JP7384263B2 - catalyst ink - Google Patents
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- JP7384263B2 JP7384263B2 JP2022176228A JP2022176228A JP7384263B2 JP 7384263 B2 JP7384263 B2 JP 7384263B2 JP 2022176228 A JP2022176228 A JP 2022176228A JP 2022176228 A JP2022176228 A JP 2022176228A JP 7384263 B2 JP7384263 B2 JP 7384263B2
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- 239000003054 catalyst Substances 0.000 title claims description 127
- 239000012528 membrane Substances 0.000 claims description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 239000005518 polymer electrolyte Substances 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 14
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 229920001940 conductive polymer Polymers 0.000 claims description 8
- 238000010030 laminating Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 4
- 229920002313 fluoropolymer Polymers 0.000 claims description 2
- 239000004811 fluoropolymer Substances 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims 2
- 239000000976 ink Substances 0.000 description 58
- 238000000034 method Methods 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 17
- 238000004519 manufacturing process Methods 0.000 description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 13
- 239000006185 dispersion Substances 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 11
- 238000010248 power generation Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- 229910052697 platinum Inorganic materials 0.000 description 6
- 230000000712 assembly Effects 0.000 description 4
- 238000000429 assembly Methods 0.000 description 4
- 239000011324 bead Substances 0.000 description 4
- -1 polyphenylene Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 229920000557 Nafion® Polymers 0.000 description 3
- 239000004695 Polyether sulfone Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920006393 polyether sulfone Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 241001149900 Fusconaia subrotunda Species 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
- 150000001298 alcohols Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 229920003934 Aciplex® Polymers 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920003935 Flemion® Polymers 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
- 239000004677 Nylon Substances 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 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
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 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
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 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
- 238000004898 kneading Methods 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000007788 liquid 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
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 125000005487 naphthalate group Chemical group 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 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
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920005649 polyetherethersulfone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene 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
- 238000001132 ultrasonic dispersion Methods 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
- 238000009736 wetting Methods 0.000 description 1
Images
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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- Inert Electrodes (AREA)
- Fuel Cell (AREA)
Description
本発明は、燃料電池の膜電極接合体(MEA:membrane-electrode
assembly)の製造方法に関する。
The present invention relates to membrane-electrode assemblies (MEA) for fuel cells.
(assembly).
従来、膜電極接合体の製造方法としては、所望の形状を有する触媒層が付与された転写基材と固体高分子電解質膜をホットプレス、熱ラミネートロールなどで熱圧着した後、基材を剥離する熱転写方法が提案されている。 Conventionally, the manufacturing method for membrane electrode assemblies has been to bond a transfer base material provided with a catalyst layer having a desired shape with a solid polymer electrolyte membrane using a hot press, a hot laminating roll, etc., and then peel the base material. A thermal transfer method has been proposed.
例えば、特許文献1には、ホットプレスを用いる手法、及び熱ラミネートロールを用いる手法が開示されている。上記熱ラミネートロールを用いる手法は、長尺の固体高分子電解質膜とその表裏面に配された所望の形状を有する触媒層が付与された転写基材とを接触させ、一対の熱ラミネートロールで熱圧着することによって、固体高分子電解質膜と触媒層とを一体的に接合し、その後転写基材から基材のみを一対の剥離ロールを用いて触媒層から剥離し、触媒層を固体高分子電解質膜表面に転写している。
For example,
特許文献1のような触媒層を固体高分子電解質膜に熱転写する方式において、触媒インクの調製が必要である。
この触媒インク中には、触媒、電解質膜同様の導電性高分子、溶媒、水が含まれている。触媒インク中に含まれる水の比率が低く、かつ水分量が少ないと、触媒インク調製中や触媒インクの塗工・乾燥工程で、触媒の作用により溶媒が酸化され、発熱・発火してしまう危険性がある。
In the method of thermally transferring a catalyst layer to a solid polymer electrolyte membrane as in
This catalyst ink contains a catalyst, a conductive polymer similar to an electrolyte membrane, a solvent, and water. If the proportion and amount of water contained in the catalyst ink is low, there is a risk that the solvent will be oxidized by the action of the catalyst during the preparation of the catalyst ink, or during the coating and drying process of the catalyst ink, causing heat generation and ignition. There is sex.
