anode side catalyst layer has an I / C (ratio of mass (I) of polymer electrolyte to mass (C) of conductive support) of 1.0 to 2 The EW (sulfonic acid equivalent weight) is in the range of 750 to 1100, and the thickness of the polymer electrolyte is in the range of 10 to 24 nm.
このようなＭＥＡを製造する方法に関して、例えば、特許文献２は、表面に触媒層を形成した触媒層形成塗工基材を、その触媒層面が固体高分子電解質膜に接するように、含水状態の固体高分子電解質膜の片面又は両面に積層した塗工基材−電解質膜積層体を、２枚のフィルムの間に挟んだ状態で加熱圧接することを特徴とする、膜電極接合体の製造方法について開示している。 With respect to a method for producing such MEA, for example, Patent Document 2 is in a water-hydrated state so that the catalyst layer-forming coated substrate having a catalyst layer formed on the surface is in contact with the solid polymer electrolyte membrane. A method for producing a membrane electrode assembly, comprising heating and pressure-bonding a coated substrate-electrolyte membrane laminate laminated on one side or both sides of a solid polymer electrolyte membrane between two films. Is disclosed.
特許文献３は、触媒層転写用ロールプレス装置を用いて、触媒層を固体高分子電解質膜に転写する方法について開示している。 Patent Document 3 discloses a method of transferring a catalyst layer to a solid polymer electrolyte membrane using a roll press apparatus for transferring a catalyst layer.
一般的に、ＭＥＡを製造する際に用いられる転写法では、塗工基材の熱膨張、設備の樹脂部品（転写面やロールにはゴムを用いることが多い）の耐熱性から、ＭＥＡを安定して生産するために、１５０℃未満の転写温度で実施することが求められる。したがって、ＭＥＡにおいて固体高分子電解質膜と触媒層とを密着させるために触媒層に用いられる電解質としては、密着強度を確保するため、１５０℃未満で軟化するアイオノマー、すなわち、１５０℃未満のガラス転移点（本明細書等では、「ガラス転移点」を「Ｔｇ」ともいう）を有するアイオノマーが好ましい。 Generally, in the transfer method used when manufacturing MEA, the MEA is stabilized from the thermal expansion of the coated substrate and the heat resistance of the resin part of equipment (the transfer surface and the roll are often made of rubber). It is required to carry out at a transfer temperature of less than 150.degree. C. for production. Therefore, as the electrolyte used in the catalyst layer to adhere the solid polymer electrolyte membrane and the catalyst layer in the MEA, an ionomer softened at less than 150 ° C., that is, a glass transition of less than 150 ° C. in order to secure the adhesion strength. An ionomer having a point (herein, “glass transition temperature” is also referred to as “Tg”) is preferred.
一方で、高性能なＭＥＡを得るためには、酸素透過性が高いアイオノマーを使用することが好ましい。しかしながら、酸素透過性が高いアイオノマーの多くは、１５０℃以上の高いＴｇを有することが判明している。 On the other hand, in order to obtain a high-performance MEA, it is preferable to use an ionomer having high oxygen permeability. However, many of the ionomers with high oxygen permeability are found to have high Tg of 150 ° C. or higher.
以上より、従来の転写法では、ＭＥＡを効率よく製造することは困難である。 From the above, it is difficult to efficiently produce MEA by the conventional transfer method.
したがって、本発明は、転写法により、転写温度以上のＴｇを有するアイオノマーを含む膜電極接合体を製造する方法を提供することを課題とする。 Therefore, an object of the present invention is to provide a method for producing a membrane electrode assembly including an ionomer having a Tg equal to or higher than a transfer temperature by a transfer method.
