JPH0245302B2 - - Google Patents
Info
- Publication number
- JPH0245302B2 JPH0245302B2 JP56026889A JP2688981A JPH0245302B2 JP H0245302 B2 JPH0245302 B2 JP H0245302B2 JP 56026889 A JP56026889 A JP 56026889A JP 2688981 A JP2688981 A JP 2688981A JP H0245302 B2 JPH0245302 B2 JP H0245302B2
- Authority
- JP
- Japan
- Prior art keywords
- aqueous solution
- added
- air electrode
- nickel
- electrode catalyst
- 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
- H01M4/90—Selection of catalytic material
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Inert Electrodes (AREA)
Description
【発明の詳細な説明】
本発明は、燃料電池、空気電池などに用いる空
気極触媒の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing an air electrode catalyst used in fuel cells, air cells, and the like.
従来、空気極の触媒としては、白金、パラジウ
ム、銀などの貴金属が用いられてきた。これらの
触媒は、触媒能がすぐれているという反面、その
価格が非常に高いという欠点があつた。したがつ
て、触媒能はこれら貴金属触媒に比べても遜色な
く、しかも安価な触媒の開発が強く望まれてい
た。 Conventionally, noble metals such as platinum, palladium, and silver have been used as catalysts for air electrodes. Although these catalysts have excellent catalytic ability, they have the drawback of being extremely expensive. Therefore, there has been a strong desire to develop a catalyst that is comparable in catalytic ability to those of these noble metal catalysts and is inexpensive.
このような要求を満す空気極触媒として、近
時、活性炭、黒鉛などの導電材粉末に触媒として
ニツケルを担持させて成るものが提案されてい
る。 As an air electrode catalyst that satisfies these requirements, one in which nickel is supported as a catalyst on powder of a conductive material such as activated carbon or graphite has recently been proposed.
これは、ニツケル塩水溶液に活性炭、炭素など
の導電材の粉末を加えて撹拌し充分懸濁させた
後、これに苛性アルカリを添加して前記導電剤表
面にニツケル水酸化物を析出、付着せしめる。次
いでこの沈殿生成物を水洗乾燥することにより、
導電材表面に析出したニツケルの水酸化物を酸化
ニツケルに変換せしめる。このようにして得た粉
末を水素、窒素などの還元雰囲気中で加熱処理す
ることにより、導電材表面の酸化ニツケルを還元
してニツケル金属触媒とするものである。 This involves adding powder of a conductive material such as activated carbon or carbon to an aqueous solution of nickel salt and stirring to sufficiently suspend the mixture, and then adding caustic alkali to the solution to precipitate and adhere nickel hydroxide to the surface of the conductive agent. . Next, by washing and drying this precipitated product,
The nickel hydroxide deposited on the surface of the conductive material is converted to nickel oxide. By heat-treating the powder thus obtained in a reducing atmosphere such as hydrogen or nitrogen, the nickel oxide on the surface of the conductive material is reduced to form a nickel metal catalyst.
しかしながら、これら上記の触媒は導電材上に
沈澱生成したニツケルの水酸化物を乾燥、酸化か
つ還元雰囲気中で加熱処理するなどの煩雑な製造
工程を経なければならず、とりわけ、還元雰囲気
中での加熱処理工程においてその還元温度を高く
すると、ニツケルが半融状態となつてニツケル触
媒の表面積が減少するのでその活性度が低下する
事態を生ずる。更には、これら触媒は金属なの
で、電池の陽極としての使用中又は保存中に、ニ
ツケルの表面に電解液等の作用によつて酸化皮膜
が生成し、その結果、触媒活性度が低下するとい
う欠点もあつた。 However, these catalysts require complicated manufacturing processes such as drying, oxidizing, and heat-treating nickel hydroxide precipitated on a conductive material in a reducing atmosphere. If the reduction temperature is increased in the heat treatment step, nickel becomes semi-molten and the surface area of the nickel catalyst decreases, resulting in a decrease in its activity. Furthermore, since these catalysts are metals, they have the disadvantage that an oxide film is formed on the surface of the nickel due to the action of electrolytes etc. during use as a battery anode or during storage, resulting in a decrease in catalytic activity. It was hot too.
