JPH0441472B2 - - Google Patents
Info
- Publication number
- JPH0441472B2 JPH0441472B2 JP57089762A JP8976282A JPH0441472B2 JP H0441472 B2 JPH0441472 B2 JP H0441472B2 JP 57089762 A JP57089762 A JP 57089762A JP 8976282 A JP8976282 A JP 8976282A JP H0441472 B2 JPH0441472 B2 JP H0441472B2
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- zinc
- hydrobromide
- electrolyte
- concentration
- 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
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Hybrid Cells (AREA)
Description
Ａ 産業上の利用分野
本発明は、電解液循環型亜鉛−臭素二次電池、
さらに詳しくは、負極面において亜鉛が樹枝状に
析出し成長する（いわゆるデンドライト）のを防
ぐことのできる負極電界液を用いた亜鉛−臭素二
次電池に関するものである。
Ｂ 発明の概要
本発明は、デンドライトの発生、成長を防止し
て長期サイクルに耐えうる亜鉛−臭素二次電池を
得るために、前記亜鉛−臭素二次電池の負極電解
液を、1.0vol％〜飽和濃度のトリプロピルアミン
臭化水素酸塩もしくは0.050vol％〜飽和濃度のト
リブチルアミン臭化水素酸塩を含有するものとす
る。
Ｃ 従来の技術
電解液循環型亜鉛−臭素二次電池の基本的構成
は、図に示した如きのものであつて、図中１は電
池反応槽、２は正極室、３は負極室、４は隔膜
（セパレータ）、５は正極、６は負極、７は正極電
解液貯槽、８は負極電解液貯槽、９，１０はバル
ブ、１１はデンドライトである。
上述の如き電池において、充電を行うときに
は、図中（＋）で示した正極側では臭素が、一方
の（−）で示した負極面上には亜鉛が析出する。
正極で析出した臭素は、電解液中に溶解し循環
するだけであるが、負極面上で析出する亜鉛は必
ずしもその面を平滑に保つたまま生成するもので
はなく、大小さまざまな樹枝状の形態を形成させ
ながら析出する（以下これをデンドライトと称す
る）ことがあり問題となる。
負極面上におけるデンドライトの形成過程は、
概ね次の如き段階によるものと考えられる。すな
わち、充電初期において負極面上に析出する金属
亜鉛は、必ずしも電極表面に亘つて一様に生成す
るものではなくスポツト的に電着するため、この
時点で既にデンドライトの核ともいうべきものが
形成されるのである。従つて、このままの状態で
充電が継続されるとスポツト的に形成されている
核のそれぞれに対して優先的に電着が行なわれ、
その結果これが最終的にデンドライトとなるので
ある。
Ｄ 発明が解決しようとする課題
前述の如く、負極面上でのデンドライトが成長
すると、電界が集中し、デンドライトの成長速度
が大きくなると共に亜鉛の負極面と新鮮な電解液
との接触の機会が少なくなり電池効率を低下させ
るばかりでなく、このデンドライトが非常に脆い
ものであることから比較的軽微な応力によつて電
極から離脱し、そしてこのようにして脱落したデ
ンドライトは電解液循環パイプをつまらせポンプ
効率を低下させる原因となる。
また、仮にこのデンドライトが電極から離脱を
せずに成長を続けた場合には、隔膜を破つたり、
あるいは更にその成長が極端に進行した場合には
正極面と直接接触して短絡を起し、結局電池を破
壊するに至る恐れがある。従つてデンドライトの
生成抑制は、極めて重要な要件の一つとなつてい
る。
このような要請から、従来よりデンドライト抑
制剤について種々検討が加えられ、例えばイオン
性または非イオン性界面活性剤、亜鉛メツキ光沢
剤などが使用されている。しかしながら、これら
は耐臭素性に改良すべき点であり、長期間に亘る
サイクル使用に対して安定した性能を維持しつづ
けることができず、またデンドライト抑制という
本来の効果の上でも未だ充分なものではなかつ
た。
本発明は、かかるる点に鑑みてなされたもので
あり、デンドライトの発生成長を防止し、良好な
亜鉛の電着状態を確保した状態で長期間にわたる
サイクル運転を行うことのできる亜鉛−臭素二次
電池を提供することを目的とするものである。
Ｅ 課題を解決するための手段
上記目的の達成のため、本発明に係る電解液循
環型亜鉛−臭素二次電池では、前記電池の負極側
に循環される電解液が、1.0vol％〜飽和トリプロ
ピルアミン臭化水素酸塩もしくは0.050vol％〜飽
和濃度のトリブチルアミン臭化水素酸塩を含有す
るものである。
Ｆ 作用
本発明の要旨とするところは、亜鉛−臭素二次
電池において、1.0vol％〜飽和トリプロピルアミ
ン臭化水素酸塩もしくは0.050vol％〜飽和濃度の
トリブチルアミン臭化水素酸塩を含有して成る負
極電解液を用いた亜鉛−臭素二次電池である。
トリプロピルアミン臭化水素酸塩の濃度は
1.0vol％〜飽和濃度の間で適宜選択し、トリブチ
ルアミン臭化水素酸塩の濃度は0.2vol％程度とす
るのが好ましい。
本発明においては、例えば60〜80mA／cm2とい
う高電流密度における充電であつても充分にデン
ドライト抑制効果を期待することができるのであ
る。
Ｇ 実施例
