JP2990516B1 - Method for producing reaction layer raw material for gas diffusion electrode - Google Patents
Method for producing reaction layer raw material for gas diffusion electrodeInfo
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- JP2990516B1 JP2990516B1 JP11024164A JP2416499A JP2990516B1 JP 2990516 B1 JP2990516 B1 JP 2990516B1 JP 11024164 A JP11024164 A JP 11024164A JP 2416499 A JP2416499 A JP 2416499A JP 2990516 B1 JP2990516 B1 JP 2990516B1
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- average particle
- carbon black
- dispersed
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
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Abstract
【要約】
【課題】 三相帯界面が増加した、著しく高性能のガス
拡散電極の反応層原料の製造方法を提供する。
【解決手段】 界面活性剤を含む水溶液中に疎水性カー
ボンブラック、親水性微粒子及びポリテトラフルオロエ
チレンディスパージョンを分散するに際して、該水溶液
中で分散した親水性微粒子の平均粒径をｒs 、疎水性カ
ーボンブラックの平均粒径をｒc 、使用するポリテトラ
フルオロエチレンディスパージョンの平均粒径をｒp と
するときに、該水溶液にその平均粒径ｒc がＤ＝ｒc ／
ｒp で０．５＜Ｄ＜２の範囲になるように疎水性カーボ
ンブラックを混合分散し、かつ平均粒径ｒs がｒs ＜２
ｒp の親水性微粒子を混合分散し、平均粒径ｒp のポリ
テトラフルオロエチレンディスパージョンを混合後、更
に、自己組織化剤を添加混合することを特徴とするガス
拡散電極の反応層原料の製造方法。An object of the present invention is to provide a method for producing a reaction layer raw material of a gas diffusion electrode having an increased three-phase zone interface and having extremely high performance. SOLUTION: When hydrophobic carbon black, hydrophilic fine particles and polytetrafluoroethylene dispersion are dispersed in an aqueous solution containing a surfactant, the hydrophilic fine particles dispersed in the aqueous solution have an average particle size of r s and a hydrophobic fine particle. the average particle diameter r c sex carbon black, the average particle diameter of the polytetrafluoroethylene dispersion to be used when the r p, the average particle diameter r c in the aqueous solution D = r c /
r 0.5 <a hydrophobic carbon black to be in the range of D <2 were mixed and dispersed in p, and the average particle size r s is r s <2
were mixed and dispersed hydrophilic particles of r p, after mixing the polytetrafluoroethylene dispersion having an average particle diameter r p, further, the reaction layer raw material of the gas diffusion electrode, which comprises admixing a self-organizing agent Production method.
Description
【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION
【０００１】[0001]
【発明の属する技術分野】本発明は、高性能のガス拡散
電極の反応層原料の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a reaction layer raw material for a high performance gas diffusion electrode.
【０００２】[0002]
【従来の技術】従来、ガス拡散電極の一種として、親水
性微粒子、疎水性カーボンブラックおよびポリテトラフ
ルオロエチレン（ＰＴＦＥ）ディスパージョンから成る
反応層を有するガス拡散電極がある。このガス拡散電極
においては、そこで使用される疎水性カーボンブラック
は、一次粒子径が、０．０４ミクロン程度であるが、二
次凝集しているので２０〜３００ミクロンとなってい
る。このガス拡散電極の製造工程において、この疎水性
カーボンブラックは、界面活性剤を含む水溶液中で数ミ
クロン程度に分散しており、これに平均粒径が０．３ミ
クロンのＰＴＦＥディスパージョンを混合、凝集、濾
過、シート化等を経て反応層が作製されていた。疎水性
カーボンブラックの分散状態は、平均粒径が数ミクロン
程度であれば実用的に充分な性能と製造再現性が確保さ
れている。その疎水性カーボンブラックを分散させるた
めの分散方法は超音波分散が最も優れているが、この方
法では作業性から１ミクロン以下の平均粒径とすること
は困難であった。2. Description of the Related Art Conventionally, as one type of gas diffusion electrode, there is a gas diffusion electrode having a reaction layer composed of hydrophilic fine particles, hydrophobic carbon black and polytetrafluoroethylene (PTFE). In this gas diffusion electrode, the hydrophobic carbon black used therein has a primary particle diameter of about 0.04 μm, but has a secondary aggregation of 20 to 300 μm. In the production process of the gas diffusion electrode, the hydrophobic carbon black is dispersed to about several microns in an aqueous solution containing a surfactant, and a PTFE dispersion having an average particle diameter of 0.3 microns is mixed with the dispersion. The reaction layer has been produced through aggregation, filtration, sheeting, and the like. As for the dispersion state of the hydrophobic carbon black, if the average particle diameter is about several microns, practically sufficient performance and production reproducibility are secured. Ultrasonic dispersion is the best dispersion method for dispersing the hydrophobic carbon black, but it is difficult to reduce the average particle diameter to 1 micron or less by this method due to workability.