燃料電池の触媒インクに用いられる触媒はカーボンの粉末からなるのが一般的で、このカーボンは疎水性であるため、水との相性が悪い。また、導電性高分子においても、水との相溶性が低いため、触媒インク中の水の比率が高くなると、触媒インクを塗工・乾燥して形成された触媒層にクラックが発生しやすい。クラックのある触媒層が形成されたMEAは、燃料電池として用いた際に、固体高分子電解質膜が破膜する恐れがあるため、MEAの耐久性が劣るという問題がある。加えて、水の比率が高い触媒インク中では導電性高分子の高分子鎖が広がりにくいため、発電性能に寄与する導電パスの形成が不十分になるため、発電性能が低下するという問題がある。 Catalysts used in catalyst inks for fuel cells are generally made of carbon powder, and since carbon is hydrophobic, it has poor compatibility with water. Furthermore, since conductive polymers also have low compatibility with water, when the proportion of water in the catalyst ink increases, cracks are likely to occur in the catalyst layer formed by applying and drying the catalyst ink. When an MEA in which a cracked catalyst layer is formed is used as a fuel cell, there is a risk that the solid polymer electrolyte membrane may rupture, so there is a problem in that the durability of the MEA is poor. In addition, in a catalyst ink with a high proportion of water, the polymer chains of the conductive polymer are difficult to spread, resulting in insufficient formation of conductive paths that contribute to power generation performance, resulting in a decrease in power generation performance. .
本発明は、上記の点に鑑みてなされたものであって、触媒層にクラックのない外観が良好な膜電極接合体が得られる膜電極接合体の製造方法および触媒インクを提供することを目的とする。 The present invention has been made in view of the above points, and an object of the present invention is to provide a method for manufacturing a membrane electrode assembly and a catalyst ink that can obtain a membrane electrode assembly with a good appearance and no cracks in the catalyst layer. shall be.
上記の課題を解決するための手段として、本発明の一態様に係る膜電極接合体の製造方法は、触媒インクを調液する工程と、転写基材上に上記触媒インクを塗工して触媒層を形成する工程と、熱転写方式により固体高分子電解質膜の表面に前記触媒層を転写する工程とを含み、
上記触媒インクを調液する工程は、揮発成分の重量比が、90%以上95%以下であり、且つ、上記揮発成分中の水の比率が15%以上40%未満の触媒インクを調製する工程である。
As a means for solving the above problems, a method for manufacturing a membrane electrode assembly according to one embodiment of the present invention includes a step of preparing a catalyst ink, and a step of coating the catalyst ink on a transfer substrate to catalyze the catalyst. a step of forming a layer; and a step of transferring the catalyst layer to the surface of the solid polymer electrolyte membrane by a thermal transfer method,
The step of preparing the catalyst ink is a step of preparing a catalyst ink in which the weight ratio of volatile components is 90% or more and 95% or less, and the ratio of water in the volatile components is 15% or more and less than 40%. It is.
また、本発明の一態様に係る膜電極接合体の製造方法においては、上記膜電極接合体の製造方法における上記触媒インクの揮発成分が、水及びアルコールであり、上記アルコールは水よりも揮発性が高いことが好ましい。 Further, in the method for manufacturing a membrane electrode assembly according to one aspect of the present invention, volatile components of the catalyst ink in the method for manufacturing a membrane electrode assembly are water and alcohol, and the alcohol is more volatile than water. is preferably high.
