JPH0578150B2 - - Google Patents
Info
- Publication number
- JPH0578150B2 JPH0578150B2 JP59164753A JP16475384A JPH0578150B2 JP H0578150 B2 JPH0578150 B2 JP H0578150B2 JP 59164753 A JP59164753 A JP 59164753A JP 16475384 A JP16475384 A JP 16475384A JP H0578150 B2 JPH0578150 B2 JP H0578150B2
- Authority
- JP
- Japan
- Prior art keywords
- electrolyte
- electrode
- negative electrode
- zinc
- charging
- 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 - Fee Related
Links
Classifications
-
- 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
- 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
〔産業上の利用分野〕
本発明は、電力貯蔵用に使用される亜鉛−臭素
電池において、充電時に電極に析出された亜鉛
を、次の放電時まで自放電等によ損耗から防止す
る運転方法の改善に関するものである。
〔従来の技術〕
第１図は、電解液循環型の亜鉛−臭素二次電池
の基本構成を示すもので、図中の符号１は単セ
ル、２は正極室、３は負極室、４は前記正極室２
と負極室３を区画するためのセパレーター（隔
膜）、５は正極、６は負極、７は正極電解液であ
り、正極電解液槽９に貯蔵されていて、前記正極
室２へ管路を介して循環するようになつている。
８は負極電解液であり、負極電解液槽１０に貯蔵
されていて、前記負極室３へ管路を介して循環す
るようになつている。１１，１２はポンプであ
る。
充電時は各電解液が矢印の方向に循環し、負極
６ではZn＋Ze-→Zn、正極５では2Br-→Br2＋
2eの反応を生じ、正極５で生成された臭素は分子
となつて電解液中に混じり、一部は溶解し大部分
は正極電解液７中の錯替剤によつて錯化物とな
り、正極電解液槽９内に沈殿して蓄積される。一
方負極６で析出された亜鉛はそのまま負極６上に
堆積された状態になつている。
また、放電時には電解液が矢印の方向に循環し
た状態で、各電極５，６では上記反応式と逆の反
応を生じ、上述の析出物（Zn、Br2）が各電極上
で消費（酸化、還元）され、電気エネルギーが放
出される。
第２図は上記亜鉛−臭素電池を産業上実用する
場合を形態としての積層数１０のバイポーラ型積
層電池の構造を示し、図中の符号２１はアルミ締
付端板、２２は樹脂締付端板、２３はパツキン
グ、２４は電極端板、２５は金属網からなる端
子、２６はサポーター、２７はセパレーター、２
８，２９は中間電極であつて、２８は単一セル、
２９は積層した状態のセルを夫夫示している。
尚、３０は上記構造の積層電池を一体化するため
に用いる締付ボルト、３１はそのナツト、３２は
そのボルト３０を挿通する穴、３３は正極又は負
極電解液の共通マニホールド、３４はチヤンネ
ル、３５はマイクロチヤンネルを夫々示し、各正
負極室は夫々マイクロチヤンネル３５、チヤンネ
ル３４を介して共通マニホールド３３に並列に接
続している。
又、上記各単セル１に設けられている正、負各
電極５，６は、おおむねカーボンプラスチツク電
極が用いられている。このカーボンプラスチツク
電極は、活物質のBr2に耐性を有する密度0.94
ｇ／cm3以上の高密度ポリエチレン等のプラスチツ
ク60〜80（重量）％と、導電性を付与するための
表面積1000m2／ｇのカーボンブラツク等の炭素系
物質40〜20（重量）％を混合・混練・成形してな
るものである。
しかして、従来のこの電池の運転システムにお
いては、充電時に負極６へ析出した亜鉛を、充電
終了後から放電開始までの期間中に、そこに介在
するセパレータを透過した僅かのBr2を含む電解
液の影響を受け、自己放電のため損耗したり、電
極自体の電解液による局部腐食のため電極と析出
亜鉛との密着性低下のため、電池効率を低下させ
るという問題があつた。
〔発明が解決しようとする問題点〕
本発明は、上記従来技術における充電終了後の
負極における亜鉛の損耗等に起因する電池効率低
下の問題を解決するためになされたものである。
〔問題点を解決するための手段〕
本発明は上記問題の解決のための手段として、
電池における充電終了時に、直ちに電解液を抜き
去り、しかも電極上に存在する電解液を該電解液
と略等温のイオン交換水によりほぼ完全に洗浄除
去することによつて、該電極上の析出亜鉛を充電
終了時点における姿のまま次の放電時まで保存す
ることを要旨とするものである。
また、その電極洗浄の際のイオン交換水の流量
を、電極面積800cm2の１セル当り50〜300ml／
min、時間を10秒〜１分間とすることにより、そ
れらの条件を超えた洗浄をした場合、洗浄が少な
すぎると効果がなく過上にすると、水酸基等の悪
影響でクーロン効率低下を防止することをも要旨
の一部とするものである。
〔作用〕
本発明においては、上記の方法を採用したこと
により、電池の充電終了時に負極６に析出した亜
鉛を、次の放電時までの期間中、電解液の影響を
全く受けることなく、略充電終了時のままの状態
で保存することが可能であり、これにより亜鉛の
自己放電を従来と比べ約1/3に減少させることが
可能となつた。
〔発明の実施例〕
() 実施例 １
第１図に示す如き単セル構成のカーボンプラス
チツク電極を負極に用いた亜鉛−臭素電解液循環
バイポーラ型積層二次電池において、充電終了後
の負極を
(i) 充電終了時のまま電解液中に放置、
(ii) 電解液を抜き、電極上に付着した電解液をそ
のままの状態で放置、
(iii) 電解液を抜き、イオン交換水中に電極を浸し