【０００３】[0003]
【発明が解決しようとする課題】しかし、上記したよう
な２０〜３００ミクロンと０．３ミクロンというような
粒径差を持つ疎水性カーボンブラックとＰＴＦＥディス
パージョンを含む分散液が自己組織化して反応層となっ
た時の状態は、大きな疎水性カーボンブラックの二次粒
子の回りに十分の一ほどの小さなＰＴＦＥ微粒子が存在
する構造となって疎水部を形成しているものである。こ
の疎水部の領域が大きいので、親水性微粒子が自己組織
化した親水部も大きくなり、その結果、反応に関与する
三相帯界面は小さくなってしまう。すなわち、材料の持
つ電極性能が極限まで発揮されていないことになる。However, the dispersion containing the PTFE dispersion and the hydrophobic carbon black having a particle size difference of 20 to 300 microns and 0.3 microns as described above reacts by self-assembly. The state when the layer is formed is a structure in which one-tenth of small PTFE fine particles are present around secondary particles of large hydrophobic carbon black to form a hydrophobic part. Since the area of the hydrophobic part is large, the hydrophilic part in which the hydrophilic fine particles are self-organized also becomes large, and as a result, the three-phase band interface involved in the reaction becomes small. That is, the electrode performance of the material is not exhibited to the utmost.
【０００４】本発明は、このような従来の問題点に鑑み
てなされたものであり、疎水性カーボンブラックの分散
微粒子径をＰＴＦＥディスパージョンの平均粒径と同程
度にして、三相帯界面を増加することによって、高性能
のガス拡散電極の反応層原料の製造方法を提供すること
を課題とする。The present invention has been made in view of such a conventional problem, and the three-phase band interface is formed by making the dispersed fine particles of the hydrophobic carbon black approximately the same as the average particle size of the PTFE dispersion. An object of the present invention is to provide a method for producing a reaction layer raw material for a high-performance gas diffusion electrode by increasing the amount.
【０００５】[0005]
【課題を解決するための手段】ガス拡散電極の高性能化
には、三相帯界面を増加させることが必須である。本発
明者は、前記課題を解決すべく鋭意研究した結果、この
三相帯界面の増加方法は、疎水性カーボンブラックとＰ
ＴＦＥ微粒子の混合状態で大きく左右されることを見出
した。すなわち、使用するＰＴＦＥディスパージョンと
ほぼ同程度の粒径に疎水性カーボンブラックを分散さ
せ、親水性微粒子はＰＴＦＥディスパージョンより小さ
な粒径とし、これらをＰＴＦＥディスパージョンと攪拌
混合したのち、アルコール等で自己組織化すれば、サブ
ミクロンの三相帯界面が形成されることを知見した。す
なわち、本発明者は、三相帯界面をミクロン以下の親水
部で構成させる方法として、界面活性剤を含む水溶液中
で、親水部と疎水部となる材料をＰＴＦＥディスパーシ
ョンとほぼ同程度の粒径に分散させ自己組織化すること
でミクロな構造を作製できることを見出した。本発明者
は、前記の知見に基づいて上記の課題を解決でき、その
結果上記の目的を達成できることを見出して本発明を完
成するに至った。In order to improve the performance of a gas diffusion electrode, it is essential to increase the three-phase zone interface. The present inventor has conducted intensive studies to solve the above-mentioned problems.