また、本発明の一態様に係る膜電極接合体の製造方法においては、上記触媒インクを調液する工程を除く全工程又は一部工程が連続であってもよい。 Further, in the method for manufacturing a membrane electrode assembly according to one aspect of the present invention, all or some of the steps except the step of preparing the catalyst ink may be continuous.
また、本発明の一態様に係る膜電極接合体の製造方法においては、全工程が不連続であってもよい。 Furthermore, in the method for manufacturing a membrane electrode assembly according to one embodiment of the present invention, all steps may be discontinuous.
また、上記の課題を解決するための手段として、本発明の一態様に係る触媒インクは、含有する揮発成分の重量比が、90%以上95%以下であり、且つ、前記揮発成分中の水の比率が15%以上40%未満である。 Further, as a means for solving the above problems, the catalyst ink according to one aspect of the present invention contains a volatile component having a weight ratio of 90% or more and 95% or less, and water in the volatile component. The ratio is 15% or more and less than 40%.
本発明の膜電極接合体の製造方法の一態様によれば、触媒層にクラックのない外観が良好なMEAを製造することができる。外観が良好なMEAが得られることによって、発電性能や耐久性の低下を抑制することができ且つ触媒の作用による発火の危険性を低減することができる。 According to one aspect of the method for manufacturing a membrane electrode assembly of the present invention, an MEA with a good appearance and no cracks in the catalyst layer can be manufactured. By obtaining an MEA with a good appearance, deterioration in power generation performance and durability can be suppressed, and the risk of ignition due to the action of the catalyst can be reduced.
以下、本発明の実施形態について、図面を用いて説明する。ただし、以下に説明する各図において相互に対応する部分には同一符号を付し、重複部分においては後述での説明を適宜省略する。また、本発明の実施形態は、本発明の技術的思想を具体化するための構成を例示するものであって、各部の材質、形状、構造、配置、寸法等を下記のものに特定するものでない。本発明の技術的思想は、特許請求の範囲に記載された請求項が規定する技術的範囲内において、種々の変更を加えることができる。 Embodiments of the present invention will be described below with reference to the drawings. However, in each of the figures described below, mutually corresponding parts are given the same reference numerals, and descriptions of overlapping parts will be omitted as appropriate. In addition, the embodiments of the present invention are examples of configurations for embodying the technical idea of the present invention, and the materials, shapes, structures, arrangements, dimensions, etc. of each part are specified as follows. Not. The technical idea of the present invention can be modified in various ways within the technical scope defined by the claims.
図1は、本発明の膜電極接合体の製造方法の一実施形態を説明するための概略図である。本実施形態の膜電極接合体の製造方法は、触媒インク(以下、インクということがある)を調液する工程(触媒インク調液工程)と、触媒インクを塗工する工程(触媒インク塗工工程)と、触媒層を転写する工程(熱転写工程)とを含む。 FIG. 1 is a schematic diagram for explaining one embodiment of the method for manufacturing a membrane electrode assembly of the present invention. The method for manufacturing a membrane electrode assembly of the present embodiment includes a step of preparing a catalyst ink (hereinafter sometimes referred to as ink) (catalyst ink preparation step) and a step of coating the catalyst ink (catalyst ink coating). step) and a step of transferring the catalyst layer (thermal transfer step).
<触媒インクを調液する工程>
まず、触媒インク1を調液(調製)する。触媒インク1には、不揮発成分として、触媒担持カーボン、導電性高分子、揮発成分として、水、溶媒が含まれる。この触媒インク1に含まれる揮発成分の重量比は、90%以上95%以下であり、且つ、上記揮発成分中の水の比率が15%以上40%未満である。
<Process of preparing catalyst ink>
First, the
上記触媒には、白金、パラジウム、ルテニウム、イリジウム、ロジウム、オスミウムの白金族元素のほか、鉄、鉛、銅、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もしくは白金とこれらの合金、又はこれ
らの酸化物、複酸化物などを用いることができる。これらの中でも、白金や白金合金がより好ましい。
The above catalysts include platinum group elements such as platinum, palladium, ruthenium, iridium, rhodium, and osmium, as well as metals such as iron, lead, copper, chromium, cobalt, nickel, manganese, vanadium, molybdenum, gallium, and aluminum, or platinum and other metals. An alloy of these, or an oxide, a double oxide, or the like of these can be used. Among these, platinum and platinum alloys are more preferred.
上記触媒の粒径は、大きすぎると触媒の活性が低下し、小さすぎると触媒の安定性が低下するため、0.5nm以上20nm以下が好ましい。 The particle size of the catalyst is preferably 0.5 nm or more and 20 nm or less, because if it is too large, the activity of the catalyst will be reduced, and if it is too small, the stability of the catalyst will be reduced.
上記触媒担持カーボンとしては、微粒子状で導電性を有し、触媒に侵さないものであれば特に限定されない。具体的には、カーボンブラックやグラファイト、黒鉛、活性炭、カーボンファイバー、カーボンナノチューブ、フラーレンなどを用いることができる。上記触媒担持カーボンの粒径は、10nm以上100nm以下程度が好適に用いられる。 The above-mentioned catalyst-supporting carbon is not particularly limited as long as it is in the form of fine particles, has conductivity, and does not attack the catalyst. Specifically, carbon black, graphite, graphite, activated carbon, carbon fiber, carbon nanotubes, fullerene, etc. can be used. The particle size of the catalyst-supporting carbon is preferably about 10 nm or more and 100 nm or less.
初めに、上記触媒担持カーボンに水を加え、十分にカーボンの表面が水に濡れた状態になるように混錬する。最初の段階で十分に表面が濡れることにより、発火の危険性が低減する。次に良好なプロトン導電性を示す導電性高分子を加え、更に攪拌し、ペースト状にする。 First, water is added to the catalyst-supported carbon and kneaded so that the surface of the carbon becomes sufficiently wet with water. Sufficient surface wetting at the initial stage reduces the risk of ignition. Next, a conductive polymer exhibiting good proton conductivity is added and further stirred to form a paste.
上記導電性高分子材料としては、具体的には、炭化水素系高分子電解質、フッ素系高分子電解質といった材料を用いることができる。
上記炭化水素系高分子電解質材料としては、スルホン化ポリエーテルケトン、スルホン化ポリエーテルスルホン、スルホン化ポリエーテルエーテルスルホン、スルホン化ポリスルフィド、スルホン化ポリフェニレンなどの電解質材料を用いることができる。
Specifically, as the conductive polymer material, a material such as a hydrocarbon polymer electrolyte or a fluorine polymer electrolyte can be used.
As the hydrocarbon polymer electrolyte material, electrolyte materials such as sulfonated polyether ketone, sulfonated polyether sulfone, sulfonated polyether ether sulfone, sulfonated polysulfide, and sulfonated polyphenylene can be used.
上記フッ素系高分子電解質材料としては、例えば、デュポン製Nafion(登録商標)、旭硝子製Flemion(登録商標)、旭化成製Aciplex(登録商標)、ゴア製Gore Select(登録商標)などを用いることができる。 As the fluorine-based polymer electrolyte material, for example, Nafion (registered trademark) manufactured by DuPont, Flemion (registered trademark) manufactured by Asahi Glass, Aciplex (registered trademark) manufactured by Asahi Kasei, Gore Select (registered trademark) manufactured by Gore, etc. can be used. .
その後、ペースト状の混合物に溶媒を加えて、更に攪拌、分散することで、触媒インク1を調液する。溶媒には、水よりも沸点の低いアルコールであることが好ましく、更にエタノール、1-プロパノール、2-プロパノールなどの低級アルコール類を用いることがより好ましい。低級アルコール類は水との相溶性が比較的高いため、安定な触媒インク1を作製することができる。触媒インクを調液するための分散方法には、各種分散方法を用いることができる。分散方法としては、例えば、超音波分散、ボールミル分散、ビーズミル分散、ホモジナイザー分散などを用いることができる。
Thereafter, a solvent is added to the paste-like mixture, and the mixture is further stirred and dispersed to prepare the
<触媒インクを塗工する工程>
次いで、触媒インク1を高分子フィルムからなる転写フィルム2上に、ダイコーター10を用いて塗工する。塗工には大量且つ安定して触媒層塗工が可能なダイコート方式が好ましい。転写フィルム2には触媒インク1の濡れが良好で、乾燥後に形成される触媒層5a(アノード)及び5c(カソード)を固体高分子電解質膜4表面に熱転写装置20にて熱転写することができれば、特に限定されるものではない。
転写フィルムとしては、例えば、ポリイミド、ポリエチレンテレフタラート、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、ポリアクリレート、ポリエチレンナフタレート等の高分子フィルムを用いることができる。また、エチレンテトラフルオロエチレン共重合体、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、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、ポリテトラフルオロエチレン等の耐熱性フッ素樹脂を用いることもできる。
<Process of applying catalyst ink>
Next, the
Examples of transfer films include polyimide, polyethylene terephthalate, polyparvanic aramid, polyamide (nylon), polysulfone, polyethersulfone, polyethersulfone, polyphenylene sulfide, polyetheretherketone, polyetherimide, polyacrylate, and polyethylene. Polymer films such as naphthalate can be used. Furthermore, heat-resistant fluororesins such as ethylene-tetrafluoroethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroperfluoroalkyl vinyl ether copolymer, and polytetrafluoroethylene can also be used.
<触媒層を転写する工程>
次に、固体高分子電解質膜4の対向する表面に、上記で作製した触媒層付き転写基材3a及び3cを配置し、熱転写装置20により、熱加圧を行った後、転写基材2のみを剥離し、固体高分子電解質膜4表面に触媒層5a及び5cが形成された膜電極接合体6を得る。熱加圧による熱転写には、熱ラミネートロールによる方法、熱プレスによる方法などを用いることができる。また、固体高分子電解質膜材料としては、触媒インク1に含まれる導電性高分子材料と同様の材料を用いることができる。
<Step of transferring the catalyst layer>
Next, the catalyst layer-coated
ここで、上記触媒インク調液工程を除く工程は、全て連続であることが、生産性を考慮した場合好ましい。しかし、歩留まりを考慮した場合には、全工程は不連続であるが、各工程がロールtoロールで連続した工程であっても良い。また、材料のロスなどを考慮した場合は、全ての工程が不連続であっても良い。 Here, in consideration of productivity, it is preferable that all steps except the catalyst ink preparation step are continuous. However, in consideration of yield, all the steps are discontinuous, but each step may be continuous roll-to-roll. Moreover, if material loss is taken into account, all steps may be discontinuous.
以下に、本発明の製造方法を実施例によって具体的に説明する。しかし、本発明はこれらの実施例にのみ限定されるものではない。 The manufacturing method of the present invention will be specifically explained below using Examples. However, the present invention is not limited only to these examples.
