JPH067488B2 - Gas diffusion electrode - Google Patents
Gas diffusion electrodeInfo
- Publication number
- JPH067488B2 JPH067488B2 JP60294429A JP29442985A JPH067488B2 JP H067488 B2 JPH067488 B2 JP H067488B2 JP 60294429 A JP60294429 A JP 60294429A JP 29442985 A JP29442985 A JP 29442985A JP H067488 B2 JPH067488 B2 JP H067488B2
- Authority
- JP
- Japan
- Prior art keywords
- gas diffusion
- diffusion layer
- layer
- current
- current collector
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/96—Carbon-based electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for 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
- 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
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は燃料電池、二次電池、電気化学的リアクター、
各種電解用陽極、めっき用陽極等に用いるガス拡散電極
の改良に関する。The present invention relates to a fuel cell, a secondary battery, an electrochemical reactor,
The present invention relates to improvement of gas diffusion electrodes used for various electrolytic anodes, plating anodes, and the like.
（従来の技術とその問題点） 従来、ガス拡散層として、Ｐｔ、カーボンブラック、ポ
リ四弗化エチレンより成る微細な親水部と疎水部を有す
る反応層に、カーボンブラック、ポリ四弗化エチレンよ
り成る疎水性のガス拡散層を接合し、そのガス拡散層の
前記反応層とは反対側の表面に、Ｃｕ線材の網より成る
集電材を接合して成るものがある。(Prior art and its problems) Conventionally, as a gas diffusion layer, a reaction layer having a fine hydrophilic portion and a hydrophobic portion made of Pt, carbon black, and polytetrafluoroethylene has been used. There is a method in which a hydrophobic gas diffusion layer is formed, and a current collector made of a net of Cu wire is joined to the surface of the gas diffusion layer opposite to the reaction layer.
このガス拡散電極は、燃料電池、二次電池、電気化学的
リアクター等に使用した場合、電解液は反応層を透過す
るが、ガス拡散層を透過せず、ガスのみガス拡散層を拡
散透過する。この場合、電解液からの分解ガスや供給ガ
スとしてのＣｌ2やＳＯ2ガスが水蒸気と共にガス拡散層
の集電材側に存在してＨＣｌやＨ2ＳＯ3が生成される
と、これらの酸によりＣｕ線材の網より成る集電材がお
かされるので、経時的に集電電流が低下するものであ
る。When this gas diffusion electrode is used in a fuel cell, a secondary battery, an electrochemical reactor, etc., the electrolyte permeates the reaction layer, but does not permeate the gas diffusion layer, only the gas diffuses and permeates the gas diffusion layer. . In this case, when decomposition gas from the electrolytic solution or Cl 2 or SO 2 gas as a supply gas is present together with water vapor on the current collector side of the gas diffusion layer to generate HCl or H 2 SO 3 , these acids generate Since the current collector made of a net of Cu wire is placed, the current collection current decreases with time.
この為、Ｃｕ線材に代えて酸におかされないＴｉ、Ｔ
ａ、ステンレス鋼、カーボンクロスより成る集電材をガ
ス拡散層の表面に接合した。Therefore, instead of Cu wire, Ti, T which is not exposed to acid
A current collector made of a, stainless steel, and carbon cloth was bonded to the surface of the gas diffusion layer.
然し乍ら、Ｔｉ、Ｔａ、ステンレス鋼等の網とすると表
面に高抵抗の酸化被膜が生成するため集電電流が著しく
小さく、また酸化被膜のできないカーボンクロスより成
る集電材も抵抗が大きい為、Ｃｕ線材の網より成る電極
に比べ集電電流の低いものである。However, when a net made of Ti, Ta, stainless steel, etc. is used, a high resistance oxide film is formed on the surface, so the current collecting current is extremely small, and the current collector made of carbon cloth, which cannot form an oxide film, also has a high resistance. The current collecting current is lower than that of the electrode composed of the net.
そこで本発明は、酸におかされず、集電する際の抵抗が
小さくて集電電流の高い集電材を備えたガス拡散電極を
提供しようとするものである。Therefore, the present invention is intended to provide a gas diffusion electrode provided with a current collecting material which is not exposed to acid and has a low resistance when collecting current and a high current collecting current.