It has been found that it greatly depends on the mixed state of TFE fine particles. That is, the hydrophobic carbon black is dispersed to a particle size substantially the same as the PTFE dispersion to be used, and the hydrophilic fine particles are made to have a smaller particle size than the PTFE dispersion. It was found that a submicron three-phase zone interface was formed by self-organization. That is, as a method of forming the three-phase zone interface with a hydrophilic portion of a micron or less, the present inventor has proposed that a material to be a hydrophilic portion and a hydrophobic portion in an aqueous solution containing a surfactant has a particle size substantially equal to that of PTFE dispersion. It has been found that a microstructure can be produced by dispersing in diameter and self-organizing. The present inventors have found that the above problems can be solved based on the above findings, and as a result, the above objects can be achieved, and have completed the present invention.
【０００６】すなわち、本発明は、次の構成からなるも
のである。 （１） 界面活性剤を含む水溶液中に疎水性カーボンブ
ラック、親水性微粒子及びポリテトラフルオロエチレン
ディスパージョンを分散するに際して、該水溶液中で分
散した親水性微粒子の平均粒径をｒs 、疎水性カーボン
ブラックの平均粒径をｒc 、使用するポリテトラフルオ
ロエチレンディスパージョンの平均粒径をｒp とすると
きに、該水溶液にその平均粒径ｒc がＤ＝ｒc ／ｒp で
０．５＜Ｄ＜２の範囲になるように疎水性カーボンブラ
ックを混合分散し、かつ平均粒径ｒ s がｒs ＜２ｒp の
親水性微粒子を混合分散し、平均粒径ｒp のポリテトラ
フルオロエチレンディスパージョンを混合後、更に、自
己組織化剤を添加混合することを特徴とするガス拡散電
極の反応層原料の製造方法。That is, the present invention has the following configuration.
It is. (1) Hydrophobic carbon powder in aqueous solution containing surfactant
Rack, hydrophilic fine particles and polytetrafluoroethylene
When dispersing the dispersion, the dispersion is dispersed in the aqueous solution.
The average particle size of the dispersed hydrophilic fine particles is represented by rs, Hydrophobic carbon
The average particle size of black is rcThe polytetrafluo used
The average particle size of the ethylene dispersion is rpThen
The aqueous solution has an average particle size rcIs D = rc/ Rpso
Hydrophobic carbon bra so that 0.5 <D <2
And the average particle size r sIs rs<2rpof
The hydrophilic fine particles are mixed and dispersed, and the average particle diameter rpPolytetra
After mixing the fluoroethylene dispersion,
Gas diffusion electrode characterized by adding and mixing a self-organizing agent
A method for producing a raw material for a reaction layer of an electrode.
【０００７】[0007]
【発明の実施の形態】界面活性剤を４％含む水に疎水性
カーボンブラックを軽く分散させ、ジェツトミルを用
い、１０００ｋｇ／ｃｍ2 の圧力で０．２ｍｍ径の２つ
のノズルで高速流を衝突させることで平均粒径０．４５
ミクロンに分散した。このカーボンブラック分散液に平
均粒径０．１ミクロンの銀コロイド分散液を添加攪拌混
合し、更に、ＰＴＦＥディスパージョンを添加、攪拌混
合するだけで分散操作を行い、最後にエチルアルコール
を添加混合して自己組織化させる。これを濾過して、乾
燥し、ロール法でシート化し、界面活性剤を除去し、乾
燥してから、銀網とガス供給層とを合わせ、ホットプレ
スしてガス拡散電極を得る。BEST MODE FOR CARRYING OUT THE INVENTION Hydrophobic carbon black is lightly dispersed in water containing 4% of a surfactant, and a jet mill is used to collide a high-speed flow with two nozzles having a diameter of 0.2 mm at a pressure of 1000 kg / cm 2 . Average particle size 0.45
Dispersed in micron. A silver colloid dispersion having an average particle size of 0.1 micron is added to this carbon black dispersion, and the mixture is stirred and mixed. Further, a PTFE dispersion is added and the mixture is stirred and mixed, and a dispersion operation is performed. Finally, ethyl alcohol is added and mixed. And self-organize. This is filtered, dried, formed into a sheet by a roll method, the surfactant is removed, dried, and then the silver mesh and the gas supply layer are combined and hot pressed to obtain a gas diffusion electrode.
【０００８】親水性微粒子は、親水性カーボンブラッ
ク、金属微粒子、金属酸化物、ＺｎＯ 2 、ＣａＣＯ3 、
アルミナ、シリカ、チタニア等の水、アルコールに溶解
せず、３８０℃の高温で安定なものが好適に用いられ
る。触媒として白金、銀をこの親水性微粒子上に担持し
て用いる。これらの微粒子は０．３ミクロン以下の粒径
が望ましい。[0008] The hydrophilic fine particles are hydrophilic carbon black.
