JPH0142467B2 - - Google Patents
Info
- Publication number
- JPH0142467B2 JPH0142467B2 JP56173926A JP17392681A JPH0142467B2 JP H0142467 B2 JPH0142467 B2 JP H0142467B2 JP 56173926 A JP56173926 A JP 56173926A JP 17392681 A JP17392681 A JP 17392681A JP H0142467 B2 JPH0142467 B2 JP H0142467B2
- Authority
- JP
- Japan
- Prior art keywords
- phthalocyanine
- air electrode
- carbon body
- copper phthalocyanine
- condensate
- 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
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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)
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。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an air electrode used in air cells, fuel cells, and the like.
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
ロシアニンは一般的な溶剤に不溶なために炭素体
に均一に付着することは困難であり、微粉砕した
金属フタロシアニンを溶液に分散し、炭素体表面
の細孔に超音波などにより含浸させ、乾燥させて
いるが、炭素体表面の細孔に均一に付着し難く空
気極としての性能が得られないのが実状である。 Conventionally, air electrodes such as air cells and fuel cells have used catalysts such as metal phthalocyanine in activated carbon to increase the oxygen reduction ability, but metal phthalocyanine is insoluble in common solvents, so it is not uniformly distributed in the carbon body. However, finely ground metal phthalocyanine is dispersed in a solution, impregnated into the pores of the carbon body surface using ultrasonic waves, and dried. The reality is that the performance as an air electrode cannot be obtained.
そこで、本発明者等は、金属フタロシアニンの
触媒としての性能を向上せしめ、優れた分極特性
が得られる空気極を得るために、金属フタロシア
ニンの形能につき種々検討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、−Ｎ＝Ｎ
−結合又は−Ｓ−Ｓ−結合により高分子化した金
属フタロシアニン系酸化縮合物を含有せしめた炭
素体からなる空気極を要旨とするものである。 Therefore, in order to improve the performance of metal phthalocyanine as a catalyst and obtain an air electrode with excellent polarization characteristics, the present inventors have finally completed the present invention as a result of various studies on the shape of metal phthalocyanine. That is, the present invention provides −N=N
The gist of the present invention is an air electrode made of a carbon body containing a metal phthalocyanine-based oxidative condensate polymerized by a - bond or a -S-S- bond.
本発明では、空気極の触媒として働く金属フタ
ロシアニンを酸化縮合することにより、１種の重
合を行なつて分子量を増大せしめ、触媒としての
性能を向上せしめたものである。 In the present invention, by oxidatively condensing the metal phthalocyanine that acts as a catalyst for the air electrode, one type of polymerization is performed to increase the molecular weight and improve the performance as a catalyst.
以下、本発明について説明する。 The present invention will be explained below.
金属フタロシアニンを高分子化させる方法とし
ては種々採用できるが、−Ｎ＝Ｎ−結合により高
分子化させる場合、例えば銅フタロシアニンな
ら、
(1) ３，3′，3″，３−テトラニトロ銅フタロシ
アニン又は４，4′，4″，４−テトラニトロ銅
フタロシアニンを硫化ソーダで環元して相当す
るテトラアミノ銅フタロシアニンとなし、この
水性分散体を過マンガ酸カリ、重クロム酸カリ
などの酸化剤で処理して酸化縮合物とする
(2) 銅フタロシアニンを濃硫酸に溶かし、ヒドロ
キシルアミンにて直接アミノ化してポリアミノ
銅フタロシアニンとし、酸化剤で処理して酸化
縮合物とする。 Various methods can be adopted to polymerize metal phthalocyanine, but when polymerizing by -N=N- bond, for example, in the case of copper phthalocyanine, (1) 3,3',3'',3-tetranitrocopper phthalocyanine or 4,4′,4″,4-tetranitrocopper phthalocyanine is ring-reduced with sodium sulfide to form the corresponding tetraaminocopper phthalocyanine, and this aqueous dispersion is treated with an oxidizing agent such as potassium permangate or potassium dichromate. (2) Copper phthalocyanine is dissolved in concentrated sulfuric acid, directly aminated with hydroxylamine to obtain polyamino copper phthalocyanine, and treated with an oxidizing agent to obtain an oxidized condensate.
他のニツケル、コバルト、鉄などのフタロシア
ニンの酸化縮合物も同様にして製造することがで
きる。 Oxidative condensates of other phthalocyanines such as nickel, cobalt, and iron can also be produced in the same manner.
