JPH0828239B2 - Halogen battery - Google Patents
Halogen batteryInfo
- Publication number
- JPH0828239B2 JPH0828239B2 JP60294430A JP29443085A JPH0828239B2 JP H0828239 B2 JPH0828239 B2 JP H0828239B2 JP 60294430 A JP60294430 A JP 60294430A JP 29443085 A JP29443085 A JP 29443085A JP H0828239 B2 JPH0828239 B2 JP H0828239B2
- Authority
- JP
- Japan
- Prior art keywords
- gas
- anode
- halogen
- gas diffusion
- halogen battery
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
- H01M12/085—Zinc-halogen cells or batteries
-
- 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
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inert Electrodes (AREA)
- Hybrid Cells (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、電力貯蔵、電気自動車等を用いるハロゲン
電池の改良に関する。Description: TECHNICAL FIELD The present invention relates to an improvement of a halogen battery for use in electric power storage, electric vehicles and the like.
（従来の技術） 従来、ハロゲン電池の陽極には、炭素をフェルト又は
炭素フェルトにパラジウム等の貴金属を担持した多孔質
の陽極が用いられていたが、充電時陽極の表面に発生す
るハロゲンガスが気泡として吸着する。従って、この吸
着ガスが陽極の表面積を実質的に減少させることにな
り、流れる電流が減り、充電に長時間要するものであ
る。この為現在ではポンプを用いて電解液を強制的にフ
ェルト状陽極に透過させてハロゲンガスの吸着を減らす
ようにしているが満足のゆくものではない。また放電時
にはハロゲンガスは電解液中に溶解しているため放電量
に応じて陽極面に速やかに供給することが難しいので、
陽極の単位面積当り取り出せる電流が少ないものであ
る。(Prior Art) Conventionally, a porous anode in which carbon felt or a noble metal such as palladium is supported on carbon felt has been used as an anode of a halogen battery, but halogen gas generated on the surface of the anode during charging is Adsorbs as bubbles. Therefore, the adsorbed gas substantially reduces the surface area of the anode, the flowing current is reduced, and charging takes a long time. Therefore, at present, a pump is used to force the electrolyte solution to pass through the felt-like anode to reduce the adsorption of halogen gas, but it is not satisfactory. Also, since halogen gas is dissolved in the electrolyte during discharge, it is difficult to quickly supply it to the anode surface according to the discharge amount.
The current that can be taken out per unit area of the anode is small.
そこで本発明は、充電時に陽極で発生するハロゲンガ
スをすばやく除去でき、また放電時にハロゲンガスを放
電量に応じてすばやく陽極に供給できる陽極を有するハ
ロゲン電池を提供せんとするものである。Therefore, the present invention provides a halogen battery having an anode capable of quickly removing the halogen gas generated at the anode during charging and rapidly supplying the halogen gas to the anode during discharging according to the discharge amount.
（問題点を解決するための手段） 上記問題点を解決するための本発明のハロゲン電池
は、陽極がガス拡散電極であることと、これに直結する
ガス貯槽を備えたことを特徴とするものであり、その構
成は、ハロゲン電池に於て、白金族金属またはその酸化
物若しくはその両者とカーボンブラックとポリ四弗化エ
チレンからなる反応層に、カーボンブラックとポリ四弗
化エチレンとの混合物からなるガス拡散層が接合された
ガス拡散電極からなる陽極と、該ガス拡散電極に直結す
るガス貯槽を備えたことを特徴とするハロゲン電池であ
る。(Means for Solving Problems) A halogen battery of the present invention for solving the above problems is characterized in that the anode is a gas diffusion electrode and a gas storage tank directly connected thereto is provided. In a halogen battery, the constitution is such that a platinum group metal or its oxide or both, a reaction layer composed of carbon black and polytetrafluoroethylene, and a mixture of carbon black and polytetrafluoroethylene are used. A halogen battery comprising: an anode composed of a gas diffusion electrode joined to the gas diffusion layer, and a gas storage tank directly connected to the gas diffusion electrode.
