JPH06333609A - Method for operating zinc-bromine battery - Google Patents
Method for operating zinc-bromine batteryInfo
- Publication number
- JPH06333609A JPH06333609A JP5119420A JP11942093A JPH06333609A JP H06333609 A JPH06333609 A JP H06333609A JP 5119420 A JP5119420 A JP 5119420A JP 11942093 A JP11942093 A JP 11942093A JP H06333609 A JPH06333609 A JP H06333609A
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- bromine
- storage tank
- battery
- electrode side
- 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
- ZRXYMHTYEQQBLN-UHFFFAOYSA-N [Br].[Zn] Chemical compound [Br].[Zn] ZRXYMHTYEQQBLN-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 57
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 57
- 239000003792 electrolyte Substances 0.000 claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 238000007599 discharging Methods 0.000 claims abstract description 8
- 239000008151 electrolyte solution Substances 0.000 claims description 31
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 18
- 239000011701 zinc Substances 0.000 claims description 18
- 229910052725 zinc Inorganic materials 0.000 claims description 18
- 239000008139 complexing agent Substances 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 3
- 238000009825 accumulation Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 claims 1
- 238000011017 operating method Methods 0.000 abstract description 3
- 230000003134 recirculating effect Effects 0.000 abstract 1
- 210000004027 cell Anatomy 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 230000007423 decrease Effects 0.000 description 4
- 210000001787 dendrite Anatomy 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- ONBQEOIKXPHGMB-VBSBHUPXSA-N 1-[2-[(2s,3r,4s,5r)-3,4-dihydroxy-5-(hydroxymethyl)oxolan-2-yl]oxy-4,6-dihydroxyphenyl]-3-(4-hydroxyphenyl)propan-1-one Chemical compound O[C@@H]1[C@H](O)[C@@H](CO)O[C@H]1OC1=CC(O)=CC(O)=C1C(=O)CCC1=CC=C(O)C=C1 ONBQEOIKXPHGMB-VBSBHUPXSA-N 0.000 description 2
- 229940126142 compound 16 Drugs 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- AOSZTAHDEDLTLQ-AZKQZHLXSA-N (1S,2S,4R,8S,9S,11S,12R,13S,19S)-6-[(3-chlorophenyl)methyl]-12,19-difluoro-11-hydroxy-8-(2-hydroxyacetyl)-9,13-dimethyl-6-azapentacyclo[10.8.0.02,9.04,8.013,18]icosa-14,17-dien-16-one Chemical compound C([C@@H]1C[C@H]2[C@H]3[C@]([C@]4(C=CC(=O)C=C4[C@@H](F)C3)C)(F)[C@@H](O)C[C@@]2([C@@]1(C1)C(=O)CO)C)N1CC1=CC=CC(Cl)=C1 AOSZTAHDEDLTLQ-AZKQZHLXSA-N 0.000 description 1
- 229940126657 Compound 17 Drugs 0.000 description 1
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000011151 fibre-reinforced plastic Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 125000006850 spacer group Chemical group 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
- Hybrid Cells (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は電解液循環型積層二次電
池、特に電力貯蔵用亜鉛−臭素電池の運転方法に関する
ものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for operating an electrolyte circulating type laminated secondary battery, in particular, a zinc-bromine battery for power storage.
【０００２】[0002]
【従来の技術】亜鉛−臭素電池は正極活物質に臭素、負
極活物質に亜鉛を用いた２次電池であり、この電池は例
えば電力の昼と夜のアンバランスを解決させるために、
電力需要が少ない夜間に電力を貯蔵して、昼間に放出さ
せるため等に使用される。2. Description of the Related Art A zinc-bromine battery is a secondary battery that uses bromine as a positive electrode active material and zinc as a negative electrode active material.
It is used to store electricity at night when electricity demand is low and to release it in the daytime.
【０００３】充電時に正極電極側で発生した臭素は、電
解液に添加した臭素錯化剤と反応し、オイル状の沈殿物
となって正極側貯蔵槽へ戻され、放電時はポンプで単電
池内へ送り込まれ還元される。電解液の成分はＺｎＢｒ
2水溶液と、抵抗を下げるためのＮＨ4Ｃｌ等の塩と、負
極亜鉛側のデンドライトを防止し、均一な電着を促進さ
せるためのＰｂ，Ｓｎ，４級アンモニウム塩類と、臭素
錯化剤とである。正極電極と負極電極の間にはセパレー
タを介挿してあり、正極電極で発生した臭素が負極電極
へ拡散して亜鉛と反応することによる自己放電を防止し
ている。Bromine generated on the positive electrode side at the time of charging reacts with the bromine complexing agent added to the electrolytic solution to be returned to the positive electrode side storage tank as an oil-like precipitate, and at the time of discharging, it is pumped to the unit cell. It is sent in and returned. The component of the electrolytic solution is ZnBr
2 aqueous solution, a salt such as NH 4 Cl for reducing resistance, Pb, Sn, quaternary ammonium salts for preventing dendrite on the negative electrode zinc side and promoting uniform electrodeposition, and a bromine complexing agent Is. A separator is inserted between the positive electrode and the negative electrode to prevent self-discharge caused by the bromine generated in the positive electrode diffusing into the negative electrode and reacting with zinc.