以下に、本発明の実施例を説明する。
実施例 １
電極としてカーボンプラスチツク電極、陽イオ
ン交換膜セパレータから構成された電池において
負極電解液として臭化亜鉛3mol溶液を用い、こ
れに表示量のトリプロピルアミン臭化水素酸塩を
加え（PH2.57）、表示の電流密度により
360mAH／cm2の充電電気量になるまで充電を行
つて下表の結果を得た。
A. Industrial Application Field The present invention relates to an electrolyte circulation type zinc-bromine secondary battery,
More specifically, the present invention relates to a zinc-bromine secondary battery using a negative electrode electrolyte that can prevent zinc from depositing and growing in dendritic forms (so-called dendrites) on the negative electrode surface. B. Summary of the Invention The present invention aims to prevent the generation and growth of dendrites and to obtain a zinc-bromine secondary battery that can withstand long-term cycles. It shall contain tripropylamine hydrobromide at a saturation concentration or tributylamine hydrobromide at a saturation concentration of 0.050vol% to 0.050vol%. C. Prior Art The basic structure of an electrolyte circulation type zinc-bromine secondary battery is as shown in the figure, in which 1 is a battery reaction tank, 2 is a positive electrode chamber, 3 is a negative electrode chamber, and 4 is a battery reaction tank. is a diaphragm (separator), 5 is a positive electrode, 6 is a negative electrode, 7 is a positive electrode electrolyte storage tank, 8 is a negative electrode electrolyte storage tank, 9 and 10 are valves, and 11 is a dendrite. When charging the battery as described above, bromine is deposited on the positive electrode side indicated by (+) in the figure, and zinc is deposited on the negative electrode side indicated by (-). Bromine deposited on the positive electrode simply dissolves and circulates in the electrolyte, but the zinc deposited on the negative electrode surface does not necessarily remain smooth, but has dendritic forms of various sizes. (hereinafter referred to as dendrite), which poses a problem. The formation process of dendrites on the negative electrode surface is
It is thought that this is mainly due to the following steps. In other words, the metallic zinc that precipitates on the negative electrode surface in the early stage of charging is not necessarily formed uniformly over the electrode surface, but is deposited in spots, so that what can be called dendrite nuclei has already formed at this point. It will be done. Therefore, if charging is continued in this state, electrodeposition will be preferentially performed on each spot-formed nucleus.