塗工基材上に配置された触媒層を固体高分子電解質膜に転写する工程を含むＭＥＡの製造方法において、アイオノマーが転写温度以上のＴｇを有する場合、触媒層が配置（塗布）されている塗工基材からの触媒層の固体高分子電解質膜への転写性を確保するためには、触媒層のカーボン重量当たりのアイオノマーのスルホン酸量を増加させることが考えられる。触媒層のカーボン重量当たりのアイオノマーのスルホン酸量を増加させることで、固体高分子電解質膜と触媒層との密着強度が向上され、１３０℃程度の低温でも転写を成立することができると推察される。 In the MEA manufacturing method including the step of transferring the catalyst layer disposed on the coated substrate to the solid polymer electrolyte membrane, the catalyst layer is disposed (coated) when the ionomer has a Tg equal to or higher than the transfer temperature. In order to secure the transferability of the catalyst layer from the coated substrate to the solid polymer electrolyte membrane, it is conceivable to increase the amount of sulfonic acid of ionomer per carbon weight of the catalyst layer. By increasing the amount of sulfonic acid of ionomer per carbon weight of the catalyst layer, the adhesion strength between the solid polymer electrolyte membrane and the catalyst layer is improved, and it is surmised that transfer can be established even at a low temperature of about 130 ° C. Ru.
しかしながら、触媒層のカーボン重量当たりのアイオノマーのスルホン酸量を増加しすぎると、固体高分子電解質膜と触媒層との密着強度以上に、触媒層が配置されている塗工基材と触媒層との密着強度が向上されてしまい、転写が成立しないことが判明した。 However, if the amount of sulfonic acid of ionomer per carbon weight of the catalyst layer is increased too much, the coated substrate and the catalyst layer in which the catalyst layer is disposed more than the adhesion strength between the solid polymer electrolyte membrane and the catalyst layer The adhesion strength was improved, and it was found that transfer was not established.
そこで、本発明者は、前記課題を解決するための手段を種々検討した結果、塗工基材上に配置された触媒層を固体高分子電解質膜に転写する工程を含むＭＥＡの製造方法において、アイオノマーが転写温度以上のＴｇを有する場合に、固体高分子電解質膜と触媒層との密着強度が、触媒層が配置されている塗工基材としてのポリテトラフルオロエチレン（ＰＴＦＥ）と触媒層との密着強度よりも大きくなるように、触媒層のカーボン重量当たりのアイオノマーのスルホン酸量を規定することによって、触媒層が配置されている塗工基材からの触媒層の固体高分子電解質膜への転写性を確保できることを見出し、本発明を完成した。 Then, as a result of examining the means for solving the above-mentioned subject variously, the inventor of the present invention is a manufacturing method of MEA including a step of transferring a catalyst layer disposed on a coated substrate to a solid polymer electrolyte membrane, When the ionomer has a Tg equal to or higher than the transfer temperature, the adhesion strength between the solid polymer electrolyte membrane and the catalyst layer is determined by the polytetrafluoroethylene (PTFE) as the coated substrate on which the catalyst layer is disposed, and the catalyst layer By defining the amount of sulfonic acid of ionomer per carbon weight of the catalyst layer so that the adhesion strength of the catalyst layer is greater than the adhesion strength of the catalyst layer from the coated substrate on which the catalyst layer is disposed The present invention has been completed by finding that the transferability of the
すなわち、本発明の要旨は以下の通りである。
（１）塗工基材上に配置された触媒層を固体高分子電解質膜に転写する工程を含む膜電極接合体の製造方法であって、
塗工基材が、ポリテトラフルオロエチレンであり、
触媒層が、転写温度以上のＴｇを有するアイオノマーと、カーボンを含む触媒担体とを含み、
以下の式
Ａ＝アイオノマーのイオン交換容量（ＩＥＣ）（ｍｅｑ／ｇ）×アイオノマーの重量（ｇ）／カーボン重量（ｇ）
により表される触媒層のカーボン重量当たりのアイオノマーのスルホン酸量Ａが、
０．５５≦Ａ≦１．２
である、膜電極接合体の製造方法。
That is, the gist of the present invention is as follows.
