JPH024989B2 - - Google Patents
Info
- Publication number
- JPH024989B2 JPH024989B2 JP57070211A JP7021182A JPH024989B2 JP H024989 B2 JPH024989 B2 JP H024989B2 JP 57070211 A JP57070211 A JP 57070211A JP 7021182 A JP7021182 A JP 7021182A JP H024989 B2 JPH024989 B2 JP H024989B2
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- electrolyte
- zinc
- bromine
- dendrites
- 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
本発明は、電解液循環型亜鉛−臭素二次電池の
負極面において亜鉛が樹枝状に析出し成長するの
を（いわゆるデンドライト）防ぐことのできる電
解液に関するものである。
ここで述べる電解液循環型亜鉛−臭素二次電池
の基本的構成は、図に示した如きものであり、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
は正極液貯蔵槽、８は負極液貯蔵槽、９，１０は
バルブである。
そして、充電時には図中で示した正極に臭素
が、一方で示し負極には亜鉛が析出する。
正極で析出した臭素は、電解液中に溶解する
が、負極面上で析出する亜鉛は、その面を必ずし
も平滑を保ちながら成長するものではなく、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）。
負極面上でデンドライトが成長すると負極面と
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はなく、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やすく、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。またこのデンドラ
イトが仮に電極から離脱をせずに成長を続けた場
合には隔膜を破損しあるいは極端な場合には正極
と短絡を起し結局電池を破壊に至らしめる惧れが
あり、このためデンドライト抑制剤は極めて重要
な役割を有するものである。
この目的のために用いられてきた従来のデンド
ライト抑制剤は、界面活性剤、亜鉛メツキ光沢剤
などがあつたが、これらは耐臭素性に問題があ
り、長時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はできなかつた。
この発明は、かかる点に鑑みてなされたもので
あり、長時間にわたるサイクル運転に際してもデ
ンドライトの発生成長を防止することのできる亜
鉛−臭素電池の電解液を提供することを目的とす
るものである。
本発明の電解液は、電解液循環型亜鉛−臭素電
池の負極側に循環される電解液であつて、上記目
的の達成のために、一般式C5H5N・RX（Ｒは炭
素数８〜12のアルキル基、ＸはBr又はCl）で示
されるアルキルピリジニウム塩が飽和濃度含有さ
れた電解液である。
ここで使用するアルキルピリジニウム塩は、電
解液中に１ｇ／100c.c.程度ないしそれ以下の濃度
で使用する。尚、当然のことながらアルキルピリ
ジニウム塩のアルキル基の炭素数が増加するに従
つて溶解度が低下し、上述の濃度を維持し得ない
場合も起るが、このときはその飽和溶解量のまま
で使用する。
以上の如きアルキルピリジニウム塩をデンドラ
イト抑制剤として添加した電解液を使用すると、
遊離の臭素を補捉して結合し安定なポリハライド
を形成するため従来の薬剤を使用したときにみら
れたような耐臭素性の問題も起らず安定して長期
間に亘る使用が可能となつたばかりでなく、20〜
60ｍＡ／cm2、特に20〜40ｍＡ／cm2という実用的な
電流密度における使用に充分耐え得るものであ
る。
本発明の電解液を使用した場合、デンドライト
の形成は殆んどなくなり電極面上にはこぶ状に亜
鉛が付着しその機械的強度も充分であるため従来
見られたような電極からの脱落及びそれに起因し
た各種の不都合な現象もなく極めて安定的に長期
間に亘つて亜鉛−臭素電池の連続使用が行なえる
ものである。
負極電解液として3mol／の臭素亜鉛水溶液、
デンドライト抑制剤としてアルキルピリジニウム
ブロマイド１ｇ／100c.c.を添加し、ないしは飽和
させた系により40ｍＡ／cm2の充電密度で360ｍ
AH／cm2の充電々気量の充電を行い、デンドライ
ト抑制状態を確認したところ次の如き結果を得
た。
The present invention relates to an electrolytic solution that can prevent zinc from depositing and growing in a dendritic form (so-called dendrites) on the negative electrode surface of a circulating electrolyte zinc-bromine secondary battery. The basic configuration of the electrolyte circulation type zinc-bromine secondary battery described here is as shown in the figure, where 1 is a battery reaction tank, 2 is a positive electrode chamber, 3 is a negative electrode chamber, and 4 is a negative electrode chamber.
