JPH0456068A - Positive electrode for metal halogen battery - Google Patents
Positive electrode for metal halogen batteryInfo
- Publication number
- JPH0456068A JPH0456068A JP2164385A JP16438590A JPH0456068A JP H0456068 A JPH0456068 A JP H0456068A JP 2164385 A JP2164385 A JP 2164385A JP 16438590 A JP16438590 A JP 16438590A JP H0456068 A JPH0456068 A JP H0456068A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- fiber
- sheet
- halogen
- activated carbon
- 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.)
- Granted
Links
- 229910052736 halogen Inorganic materials 0.000 title claims abstract description 35
- 150000002367 halogens Chemical class 0.000 title claims abstract description 35
- 239000002184 metal Substances 0.000 title claims description 14
- 229910052751 metal Inorganic materials 0.000 title claims description 14
- 239000000835 fiber Substances 0.000 claims abstract description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000005349 anion exchange Methods 0.000 claims abstract description 12
- 239000007774 positive electrode material Substances 0.000 claims abstract description 11
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 9
- 239000004033 plastic Substances 0.000 claims abstract description 9
- 229920003023 plastic Polymers 0.000 claims abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 9
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 9
- 229920005672 polyolefin resin Polymers 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 abstract description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical group OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 229920000098 polyolefin Polymers 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 125000000524 functional group Chemical group 0.000 abstract 1
- 239000011347 resin Substances 0.000 abstract 1
- 229920005989 resin Polymers 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 description 6
- -1 polyethylene Polymers 0.000 description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
- 229910052794 bromium Inorganic materials 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- ZRXYMHTYEQQBLN-UHFFFAOYSA-N [Br].[Zn] Chemical compound [Br].[Zn] ZRXYMHTYEQQBLN-UHFFFAOYSA-N 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 239000003351 stiffener Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
-
- 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
- Inert Electrodes (AREA)
- Hybrid Cells (AREA)
Abstract
Description
【発明の詳細な説明】
Ａ、産業上の利用分野
本発明は金属ハロゲン電池の正極電極に関し、特にハロ
ゲン保持機能を有することから、臭素がセパレーターを
通過して亜鉛極と反応することにより生ずる自己放電を
減少し、これにより放電特性に優れた金属ハロゲン電池
の正極電極に関する。DETAILED DESCRIPTION OF THE INVENTION A. Industrial Application Field The present invention relates to a positive electrode for a metal halogen battery, and in particular has a halogen retention function. The present invention relates to a positive electrode for a metal halogen battery that reduces discharge and thereby has excellent discharge characteristics.
Ｂ９発明の概要
本発明は金属ハロゲン電池の正極電極において、活性炭
素繊維、アニオン交換繊維及びポリオレフィン系樹脂繊
維を混合してシート状に成形された正極材とカーボンプ
ラスチック基板とを一体として成形することにより、
金属ハロゲン電池における充電により生ずるハロゲンの
保持力を向上させ、これにより自己放電を減少させ、放
電特性の向上を可能とする。B9 Summary of the Invention The present invention provides a positive electrode for a metal halogen battery, in which a positive electrode material formed into a sheet by mixing activated carbon fibers, anion exchange fibers, and polyolefin resin fibers and a carbon plastic substrate are integrally molded. This improves the holding power of halogen generated by charging in a metal halogen battery, thereby reducing self-discharge and making it possible to improve discharge characteristics.
Ｃ０従来の技術
金属ハロゲン電池、例えば亜鉛臭素電池の電極における
正極側は臭素と直接反応を行なわせるため種々の表面活
性化処理が必要である。C0 Prior Art The positive electrode side of the electrode of a metal halogen battery, such as a zinc bromine battery, requires various surface activation treatments in order to react directly with bromine.
このため近年、亜鉛臭素電池の正極材として活性炭素繊
維を用い、これを熱圧着によりカーボンプラスチック基
板へ張り付ける方法が多く利用されている。For this reason, in recent years, a method of using activated carbon fiber as the positive electrode material of zinc-bromine batteries and attaching it to a carbon plastic substrate by thermocompression bonding has been widely used.
この方法は正極側の活性度が未処理のものに比し、著し
く向上し、特に放電過電圧の減少が大きく、そのため電
圧効率を増加させる点で注目される。This method is attracting attention because the activity on the positive electrode side is significantly improved compared to the untreated one, and in particular, the discharge overvoltage is greatly reduced, thereby increasing the voltage efficiency.