(1) A method for producing a membrane electrode assembly, comprising the step of transferring a catalyst layer disposed on a coated substrate to a solid polymer electrolyte membrane,
The coated substrate is polytetrafluoroethylene,
The catalyst layer comprises an ionomer having a Tg above the transfer temperature and a catalyst support comprising carbon;
The following formula A = ion exchange capacity (IEC) of ionomer (meq / g) × weight of ionomer (g) / weight of carbon (g)
The sulfonic acid amount A of the ionomer per carbon weight of the catalyst layer represented by
0.55 ≦ A ≦ 1.2
A method for producing a membrane electrode assembly.
本発明により、転写法により、転写温度以上のＴｇを有するアイオノマーを使用して、膜電極接合体を製造する方法が提供される。 The present invention provides a method for producing a membrane electrode assembly using an ionomer having a Tg equal to or higher than the transfer temperature by the transfer method.
以下、本発明の好ましい実施形態について詳細に説明する。
本発明の膜電極接合体の製造方法は、下記実施形態に限定されるものではなく、本発明の要旨を逸脱しない範囲において、当業者がおこない得る変更、改良などを施した種々の形態にて実施することができる。
Hereinafter, preferred embodiments of the present invention will be described in detail.
The method for producing a membrane electrode assembly of the present invention is not limited to the following embodiments, and various modifications may be made to those skilled in the art without departing from the scope of the present invention. It can be implemented.
本発明は、塗工基材上に配置された触媒層を固体高分子電解質膜に転写する工程を含む膜電極接合体の製造方法であって、塗工基材が、ポリテトラフルオロエチレンであり、触媒層が、転写温度以上のＴｇを有するアイオノマーと、カーボンを含む触媒担体とを含み、触媒層のカーボン重量当たりのアイオノマーのスルホン酸量Ａが、一定の範囲である、膜電極接合体の製造方法に関する。 The present invention is a method for producing a membrane electrode assembly including the step of transferring a catalyst layer disposed on a coated substrate to a solid polymer electrolyte membrane, wherein the coated substrate is polytetrafluoroethylene. A membrane electrode assembly, wherein the catalyst layer comprises an ionomer having a Tg higher than the transfer temperature, and a catalyst carrier containing carbon, and the sulfonic acid amount A of the ionomer per carbon weight of the catalyst layer is within a certain range. It relates to the manufacturing method.
本発明において、以下の式
Ａ＝アイオノマーのイオン交換容量（ＩＥＣ）（ｍｅｑ／ｇ）×アイオノマーの重量（ｇ）／カーボン重量（ｇ）
により表される触媒層のカーボン重量当たりのアイオノマーのスルホン酸量Ａは、０．５５≦Ａ≦１．２、好ましくは、０．７０≦Ａ≦１．０である。
In the present invention, the following formula A = ion exchange capacity (IEC) of ionomer (meq / g) × weight of ionomer (g) / weight of carbon (g)
The sulfonic acid amount A of the ionomer per carbon weight of the catalyst layer represented by the following formula is 0.55 ≦ A ≦ 1.2, preferably 0.70 ≦ A ≦ 1.0.
ここで、イオン交換容量（ＩＥＣ）は、一定量の物質が保持できるイオンの量であり、単位重量当たりの交換できるイオンのミリ当量（ｍｅｑ／ｇ）で表される。 Here, the ion exchange capacity (IEC) is the amount of ions that can be held by a fixed amount of substance, and is expressed in milliequivalents (meq / g) of exchangeable ions per unit weight.
Ａが前記範囲であることにより、固体高分子電解質膜と触媒層との密着強度が、触媒層が配置されている塗工基材としてのＰＴＦＥと触媒層との密着強度よりも大きくなり、触媒層が配置されている塗工基材からの触媒層の固体高分子電解質膜への転写性を確保することができる。 When A is in the above range, the adhesion strength between the solid polymer electrolyte membrane and the catalyst layer becomes larger than the adhesion strength between PTFE and the catalyst layer as the coating base on which the catalyst layer is disposed, and the catalyst The transferability to the solid polymer electrolyte membrane of the catalyst layer from the coating base material in which the layer is arrange | positioned can be ensured.