is a diaphragm (separator), 5 is a positive electrode, 6 is a negative electrode, 7
8 is a positive electrode liquid storage tank, 8 is a negative electrode liquid storage tank, and 9 and 10 are valves. During charging, bromine is deposited on the positive electrode shown in the figure, while zinc is deposited on the negative electrode shown in the figure. Bromine deposited on the positive electrode dissolves in the electrolyte, but zinc deposited on the negative electrode surface does not necessarily grow while keeping the surface smooth, but instead forms dendritic forms of various sizes. (hereinafter referred to as dendrites). When dendrites grow on the negative electrode surface, there are fewer opportunities for contact between the negative electrode surface and fresh electrolyte, which not only reduces battery efficiency, but also because these dendrites are extremely brittle, they cannot be easily affected by relatively slight stress. The dendrites are easily separated from the electrodes, and the dendrites that fall off clog the electrolyte circulation pipe and reduce pump efficiency. In addition, if these dendrites continue to grow without detaching from the electrode, there is a risk that the diaphragm will be damaged or, in extreme cases, a short circuit will occur with the positive electrode, eventually leading to the destruction of the battery. Inhibitors have a very important role. Conventional dendrite inhibitors used for this purpose include surfactants and galvanizing brighteners, but these have problems with bromine resistance and are not stable for long-term cycle use. It was not possible to continue to maintain this level of performance. The present invention has been made in view of these points, and it is an object of the present invention to provide an electrolytic solution for a zinc-bromine battery that can prevent the generation and growth of dendrites even during long-term cycle operation. . The electrolyte of the present invention is an electrolyte that is circulated to the negative electrode side of a circulating electrolyte zinc-bromine battery, and has the general formula C 5 H 5 N.RX (R is the carbon number The electrolytic solution contains an alkylpyridinium salt represented by 8 to 12 alkyl groups (X is Br or Cl) at a saturated concentration. The alkylpyridinium salt used here is used in the electrolytic solution at a concentration of about 1 g/100 c.c. or less. Naturally, as the number of carbon atoms in the alkyl group of the alkylpyridinium salt increases, the solubility decreases, and there may be cases where the above concentration cannot be maintained, but in this case, the saturated solubility remains the same. use. When using an electrolyte containing the above alkylpyridinium salt as a dendrite inhibitor,
Because it captures and binds free bromine to form a stable polyhalide, there are no problems with bromine resistance that occur when using conventional chemicals, and it can be used stably for a long period of time. Not only summer, but also 20～
It can withstand use at a practical current density of 60 mA/cm 2 , particularly 20 to 40 mA/cm 2 . When the electrolyte of the present invention is used, the formation of dendrites is almost eliminated, and the zinc adheres to the electrode surface in the form of nodules, and its mechanical strength is sufficient, so that it does not fall off from the electrode or cause problems such as those seen in the past. The zinc-bromine battery can be used continuously for a long period of time in an extremely stable manner without causing various disadvantageous phenomena. 3 mol/zinc bromine aqueous solution as negative electrode electrolyte,
360 m at a charging density of 40 mA/cm 2 by adding 1 g/100 c.c. of alkylpyridinium bromide as a dendrite suppressor or by using a saturated system.
When charging was carried out at a charging volume of AH/cm 2 and the state of dendrite suppression was confirmed, the following results were obtained.
【表】【table】
【表】
評価欄中Ａは負極電極表面は平滑、デンドライ
トなし、Ｂは微少なデンドライトの発生を認め
る、比較的平滑面を保つている。Ｃは電極表面不
均一、デンドライト多数を示す。
尚、この確認試験にはカーボンプラスチツク電
極を使用している。また電流密度を20及び60ｍ
Ａ／cm2とした場合にも上記の結果と概ね同じ傾向
であることが確認された。
以下本発明の効果を数例の具体例を以て説明す
る。
実施例 １
図面に示した基本的構成の二次電池において、
負極電極としてカーボンプラスチツク電極（導電
性カーボンをプラスチツクに配合し電極板を形成
させたもの）を使用し、3mol／を臭素亜鉛水
溶液を負極電解液とし、この負極電解液にオクチ
ルピリジニウムブロマイド５ｇ／の割合で添加
し飽和させ表示の各電流密度において充電電気量
が360ｍAH／cm2となるまで充電を行つた時の電
極板表面状態を観察し、その結果を得た。尚、評
価方法は、前記確認試験と同一である。[Table] In the evaluation column, A indicates that the negative electrode surface is smooth and has no dendrites, and B indicates that the surface of the negative electrode is smooth with the occurrence of minute dendrites and maintains a relatively smooth surface. C indicates nonuniform electrode surface and large number of dendrites. Note that carbon plastic electrodes are used in this confirmation test. In addition, the current density is 20 and 60 m.
