JPH0119624B2 - - Google Patents
Info
- Publication number
- JPH0119624B2 JPH0119624B2 JP56155052A JP15505281A JPH0119624B2 JP H0119624 B2 JPH0119624 B2 JP H0119624B2 JP 56155052 A JP56155052 A JP 56155052A JP 15505281 A JP15505281 A JP 15505281A JP H0119624 B2 JPH0119624 B2 JP H0119624B2
- Authority
- JP
- Japan
- Prior art keywords
- phthalocyanine
- carbon body
- aqueous solution
- carbon
- metal
- 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
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
- H01M4/90—Selection of catalytic material
- H01M4/9008—Organic or organo-metallic compounds
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inert Electrodes (AREA)
Description
【発明の詳細な説明】
本発明は、空気電池や燃料電池などに使用する
空気極の製造方法に関し、更に詳しくは、炭素体
への触媒の付加方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing an air electrode used in an air cell, a fuel cell, etc., and more specifically to a method for adding a catalyst to a carbon body.
従来、空気電池や燃料電池などの空気極は、活
性炭などに酸素還元能力を高めるために金属フタ
ロシアニンなどの触媒を用いていたが、金属フタ
ロシアニンは水に不溶のため、キノリンなどの有
機溶媒に飽和になるまで溶解し、この溶液に活性
炭を浸漬し引き上げ乾燥し、有機溶媒を飛散させ
た活性炭表面に金属フタロシアニンを触媒として
付着せしめていたが、金属フタロシアニンは、飽
和溶解量が少ないため、上述のような操作を何回
も繰り返す必要があつた。又、特殊な有機溶媒を
使用しているところから、乾燥させるために高価
な装置を使用する必要があり、さらに蒸発飛散さ
せた有機溶媒の蒸気は安全性に問題があつた。 Conventionally, air electrodes such as air cells and fuel cells have used catalysts such as metal phthalocyanine in activated carbon to increase oxygen reduction ability.However, metal phthalocyanine is insoluble in water, so it cannot be saturated with organic solvents such as quinoline. Activated carbon was immersed in this solution, pulled up and dried, and metal phthalocyanine was attached as a catalyst to the surface of the activated carbon after the organic solvent was scattered. It was necessary to repeat such operations many times. Furthermore, since a special organic solvent is used, it is necessary to use expensive equipment for drying, and furthermore, the vapor of the organic solvent that evaporates and scatters poses a safety problem.
そこで、金属フタロシアニンにスルフオン基な
どの水溶性基をつけて水に可溶にさせて、上述の
問題を解消せんとしたものもあるが、金属フタロ
シアニンの炭素体への付着量は未だ十分なもので
はなかつた。 Therefore, some attempts have been made to solve the above problem by attaching a water-soluble group such as a sulfon group to metal phthalocyanine to make it soluble in water, but the amount of metal phthalocyanine attached to carbon bodies is still insufficient. It wasn't.
本発明者らは、金属フタロシアニンを炭素体に
そのまま付着せしめるのではなく、アミノ酸塩と
フタロシアニンの前駆体が水に可溶であることを
利用し、これらを炭素体に含浸させることによつ
て金属フタロシアニンにせしめれば、金属フタロ
シアニンの炭素体への付着量も増し、しかも均一
に付着するとの発想に立ち、鋭意研究の結果、遂
に本発明を完成したものであつて、即ち、本発明
は、炭素体に遷移金属のアミノ酸塩を溶解した水
溶液と、フタロシアニン前駆体を溶解した水溶液
とを含浸せしめ、熱処理して、炭素体に遷移金属
のフタロシアニンを付着せしめたことを特徴とす
る空気極の製造方法を要旨とするものである。 The present inventors did not directly attach metal phthalocyanine to a carbon body, but took advantage of the fact that amino acid salts and phthalocyanine precursors are soluble in water, and impregnated the carbon body with the metal. Based on the idea that if the metal phthalocyanine is attached to the carbon body, the amount of metal phthalocyanine attached to the carbon body will increase, and the attachment will be uniform.As a result of intensive research, the present invention was finally completed. Manufacture of an air electrode characterized in that a carbon body is impregnated with an aqueous solution in which an amino acid salt of a transition metal is dissolved and an aqueous solution in which a phthalocyanine precursor is dissolved, and then heat-treated to adhere a transition metal phthalocyanine to the carbon body. The gist is the method.