固体高分子電解質膜と触媒層との密着強度及びＰＴＦＥと触媒層との密着強度は、９０°剥離試験により測定することができる。 The adhesion strength between the solid polymer electrolyte membrane and the catalyst layer and the adhesion strength between the PTFE and the catalyst layer can be measured by a 90 ° peel test.
固体高分子電解質膜と触媒層との密着強度は、ＰＴＦＥと触媒層との密着強度よりも大きくなる限り限定されないが、通常０．１０Ｎ／ｍｍ〜０．２５Ｎ／ｍｍ、好ましくは０．１５Ｎ／ｍｍ〜０．２０Ｎ／ｍｍである。 The adhesion strength between the solid polymer electrolyte membrane and the catalyst layer is not limited as long as it becomes larger than the adhesion strength between PTFE and the catalyst layer, but it is usually 0.10 N / mm to 0.25 N / mm, preferably 0.15 N / mm to 0.20 N / mm.
ＰＴＦＥと触媒層との密着強度は、固体高分子電解質膜と触媒層との密着強度よりも小さくなる限り限定されないが、通常０．０Ｎ／ｍｍ〜０．２Ｎ／ｍｍ、好ましくは０．０５Ｎ／ｍｍ以下である。 The adhesion strength between PTFE and the catalyst layer is not limited as long as it is smaller than the adhesion strength between the solid polymer electrolyte membrane and the catalyst layer, but it is usually 0.0 N / mm to 0.2 N / mm, preferably 0.05 N / mm. It is less than mm.
本発明において、転写温度は、通常１２０℃〜１４０℃、好ましくは１３０℃である。 In the present invention, the transfer temperature is usually 120 ° C to 140 ° C, preferably 130 ° C.
転写温度が前記温度範囲であることにより、塗工基材及び設備の樹脂部品が熱により劣化することなく、ＭＥＡを安定して生産することができる。 When the transfer temperature is in the above temperature range, MEA can be stably produced without deterioration of the coated base material and the resin part of the equipment due to heat.
本発明において、転写温度以上のＴｇを有するアイオノマーは、例えば１５０℃以上と高いＴｇを有する。 In the present invention, an ionomer having a Tg above the transfer temperature has a high Tg of, for example, 150 ° C. or more.
転写温度以上のＴｇを有するアイオノマーのイオン交換容量は、Ａが前記範囲になる限り限定されないが、通常１．０ｍｅｑ／ｇ以上である。 The ion exchange capacity of the ionomer having a Tg equal to or higher than the transfer temperature is not limited as long as A falls in the above range, but is usually 1.0 meq / g or more.
本発明において、触媒担体は、カーボンを含む。カーボンは、当該技術分野で公知のカーボンを使用することができる。カーボンを含む触媒担体としては、限定されないが、例えば、アセチレンブラック、サーマルブラック、それらの混合物などが挙げられる。触媒担体は、カーボンからなることが好ましい。 In the present invention, the catalyst support comprises carbon. As carbon, carbon known in the art can be used. The catalyst support containing carbon includes, but is not limited to, for example, acetylene black, thermal black, a mixture thereof and the like. The catalyst support is preferably made of carbon.
本発明において、カーボンを含む触媒担体に担持される触媒は、当該技術分野で公知の触媒を使用することができる。触媒としては、限定されないが、例えば、白金、ルテニウム、イリジウム、ロジウム、パラジウム、オスニウム、タングステン、鉛、鉄、クロム、コバルト、ニッケル、マンガン、バナジウム、モリブデン、ガリウム、アルミニウムなどの金属、又はそれらの合金、例えば白金コバルトなどがある。 In the present invention, as the catalyst supported on the catalyst support containing carbon, catalysts known in the art can be used. The catalyst includes, but is not limited to, for example, platinum, ruthenium, iridium, rhodium, palladium, osmium, tungsten, lead, iron, chromium, cobalt, nickel, manganese, vanadium, molybdenum, gallium, aluminum and the like, or metals thereof There is an alloy such as platinum cobalt.