It was confirmed that the same tendency as the above result was obtained even when A/cm 2 was used. The effects of the present invention will be explained below using several specific examples. Example 1 In a secondary battery having the basic configuration shown in the drawings,
A carbon plastic electrode (conductive carbon is blended with plastic to form an electrode plate) is used as the negative electrode, 3 mol of zinc bromine aqueous solution is used as the negative electrode electrolyte, and 5 g of octylpyridinium bromide is added to this negative electrode electrolyte. The surface condition of the electrode plate was observed when charging was carried out at each indicated current density until the charging amount reached 360 mAH/cm 2 to saturation, and the results were obtained. The evaluation method was the same as the confirmation test described above.
【表】
実施例 ２
オクチルピリジニウムブロマイドに替えて、約
１ｇ／のドデシルピリジニウムブロマイドを用
いて飽和させたほかは実施例１と繰返して次表の
結果を得た。[Table] Example 2 Example 1 was repeated except that about 1 g/dodecylpyridinium bromide was used for saturation instead of octylpyridinium bromide, and the results shown in the following table were obtained.
【表】
実施例 ３
ドデシルピリジニウムブロマイドに替え、デシ
ルピリジニウムクロライドを用いて実施例２を繰
返し次表の結果を得た。[Table] Example 3 Example 2 was repeated using decylpyridinium chloride instead of dodecylpyridinium bromide to obtain the results shown in the following table.
【表】
実施例 ４
図面に示した基本的構成を有する二次電池にお
いて、デシルピリジニウムクロライドを飽和させ
ている3mol／臭化亜鉛水溶液を負極電解液、
カーボンプラスチツク電極を負極電極とし、充電
時電流密度２ｍＡ／cm2で８時間充電したのち８時
間放電を行う充放電サイクル試験を行つて電極表
面状態を観察し次表の結果を得た。[Table] Example 4 In a secondary battery having the basic configuration shown in the drawing, a 3 mol/zinc bromide aqueous solution saturated with decylpyridinium chloride was added to the negative electrode electrolyte,
A charge/discharge cycle test was conducted using a carbon plastic electrode as a negative electrode, charging at a charging current density of 2 mA/cm 2 for 8 hours, and then discharging for 8 hours.The electrode surface condition was observed and the results shown in the following table were obtained.
【表】
上表が示す通り、サイクルを重ねても電極表面
の状態は極めて満足な状態を維持しつづけている
ことが認められた。尚、このサイクル試験は、オ
クチルピリジニウムブロマイド及びドデシルピリ
ジニウムブロマイドを使用した場合も20サイクル
でＡの評価を維持していた。
以上の各実施例の結果からも認められるよう
に、本発明に従つて充電を行つた場合は電着状態
が極めて安定しており、良好な電着状態を維持し
ていることが認められた。
本発明の電解液を用いると、実用的な電流密度
で長時間にわたるサイクル運転を行なう場合にも
デンドライトの発生をほぼ完全に防止することが
でき、高い効率を維持しながら亜鉛−臭素電池を
連続運転させることができる。[Table] As shown in the above table, it was observed that the electrode surface continued to maintain an extremely satisfactory state even after repeated cycles. In this cycle test, even when octylpyridinium bromide and dodecylpyridinium bromide were used, the evaluation of A was maintained after 20 cycles. As can be seen from the results of the above examples, when charging according to the present invention, the electrodeposition state was extremely stable, and it was observed that a good electrodeposition state was maintained. . Using the electrolyte of the present invention, it is possible to almost completely prevent the formation of dendrites even during long-term cycle operation at practical current densities, allowing continuous zinc-bromine batteries to maintain high efficiency. You can drive it.
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)
される電解液において、 一般式C5H5N・RX（Ｒは炭素数８〜12のアル
キル基、ＸはBr又はCl） で示されるアルキルピリジニウム塩が飽和濃度含
有されたことを特徴とする亜鉛−臭素電池の電解
液。[Claims] 1. In the electrolyte circulated to the negative electrode side of a circulating electrolyte zinc-bromine battery, the general formula C 5 H 5 N.RX (R is an alkyl group having 8 to 12 carbon atoms, X is Br An electrolytic solution for a zinc-bromine battery, characterized in that it contains an alkylpyridinium salt represented by (or Cl) at a saturation concentration.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57070211A JPS58188068A (en) | 1982-04-28 | 1982-04-28 | Inhibitor of dendrite generation of secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57070211A JPS58188068A (en) | 1982-04-28 | 1982-04-28 | Inhibitor of dendrite generation of secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58188068A JPS58188068A (en) | 1983-11-02 |
| JPH024989B2 true JPH024989B2 (en) | 1990-01-31 |
Family
ID=13424955
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57070211A Granted JPS58188068A (en) | 1982-04-28 | 1982-04-28 | Inhibitor of dendrite generation of secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58188068A (en) |
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
- 1982-04-28 JP JP57070211A patent/JPS58188068A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58188068A (en) | 1983-11-02 |
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