本発明の製造法によれば、炭素体に遷移金属の
アミノ酸塩の水溶液とフタロシアニン前駆体の水
溶液とを含浸せしめることにより、炭素体表面お
よびその細孔に容易に遷移金属のアミノ酸塩およ
びフタロシアニン前駆体が吸着もしくは浸透し、
熱処理、更に必要に応じて還元することにより、
化学量的に炭素体表面、細孔に遷移金属のフタロ
シアニンが均一にしかも多量に付着しているもの
と推考される。 According to the production method of the present invention, by impregnating a carbon body with an aqueous solution of an amino acid salt of a transition metal and an aqueous solution of a phthalocyanine precursor, the amino acid salt of a transition metal and the phthalocyanine precursor can be easily deposited on the surface of the carbon body and its pores. The body absorbs or penetrates,
By heat treatment and further reduction as necessary,
It is assumed that the transition metal phthalocyanine is stoichiometrically adhered uniformly and in large quantities to the surface of the carbon body and to the pores.
以下、本発明について詳細に説明する。 The present invention will be explained in detail below.
本発明に使用する炭素体としては、一般に使用
されているフアーネスブラツク、チヤンネルブラ
ツク、サーマルブラツクなどのカーボンブラツク
や、木材、木炭、ヤシ殻炭、パーム核炭、石炭、
石油残査、合成樹脂、有機廃棄物などを使用して
作られた活性炭や黒鉛などの１種もしくは２種以
上の混合物が挙げられ、必要に応じて押出成形、
射出成形、加圧成形などにより一定の形状とす
る。 The carbon bodies used in the present invention include commonly used carbon blacks such as furnace black, channel black, and thermal black, as well as wood, charcoal, coconut shell charcoal, palm kernel charcoal, coal,
Examples include one or a mixture of two or more of activated carbon and graphite made using petroleum residue, synthetic resin, organic waste, etc., and extrusion molding, as necessary.
It is made into a certain shape by injection molding, pressure molding, etc.
遷移金属のアミノ酸塩は、ニツケル、コバル
ト、クロム、鉄、銅などの遷移金属の水溶性金属
塩と下記構造式で表わされるβ―ヒドロキシエチ
ル基を有するアミノ酸などのアルカリ金属塩を加
えることにより容易に得られる。例えば、ビス
（β―ヒドロキシエチル）グリシンのナトリウム
塩の水溶液に塩化第二銅水溶液を加えて、溶液を
濃縮すると、ビス（β―ヒドロキシエチル）グリ
シン銅が紺色の結晶として得られる。 Amino acid salts of transition metals can be easily prepared by adding water-soluble metal salts of transition metals such as nickel, cobalt, chromium, iron, and copper and alkali metal salts such as amino acids having a β-hydroxyethyl group represented by the following structural formula. can be obtained. For example, when a cupric chloride aqueous solution is added to an aqueous solution of the sodium salt of bis(β-hydroxyethyl)glycine and the solution is concentrated, copper bis(β-hydroxyethyl)glycine is obtained as dark blue crystals.
（グリシン誘導体）
（グリシン誘導体）
（ザルコシン誘導体）
（アラニン誘導体）
（アラニン誘導体）
（セリン誘導体）
（セリン誘導体）
（HOCH2CH2）NCH2CH2SO3H
（タウリン誘導体）
フタロシアニン前駆体としては、１，３―ジイ
ミノイソインドレニンまたはその誘導体や、１，
１―ジアルコキシ―３―イミノイソインドレニン
が使用でき、具体例を挙げると下記構造式で表わ
されるものが挙げられる。 (glycine derivative) (glycine derivative) (sarcosine derivative) (alanine derivative) (alanine derivative) (serine derivative) (Serine derivative) (HOCH 2 CH 2 )NCH 2 CH 2 SO 3 H (Taurine derivative) Phthalocyanine precursors include 1,3-diiminoisoindolenine or its derivatives, 1,
1-Dialkoxy-3-iminoisoindolenine can be used, and specific examples include those represented by the following structural formula.
（１，３―ジイミノイソインドレニン）
（１，３―ジイミノイソインドレニンの誘導体）
（１，３―ジイミノイソインドレニンの誘導体）
（１，３―ジイミノイソインドレニンの誘導体）
（１，１―ジメトキシ―３―イミノイソインドレ
ニン）
（１，１―ジエトキシ―３―イミノイソインドレ
ニン）
（１，１―ビス（β―オキシエトキシ）―３―イ
ミノイソインドレニン）
このフタロシアニン前駆体の使用量は、炭素体
に対して１〜30重量％が好ましく特に５〜20重量
％が好ましい。 (1,3-diiminoisoindolenine) (Derivative of 1,3-diiminoisoindolenine) (Derivative of 1,3-diiminoisoindolenine) (Derivative of 1,3-diiminoisoindolenine) (1,1-dimethoxy-3-iminoisoindolenine) (1,1-diethoxy-3-iminoisoindolenine) (1,1-bis(β-oxyethoxy)-3-iminoisoindolenine) The amount of this phthalocyanine precursor used is preferably 1 to 30% by weight, particularly preferably 5 to 20% by weight, based on the carbon body.
