JPS59194362A - Air electrode - Google Patents
Air electrodeInfo
- Publication number
- JPS59194362A JPS59194362A JP58068874A JP6887483A JPS59194362A JP S59194362 A JPS59194362 A JP S59194362A JP 58068874 A JP58068874 A JP 58068874A JP 6887483 A JP6887483 A JP 6887483A JP S59194362 A JPS59194362 A JP S59194362A
- Authority
- JP
- Japan
- Prior art keywords
- air electrode
- acid dichloride
- transition metal
- carbon material
- chloride
- 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.)
- Pending
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
- 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)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inert Electrodes (AREA)
Abstract
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に関
するものである。従来空気電池や燃料電池の空気極はカ
ーボンブラック活性炭などの炭素体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の付着は次のような困難さが
あった。即ち
■ 金属フタロシアニンは一般に、有機溶媒に難溶であ
るだめ、触媒として有効な量を付着せしめることは困難
でおった。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an air electrode used in air cells, fuel cells, and the like. Conventionally, the air electrodes of air cells and fuel cells have used catalysts such as metal phthalocyanines to increase the oxygen reduction ability of carbon bodies such as carbon black activated carbon, but the attachment of metal phthalocyanines has the following difficulties. Ta. Namely: (1) Since metal phthalocyanines are generally poorly soluble in organic solvents, it has been difficult to deposit them in an amount effective as a catalyst.
■ 壕だ金属フタロシアニンを水に可溶とするために、
スルホン基などを導入して使用することもあるが、アル
カリ電解質を用いた電池では、この種の触媒が溶出して
しまい、触媒の効果がなくなる問題があった。■ In order to make the metal phthalocyanine soluble in water,
Sulfone groups and the like are sometimes introduced and used, but in batteries using alkaline electrolytes, this type of catalyst tends to elute, causing the problem that the catalyst becomes ineffective.
■ さらに触媒の耐久性や活性をより強化するために金
属フタロシアニンの高分子量化したものを使用する例も
散見されるが、高分子量化の方法や炭素体への付着方法
が確立されていない。■ Furthermore, there are some cases where high molecular weight metal phthalocyanines are used to further strengthen the durability and activity of catalysts, but the method for increasing the molecular weight and the method for attaching them to carbon bodies has not been established.
我々はかかる問題点を改良すべく、鋭意研究した結果容
易に金属を含有する縮合型フタロシアニンを付着せしめ
た空気極を得ることを見出しだのである。即ち本発明は
炭素体に予め遷移金属である銅、ニッケル、クロム、コ
バルト。In order to improve this problem, we conducted extensive research and found that it was possible to easily obtain an air electrode to which condensed phthalocyanine containing metal was attached. That is, the present invention uses transition metals such as copper, nickel, chromium, and cobalt in advance in the carbon body.
鉄、マンガンを含有するポリアミノフタロシアニン（ア
ミン基は１分子あたり２ケ以上含１れる）を付着せしめ
９次に二塩基酸・・ライド（特に塩化物）１例えばホス
ゲン、マロン酸ジクロライド、コハク酸ジクロライド、
ゲルタール酸クロライド、アジピン酸クロライド、フタ
ール酸ジクロライド、テレフタール酸ジクロライド。Polyaminophthalocyanine (containing 2 or more amine groups per molecule) containing iron and manganese is attached to it. ,
Geltaric acid chloride, adipic acid chloride, phthalic acid dichloride, terephthalic acid dichloride.
キノリン酸クロライドにて処理することによって遷移金
属の縮合型フタロンアニンに変えることが可能となり、
触媒としての耐久性および活性が良好な空気極を提供す
ることに至ったものである。By treating with quinolinic acid chloride, it is possible to convert it into a condensed transition metal phthalonanine.
This has led to the provision of an air electrode with good durability and activity as a catalyst.
本発明に使用する遷移金属のボリア≧ノックロシアニン
は常法通り遷移金属の粉末または塩化物、硫酸塩などと
、３−二トロフクール酸または４−ニトロフクール酸と
尿素、モリブデン酸アンモン、沸点２００℃以上の有機
溶剤中加熱して、相当する金属を含むポリニトロフクロ
シアニンを合成して還元するか、遷移金属のフタロシア
ニンを濃硫酸中ヒドロキシルアミン。The transition metal boria≧knockcyanine used in the present invention is prepared by combining transition metal powder, chloride, sulfate, etc., 3-nitrophucuric acid or 4-nitrophucuric acid, urea, ammonium molybdate, boiling point 200°C, as usual. Either synthesize and reduce polynitrofuccyanine containing the corresponding metal by heating in the above organic solvent, or convert transition metal phthalocyanine to hydroxylamine in concentrated sulfuric acid.