(実施例1)
<膜電極接合体の製造>
触媒インク1の調液は、白金触媒(田中貴金属製TEC10E50E)に水を加えて触媒を混錬する。次に、フッ素系高分子電解質膜分散溶液(ケマーズ製20%Nafion分散液 DE2020CS)を加えた後、攪拌装置にて攪拌を行った。次に、1-プロパノールを追加し、再度攪拌を行った後、ビーズミル分散装置を用いて分散を行った。このとき、揮発成分の重量比が90%、揮発成分中の水の比率が15%になるよう、各材料の量を調整した。
(Example 1)
<Manufacture of membrane electrode assembly>
The
転写基材(旭硝子製アフレックス、厚み50μm)上にダイコーター10にて触媒インク1を塗工し、乾燥し、アノード用カソード用触媒層付き転写基材3a及び3cを得た。
アノード触媒層用には、不揮発成分中に含まれる白金量が0.1mg/cm2になるように厚み調整をし、触媒層付き転写基材3aを、カソード触媒層用には、0.4mg/cm2になるように厚みを調整し、触媒層付き転写基材3cを作製した。得られた触媒層付き転写基材3a及び3cでフッ素系電解質膜4(ケマーズ製Nafion HP)の表面を狭持し、130℃の熱ラミネートロール20で加圧した後、転写基材2のみを剥離し、膜電極接合体6を得た。
For the anode catalyst layer, the thickness was adjusted so that the amount of platinum contained in the nonvolatile component was 0.1 mg/cm 2 , and for the cathode catalyst layer, the thickness was adjusted so that the amount of platinum contained in the catalyst layer was 0.4 mg/cm2. The thickness was adjusted so as to be /cm 2 , and a
(実施例2)
実施例2として、触媒インクの揮発成分中の水の比率が35%にした以外には実施例1と同様の方法で、触媒層付き転写基材を作製した後、膜電極接合体を作製した。
(Example 2)
As Example 2, a transfer substrate with a catalyst layer was prepared in the same manner as in Example 1, except that the proportion of water in the volatile components of the catalyst ink was 35%, and then a membrane electrode assembly was prepared. .
(実施例3)
実施例3として、触媒インクの揮発成分の重量比95%にした以外には実施例1と同様の方法で、触媒層付き転写基材を作製した後、膜電極接合体を作製した。
(Example 3)
As Example 3, a transfer substrate with a catalyst layer was prepared in the same manner as in Example 1, except that the weight ratio of the volatile components of the catalyst ink was 95%, and then a membrane electrode assembly was prepared.
(比較例1~3)
触媒インクの水の比率を12%(比較例1)、40%(比較例2)、58%(比較例3)とした以外には実施例1と同様の方法で、触媒層付き転写基材を作製した後、膜電極接合体を作製した。実施例1と同様の方法で評価を行った結果を表1、図2に示す。
(Comparative Examples 1 to 3)
A transfer substrate with a catalyst layer was prepared in the same manner as in Example 1, except that the proportion of water in the catalyst ink was 12% (Comparative Example 1), 40% (Comparative Example 2), and 58% (Comparative Example 3). After that, a membrane electrode assembly was produced. The results of evaluation performed in the same manner as in Example 1 are shown in Table 1 and FIG. 2.
(比較例4,5)
触媒インクの揮発成分の重量比を88%(比較例4)、96%(比較例5)にした以外
には実施例1と同様の方法で、触媒層付き転写基材を作製した後、膜電極接合体を作製した。
(Comparative Examples 4 and 5)
After preparing a transfer substrate with a catalyst layer in the same manner as in Example 1 except that the weight ratio of volatile components of the catalyst ink was changed to 88% (Comparative Example 4) and 96% (Comparative Example 5), An electrode assembly was produced.
(評価結果1)
実施例1,2、および比較例1~3について、「触媒インクの揮発成分中の水の比率」による触媒インク温度および外観を評価した。触媒インク調液時の触媒インクの発熱の目安である温度の評価結果、および触媒層の外観の評価結果を表1に示し、膜電極接合体の発電性能結果を図2に示す。
表1における触媒インク温度の良否判断は、ビーズミル分散中の触媒インクの温度上昇が10℃未満であるケースを○、10℃以上であるケースを×判断とした。これは、触媒インク温度が上昇することで溶媒の揮発が進みやすく、触媒インクの組成に変化が生じる恐れがあることによる。
実施例1より、揮発成分における水の比率が15%以上であると触媒インク温度評価が良好なのは、最初に触媒が水で十分濡れるため、溶媒を混合したときの触媒反応による触媒インクの発熱が抑制されたのが原因である。
比較例1の水の比率12%の場合では、10℃以上の触媒インクの温度上昇がみられたため、×評価とした。また、最初に投入する水の量が少なかったため、調液容器底部に触媒のダマ残りの発生が確認された。
(Evaluation result 1)
For Examples 1 and 2 and Comparative Examples 1 to 3, the catalyst ink temperature and appearance were evaluated based on the "ratio of water in the volatile components of the catalyst ink." Table 1 shows the evaluation results of the temperature, which is a measure of the heat generation of the catalyst ink when preparing the catalyst ink, and the evaluation result of the appearance of the catalyst layer, and the power generation performance results of the membrane electrode assembly are shown in FIG. 2.