Ｄ１発明が解決しようとする課題
しかしながら、金属ハロゲン電池システムにおける総電
解液量が一定の又は液循環型に比し極めて少ない状態の
液静止型では充電により発生したハロゲン分子又はハロ
ゲン分子が、電解液中に加えられているハロゲン剛化剤
と結合して生成するハロゲンコンプレックスを電極表面
に保持させる機能が重要である。D1 Problem to be Solved by the Invention However, in a stationary liquid type where the total amount of electrolyte in a metal halogen battery system is constant or extremely small compared to a liquid circulating type, halogen molecules or halogen molecules generated during charging are An important function is to hold the halogen complex formed by combining with the halogen stiffening agent added therein on the electrode surface.
従って、本発明はハロゲン又はハロゲンコンプレックス
保持力をも向上させ、これにより臭素等がセパレーター
を通過して亜鉛極と反応することに・より生ずる自己放
電を減少し、放電特性を向上させることにより、液静止
型電池システムにおける電圧効率を増加させることを可
能とする金属ノ＼ロゲン電池の正極電極を提供すること
を目的とする。Therefore, the present invention also improves halogen or halogen complex retention, thereby reducing self-discharge caused by bromine etc. passing through the separator and reacting with the zinc electrode, and improving discharge characteristics. An object of the present invention is to provide a positive electrode for a metallogen battery that makes it possible to increase the voltage efficiency in a liquid stationary battery system.
Ｅ１課題を解決するための手段
本発明者らは金属ハロゲン電池における正極側でハロゲ
ンがＸ−（ハロゲン分子）又はＱ＋・Ｘ−（ハロゲン分
子が電解液中に加えられているハロゲン剛化剤と結合し
て生成するハロゲンコンプレックス）として存在するこ
とに着目し、鋭意研究した結果、正極材としてアニオン
交換繊維を使用することでハロゲン分子等を保持させる
ことに成功し、本発明を完成した。E1 Means for Solving the Problem The present inventors have developed a method in which halogen is X- (halogen molecules) or Q+/X- (halogen molecules are added to the electrolyte as a halogen stiffening agent) on the positive electrode side of a metal halogen battery. Focusing on the fact that halogen molecules exist as halogen complexes, which are formed by bonding, and as a result of intensive research, we succeeded in retaining halogen molecules by using anion exchange fibers as a positive electrode material, and completed the present invention.
即ち、本発明は活性炭素繊維、アニオン交換繊維及びポ
リオレフィン系樹脂繊維を混合してシート状に成形され
た正極材とカーボンプラスチック基板とを一体として成
形することを、その解決手段としている。That is, the present invention solves the problem by integrally molding a positive electrode material formed into a sheet by mixing activated carbon fibers, anion exchange fibers, and polyolefin resin fibers and a carbon plastic substrate.
以下、本発明について更に詳細に説明する。The present invention will be explained in more detail below.
まず本発明に使用する活性炭素繊維としては例えばフェ
ノール系、アクリル系、ＰＶＡ系及びピッチ系などが挙
げられ、好ましくはフェノール系活性炭素繊維、より好
ましくは比表面積１５００〜２０００ｍ２／ｇのフェノ
ール系活性炭素繊維を用いる。これにより活性炭素が有
するミクロボアを反応活性点として電解液中で有効に作
用して過電圧を減少できる。First, the activated carbon fibers used in the present invention include, for example, phenol-based, acrylic-based, PVA-based, and pitch-based activated carbon fibers, preferably phenolic activated carbon fibers, and more preferably phenolic activated carbon fibers with a specific surface area of 1500 to 2000 m2/g. Uses carbon fiber. This allows the micropores of the activated carbon to act effectively in the electrolytic solution as reaction active sites, thereby reducing overvoltage.
次に、本発明において最も特徴をなすアニオン交換繊維
としては、活性物質であるハロゲン分子を保持できる機
能を有するものであればいずれの材料を用いても良いが
、好ましくは四級アミンの官能基を有するアニオン交換
繊維を用いる。これにより充電時に形成されたハロゲン
を電極表面で保持することができる。このことはハロゲ
ンがセパレーターを通過して亜鉛極と反応することによ
り生ずる自己放電を減少し、これにより放電特性を向上
させることができることを意味する。Next, as the anion exchange fiber, which is the most characteristic feature of the present invention, any material can be used as long as it has the function of retaining halogen molecules, which are active substances, but it is preferable to use quaternary amine functional groups. An anion exchange fiber having the following properties is used. This allows the halogen formed during charging to be retained on the electrode surface. This means that the self-discharge caused by the halogen passing through the separator and reacting with the zinc electrode can be reduced, thereby improving the discharge characteristics.