又、遷移金属のアミノ酸塩の使用量は、フタロ
シアニン前駆体に対するモル比でフタロシアニン
前駆体：遷移金属のアミノ酸塩＝４：1.5〜２が
好ましい。 The amount of transition metal amino acid salt to be used is preferably phthalocyanine precursor:transition metal amino acid salt=4:1.5 to 2 in terms of molar ratio to the phthalocyanine precursor.
空気極の製造に際しては、上述のフタロシアニ
ン前駆体の５％水溶液（フタロシアニン前駆体の
種類によつては、アルコール、グリコールを適宜
使用）に、フタロシアニン前駆体とアミノ酸金属
塩を溶解させ、この溶液に炭素体を浸漬し、常乾
して150℃で加熱するか、溶液中ハイドロキノン、
ヒドラジンなどの還元剤を１％添加して80℃に加
温することにより、炭素体表面に金属フタロシア
ニンを均一に付着せしめることができる。尚、フ
タロシアニン前駆体の水溶液もしくはアミノ酸金
属塩を炭素体に浸漬し、常乾後、残りの水溶液に
更に浸漬してもよい。 When manufacturing the air electrode, the phthalocyanine precursor and the amino acid metal salt are dissolved in a 5% aqueous solution of the above-mentioned phthalocyanine precursor (alcohol or glycol may be used as appropriate depending on the type of phthalocyanine precursor), and the phthalocyanine precursor and the amino acid metal salt are dissolved in this solution. Either soak the carbon body, dry it at room temperature and heat it at 150℃, or add hydroquinone in solution,
By adding 1% of a reducing agent such as hydrazine and heating to 80°C, metal phthalocyanine can be uniformly adhered to the surface of the carbon body. Incidentally, the carbon body may be immersed in an aqueous solution of a phthalocyanine precursor or an amino acid metal salt, and after air drying, it may be further immersed in the remaining aqueous solution.
以下、実施例に従い本発明を更に詳細に説明す
るが、実施例中「部」とあるのは「重量部」を示
す。 Hereinafter, the present invention will be explained in more detail with reference to Examples, where "parts" in the Examples indicate "parts by weight."
実施例 １
粒径0.1〜1μのヤシ殻活性炭10部、粒径0.1〜
0.5μの黒鉛10部、熱可塑性樹脂（塩化ビニル樹
脂）５部を混合し、押出成型により直径10mmの丸
棒を作り、その後、200℃に加熱して熱可塑性樹
脂を分解して炭素体とした。Example 1 10 parts of coconut shell activated carbon with a particle size of 0.1 to 1μ, particle size of 0.1 to 1μ
10 parts of 0.5μ graphite and 5 parts of thermoplastic resin (vinyl chloride resin) are mixed and extruded to make a round bar with a diameter of 10 mm, and then heated to 200°C to decompose the thermoplastic resin and form a carbon body. did.
この炭素体を１，３―ジアミノイソインドレニ
ンの５％水溶液とＮ，Ｎ―ビス（β―ヒドロキシ
エチル）グリシンの鉄塩（１，３―ジアミノイソ
インドレニンの４モルに対して1.5モルとなる量）
の水溶液との混合溶液に浸漬してから室温下、空
気気流中乾燥させる。乾燥した炭素体を150℃、
10分加熱することにより、鉄フタロシアニンを炭
素体表面に均一に付着せしめた空気極を得た。 This carbon body was mixed with a 5% aqueous solution of 1,3-diaminoisoindolenine and an iron salt of N,N-bis(β-hydroxyethyl)glycine (1.5 mol per 4 mol of 1,3-diaminoisoindolenine). amount)
and an aqueous solution, and then dried in a stream of air at room temperature. Dry carbon body at 150℃,
By heating for 10 minutes, an air electrode with iron phthalocyanine uniformly adhered to the surface of the carbon body was obtained.
実施例 ２
粒径0.1〜1μのヤシ殻活性炭10部、粒径0.1〜
0.5μの黒鉛10部、熱可塑性樹脂（塩化ビニル樹
脂）10部を加圧成形により断面が10mm×10mmの角
棒を作り、その後200℃に加熱して熱可塑性樹脂
を分解して炭素体とした。Example 2 10 parts of coconut shell activated carbon with a particle size of 0.1 to 1μ, particle size of 0.1 to 1μ
A square rod with a cross section of 10 mm x 10 mm is made by pressure molding 10 parts of 0.5μ graphite and 10 parts of thermoplastic resin (vinyl chloride resin), and then heated to 200°C to decompose the thermoplastic resin and form a carbon body. did.
