JPS5925181A - Air electrode - Google Patents
Air electrodeInfo
- Publication number
- JPS5925181A JPS5925181A JP57134248A JP13424882A JPS5925181A JP S5925181 A JPS5925181 A JP S5925181A JP 57134248 A JP57134248 A JP 57134248A JP 13424882 A JP13424882 A JP 13424882A JP S5925181 A JPS5925181 A JP S5925181A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- reduction
- air electrode
- oxidation
- carbon substance
- 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。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の空気極ｄ、カーボンブラッ
ク、活性炭などを成形してなる炭素体に酸化還元能力を
高めるに白金、パラジウムなどの貴金属や金属フタロノ
アニ／々とを１ケ浸せしめていた。Conventionally, in order to increase the oxidation-reduction ability of the air electrodes of air cells and fuel cells, carbon bodies formed by molding carbon black, activated carbon, etc., noble metals such as platinum and palladium and metal phthalonanoani were immersed. .
然し乍ら、 Ａ４１者は高価であり、コスト的に不利で
あり、後者は、適当な溶剤がなくて含ｆＪさせるのに困
離であるという欠点をイラしてぃ／こ。However, the A41 type is expensive and disadvantageous in terms of cost, and the latter has the disadvantage that it is difficult to contain fJ due to the lack of a suitable solvent.
本発明者等は、コスト的に白金、パラジウムなどの貴金
属に比較し安価であり、その酸素還元能力も金属フタロ
ンアニンとほぼ同勢であるものとして酸化還元樹脂の還
元型が使用できることを見い出し本発明を完成したもの
である。The present inventors discovered that a reduced form of redox resin can be used as it is cheaper than noble metals such as platinum and palladium, and its oxygen reduction ability is almost on par with metal phthalonanine, and the present invention This is the completed version.
即ち、還元型の酸化還元樹脂を炭素体に分１１＋せしめ
てなることを特徴とする空気極を要旨とするものである
。That is, the gist of the present invention is an air electrode characterized in that it is made of a carbon body containing a reduced oxidation-reduction resin.
以下１本発明について詳細に説明する。The present invention will be explained in detail below.
本発明の骨子をなす酸化還元樹脂としては。The redox resin that forms the gist of the present invention is as follows.
■キノン系樹脂としては、ビニルヒドロキノンの単独重
合体、ビニルヒドロキノンとスチレンやメタクリル酸メ
チルなどのビニルモノマーとのラジカル共重合体、ヒド
ロキノンビニルスルホン酸の単独重合体およびスチレン
。■ Quinone resins include vinyl hydroquinone homopolymers, radical copolymers of vinyl hydroquinone and vinyl monomers such as styrene and methyl methacrylate, hydroquinone vinyl sulfonic acid homopolymers, and styrene.
ジビニルベンゼンとの共重合体、ヒドロキノンとホルム
アルデヒドとの縮合による重合体。Copolymer with divinylbenzene, polymer produced by condensation of hydroquinone and formaldehyde.
ヒドロキノンのマンニッヒ反応による重合体。A polymer produced by the Mannich reaction of hydroquinone.
クロルメチル化ポリスチレンと７・イドロキノンの反応
物、ジアゾ化ポリスチレンとノ・イドロキノンの反応物
、ポリスチレンスルホクロライドとアミツノ・イドロキ
ノンの縮合物などがある。These include a reaction product of chloromethylated polystyrene and 7-hydroquinone, a reaction product of diazotized polystyrene and 7-hydroquinone, and a condensation product of polystyrene sulfochloride and 7-hydroquinone.
■ピリジン系樹脂としては、クロルメチルチレンとニコ
チン酸アミドの第４級アンモニウム塩の重合体もしくは
クロルメチル化ポリスチレンとニコチン酸アミドの第４
級アンモニウム塩がある。■Pyridine-based resins include polymers of quaternary ammonium salts of chloromethyltyrene and nicotinamide, or polymers of quaternary ammonium salts of chloromethylated polystyrene and nicotinamide.
There are class ammonium salts.
■チオール系樹脂としては．メルカプトポリスチレン、
メルカプトメチルポリスチレンなどがある。■As a thiol-based resin. mercapto polystyrene,
Examples include mercaptomethyl polystyrene.
■フェロセン系樹脂としては，ビニルフェロセンの単独
重合体，フェロセン官能基を含むアクリル酸エステル、
メタクリル酸エステルの単独重合体および他のビニル化
合物との共重合体などがある。■ Ferrocene resins include vinyl ferrocene homopolymers, acrylic esters containing ferrocene functional groups,
Examples include homopolymers of methacrylic acid esters and copolymers with other vinyl compounds.
これらの酸化還元樹脂は容易に合成でき。These redox resins can be easily synthesized.
触媒として必須の還元型として使用する。例えばキノン
系樹脂として．ヒドロキノンとホルムアルデヒドの縮合
による重合体は，ヒドロキノンとホルマリン、触媒量の
水酸化すｌ・リウムの存在下，窒素ふん囲気中１８０℃
にて反応させることにより簡単に合成できる。It is used in the reduced form, which is essential as a catalyst. For example, as a quinone resin. A polymer formed by the condensation of hydroquinone and formaldehyde is produced at 180°C in a nitrogen atmosphere in the presence of hydroquinone, formalin, and a catalytic amount of sulfur and lithium hydroxide.
It can be easily synthesized by reaction.
その推定構造式は（Ｉ１式で表わされ，酸素を消費して
，キノン構造ＣＩ［＋となり，更に還元によって，ヒド
ロキノン構造となる。Its estimated structural formula is represented by the formula (I1), which consumes oxygen to form a quinone structure CI[+, and further reduces to a hydroquinone structure.
（Ｉ＋ （１）還元
型のヒドロキノン構造（１．１の重合体のその還元性能
を利用して，空気極の触媒とするものである。(I+ (1) Reduced hydroquinone structure (Using the reducing ability of the polymer in 1.1, it is used as a catalyst for the air electrode.
次に炭素体への添加であるが，次の二つの方法がある。Next, there are two methods for adding carbon to the carbon body.
（１）炭素体を成形する際に予め原料に酸化還元＋ｆｆ
ｊ樹を添加し，成形して空気極とする。(1) Oxidation-reduction +ff applied to the raw material in advance when forming the carbon body
J tree is added and molded to form an air electrode.
（２）成形した炭素体に，酸化還冗但１脂の水溶液また
は有機溶剤にとかした溶液を含浸させ，水捷たは有機溶
媒を除去する。(2) The formed carbon body is impregnated with an aqueous solution of redox resin or a solution dissolved in an organic solvent, and the water or organic solvent is removed.
上述した方法によって目的の空気極を得る。A desired air electrode is obtained by the method described above.
どの方法を選択するかは．酸化．還元樹脂によるもので
，含浸の場合キノン系樹脂なら水溶液，ピリジン系樹脂
ならベンゼ／！ｉたけンクロへキザノン溶液．チオール
系樹脂なら水溶液，ヘンゼン捷だは／クロヘギザノン溶
液。Which method should you choose? Oxidation. It is based on a reducing resin, and in the case of impregnation, it is an aqueous solution for quinone resin, and benzene /! for pyridine resin. itakencrohe xanone solution. For thiol-based resins, use an aqueous solution, Hensen's Katsuda/Clohegizanone solution.
フェロセン系樹脂はベンゼン溶液から炭素体に付着せし
むることか出来る。Ferrocene resin can be attached to carbon bodies from a benzene solution.
酸化還元樹脂の炭素体への伺着量は０１１Ｆ量係以下で
は効果が少なく，５重量部以上では最早それ以上の性能
を望むことが出来ないし．コスト的に不利であり，炭素
体全量に対して０１〜５重量部が好ましい。If the amount of redox resin adhering to the carbon body is less than 011F, the effect will be small, and if it is more than 5 parts by weight, it is no longer possible to expect better performance. Since it is disadvantageous in terms of cost, it is preferably 01 to 5 parts by weight based on the total amount of the carbon body.
以下実施例に従い更に詳細に説明するが，実施例中「部
」とあるのは１重量部」、「％」とあるのは「重量係」
を示す。A more detailed explanation will be given below according to the examples. In the examples, "part" means 1 part by weight, and "%" means "weight part".
shows.
実施例１
活性炭，黒鉛を主成分とする炭素体（直杆１０賜，長さ
１ ０ ０ ｗｒｂ 、 気孔率５０％）をヒドロキ
ノ／−ホルムアルデヒド縮合重合体の１０％水に；液（
０５％苛性ノーダを予め溶解しておく）にυ漬し、乾燥
する。次に１係塩酸水溶液に含浸させて、中和し、水洗
、乾燥することにより、キノン系樹脂を１係含有した空
気極を得た。Example 1 A carbon body mainly composed of activated carbon and graphite (10 straight rods, 100 wrb length, 50% porosity) was added to 10% water of hydroquino/-formaldehyde condensation polymer;
05% caustic noda (dissolved in advance) and dried. Next, it was impregnated with a 1% hydrochloric acid aqueous solution, neutralized, washed with water, and dried to obtain an air electrode containing 1% quinone resin.
実施例２
実施例１にて使用した炭素体をクロルノチル化ポリスチ
レンとニコチン酸アミドの第４級アンモニウム塩の５係
ベンゼン溶液に浸漬し、５０℃真空乾燥することにより
、ピリジン系樹脂を０１係伺着せしめた空気極を得た。Example 2 The carbon body used in Example 1 was immersed in a 5-benzene solution of chloronotylated polystyrene and a quaternary ammonium salt of nicotinic acid amide, and vacuum-dried at 50°C to form a pyridine-based resin. I got a dressed air pole.
実施例６
ヤシ殻活性炭４５部、黒鉛４５部、熱可塑性樹脂６０部
およびメルカプトポリスチレン５部を混合し、押出し成
形により、直径１０閏の丸棒を作り、その後２００℃に
加熱して、チメーール系樹脂５％添加した空気極を得た
。Example 6 45 parts of coconut shell activated carbon, 45 parts of graphite, 60 parts of thermoplastic resin and 5 parts of mercapto polystyrene were mixed, extrusion molded to make a round bar with a diameter of 10, and then heated to 200°C to form a thymer-based product. An air electrode containing 5% resin was obtained.
実施例４
実施例１に使用した炭素体にポリスチレンジオゾニウム
塩とフェロセンと反応させて得られた樹脂を０５重量％
付着せしめた空気極を得た。Example 4 05% by weight of a resin obtained by reacting the carbon body used in Example 1 with polystyrene diozonium salt and ferrocene.
An attached air electrode was obtained.
実施例１に使用した炭素体をその１＼空気極とした。The carbon body used in Example 1 was used as the 1\ air electrode.
比較例２゜
実施例１に使用した炭素体を鉄フタロンアニンの飽和キ
ノリン゛溶液に浸漬して１次に２００℃減圧乾燥するこ
とにより、空気極を得た。Comparative Example 2 An air electrode was obtained by immersing the carbon body used in Example 1 in a saturated quinoline solution of iron phthalonanine and drying it under reduced pressure at 200°C.
比較例６゜
実施例３で、メルカプトポリスチレン５部の代りにコバ
ルトフクロシアニン５部を使用し。Comparative Example 6 In Example 3, 5 parts of cobalt fucrocyanine was used instead of 5 parts of mercapto polystyrene.
以下全く同じように処理して空気極を得た。Thereafter, an air electrode was obtained by processing in exactly the same manner.
比較例４
実施例１に使用した炭素体を銅フタ四／アニンの飽和キ
ノリン溶液に浸漬して１次に２００℃減圧乾燥すること
によシ空気極を得た。Comparative Example 4 An air electrode was obtained by immersing the carbon body used in Example 1 in a saturated quinoline solution of copper chloride/anine and drying it under reduced pressure at 200°C.
本発明の空気極は１図面に示すように優れた分極特性を
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。The air electrode of the present invention exhibits excellent polarization characteristics as shown in Figure 1, 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
曲線であり、第２図（ｄ実施ψ１ｊ２．比較例２で得ら
れた空気極の分極曲線を、第６図は実施例６．比較例６
で得られた空気極の分極曲線を第４図は実施例４．比較
例４でＶ４＋られた分極曲線を表わし、■〜■は順に実
施ｆ１ ＋ 、 Ｊ：し軸側１．実施例２．比較例２．
実施９１１３．上ヒ軸側５．実施例４．比較例４で得ら
れた空気極の分極曲線を示し、縦軸は電流密度（ｍＡ／
Ｊ ） 。
横軸は電位（■／ＳＣＪシ）を示す。
特許出願人 ぺんてる株式会社
３６１FIG. 1 shows Example 1. FIG. 2 shows the polarization curve of the air electrode obtained in Comparative Example 1, and FIG. 6 shows the polarization curve of the air electrode obtained in Comparative Example 2.
FIG. 4 shows the polarization curve of the air electrode obtained in Example 4. The polarization curve obtained by applying V4+ in Comparative Example 4 is shown, and ■ to ■ are the polarization curves obtained in order f1 + , J: axial side 1. Example 2. Comparative example 2.
Implementation 9113. Upper axis side 5. Example 4. The polarization curve of the air electrode obtained in Comparative Example 4 is shown, and the vertical axis represents the current density (mA/mA/
J). The horizontal axis indicates the potential (■/SCJ). Patent applicant Pentel Co., Ltd. 361
Claims (1)
ることを特徴とする空気極。 ＋２１酸化還元樹脂がキノン系樹脂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）酸化還元樹脂がピリジン系樹脂であることを特徴
とする特許請求の範囲第１項記載の空気極。 （４）酸化還元樹脂がチオール系樹脂であることを特徴
とする特許請求の範囲第１項記載の空気極。 （５）酸化還元樹脂がフェロセン系樹脂であることを特
徴とする特許請求の範囲第１項記載の空気極。[Claims] (An air electrode characterized in that a redundant redox resin is dispersed in a carbon body. A claim in which the +21 redox resin is a quinone resin. The air electrode according to claim 1. (3) The air electrode according to claim 1, wherein the redox resin is a pyridine resin. (4) The redox resin is a thiol resin. (5) The air electrode according to claim 1, characterized in that the redox resin is a ferrocene resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57134248A JPS5925181A (en) | 1982-07-31 | 1982-07-31 | Air electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57134248A JPS5925181A (en) | 1982-07-31 | 1982-07-31 | Air electrode |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS5925181A true JPS5925181A (en) | 1984-02-09 |
Family
ID=15123854
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57134248A Pending JPS5925181A (en) | 1982-07-31 | 1982-07-31 | Air electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5925181A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001043215A1 (en) * | 1999-12-10 | 2001-06-14 | Nitto Denko Corporation | Fuel cell |
-
1982
- 1982-07-31 JP JP57134248A patent/JPS5925181A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001043215A1 (en) * | 1999-12-10 | 2001-06-14 | Nitto Denko Corporation | Fuel cell |
| US7468219B2 (en) | 1999-12-10 | 2008-12-23 | Nitto Denko Corporation | Fuel cell |
| US7537711B2 (en) | 1999-12-10 | 2009-05-26 | Nitto Denko Corporation | Electrically conductive polyaniline composition and method |
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