（作用） 上記の如く本発明のハロゲン電池は、陽極としてガス
拡散電極が用いられ、かつこれに直結するガス貯槽が備
えられているので、充電時には陽極の反応層に発生する
ハロゲンガスをガス拡散層にすばやく吸収透過し、陽極
の反応面積を減少させず、他方放電時にはガス拡散層か
らハロゲンガスをすばやく陽極の反応層に供給できる。
従って、陽極の単位面積当りの流せる電流が多くて充電
及び放電効率が非常に高く、短時間に充電でき、また大
きな電流が取り出せるものである。(Operation) As described above, the halogen battery of the present invention uses the gas diffusion electrode as the anode and is provided with the gas storage tank directly connected thereto, so that the halogen gas generated in the reaction layer of the anode during gas charging is diffused. The layer quickly absorbs and permeates and does not reduce the reaction area of the anode, while the halogen gas can be quickly supplied from the gas diffusion layer to the reaction layer of the anode during discharge.
Therefore, a large amount of current can flow per unit area of the anode, so that charging and discharging efficiency is very high, charging can be performed in a short time, and a large current can be taken out.
（実施例） 本発明によるハロゲン電池の一実施例を図によって説
明する。第１図に於いて、１は電解液槽で、ZnCl2、KC
l、NaClから成る水溶液２が収容されている。この水溶
液２中には負極としてカーボンより成る電極３と、陽極
としてガス拡散電極４が配されている。前記ガス拡散電
極４は、第２図に示す如く、平均粒径150ÅのRuO2の粉
末と、平均粒径420Åの親水性のカーボンブラックと、
平均粒径0.3μのポリ四弗化エチレン粉末とを4:5:3の割
合で混合成形されて成る厚さ0.1mm、幅100mm、長さ100m
mの反応層７に、平均粒径450Åの撥水性のカーボンブラ
ックと平均粒径0.3μのポリ四弗化エチレン粉末とを7:3
の割合で混合成形されて成る厚さ0.5mmのガス拡散層８
を接合し更に多孔の集電板12を接合して成るものであ
る。第１図に於いて、９は電解液槽１に設けられたバル
ブ10付ガス通路で、ガス貯槽11に連結され、さらに電解
液を循環させるために電解液槽１に電解液貯蔵タンク12
及びポンプ13がパイプ14にて連結されている。(Example) An example of the halogen battery according to the present invention will be described with reference to the drawings. In FIG. 1, 1 is an electrolytic solution tank, ZnCl 2 , KC
An aqueous solution 2 consisting of 1 and NaCl is contained. In this aqueous solution 2, an electrode 3 made of carbon as a negative electrode and a gas diffusion electrode 4 as an anode are arranged. As shown in FIG. 2, the gas diffusion electrode 4 comprises RuO 2 powder having an average particle size of 150Å and hydrophilic carbon black having an average particle size of 420Å.
It is made by mixing and molding polytetrafluoroethylene powder with an average particle size of 0.3μ in the ratio of 4: 5: 3, thickness 0.1mm, width 100mm, length 100m.
In the reaction layer 7 of m, water-repellent carbon black having an average particle diameter of 450Å and polytetrafluoroethylene powder having an average particle diameter of 0.3μ are mixed at 7: 3.
Gas diffusion layer 8 with a thickness of 0.5mm
And the porous collector plate 12 are joined together. In FIG. 1, reference numeral 9 denotes a gas passage with a valve 10 provided in the electrolytic solution tank 1, which is connected to a gas storage tank 11 and further has an electrolytic solution storage tank 12 in the electrolytic solution tank 1 for circulating the electrolytic solution.
The pump 13 is connected by a pipe 14.
上記の如く構成されたハロゲン電池に於いて、充電時
ZnCl2、KCl、NaClから成る水溶液２はガス拡散電極４の
親水性の反応層７中に浸透し、そこで反応によって発生
したCl2ガスはすばやくガス拡散層８に吸収浸透する。
ガス拡散層８を透過したCl2ガスは、バルブ10の開かれ
たガス通路９を通って、ガス貯槽11内の冷水に放出さ
れ、塩素水和物として貯蔵される。一方電極３の表面に
はZnが析出し、ZnCl2、KCl、NaClから成る水溶液２のZn
濃度は次第に薄くなり、充電完了時には低濃度のZnCl2
水溶液となった。When charging the halogen battery configured as above
The aqueous solution 2 composed of ZnCl 2 , KCl, and NaCl permeates into the hydrophilic reaction layer 7 of the gas diffusion electrode 4, and the Cl 2 gas generated by the reaction therein quickly permeates into the gas diffusion layer 8.