【０００４】この亜鉛−臭素電池は、主に電極をバイポ
ーラ型とし、複数個の単電池（単セル）を電気的に直列
に積層した電池本体と、電解液貯蔵槽と、これらの間に
電解液を循環させるポンプおよび配管系とで構成されて
いる。In this zinc-bromine battery, the electrodes are mainly of a bipolar type, a battery body in which a plurality of unit cells (unit cells) are electrically stacked in series, an electrolytic solution storage tank, and an electrolytic solution between them. It is composed of a pump and a piping system for circulating the liquid.
【０００５】図３は上記亜鉛−臭素電池を構成する電池
本体の一例を示す分解斜視図であり、矩形平板状のバイ
ポーラ型中間電極１の電極部１ａの外周に絶縁性の枠体
１ｂが配置され、同様に矩形平板状のセパレータ板２
は、セパレータ３の外周に枠体２ａが形成されている。
そして上記中間電極１にセパレータ板２及び必要に応じ
てパッキン４，スペーサメッシュ５を重ねて単セルを構
成し、この単セルを複数個積層して電池本体が構成され
ている。FIG. 3 is an exploded perspective view showing an example of a battery main body constituting the zinc-bromine battery, in which an insulating frame 1b is arranged on the outer periphery of an electrode portion 1a of a rectangular flat bipolar intermediate electrode 1. Similarly, a rectangular flat plate-shaped separator plate 2
The frame 2a is formed on the outer periphery of the separator 3.
The separator plate 2 and, if necessary, the packing 4 and the spacer mesh 5 are stacked on the intermediate electrode 1 to form a single cell, and a plurality of the single cells are stacked to form a battery body.
【０００６】積層された電池本体の両端部には、集電メ
ッシュ６を有する集電電極７と、一対の締付端板８と、
その内側に位置する押さえ用の積層端板９とが配置され
ている。そして両締付端板８，８間に図外の締付用のボ
ルトを通して、このボルトを締め付けることにより、一
体的に積層固定された電池本体が構成される。A collector electrode 7 having a collector mesh 6 and a pair of tightening end plates 8 are provided at both ends of the stacked battery bodies.
A pressing laminated end plate 9 located inside thereof is arranged. Then, a tightening bolt (not shown) is passed between both tightening end plates 8 and 8 and tightened to form a battery body integrally laminated and fixed.
【０００７】上記のように構成された電池本体の各単セ
ル内には、各中間電極１及びセパレータ板２の枠体２ａ
の上下２箇所の隅角部に形成した正極マニホールド１０
と、負極マニホールド１１より、セパレータ板２の枠体
２ａに設けられたチャンネル１２及びマイクロチャンネ
ル１３を介して電解液が夫々流入排出する。In each unit cell of the battery body constructed as described above, each intermediate electrode 1 and the frame body 2a of the separator plate 2 are provided.
Positive electrode manifold 10 formed in two corners above and below
Then, the electrolytic solution flows in and out from the negative electrode manifold 11 through the channels 12 and the microchannels 13 provided in the frame body 2a of the separator plate 2, respectively.
【０００８】通常上記の締付端板８は、繊維強化プラス
チック樹脂（ＦＲＰ）が採用され、中間電極１の枠体１
ｂは塩化ビニル樹脂（ＰＶＣ）が、セパレータ板２には
比較的硬いポリエチレン樹脂が採用されている。Usually, the tightening end plate 8 is made of fiber reinforced plastic resin (FRP), and the frame body 1 of the intermediate electrode 1 is used.
A vinyl chloride resin (PVC) is used for b, and a relatively hard polyethylene resin is used for the separator plate 2.