この金属フタロシアニン酸化縮合物を炭素体と
共に成形するか、成形した炭素体に吸着せしめる
ことなどにより空気極を製造することができる。 An air electrode can be manufactured by molding this metal phthalocyanine oxidation condensate together with a carbon body, or by adsorbing it onto a molded carbon body.
−Ｓ−Ｓ−結合により高分子化させる場合、例
えば銅フタロシアニンなら、
(1) ３，3′，3″，３−テトラアミノ銅フタロシ
アニンまたは４，4′，4″，４−テトラアミノ
銅フタロシアニンをジアゾ化し、チオシアン酸
アルカリを反応せしめて３，3′，3″，３−テ
トラチオシアノ銅フタロシアニン又は、４，
4′，4″，４−テトラチオシアノ銅フタロシア
ニンを得る。 When polymerizing by -S-S- bond, for example, copper phthalocyanine, (1) 3,3',3'',3-tetraamino copper phthalocyanine or 4,4',4'',4-tetraamino copper phthalocyanine is diazotized and reacted with alkali thiocyanate to form 3,3′,3″,3-tetrathiocyanocopper phthalocyanine or 4,
4′,4″,4-tetrathiocyanocopper phthalocyanine is obtained.
(2) 銅フタロシアニンをクロルスルホン酸で処理
して、銅フタロシアニンテトラスルホクロライ
ドとし、塩酸と亜鉛末で還元してテトラメルカ
プト銅フタロシアニンを得る。(2) Copper phthalocyanine is treated with chlorosulfonic acid to produce copper phthalocyanine tetrasulfochloride, which is then reduced with hydrochloric acid and zinc powder to obtain tetramercaptocopper phthalocyanine.
(3) 銅フタロシアニンテトラスルホクロライドを
塩酸と亜鉛末で還元する際、チオ尿素を添加し
て、テトラチオ尿素銅フタロシアニンを得る。(3) When copper phthalocyanine tetrasulfochloride is reduced with hydrochloric acid and zinc powder, thiourea is added to obtain tetrathiourea copper phthalocyanine.
これらの銅フタロシアニンを酸化することによ
り高分子化することができるが、チオシアノ基、
メルカプト基、又はチオ尿素基を有する銅フタロ
シアニンは、硫化アルカリ水溶液に易溶であるた
め、硫化アルカリ水溶液にこれらの銅フタロシア
ニンを溶かし、この水溶液に炭素体を浸漬した
後、酸化させて、銅フタロシアニン酸化縮合物を
含有せしめた炭素体からなる空気極が製造され
る。 These copper phthalocyanines can be made into polymers by oxidizing them, but thiocyano groups,
Copper phthalocyanines having a mercapto group or a thiourea group are easily soluble in an alkali sulfide aqueous solution, so these copper phthalocyanines are dissolved in an alkali sulfide aqueous solution, a carbon body is immersed in this aqueous solution, and then oxidized to form a copper phthalocyanine. An air electrode made of a carbon body containing an oxidation condensate is produced.
炭素体としては、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、ヤシ殼炭、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、黒鉛などの１種もし
くは２種以上の混合物が挙げられる。 Carbon materials include carbon blacks such as furnace blacks, channel blacks, and thermal blacks, as well as wood, charcoal, palm shell charcoal, palm kernel charcoal, coal, petroleum residue, synthetic resins, and organic waste. Examples include activated carbon, graphite, etc., or a mixture of two or more thereof.
本発明の空気極における金属フタロシアニン系
酸化縮合物の量は、空気極としての性能、空気極
の強度を考慮すれば、１〜20重量％が好ましい。 The amount of the metal phthalocyanine-based oxidative condensate in the air electrode of the present invention is preferably 1 to 20% by weight, considering the performance as an air electrode and the strength of the air electrode.
以下実施例に従い本発明を詳細に説明するが、
実施例中「部」とあるのは「重量部」を示す。 The present invention will be explained in detail below according to Examples.
In the examples, "parts" indicate "parts by weight."