モノクロルアミンなどによりアミン化することにより得
られる。Obtained by amination with monochloroamine or the like.
この遷移金属を含むポリアミノフタロシアニンを塩酸水
溶液に溶解し、炭素極に含浸させ乾燥する。次て二塩基
酸クロライドのインゼン溶液に炭素極をつけて縮合反応
をさせ、相当する金属を含む縮合型フタロシアニンの付
着した空気極を得る。This polyaminophthalocyanine containing a transition metal is dissolved in an aqueous hydrochloric acid solution, impregnated into a carbon electrode, and dried. Next, a carbon electrode is attached to an inzene solution of dibasic acid chloride to cause a condensation reaction, thereby obtaining an air electrode to which a condensed phthalocyanine containing the corresponding metal is attached.
次に触媒を付着せしめる炭素体はファーネスブランク、
チャンネルブラック、サーマルブラックなどのカーボン
ブラックや、木炭、ヤシ殻炭、パーム核炭１石炭１石油
残渣２合成樹脂。Next, the carbon body to which the catalyst is attached is a furnace blank.
Carbon black such as channel black and thermal black, charcoal, coconut shell charcoal, palm nuclear charcoal 1 coal 1 petroleum residue 2 synthetic resin.
有機廃棄物などを使用して作られた活性炭および黒鉛な
どから常法通り作られる。どの炭素体への触媒の付着量
は、空気極としての性能９強度を考慮すれば０１〜１０
重量係が好ましい。It is made in the usual way from activated carbon and graphite made from organic waste. The amount of catalyst attached to which carbon body is 01 to 10, considering the performance 9 strength as an air electrode.
Weight clerk is preferred.
以下実施例に従い本発明の詳細な説明するが実施例中「
部」とあるのは「重量部」を示す。The present invention will be described in detail below according to Examples.
"Parts" indicates "parts by weight."
（炭素体の製造）
粒径０１〜１μのヤシ殻活性炭１０部７粒径０１〜０５
μの黒鉛１０部、熱可塑性樹脂（塩化ビニル樹脂）５部
と混合し、押出成型によシ直径１０冠の丸棒を作る。こ
れを２００℃に加熱し、更にｉ、 ｏ ｏ ｏ℃まで熱
処理し熱可塑性樹脂を分解して炭素体としだ。(Manufacture of carbon body) 10 parts of coconut shell activated carbon with a particle size of 01 to 1μ, 7 parts with a particle size of 01 to 05
10 parts of μ graphite and 5 parts of thermoplastic resin (vinyl chloride resin) were mixed and extruded to form a round bar with a diameter of 10 crowns. This was heated to 200°C and further heat-treated to 1,000°C to decompose the thermoplastic resin and produce a carbon body.
実施例１
炭素体に４．４１ 、４ ＩＩ、 ４ Ｉｌｌ −
テトラアミノ鉄フタロシアニンを２重量％付着せしめ９
次にアジピン酸ジクロライドの２重量％ベンゼン溶液に
て処理することによシ鉄フタロシアニン縮合物を付着せ
しめた空気極を得る。Example 1 Carbon body has 4.41, 4 II, 4 Ill −
Deposit 2% by weight of tetraaminoiron phthalocyanine9
Next, by treating with a 2% by weight solution of adipic acid dichloride in benzene, an air electrode to which the iron phthalocyanine condensate is adhered is obtained.
比較例１
炭素体に鉄フタロシアニンを２重量％付着せしめて空気
極を得る。Comparative Example 1 An air electrode was obtained by depositing 2% by weight of iron phthalocyanine on a carbon body.
実施例２
炭素体に３，３’、４．４’−テトラアミノクロムフタ
ロシアニンを１重量％付着せしめ９次にテレフタール酸
ジクロライドのインゼン溶液にて処理することにより、
クロムフタロシアニン縮合物を付着せしめた空気極を得
る。Example 2 1% by weight of 3,3',4,4'-tetraaminochrome phthalocyanine was attached to the carbon body, and then treated with an inzene solution of terephthalic acid dichloride.
An air electrode to which a chromium phthalocyanine condensate is attached is obtained.
比較例２
炭素体にクロムフタロシアニンを１重量％付着せしめて
空気極を得る。Comparative Example 2 An air electrode was obtained by depositing 1% by weight of chromium phthalocyanine on a carbon body.
実施例６
炭素体にポリアミノ銅フタロシアニン（銅フタロシアニ
ンを１００％硫酸に溶かし、とドロキシルアミンを加え
てアミン化をすることで得られる）を０．５重量係付着
せしめ９次にマレイン酸ジクロライドのインゼン溶液に
て処理すること尾より、銅フタロシアニン縮合物を付着
せしめた空気極を得る。Example 6 0.5 weight percent of polyamino copper phthalocyanine (obtained by dissolving copper phthalocyanine in 100% sulfuric acid and adding droxylamine for amination) was attached to a carbon body, and then 90% of maleic acid dichloride was attached. After treatment with an inzene solution, an air electrode to which a copper phthalocyanine condensate is attached is obtained.