【０００９】図４は上記亜鉛−臭素電池の作動原理を説
明するための概要図であり、図中の１４は正極側貯蔵槽
であって該正極側貯蔵槽１４内に正極電解液１５と臭素
錯化合物１６とが貯蔵されている。１７は負極側貯蔵槽
であって該負極側貯蔵槽１７内に負極電解液１８が貯蔵
されている。そして正極電解液１５は正極側ポンプ１９
の駆動に伴って、四方弁２０を介して図中の矢印に示し
た如く電池本体の正極マニホールド１０から正極室内を
流通し、正極側貯蔵槽１４に還流する一方、負極電解液
１８は負極側ポンプ２１の駆動に伴って、電池本体の負
極マニホールド１１からセパレータ３に隔てられた負極
室内を流通して負極側貯蔵槽１７に還流する。FIG. 4 is a schematic diagram for explaining the operating principle of the zinc-bromine battery, in which 14 is a positive electrode side storage tank, and the positive electrode electrolyte solution 15 and bromine are contained in the positive electrode side storage tank 14. Complex compound 16 is stored. Reference numeral 17 denotes a negative electrode side storage tank in which the negative electrode electrolytic solution 18 is stored. The positive electrode electrolyte solution 15 is supplied to the positive electrode side pump 19
Driven by the four-way valve 20, flows from the positive electrode manifold 10 of the battery main body into the positive electrode chamber through the four-way valve 20, and returns to the positive electrode side storage tank 14, while the negative electrode electrolyte solution 18 flows to the negative electrode side. Along with the driving of the pump 21, it flows from the negative electrode manifold 11 of the battery main body through the negative electrode chamber separated by the separator 3 and returns to the negative electrode side storage tank 17.
【００１０】上記亜鉛−臭素電池は、充放電運転の数サ
イクルに１度は完全放電を実施する必要がある。この完
全放電とは、通常の放電後に負極上に残留している亜鉛
を溶解することを目的として行うものである。前記した
ように電解液の成分中には、抵抗を下げるためのＮＨ4
Ｃｌ等の塩類の外、負極亜鉛側のデンドライトを防止す
るためのＰｂ，Ｓｎ，４級アンモニウム塩類が含まれて
いるが、通常の放電後に負極上に亜鉛のデンドライトが
残留することがあり、これに対処して電池電圧が零以下
になっても強制的に放電方向に電流を流す完全放電を行
って、亜鉛の溶解を促進している。The zinc-bromine battery needs to be completely discharged once every several cycles of charge / discharge operation. This complete discharge is intended to dissolve zinc that remains on the negative electrode after normal discharge. As described above, NH 4 for reducing the resistance is included in the components of the electrolytic solution.
In addition to salts such as Cl, Pb, Sn, and quaternary ammonium salts for preventing dendrites on the negative electrode zinc side are contained, but zinc dendrites may remain on the negative electrode after normal discharge. In response to this, even if the battery voltage becomes zero or less, a complete discharge in which a current is forcibly supplied in the discharge direction is performed to promote the dissolution of zinc.
【００１１】[0011]
【発明が解決しようとする課題】しかしながらこのよう
な亜鉛−臭素電池の場合、前記したように電池の運転を
継続するために数サイクルに１度完全放電を実施するの
に伴って負極上に残留する亜鉛の溶解が促進されるが、
負極上の亜鉛が残留していない場所では臭素が発生し、
この臭素が負極側貯蔵槽の底壁面上に臭素錯化合物とし
て滞留することがある。この臭素錯化合物は電池の充放
電作用に寄与しない上、その分だけ電解液中の臭素の絶
対量が減少してしまい、且つ次の充電時には負極上に電
着した亜鉛の自己放電を促してエネルギー効率を低下さ
せる惧れがあり、更にこの臭素が負極電解液中に拡散す
ることにより、充電中の臭素還元が遅くなり、且つ電池
電圧が高い状態で臭素の還元作用が進行するため、エネ
ルギー損失が大きくなってしまうという問題点が生じ
る。However, in the case of such a zinc-bromine battery, as described above, the zinc-bromine battery remains on the negative electrode as the battery is completely discharged once every few cycles in order to continue the operation of the battery. Dissolution of zinc is accelerated,
Bromine is generated in the place where zinc does not remain on the negative electrode,
This bromine may stay as a bromine complex compound on the bottom wall surface of the negative electrode side storage tank. This bromine complex compound does not contribute to the charging / discharging action of the battery, and the absolute amount of bromine in the electrolytic solution decreases by that amount, and promotes self-discharge of zinc electrodeposited on the negative electrode during the next charging. There is a risk of lowering energy efficiency, and further, because bromine diffuses into the negative electrode electrolyte, bromine reduction during charging is slowed down, and the reduction action of bromine proceeds at a high battery voltage. There is a problem that the loss becomes large.
【００１２】そのため、一定量以上の臭素錯化合物が滞
留した場合には、汲上げポンプ等を利用して負極側貯蔵
槽から臭素錯化合物を汲み上げて正極側貯蔵槽へ移す等
の煩瑣な作業を実施しなければならない。Therefore, when a certain amount or more of the bromine complex compound stays, a troublesome work such as pumping the bromine complex compound from the negative electrode side storage tank and transferring it to the positive electrode side storage tank using a pump or the like is required. Must be implemented.