実施例 １
（銅フタロシアニン酸化縮合物の合成）
４−ニトロフタールイミド、尿素、塩化第一
銅、モリブデン酸アンモンをニトロベンゼン中
180〜185℃４時間撹拌し、過アセトン洗滌
後、５％苛性ソーダ水溶液、５％塩酸水溶液で
洗滌して、４，4′，4″，４−テトラニトロ銅
フタロシアニンを得る。Example 1 (Synthesis of copper phthalocyanine oxidation condensate) 4-nitrophthalimide, urea, cuprous chloride, and ammonium molybdate in nitrobenzene
The mixture was stirred at 180-185°C for 4 hours, washed with peracetone, and then washed with a 5% aqueous sodium hydroxide solution and a 5% aqueous hydrochloric acid solution to obtain 4,4',4'',4-tetranitrocopper phthalocyanine.
得られた４，4′，4″，４−テトラニトロ銅
フタロシアニンを10倍量の98％硫酸に溶かし、
水に注入して過水洗し、そのサスペンジヨン
に硫化ソーダを添加し、90〜95℃１時間撹拌
し、還元後、過水洗する。 The obtained 4,4′,4″,4-tetranitrocopper phthalocyanine was dissolved in 10 times the volume of 98% sulfuric acid,
Pour into water and wash with water, add sodium sulfide to the suspension, stir for 1 hour at 90-95°C, reduce and wash with water.
この４，4′，4″，４−テトラアミノ銅フタ
ロシアニンの水性分散体に重クロム酸カリを添
加し、常温で２時間撹拌し、目的の銅フタロシ
アニン酸化縮合物を得た。 Potassium dichromate was added to this aqueous dispersion of 4,4',4'',4-tetraamino copper phthalocyanine and stirred at room temperature for 2 hours to obtain the desired copper phthalocyanine oxidation condensate.
（炭素体の製造）
粒径0.1〜1μのヤシ殼活性炭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、200℃に加熱し、熱可塑性樹脂を分解
して、炭素体とする。 (Production of carbon body) 10 parts of coconut shell activated carbon with a particle size of 0.1 to 1μ, a particle size of 0.1 to 1μ
Mix 10 parts of 0.5μ graphite and 5 parts of thermoplastic resin (vinyl chloride resin), make a round bar with a diameter of 10 mm by extrusion molding, heat it to 200℃, decompose the thermoplastic resin, and make a carbon body. .
（空気極の製造）
上記で得られた銅フタロシアニン酸化縮合物の
５重量％分散溶液に炭素体を含浸させ、超音波処
理をして炭素体に銅フタロシアニン酸化縮合物を
５重量％付着せしめ、溶媒を除去する為に50℃真
空乾燥させて空気極を得る。 (Manufacture of air electrode) Impregnating a carbon body with a 5% by weight dispersion solution of the copper phthalocyanine oxidative condensate obtained above, and applying ultrasonic treatment to adhere 5% by weight of the copper phthalocyanine oxidative condensate to the carbon body, To remove the solvent, vacuum dry at 50°C to obtain an air electrode.
比較例 １
実施例１中の銅フタロシアニン酸化縮合物の代
りに銅フタロシアニンを使用した他は実施例１と
同様にして空気極を製造した。Comparative Example 1 An air electrode was produced in the same manner as in Example 1 except that copper phthalocyanine was used instead of the copper phthalocyanine oxidation condensate in Example 1.
実施例 ２
（ポリアミノ鉄フタロシアニンの合成）
無水フタノール酸、尿素、硫酸第一鉄、モリ
ブデン酸アンモンをニトロベンゼン中180〜185
℃４時間撹拌し鉄フタロシアニンを得る。Example 2 (Synthesis of polyaminoiron phthalocyanine) Phthanolic anhydride, urea, ferrous sulfate, and ammonium molybdate in nitrobenzene from 180 to 185
C. and stirred for 4 hours to obtain iron phthalocyanine.
鉄フタロシアニンをその８〜10倍量の100％
硫酸に溶解し、硫酸ヒドロキシルアミンを添加
して、50〜55℃３時間撹拌し、アミノ基が平均
3.5個導入されたポリアミノ鉄フタロシアニン
を得る。 100% iron phthalocyanine, 8 to 10 times the amount
Dissolved in sulfuric acid, added hydroxylamine sulfate, and stirred at 50-55℃ for 3 hours until the amino groups were on average
3.5 polyamino iron phthalocyanines are obtained.