更に、本発明ではポリオレフィン系樹脂、例えばポリエ
チレン繊維、チョップ又はポリプロピレン繊維、チョッ
プ、好ましくはポリエチレン繊維を上記活性炭素繊維と
アニオン交換繊維を混合し、シート状に固めるためのバ
インダーとして用いる。Further, in the present invention, a polyolefin resin such as polyethylene fiber, chopped or polypropylene fiber, chopped, preferably polyethylene fiber is used as a binder for mixing the activated carbon fiber and anion exchange fiber and solidifying the mixture into a sheet.
これによりアニオン交換繊維やポリオレフィン繊維で形
成されたトランジショナルボアが電解液中で有効に作用
し、従来の正極材に比し充放電特性がより一層向上でき
る。As a result, the transitional bores made of anion exchange fibers or polyolefin fibers can effectively act in the electrolyte, and the charging and discharging characteristics can be further improved compared to conventional cathode materials.
以上の活性炭素繊維、カチオン交換繊維及びポリオレフ
ィン系繊維を適当な重合比、好ましくはそれぞれ５：２
：３の割合で混合分散させ、７０〜３００℃好ましくは
１３０℃で圧着してシート状に成形し、正極材とする。The above activated carbon fibers, cation exchange fibers and polyolefin fibers are combined in an appropriate polymerization ratio, preferably 5:2, respectively.
:3 and then press-bonded at 70 to 300°C, preferably 130°C, to form a sheet to form a positive electrode material.
この正極材は、シート状であればよく、例えば、編物、
織物、不織布あるいは抄紙状のものを使用することが出
来る。This positive electrode material may be in the form of a sheet, for example, a knitted material,
Woven, non-woven or paper-like materials can be used.
この場合、編物、織物、不織布あるいは抄紙を構成する
各繊維は、ファイバ状あるいは、チョップ状等から任意
に選択することが用来る。In this case, the fibers constituting the knitted fabric, woven fabric, nonwoven fabric, or paper may be arbitrarily selected from fibers, chopped fibers, and the like.
こうして得られるシート状にした正極材をカーボンプラ
スチック電極基板に熱圧着して一体成形し、金属ハロゲ
ン電池、例えば亜鉛臭素電池などの正極電極として用い
る。The sheet-shaped positive electrode material thus obtained is thermocompressed and integrally molded onto a carbon plastic electrode substrate, and used as a positive electrode for a metal halogen battery, such as a zinc bromine battery.
Ｆ、実施例
以下、本発明に係る金属ハロゲン電池の正極電極の詳細
を実施例に基づいて説明する。F. Examples Hereinafter, details of the positive electrode of the metal halogen battery according to the present invention will be explained based on examples.
実施例１
比表面積１５００〜２０００ｍ２／ｇのフェノール系活
性炭素繊維（日本カイノール製、ファイバー形態）、ア
ニオン交換繊維にチビ製、チョップ形態）、及びポリエ
チレン繊維（昭和電工製、ファイバー形態）をそれぞれ
５：２＋３の割合で混合分散させたものを抄紙状に成形
してシートを得た。Example 1 5 each of phenolic activated carbon fiber (manufactured by Nippon Kynol, fiber form) with a specific surface area of 1500 to 2000 m2/g, anion exchange fiber manufactured by Chibi (chopped form), and polyethylene fiber (manufactured by Showa Denko, fiber form) : The mixture was mixed and dispersed in a ratio of 2+3 and formed into a paper-like shape to obtain a sheet.
次に得られたシートをカーボンプラスチック電極基板に
熱圧着させ本発明に係る金属ハロゲン電池の正極電極（
Ａ）とした。Next, the obtained sheet was thermocompression bonded to a carbon plastic electrode substrate, and the positive electrode of the metal halide battery according to the present invention (
A).
更に比表面積１５００〜２０００ｍ２／ｇのフェノール
系活性炭素繊維のみを同様にシート状とし、これをカー
ボンプラスチック基板に熱圧着した正極電極（Ｂ）を比
較例として用いた。Furthermore, a positive electrode (B) was used as a comparative example, in which only a phenolic activated carbon fiber having a specific surface area of 1500 to 2000 m2/g was formed into a sheet and this was thermocompression bonded to a carbon plastic substrate.
このようにして得られた本発明に係る正極電極（Ａ）と
従来の正極電極（Ｂ）を用いて、それぞれ単セル（Ａ）
及び（Ｂ）を構成し、液静止型電池として充放電特性を
検討した。Using the thus obtained positive electrode (A) according to the present invention and the conventional positive electrode (B), a single cell (A) was prepared.
and (B) were constructed, and the charging and discharging characteristics were investigated as a liquid stationary battery.