【００１３】例えば電極面積が１６００ｃｍ2で３０セ
ルの電池本体を製作し、負極電解液と正極電解液をそれ
ぞれ３０リットル用いた循環系で特性試験を実施した結
果を図５の電池電圧電流特性図に基づいて説明すると、
先ず第１サイクルとして、２０Ａで３時間充電し、その
後２０Ａで３時間放電する運転条件とし、放電終了電圧
３０Ｖで効率を計算したところ、この第１サイクル時に
は負極電解液中に臭素がない状態であるため、電流効率
は９２％，電圧効率は８６％，エネルギー効率は７９．
１％であった。For example, a battery main body of 30 cells having an electrode area of 1600 cm 2 was manufactured, and a characteristic test was conducted in a circulation system using 30 liters of a negative electrode electrolyte and a positive electrode electrolyte, respectively. The results are shown in FIG. Based on
First, as the first cycle, operating conditions of charging at 20 A for 3 hours and then discharging at 20 A for 3 hours and calculating the efficiency at a discharge end voltage of 30 V showed that in the first cycle, there was no bromine in the negative electrode electrolyte. Therefore, current efficiency is 92%, voltage efficiency is 86%, energy efficiency is 79.
It was 1%.
【００１４】第１サイクル終了後、前後に休止時間を設
定して、完全放電を行うために放電方向に２０Ａで３０
分間の通電を行い、第２サイクル目の運転を開始した
が、充電初期には完全放電時に発生した臭素によって負
極電解液が赤く染まり、充電３時間終了時点では負極電
解液中にあった臭素のほとんどが還元され、負極電解液
は薄黄色になった。After the end of the first cycle, a pause time is set before and after the first cycle, and in order to perform a complete discharge, 30 A at 20 A in the discharge direction.
The power was supplied for 3 minutes, and the operation of the second cycle was started. However, the bromine generated at the time of complete discharge dyed the negative electrode electrolyte red in the early stage of charging, and the bromine in the negative electrode electrolyte remained at the end of 3 hours of charging. Most was reduced and the negative electrode electrolyte became a light yellow color.
【００１５】そして第１サイクルと同じ運転条件である
２０Ａで３時間の充電を行い、その後２０Ａで放電して
放電終了電圧３０Ｖで効率を計算したところ、電流効率
は８８％，電圧効率は８５％，エネルギー効率は７４．
８％となっており、特に電流効率が４％もの低下を示し
た。Then, charging was carried out for 3 hours at 20 A, which is the same operating condition as in the first cycle, and then discharge was carried out at 20 A and the efficiency was calculated at a discharge end voltage of 30 V. Current efficiency was 88% and voltage efficiency was 85%. , Energy efficiency is 74.
It was 8%, and particularly the current efficiency showed a decrease of 4%.
【００１６】本発明は上記の問題点に鑑みてなされたも
のであり、完全放電時に負極側貯蔵槽での臭素の発生を
防止して、この臭素が負極側貯蔵槽の底壁面上に臭素錯
化合物として滞留することがない運転方法を提供するこ
とを目的とするものである。The present invention has been made in view of the above problems, and prevents generation of bromine in the negative electrode side storage tank at the time of complete discharge, and the bromine complex is formed on the bottom wall surface of the negative electrode side storage tank. It is intended to provide an operation method in which a compound does not stay.
【００１７】[0017]
【課題を解決するための手段】本発明は上記目的を達成
するために、充放電時に電池本体と別置きにした正極側
貯蔵槽及び負極側貯蔵槽から電池本体の正極室及び負極
室に電解液がポンプで循環され、充電時に正極で発生し
た臭素が電解液に添加した臭素錯化剤と反応して正極側
貯蔵へ戻されるとともに、放電時には臭素錯化合物がポ
ンプで電池本体内へ送り込まれて還元されるようにした
亜鉛−臭素電池において、上記負極側貯蔵槽と電池本体
間に配設された負極電解液循環用の管路に、完全放電時
に負極電解液が負極側貯蔵槽へ還流することを停止する
バルブを配備するとともに、上記負極電解液循環用の管
路に該負極電解液が流通するバルブ付きバイパス管路を
設け、完全放電時に負極電解液を電池本体から該バイパ
ス管路を通って循環させることにより、負極側貯蔵槽に
おける臭素錯化合物の滞留を防止するようにした亜鉛−
臭素電池の運転方法を提供する。In order to achieve the above-mentioned object, the present invention electrolyzes from a positive electrode side storage tank and a negative electrode side storage tank, which are placed separately from the battery body during charging and discharging, into a positive electrode chamber and a negative electrode chamber of the battery body. The liquid is circulated by a pump, and the bromine generated at the positive electrode during charging reacts with the bromine complexing agent added to the electrolytic solution to return to the positive electrode side storage, and at the time of discharge the bromine complex compound is pumped into the battery body. In a zinc-bromine battery adapted to be reduced by a negative electrode, the negative electrode electrolyte circulates to the negative electrode side storage tank at the time of complete discharge in the negative electrode electrolyte solution circulating pipe provided between the negative electrode side storage tank and the battery body. A valve for stopping the operation is provided, and a bypass conduit with a valve for circulating the negative electrode electrolyte is provided in the conduit for circulating the negative electrode electrolyte, and the negative electrode electrolyte is discharged from the battery main body to the bypass conduit at the time of complete discharge. Cycle through By, zinc so as to prevent stagnation of the bromine complex compound in the negative electrode side reservoir -
A method for operating a bromine battery is provided.