（問題点を解決するための手段） 上記問題点を解決するための本発明のガス拡散電極は、
白金族金属又はその酸化物若しくはそれら両方とカーボ
ンブラックとポリ四弗化エチレンより成る微細な親水部
と疎水部を有する反応層に、カーボンブラックとポリ四
弗化エチレンより成る疎水性のガス拡散層が接合され、
前記反応層とは反対側のガス拡散層の表面に、Ｔｉ又は
Ｔａ若しくはＴｉ又はＴａ被覆のＣｕより成る線材にて
編組した網又は多数の線若しくは多数の透孔を有する板
の少なくとも前記ガス拡散電極と接する部分に白金族金
属又はその酸化物若しくはそれら両方をコーティングし
た集電材が接合又は埋込まれて成るものである。(Means for Solving Problems) The gas diffusion electrode of the present invention for solving the above problems is
Hydrophobic gas diffusion layer composed of carbon black and polytetrafluoroethylene on a reaction layer having a fine hydrophilic part and a hydrophobic part composed of platinum group metal or its oxide or both, carbon black and polytetrafluoroethylene Are joined,
At least the gas diffusion of a net braided with a wire made of Ti or Ta or Cu coated with Ti or Ta or Ta or a plate having a large number of wires or a large number of through holes on the surface of the gas diffusion layer opposite to the reaction layer. A current collector coated with a platinum group metal or an oxide thereof or both is bonded or embedded in a portion in contact with the electrode.
（作用） 上記の如く構成された本発明のガス拡散電極は、ガス拡
散層の表面に接合又は埋込まれた集電材が、Ｔｉ又はＴ
ａ若しくはＴｉ又はＴａ被覆のＣｕより成る線材にて編
組した網、又は多数の線若しくは多数の透孔を有する板
の少なくとも前記拡散層に接する部分に例えばＰｔ、Ｐ
ｕＯ2、ＩｒＯ2、ＰｄＯ、ＲｕＯ2＋ＩｒＯ2、Ｐｔ＋Ｉ
ｒＯ2のいずれかをコーティングしたものより成るの
で、燃料電池、二次電池、電気化学的リアクター等に使
用した場合、反応により生成したガスあるいは供給ガス
が水蒸気と共にガス拡散層の集電材側に存在し酸が生成
されても、集電材は耐酸性を有していて浸食されること
がなく、また電気抵抗が小さくて集電電流の高いもので
ある。(Operation) In the gas diffusion electrode of the present invention configured as described above, the current collector joined or embedded in the surface of the gas diffusion layer is Ti or T.
a, a net braided with a wire made of Cu coated with Ti or Ta, or a plate having a large number of wires or a large number of through holes, for example Pt, P
uO 2 , IrO 2 , PdO, RuO 2 + IrO 2 , Pt + I
Since made than those coated with either and rO 2, the fuel cell, present in the secondary battery, when used in electrochemical reactors such as the current collector side of the gas diffusion layer the gas produced or supplied gas with water vapor by reaction Even if oxalic acid is generated, the current collector has acid resistance and is not corroded, and has low electric resistance and high current collection.
本発明のガス拡散電極の実施例を図面によって （実施例１） 説明する。An example of a gas diffusion electrode of the present invention will be described with reference to the drawings (Example 1).
第１図に示すガス拡散電極１は平均粒径250ÅのＲｕＯ2
＋ＩｒＯ2触媒と平均粒径450Åの疎水性カーボンブラッ
クと平均粒径0.3μのポリ四弗化エチレンとが３：３：
２の割合から成る厚さ0.1mm、幅120mm、長さ120mmの微
細な親水部と疎水部を有する反応層２に、平均粒径420
Åの疎水性カーボンブラックと平均粒径0.3μのポリ四
弗化エチレンとが７：３の割合から成る厚さ0.5mmのガ
ス拡散層３を接合し、前記反応層２とは反対側のガス拡
散層３の表面に、第２図に示す如く直径0.3mmのＴｉ線
４にＰｔ５を５μコーティングした線材６にて第１図に
示す如く目合0.5mmで編組した幅120mm、長さ120mmの鋼
の集電材７を接合して成るものである。The gas diffusion electrode 1 shown in FIG. 1 is made of RuO 2 having an average particle size of 250 Å.
3: IrO 2 catalyst, hydrophobic carbon black having an average particle size of 450 Å, and polytetrafluoroethylene having an average particle size of 0.3 μ are 3: 3:
The average particle size is 420 in the reaction layer 2 having a fine hydrophilic portion and a hydrophobic portion having a thickness of 0.1 mm, a width of 120 mm, and a length of 120 mm and having a ratio of 2.
Å Hydrophobic carbon black and polytetrafluoroethylene having an average particle size of 0.3μ are joined together to form a gas diffusion layer 3 having a thickness of 0.5 mm and having a thickness of 0.5 mm. On the surface of the diffusion layer 3, as shown in FIG. 2, a Ti wire 4 having a diameter of 0.3 mm and 5 μm of Pt 5 coated with 5 μm were braided with a mesh of 0.5 mm as shown in FIG. 1 to have a width of 120 mm and a length of 120 mm. It is formed by joining steel current collectors 7.
（実施例２） 第３図に示すガス拡散電極８はガス拡散層３の厚さが0.
8mm以外前記と同一寸法、同一材質の反応層２とガス拡
散層３とを接合し、反応層２とは反対側のガス拡散層３
の表面に、第４図に示す如く直径0.3mmのＣｕ線９に厚
さ0.1mmのＴｉ10を被覆したクラッド線11にＲｕＯ212を
２μコーティングした線13が80本より成る集電材14を第
３図に示す如く幅方向に1.5mm間隔に埋込んで成るもの
である。(Example 2) In the gas diffusion electrode 8 shown in FIG. 3, the gas diffusion layer 3 has a thickness of 0.
Other than 8 mm, the reaction layer 2 and the gas diffusion layer 3 having the same dimensions and the same material as those described above are joined, and the gas diffusion layer 3 on the side opposite to the reaction layer 2 is joined.
As shown in FIG. 4, a current collector 14 consisting of 80 wires 13 having a Cu wire 9 having a diameter of 0.3 mm and a Ti wire 10 having a thickness of 0.1 mm and a RuO 2 12 coating of 2 μ was formed on the surface of the first wire 14 as shown in FIG. As shown in FIG. 3, it is embedded at intervals of 1.5 mm in the width direction.
これらのガス拡散電極１、８と集電材が直径８μのカー
ボン繊維にて編組した幅120mm、長さ120mmのクロスであ
る第１図と同一寸法の従来のガス拡散電極とを夫々電解
液ＺｎＣｌ2＋ＫＣｌ＋ＮａＣｌの二次電池に使用した
処、従来例のガス拡散電極のカーボンより成る集電材
は、充電時の反応により生成されたＣｌ2ガスが水蒸気
と共にガス拡散層３を拡散透過してＨＣｌが生成されて
もそのＨＣｌに浸食されないが、電気抵抗が大きい為、
集電電流が50ｍＡ／cm2と低かったのに対し、実施例の
ガス拡散電極１、８の集電材７、14は共に充電時の反応
により生成されたＣｌ2ガスが水蒸気と共にガス拡散層
３を拡散透過してＨＣｌが生成されてもそのＨＣｌに浸
食されず、しかも電気抵抗が小さい為、集電電流が500
ｍＡ／cm2と高く、時間経過後も殆ど大差がなく高いも
のであった。These gas diffusion electrodes 1 and 8 and a conventional gas diffusion electrode having the same dimensions as in FIG. 1, which is a cloth having a width of 120 mm and a length of 120 mm, in which a current collector is braided with carbon fiber having a diameter of 8 μ, are used as electrolytes ZnCl 2 When used in a + KCl + NaCl secondary battery, the current collector made of carbon of the gas diffusion electrode of the conventional example, Cl 2 gas generated by the reaction during charging diffuses and permeates the gas diffusion layer 3 along with water vapor to generate HCl. Even if it is done, it is not eroded by the HCl, but due to its large electrical resistance,
The current collecting current was as low as 50 mA / cm 2 , whereas the current collecting materials 7 and 14 of the gas diffusion electrodes 1 and 8 of the examples were both the Cl 2 gas generated by the reaction during charging and the gas diffusion layer 3 together with water vapor. Even if HCl is generated by diffusion and permeation through, it is not eroded by HCl and its electrical resistance is small.
It was as high as mA / cm 2 , which was high with almost no difference even after the passage of time.
また反応層にＲｕＯ2を担持した以外は実施例１及び従
来例と夫々同一寸法、同一材質のガス拡散電極を食塩電
解の塩素発生極に用いて、25％ＮａＣｌを90℃で電解し
たところ、本発明の電極では２Ａ／cm2の電流密度で35
ｍＶという低過電圧で電解が可能であり、経時変化もな
く安定していたのに対し、従来例のガス拡散電極は経時
変化はなく安定であったが、0.5Ａ／cm2の電極密度にお
いて200ｍＶと過電圧が高かった。When 25% NaCl was electrolyzed at 90 ° C. using a gas diffusion electrode having the same dimensions and the same material as in Example 1 and the conventional example, except for supporting RuO 2 in the reaction layer, for the chlorine generation electrode of salt electrolysis. With the electrode of the present invention, a current density of 2 A / cm 2
Electrolysis was possible at a low overvoltage of mV and was stable without change over time, whereas the conventional gas diffusion electrode was stable without change over time, but was 200 mV at an electrode density of 0.5 A / cm 2. And the overvoltage was high.
尚、上記実施例１では集電材として網を１枚使用した例
について述べたが、これに限るものではなく、例えば網
を複数枚重ねて用いたり、板状のものを用いて電極自体
を補強するようにしてもよいものである。In addition, although the example in which one net is used as the current collector has been described in the first embodiment, the present invention is not limited to this. For example, a plurality of nets may be stacked or a plate-like member may be used to reinforce the electrode itself. You may choose to do this.