本発明において、固体高分子電解質膜は、当該技術分野で公知の固体高分子電解質膜を使用することができる。固体高分子電解質膜は、限定されないが、例えばゴアセレクト（登録商標）を挙げることができる。 In the present invention, as the solid polymer electrolyte membrane, solid polymer electrolyte membranes known in the art can be used. Examples of the solid polymer electrolyte membrane include, but are not limited to, Gore Select (registered trademark).
本発明では、塗工基材上に配置された触媒層を固体高分子電解質膜に転写する工程を含む膜電極接合体の製造方法において、塗工基材が、ポリテトラフルオロエチレンであり、触媒層が、転写温度以上のＴｇを有するアイオノマーと、カーボンを含む触媒担体とを含み、触媒層のカーボン重量当たりのアイオノマーのスルホン酸量Ａが、前記範囲であること以外は、当該技術分野で公知の方法を利用して、膜電極接合体を製造することができる。 In the present invention, in the method of producing a membrane electrode assembly including the step of transferring the catalyst layer disposed on the coated substrate to the solid polymer electrolyte membrane, the coated substrate is polytetrafluoroethylene, and the catalyst The layer is known in the art except that the layer contains an ionomer having a Tg higher than the transfer temperature, and a catalyst carrier containing carbon, and the sulfonic acid amount A of the ionomer per carbon weight of the catalyst layer is in the above range. The membrane electrode assembly can be manufactured using the method of
本発明において製造された膜電極接合体は、燃料電池に使用することができる。 The membrane electrode assembly manufactured in the present invention can be used in a fuel cell.
以下、本発明に関するいくつかの実施例につき説明するが、本発明をかかる実施例に示すものに限定することを意図したものではない。 The present invention will now be described with reference to several examples, which are not intended to limit the present invention to those shown.
密着強度の測定
（１）ＰＴＦＥと触媒層との密着強度
Ｔｇが１５０℃以上であるアイオノマー（アクイヴィオン、Ｓｏｌｖｅｙ社製）と、触媒担体を含むカーボンと、エタノールと、水とを混合し、触媒インクを調製した。触媒インクは、アイオノマーとカーボンの量を変更して、触媒層のカーボン重量当たりのアイオノマーのスルホン酸量Ａ（Ａ＝アイオノマーのイオン交換容量（ＩＥＣ）（ｍｅｑ／ｇ）×アイオノマーの重量（Ｉ）（ｇ）／カーボン重量（Ｃ）（ｇ））がそれぞれ異なるように、７種類調製した。７種類の触媒インクを、それぞれ塗工基材としてのＰＴＦＥ上に塗布した。７種類のＰＴＦＥ−触媒層について、９０°剥離試験により、ＰＴＦＥと触媒層との密着強度を測定した。
Measurement of adhesion strength (1) Adhesion strength between PTFE and catalyst layer An ionomer (Aquivion, manufactured by Solvey) having a Tg of 150 ° C. or higher, carbon containing a catalyst carrier, ethanol, and water are mixed to obtain a catalyst ink Was prepared. In the catalyst ink, the amount of sulfonic acid in the ionomer per carbon weight of the catalyst layer is changed by changing the amount of ionomer and carbon A (A = ion exchange capacity (IEC) of ionomer (meq / g) × weight of ionomer (I) Seven types of (g) / carbon weight (C) (g) were prepared so as to be different from one another. Seven types of catalyst inks were each coated on PTFE as a coating substrate. The adhesion strength between the PTFE and the catalyst layer was measured for the seven types of PTFE-catalyst layers by a 90 ° peeling test.