Metal, metal fine particles, metal oxide, ZnO Two, CaCOThree,
Dissolves in water and alcohol such as alumina, silica and titania
It is preferable to use a material which is stable at a high temperature of 380 ° C.
You. Platinum and silver are supported on the hydrophilic fine particles as a catalyst.
Used. These particles have a particle size of less than 0.3 microns
Is desirable.
【０００９】[0009]
【実施例】以下実施例により本発明を具体的に説明す
る。ただし、本発明は、これらの実施例のみに限定され
るものではない。なお、全実施例および比較例を通じ
て、部は全て重量部を、％は全て重量％を意味する。The present invention will be described in detail with reference to the following examples. However, the present invention is not limited to only these examples. In all examples and comparative examples, all parts are parts by weight, and all parts are% by weight.
【００１０】実施例１ ４％トライトン（界面活性剤、以下同様）２００部に疎
水性カーボンブラック（デンカブラック、平均粒径３９
０オングストローム、電気化学工業社製）２部を添加攪
拌分散した。このカーボンブラック分散液をジェットミ
ル（ジーナス製、ノズル径０．２ｍｍ）で１５００ｋｇ
／ｃｍ2 の圧力で５回通過させた。その結果、平均粒子
径は０．４ミクロンとなり、１ミクロン以上の粒子がな
いシャープな分布になった。この高分散液に銀コロイド
（田中貴金属社製試作品、平均粒径０．１ミクロン）１
０部を加え、攪拌混合した。更に、ＰＴＦＥディスパー
ジョン（Ｄ−１、平均粒径０．３ミクロン、ダイキン工
業社製）１．５部を加え、攪拌混合した。この分散液に
イソプロピルアルコールを３００部加え自己組織化さ
せ、濾過して反応層原料とした。ロール法で反応層とガ
ス供給層から成るガス拡散電極シートを製造し、８０℃
で３時間乾燥し、界面活性剤をエタノール抽出装置で除
去した。乾燥後、銀網と共に５０ｋｇ／ｃｍ2 で３５０
℃、６０秒間プレスして電極を得た。この電極の酸素還
元性能を８０℃、３２％ＮａＯＨ中で測定したところ、
３０Ａ／ｄｍ2 で０．８４６Ｖ（ｖｓ．ＲＨＥ）の高い
性能が得られた。Example 1 200 parts of 4% Triton (surfactant, the same applies hereinafter) was added to a hydrophobic carbon black (Denka Black, average particle size 39).
(0 Angstrom, manufactured by Denki Kagaku Kogyo KK) was added and dispersed by stirring. 1500 kg of this carbon black dispersion was jet-milled (Genus, nozzle diameter 0.2 mm).
5 passes at a pressure of / cm 2 . As a result, the average particle diameter was 0.4 μm, and a sharp distribution without particles of 1 μm or more was obtained. A silver colloid (prototype made by Tanaka Kikinzoku Co., average particle size 0.1 micron)
0 parts were added and mixed with stirring. Further, 1.5 parts of a PTFE dispersion (D-1, average particle diameter: 0.3 μm, manufactured by Daikin Industries, Ltd.) was added and mixed by stirring. 300 parts of isopropyl alcohol was added to this dispersion to form a self-assembly, and filtered to obtain a reaction layer material. A gas diffusion electrode sheet comprising a reaction layer and a gas supply layer is manufactured by a roll method,
For 3 hours, and the surfactant was removed with an ethanol extractor. After drying, 350 kg / cm 2 with silver screen
Pressing at 60 ° C. for 60 seconds gave an electrode. The oxygen reduction performance of this electrode was measured at 80 ° C. in 32% NaOH.
High performance of 0.846 V (vs. RHE) was obtained at 30 A / dm 2 .
【００１１】比較例１ ４％トライトン２００部に疎水性カーボンブラック（デ
ンカブラック、平均粒径３９０オングストローム、電気
化学工業社製）２部を添加攪拌分散した。このカーボン
ブラック分散液を水で冷却しながら超音波分散機（ブラ
ンソン製、５００Ｗ）で５分間分散させた。その結果、
平均粒子径は１．６ミクロンとなった。この分散液に銀
コロイド（田中貴金属社製試作品、平均粒径０．１ミク
ロン）１０部を加え、攪拌混合した。更に、ＰＴＦＥデ
ィスパージョン（Ｄ−１、平均粒径０．３ミクロン、ダ
イキン工業社製）１．５部を加え、攪拌混合した。この
分散液にイソプロピルアルコールを３００部加え自己組
織化させ、濾過して反応層原料とした。ロール法で反応
層とガス供給層から成るガス拡散電極シートを製造し、
８０℃で３時間乾燥し、界面活性剤をエタノール抽出装
置で除去した。乾燥後、銀網と共に５０ｋｇ／ｃｍ2 で
３５０℃、６０秒間プレスして電極を得た。この電極の
酸素還元性能を８０℃、３２％ＮａＯＨ中で測定したと
ころ、３０Ａ／ｄｍ2 で０．７９３Ｖ（ｖｓ．ＲＨＥ）
の性能しか得られなかった。Comparative Example 1 To 200 parts of 4% Triton, 2 parts of hydrophobic carbon black (Denka Black, average particle size: 390 angstroms, manufactured by Denki Kagaku Kogyo) were added and dispersed by stirring. The carbon black dispersion was dispersed for 5 minutes by an ultrasonic disperser (500 W, manufactured by Branson) while cooling with water. as a result,
The average particle size was 1.6 microns. To this dispersion, 10 parts of silver colloid (produced by Tanaka Kikinzoku Co., Ltd., average particle size: 0.1 micron) was added and mixed by stirring. Further, 1.5 parts of a PTFE dispersion (D-1, average particle diameter: 0.3 μm, manufactured by Daikin Industries, Ltd.) was added and mixed by stirring. 300 parts of isopropyl alcohol was added to this dispersion to form a self-assembly, and filtered to obtain a reaction layer material. Producing a gas diffusion electrode sheet composed of a reaction layer and a gas supply layer by a roll method,
After drying at 80 ° C. for 3 hours, the surfactant was removed with an ethanol extractor. After drying, the resultant was pressed with a silver mesh at 50 kg / cm 2 at 350 ° C. for 60 seconds to obtain an electrode. When the oxygen reduction performance of this electrode was measured at 80 ° C. and 32% NaOH, it was 0.793 V (vs. RHE) at 30 A / dm 2.
Only the performance of was obtained.
【００１２】実施例２ ２％トライトン３５０部に親水性カーボンブラック（Ａ
Ｂ−１２、平均粒径４００オングストローム、試作品、
電気化学工業社製）７部、疎水性カーボンブラック（Ｎ
ｏ．６、平均粒径５００オングストローム、試作品、電
気化学工業社製）３部を添加攪拌分散した。このカーボ
ンブラック分散液をジェットミル（ジーナス製、ノズル
径０．２ｍｍ）で１５００ｋｇ／ｃｍ2 の圧力で５回分
散させた。その結果、平均粒子径は０．４５ミクロンと
なった。更に、ＰＴＦＥディスパージョン（Ｄ−１、平
均粒径０．３ミクロン、ダイキン工業社製）４部を加
え、攪拌混合した。この分散液にイソプロピルアルコー
ルを３００部加え自己組織化させ、濾過して反応層原料
とした。ロール法で反応層とガス供給層から成るガス拡
散電極シートを製造し、８０℃で３時間乾燥し、界面活
性剤をエタノール抽出装置で除去した。乾燥後、銀網と
共に５０ｋｇ／ｃｍ2 で３８０℃、６０秒間プレスして
電極を得た。この電極に塗布法で白金を０．５６ｍｇ／
ｃｍ2 担持した。この電極の酸素還元性能を８０℃、３
２％ＮａＯＨ中で測定したところ、３０Ａ／ｄｍ2 で
０．８５０Ｖ（ｖｓ．ＲＨＥ）の著しく高い性能の電極
が得られた。Example 2 A hydrophilic carbon black (A) was added to 350 parts of 2% Triton.