この炭素体を１―ビス（β―ヒドロキシエチ
ル）―３―イミノイソインドレニンの５％水溶液
とＮ―β―ヒドロキシエチルザルコシンのコバル
ト塩（１―ビス（β―ヒドロキシエチル）―３―
アミノイソインドレニン４モルに対して1.5モル
となる量）との混合水溶液に浸漬してから、室温
下、空気気流中乾燥させる。乾燥した炭素体を
150℃、10分加熱することによりコバルトフタロ
シアニンを炭素体表面に均一に付着せしめた空気
極を得た。 This carbon body was mixed with a 5% aqueous solution of 1-bis(β-hydroxyethyl)-3-iminoisoindolenine and a cobalt salt of N-β-hydroxyethylsarcosine (1-bis(β-hydroxyethyl)-3-
The sample is immersed in a mixed aqueous solution of 1.5 moles per 4 moles of aminoisoindolenine, and then dried in a stream of air at room temperature. dry carbon body
By heating at 150°C for 10 minutes, an air electrode with cobalt phthalocyanine uniformly adhered to the surface of the carbon body was obtained.
比較例 １
実施例１の炭素体をスルホン化した鉄フタロシ
アニン５％水溶液に浸漬した後、室温下、空気気
流中乾燥させる。乾燥した炭素体を150℃、10分
加熱することにより鉄フタロシアニンを炭素体表
面に付着せしめた空気極を得た。Comparative Example 1 The carbon body of Example 1 was immersed in a 5% aqueous solution of sulfonated iron phthalocyanine, and then dried in a stream of air at room temperature. By heating the dried carbon body at 150°C for 10 minutes, an air electrode with iron phthalocyanine attached to the surface of the carbon body was obtained.
上記実施例１、２、比較例１で得られた空気極
の分極曲線を第１図に示す。 The polarization curves of the air electrodes obtained in Examples 1 and 2 and Comparative Example 1 are shown in FIG.
以上のように本発明の製造方法に得られた空気
極は、金属フタロシアニンが炭素体表面に均一、
多量に付着されているために空気極の分極特性が
優れているものである。 As described above, in the air electrode obtained by the manufacturing method of the present invention, the metal phthalocyanine is uniformly distributed on the surface of the carbon body.
The polarization characteristics of the air electrode are excellent because a large amount of it is attached.
第１図は、実施例１、２、比較例１で得られた
空気極の分極曲線であり、〜は順に実施例
１、実施例２、比較例１で得られた分極曲線を示
すものであり、縦軸は電流密度（mA／cm2）、横
軸は電位（Ｖ／SCE）を示すものである。
Figure 1 shows the polarization curves of the air electrodes obtained in Examples 1 and 2 and Comparative Example 1, and ~ indicates the polarization curves obtained in Example 1, Example 2, and Comparative Example 1 in this order. The vertical axis shows the current density (mA/cm 2 ), and the horizontal axis shows the potential (V/SCE).
Claims (1)
液と、フタロシアニン前駆体を溶解した水溶液と
を含浸せしめ、熱処理して、炭素体に遷移金属の
フタロシアニンを付着せしめたことを特徴とする
空気極の製造方法。1. An air electrode characterized in that a carbon body is impregnated with a solution in which an amino acid salt of a transition metal is dissolved and an aqueous solution in which a phthalocyanine precursor is dissolved, and then heat-treated to adhere a transition metal phthalocyanine to the carbon body. Production method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56155052A JPS5857266A (en) | 1981-09-30 | 1981-09-30 | Manufacture of air electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56155052A JPS5857266A (en) | 1981-09-30 | 1981-09-30 | Manufacture of air electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5857266A JPS5857266A (en) | 1983-04-05 |
| JPH0119624B2 true JPH0119624B2 (en) | 1989-04-12 |
Family
ID=15597613
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56155052A Granted JPS5857266A (en) | 1981-09-30 | 1981-09-30 | Manufacture of air electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5857266A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0677460B2 (en) * | 1984-01-24 | 1994-09-28 | 日本電信電話株式会社 | Method for producing positive electrode for fuel cell / air cell |
| JP2745369B2 (en) * | 1993-01-21 | 1998-04-28 | 株式会社日本製鋼所 | Manufacturing method of iron-based heat-resistant alloy |
| JP2622796B2 (en) * | 1992-06-11 | 1997-06-18 | 株式会社日本製鋼所 | Electroslag for remelting electroslag and method for producing alloy using the electrode |
| JP6853630B2 (en) * | 2016-08-18 | 2021-03-31 | 埼玉県 | Oxygen reduction catalyst, its manufacturing method and fuel cell |
-
1981
- 1981-09-30 JP JP56155052A patent/JPS5857266A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5857266A (en) | 1983-04-05 |
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