JPH02162663A - Zinc-bromine battery separator - Google Patents
Zinc-bromine battery separatorInfo
- Publication number
- JPH02162663A JPH02162663A JP63317154A JP31715488A JPH02162663A JP H02162663 A JPH02162663 A JP H02162663A JP 63317154 A JP63317154 A JP 63317154A JP 31715488 A JP31715488 A JP 31715488A JP H02162663 A JPH02162663 A JP H02162663A
- Authority
- JP
- Japan
- Prior art keywords
- bromine
- polyolefin
- separator
- zinc
- treatment
- 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 19
- 229920000098 polyolefin Polymers 0.000 claims abstract description 47
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 13
- 239000012982 microporous membrane Substances 0.000 claims description 24
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract description 69
- 229910052794 bromium Inorganic materials 0.000 abstract description 67
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract description 66
- 230000035699 permeability Effects 0.000 abstract description 27
- 230000000694 effects Effects 0.000 abstract description 14
- 239000003792 electrolyte Substances 0.000 abstract description 14
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 238000007599 discharging Methods 0.000 abstract description 4
- 210000000352 storage cell Anatomy 0.000 abstract 3
- 210000004027 cell Anatomy 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 21
- 239000007788 liquid Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 12
- 239000011148 porous material Substances 0.000 description 11
- 239000012528 membrane Substances 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 8
- 230000007423 decrease Effects 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 8
- 230000002209 hydrophobic effect Effects 0.000 description 7
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 6
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 6
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Chemical class O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000007654 immersion Methods 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 238000010306 acid treatment Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000002800 charge carrier Substances 0.000 description 3
- 239000008139 complexing agent Substances 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229940102001 zinc bromide Drugs 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- -1 bromine ions Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- CMMUKUYEPRGBFB-UHFFFAOYSA-L dichromic acid Chemical compound O[Cr](=O)(=O)O[Cr](O)(=O)=O CMMUKUYEPRGBFB-UHFFFAOYSA-L 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- XMXNVYPJWBTAHN-UHFFFAOYSA-N potassium chromate Chemical compound [K+].[K+].[O-][Cr]([O-])(=O)=O XMXNVYPJWBTAHN-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/417—Polyolefins
-
- 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】
〔産業上の利用分野〕
本発明は、充放電時のクーロン効率を改善した亜鉛−臭
素電池セパレータに関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a zinc-bromine battery separator with improved coulombic efficiency during charging and discharging.
亜鉛−臭素電池は、電解液循環型の金属−ハロゲン電池
の一種として、電解液に臭化亜鉛水溶液を用いたもので
、電気自動車の駆動源等の動力用二次電池の有力な候補
電池である。A zinc-bromine battery is a type of metal-halogen battery with a circulating electrolyte that uses a zinc bromide aqueous solution as the electrolyte, and is a promising candidate battery for secondary batteries for power such as electric vehicle drive sources. be.
このような亜鉛−臭素電池は９反応物質及び構成材料が
安価のため、低コストが期待され、しかも発電電圧が高
く、電極反応の可逆性も良いため。Such a zinc-bromine battery is expected to be low cost because the reactants and constituent materials are inexpensive, and the generated voltage is high and the reversibility of the electrode reaction is also good.
電気自動車のみでなく、他の各種分野においても広範囲
に実用化されようとしている。It is expected to be put into widespread practical use not only in electric vehicles but also in various other fields.
第１図は、前記亜鉛−臭素電池の原理図を示すもので、
電池本体３はセパレータ３０によって正極室３１と負極
室３２に仕切られている。FIG. 1 shows the principle diagram of the zinc-bromine battery,
The battery body 3 is partitioned into a positive electrode chamber 31 and a negative electrode chamber 32 by a separator 30.
そして、前記各電極室３１．３２はそれぞれ配管１５．
２３によって正極液貯蔵槽１１及び負極液貯蔵槽２１に
接続され、各々の電解液循環経路を形成している。各電
解液はポンプ１４．２２により各々の電極室３１．３２
に送られる。また。Each of the electrode chambers 31 and 32 is connected to a pipe 15.
It is connected to the positive electrode liquid storage tank 11 and the negative electrode liquid storage tank 21 by 23 to form respective electrolyte circulation paths. Each electrolyte is pumped into each electrode chamber 31.32 by a pump 14.22.
sent to. Also.
前記正極液貯蔵槽１１内には臭素錯化合物貯蔵槽１２が
形成されており、正極室３１で生成する臭素錯化合物３
００を貯蔵し、その一部をバルブ１３を介して配管１５
内に供給する。A bromine complex compound storage tank 12 is formed in the positive electrode liquid storage tank 11 and stores the bromine complex compound 3 generated in the positive electrode chamber 31.
00 is stored and a part of it is passed through the valve 13 to the pipe 15.
supply within.
これら従来の亜鉛−臭素電池としては、特開昭５２−１
２２８３５．特開昭５８−１９９１６７゜米国特許４，
１０５，８２９等に示されている。These conventional zinc-bromine batteries include JP-A-52-1
22835. JP 58-199167゜U.S. Patent 4,
105,829 etc.