【００１８】[0018]
【作用】かかる亜鉛−臭素電池の運転方法によれば、通
常の充放電終了後に完全放電を実施する前に、負極電解
液循環用の管路に配備されたバルブを「閉」にして負極
電解液の負極側貯蔵槽への還流を停止し、更にバイパス
管路のバルブを「開」にしてから完全放電を行うことに
より、電解液が電池本体からバイパス管路を通って循環
して負極側貯蔵槽内には流入しないため、負極側貯蔵槽
内において臭素が発生せず、このような臭素が負極側貯
蔵槽の底壁面上に臭素錯化合物として滞留することがな
いという作用が得られる。According to the operation method of such a zinc-bromine battery, the valve provided in the conduit for circulating the negative electrode electrolyte is closed to perform the negative electrode electrolysis after the normal charge / discharge and before the complete discharge. The electrolyte is circulated from the battery body through the bypass line by stopping the reflux of the liquid to the negative electrode side storage tank and further opening the valve of the bypass line and then performing a complete discharge. Since it does not flow into the storage tank, bromine is not generated in the storage tank on the negative electrode side, and such bromine does not stay as a bromine complex compound on the bottom wall surface of the storage tank on the negative electrode side.
【００１９】[0019]
【実施例】以下図面を参照しながら本発明にかかる亜鉛
−臭素電池の運転方法の一実施例を、前記従来の構成部
分と同一の構成部分に同一の符号を付して詳述する。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of a method for operating a zinc-bromine battery according to the present invention will be described below in detail with reference to the drawings, in which the same reference numerals are given to the same components as those of the conventional one.
【００２０】図１は本発明の基本的実施例を示す概要図
であり、図中の１４は正極側貯蔵槽であって、該正極側
貯蔵槽１４内に正極電解液１５と臭素錯化合物１６とが
貯蔵されている。１７は負極側貯蔵槽であって該負極側
貯蔵槽１７内に負極電解液１８が貯蔵されている。１９
は正極側ポンプ、２０は四方弁、３０は電池本体であ
る。FIG. 1 is a schematic diagram showing a basic embodiment of the present invention, in which 14 is a storage tank on the positive electrode side. In the storage tank 14 on the positive electrode side, a positive electrode electrolyte solution 15 and a bromine complex compound 16 are provided. And are stored. Reference numeral 17 denotes a negative electrode side storage tank in which the negative electrode electrolytic solution 18 is stored. 19
Is a positive electrode side pump, 20 is a four-way valve, and 30 is a battery main body.
【００２１】上記負極側貯蔵槽１７と電池本体３０間に
は負極電解液循環用の管路２４，２５が配設されてい
て、一方の管路２４には第１のバルブ２６と負極側ポン
プ２１が配備されており、他方側の管路２５には第２の
バルブ２７が配備されている。そして両管路２４，２５
間にバイパス管路２８が設けられ、このバイパス管路２
８の中途部に第３のバルブ２９が配備されている。Between the negative electrode side storage tank 17 and the battery main body 30, pipe lines 24 and 25 for circulating the negative electrode electrolyte are provided, and one pipe line 24 has a first valve 26 and a negative electrode side pump. 21 is provided, and the second valve 27 is provided in the conduit 25 on the other side. And both pipelines 24, 25
A bypass line 28 is provided between the bypass line 2 and
A third valve 29 is provided in the middle of 8.
【００２２】かかる構成によれば、電池の運転に際して
先ず第３のバルブ２９を「閉」とし、第１のバルブ２６
と第２のバルブ２７を「開」として、正極側ポンプ１９
と負極側ポンプ２１の駆動を開始する。According to this structure, when the battery is operated, the third valve 29 is first closed and the first valve 26 is closed.
Then, the second valve 27 is opened and the positive pump 19 is opened.
Then, driving of the negative electrode side pump 21 is started.
【００２３】すると正極電解液１５は正極側ポンプ１９
の駆動に伴って、図中の矢印に示したように、四方弁２
０を介して電池本体３０の正極マニホールドから正極室
内を流通し、正極側貯蔵槽１４に還流する一方、負極電
解液１８は負極側ポンプ２１の駆動に伴って第１のバル
ブ２６，管路２４を介して電池本体の負極マニホールド
からセパレータに隔てられた負極室内を流通し、管路２
５及び第２のバルブ２７を介して負極側貯蔵槽１７に還
流する。Then, the positive electrode electrolyte solution 15 is supplied to the positive electrode side pump 19
As shown by the arrow in the figure, the four-way valve 2
0 flows from the positive electrode manifold of the battery body 30 into the positive electrode chamber and returns to the positive electrode side storage tank 14, while the negative electrode electrolytic solution 18 is driven by the negative electrode side pump 21 and the first valve 26 and the conduit 24 are connected. Through the negative electrode manifold of the battery main body through the negative electrode chamber separated by the separator,
Reflux to the negative electrode side storage tank 17 via 5 and the second valve 27.
【００２４】そして図２の電池電圧電流特性図に示した
ように、運転の第１サイクルとして２０Ａで３時間充電
してから２０Ａで３時間放電し、放電終了電圧３０Ｖで
効率を計算したところ、この第１サイクル時には負極電
解液１８中に臭素がない状態であるため、従来例と同様
に電流効率は９２％，電圧効率は８６％，エネルギー効
率は７９％であった。As shown in the battery voltage-current characteristic diagram of FIG. 2, when the battery was charged at 20 A for 3 hours as the first cycle of operation and then discharged at 20 A for 3 hours, the efficiency was calculated at the discharge end voltage of 30 V. At the time of this first cycle, since there was no bromine in the negative electrode electrolyte solution 18, the current efficiency was 92%, the voltage efficiency was 86%, and the energy efficiency was 79% as in the conventional example.
【００２５】次に第１サイクル終了後、完全放電を実施
する前にバイパス管路２８の中途部に配備された第３の
バルブ２９を「開」とし、第１のバルブ２６と第２のバ
ルブ２７を「閉」として前後に休止時間を設定してから
放電方向に２０Ａで３０分間通電して完全放電を行う。
この時に負極電解液１８は電池本体３０からバイパス管
路２８を通って循環しており、負極側貯蔵槽１７内には
流入しない状態となっている。After the completion of the first cycle and before the complete discharge is performed, the third valve 29 provided in the middle of the bypass line 28 is opened to open the first valve 26 and the second valve. 27 is set to “closed”, a pause time is set before and after, and a complete discharge is performed by energizing in the discharge direction at 20 A for 30 minutes.
At this time, the negative electrode electrolytic solution 18 circulates from the battery main body 30 through the bypass conduit 28, and is in a state where it does not flow into the negative electrode side storage tank 17.
【００２６】次に運転の第２サイクルとして、第１サイ
クルと同じ運転条件である２０Ａで３時間の充電を開始
し、電池電圧が３０Ｖ以上になったところで第３のバル
ブ２９を「閉」にするとともに第１のバルブ２６と第２
のバルブ２７を「開」にする。このまま第２サイクルの
運転を継続して、放電終了電圧３０Ｖになったところで
効率を計算したところ、電流効率は８８％，電圧効率は
８８％，エネルギー効率は７７．４％という従来の運転
方法よりもエネルギー効率にして２．６％高い結果が得
られた。Next, as the second cycle of operation, charging is started for 3 hours at 20 A, which is the same operating condition as in the first cycle, and the third valve 29 is closed when the battery voltage becomes 30 V or higher. And the first valve 26 and the second
The valve 27 of is opened. The operation of the second cycle was continued as it was, and the efficiency was calculated at the discharge end voltage of 30 V. Current efficiency was 88%, voltage efficiency was 88%, and energy efficiency was 77.4%. The energy efficiency was 2.6% higher.
【００２７】これはバイパス管路２８を通って負極電解
液１８が循環するため、該負極電解液１８内での臭素濃
度が高くなって、臭素を還元するための電圧は低くなる
ため、臭素還元に必要とするエネルギーは少なくてすむ
ものと考察される。This is because the negative electrode electrolyte solution 18 circulates through the bypass line 28, so that the bromine concentration in the negative electrode electrolyte solution 18 becomes high and the voltage for reducing bromine becomes low, so that the bromine reduction occurs. It is considered that less energy is required for this.
【００２８】上記したように、本発明にかかる亜鉛−臭
素電池の運転方法によれば、完全放電時に第１のバルブ
２６と第２のバルブ２７を「閉」にして第３のバルブ２
９を「開」にすることにより、負極電解液１８が電池本
体３０からバイパス管路２８を通って循環するため、負
極側貯蔵槽１７内において臭素が発生せず、このような
臭素が負極側貯蔵槽１７の底壁面上に臭素錯化合物とし
て滞留することがないという特徴がある。As described above, according to the operating method of the zinc-bromine battery of the present invention, the first valve 26 and the second valve 27 are "closed" at the time of complete discharge, and the third valve 2 is closed.
9 is “open”, the negative electrode electrolyte solution 18 circulates from the battery main body 30 through the bypass line 28, so that bromine is not generated in the negative electrode side storage tank 17, and such bromine is generated on the negative electrode side. It is characterized in that it does not stay as a bromine complex compound on the bottom wall surface of the storage tank 17.
【００２９】更に本実施例によれば、一般に充電の初期
及び完全放電時に溶解亜鉛によって電池本体３０及びバ
イパス管路２８内の亜鉛濃度が高くなる傾向があるが、
この対策として、充電末期の亜鉛濃度が低くなった時点
で本実施例にかかる第３のバルブ２９を一時「開」にす
ることにより、該バイパス管路２８内の亜鉛濃度が下が
り、完全放電及び充電初期における亜鉛濃度を低く抑え
ることができるという作用が得られる。Further, according to this embodiment, generally, the zinc concentration in the battery main body 30 and the bypass line 28 tends to increase due to the dissolved zinc at the initial stage of charging and at the time of complete discharge.
As a countermeasure against this, when the zinc concentration at the end of charging becomes low, the third valve 29 according to the present embodiment is temporarily “opened” to reduce the zinc concentration in the bypass conduit 28, resulting in complete discharge and It is possible to obtain the effect that the zinc concentration in the initial stage of charging can be suppressed to a low level.
【００３０】[0030]
【発明の効果】以上詳細に説明したように、本発明にか
かる亜鉛−臭素電池の運転方法によれば、完全放電を実
施する際に負極電解液が電池本体からバイパス管路を通
って循環するため、該負極電解液が負極側貯蔵槽内に流
入せず、従って負極側貯蔵槽内において臭素が発生する
ことが防止され、負極側貯蔵槽の底壁面上に臭素錯化合
物として滞留することを防止することが出来る。それに
伴って臭素錯化合物が滞留した場合の汲上げポンプ等を
利用した臭素錯化合物の正極側貯蔵槽への移動等の煩瑣
な作業は実施しなくても良いという利点がある。As described in detail above, according to the operating method of the zinc-bromine battery of the present invention, the negative electrode electrolyte circulates from the battery main body through the bypass line when performing the complete discharge. Therefore, the negative electrode electrolytic solution does not flow into the negative electrode side storage tank, and therefore bromine is prevented from being generated in the negative electrode side storage tank, and it may remain as a bromine complex compound on the bottom wall surface of the negative electrode side storage tank. It can be prevented. Along with this, when the bromine complex compound stays, there is an advantage that it is not necessary to carry out a troublesome work such as moving the bromine complex compound to the positive electrode side storage tank using a pump or the like.
【００３１】又、負極電解液循環用の管路内の臭素濃度
が高くなって電解液中の臭素を還元するための電圧は低
くなるため、臭素還元に必要とするエネルギーは少なく
てすむという効果が得られる。Further, since the bromine concentration in the conduit for circulating the negative electrode electrolyte is increased and the voltage for reducing bromine in the electrolyte is reduced, the energy required for bromine reduction is small. Is obtained.
【００３２】更に電解液中の臭素の絶対量が減少するこ
とがなくなり、充電時に負極上に電着した亜鉛の自己放
電によるエネルギー効率の低下がなく、且つ臭素の負極
電解液中への拡散に伴う充電中の臭素還元率の低下がな
い上、エネルギー損失は最小限にすることが出来る。Furthermore, the absolute amount of bromine in the electrolytic solution does not decrease, there is no decrease in energy efficiency due to self-discharge of zinc electrodeposited on the negative electrode during charging, and bromine diffuses into the negative electrode electrolytic solution. There is no reduction in the bromine reduction rate during charging, and energy loss can be minimized.
【図１】本発明の基本的実施例を示す概要図。FIG. 1 is a schematic diagram showing a basic embodiment of the present invention.
【図２】本実施例における亜鉛−臭素電池の運転時の電
池電圧電流特性図。FIG. 2 is a battery voltage-current characteristic diagram during operation of the zinc-bromine battery in this example.
【図３】亜鉛−臭素電池本体の構成を示す分解斜視図。FIG. 3 is an exploded perspective view showing the structure of a zinc-bromine battery body.
【図４】亜鉛−臭素電池の動作原理を示す概要図。FIG. 4 is a schematic diagram showing the operating principle of a zinc-bromine battery.
【図５】従来の亜鉛−臭素電池の運転時の電池電圧電流
特性図。FIG. 5 is a battery voltage-current characteristic diagram during operation of a conventional zinc-bromine battery.