The Cl 2 gas that has passed through the gas diffusion layer 8 is released into the cold water in the gas storage tank 11 through the gas passage 9 in which the valve 10 is opened, and stored as chlorine hydrate. On the other hand, Zn is deposited on the surface of the electrode 3 and Zn of the aqueous solution 2 consisting of ZnCl 2 , KCl and NaCl
The concentration gradually diminishes, and when charging is complete, low concentration ZnCl 2
It became an aqueous solution.
上記の如くガス拡散電極４の反応層７での活発な触媒
反応により大量にCl2ガスが生成される結果、単位時間
当りの充電量は従来の炭素フェルトにパラジウムを担持
した多孔質の陽極を用いたハロゲン電池に比べ10数倍と
高く、充電時間が10数分の１と極めて短いものであっ
た。As described above, a large amount of Cl 2 gas is generated by the active catalytic reaction in the reaction layer 7 of the gas diffusion electrode 4, and as a result, the charged amount per unit time is the same as that of the conventional porous anode in which palladium is supported on carbon felt. It was 10 times higher than the halogen battery used, and the charging time was extremely short at 1/10.
然して放電時にガス貯槽11内の塩素水和物を加熱分解
してCl2ガスを発生させ、これをガス拡散層８側からガ
ス拡散電極４を透過して電極反応により2Cl-に変換させ
て電解液槽１内に供給し、一方電極３の表面のZnをZn2+
に変換させて、夫々電解液槽１内にZnCl2低濃度の水溶
液２中に溶出してZnCl2の濃度を高めていく。この放電
時の際、ガス拡散電極４ではCl2ガスが反応層７中で電
極反応により大量に2Cl-に変換されて、反応層７中に浸
透している水溶液２中に溶出するので、極めて放電量が
多いものである。However, at the time of discharge, the chlorine hydrate in the gas storage tank 11 is thermally decomposed to generate Cl 2 gas, which is transmitted from the gas diffusion layer 8 side through the gas diffusion electrode 4 and converted into 2Cl − by an electrode reaction to be electrolyzed. The Zn on the surface of the electrode 3 is supplied to the Zn 2+
And is dissolved in the electrolytic solution tank 1 into the low-concentration ZnCl 2 aqueous solution 2 to increase the concentration of ZnCl 2 . At the time of this discharge, a large amount of Cl 2 gas is converted into 2Cl − by the electrode reaction in the reaction layer 7 at the gas diffusion electrode 4 and is eluted into the aqueous solution 2 permeating into the reaction layer 7. The amount of discharge is large.
尚、上記実施例では、ガス拡散電極４の反応層７中の
触媒がRuO2であるが、これに限るものではなく、白金族
金属ならいずれでも良く、またその酸化物でも良く、若
しくはそれらの両方でも良いものである。Although the catalyst in the reaction layer 7 of the gas diffusion electrode 4 is RuO 2 in the above embodiment, the catalyst is not limited to this, and any platinum group metal or oxide thereof may be used. Both are good.
また上記実施例では電解液がZnCl2水溶液であるが、C
dCl2水溶液やZnBr2水溶液でも良いものである。ZnBr2水
溶液を用いた場合は、充電時2Br-をガス化する為、60℃
以上に加熱する。Further, in the above example, the electrolytic solution is a ZnCl 2 aqueous solution, but C
A dCl 2 aqueous solution or a ZnBr 2 aqueous solution may also be used. When using a ZnBr 2 aqueous solution, 60 ° C for gasifying 2Br − during charging.
Heat to above.
さらに負極にはH2ガスの発生の少ない電極（炭素電
極、白金族の付いていないガス拡散電極など）ならばど
のような電極でも良いが、表面が平滑だとZnやCdが剥離
するので粗面のものが良い。Further, the negative electrode may be any electrode as long as it does not generate H 2 gas (carbon electrode, gas diffusion electrode without platinum group, etc.), but if the surface is smooth, Zn or Cd will peel off, so The one on the surface is good.