本発明は、上記の欠点を解消し、簡単な製造工
程を経て得ることができ、安価で活性度の高い空
気極触媒の製造方法を提供することを目的とす
る。 An object of the present invention is to eliminate the above-mentioned drawbacks, to provide a method for producing an air electrode catalyst that can be obtained through a simple production process, is inexpensive, and has high activity.
すなわち、本発明方法は、ニツケル塩水溶液と
水酸化アルカリ水溶液と酸化剤水溶液から成る３
成分反応溶液中で、導電材粉末の表面に酸化ニツ
ケルを沈着することを特徴とするものである。 That is, the method of the present invention involves the use of a 3.
This method is characterized by depositing nickel oxide on the surface of conductive material powder in a component reaction solution.
本発明方法に用いる導電剤としては、表面積及
び酸素吸着量が大である活性炭、黒鉛の粉末など
が好適である。 As the conductive agent used in the method of the present invention, activated carbon, graphite powder, etc., which have a large surface area and a large amount of oxygen adsorption, are suitable.
本発明の空気極触媒の製造に当つては、まず、
ニツケル塩水溶液に導電材粉末を懸濁するか又は
水酸化アルカリ水溶液に導電材粉末を懸濁する。
このとき、ニツケル塩水溶液としては、硫酸ニツ
ケル、硝酸ニツケル、塩化ニツケル水溶液等があ
げられるが通常硫酸ニツケル水溶液が好んで用い
られる。また水酸化アルカリ水溶液としては水酸
化カリウム、水酸化ナトリウム、水酸化リチウム
水溶液等があげられるが通常、水酸化カリウム水
溶液が好んで用いられる。用いる酸化剤として
は、次亜塩素酸ナトリウム、過酸化水素、チオ硫
酸ナトリウムなどをあげることができるが、酸化
反応を確実に行なうこと、生成した酸化ニツケル
の純度を高め活性を高位に保つなどの点から次亜
塩素酸ナトリウムが好んで用いられる。酸化剤の
濃度は８〜12％が好適である。 In manufacturing the air electrode catalyst of the present invention, first,
A conductive material powder is suspended in a nickel salt aqueous solution or a conductive material powder is suspended in an alkali hydroxide aqueous solution.
At this time, examples of the nickel salt aqueous solution include nickel sulfate, nickel nitrate, nickel chloride aqueous solution, etc., but nickel sulfate aqueous solution is usually preferably used. Examples of alkali hydroxide aqueous solutions include potassium hydroxide, sodium hydroxide, lithium hydroxide aqueous solutions, etc., but potassium hydroxide aqueous solution is usually preferably used. Examples of oxidizing agents used include sodium hypochlorite, hydrogen peroxide, and sodium thiosulfate. From this point of view, sodium hypochlorite is preferably used. The concentration of the oxidizing agent is preferably 8 to 12%.
本発明方法は次のような態様を含むことができ
る。 The method of the present invention can include the following aspects.
(1) 水酸化アルカリ水溶液に酸化剤水溶液を添加
し、ここに導電剤粉末を懸濁して成るニツケル
塩水溶液を添加する。(1) Add an oxidizing agent aqueous solution to an alkali hydroxide aqueous solution, and add thereto a nickel salt aqueous solution in which a conductive agent powder is suspended.
(2) 導電剤粉末を水酸化アルカリ水溶液に懸濁
し、ここに酸化剤水溶液を添加し、ついでニツ
ケル塩水溶液を添加する。(2) The conductive agent powder is suspended in an aqueous alkali hydroxide solution, an oxidizing agent aqueous solution is added thereto, and then a nickel salt aqueous solution is added thereto.
(3) ニツケル塩水溶液に酸化剤水溶液を添加し、
ここに導電剤粉末を懸濁して成る水酸化アルカ
リ水溶液を添加する。(3) Adding an oxidizing agent aqueous solution to a nickel salt aqueous solution,
An aqueous alkali hydroxide solution containing conductive agent powder suspended therein is added.
(4) 導電剤粉末をニツケル塩水溶液に懸濁し、こ
こに酸化剤水溶液を添加し、ついで水酸化アル
カリ水溶液を添加する。(4) The conductive agent powder is suspended in a nickel salt aqueous solution, an oxidizing agent aqueous solution is added thereto, and then an alkali hydroxide aqueous solution is added thereto.