この種の亜鉛−臭素電池に用いられる電解液としては、
活物質である臭化亜鉛の他に臭素と反応して電解液に不
溶で電解液より比重の大きな錯化合物を形成する錯化剤
を加えた水溶液が使用されている。そして、更に、必要
に応じて電解液の導電率を向上させるためＫＣＩやＮＨ
，ＣＩ等の支持電解質を加えた電解液も使用される。特
開昭５２−１２２８３６及び特開昭５２−１２４１３４
には、錯化剤の例として、メチル・エチルピロジニウム
ブロマイド、メチル・エチルピロジニウムブロマイド等
が示されている。The electrolyte used in this type of zinc-bromine battery is
In addition to the active material zinc bromide, an aqueous solution containing a complexing agent that reacts with bromine to form a complex compound that is insoluble in the electrolyte and has a higher specific gravity than the electrolyte is used. Furthermore, KCI and NH are added to improve the conductivity of the electrolyte as necessary.
, CI, and other supporting electrolytes are also used. JP-A-52-122836 and JP-A-52-124134
shows methyl-ethylpyrodinium bromide, methyl-ethylpyrodinium bromide, etc. as examples of complexing agents.
第１図において、電池の充電時には正極で臭素イオンの
酸化が、負極で亜鉛イオンの還元が起こるため、正極で
は臭素の生成が、負極では亜鉛の電着が起こる。なお、
正極で生成した臭素は電解液中の錯化剤と反応してオイ
ル状の錯化合物３００を形成し、前記臭素錯体化合物貯
蔵槽１２に分離貯蔵される。In FIG. 1, when a battery is charged, bromine ions are oxidized at the positive electrode and zinc ions are reduced at the negative electrode, so that bromine is produced at the positive electrode and zinc is electrodeposited at the negative electrode. In addition,
Bromine generated at the positive electrode reacts with the complexing agent in the electrolyte to form an oil-like complex compound 300, which is separated and stored in the bromine complex compound storage tank 12.
しかしながら、このような亜鉛−臭素電池において充電
時正極で生成した臭素はそのすべてがオイル状の臭素錯
体化合物とはならず、解離平衡によって９通常５０〜２
００．遊離の臭素として正極液中に溶解している。However, in such a zinc-bromine battery, not all of the bromine generated at the positive electrode during charging becomes an oil-like bromine complex compound, and due to dissociation equilibrium, 9
00. Dissolved in the catholyte as free bromine.
しかして、この遊離の臭素がセパレータ３０を通って負
極液側へ拡散し、負極活物質である亜鉛と直接反応する
。この直接反応量は、自己放電量となるわけで、この分
、充電に要した電気量が失われることになる。したがっ
て、セパレータを通る臭素量が多いほど充電電気量に対
する放電電気量の割合、つまり充放電のクーロン効率は
小さくなる。This free bromine then diffuses to the negative electrode liquid side through the separator 30 and reacts directly with zinc, which is the negative electrode active material. This amount of direct reaction becomes the amount of self-discharge, and the amount of electricity required for charging is lost accordingly. Therefore, the larger the amount of bromine passing through the separator, the smaller the ratio of the amount of discharged electricity to the amount of charged electricity, that is, the coulombic efficiency of charging and discharging.
このように、セパレータ３０による臭素透過性が電池の
クーロン効率に太き（影響を及ぼし、セパレータ３０の
臭素透過性が小さいほど電池クーロン効率は向上するこ
とが知られている。In this way, it is known that the bromine permeability of the separator 30 greatly affects the coulombic efficiency of the battery, and that the smaller the bromine permeability of the separator 30, the better the battery coulombic efficiency.
また、前記セパレータには通常、シリカを含むポリオレ
フィン系の微細多孔膜が用いられているが、その臭素透
過性はあまり小さくなく、十分なり−ロン効率を得るこ
とができなかった。従来においても、特開昭５８−２０
６０４５で示されるごとく、＠細条孔膜の孔径或いは多
孔度を改良してエネルギー効率を改善しようとする提案
もなされている。Further, although a polyolefin microporous membrane containing silica is usually used as the separator, its permeability to bromine is not so low that it has not been possible to obtain a sufficient bromine efficiency. In the past, Japanese Patent Application Laid-open No. 58-20
As shown in No. 6045, proposals have also been made to improve energy efficiency by improving the pore size or porosity of @striped membranes.
しかし、臭素透過性を小さくするために細孔径を小さく
すると電荷担体であるイオンの透過も抑えられるのでセ
パレータの電気抵抗が上昇してしまい、充分な特性を得
ることができなかった。However, when the pore diameter is made smaller in order to reduce bromine permeability, the permeation of ions, which are charge carriers, is also suppressed, resulting in an increase in the electrical resistance of the separator, making it impossible to obtain sufficient properties.
本発明は、かかる従来の問題点に鑑み、電気抵抗を増大
させることなく、充放電時のクーロン効率を向上させ、
優れた電池性能を発揮することができる亜鉛−臭素電池
を提供しようとするものである。In view of such conventional problems, the present invention improves coulombic efficiency during charging and discharging without increasing electrical resistance.
The present invention aims to provide a zinc-bromine battery that can exhibit excellent battery performance.
本発明は、亜鉛−臭素電池のセパレータとして用いる。 The present invention is used as a separator for zinc-bromine batteries.
ポリオレフィンとシリカとよりなるポリオレフィン系微
細多孔膜において、ポリオレフィン部分を親水化処理し
てなることを特徴とする亜鉛−臭素電池セパレータにあ
る。A zinc-bromine battery separator characterized in that the polyolefin portion of a microporous polyolefin membrane made of polyolefin and silica is treated to make it hydrophilic.
しかして９本発明は、下記の知見に基づいてなされたも
のである。The present invention has been made based on the following findings.