Regarding the quality of the catalyst ink temperature in Table 1, cases where the temperature rise of the catalyst ink during bead mill dispersion was less than 10°C were evaluated as ○, and cases where it was 10°C or higher were evaluated as ×. This is because as the temperature of the catalyst ink increases, the solvent tends to evaporate, which may cause a change in the composition of the catalyst ink.
From Example 1, the reason why the catalyst ink temperature evaluation is good when the proportion of water in the volatile components is 15% or more is because the catalyst is sufficiently wetted with water at the beginning, so that the heat generated by the catalyst ink due to the catalytic reaction when the solvent is mixed is reduced. This is because it was suppressed.
In the case of Comparative Example 1 with a water ratio of 12%, the temperature of the catalyst ink increased by 10° C. or more, so it was rated as ×. In addition, because the amount of water initially added was small, catalyst lumps were observed at the bottom of the liquid preparation container.
次に外観の評価では、実施例1、2、比較例1では外観に不良が確認されなかったため、○評価とした。しかし、比較例2の水の比率40%以上であると、触媒層付き転写基材の外観にクラックが多数確認されたため、×評価とした。 Next, in the evaluation of appearance, Examples 1 and 2 and Comparative Example 1 were given a rating of ○ because no defects were observed in their appearance. However, when the proportion of water in Comparative Example 2 was 40% or more, many cracks were observed in the appearance of the transfer substrate with a catalyst layer, so it was rated as ×.
実施例1、2、および比較例1~3の膜電極接合体の発電性能をそれぞれ評価したところ、図2の発電評価結果が得られた。クラックの多い比較例2及び3において顕著に性能低下が生じた。 When the power generation performance of the membrane electrode assemblies of Examples 1 and 2 and Comparative Examples 1 to 3 was evaluated, the power generation evaluation results shown in FIG. 2 were obtained. In Comparative Examples 2 and 3, which had many cracks, the performance deteriorated significantly.
(評価結果2)
次に、実施例1,3、および比較例1~3について、「触媒インクの揮発成分の重量比」による触媒インク温度および外観を評価した。評価結果を表2に示す。なお、評価基準は表1と同様である。
(Evaluation result 2)
Next, for Examples 1 and 3 and Comparative Examples 1 to 3, the catalyst ink temperature and appearance were evaluated based on the "weight ratio of volatile components of the catalyst ink". The evaluation results are shown in Table 2. Note that the evaluation criteria are the same as in Table 1.
表2に示すように、重量比が90%以上95%以下である実施例1,3は、ビーズミル分散中の触媒インクの温度上昇が10℃未満であり良好であった。また、触媒層付き転写基材の外観にも不良は発見されなかった。 As shown in Table 2, Examples 1 and 3 in which the weight ratio was 90% or more and 95% or less were good, with the temperature rise of the catalyst ink during bead mill dispersion being less than 10°C. Furthermore, no defects were found in the appearance of the catalyst layer-equipped transfer base material.