（発明の効果） 以上の説明で判るように本発明のハロゲン電池は、陽
極にガス拡散電極が用いられているので、充電時には陽
極の反応層に発生するハロゲンガスをガス拡散層にすば
やく吸収透過し、陽極の反応面積を減少させず、他方放
電時にはガス拡散層からハロゲンガスをすばやく陽極の
反応層に供給できる。従って陽極の単位面積当りの流せ
る電流が多くて短時間に充電でき、また大きな電流が取
り出せるものである。このように本発明のハロゲン電池
は著しくパワーアップするので、従来のハロゲン電池に
とって代わることのできる画期的なものと云える。(Effects of the Invention) As can be seen from the above description, the halogen battery of the present invention uses the gas diffusion electrode for the anode, so that the halogen gas generated in the reaction layer of the anode during charging is quickly absorbed and transmitted to the gas diffusion layer. However, the reaction area of the anode is not reduced, while the halogen gas can be quickly supplied from the gas diffusion layer to the reaction layer of the anode during discharge. Therefore, a large amount of current can flow per unit area of the anode, and charging can be performed in a short time, and a large amount of current can be taken out. As described above, the halogen battery of the present invention is remarkably powered up, and thus it can be said that it is an epoch-making thing that can replace the conventional halogen battery.
第一図は本発明のハロゲン電池の一実施例を示す概略
図、第２図はそのハロゲン電池に於ける陽極としてのガ
ス拡散電極の拡大断面図である。FIG. 1 is a schematic view showing an embodiment of the halogen battery of the present invention, and FIG. 2 is an enlarged sectional view of a gas diffusion electrode as an anode in the halogen battery.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭58−197669（ＪＰ，Ａ) 特開 昭59−139573（ＪＰ，Ａ) 特開 昭59−151768（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of front page (56) Reference JP-A-58-197669 (JP, A) JP-A-59-139573 (JP, A) JP-A-59-151768 (JP, A)
Claims (1)
の酸化物若しくはその両者とカーボンブラックとポリ四
弗化エチレンからなる反応層に、カーボンブラックとポ
リ四弗化エチレンとの混合物からなるガス拡散層が接合
されたガス拡散電極からなる陽極と、該ガス拡散電極に
直結するガス貯槽を備えたことを特徴とするハロゲン電
池。1. In a halogen battery, a gas comprising a mixture of carbon black and polytetrafluoroethylene in a reaction layer comprising a platinum group metal or its oxide or both, carbon black and polytetrafluoroethylene. A halogen battery comprising an anode composed of a gas diffusion electrode joined to a diffusion layer and a gas storage tank directly connected to the gas diffusion electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60294430A JPH0828239B2 (en) | 1985-12-27 | 1985-12-27 | Halogen battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60294430A JPH0828239B2 (en) | 1985-12-27 | 1985-12-27 | Halogen battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62154585A JPS62154585A (en) | 1987-07-09 |
| JPH0828239B2 true JPH0828239B2 (en) | 1996-03-21 |
Family
ID=17807661
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60294430A Expired - Lifetime JPH0828239B2 (en) | 1985-12-27 | 1985-12-27 | Halogen battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0828239B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06212469A (en) * | 1992-07-16 | 1994-08-02 | Imura Japan Kk | Gas diffusion electrode and electrochemical reaction device using the gas diffusion electrode |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58197669A (en) * | 1982-05-11 | 1983-11-17 | Meidensha Electric Mfg Co Ltd | Electrode for layer-built cell |
| JPS59139573A (en) * | 1983-01-28 | 1984-08-10 | Meidensha Electric Mfg Co Ltd | Plastic electrodes for metal halogen batteries |
| JPS59151768A (en) * | 1983-02-18 | 1984-08-30 | Meidensha Electric Mfg Co Ltd | Plastic electrode of zinc-bromine battery |
-
1985
- 1985-12-27 JP JP60294430A patent/JPH0828239B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62154585A (en) | 1987-07-09 |
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