即ち、ポリオレフィン系微細多孔膜の多孔構造はポリオ
レフィンで形成されるが、ポリオレフィンは疎水性であ
るため、それだけでは水を弾いてしまい水溶液系の電池
ではセパレータには用いることができない。そこで、水
溶液系の電池に用いるセパレータにはシリカを添加して
親水性を付与したポリオレフィン乎微細多孔膜が用いら
れている。そのため、ポリオレフィン系微細多孔膜では
シリカが露出している近傍では親水性となり水に良く濡
れる。しかし、ポリオレフィンが露出している部分では
疎水性となり、水に濡れない部分が膜中に生成する。That is, the porous structure of the polyolefin-based microporous membrane is formed of polyolefin, but since polyolefin is hydrophobic, it alone repels water and cannot be used as a separator in an aqueous battery. Therefore, microporous polyolefin membranes to which silica is added to impart hydrophilic properties are used as separators for use in aqueous batteries. Therefore, in the polyolefin-based microporous membrane, the vicinity of exposed silica becomes hydrophilic and wets well with water. However, the exposed portions of the polyolefin become hydrophobic, creating areas in the membrane that do not get wet with water.
一方１本発明者らはポリオレフィン系多孔膜を臭素が透
過する機構として５主にイオン（Ｂｒ。On the other hand, the present inventors mainly used ions (Br) as the mechanism by which bromine permeates through a polyolefin porous membrane.
、Ｂｒ５−等）の形で水中を移動して透過する機構と気
体状の臭素（Ｂｒ２）が膜中の水に濡れない部分を拡散
していく機構の２通りがあることを見出した。It was discovered that there are two mechanisms: one is that bromine (Br2) moves through water in the form of bromine (Br5-, etc.) and permeates through the water, and the other is that gaseous bromine (Br2) diffuses through parts of the membrane that are not wetted by water.
第１表はシリカ−ポリエチレン系微細多孔膜のシリカを
フッ酸で溶出し完全に疎水性にしたちのと、未処理のも
のの臭素透過性を比較したものである。完全に疎水処理
したものは処理をしないものに較べ約１０倍も臭素透過
性が増大している。Table 1 compares the bromine permeability of a silica-polyethylene microporous membrane made completely hydrophobic by eluting the silica with hydrofluoric acid and that of an untreated membrane. The completely hydrophobically treated material has approximately 10 times more bromine permeability than the untreated material.
未処理品は、上記臭素透過機構の両者が起こっていると
考えられるが、疎水処理品では臭素透過は気体状の臭素
透過だけであることから、気体状の臭素透過はイオンの
形での臭素透過に較べ著しく速いと言える。It is thought that both of the above-mentioned bromine permeation mechanisms occur in the untreated product, but in the hydrophobically treated product, bromine permeation is only in gaseous form. It can be said that it is significantly faster than transmission.
そこで、ポリオレフィン系微細多孔膜中の疎水部分、即
ちポリオレフィン表面を親水化すれば気体状の臭素透過
は抑えられるため、全体として臭素透過性は減少すると
考えられた。Therefore, it was thought that if the hydrophobic portion of the polyolefin microporous membrane, that is, the surface of the polyolefin, was made hydrophilic, gaseous bromine permeation could be suppressed, resulting in a decrease in bromine permeability as a whole.
＊２ｍｏｌ／ｌ ＺｎＢｒｚ水溶液で測定また。電気抵
抗は電荷担体であるイオンがどれくらい通り易いかで支
配されるので、疎水性にすれば水に濡れ難くなるため、
第１表に示すシリカ溶出膜のように増大する。しかし、
親水化すれば水に良（濡れるようになるため、電気抵抗
の減少になりこそすれ、増大にはつながらない。*Measured using 2 mol/l ZnBrz aqueous solution. Electrical resistance is determined by how easily ions, which are charge carriers, can pass through, so making it hydrophobic makes it difficult to get wet with water.
The silica elution film increases as shown in Table 1. but,
If it becomes hydrophilic, it will become wettable with water, which will only lead to a decrease in electrical resistance, not an increase in it.
以上詳述したごとく、ポリオレフィン系微細多孔膜を亜
鉛−臭素電池セパレータに用いる場合には親水化するこ
とが重要である。なお、親水性を向上させるためには特
開昭６２−３１３２９２のごとく表面に露出するシリカ
を多くすることも有効であるが、露出面金てをシリカで
覆うことは不可能である。As detailed above, when using a polyolefin microporous membrane for a zinc-bromine battery separator, it is important to make it hydrophilic. In order to improve the hydrophilicity, it is effective to increase the amount of silica exposed on the surface as disclosed in JP-A-62-313292, but it is impossible to cover the exposed metal surface with silica.
本発明において注目すべきことは、上記のごとく、微細
多孔膜中のポリオレフィンが親水化処理しであることで
ある。かかる親水化処理手段としては１例えば上記微細
多孔膜をクロロスルフォン酸、硫酸５発煙硫酸重クロム
酸と硫酸の混合液など、ポリオレフィンを酸化する力の
ある液体により処理する。即ち、上記微細多孔膜を該液
体中に浸漬することなどにより処理する。これにより２
微細多孔膜内の細孔表面のポリオレフィンまで。What should be noted in the present invention is that, as mentioned above, the polyolefin in the microporous membrane has been subjected to hydrophilic treatment. Such hydrophilic treatment means include, for example, treating the microporous membrane with a liquid capable of oxidizing polyolefins, such as chlorosulfonic acid, sulfuric acid, fuming sulfuric acid, a mixture of dichromic acid and sulfuric acid. That is, the microporous membrane is treated by immersing it in the liquid. This results in 2
down to the polyolefin on the surface of the pores within the microporous membrane.
親水化することができる。Can be made hydrophilic.
この点について、詳述すれば次のようである。This point will be explained in detail as follows.
