JPS587773A - Zinc-halogen cell - Google Patents
Zinc-halogen cellInfo
- Publication number
- JPS587773A JPS587773A JP56105640A JP10564081A JPS587773A JP S587773 A JPS587773 A JP S587773A JP 56105640 A JP56105640 A JP 56105640A JP 10564081 A JP10564081 A JP 10564081A JP S587773 A JPS587773 A JP S587773A
- Authority
- JP
- Japan
- Prior art keywords
- zinc
- halogen
- electrolyte
- period
- dendrite
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/365—Zinc-halogen accumulators
-
- 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
Abstract
Description
【発明の詳細な説明】
本発明は亜鉛−ハロゲン電池に関するもので、特に亜鉛
のデ゜ンドライト析出を防止したものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a zinc-halogen battery, and in particular to one in which dendrite precipitation of zinc is prevented.
亜鉛−ハロゲン電池は、亜鉛極を負極、／％ロゲン極を
正極とし、ハロゲン化亜鉛を主成分とする水溶液を電解
液に用いて、充電時に負極に亜鉛を析出し、放電時に析
出した亜鉛を溶解させる電池であり、亜鉛は負極活物質
として安価で、エネルギー密度が高く、優れた特性を示
す。A zinc-halogen battery uses a zinc electrode as a negative electrode and a % halogen electrode as a positive electrode, and uses an aqueous solution containing zinc halide as its main component as an electrolyte. Zinc is deposited on the negative electrode during charging, and the deposited zinc is removed during discharging. It is a battery that is dissolved, and zinc is inexpensive as a negative electrode active material, has high energy density, and exhibits excellent characteristics.
−しかしながら充電時に亜鉛は平滑に析出せず、−１７
状、いわゆるデンドライト析出となって正短絡したり、
析出したものが脱落するなど，リ１欠点がある。亜鉛の
デンドライト析出防止にＮｕてはアルカリ系の電池、た
とえばニッケルη一亜鉛電池などにおいて既に多く検討
され、有１効な添加剤が見い出されている。しかしなが
ら亜鉛一ハロゲン電池は酸性電解液を使用する電池であ
り、酸性系における添加・剤の挙動はアルカリ系とはま
ったく異っている。たとえばアルカリ系電池でデンドラ
イト析出防止に効果があると報告されている鉛を酸性系
電池に添加するとデンドライト析出はかえって助長され
てしまう。従って酸性系電池で有効な添加剤はアルカリ
系とはまったく別（二見い出すことが必要である。亜鉛
一ハロゲン電池の添加剤としては、最近有機化合物であ
る可溶性ポリエーテル化合物やアミ゛ンとエビクロルヒ
ドリンとの反応生成物を電解液に添加する方法が提案さ
れ、実際｛二相当の効果を上げている。しかしながら亜
鉛一ノ１ロゲン電池の電解液には極めて反応性が大きい
ｍゲカ高濃度で溶解してしるため前己有化合物は使用中
塩素により反応又は分解を起、亜鉛のデンドライト析出
を防止する効果が失なわれ、初期の効果を長期間持続す
ることができなかった。-However, zinc does not deposit smoothly during charging, -17
This may result in so-called dendrite precipitation, resulting in a positive short circuit, or
There is one drawback, such as the precipitated material falling off. Many studies have already been conducted to prevent the precipitation of zinc dendrites in alkaline batteries, such as nickel η-zinc batteries, and effective additives have been found. However, a zinc-halogen battery uses an acidic electrolyte, and the behavior of additives and agents in an acidic system is completely different from that in an alkaline system. For example, if lead, which is reported to be effective in preventing dendrite precipitation in alkaline batteries, is added to acidic batteries, dendrite precipitation will be accelerated. Therefore, it is necessary to find effective additives for acid-based batteries that are completely different from those for alkaline-based batteries.As additives for zinc-halogen batteries, recently organic compounds such as soluble polyether compounds, amines, and shrimp have been used as additives for zinc-halogen batteries. A method has been proposed in which a reaction product with chlorohydrin is added to the electrolyte, and in fact it has achieved a comparable effect. Since the former self-containing compound dissolves at a high concentration, it reacts or decomposes with chlorine during use, and the effect of preventing zinc dendrite precipitation is lost, making it impossible to maintain the initial effect for a long period of time.
本発明はこれに鑑み、高い耐ハロゲン性が期１される無
機早添加剤って電池の充電時おける亜鉛のデンドライト
析出防止効果を鋭研究の結果、長期間安定して亜鉛のデ
ンドラト析出を起さない亜鉛−ハロゲン電池を開発した
もので、亜鉛極を負極、ハロゲン極を正極ハロゲン化亜
鉛を主成分とする水溶液を電解液とする電池において、
電解液に周期律表第璽族第４〜第６周期に属する元素又
はその化合物を１種又は２種以上添加したことを特徴と
するものである。In view of this, the present invention was developed as a result of intensive research into the effect of inorganic early additives, which are expected to have high halogen resistance, on the prevention of zinc dendrite precipitation during battery charging. A zinc-halogen battery has been developed in which the zinc electrode is the negative electrode and the halogen electrode is the positive electrode.
The electrolytic solution is characterized in that one or more elements belonging to the fourth to sixth periods of the fifth group of the periodic table or compounds thereof are added to the electrolytic solution.
即ち本発明は、亜鉛極を正極、ハロゲン極を負極とし、
八アゲン化亜鉛を主成分とする水溶液を電解液に用い、
充電時に負極に亜鉛を析出し、放電時に析出した亜鉛を
溶解させる亜鉛一ハロゲン電池の電解液《二、周期律表
第璽族第４〜第６周期に属する元素、例えばガリウム（
Ｇａ）、インジウム（Ｉｎ）、タリウムＣＴｌ）、又は
その化合物例えば塩化物、硫酸塩、硝酸塩の何れが１種
又は２種以上を添加したものである。That is, the present invention uses a zinc electrode as a positive electrode and a halogen electrode as a negative electrode,
Using an aqueous solution containing zinc octagenide as the main component,
Electrolyte solution for zinc-halogen batteries that deposits zinc on the negative electrode during charging and dissolves the zinc deposited during discharge.
One or more of Ga), indium (In), thallium (CTl), or compounds thereof such as chlorides, sulfates, and nitrates are added.
周期律表第ｌ族第４〜１６周期に属する元素又はその化
合物は、何れも電解液中に溶けて単独のカテオン又は錯
イオンを形成し、電池の充電時における亜鉛のデンドラ
イト析出を防止する。しかしてこれ等元素又は化合物の
添加濃度１１種又は２種以上のそれそれの元素つりｌＯ
−’〜ｌｏ−’ｍｏｌ／ｌの範囲で用いるコトがＢｉ．
！，Ｉましく、これより添加濃度が薄いと無添加の一
場合と同様亜鉛のデンドライト析出が起り、また添加濃
度が濃いと添加しだ元素が金属として析出し、電池の充
放電効率を低下する。Any element or compound thereof belonging to Group I, Periods 4 to 16 of the Periodic Table dissolves in the electrolytic solution to form a single cation or a complex ion, thereby preventing dendrite precipitation of zinc during battery charging. However, the addition concentration of these elements or compounds of 11 types or 2 or more types is 1O
Bi.
! However, if the additive concentration is lower than this, dendrite precipitation of zinc will occur as in the case without additives, and if the additive concentration is higher than this, the added element will precipitate as a metal, reducing the charging and discharging efficiency of the battery. .
電解液には従来同様八ロゲン化亜鉛単独の水溶液又はこ
れに電導性を増すための強電解質としてハロゲン化ナト
リウム、ハロゲン化カリウム等を加えたもので、ｐＨＯ
〜５、望ましくは０１〜ｌの範囲のものが用いられる。As before, the electrolytic solution is an aqueous solution of zinc octahalide alone, or an aqueous solution containing sodium halide, potassium halide, etc. as a strong electrolyte to increase conductivity.
-5, preferably in the range of 01-1.
また電流密度の範囲は５〜１００ｍＡ／ＴＩ、電解液の
温度は特に限定するものではないが、室温から７０℃位
までが望ましい。Further, the current density range is 5 to 100 mA/TI, and the temperature of the electrolytic solution is not particularly limited, but is preferably from room temperature to about 70°C.
尚インジウムを添加する場合には、インジウムを塩酸、
硫酸等の酸性溶液に溶解し、ｐＨを０〜５に調整してか
ら電解液に添加混合すればよい。When adding indium, add indium to hydrochloric acid,
What is necessary is just to dissolve it in acidic solutions, such as sulfuric acid, and to adjust pH to 0-5, and to add it to an electrolyte solution, and to mix.
以下本発明を実施例について説明する。The present invention will be described below with reference to Examples.
実施例（１）
］多孔質グフファイト板を正極硬質グフファト板を負極
とし、電解液に塩化亜鉛２ｍＯｌ／１塩化カリウムｌｍ
ｏｌ／ｌをｌ含む水溶液を用い、一で■れ１周期律表第
ｌ族第６周期のタノウムの塩物を１０−’ｍ０１／ｌ添
加し、ｐＨを０．ＩＣ調整だ。この電池を用いて電流密
度３０ｍＡ／＋ｆ、一“一
液温２７℃で４時間充電し、正極上に亜鉛を析出させた
ところ参考写真１お゛よび第１図に示すように正極ｌ上
の電析亜鉛２には亜鉛のデンド，−一ヨイト析出は全く
認められなかった。またこれ４１放電した後同一条件で
再充電することを４０・（
．嗜繰返したが亜鉛のデンドライト析出は全く認一．！
−’Ｊられなかった。Example (1)] A porous goufite plate was used as the positive electrode, a hard goufite plate was used as the negative electrode, and the electrolyte contained 2 mOl of zinc chloride/1 lm of potassium chloride.
Using an aqueous solution containing 1 ol/l, 10-'m01/l of a salt of tanium, which belongs to group I, period 6 of the periodic table, is added at once, and the pH is adjusted to 0. It's IC adjustment. This battery was charged for 4 hours at a current density of 30 mA/+f and a liquid temperature of 27°C to deposit zinc on the positive electrode. No dendrite or -1-yoite precipitation of zinc was observed in the deposited zinc 2.Also, after 41 discharges, recharging under the same conditions was repeated, but no dendrite precipitation of zinc was observed. one.!
-'J couldn't do it.
比較のため、電解液にタリウムの塩化物を添加すること
なく、ｐＨを０１に調整して同一条件で充電し、正極上
に亜鉛を析出させたところ、参考写真２および第２図に
示すよう《二正極１上の電析亜鉛２には亜鉛のデンドラ
イト析出３が生じ、デンドライトの長さは約２ｍ１１で
あった。For comparison, we adjusted the pH to 01 and charged the electrolyte under the same conditions without adding thallium chloride to deposit zinc on the positive electrode, as shown in Reference Photo 2 and Figure 2. <<A dendrite precipitation 3 of zinc was formed on the deposited zinc 2 on the two positive electrodes 1, and the length of the dendrite was about 2 m11.
またタリウムの塩化物を添加することなく、電解液１二
非イオン系界面活性剤エマルゲン９０９（商品名、花王
石鹸）を０．ＯＩＶＯｌ％添加し、ｐＨを０．１に調整
して同一条件で充電し、正極＝２ｐに亜鉛を析出させた
ところ亜鉛のデノトライ析出は認められなかった。しか
し同様の充放｛，＋；，’Ｉ、奥を繰返したところ５回
目で亜鉛のデンドライ摺］析出が認められた。In addition, without adding thallium chloride, the electrolyte solution 12 nonionic surfactant Emulgen 909 (trade name, Kao Soap) was added at 0.00%. When OIVOl% was added, the pH was adjusted to 0.1, the battery was charged under the same conditions, and zinc was deposited on the positive electrode=2p, no denotrite precipitation of zinc was observed. However, when the same charging and discharging {,+;,'I, inner side was repeated, the deposition of zinc dendrite was observed at the fifth time.
１１
１“ｔ施例（２）
冒，，’ｉ−ｉｊ実施例（１）において、タリウムの塩
化物に代え１、周期律表第璽族弟５周期のインジウムの
塩化物と同族第６周期のタリウムの塩化物をそれぞれ１
ｏ−’ｍｏｌ／ｌ添加し、ｐＨを０．１１ｍ調整してか
ら実施例（１）と同一条件で充電し、正極に亜鉛を析出
させたところ、参考写真３および第一に示すように正極
ｌ上の亜鉛電析２には亜鉛のデンドライト析出は全く認
められながった。また同一条件の充放電を４０回繰り返
したが、亜鉛のデンドライト析出は全く認められず、長
期間亜鉛のデンドライト析出を防止し得ることが判る。11 1"t Example (2) In Example (1), in place of the chloride of thallium, 1, the chloride of indium in the fifth period of the fifth group of the fifth group of the periodic table and the sixth period of the same group. 1 each of thallium chloride
o-'mol/l was added, the pH was adjusted to 0.11m, and then charging was performed under the same conditions as in Example (1) to deposit zinc on the positive electrode. As shown in Reference Photo 3 and the first example, the positive electrode No dendrite precipitation of zinc was observed at all in the zinc electrodeposition 2 on the surface of the metal. Further, charging and discharging under the same conditions were repeated 40 times, but no zinc dendrite precipitation was observed, indicating that zinc dendrite precipitation could be prevented for a long period of time.
実施例（３）
周期律表弟■族第５周期のインジウム１１Ｉ９を１ｍｏ
ｌ／Ｉｔの塩酸２０ｍ７に溶解し、これに蒸留水を加え
、更に塩化亜鉛、塩化カリウム及び塩酸を加えて、塩化
亜鉛濃度を２ｍＯｌ／１！、塩化カリウムを１ｍｏＪ／
ｌ，ｐＨを０．１に調整して電］７液を作成した。この
電解液を用い、正極に多質グラファイト板、負極に硬質
グラファイト」板を用いて電池を形成し、実施例（１）
と同じ条件で充電し、正極上に亜鉛を析出させたところ
、亜鉛のデンドライト析出は全く認められなかった。ま
た実施例（１１と同様ｉ二して充放電を４０回繰り返し
たが、亜鉛のデンドライト析出は全く１められな力った
。Example (3) 1 mo of indium 11I9 in the 5th period of group II of the periodic table
Dissolve the zinc chloride concentration in 20 m7 of hydrochloric acid (1/It), add distilled water, and further add zinc chloride, potassium chloride, and hydrochloric acid to bring the concentration of zinc chloride to 2 mOl/1! , potassium chloride 1 moJ/
7 liquid was prepared by adjusting the pH to 0.1. Using this electrolyte, a battery was formed using a polymorphous graphite plate for the positive electrode and a hard graphite plate for the negative electrode, and Example (1)
When the battery was charged under the same conditions as above and zinc was deposited on the positive electrode, no zinc dendrite precipitation was observed at all. Further, charging and discharging were repeated 40 times in the same manner as in Example 11, but no zinc dendrite precipitation occurred at all.
このように本発明電池は、亜鉛のデンドライー′・“；
ｌ
・」析Ｉ′１″′長期間防′Ｊ″Ｌ＊ｔ（７）”Ｃ・９
池０充放電７・・１
一一一効率を高め、電池の寿命を著しく向上し得る等、
顕著な効果を奏するものである。In this way, the battery of the present invention has zinc dendrites'.
l ・"AnalysisI'1"'Long-term protection'J"L*t(7)"C・9
Battery 0 Charging/discharging 7...1 111 Increase efficiency and significantly improve battery life, etc.
This has a remarkable effect.
第１図はタリウムを添加した場合の電析状態断面図、第
２図は無添加の場合の電析状態断面図、第３図はインジ
ウムータリウムニ成分系を添加した場合の電析状態断面
図である。Figure 1 is a sectional view of the electrodeposition state when thallium is added, Figure 2 is a sectional view of the electrodeposition state when no addition is made, and Figure 3 is the electrodeposition state when the indium-thallium two-component system is added. FIG.
Claims (1)
成分とする水溶液を電解液とする電坤において、電解液
に周期律表第璽族弟４〜第′６周期に属する元素又はそ
の化合物を１種又は２一種以上添加したことを特徴と丁
る亜鉛−ハロゲン電池。In an electrolyte in which a bone lead electrode is used as a negative electrode, a halogen electrode is used as a positive electrode, and an aqueous solution containing zinc octahalide as a main component is used as an electrolyte, the electrolyte contains an element belonging to the 4th to '6th periods of the 1st group of the periodic table, or A zinc-halogen battery characterized by adding one or more of these compounds.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56105640A JPS587773A (en) | 1981-07-08 | 1981-07-08 | Zinc-halogen cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56105640A JPS587773A (en) | 1981-07-08 | 1981-07-08 | Zinc-halogen cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS587773A true JPS587773A (en) | 1983-01-17 |
Family
ID=14413050
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56105640A Pending JPS587773A (en) | 1981-07-08 | 1981-07-08 | Zinc-halogen cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS587773A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60114165U (en) * | 1984-01-09 | 1985-08-02 | 株式会社 昭和丸筒 | Hard bobbin for thread winding |
| US10056636B1 (en) | 2013-10-03 | 2018-08-21 | Primus Power Corporation | Electrolyte compositions for use in a metal-halogen flow battery |
| US10062918B2 (en) | 2015-03-19 | 2018-08-28 | Primus Power Corporation | Flow battery electrolyte compositions containing a chelating agent and a metal plating enhancer |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5227338A (en) * | 1975-08-27 | 1977-03-01 | Advantest Corp | High harmonic waves selection unit |
-
1981
- 1981-07-08 JP JP56105640A patent/JPS587773A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5227338A (en) * | 1975-08-27 | 1977-03-01 | Advantest Corp | High harmonic waves selection unit |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60114165U (en) * | 1984-01-09 | 1985-08-02 | 株式会社 昭和丸筒 | Hard bobbin for thread winding |
| US10056636B1 (en) | 2013-10-03 | 2018-08-21 | Primus Power Corporation | Electrolyte compositions for use in a metal-halogen flow battery |
| US10062918B2 (en) | 2015-03-19 | 2018-08-28 | Primus Power Corporation | Flow battery electrolyte compositions containing a chelating agent and a metal plating enhancer |
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