たまま放置、
(iv) 電解液を抜き、電極をイオン交換水で洗浄後
そのまま放置、
(v) 電解液を抜き、電極をイオン交換水で洗浄後
乾燥、
以上(i)〜(v)の放置日数１日後のクーロン効率を
次の第１表に示す。
[Industrial Application Field] The present invention provides an operating method for a zinc-bromine battery used for power storage, in which zinc deposited on the electrode during charging is prevented from being damaged by self-discharge until the next discharge. This is related to the improvement of [Prior Art] Figure 1 shows the basic configuration of an electrolyte circulation type zinc-bromine secondary battery. In the figure, 1 is a single cell, 2 is a positive electrode chamber, 3 is a negative electrode chamber, and 4 is a negative electrode chamber. The positive electrode chamber 2
5 is a positive electrode, 6 is a negative electrode, and 7 is a positive electrode electrolyte, which is stored in a positive electrode electrolyte tank 9 and is connected to the positive electrode chamber 2 via a conduit. It has become a cycle.
Reference numeral 8 denotes a negative electrode electrolyte, which is stored in a negative electrode electrolyte tank 10 and circulated to the negative electrode chamber 3 via a conduit. 11 and 12 are pumps. During charging, each electrolyte circulates in the direction of the arrow, and the negative electrode 6 has Zn + Ze - → Zn, and the positive electrode 5 has 2Br - →Br 2 +
The reaction 2e occurs, and the bromine generated at the positive electrode 5 becomes a molecule and mixes in the electrolyte, some of which dissolves, and the majority of which becomes a complex with the complexing agent in the positive electrode electrolyte 7, and the bromine that is generated at the positive electrode 5 becomes a molecule and mixes in the electrolyte. It precipitates and accumulates in the liquid tank 9. On the other hand, the zinc deposited on the negative electrode 6 remains deposited on the negative electrode 6 as it is. In addition, during discharge, with the electrolyte circulating in the direction of the arrow, a reaction opposite to the above reaction formula occurs at each electrode 5, 6, and the above-mentioned precipitates (Zn, Br 2 ) are consumed (oxidized) on each electrode. , reduction), and electrical energy is released. Figure 2 shows the structure of a bipolar stacked battery with 10 layers, in which the above-mentioned zinc-bromine battery is used industrially. In the figure, numeral 21 is an aluminum clamping end plate, and 22 is a resin clamping end. 23 is a packing board, 24 is an electrode end plate, 25 is a terminal made of metal mesh, 26 is a supporter, 27 is a separator, 2
8 and 29 are intermediate electrodes, 28 is a single cell,
Reference numeral 29 indicates cells in a stacked state.