１…中間電極 １ｂ…枠体 ２…セパレータ板 ２ｂ…枠体 ３…セパレータ ８…締付端板 ９…積層端板 １０…正極マニホールド １１…負極マニホールド １２…チャンネル １３…マイクロチャンネル １４…正極側貯蔵槽 １５…正極電解液 １６…臭素錯化合物 １７…負極側貯蔵槽 １８…負極電解液 １９…正極側ポンプ ２１…負極側ポンプ ２４，２５…（循環用）管路 ２６…第１のバルブ ２７…第２のバルブ ２８…バイパス管路 ２９…第３のバルブ ３０…電池本体 DESCRIPTION OF SYMBOLS 1 ... Intermediate electrode 1b ... Frame body 2 ... Separator plate 2b ... Frame body 3 ... Separator 8 ... Clamping end plate 9 ... Laminated end plate 10 ... Positive electrode manifold 11 ... Negative electrode manifold 12 ... Channel 13 ... Micro channel 14 ... Positive side storage Tank 15 ... Positive electrode electrolyte solution 16 ... Bromine complex compound 17 ... Negative electrode side storage tank 18 ... Negative electrode electrolyte solution 19 ... Positive electrode side pump 21 ... Negative electrode side pump 24, 25 ... (For circulation) pipe line 26 ... First valve 27 ... Second valve 28 ... Bypass conduit 29 ... Third valve 30 ... Battery body
Claims (1)
側貯蔵槽及び負極側貯蔵槽から電池本体の正極室及び負
極室に電解液がポンプで循環され、充電時に正極で発生
した臭素が電解液に添加した臭素錯化剤と反応して正極
側貯蔵へ戻されるとともに、放電時には臭素錯化合物が
ポンプで電池本体内へ送り込まれて還元されるようにし
た亜鉛−臭素電池において、 上記負極側貯蔵槽と電池本体間に配設された負極電解液
循環用の管路に、完全放電時に負極電解液が負極側貯蔵
槽へ還流することを停止するバルブを配備するととも
に、上記負極電解液循環用の管路に該負極電解液が流通
するバルブ付きバイパス管路を設け、完全放電時に負極
電解液を電池本体から該バイパス管路を通って循環させ
ることにより、負極側貯蔵槽における臭素錯化合物の滞
留を防止するようにしたことを特徴とする亜鉛−臭素電
池の運転方法。1. An electrolytic solution is circulated by a pump from a positive electrode side storage tank and a negative electrode side storage tank, which are placed separately from the battery main body during charging and discharging, into a positive electrode chamber and a negative electrode chamber of the battery main body, and bromine generated in the positive electrode during charging is generated. In the zinc-bromine battery, which reacts with the bromine complexing agent added to the electrolytic solution and is returned to the positive electrode side storage, and at the time of discharge, the bromine complex compound is pumped into the battery main body and reduced. A pipe for circulating the negative electrode electrolyte disposed between the side storage tank and the battery main body is provided with a valve for stopping the reflux of the negative electrode electrolyte solution to the negative electrode side storage tank at the time of complete discharge, and the negative electrode electrolyte solution. A bromine complex in the negative electrode side storage tank is provided by providing a bypass pipeline with a valve for circulating the negative electrode electrolyte in the circulation pipeline and circulating the negative electrode electrolyte from the battery body through the bypass pipeline at the time of complete discharge. Conversion Zinc is characterized in that so as to prevent the accumulation of objects - The method of operating a bromine battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5119420A JPH06333609A (en) | 1993-05-21 | 1993-05-21 | Method for operating zinc-bromine battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5119420A JPH06333609A (en) | 1993-05-21 | 1993-05-21 | Method for operating zinc-bromine battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06333609A true JPH06333609A (en) | 1994-12-02 |
Family
ID=14761023
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5119420A Pending JPH06333609A (en) | 1993-05-21 | 1993-05-21 | Method for operating zinc-bromine battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06333609A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109546183A (en) * | 2018-11-26 | 2019-03-29 | 上海电气集团股份有限公司 | A kind of leveling blending system and method for all-vanadium flow battery positive and negative electrode electrolyte |
| CN114551935A (en) * | 2020-11-25 | 2022-05-27 | 中国科学院大连化学物理研究所 | Performance recovery method of zinc-bromine single flow battery |
| WO2025213645A1 (en) * | 2024-04-07 | 2025-10-16 | 宁德时代新能源科技股份有限公司 | Slurry conveying device, battery coating line, and slurry conveying method |
-
1993
- 1993-05-21 JP JP5119420A patent/JPH06333609A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109546183A (en) * | 2018-11-26 | 2019-03-29 | 上海电气集团股份有限公司 | A kind of leveling blending system and method for all-vanadium flow battery positive and negative electrode electrolyte |
| CN109546183B (en) * | 2018-11-26 | 2021-07-20 | 上海电气集团股份有限公司 | Leveling blending system and method for positive and negative electrolytes of all-vanadium redox flow battery |
| CN114551935A (en) * | 2020-11-25 | 2022-05-27 | 中国科学院大连化学物理研究所 | Performance recovery method of zinc-bromine single flow battery |
| CN114551935B (en) * | 2020-11-25 | 2023-09-15 | 中国科学院大连化学物理研究所 | Performance recovery method of zinc-bromine single flow battery |
| WO2025213645A1 (en) * | 2024-04-07 | 2025-10-16 | 宁德时代新能源科技股份有限公司 | Slurry conveying device, battery coating line, and slurry conveying method |
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