本発明方法によつて処理された導電材粉末は、
過、乾燥後、所定の粒径に粉砕してそろえ、空
気極触媒として用いられる。 The conductive material powder treated by the method of the present invention is
After filtering and drying, it is ground to a predetermined particle size and used as an air electrode catalyst.
以下に本発明を実施例に基づいて説明する。 The present invention will be explained below based on examples.
実施例
14N−水酸化カリウム水溶液４を100℃に保
つた。ここに50℃に加熱した12％次亜塩素酸ナト
リウム水溶液２を添加した。この混合溶液にあ
らかじめ100ｇの活性炭粉末を懸濁して90℃に保
つておいた2M−硫酸ニツケル水溶液１を添加
して撹拌した。全体の液温を100℃に保ち約５分
間撹拌した後、そのまま４時間放置した。その後
0.1N−水酸化カリウム水溶液２を加えて洗浄
し、この操作を６回繰り返した。沈殿を常法によ
り過し、80℃で乾燥し、ついで粉砕して80メツ
シユ通過の粉末を得た。該粉末を常法により化学
分析したところ酸化ニツケルが約40重量％担持さ
れていることが確認された。Example 14N-Potassium hydroxide aqueous solution 4 was kept at 100°C. A 12% aqueous sodium hypochlorite solution 2 heated to 50°C was added thereto. A 2M nickel sulfate aqueous solution 1, in which 100 g of activated carbon powder had been suspended in advance and kept at 90°C, was added to this mixed solution and stirred. After stirring for about 5 minutes while keeping the entire liquid temperature at 100°C, it was left as it was for 4 hours. after that
A 0.1N aqueous potassium hydroxide solution 2 was added for washing, and this operation was repeated six times. The precipitate was filtered in a conventional manner, dried at 80°C, and then ground to obtain a powder that passed through 80 meshes. When the powder was chemically analyzed by a conventional method, it was confirmed that about 40% by weight of nickel oxide was supported.
得られた粉末を25％テフロンデイスパージヨン
で混練した後、厚み0.6mmのシートとした。該シ
ートを0.15mmφ60メツシユのニツケルネツトに圧
着し空気極とした。 The obtained powder was kneaded with a 25% Teflon dispersion and then made into a sheet with a thickness of 0.6 mm. The sheet was pressed onto a 0.15 mm diameter 60 mesh nickel net to form an air electrode.
この空気極を、亜鉛ゲルを対極としてアルカリ
電解液中で放電させ電池電圧（Ｖ）−電流密度
（ｍＡ／cm2）特性を測定した。 This air electrode was discharged in an alkaline electrolyte using zinc gel as a counter electrode, and the battery voltage (V)-current density (mA/cm 2 ) characteristics were measured.
なお比較のため空気極として従来から用いられ
ている白金、パラジウム、銀を触媒とするものに
ついても同様に電池電圧−電流密度特性を測定し
た。 For comparison, battery voltage-current density characteristics were similarly measured for air electrodes using platinum, palladium, and silver as catalysts, which have been conventionally used as air electrodes.
以上の結果を図に一括して示した。図において
曲線ａは本発明空気極触媒、ｂは白金、ｃはパラ
ジウム、ｄは銀を触媒とする電池電圧−電流密度
特性である。 The above results are collectively shown in the figure. In the figure, curve a is the cell voltage-current density characteristic using the air electrode catalyst of the present invention, b is platinum, c is palladium, and d is silver.
図から明らかな様に、本発明の空気極触媒は、
従来の貴金属触媒に比べても遜色のない触媒能を
有していることが判明した。しかも、製造方法が
簡単でありかつ貴金属を用いることがないから安
価であるなどの経済的メリツトも大きい。 As is clear from the figure, the air electrode catalyst of the present invention is
It was found that it has a catalytic ability comparable to that of conventional noble metal catalysts. Furthermore, it has great economic merits, such as a simple manufacturing method and low cost since no precious metals are used.
図は、本発明の空気極触媒ａ、従来の貴金属触
媒である白金ｂ、パラジウムｃ、銀ｄを空気極と
して用いた電池電圧−電流密度特性を示すもので
ある。
The figure shows battery voltage-current density characteristics using the air electrode catalyst a of the present invention and conventional noble metal catalysts platinum b, palladium c, and silver d as the air electrode.