即ち、微細多孔膜の内部の細孔表面まで親水化処理する
ためには、酸化力のある液体に微細多孔膜を浸漬するこ
とが有効である。浸漬する液としては、具体的には、ク
ロロスルフォン酸液３種々のクロム酸混液〔例えば（ａ
）重クロム酸カリ３０ｇ／ １００ ｍ ｌ水＋濃硫酸
２００ｍＬ（ｂ）無水クロム酸７５ｇ＋硫酸２５０ｍＩ
Ｖ、に水に加え１１にする。（Ｃ）重クロム酸カリウム
２５ｇ＋硫酸５００ｍＡ＋リン酸１５０ｍｆｆ１＋水３
５０ｍｆ！など〕、濃硫酸または５〜２５％の発煙硫酸
液などが挙げられる。That is, in order to hydrophilize the surface of the pores inside the microporous membrane, it is effective to immerse the microporous membrane in an oxidizing liquid. Specifically, the liquid to be immersed in is a mixture of three chlorosulfonic acid solutions and various chromic acids [for example, (a
) Potassium dichromate 30g/100ml water + concentrated sulfuric acid 200ml (b) Chromic anhydride 75g + sulfuric acid 250ml
V, add water to 11. (C) Potassium dichromate 25g + sulfuric acid 500mA + phosphoric acid 150mff1 + water 3
50mf! etc.], concentrated sulfuric acid, or a 5-25% oleum solution.
ポリオレフィンには２通常、親水性の官能基がついてお
らず疎水性のアルキル基が直接露出しているため水に濡
れにくい、上記液体にポリオレフィンを浸漬した場合に
は、上記液体の酸化力のためにポリオレフィン鎖に酸素
が付加し、ケトン基（−ＣＯ）、カルボキシル基（−Ｃ
ＯＯＨ）、水酸基（−ＯＨ）などの親水性の官能基が導
入される。このためこれらの液に浸漬した場合、ポリオ
レフィンに親水性が付加されることになり、水に濡れ易
くなる。Polyolefins usually do not have hydrophilic functional groups and hydrophobic alkyl groups are directly exposed, making them difficult to wet with water. Oxygen is added to the polyolefin chain to form a ketone group (-CO), a carboxyl group (-C
Hydrophilic functional groups such as OOH) and hydroxyl groups (-OH) are introduced. Therefore, when immersed in these liquids, polyolefin becomes hydrophilic and becomes easily wetted by water.
この様な浸漬による酸化処理では、いずれの液でも浸漬
時間が長いほどポリオレフィンの親水性向上の効果は大
きくなるが、浸漬時間をある程度以上長くすれば、それ
以上効果は大きくならない。In such oxidation treatment by immersion, the effect of improving the hydrophilicity of polyolefin increases as the immersion time increases in any liquid, but if the immersion time is increased beyond a certain point, the effect does not become any greater.
クロロスルフォン酸の場合には８時間程度、クロム酸混
液では１時間程度１発煙硫酸では１時間程度で親水性向
上の効果はほぼ飽和する。なお２発煙硫酸の場合１発煙
硫酸濃度を高くすると酸化効果が向上するが、あまり濃
くし過ぎると内部まで処理が進行しないうちに１表面が
極端に酸化され脱落を起こす、そのため５発煙硫酸濃度
は上記５〜２５％の範囲にとどめるのが望ましい。The effect of improving hydrophilicity is almost saturated in about 8 hours in the case of chlorosulfonic acid, about 1 hour in the case of a chromic acid mixture, and about 1 hour in the case of fuming sulfuric acid. In the case of 2-fuming sulfuric acid, increasing the concentration of 1-fuming sulfuric acid will improve the oxidation effect, but if the concentration is too high, the surface of 1-1 will be extremely oxidized and fall off before the treatment progresses to the inside, so the concentration of 5-fuming sulfuric acid will be It is desirable to keep it within the above range of 5 to 25%.
なお、セパレータ中のポリオレフィンを酸化し親水性を
付与するためには、上記の薬品以外で行っても良く９本
発明はポリオレフィン親水性付与の手段として上記薬品
による処理に限定するものではない、また、上記薬品処
理とは異なり、親水化処理手段としては、微細多孔膜を
火災で焼くとか、プラズマ照射を行なうとかの方法もあ
る。しかし、この方法は微細多孔膜の内部まで充分に親
水化を行なうことができず、効果は少ない。Note that in order to oxidize the polyolefin in the separator and impart hydrophilicity to it, chemicals other than those mentioned above may be used.9 The present invention is not limited to treatment with the above-mentioned chemicals as a means of imparting hydrophilicity to polyolefin. Unlike the above-mentioned chemical treatment, other hydrophilic treatment methods include burning the microporous membrane with fire or plasma irradiation. However, this method cannot sufficiently make the inside of the microporous membrane hydrophilic and has little effect.
（作用及び効果）
ポリオレフィン系微細多孔膜には、前記親水性を付与す
るためにシリカが添加されている。しかし、セパレータ
内の細孔表面全てをシリカが覆うように分散されること
は困難で、ポリオレフィンが露出する部分が生じてしま
う。(Functions and Effects) Silica is added to the polyolefin microporous membrane in order to impart the above-mentioned hydrophilicity. However, it is difficult for the silica to be dispersed so as to cover all the pore surfaces within the separator, resulting in areas where the polyolefin is exposed.
そして、このポリオレフィンが露出している部分は、ポ
リオレフィンが疎水性のため水とのｇＩ染みが悪く、１
ｉ解液に濡れない気孔が生じてしまう。Since polyolefin is hydrophobic, the area where this polyolefin is exposed has poor gI staining with water.
i Pores are created that cannot be wetted by the solution.
一方、電解液中の臭素がセパレータを透過する機構には
、前記のごとく、イオンとして電解液中を泳動して透過
する場合と、気体状の臭素としてセパレータ中の気孔を
拡散するものの２通りがあり、後者は前者に較べ移動速
度が遥かに速い。そのため、セパレータ中の気孔を減少
させてやれば臭素透過速度を抑制することができる。ま
た、電気抵抗には電荷担体であるイオンの移動しやすさ
が関係するので、セパレータを親水化し気孔を減少させ
ることで電気抵抗が増大することはなくむしろ減少の方
向に作用する。On the other hand, as mentioned above, there are two mechanisms by which bromine in the electrolyte permeates through the separator: bromine migrates through the electrolyte as ions and diffuses through the pores in the separator. Yes, the latter moves much faster than the former. Therefore, by reducing the pores in the separator, the bromine permeation rate can be suppressed. Further, since electrical resistance is related to the ease of movement of ions, which are charge carriers, by making the separator hydrophilic and reducing pores, the electrical resistance does not increase, but rather decreases.
本発明では、微細多孔膜の細孔内に露出しているポリオ
レフィンを酸化処理して、水との馴染みを改善しく親水
性付与）セパレータ内に気孔を生じ難くしたため、気体
状の臭素透過が大幅に減少し、全体として臭素透過の低
下が図れた。In the present invention, the polyolefin exposed in the pores of the microporous membrane is oxidized to improve its compatibility with water and make it hydrophilic.This makes it difficult to form pores in the separator, which significantly reduces the permeation of gaseous bromine. This resulted in an overall reduction in bromine permeation.
また、臭素透過の少ないセパレータを用いれば正極から
負極に拡散する臭素量が減少するため負極に電析した亜
鉛と臭素の直接反応による自己放電も低下し、電池のク
ーロン効率の向上が図られる。Furthermore, if a separator with low bromine permeation is used, the amount of bromine that diffuses from the positive electrode to the negative electrode will be reduced, thereby reducing self-discharge due to the direct reaction between zinc and bromine deposited on the negative electrode, thereby improving the Coulombic efficiency of the battery.
したがって２本発明によれば、電気抵抗を増大させるこ
とな（臭素透過性を低下させ、クーロン効率の向上を図
ることができる。電池性能に優れた亜鉛−臭素電池を提
供することができる。Therefore, according to the present invention, it is possible to improve the coulombic efficiency without increasing the electrical resistance (lowering the bromine permeability), and to provide a zinc-bromine battery with excellent battery performance.
また９本発明によれば５通常のポリオレフィン系微細多
孔膜を単に処理液に浸漬するだけであるため、極めて簡
単に廉価に性能改善が達成される。Further, according to the present invention, since a conventional polyolefin microporous membrane is simply immersed in a treatment liquid, performance improvement can be achieved extremely easily and at low cost.
第１実施例
ポリオレフィン系微細多孔膜中のポリオレフィンを親水
化するため、１００％クロロスルフォン酸を使用し、浸
漬時間を変えてその効果を検討した。First Example In order to make the polyolefin in a microporous polyolefin membrane hydrophilic, 100% chlorosulfonic acid was used and the effect was examined by changing the immersion time.
まず、親水化処理手順は次の通りである。予め十分水洗
いしたポリオレフィン系微細多孔膜を１００％クロロス
ルフォン酸液中に所定時間浸漬し。First, the hydrophilic treatment procedure is as follows. A polyolefin microporous membrane that had been thoroughly washed with water in advance was immersed in a 100% chlorosulfonic acid solution for a predetermined period of time.
その後これを９８％濃硫酸、５０％濃硫酸、２５％濃硫
酸の順に、徐々に硫酸濃度の薄い水溶液で洗浄し、最後
に良く水洗を行った。Thereafter, this was washed with an aqueous solution of gradually dilute sulfuric acid concentration in the order of 98% concentrated sulfuric acid, 50% concentrated sulfuric acid, and 25% concentrated sulfuric acid, and finally thoroughly washed with water.
次に、上記のごとくして得た。親水化した微細多孔膜を
前記セパレータとして用い、＠気抵抗を測定した。It was then obtained as described above. The hydrophilic microporous membrane was used as the separator, and the air resistance was measured.
第２図に、セパレータの電気抵抗測定に用いた測定セル
を示す、該測定セルは、セパレータ４０を内板４３．４
４で挟み、該内板４３．４４と外板４５．４６との間に
はカーボン電極５１．５２を設けたものである。そして
、セパレータ４０の両側にカーボン電極５１．５２との
間に電解液室４１．４２を設ける。なお、符号５０は測
定メータ（ＬＣＲメータ）である。FIG. 2 shows a measurement cell used to measure the electrical resistance of the separator.
4, and a carbon electrode 51.52 is provided between the inner plate 43.44 and the outer plate 45.46. Further, electrolyte chambers 41.42 are provided on both sides of the separator 40 between the carbon electrodes 51.52. In addition, the code|symbol 50 is a measurement meter (LCR meter).
しかして、上記のごとく９測定セル中央部にセパレータ
を挟んだ場合と挟まない場合で、カーボン電極間の抵抗
を交流で測定し、その差からセパレータの抵抗を計算す
る。なお、測定電解液には２ ｍ ｏ ｌ ／ １の臭
素亜鉛水溶液を用いた。As described above, the resistance between the carbon electrodes is measured using alternating current, with and without a separator sandwiched in the center of the 9 measurement cells, and the resistance of the separator is calculated from the difference. Note that a 2 mol/1 zinc bromine aqueous solution was used as the electrolytic solution for measurement.
次に、上記親水化した微細多孔膜について、臭素透過係
数を測定した。第３図に、臭素透過係数測定セル６を示
す。本セル６は、中央のセパレータ４０により二つの室
に仕切られている。なお。Next, the bromine permeability coefficient of the hydrophilized microporous membrane was measured. FIG. 3 shows the bromine permeability coefficient measuring cell 6. This cell 6 is partitioned into two chambers by a separator 40 in the center. In addition.
符号６３はスターシーである。一方の濃厚室６１には２
ｍｏｌ／ｊ！ＺｎＢｒｚ 、０．２ｍｏｆｆｉ／／！Ｂ
ｒ、の臭素濃度濃厚液を、他方の希薄室６２には２ｍｏ
ｌ／１ＺｎＢｒｚ、０．０２ｍｏｊ２／ｊ！Ｂｒ、をそ
れぞれ同量入れ１画室の臭素（Ｂｒ。Reference numeral 63 is Starcy. In one concentration room 61, there are 2
mol/j! ZnBrz, 0.2moffi//! B
bromine concentration concentrated liquid of 2 mo in the other dilution chamber 62.
l/1ZnBrz, 0.02moj2/j! Add the same amount of each bromine (Br) to one chamber.
）濃度を経時的に測定する。臭素は濃い方の濃厚室６１
から薄い方の希薄室６２に拡散するため。) Measure the concentration over time. Bromine is concentrated in the concentrated chamber 61
in order to diffuse into the thinner dilution chamber 62.
ｆＡｗ−室６１の臭素濃度は経時的に低下し、希薄室
理によっても電気抵抗は変化せず、低いまま維持６
２の臭素濃度は経時的に増加する。この時の変 で
きることが分る。The bromine concentration in fAw-chamber 61 decreases over time, and the bromine concentration in the dilute chamber
Electrical resistance does not change and remains low even if
The bromine concentration of 2 increases over time. At this time, I know that I can change things.
化は、Ｆｉｃｋの第１法則から次式で表せられる。
第２表 （クロロスルフォン酸処理）Ｐ ： 透過係数
（ｃｔｓ／ ｓ ｅ ｃ ）Ａ ： セパレータ面積（
ｃＪ）
Ｖ ： 電解液量（ｃｄ）
Ｃ： 時刻りでの臭素濃度（ｍｏｌ／＃）Ｃ６： 初期
臭素濃度（ｍｏｌ／ｊ２）ｔ ： 時間（ｓｅｃ）
上記の画室それぞれについて、上記（１）式の左辺を時
間に対してプロットすると直線が得られ。can be expressed by the following equation from Fick's first law.
Table 2 (Chlorosulfonic acid treatment) P: Permeability coefficient (cts/sec) A: Separator area (
cJ) V: Electrolyte volume (cd) C: Bromine concentration at time (mol/#) C6: Initial bromine concentration (mol/j2) t: Time (sec) For each of the above compartments, the above formula (1) Plotting the left-hand side of against time yields a straight line.
その傾きから臭素透過係数が計算される。The bromine permeability coefficient is calculated from the slope.
第２表は、処理時間を変えたときの臭素透過係数の測定
結果を、まとめたものである。Table 2 summarizes the measurement results of the bromine permeability coefficient when the treatment time was changed.
同表より知られるごとく、短時間の処理では効果はない
が、４時間以上処理したものでは、未処理に比べ、臭素
透過係数が低下しており、臭素透過性の抑制改善効果が
認められた。また、上記処＊ ２ ｍ ｏ ｌ ／ ｌ
Ｚ ｎ Ｂ ｒ ２水溶液で測定第２実施例
ポリオレフィン系微細多孔膜中のポリオレフィンを親水
化するために、クロム酸混液を使用し。As can be seen from the table, short-term treatment has no effect, but when treated for 4 hours or more, the bromine permeability coefficient was lower than that without treatment, indicating an improvement effect in suppressing bromine permeability. . In addition, the above * 2 m o l / l
Measurement using Z n B r 2 aqueous solution Second Example A chromic acid mixture was used to make the polyolefin in the microporous polyolefin membrane hydrophilic.
処理温度、処理時間を変えたときの処理効果を検討した
。We investigated the treatment effects when changing the treatment temperature and treatment time.
クロム酸混液としては１重クロム酸カリ （Ｋ。As a chromic acid mixture, potassium monochromate (K.
Ｃｒｚ Ｏｑ ）３０ｇを水１００ｍｆｆ１に溶解した
ものに、濃硫酸２００ｍｆｆ１を加え十分撹拌後、ｎ置
して、その上澄み液を用いた。処理温度は室温と８０°
Ｃの二通りとし、８０″Ｃの処理の時には処理液を８０
°Ｃの恒温槽に浸漬して処理を行った。200 mff1 of concentrated sulfuric acid was added to a solution of 30 g of CrzOq) dissolved in 100 mff1 of water, and after thorough stirring, the mixture was left to stand, and the supernatant liquid was used. Processing temperature is room temperature and 80°
There are two types of C, and when processing at 80"C, the processing solution is 80"C.
The treatment was performed by immersing it in a constant temperature bath at °C.
処理手順は次の通りである。予め十分水洗したポリオレ
フィン系微細多孔膜を上記クロム酸混液中に所定時間浸
漬後、処理した膜を水で十分洗浄した。そして、第１実
施例と同様の測定を行った。The processing procedure is as follows. The polyolefin microporous membrane, which had been thoroughly washed in advance with water, was immersed in the chromic acid mixture for a predetermined time, and then the treated membrane was thoroughly washed with water. Then, the same measurements as in the first example were performed.
第３表は各々の温度で処理したときの、処理時間と臭素
透過係数の関係を測定した結果である。Table 3 shows the results of measuring the relationship between treatment time and bromine permeability coefficient when treated at each temperature.
同表より知られるごとく、未処理に較べ、５分以上処理
したものでは臭素透過係数が大きく減少したことが認め
られ、処理時間が多いほど臭素透過係数の減少は大きく
なった。しかし、３０分処理品と６０分処理品では臭素
透過係数は変わらずこれ以上処理時間を伸ばしても処理
効果は増加しない。また、上記処理によっても、電気抵
抗は変化せず、低いまま維持できることがわかる。As can be seen from the table, it was observed that the bromine permeability coefficient decreased significantly in the samples treated for 5 minutes or more compared to the untreated sample, and the longer the treatment time, the greater the decrease in the bromine permeability coefficient. However, the bromine permeability coefficient remains unchanged between the products treated for 30 minutes and the products treated for 60 minutes, and the treatment effect does not increase even if the treatment time is extended any further. Further, it can be seen that even with the above treatment, the electrical resistance does not change and can be maintained at a low level.
第３表 （クロム酸混液処理）
＊２ｍｏＩ！、／ＩＺｎＢｒｇ水溶液で測定第３実施例
ポリオレフィン系微細多孔膜中のポリオレフィンを親水
化するために１発煙硫酸を使用し、その濃度、処理時間
を変えて処理効果を検討した。Table 3 (Chromic acid mixture treatment) *2 moI! , /IZnBrg aqueous solution Third Example In order to make the polyolefin in the polyolefin microporous membrane hydrophilic, fuming sulfuric acid was used, and the treatment effect was examined by changing its concentration and treatment time.
発煙硫酸溶液は試薬の６０％発煙硫酸液（Ｈ２Ｓ０４ｘ
ＳＯｉ）を濃硫酸で稀釈し それぞれＳＯツ濃度が６．
１２．２４％の処理液を調製した。The fuming sulfuric acid solution is a reagent of 60% oleum solution (H2S04x
SOi) was diluted with concentrated sulfuric acid until the SO concentration was 6.
A 12.24% treatment solution was prepared.
処理手順は次の通りである。予め十分水洗したポリオレ
フィン系微細多孔膜を上記処理液に所定時間浸漬し、そ
の後９８％濃硫酸、５０％濃硫酸。The processing procedure is as follows. A polyolefin microporous membrane that had been sufficiently washed with water in advance was immersed in the above treatment solution for a predetermined time, and then 98% concentrated sulfuric acid and 50% concentrated sulfuric acid.
２５％濃硫酸の順に２次第に硫酸濃度の低い水溶液で洗
浄してから十分水洗を行った。It was washed with 25% concentrated sulfuric acid and then with aqueous solutions with progressively lower sulfuric acid concentrations, and then thoroughly washed with water.
第４図は、１２％発煙硫酸液で処理したときの処理時間
と臭素透過係数の関係を示したものである。１時間まで
は処理時間が長いほど上記係数は減少しており、１時間
では係数は２０％以上も低減されている。しかし、１時
間以降は処理時間を長くしても係数の低下は認められず
、１時間で処理効果はほぼ飽和することが分かった。FIG. 4 shows the relationship between treatment time and bromine permeability coefficient when treated with a 12% oleum solution. The coefficient decreases as the processing time increases up to 1 hour, and the coefficient decreases by more than 20% at 1 hour. However, after 1 hour, no decrease in the coefficient was observed even if the treatment time was increased, and it was found that the treatment effect was almost saturated after 1 hour.
第５図は１発煙硫酸濃度の異なる処理液で処理時間５分
の処理を行ったときの臭素透過係数の測定結果であるが
１発煙硫酸濃度による差は認められなかった。また 発
煙硫酸濃度をさらに高くした処理液を用いると、被処理
膜は即座に炭化される傾向が強くなるため、処理液の発
煙硫酸濃度は２５％以下程度が良い。FIG. 5 shows the measurement results of the bromine permeability coefficient when treatment was carried out for 5 minutes using treatment solutions with different concentrations of oleum, and no difference was observed depending on the concentration of oleum. Furthermore, if a treatment liquid with a higher concentration of fuming sulfuric acid is used, the film to be treated tends to be immediately carbonized, so the concentration of oleum in the treatment liquid is preferably about 25% or less.
なお、第６図は１２％発煙硫酸を行ったときの電気抵抗
を測定した結果である。同図に示されるように２発煙硫
酸処理による電気抵抗の増加は全く認められなかった。Note that FIG. 6 shows the results of measuring electrical resistance when 12% oleum was added. As shown in the figure, no increase in electrical resistance was observed due to the oleum treatment.
上記実施例から知られるごとく１本発明によれば、電気
抵抗を増大させることなく、臭素透過性を低下させるこ
とができた。As can be seen from the above examples, according to the present invention, bromine permeability could be reduced without increasing electrical resistance.
第１図は本発明に関するセパレータを用いた亜鉛−臭素
電池の概略構成図、第２図はセパレータ抵抗測定用セル
の断面図、第３図はセパレータ臭素透過係数測定用セル
の断面図、第４図は発煙硫酸処理を行った場合の処理時
間と臭素透過係数の関係を示す線図、第５図は発煙硫酸
処理時の発煙硫酸濃度と臭素透過係数の関係を示す線図
、第６図は発煙硫酸処理を行った場合の処理時間と電気
抵抗との関係を示す線図である。
３１１．電池本体。
３０．４０．、、 セパレータ。
３００、、、臭素錯化合物。
３１、、、正極室
３２、、、負極室。
６１、、、臭素濃度濃厚室。
６２、、、臭素濃度希薄室。
第１図FIG. 1 is a schematic diagram of a zinc-bromine battery using a separator according to the present invention, FIG. 2 is a cross-sectional view of a cell for measuring separator resistance, FIG. 3 is a cross-sectional view of a cell for measuring separator bromine permeability coefficient, and FIG. The figure is a diagram showing the relationship between treatment time and bromine permeability coefficient when oleum treatment is performed, Figure 5 is a diagram showing the relationship between fuming sulfuric acid concentration and bromine permeability coefficient during fuming sulfuric acid treatment, and Figure 6 is a diagram showing the relationship between oleum concentration and bromine permeability coefficient. FIG. 3 is a diagram showing the relationship between treatment time and electrical resistance when performing fuming sulfuric acid treatment. 311. Battery body. 30.40. ,, separator. 300, Bromine complex compound. 31,,,Positive electrode chamber 32,,,Negative electrode chamber. 61, Bromine concentration chamber. 62, Bromine concentration dilution chamber. Figure 1
Claims (1)
ィンとシリカとよりなるポリオレフィン系微細多孔膜に
おいて、ポリオレフィン部分を親水化処理してなること
を特徴とする亜鉛−臭素電池セパレータ。A zinc-bromine battery separator, which is used as a separator for a zinc-bromine battery, and is made of a polyolefin microporous membrane made of polyolefin and silica, in which the polyolefin portion is treated to make it hydrophilic.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63317154A JPH02162663A (en) | 1988-12-15 | 1988-12-15 | Zinc-bromine battery separator |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63317154A JPH02162663A (en) | 1988-12-15 | 1988-12-15 | Zinc-bromine battery separator |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02162663A true JPH02162663A (en) | 1990-06-22 |
Family
ID=18085051
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63317154A Pending JPH02162663A (en) | 1988-12-15 | 1988-12-15 | Zinc-bromine battery separator |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02162663A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014241254A (en) * | 2013-06-12 | 2014-12-25 | トヨタ自動車株式会社 | Metal air battery |
-
1988
- 1988-12-15 JP JP63317154A patent/JPH02162663A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014241254A (en) * | 2013-06-12 | 2014-12-25 | トヨタ自動車株式会社 | Metal air battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6581635B2 (en) | Redox flow battery based on support solution containing chloride | |
| Gao et al. | Poly (vinylidene fluoride)-based hybrid gel polymer electrolytes for additive-free lithium sulfur batteries | |
| KR102410425B1 (en) | All-vanadium sulfate acid redox flow battery system | |
| KR100350840B1 (en) | Modified cation exchange membranes and methods of making such membranes for use in electrochemical cells | |
| JP7013306B2 (en) | Ionic liquid as a promoter to improve the performance of oxygen reduction catalysts used in fuel cells | |
| Dewi et al. | Cationic polysulfonium membrane as separator in zinc–air cell | |
| Braun et al. | Thermodynamic aspects of redox reactions on electrodes coated with thin, ion exchanging polymer films | |
| Wu et al. | A polymer lithium–oxygen battery based on semi-polymeric conducting ionomers as the polymer electrolyte | |
| US20060008692A1 (en) | Solid electrolyte and electrochemical system including the solid electrolyte | |
| JP2022535691A (en) | Redox flow battery system and methods of manufacture and operation | |
| Nishikami et al. | Oxygen-enriched electrolytes based on perfluorochemicals for high-capacity lithium–oxygen batteries | |
| CN1417252A (en) | Ionic solid electrolyte, its preparation process and electrochemical system with the electrolyte | |
| Stadniychuk et al. | Sol‐Gel‐Derived Thin‐Film Manganese Dioxide Cathodes | |
| Kondou et al. | Rate performance of LiCoO2 half-cells using highly concentrated lithium bis (fluorosulfonyl) amide electrolytes and their relevance to transport properties | |
| CN105789657A (en) | Modified PES (polyether sulfones)-PVP (polyvinylpyrrolidone) hybrid anion exchange membrane for vanadium redox battery and preparation method of modified PES-PVP hybrid anion exchange membrane | |
| JP7207130B2 (en) | flow battery | |
| JPH02162663A (en) | Zinc-bromine battery separator | |
| Harth et al. | Application of nafion as a polymer solid electrolyte for voltammetry in the absence of a contacting electrolyte solution | |
| Vijayakumar et al. | Investigation on electrochemical performance of new flexible nanocomposite poly (vinylidene fluoride-co-hexafluoropropylene) polymer electrolytes | |
| Seeponkai et al. | The effects of sulfonated graphene oxides (sGO) on ion conductivity and permeability of the vanadium redox flow batteries membranes based on sulfonated poly (ether ether ketone) composite | |
| WO2021253128A1 (en) | Separators for aqueous zinc-ion cells and batteries, zinc metal batteries, and methods of fabricating a separator for use in a zinc metal battery | |
| JPH04312764A (en) | Separator for zinc-bromine battery | |
| CN108134096B (en) | Modification method of carbon felt electrode for all-vanadium redox flow battery | |
| JPH0395856A (en) | Lithium secondary battery | |
| JPH01157071A (en) | Separator for zinc-bromine battery |