In addition, 30 is a tightening bolt used to integrate the stacked battery of the above structure, 31 is the nut, 32 is a hole through which the bolt 30 is inserted, 33 is a common manifold for the positive electrode or negative electrode electrolyte, 34 is a channel, Reference numerals 35 indicate microchannels, and the positive and negative electrode chambers are connected in parallel to the common manifold 33 via the microchannels 35 and 34, respectively. Further, the positive and negative electrodes 5 and 6 provided in each unit cell 1 are generally carbon plastic electrodes. This carbon plastic electrode has a density of 0.94 with active material resistant to Br2 .
A mixture of 60-80% (by weight) of plastic such as high-density polyethylene of g/cm 3 or more and 40-20% (by weight) of carbon-based material such as carbon black with a surface area of 1000 m 2 /g to impart conductivity.・It is made by kneading and molding. However, in the conventional battery operation system, the zinc deposited on the negative electrode 6 during charging is removed from the electrolysis containing a small amount of Br 2 that has passed through the intervening separator during the period from the end of charging to the start of discharging. There were problems in that the electrodes were damaged due to self-discharge due to the influence of the liquid, and the adhesion between the electrodes and the deposited zinc was reduced due to local corrosion of the electrode itself due to the electrolyte, resulting in a reduction in battery efficiency. [Problems to be Solved by the Invention] The present invention has been made in order to solve the above-mentioned problem of the prior art in which battery efficiency decreases due to loss of zinc in the negative electrode after charging is completed. [Means for solving the problems] As a means for solving the above problems, the present invention has the following features:
At the end of charging the battery, the electrolyte is immediately removed, and the electrolyte present on the electrode is almost completely washed away with ion-exchanged water that is approximately isothermal to the electrolyte, thereby removing the zinc deposited on the electrode. The main idea is to preserve the same state as it was at the end of charging until the next discharge. In addition, the flow rate of ion exchange water during electrode cleaning was set at 50 to 300 ml per cell with an electrode area of 800 cm2 .
By setting the min and time to 10 seconds to 1 minute, if the cleaning exceeds these conditions, too little cleaning will not be effective, and if it is too much, it will prevent a decrease in coulomb efficiency due to adverse effects such as hydroxyl groups. should also be included as part of the abstract. [Function] In the present invention, by adopting the above method, the zinc deposited on the negative electrode 6 at the end of charging of the battery is almost completely unaffected by the electrolytic solution during the period until the next discharge. It is possible to store the battery in the same state as when it is fully charged, making it possible to reduce self-discharge of zinc to about 1/3 compared to conventional methods. [Embodiments of the Invention] () Example 1 In a zinc-bromine electrolyte circulation bipolar type stacked secondary battery using a carbon plastic electrode with a single cell structure as the negative electrode as shown in Fig. 1, the negative electrode after charging is i) Leave the electrode in the electrolyte as it is after charging, (ii) Remove the electrolyte and leave the electrolyte attached to the electrode as it is, (iii) Remove the electrolyte and immerse the electrode in ion-exchanged water. (iv) Remove the electrolytic solution, wash the electrode with ion-exchanged water, and leave it as it is; (v) Remove the electrolytic solution, wash the electrode with ion-exchanged water, and then dry it. The coulombic efficiency after one day of standing is shown in Table 1 below.
上記の本発明の実施例に示されている通り、充
電終了後電解液をセルから抜き、その後充電時の
電解液温と略等温のイオン交換水でセル内を洗浄
する。但しこの場合の洗浄水量を１セル当り50〜
300ml／min以内、洗浄時間10秒〜１分間以内と
することにより次の第２表に示す効果が得られ
た。
As shown in the above-described embodiment of the present invention, after charging is completed, the electrolytic solution is removed from the cell, and then the inside of the cell is washed with ion-exchanged water that is approximately the same temperature as the electrolytic solution temperature at the time of charging. However, in this case, the amount of washing water should be 50 ~
By setting the washing rate to within 300 ml/min and the washing time to within 10 seconds to 1 minute, the effects shown in Table 2 below were obtained.