（空気極の製造）
実施例１の炭素体を上記のポリアミノ鉄フタロ
シアニンの水性分散溶液に浸漬し、50℃真空乾燥
後、５％過マンガン酸カリ水溶液で処理して、鉄
フタロシアニン酸化縮合物を10％含有した空気極
を得た。 (Manufacture of air electrode) The carbon body of Example 1 was immersed in the above aqueous dispersion solution of polyamino iron phthalocyanine, vacuum dried at 50°C, and then treated with a 5% potassium permanganate aqueous solution to form the iron phthalocyanine oxidation condensate. An air electrode containing 10% was obtained.
実施例 ３
実施例１の炭素体をテトラチオシアノ銅フタロ
シアニンを硫化ソーダ水溶液に５％溶解した溶液
に含浸させ、常温乾燥後、３％過酸化水素水溶液
に含浸させて、−Ｓ−Ｓ−結合を生成させて空気
極を製造した。Example 3 The carbon body of Example 1 was impregnated with a 5% solution of tetrathiocyano copper phthalocyanine in an aqueous sodium sulfide solution, dried at room temperature, and then impregnated with a 3% aqueous hydrogen peroxide solution to form -S-S- bonds. An air electrode was manufactured by producing the following.
実施例 ４
実施例１の炭素体を10重量％のテトラメルカプ
ト鉄フタロシアニンの硫化カリウム水溶液に浸漬
し、常温乾燥後、１％過ホウ酸ナトリウム水溶液
に含浸させてから50℃で乾燥させ空気極を得た。Example 4 The carbon body of Example 1 was immersed in a 10% by weight potassium sulfide aqueous solution of tetramercaptoiron phthalocyanine, dried at room temperature, impregnated with a 1% aqueous sodium perborate solution, and dried at 50°C to form an air electrode. Obtained.
実施例１〜４、比較例１の空気極の分極特性を
第１図、第２図に示す。 The polarization characteristics of the air electrodes of Examples 1 to 4 and Comparative Example 1 are shown in FIGS. 1 and 2.
以上のように本発明の製造方法により得られた
空気極は、優れた分極特性を有するものである。 As described above, the air electrode obtained by the manufacturing method of the present invention has excellent polarization characteristics.
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、第２図は実施例３，
４、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、実施例
３、実施例４、比較例１で得られた空気極の分極
曲線を示し、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 Figure 2 shows the polarization curves of the air electrodes obtained in Examples 1 and 2 and Comparative Example 1.
4. This is the polarization curve of the air electrode obtained in Comparative Example 1, and ~ indicates the polarization curve of the air electrode obtained in Example 1, Example 2, Example 3, Example 4, 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)
分子化した金属フタロシアニン系酸化縮合物を含
有せしめた炭素体からなる空気極。 ２ 金属フタロシアニン系酸化縮合物の金属が、
鉄、コバルト、ニツケル、銅を含んでいることを
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 made of a carbon body containing a metal phthalocyanine-based oxidative condensate polymerized by -N=N- bonds or -S-S- bonds. 2 The metal of the metal phthalocyanine-based oxidation condensate is
The air electrode according to claim 1, characterized in that the air electrode contains iron, cobalt, nickel, and copper.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56173926A JPS5875775A (en) | 1981-10-30 | 1981-10-30 | Air electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56173926A JPS5875775A (en) | 1981-10-30 | 1981-10-30 | Air electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5875775A JPS5875775A (en) | 1983-05-07 |
| JPH0142467B2 true JPH0142467B2 (en) | 1989-09-12 |
Family
ID=15969628
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56173926A Granted JPS5875775A (en) | 1981-10-30 | 1981-10-30 | Air electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5875775A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0616094D0 (en) * | 2006-08-12 | 2006-09-20 | Aquafuel Res Ltd | Coal combustion improvement additives |
| JP5403601B2 (en) * | 2009-05-26 | 2014-01-29 | 帝人株式会社 | Carbon material and manufacturing method thereof |
| JP5414104B2 (en) * | 2009-05-26 | 2014-02-12 | 帝人株式会社 | Carbon material and manufacturing method thereof |
| JP5403799B2 (en) * | 2009-06-26 | 2014-01-29 | 帝人株式会社 | Carbon material and manufacturing method thereof |
-
1981
- 1981-10-30 JP JP56173926A patent/JPS5875775A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5875775A (en) | 1983-05-07 |
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