As a result, this finally becomes a dendrite. D Problems to be Solved by the Invention As mentioned above, when dendrites grow on the negative electrode surface, the electric field concentrates, increasing the growth rate of the dendrites and increasing the chance of contact between the zinc negative electrode surface and fresh electrolyte. Not only does this decrease the battery efficiency, but since these dendrites are extremely brittle, they can detach from the electrodes under relatively slight stress, and dendrites that have fallen off in this way can clog the electrolyte circulation pipe. This causes a decrease in pump efficiency. In addition, if this dendrite continues to grow without detaching from the electrode, it may rupture the diaphragm or
Alternatively, if the growth progresses to an extreme level, it may come into direct contact with the positive electrode surface, causing a short circuit, which may eventually destroy the battery. Therefore, suppression of dendrite formation has become one of the extremely important requirements. In response to such demands, various studies have been made on dendrite inhibitors, and for example, ionic or nonionic surfactants, galvanizing brighteners, etc. have been used. However, these are points that need to be improved in terms of bromine resistance, and stable performance cannot be maintained over long periods of cycle use, and the original effect of suppressing dendrites is still insufficient. It wasn't. The present invention has been made in view of these points, and is a zinc-bromine diamide which prevents the generation and growth of dendrites and allows long-term cycle operation while ensuring a good state of zinc electrodeposition. The purpose is to provide rechargeable batteries. E. Means for Solving the Problems In order to achieve the above object, in the electrolyte circulation type zinc-bromine secondary battery according to the present invention, the electrolyte circulated to the negative electrode side of the battery has a concentration of 1.0 vol% to saturated triglyceride. It contains propylamine hydrobromide or tributylamine hydrobromide at a concentration of 0.050 vol% to saturation. F Effect The gist of the present invention is to provide a zinc-bromine secondary battery containing tributylamine hydrobromide at a concentration of 1.0 vol% to saturated tripropylamine hydrobromide or 0.050 vol% to saturated concentration. This is a zinc-bromine secondary battery using a negative electrode electrolyte consisting of: The concentration of tripropylamine hydrobromide is
The concentration is appropriately selected between 1.0 vol% and saturation concentration, and the concentration of tributylamine hydrobromide is preferably about 0.2 vol%. In the present invention, a sufficient dendrite suppression effect can be expected even when charging at a high current density of 60 to 80 mA/ cm2 , for example. G Examples Examples of the present invention will be described below. Example 1 In a battery consisting of a carbon plastic electrode and a cation exchange membrane separator, a 3 mol solution of zinc bromide was used as the negative electrode electrolyte, and the indicated amount of tripropylamine hydrobromide was added thereto (PH2. 57), depending on the indicated current density.
The battery was charged until the amount of electricity reached 360mAH/cm 2 and the results shown in the table below were obtained.
【表】
表の結果から、本発明の電池を使用すると好結
果が得られること、特に電流密度が20〜60mA／
cm2であるときは優れた結果となることが認められ
る。
またこの場合、負極面上に金属亜鉛の析出はあ
つたが、デンドライトとはなつておらず、その形
状はコブ状であつて負極面との接着強度はもとよ
りその析出物自体の機械的な強度が充分に大きい
ものであつた。
上述の組合せのうち、臭化亜鉛3mo／、トリ
プロピルアミン4vol％の系からなる負極液を用い
て下記記載の条件による充・放電サイクル試験を
行つたが、50サイクル行つても電極面の状態には
異常が認められず、また液PHの上昇もなく安定し
た充・放電を行うことができた。
充・放電：40mA／cm2、5Hr充電、5Hr放電
電解液PH：（初期）2.5
電極：カーボンプラスチツク電極
セパレータ：多孔質膜
実施例 ２
トリプロピルアミン臭化水素酸塩の代りに表示
量のトリブチルアミン臭化水素酸塩を用いたほか
は実施例１を繰り返し下表の結果を得た。[Table] From the results in the table, it can be seen that good results can be obtained when using the battery of the present invention, especially when the current density is 20 to 60 mA/
It is observed that excellent results are obtained when the temperature is cm 2 . In this case, metallic zinc was precipitated on the negative electrode surface, but it did not become a dendrite, and its shape was knob-like, which affected not only the adhesive strength with the negative electrode surface but also the mechanical strength of the precipitate itself. was sufficiently large. Among the above combinations, a charge/discharge cycle test was conducted under the conditions described below using a negative electrode solution containing 3 mo of zinc bromide and 4 vol% of tripropylamine, but even after 50 cycles, the condition of the electrode surface remained No abnormalities were observed, and stable charging and discharging could be performed without any rise in liquid pH. Charge/discharge: 40mA/cm 2 , 5Hr charge, 5Hr discharge Electrolyte PH: (initial) 2.5 Electrode: Carbon plastic Electrode Separator: Porous membrane Example 2 In place of tripropylamine hydrobromide, the indicated amount of tripropylamine was used. Example 1 was repeated except that butylamine hydrobromide was used to obtain the results shown in the table below.