一方、比較例4に示すように、重量比が90%より小さいと、触媒表面を水で十分に濡らすことができないため、触媒インク温度が上昇した。また、分散時にダマになりやすく、塗工時に凹凸が生じ、乾燥後の触媒層にムラが発生したため、外観評価を×評価とした。
また、比較例5に示すように重量比が95%より大きいと、水の絶対量が増えすぎてしまい、乾燥の過程で水比率が上がってしまい、クラックが生じてしまったため、外観評価を×評価とした。
On the other hand, as shown in Comparative Example 4, when the weight ratio was less than 90%, the catalyst surface could not be sufficiently wetted with water, so the catalyst ink temperature rose. In addition, the appearance was rated as x because it was easy to form lumps during dispersion, unevenness occurred during coating, and unevenness occurred in the catalyst layer after drying.
In addition, as shown in Comparative Example 5, when the weight ratio is greater than 95%, the absolute amount of water increases too much, and the water ratio increases during the drying process, resulting in cracks, so the appearance evaluation is It was evaluated.
以上説明したように、本発明の一実施形態によれば、触媒インクの水比率を低く維持することで、膜電極接合体の外観及び発電性能低下を抑制し、揮発成分の比率を高くすることで安全性を考慮した、膜電極接合体の製造方法およびそれに用いられる有用な触媒インクを提供することができる。 As explained above, according to one embodiment of the present invention, by keeping the water ratio of the catalyst ink low, deterioration in the appearance and power generation performance of the membrane electrode assembly can be suppressed, and the ratio of volatile components can be increased. It is possible to provide a method for manufacturing a membrane electrode assembly and a useful catalyst ink used therein, which takes safety into consideration.
1・・・触媒インク
2・・・転写基材
3a、3c・・・触媒層付き転写基材
4・・・固体高分子電解質膜
5a、5c・・・触媒層
6・・・膜電極接合体
10・・・ダイコーター
20・・・熱転写装置
1...
Claims (4)
前記触媒インクは、揮発成分と、触媒担持カーボンとを含み、
含有する揮発成分の重量比が、90%以上95%以下であり、
且つ、前記揮発成分中の水の比率が15%以上40%未満であり、
前記揮発成分は、水及びアルコールであり、
前記アルコールは1-プロパノールであることを特徴とする触媒インク。 After sandwiching the surface of the solid polymer electrolyte membrane with a transfer substrate with a catalyst layer on which a catalyst layer is formed and applying pressure with a hot laminating roll, only the transfer substrate is peeled off, and the A catalyst ink for forming the catalyst layer provided in a membrane electrode assembly formed by transferring the catalyst layer onto the surface of a solid polymer electrolyte membrane and then performing a drying process, the catalyst ink comprising:
The catalyst ink includes volatile components and catalyst-supported carbon,
The weight ratio of the volatile components contained is 90% or more and 95% or less,
and the ratio of water in the volatile component is 15% or more and less than 40%,
The volatile components are water and alcohol,
A catalyst ink characterized in that the alcohol is 1-propanol.
前記触媒インクは、揮発成分と、触媒担持カーボンとを含み、
含有する揮発成分の重量比が、90%以上95%以下であり、
且つ、前記揮発成分中の水の比率が15%以上40%未満であり、
前記揮発成分は、水及びアルコールであり、
前記アルコールは1-プロパノールであることを特徴とする触媒インク。 Coating a catalyst ink on a transfer base material to form a catalyst layer, sandwiching the surface of the solid polymer electrolyte membrane with a catalyst layer-attached transfer base material on which the catalyst layer is formed on the transfer base material, After applying pressure with a hot laminating roll, only the transfer base material is peeled off, and the catalyst layer is transferred to the surface of the solid polymer electrolyte membrane, and then a membrane electrode assembly is formed without going through a drying process. A catalyst ink for forming a catalyst layer, comprising:
The catalyst ink includes volatile components and catalyst-supported carbon,
The weight ratio of the volatile components contained is 90% or more and 95% or less,
and the ratio of water in the volatile component is 15% or more and less than 40%,
The volatile components are water and alcohol,
A catalyst ink characterized in that the alcohol is 1-propanol.
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