その結果を第１図に示す。The results are shown in FIG.
第１図に示すように本発明に係る正極電極（Ａ）を用い
た単セル（Ａ）の方が従来の正極電極（Ｂ）に比し充放
電特性が優れていることがわかる。このことはアニオン
交換繊維を有する正極電極（Ａ、）は臭素保持力がよく
そのため正極活性層内部及びその近傍に発生臭素を保ち
、これにより臭素の拡散による自己放電を防止できるた
めである。As shown in FIG. 1, it can be seen that the single cell (A) using the positive electrode (A) according to the present invention has better charge/discharge characteristics than the conventional positive electrode (B). This is because the positive electrode (A,) having anion exchange fibers has a good bromine retention ability, and therefore keeps generated bromine inside and near the positive active layer, thereby preventing self-discharge due to bromine diffusion.
なお、亜鉛臭素電池の電解液量は２００ ｃ ｃ。The amount of electrolyte in the zinc bromine battery is 200 cc.
セパレーターは多孔質膜を用い、負極に亜鉛板を用い、
その電極面積を３００ｆｆ１２とした。また、第１図に
示した充放電特性は初期の電解液濃度が３Ｍ／／ＺｎＢ
ｒ２ と０．１ Ｍ／Ｉ Ｂ ｒ ２で１０ｍＡ／ｃＩ
２の電流密度で２５℃、４時間充電したときの測定値で
ある。A porous membrane is used as the separator, and a zinc plate is used as the negative electrode.
The electrode area was set to 300ff12. In addition, the charge/discharge characteristics shown in Figure 1 show that the initial electrolyte concentration is 3M//ZnB.
10 mA/cI at r2 and 0.1 M/I B r2
These are the measured values when charging was performed at 25° C. for 4 hours at a current density of 2.
Ｇ０発明の効果
本発明は上述のように構成することにより、ハロゲン保
持能力を向上でき、そのため正極側で発生したハロゲン
がセパレーターを通過して負極側の亜鉛と反応すること
により生ずる自己放電を減少でき、これにより金属ハロ
ゲン電池の充放電特性の向上を可能とする。G0 Effects of the Invention By having the structure as described above, the present invention can improve the halogen retention ability, thereby reducing self-discharge caused by halogen generated on the positive electrode side passing through the separator and reacting with zinc on the negative electrode side. This makes it possible to improve the charging and discharging characteristics of metal halogen batteries.
従って本発明に係る金属ハロゲン電池の正極電極を使用
した金属ハロゲン電池によれば、電池システムにおける
総電解液量が一定の又は液循環型に比し極めて少ない状
態の液静止型でも高い電圧効率を得ることができる。Therefore, according to the metal halogen battery using the positive electrode of the metal halogen battery according to the present invention, high voltage efficiency can be achieved even in a liquid stationary type in which the total amount of electrolyte in the battery system is constant or extremely small compared to a liquid circulation type. Obtainable.
第１図は本発明に係る正極電極（Ａ）と従来の正極電極
（Ｂ）との充放電特性を示すグラフである。
第１図FIG. 1 is a graph showing the charge/discharge characteristics of the positive electrode (A) according to the present invention and the conventional positive electrode (B). Figure 1
Claims (1)
ィン系樹脂繊維を混合してシート状に成形された正極材
とカーボンプラスチック基板とを一体として成形するこ
とを特徴とする金属ハロゲン電池の正極電極。(1) A positive electrode for a metal halogen battery, characterized by integrally molding a positive electrode material formed into a sheet by mixing activated carbon fibers, anion exchange fibers, and polyolefin resin fibers and a carbon plastic substrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2164385A JP3003167B2 (en) | 1990-06-22 | 1990-06-22 | Positive electrode of metal halogen battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2164385A JP3003167B2 (en) | 1990-06-22 | 1990-06-22 | Positive electrode of metal halogen battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0456068A true JPH0456068A (en) | 1992-02-24 |
| JP3003167B2 JP3003167B2 (en) | 2000-01-24 |
Family
ID=15792126
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2164385A Expired - Fee Related JP3003167B2 (en) | 1990-06-22 | 1990-06-22 | Positive electrode of metal halogen battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3003167B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6399234A (en) * | 1986-06-02 | 1988-04-30 | Toray Ind Inc | Polyimide coating agent composition |
-
1990
- 1990-06-22 JP JP2164385A patent/JP3003167B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6399234A (en) * | 1986-06-02 | 1988-04-30 | Toray Ind Inc | Polyimide coating agent composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3003167B2 (en) | 2000-01-24 |
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