Claims (1)
び酸化剤水溶液から成る３成分溶液反応系中で、
導電剤粉末の表面に酸化ニツケルを沈着せしめる
ことを特徴とする空気極触媒の製造方法。 ２ 該水酸化アルカリ水溶液に該酸化剤水溶液を
添加し、ここに該導電剤粉末を懸濁して成る該ニ
ツケル塩水溶液を添加する特許請求の範囲第１項
記載の空気極触媒の製造方法。 ３ 該導電剤粉末を該水酸化アルカリ水溶液に懸
濁し、ここに該酸化剤水溶液を添加し、ついで該
ニツケル塩水溶液を添加する特許請求の範囲第１
項記載の空気極触媒の製造方法。 ４ 該ニツケル塩水溶液に該酸化剤水溶液を添加
し、ここに該導電剤粉末を懸濁して成る該水酸化
アルカリ水溶液を添加する特許請求の範囲第１項
記載の空気極触媒の製造方法。 ５ 該導電剤粉末を該ニツケル塩水溶液に懸濁
し、ここに該酸化剤水溶液を添加し、ついで該水
酸化アルカリ水溶液を添加する特許請求の範囲第
１項記載の空気極触媒の製造方法。 ６ 該ニツケル塩水溶液が硫酸ニツケル水溶液、
該水酸化アルカリ水溶液が水酸化カリウム水溶
液、該酸化剤水溶液が次亜塩素酸水溶液及び導電
剤粉末が活性炭である特許請求の範囲第１〜５項
のいずれかに記載の空気極触媒の製造方法。[Claims] 1. In a three-component solution reaction system consisting of a nickel salt aqueous solution, an alkali hydroxide aqueous solution, and an oxidizing agent aqueous solution,
A method for producing an air electrode catalyst, comprising depositing nickel oxide on the surface of conductive agent powder. 2. The method for producing an air electrode catalyst according to claim 1, wherein the oxidizing agent aqueous solution is added to the alkali hydroxide aqueous solution, and the nickel salt aqueous solution containing the conductive agent powder suspended therein is added thereto. 3. Claim 1, in which the conductive agent powder is suspended in the alkali hydroxide aqueous solution, the oxidizing agent aqueous solution is added thereto, and then the nickel salt aqueous solution is added thereto.
A method for producing an air electrode catalyst as described in Section 1. 4. The method for producing an air electrode catalyst according to claim 1, wherein the oxidizing agent aqueous solution is added to the nickel salt aqueous solution, and the alkali hydroxide aqueous solution in which the conductive agent powder is suspended is added thereto. 5. The method for producing an air electrode catalyst according to claim 1, wherein the conductive agent powder is suspended in the nickel salt aqueous solution, the oxidizing agent aqueous solution is added thereto, and then the alkali hydroxide aqueous solution is added thereto. 6 The nickel salt aqueous solution is a nickel sulfate aqueous solution,
The method for producing an air electrode catalyst according to any one of claims 1 to 5, wherein the alkali hydroxide aqueous solution is a potassium hydroxide aqueous solution, the oxidizing agent aqueous solution is a hypochlorous acid aqueous solution, and the conductive agent powder is activated carbon. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56026889A JPS57143267A (en) | 1981-02-27 | 1981-02-27 | Manufacture of catalyst for air electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56026889A JPS57143267A (en) | 1981-02-27 | 1981-02-27 | Manufacture of catalyst for air electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57143267A JPS57143267A (en) | 1982-09-04 |
| JPH0245302B2 true JPH0245302B2 (en) | 1990-10-09 |
Family
ID=12205816
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56026889A Granted JPS57143267A (en) | 1981-02-27 | 1981-02-27 | Manufacture of catalyst for air electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57143267A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2676316A1 (en) * | 2011-02-16 | 2013-12-25 | Toyota Jidosha Kabushiki Kaisha | Method for producing cathode material for rechargeable lithium-air batteries, cathode material for rechargeable lithium-air batteries and rechargeable lithium-air battery |
-
1981
- 1981-02-27 JP JP56026889A patent/JPS57143267A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57143267A (en) | 1982-09-04 |
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