（２）固体高分子電解質膜と触媒層との密着強度
（１）で調製した７種類の触媒インクを、それぞれ固体高分子電解質膜上に塗布した。７種類の固体高分子電解質膜−触媒層膜について、９０°剥離試験により、固体高分子電解質膜と触媒層との密着強度を測定した。
(2) Adhesion Strength Between Solid Polymer Electrolyte Membrane and Catalyst Layer The seven types of catalyst inks prepared in (1) were each coated on a solid polymer electrolyte membrane. The adhesion strength between the solid polymer electrolyte membrane and the catalyst layer was measured for the seven types of solid polymer electrolyte membrane-catalyst layer membranes by a 90 ° peeling test.
（１）及び（２）で測定した密着強度を、Ａに対してプロットした。結果を図１に示す。 The adhesion strengths measured in (1) and (2) were plotted against A. The results are shown in FIG.
図１より、固体高分子電解質膜と触媒層との密着強度と、ＰＴＦＥと触媒層との密着強度とには、一定の関係が存在することがわかった。固体高分子電解質膜と触媒層との密着強度が、ＰＴＦＥと触媒層との密着強度よりも大きくなることにより転写が成立するため、Ａが０．５５≦Ａ≦１．２である場合に、触媒層が塗布されているＰＴＦＥからの触媒層の固体高分子電解質膜への転写が安定して成立し、さらに、Ａが０．７０≦Ａ≦１．０である場合に、当該転写がさらに安定して成立することがわかった。 It was found from FIG. 1 that a certain relationship exists between the adhesion strength between the solid polymer electrolyte membrane and the catalyst layer and the adhesion strength between the PTFE and the catalyst layer. When the adhesion strength between the solid polymer electrolyte membrane and the catalyst layer is larger than the adhesion strength between the PTFE and the catalyst layer, the transfer is established, so that when A is 0.55 ≦ A ≦ 1.2, Transfer of the catalyst layer from the PTFE to which the catalyst layer is applied to the solid polymer electrolyte membrane is stably established, and further, when A is 0.70 ≦ A ≦ 1.0, the transfer is further performed. It turned out that it was established stably.
Claims (1)
塗工基材が、ポリテトラフルオロエチレンであり、
触媒層が、転写温度以上のＴｇを有するアイオノマーと、カーボンを含む触媒担体とを含み、
以下の式
Ａ＝アイオノマーのイオン交換容量（ＩＥＣ）（ｍｅｑ／ｇ）×アイオノマーの重量（ｇ）／カーボン重量（ｇ）
により表される触媒層のカーボン重量当たりのアイオノマーのスルホン酸量Ａが、
０．５５≦Ａ≦１．２
である、膜電極接合体の製造方法。 A process for producing a membrane electrode assembly, comprising the step of transferring a catalyst layer disposed on a coated substrate to a solid polymer electrolyte membrane,
The coated substrate is polytetrafluoroethylene,
The catalyst layer comprises an ionomer having a Tg above the transfer temperature and a catalyst support comprising carbon;
The following formula A = ion exchange capacity (IEC) of ionomer (meq / g) × weight of ionomer (g) / weight of carbon (g)
The sulfonic acid amount A of the ionomer per carbon weight of the catalyst layer represented by
0.55 ≦ A ≦ 1.2
A method for producing a membrane electrode assembly.
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| JP2011008940A (en) * | 2009-06-23 | 2011-01-13 | Toyota Motor Corp | Membrane-electrode assembly, and fuel battery |
| JP2012204272A (en) * | 2011-03-28 | 2012-10-22 | Toppan Printing Co Ltd | Membrane electrode assembly for solid polymer fuel cell, method of manufacturing membrane electrode assembly, unit cell of solid polymer fuel cell, and solid polymer fuel cell stack |
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| JP2011008940A (en) * | 2009-06-23 | 2011-01-13 | Toyota Motor Corp | Membrane-electrode assembly, and fuel battery |
| JP2012204272A (en) * | 2011-03-28 | 2012-10-22 | Toppan Printing Co Ltd | Membrane electrode assembly for solid polymer fuel cell, method of manufacturing membrane electrode assembly, unit cell of solid polymer fuel cell, and solid polymer fuel cell stack |
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