比較例３
炭素体罠銅フタロシアニンを０．５重量係付着せしめて
空気極を得る。Comparative Example 3 An air electrode was obtained by depositing 0.5 weight percent of carbon trapping copper phthalocyanine.
実施例１，２．３および比較例１，２．３の空気極の分
極特性を第１図、第２図、第６図に示す。The polarization characteristics of the air electrodes of Examples 1 and 2.3 and Comparative Examples 1 and 2.3 are shown in FIGS. 1, 2, and 6.
以上のように本発明の空気極は、優れた分極特性を示し
、空気電池、燃料電池の空気極として好適なものである
。As described above, the air electrode of the present invention exhibits excellent polarization characteristics and is suitable as an air electrode for air cells and fuel cells.
第１図は、実施例１．比較例１で得られた空気極の分極
曲線であシ、第２図は実施例２．比較例２で得られた空
気極の分極曲線であり、第６図は実施例６．比較例６で
得られた分極曲線であり、■〜■は順に実施例１．比較
例１．実施例２．比較例２．実施例６．比較例６で得ら
れ九分極曲線を示し、縦軸は、電流密度（ｍＡ／ｃｒ＆
） 、横軸は電位（Ｖ／５ＯＥ）を示すものである。
特許出願人 ぺんてる株式会社FIG. 1 shows Example 1. The polarization curve of the air electrode obtained in Comparative Example 1 is shown in FIG. FIG. 6 shows the polarization curve of the air electrode obtained in Comparative Example 2, and FIG. 6 shows the polarization curve of the air electrode obtained in Comparative Example 2. These are the polarization curves obtained in Comparative Example 6, and ■ to ■ are the polarization curves obtained in Example 1. Comparative example 1. Example 2. Comparative example 2. Example 6. The nine polarization curves obtained in Comparative Example 6 are shown, and the vertical axis is the current density (mA/cr&
), the horizontal axis indicates the potential (V/5OE). Patent applicant Pentel Co., Ltd.
Claims (1)
ロライドにて三量化した締金型フタロシアニンを含有し
てなることを特徴とする空気極。 ２）前記二塩基酸クロライドが、ホスゲン、マロン酸ジ
クロライド、マレイン酸ジクロライド、コハク酸ジクロ
ライド、ゲルタール酸ジクロライド、アジピン酸ジクロ
ライド、フタール酸ジクロライド、キノリン酸ジクロラ
イドであることを特徴とする特許請求の範囲第１項記載
の空気極。 ３ ） ＠ Ｒｅ ／ｌａ 金型ンタロンアニンがＭ
、＝ッヶル。 クロム・ コバルト、鉄、マンガンの縮合型フタロンア
ニンであることを特徴とする特許請求の範囲第１項記載
の空気極。[Scope of Claims] 1) An air electrode comprising a clamp-type phthalocyanine obtained by trimerizing a transition metal polyaminophthalocyanine with a dibasic acid chloride. 2) Claim No. 2, characterized in that the dibasic acid chloride is phosgene, malonic acid dichloride, maleic acid dichloride, succinic acid dichloride, geltaric acid dichloride, adipic acid dichloride, phthalic acid dichloride, and quinolinic acid dichloride. The air electrode described in item 1. 3) @Re/la Mold talonanine is M
,=kgal. The air electrode according to claim 1, wherein the air electrode is a condensed phthalonanine of chromium-cobalt, iron, and manganese.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58068874A JPS59194362A (en) | 1983-04-19 | 1983-04-19 | Air electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58068874A JPS59194362A (en) | 1983-04-19 | 1983-04-19 | Air electrode |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS59194362A true JPS59194362A (en) | 1984-11-05 |
Family
ID=13386240
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58068874A Pending JPS59194362A (en) | 1983-04-19 | 1983-04-19 | Air electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59194362A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008111569A1 (en) * | 2007-03-09 | 2008-09-18 | National Institute Of Advanced Industrial Science And Technology | Electrode catalyst for fuel cell |
| JP2008258150A (en) * | 2007-03-09 | 2008-10-23 | Sumitomo Chemical Co Ltd | Electrode catalyst for fuel cell |
-
1983
- 1983-04-19 JP JP58068874A patent/JPS59194362A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008111569A1 (en) * | 2007-03-09 | 2008-09-18 | National Institute Of Advanced Industrial Science And Technology | Electrode catalyst for fuel cell |
| JP2008258150A (en) * | 2007-03-09 | 2008-10-23 | Sumitomo Chemical Co Ltd | Electrode catalyst for fuel cell |
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