【表】
＊：実施例１と同じ
実施例１と同様にトリブチルアミン臭化水素酸
塩0.2vol％のZnBr2 3mol／負極電解液を用い
て同様の充・放電サイクル試験を行つたところ50
サイクルまで行つても電極面の状態には異常が認
められなかつた。
Ｈ 発明の効果
本発明は以上に説明したとおり、本発明の亜鉛
−臭素二次電池に用いられる負極電解液が、
1.0vol％〜飽和のトリプロピルアミン臭化水素酸
塩もしくは0.050vol％〜飽和濃度のトリブチルア
ミン臭化水素酸塩を含有して成るものであるた
め、負極面上における金属の析出の状態は極めて
安定なコブ状であり、その機械的強度も充分に高
く特に０〜60mA／cm2という高電流密度であつて
もPHの上昇も認められず、充分実用可能な状態を
維持しつづけることができるものである。[Table] *: Same as Example 1 Similar charge/discharge cycle test was conducted using tributylamine hydrobromide 0.2 vol% ZnBr 2 3 mol/negative electrode electrolyte as in Example 1.50
No abnormality was observed in the condition of the electrode surface even after the cycle. H Effects of the Invention As explained above, the negative electrode electrolyte used in the zinc-bromine secondary battery of the present invention is
Since it contains tripropylamine hydrobromide at a concentration of 1.0 vol% to saturated or tributylamine hydrobromide at a saturated concentration of 0.050 vol%, the state of metal precipitation on the negative electrode surface is extremely low. It has a stable knob shape, has a sufficiently high mechanical strength, and does not show any increase in pH even at high current densities of 0 to 60 mA/ cm2 , and can continue to maintain a sufficiently usable state. It is something.
図は、電解液循環型二次電池の基本構造を示し
た概念図である。
２……正極室、３……負極室、４……隔膜、６
……負極、８……負極液貯槽。
The figure is a conceptual diagram showing the basic structure of an electrolyte circulation type secondary battery. 2...Positive electrode chamber, 3...Negative electrode chamber, 4...Diaphragm, 6
...Negative electrode, 8...Negative electrode liquid storage tank.
Claims (1)
1.0vol％〜飽和濃度のトリプロピルアミン臭化水
素酸塩もしくは0.050vol％〜飽和濃度のトリブチ
ルアミン臭化水素酸塩を含有するものであること
特徴とする亜鉛−臭素二次電池。[Claims] 1. In a circulating electrolyte zinc-bromine secondary battery, the electrolyte circulated to the negative electrode side of the battery is
A zinc-bromine secondary battery characterized in that it contains tripropylamine hydrobromide at a concentration of 1.0 vol% to saturation or tributylamine hydrobromide at a concentration of 0.050 vol% to saturation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57089762A JPS58209074A (en) | 1982-05-28 | 1982-05-28 | Dendrite-suppressing agent for zinc-bromine secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57089762A JPS58209074A (en) | 1982-05-28 | 1982-05-28 | Dendrite-suppressing agent for zinc-bromine secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58209074A JPS58209074A (en) | 1983-12-05 |
| JPH0441472B2 true JPH0441472B2 (en) | 1992-07-08 |
Family
ID=13979717
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57089762A Granted JPS58209074A (en) | 1982-05-28 | 1982-05-28 | Dendrite-suppressing agent for zinc-bromine secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58209074A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5650060A (en) * | 1994-01-28 | 1997-07-22 | Minnesota Mining And Manufacturing Company | Ionically conductive agent, system for cathodic protection of galvanically active metals, and method and apparatus for using same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3944430A (en) * | 1970-09-18 | 1976-03-16 | Union Carbide Corporation | Rechargeable galvanic cell and electrolyte therefor-II |
-
1982
- 1982-05-28 JP JP57089762A patent/JPS58209074A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58209074A (en) | 1983-12-05 |
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