B-12, average particle size 400 Å, prototype,
7 parts, manufactured by Denki Kagaku Kogyo Co., Ltd., hydrophobic carbon black (N
o. 6, 500 parts of average particle size, prototype, manufactured by Denki Kagaku Kogyo Co., Ltd.) and 3 parts were stirred and dispersed. This carbon black dispersion was dispersed five times with a jet mill (Genus, nozzle diameter 0.2 mm) at a pressure of 1500 kg / cm 2 . As a result, the average particle size was 0.45 microns. Further, 4 parts of a PTFE dispersion (D-1, average particle size: 0.3 μm, manufactured by Daikin Industries, Ltd.) was added and mixed by stirring. 300 parts of isopropyl alcohol was added to this dispersion to form a self-assembly, and filtered to obtain a reaction layer material. A gas diffusion electrode sheet comprising a reaction layer and a gas supply layer was manufactured by a roll method, dried at 80 ° C. for 3 hours, and the surfactant was removed by an ethanol extraction device. After drying, it was pressed at 380 ° C. for 60 seconds at 50 kg / cm 2 together with a silver screen to obtain an electrode. 0.56 mg of platinum was applied to this electrode by a coating method.
cm 2 . The oxygen reduction performance of this electrode was
When measured in 2% NaOH, an electrode with a remarkably high performance of 0.850 V (vs. RHE) at 30 A / dm 2 was obtained.
【００１３】比較例２ ２％トライトン３５０部に親水性カーボンブラック（Ａ
Ｂ−１２、平均粒径４００オングストローム、試作品、
電気化学工業社製）７部、疎水性カーボンブラック（Ｎ
ｏ．６、平均粒径５００オングストローム、試作品、電
気化学工業社製）３部を添加攪拌分散した。このカーボ
ンブラック分散液を水で冷却しながら超音波分散機（プ
ランソン製、５００Ｗ）で５分間分散させた。その結
果、平均粒子径は１．５ミクロンとなった。更に、ＰＴ
ＦＥディスパージョン（Ｄ−１、平均粒径０．３ミクロ
ン、ダイキン工業社製）４部を加え、攪拌混合した。こ
の分散液にイソプロピルアルコールを３００部加え自己
組織化させ、濾過して反応層原料とした。ロール法で反
応層とガス供給層から成るガス拡散電極シートを製造
し、８０℃で３時間乾燥し、界面活性剤をエタノール抽
出装置で除去した。乾燥後、銀網と共に５０ｋｇ／ｃｍ
2 で３８０℃、６０秒間プレスして電極を得た。この電
極に塗布法で白金を０．５６ｍｇ／ｃｍ2 担持した。こ
の電極の酸素還元性能を８０℃、３２％ＮａＯＨ中で測
定したところ、３０Ａ／ｄｍ2 で０．８０Ｖ（ｖｓ．Ｒ
ＨＥ）の性能しか得られなかった。Comparative Example 2 A hydrophilic carbon black (A) was added to 350 parts of 2% Triton.
B-12, average particle size 400 Å, prototype,
7 parts, manufactured by Denki Kagaku Kogyo Co., Ltd., hydrophobic carbon black (N
o. 6, 500 parts of average particle size, prototype, manufactured by Denki Kagaku Kogyo Co., Ltd.) and 3 parts were stirred and dispersed. This carbon black dispersion was dispersed with an ultrasonic disperser (500 W, manufactured by Pranson) for 5 minutes while cooling with water. As a result, the average particle size was 1.5 microns. Furthermore, PT
4 parts of FE dispersion (D-1, average particle size 0.3 micron, manufactured by Daikin Industries, Ltd.) were added and mixed by stirring. 300 parts of isopropyl alcohol was added to this dispersion to form a self-assembly, and filtered to obtain a reaction layer material. A gas diffusion electrode sheet comprising a reaction layer and a gas supply layer was manufactured by a roll method, dried at 80 ° C. for 3 hours, and the surfactant was removed by an ethanol extraction device. After drying, 50 kg / cm with silver screen
Pressing at 380 ° C. for 2 seconds at 2 gave an electrode. 0.56 mg / cm 2 of platinum was supported on this electrode by a coating method. When the oxygen reduction performance of this electrode was measured at 80 ° C. and 32% NaOH, it was 0.80 V (vs. R) at 30 A / dm 2.
HE).
【００１４】[0014]
【発明の効果】本発明によれば、疎水性カーボンブラッ
クの分散粒子径をＰＴＦＥディスパージョンと同程度に
し、親水性微粒子の平均粒径をＰＴＦＥディスパージョ
ンの平均粒径よりも小さくしたことにより三相帯界面が
増加したガス拡散電極の反応層原料が得られた。この反
応層原料を用いれば著しく高性能のガス拡散電極を製造
することができる。According to the present invention, the dispersed particle size of the hydrophobic carbon black is made substantially equal to that of the PTFE dispersion, and the average particle size of the hydrophilic fine particles is made smaller than the average particle size of the PTFE dispersion. A reaction layer raw material for a gas diffusion electrode having an increased phase zone interface was obtained. By using this reaction layer raw material, a gas diffusion electrode having extremely high performance can be manufactured.
フロントページの続き (56)参考文献 特開 平９−302493（ＪＰ，Ａ) 特開 平７−207482（ＪＰ，Ａ) 特開 平２−30784（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) C25B 1/00 - 15/08 Continuation of the front page (56) References JP-A-9-302493 (JP, A) JP-A-7-207482 (JP, A) JP-A-2-30784 (JP, A) (58) Fields investigated (Int .Cl. 6 , DB name) C25B 1/00-15/08
Claims (1)
ボンブラック、親水性微粒子及びポリテトラフルオロエ
チレンディスパージョンを分散するに際して、該水溶液
中で分散した親水性微粒子の平均粒径をｒs 、疎水性カ
ーボンブラックの平均粒径をｒc 、使用するポリテトラ
フルオロエチレンディスパージョンの平均粒径をｒp と
するときに、該水溶液にその平均粒径ｒc がＤ＝ｒc ／
ｒp で０．５＜Ｄ＜２の範囲になるように疎水性カーボ
ンブラックを混合分散し、かつ平均粒径ｒs がｒs ＜２
ｒp の親水性微粒子を混合分散し、平均粒径ｒp のポリ
テトラフルオロエチレンディスパージョンを混合後、更
に、自己組織化剤を添加混合することを特徴とするガス
拡散電極の反応層原料の製造方法。When dispersing hydrophobic carbon black, hydrophilic fine particles and polytetrafluoroethylene dispersion in an aqueous solution containing a surfactant, the hydrophilic fine particles dispersed in the aqueous solution have an average particle size of r s , the average particle diameter r c hydrophobic carbon black, the average particle diameter of the polytetrafluoroethylene dispersion to be used when the r p, the average particle diameter r c in the aqueous solution D = r c /
r 0.5 <a hydrophobic carbon black to be in the range of D <2 were mixed and dispersed in p, and the average particle size r s is r s <2
were mixed and dispersed hydrophilic particles of r p, after mixing the polytetrafluoroethylene dispersion having an average particle diameter r p, further, the reaction layer raw material of the gas diffusion electrode, which comprises admixing a self-organizing agent Production method.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11024164A JP2990516B1 (en) | 1999-02-01 | 1999-02-01 | Method for producing reaction layer raw material for gas diffusion electrode |
| US09/600,114 US6428722B1 (en) | 1998-11-12 | 1999-06-28 | Gas diffusion electrode material, process for producing the same, and process for producing gas diffusion electrode |
| CNB998021105A CN1134556C (en) | 1998-11-12 | 1999-06-28 | Gas diffusion electrode material, process for producing same, and process for producing gas diffusion electrode |
| EP99972265A EP1055748A4 (en) | 1998-11-12 | 1999-06-28 | Gas diffusion electrode material, process for producing the same, and process for producing gas diffusion electrode |
| PCT/JP1999/003440 WO2000029643A1 (en) | 1998-11-12 | 1999-06-28 | Gas diffusion electrode material, process for producing the same, and process for producing gas diffusion electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11024164A JP2990516B1 (en) | 1999-02-01 | 1999-02-01 | Method for producing reaction layer raw material for gas diffusion electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2990516B1 true JP2990516B1 (en) | 1999-12-13 |
| JP2000219987A JP2000219987A (en) | 2000-08-08 |
Family
ID=12130716
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11024164A Expired - Fee Related JP2990516B1 (en) | 1998-11-12 | 1999-02-01 | Method for producing reaction layer raw material for gas diffusion electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2990516B1 (en) |
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1999
- 1999-02-01 JP JP11024164A patent/JP2990516B1/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| JP2000219987A (en) | 2000-08-08 |
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