（発明の効果） 以上の説明で判るように本発明のガス拡散電極は、その
ガス拡散層の表面に接合又は埋込んだ集電材は耐酸性を
有するので、燃料電池、二次電池、電気化学的リアクタ
ー、各種電解用陽極、めっき用陽極等に使用した際、生
成された酸に浸食されることがないので経時的に集電電
流が低下するようなことはなく、また集電材の電気抵抗
が小さいので、大きな電流を集電することができ、その
実用上の効果極めて大なるものがある。(Effects of the Invention) As can be seen from the above description, in the gas diffusion electrode of the present invention, the current collector that is bonded or embedded in the surface of the gas diffusion layer has acid resistance, so that the fuel cell, the secondary battery, the electrochemical When used as a catalytic reactor, various electrolysis anodes, plating anodes, etc., it does not corrode with the generated acid, so the current collection current does not decrease over time, and the electrical resistance of the current collector Since it is small, a large amount of current can be collected, and its practical effect is extremely large.
第１図は本発明によるガス拡散電極の一実施例を示す一
部破断斜視図、第２図はそのガス拡散電極に於ける集電
材を作る線材の拡大断面図、第３図は本発明によるガス
拡散電極の他の実施例を示す一部破断斜視図、第４図は
そのガス拡散電極に於ける集電材を作る線材の拡大断面
図である。FIG. 1 is a partially cutaway perspective view showing an embodiment of a gas diffusion electrode according to the present invention, FIG. 2 is an enlarged sectional view of a wire for forming a current collector in the gas diffusion electrode, and FIG. 3 is according to the present invention. FIG. 4 is a partially cutaway perspective view showing another embodiment of the gas diffusion electrode, and FIG. 4 is an enlarged cross-sectional view of a wire rod that forms a current collector in the gas diffusion electrode.
Claims (1)
両方、カーボンブラック、ポリ四弗化エチレンより成る
微細な親水部と疎水部を有する反応層に、カーボンブラ
ック、ポリ四弗化エチレンより成る疎水性のガス拡散層
が接合され、前記反応層とは反対側のガス拡散層の表面
に、Ｔｉ又はＴａ若しくはＴｉ又はＴａ被覆のＣｕより
成る線材にて編組した網又は多数の線若しくは多数透孔
を有する板の少なくとも前記ガス拡散層と接する部分に
白金族金属又はその酸化物若しくはそれら両方をコーテ
ィングした集電材が接合又は埋込まれて成るガス拡散電
極。1. A reaction layer having a fine hydrophilic portion and a hydrophobic portion made of a platinum group metal or an oxide thereof or both thereof, carbon black and polytetrafluoroethylene, and a hydrophobic layer made of carbon black and polytetrafluoroethylene. Gas diffusion layer is joined, and the surface of the gas diffusion layer opposite to the reaction layer is braided with a wire made of Ti or Ta or Cu coated with Ti or Ta or a net or a large number of wires or a large number of through holes. A gas diffusion electrode formed by joining or embedding a current collector coated with a platinum group metal or an oxide thereof or both of them at least in a portion in contact with the gas diffusion layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60294429A JPH067488B2 (en) | 1985-12-27 | 1985-12-27 | Gas diffusion electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60294429A JPH067488B2 (en) | 1985-12-27 | 1985-12-27 | Gas diffusion electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62154571A JPS62154571A (en) | 1987-07-09 |
| JPH067488B2 true JPH067488B2 (en) | 1994-01-26 |
Family
ID=17807647
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60294429A Expired - Lifetime JPH067488B2 (en) | 1985-12-27 | 1985-12-27 | Gas diffusion electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH067488B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0753208A1 (en) * | 1994-03-31 | 1997-01-15 | Motorola Energy Systems Inc. | Improved metal hydride hydrogen storage electrodes |
| AUPN876896A0 (en) * | 1996-03-18 | 1996-04-18 | Ceramic Fuel Cells Limited | An electrical interconnect for a planar fuel cell |
| US6838205B2 (en) | 2001-10-10 | 2005-01-04 | Lynntech, Inc. | Bifunctional catalytic electrode |
| JP3747888B2 (en) * | 2002-06-24 | 2006-02-22 | 日本電気株式会社 | FUEL CELL, FUEL CELL ELECTRODE AND METHOD FOR PRODUCING THE SAME |
| FR2857162B1 (en) * | 2003-07-01 | 2014-04-11 | Commissariat Energie Atomique | FUEL CELL COMPRISING INTEGRATED CURRENT COLLECTORS IN THE ELECTRODE-MEMBRANE-ELECTRODE STACK. |
| US7608358B2 (en) | 2006-08-25 | 2009-10-27 | Bdf Ip Holdings Ltd. | Fuel cell anode structure for voltage reversal tolerance |
-
1985
- 1985-12-27 JP JP60294429A patent/JPH067488B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62154571A (en) | 1987-07-09 |
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