第１図は亜鉛−臭素電池の基本構成を示す概念
図、第２図は10セル積層電池の構成を示す概念
図、第３，４図は共に本発明の実施例２における
放電時間とセル電圧の関係を示すグラフ、第５図
は本発明実施例２における洗浄水量とクーロン効
率の関係を示すグラフである。
１……単セル、２……正極室、３……負極室、
４……セパレーター、５……正極、６……負極、
７……正極電解液、８……負極電解液、９……正
極電解液槽、１０……負極電解液槽、１１，１２
……ポンプ、２１……アルミ締付端板、２２……
樹脂締付端板、２３……パツキング、２４……電
極端板、２５……端子、２６……サポーター、２
７……セパレーター、２８……中間電極、２９…
…中間電極（積層）、３０……締付ボルト、３１
……同ナツト、３２……穴、３３……マニホール
ド、３４……チヤンネル、３５……マイクロチヤ
ンネル。
Figure 1 is a conceptual diagram showing the basic configuration of a zinc-bromine battery, Figure 2 is a conceptual diagram showing the configuration of a 10-cell stacked battery, and Figures 3 and 4 are both discharge time and cell voltage in Example 2 of the present invention. FIG. 5 is a graph showing the relationship between the amount of washing water and the coulombic efficiency in Example 2 of the present invention. 1 ...Single cell, 2...Positive electrode chamber, 3...Negative electrode chamber,
4...Separator, 5...Positive electrode, 6...Negative electrode,
7... Positive electrode electrolyte, 8... Negative electrode electrolyte, 9... Positive electrode electrolyte tank, 10... Negative electrode electrolyte tank, 11, 12
... Pump, 21 ... Aluminum tightening end plate, 22 ...
Resin fastening end plate, 23... Packing, 24... Electrode end plate, 25... Terminal, 26... Supporter, 2
7...Separator, 28...Intermediate electrode, 29...
...Intermediate electrode (laminated), 30...Tightening bolt, 31
...Same nut, 32...hole, 33...manifold, 34...channel, 35...microchannel.
Claims (1)
し、前記充電期間及び前記放電期間は電解液をセ
ル内に循環させ、前記停止期間には前記電解液の
循環を停止する、電力貯蔵用に使用される亜鉛−
臭素電池の運転方法において、 前記充電期間終了後セル内から前記電解液を抜
き、充電時の電解液液温と略等温のイオン交換水
により負極を洗浄し、放電開始まで保存すること
を特徴とする亜鉛−臭素電池の運転方法。 ２ 前記イオン交換水の流量を１セル単位電極当
り0.4ml／min・cm2以内、洗浄時間を１分間以内
とすることを特徴とする特許請求の範囲第１項記
載の亜鉛−臭素電池の運転方法。[Claims] 1. A stop period is provided between a charging period and a discharging period, and during the charging period and the discharging period, an electrolytic solution is circulated within the cell, and during the stopping period, the electrolytic solution is not circulated. Zinc used for power storage -
The method for operating a bromine battery is characterized in that after the end of the charging period, the electrolyte is removed from the cell, the negative electrode is washed with ion-exchanged water whose temperature is approximately equal to the temperature of the electrolyte at the time of charging, and the negative electrode is stored until the start of discharging. How to operate a zinc-bromine battery. 2. Operation of the zinc-bromine battery according to claim 1, characterized in that the flow rate of the ion-exchanged water is within 0.4 ml/min·cm 2 per cell unit electrode, and the cleaning time is within 1 minute. Method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59164753A JPS6145573A (en) | 1984-08-08 | 1984-08-08 | How to operate a zinc-bromine battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59164753A JPS6145573A (en) | 1984-08-08 | 1984-08-08 | How to operate a zinc-bromine battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6145573A JPS6145573A (en) | 1986-03-05 |
| JPH0578150B2 true JPH0578150B2 (en) | 1993-10-28 |
Family
ID=15799261
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59164753A Granted JPS6145573A (en) | 1984-08-08 | 1984-08-08 | How to operate a zinc-bromine battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6145573A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2503786B2 (en) * | 1991-01-22 | 1996-06-05 | トヨタ自動車株式会社 | Zinc halogen battery |
-
1984
- 1984-08-08 JP JP59164753A patent/JPS6145573A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6145573A (en) | 1986-03-05 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |