JP2005209453A - Stationary electrolyte zinc-bromine secondary battery for power - Google Patents

Stationary electrolyte zinc-bromine secondary battery for power Download PDF

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JP2005209453A
JP2005209453A JP2004013511A JP2004013511A JP2005209453A JP 2005209453 A JP2005209453 A JP 2005209453A JP 2004013511 A JP2004013511 A JP 2004013511A JP 2004013511 A JP2004013511 A JP 2004013511A JP 2005209453 A JP2005209453 A JP 2005209453A
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bromine
secondary battery
zinc
negative electrode
electrolyte
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JP4578812B2 (en
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Yasuo Nagano
泰男 永野
Kozo Osawa
幸造 大澤
Shigeru Sakai
酒井　　茂
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a stationary electrolyte zinc-bromine secondary battery for power capable of displaying satisfactory performance of secondary batteries for power, having simple construction, and capable of being easily assembled. <P>SOLUTION: The battery is a one-pack type stationary electrolyte zinc-bromine secondary battery for power equipped with a negative pole 24 and a positive pole 20 having corrosion resistance to an electrolyte containing zinc bromide. On the positive pole 20 side of the negative pole 24, a non-conductive bromine adsorption filter layer 16 which is made of nonwoven fabric made up of glass fiber whose superficial area measured by a BET method is 0.5 m<SP>2</SP>/g or more, adsorbs bromine in the electrolyte and prevents the bromine from reaching the negative pole, is provided, and between the filter layer 16 and the positive pole 20, a conductive bromine accumulation layer 18 which is made of graphite particles, adsorbs and accumulates bromine generated on the positive pole 20 when charging is performed, is provided. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

本発明は電力用電解液静止型亜鉛―臭素二次電池に関し、更に詳細には臭化亜鉛を含有する電解液に対して耐食性を有する導電性材料から成る正極と負極とを具備する電力用電解液静止型亜鉛―臭素二次電池に関する。   TECHNICAL FIELD The present invention relates to a power electrolyte stationary zinc-bromine secondary battery, and more particularly, to a power electrolyte comprising a positive electrode and a negative electrode made of a conductive material having corrosion resistance to an electrolyte containing zinc bromide. The present invention relates to a liquid static zinc-bromine secondary battery.

亜鉛―臭素二次電池は、電極反応の起電力が１．８２Ｖ、理論エネルギー密度が４３０Ｗｈ／ｋｇと比較的高いため、近年、深夜電力の充電用や電気自動車用の電力用二次電池として見直されつつある。
かかる電力用亜鉛―臭素二次電池としては、従来、図５に示すものが知られていた。図５に示す電力用亜鉛―臭素二次電池は、セル１００がイオン交換膜や多孔質膜から成るセパレータ１０２によって正極室１０４と負極室１０６とに隔されて、正極室１０４には、白金等の耐酸性の金属から成る正極１０８が設けられており、負極室１０６には、亜鉛金属から成る負極１１０が設けられている。
また、正極室１０４には、臭化亜鉛を含有する正極電解液１１２を貯留する正極タンク１１４が設けられており、正極タンク１１４と正極室１０４との間には、正極電解液１１２を循環する循環ポンプ１１６が設けられいる。
更に、負極室１０６には、臭化亜鉛を含有する負極電解液１１８を貯留する負極タンク１２０が設けられており、負極タンク１０６と負極室１２０との間には、負極電解液１１８を循環する循環ポンプ１２２が設けられいる。
図５に示す電力用亜鉛―臭素二次電池では、充電の際には、負極１１０でＺｎ2+＋２ｅ→Ｚｎの電気化学反応が生じ、正極１０８で２Ｂｒ-→Ｂｒ2＋２ｅの電気化学反応が生じる。正極１０８での反応によって生じた臭素の一部分は電解液中に溶解するが、大部分は電解液中に配合された錯化剤によって錯化合物となって正極タンク１１４内に蓄積される。
一方、放電の際には、負極１１０及び正極１０８の各々に、充電の際と逆の反応が生じ、電気エネルギーが放出される。 Zinc-bromine secondary batteries have a relatively high electromotive force of electrode reaction of 1.82 V and a theoretical energy density of 430 Wh / kg, which has recently been reviewed as a secondary battery for charging late-night power and electric vehicles. It is being
As such a power zinc-bromine secondary battery, one shown in FIG. 5 has been conventionally known. In the power zinc-bromine secondary battery shown in FIG. 5, a cell 100 is separated into a positive electrode chamber 104 and a negative electrode chamber 106 by a separator 102 made of an ion exchange membrane or a porous membrane. A positive electrode 108 made of acid-resistant metal is provided, and a negative electrode 110 made of zinc metal is provided in the negative electrode chamber 106.
The positive electrode chamber 104 is provided with a positive electrode tank 114 that stores a positive electrode electrolyte solution 112 containing zinc bromide. The positive electrode electrolyte solution 112 is circulated between the positive electrode tank 114 and the positive electrode chamber 104. A circulation pump 116 is provided.
Further, the negative electrode chamber 106 is provided with a negative electrode tank 120 that stores a negative electrode electrolyte 118 containing zinc bromide, and the negative electrode electrolyte 118 is circulated between the negative electrode tank 106 and the negative electrode chamber 120. A circulation pump 122 is provided.
In the power zinc-bromine secondary battery shown in FIG. 5, during charging, an electrochemical reaction of Zn 2+ + 2e → Zn occurs at the negative electrode 110, and an electrochemical reaction of 2 Br − → Br 2 + 2e occurs at the positive electrode 108. Arise. A part of bromine generated by the reaction at the positive electrode 108 is dissolved in the electrolytic solution, but most of the bromine is accumulated in the positive electrode tank 114 as a complex compound by the complexing agent blended in the electrolytic solution.
On the other hand, during discharge, each of the negative electrode 110 and the positive electrode 108 undergoes a reaction opposite to that during charging, and electric energy is released.

しかし、図５に示す電力用亜鉛―臭素二次電池は、正極タンク１１４、負極タンク１２０、及び循環ポンプ１１６，１２２を必要とするため、小型化には限界がある。
一方、ビルや病院の非常用電源用等に用いる場合には、設置スペース等の関係から正極タンク１１４、負極タンク１２０、及び循環ポンプ１１６，１２２を要しない省スペースを図ることができる小型の電力用亜鉛―臭素二次電池が求められている。
これに対し、下記特許文献１には、循環ポンプ等を用いない電解液静止型亜鉛―臭素二次電池が提案されている。
かかる特許文献１に提案された電解液静止型亜鉛―臭素二次電池の概要を図６に示す。図６に示す電解液静止型亜鉛―臭素二次電池は、正極２００及び負極２０２の間にイオン交換膜や多孔質膜から成るセパレータ２０４で隔離して正極室２１０及び負極室２１２を形成し、正極室２１０内には、臭素亜鉛を含有する正極電解液を含浸した導電性カーボン層２０６が充填されて密閉されている共に、負極室２１２内には、臭素亜鉛及び四級アンモニウムブロマイド等の錯塩形成剤を含有する負極電解液を含浸した親水性多孔質プラスチック層２０８が密閉されている。
特許第２８５３２９４号公報（特許請求の範囲、図１） However, since the power zinc-bromine secondary battery shown in FIG. 5 requires the positive electrode tank 114, the negative electrode tank 120, and the circulation pumps 116 and 122, there is a limit to downsizing.
On the other hand, when used for an emergency power source in a building or hospital, etc., small power that can save space that does not require the positive electrode tank 114, the negative electrode tank 120, and the circulation pumps 116 and 122 due to the installation space and the like. There is a need for zinc-bromine secondary batteries.
On the other hand, Patent Document 1 below proposes an electrolyte stationary zinc-bromine secondary battery that does not use a circulation pump or the like.
FIG. 6 shows an outline of the electrolyte stationary zinc-bromine secondary battery proposed in Patent Document 1. The electrolyte stationary zinc-bromine secondary battery shown in FIG. 6 is formed by separating a positive electrode chamber 210 and a negative electrode chamber 212 between a positive electrode 200 and a negative electrode 202 with a separator 204 made of an ion exchange membrane or a porous membrane. The positive electrode chamber 210 is filled and sealed with a conductive carbon layer 206 impregnated with a positive electrode electrolyte containing zinc bromide, and the negative electrode chamber 212 has a complex salt such as zinc bromide and quaternary ammonium bromide. A hydrophilic porous plastic layer 208 impregnated with a negative electrode electrolyte containing a forming agent is sealed.
Japanese Patent No. 2853294 (Claims, FIG. 1)

図６に示す電解液静止型亜鉛―臭素二次電池を電力用二次電池に適用すると、図５に示す電力用亜鉛―臭素二次電池に比較して、正極タンク１１４、負極タンク１２０、及び循環ポンプ１１６，１２２を要しないため、小型化を図ることができる。
しかしながら、図６に示す電解液静止型亜鉛―臭素二次電池では、セパレータ２０４としてイオン交換膜や多孔質膜を用いているが、イオン交換膜から成るセパレータ２０４では、電力用二次電池での充電や放電の際に、大量に生成するイオンの通過量が制限され易く、充分に満足し得る電池性能を呈し難い。
一方、多孔質膜からセパレータ２０４では、多孔質膜に孔径が１μｍ以下の微細孔が形成されているものの、臭素イオン半径（１．８２×１０-4μｍ）や臭素原子半径（１．１４×１０-4μｍ）を考えると、極めて巨大な分子集団を形成しないと臭素の錯体も容易に通過し、充電の際に、正極で発生した臭素が負極に到達して、負極に析出している亜鉛と反応して電力ロスを生じ易い。
また、正極室２１０及び負極室２１２を形成し、正極室２１０及び負極室２１２内には、正極電解液を含浸した導電性カーボン層２０６や負極電解液を含浸した親水性多孔質プラスチック層２０８を充填することを要する。このため、図６に示す電解液静止型亜鉛―臭素二次電池は、構造が複雑である。
更に、図６に示す電解液静止型亜鉛―臭素二次電池で用いる正極電解液と負極電解液とは、互いの組成が異なる電解液であるため、構造が複雑であることと相俟って、電池の組立の際に、特別の注意を払う必要ある。
そこで、本発明の課題は、満足し得る電力用二次電池の性能を呈することができ、且つ構造が簡単であって、組立が容易な電力用電解液静止型亜鉛―臭素二次電池を提供することにある。 When the electrolyte stationary zinc-bromine secondary battery shown in FIG. 6 is applied to a power secondary battery, compared to the power zinc-bromine secondary battery shown in FIG. Since the circulation pumps 116 and 122 are not required, the size can be reduced.
However, in the electrolytic solution static zinc-bromine secondary battery shown in FIG. 6, an ion exchange membrane or a porous membrane is used as the separator 204. However, the separator 204 made of an ion exchange membrane is used in a power secondary battery. During charging and discharging, the amount of ions that are generated in large quantities is easily limited, and it is difficult to exhibit sufficiently satisfactory battery performance.
On the other hand, in the separator 204 from the porous membrane, although a fine pore having a pore diameter of 1 μm or less is formed in the porous membrane, a bromine ion radius (1.82 × 10 −4 μm) or a bromine atom radius (1.14 × 10 -4 μm), bromine complexes easily pass through unless a very large molecular group is formed. During charging, bromine generated at the positive electrode reaches the negative electrode and is deposited on the negative electrode. It easily reacts with zinc to cause power loss.
In addition, a positive electrode chamber 210 and a negative electrode chamber 212 are formed. In the positive electrode chamber 210 and the negative electrode chamber 212, a conductive carbon layer 206 impregnated with a positive electrode electrolyte and a hydrophilic porous plastic layer 208 impregnated with a negative electrode electrolyte are provided. Requires filling. Therefore, the structure of the electrolyte stationary zinc-bromine secondary battery shown in FIG. 6 is complicated.
Furthermore, the positive electrode electrolyte and the negative electrode electrolyte used in the electrolyte stationary zinc-bromine secondary battery shown in FIG. 6 are electrolytes having different compositions from each other, so that the structure is complicated. Special care must be taken during battery assembly.
Accordingly, an object of the present invention is to provide a power electrolyte stationary zinc-bromine secondary battery that can exhibit satisfactory power secondary battery performance, has a simple structure, and is easy to assemble. There is to do.

本発明者等は、前記課題を解決するには、正極室及び負極室を形成することなく一種類の電解液を用いる一液性の電力用電解液静止型亜鉛―臭素二次電池が有効であると考え検討したところ、負極の正極側に電解液中の臭素を吸着して負極への臭素の到達を阻止する非導電性の臭素吸着遮断層を設けることが有効であり、細いガラス繊維から成る広い表面積の不織布は臭素を効率よく吸着できることを見出し、本発明に到達した。
すなわち、本発明は、臭化亜鉛を含有する電解液に対して耐食性を有する導電性材料から成る正極と負極とを具備する一液性の電力用電解液静止型亜鉛―臭素二次電池であって、該負極の正極側に、ＢＥＴ法で測定した表面積が０．５ｍ2／ｇ以上のガラス繊維から成る不織布によって形成され、前記電解液中の臭素を吸着して負極への臭素の到達を阻止する非導電性の臭素吸着遮断層と、前記臭素吸着遮断層と正極との間に、無機材料によって形成され、充電の際に、前記正極で生じた臭素を吸収して蓄積する導電性の臭素蓄積層とが設けられていることを特徴とする電力用電解液静止型亜鉛―臭素二次電池にある。
かかる本発明において、臭素吸着遮断層を、不織布を形成するガラス繊維間にシリカ粉末を充填することによって、負極近傍の臭素を効果的に補足でき、充電の際に、正極で発生した臭素が負極に到達して惹起される電力ロスを防止できる。この不織布としては、ＢＥＴ法で測定した表面積が３ｍ2／ｇ以下の工業的に得られ易い不織布を用いることができる。
また、臭素蓄積層を、黒鉛粒子を主とする炭素材料によって形成することにより、大量の臭素を吸収貯蔵できる。
更に、臭素吸着遮断層と負極との間に、活性炭素繊維層又は多孔質炭素板を設けることによって、負極の電極面積を拡大でき、負極の接触抵抗を低下できる。 In order to solve the above-mentioned problems, the present inventors have effectively used a one-component liquid electrolyte-type zinc-bromine secondary battery for electric power that uses one type of electrolyte without forming a positive electrode chamber and a negative electrode chamber. As a result of consideration, it is effective to provide a non-conductive bromine adsorption blocking layer that adsorbs bromine in the electrolyte and prevents bromine from reaching the negative electrode on the positive electrode side of the negative electrode. It was found that the non-woven fabric having a large surface area can adsorb bromine efficiently, and the present invention has been achieved.
That is, the present invention is a one-component power electrolyte stationary zinc-bromine secondary battery having a positive electrode and a negative electrode made of a conductive material having corrosion resistance to an electrolyte containing zinc bromide. The negative electrode is formed of a non-woven fabric made of glass fibers having a surface area measured by the BET method of 0.5 m 2 / g or more, and adsorbs bromine in the electrolyte so that the bromine reaches the negative electrode. A non-conductive bromine adsorption blocking layer for blocking, and an electrically conductive material that is formed of an inorganic material between the bromine adsorption blocking layer and the positive electrode and absorbs and accumulates bromine generated at the positive electrode during charging. A bromine storage layer is provided in the stationary electrolyte for electric power zinc-bromine secondary battery.
In the present invention, the bromine adsorption blocking layer can be effectively supplemented with bromine in the vicinity of the negative electrode by filling the silica powder between the glass fibers forming the nonwoven fabric. It is possible to prevent power loss caused by reaching As this non-woven fabric, a non-woven fabric that is industrially easily obtained having a surface area measured by the BET method of 3 m 2 / g or less can be used.
Moreover, a large amount of bromine can be absorbed and stored by forming the bromine storage layer from a carbon material mainly composed of graphite particles.
Furthermore, by providing an activated carbon fiber layer or a porous carbon plate between the bromine adsorption blocking layer and the negative electrode, the electrode area of the negative electrode can be expanded and the contact resistance of the negative electrode can be reduced.

電力用亜鉛―臭素二次電池では、充電の際に、正極で発生した臭素が負極に到達すると、負極に析出している亜鉛と反応して電力ロスを生ずる。このため、臭素が負極に到達することを阻止することが必要である。
また、一種類の電解液を用いる一液性の電力用電解液静止型亜鉛―臭素二次電池では、その充電の際に、負極に亜鉛が析出して樹枝状結晶（デントライト）を生成し易い。かかるデントライトの形成は、両極間の短絡を引き起こすおそれがある。
この点、本発明においては、負極の正極側に、ＢＥＴ法で測定した表面積が０．５ｍ2／ｇ以上のガラス繊維から成る不織布によって形成され、電解液中の臭素を吸着して負極への臭素の到達を阻止する非導電性の臭素吸着遮断層を設け、この臭素吸着遮断層と正極との間に、無機材料から形成され、臭素を吸収して蓄積する導電性の臭素蓄積層を設けている。
このため、充電の際に、正極で発生した臭素の一部分は電解液に溶解するが、大部分は臭素蓄積層によって吸収し蓄積され、電解液に溶解した臭素も臭素吸着遮断層とによって吸着される。
したがって、正極で発生した臭素の負極への到達を阻止でき、臭素との錯塩を形成する錯塩形成剤を添加した電解液を用い、臭素の錯塩の通過を阻止するセパレータを設けることを要しない。
また、非導電性の臭素吸着遮断層は、導電性の臭素蓄積層と負極とを絶縁していると共に、臭素吸着遮断層に吸着された臭素は、負極から侵入してきた亜鉛を溶解するため、一液性の電力用電解液静止型亜鉛―臭素二次電池において問題となる負極での亜鉛のデントライトの生成・成長を防止できる。
更に、導電性の臭素蓄積層は、充放電の際に、層全体が正極となるため、内部抵抗を低下することができ、電池性能を向上できる。
この様に、本発明に係る一液性の電力用電解液静止型亜鉛―臭素二次電池は、錯形成剤が無添加の臭化亜鉛を含有する電解液を用いることができ、且つ臭素が負極に到達することによる電力ロスや負極に生成する亜鉛のデントライトを防止できるものであって、負極と正極との間に、無機材料から成る、非導電性の臭素吸着遮断層と導電性の臭素蓄積層とを設けた簡単な構造であって、組立を容易に行なうことができる。
その結果、本発明に係る一液性の電力用電解液静止型亜鉛―臭素二次電池は、小型化も容易に図ることができ、ビルや病院の非常用電源用等に好適に用いることができる。 In a power zinc-bromine secondary battery, when bromine generated at the positive electrode reaches the negative electrode during charging, it reacts with zinc deposited on the negative electrode to cause power loss. For this reason, it is necessary to prevent bromine from reaching the negative electrode.
Also, in a one-component power electrolyte static zinc-bromine secondary battery that uses one type of electrolyte, zinc is deposited on the negative electrode to form dendritic crystals (dentite) during charging. easy. The formation of such dent light may cause a short circuit between the two electrodes.
In this respect, in the present invention, the negative electrode is formed of a nonwoven fabric made of glass fibers having a surface area measured by the BET method of 0.5 m 2 / g or more on the positive electrode side, and adsorbs bromine in the electrolytic solution to the negative electrode. A non-conductive bromine adsorption blocking layer that blocks the arrival of bromine is provided, and a conductive bromine storage layer that is formed from an inorganic material and absorbs and accumulates bromine is provided between the bromine adsorption blocking layer and the positive electrode. ing.
For this reason, during charging, a part of bromine generated at the positive electrode dissolves in the electrolytic solution, but most of it is absorbed and accumulated by the bromine accumulating layer, and bromine dissolved in the electrolytic solution is also adsorbed by the bromine adsorption blocking layer. The
Therefore, it is possible to prevent bromine generated in the positive electrode from reaching the negative electrode, and it is not necessary to use an electrolytic solution to which a complex salt forming agent that forms a complex salt with bromine is added, and to provide a separator that prevents passage of the complex salt of bromine.
The non-conductive bromine adsorption blocking layer insulates the conductive bromine accumulation layer from the negative electrode, and bromine adsorbed on the bromine adsorption blocking layer dissolves zinc that has entered from the negative electrode. It can prevent the formation and growth of zinc dentlite at the negative electrode, which is a problem in a one-component liquid electrolyte electrolyte-type zinc-bromine secondary battery.
Furthermore, since the conductive bromine storage layer becomes the positive electrode during charging and discharging, the internal resistance can be reduced and the battery performance can be improved.
As described above, the one-component power electrolyte static zinc-bromine secondary battery according to the present invention can use an electrolyte solution containing zinc bromide to which no complexing agent is added, and It is possible to prevent power loss due to reaching the negative electrode and zinc dentlite generated in the negative electrode. Between the negative electrode and the positive electrode, a non-conductive bromine adsorption blocking layer made of an inorganic material and conductive It is a simple structure provided with a bromine storage layer, and can be assembled easily.
As a result, the one-component electrolytic solution stationary zinc-bromine secondary battery for electric power according to the present invention can be easily reduced in size, and can be suitably used for emergency power supplies in buildings and hospitals. it can.

本発明に係る電力用電解液静止型亜鉛―臭素二次電池の一例を図１に示す。図１に示す電力用電解液静止型亜鉛―臭素二次電池（以下、単に電力用二次電池と称することがある）は、ガラス製の円筒電槽１０の内周面に沿って亜鉛板から成る負極１２を配置し、その一部を円筒電槽１０の上面から突出して突出負極１２ａとする。この亜鉛板から成る負極１２は、臭化亜鉛を含む電解液に対して耐食性を有している。
かかる負極１２の内周面に沿って活性炭素繊維フェルトを配置し、活性炭素繊維層１４を形成する。この活性炭素繊維層１４は、負極１２の電極面積を大きくして負極１２の接触抵抗を低下するものである。
更に、活性炭素繊維層１４の内側には、ガラス繊維から成る不織布から成り、ガラス繊維間にシリカ粉末が充填された非導電性の臭素吸着遮断層１６が形成されている。この臭素吸着遮断層１６を形成するガラス繊維は、臭素を吸着する性質を有する。
尚、黒鉛板に貼り付けたガラス繊維から成る不織布内に臭素が満たされた後、ガラス繊維に吸着されない臭素は、電解液中に放出される。 An example of a power electrolyte stationary zinc-bromine secondary battery according to the present invention is shown in FIG. A power electrolyte stationary zinc-bromine secondary battery (hereinafter sometimes simply referred to as a power secondary battery) shown in FIG. 1 is formed from a zinc plate along the inner peripheral surface of a glass cylindrical battery case 10. The negative electrode 12 is disposed, and a part of the negative electrode 12 protrudes from the upper surface of the cylindrical battery case 10 to form a protruding negative electrode 12a. The negative electrode 12 made of this zinc plate has corrosion resistance against an electrolytic solution containing zinc bromide.
An activated carbon fiber felt is disposed along the inner peripheral surface of the negative electrode 12 to form the activated carbon fiber layer 14. The activated carbon fiber layer 14 increases the electrode area of the negative electrode 12 and decreases the contact resistance of the negative electrode 12.
Further, inside the activated carbon fiber layer 14, a nonconductive bromine adsorption blocking layer 16 made of a nonwoven fabric made of glass fibers and filled with silica powder between the glass fibers is formed. The glass fiber forming the bromine adsorption blocking layer 16 has a property of adsorbing bromine.
In addition, after the bromine is filled in the nonwoven fabric made of glass fibers attached to the graphite plate, bromine that is not adsorbed on the glass fibers is released into the electrolytic solution.

かかる臭素吸着遮断層１６は、臭素の通過を阻止するが、亜鉛イオンや臭素イオンは通過し、負極１２において所定の電気化学反応が進行する。
この臭素吸着遮断層１６を形成する不織布としては、１μｍ以下のガラス繊維を湿式抄紙法又は乾式抄紙法で抄紙して得た不織布を用いることができるが、湿式抄紙法で抄紙して得た不織布は、乾式抄紙法で抄紙して得た不織布に比較して厚さが均一であるため好ましい。
かかる不織布を形成するガラス繊維としては、耐酸性のものであればよいが、ケミカルガラス繊維が好ましい。
また、このガラス繊維から成る不織布としては、ＢＥＴ法で測定した表面積が０．５ｍ2／ｇ以上の不織布を用いる。表面積が０．５ｍ2／ｇ未満の不織布では、臭素を吸着する吸着面積が少なくなり、負極１２への臭素の到達を充分に阻止できず、電力ロスが生じる。
尚、かかる不織布としては、不織布の生産性等の観点からＢＥＴ法で測定した表面積が３ｍ2／ｇ以下の不織布を好適に用いることができる。 The bromine adsorption blocking layer 16 blocks the passage of bromine, but allows zinc ions and bromine ions to pass therethrough, and a predetermined electrochemical reaction proceeds in the negative electrode 12.
As the non-woven fabric forming the bromine adsorption blocking layer 16, a non-woven fabric obtained by making a paper fiber of 1 μm or less by a wet paper making method or a dry paper making method can be used. Is preferable because the thickness is uniform as compared with a non-woven fabric obtained by papermaking by a dry papermaking method.
The glass fiber forming the nonwoven fabric may be acid-resistant, but chemical glass fiber is preferable.
In addition, as the nonwoven fabric made of this glass fiber, a nonwoven fabric having a surface area measured by the BET method of 0.5 m 2 / g or more is used. In the nonwoven fabric having a surface area of less than 0.5 m 2 / g, the adsorption area for adsorbing bromine is reduced, and the arrival of bromine to the negative electrode 12 cannot be sufficiently prevented, resulting in power loss.
In addition, as this nonwoven fabric, the nonwoven fabric whose surface area measured by BET method is 3 m < 2 > / g or less can be used suitably from viewpoints, such as productivity of a nonwoven fabric.

図１に示す臭素吸着遮断層１６を形成する不織布には、ガラス繊維間にシリカ粉末が充填されている。かかるシリカ粉末は、臭素吸着遮断層１６に含浸された電解液の水分子の熱分子運動等に因る電解液の流動を可及的に抑制し、ガラス繊維に吸着された臭素が電解液の流動によって剥離することを防止するためである。
ガラス繊維間にシリカ粉末が充填された不織布は、例えばガラス繊維から成る不織布を、シリカ粉末が縣濁されている電解液に所定時間浸漬してから取り出すことによって得ることができる。或いは、ガラス繊維から成る不織布を二重にして、その間にシリカ粉末を充填することによっても得ることができる。
尚、不織布を浸漬したシリカ粉末を縣濁した電解液は、電池の電解液としては使用しない。 The nonwoven fabric forming the bromine adsorption blocking layer 16 shown in FIG. 1 is filled with silica powder between glass fibers. Such silica powder suppresses as much as possible the flow of the electrolytic solution caused by the thermal molecular motion of the water molecules of the electrolytic solution impregnated in the bromine adsorption blocking layer 16, and bromine adsorbed on the glass fiber is contained in the electrolytic solution. This is to prevent separation due to flow.
The nonwoven fabric in which the silica powder is filled between the glass fibers can be obtained by, for example, immersing the nonwoven fabric made of glass fibers in an electrolytic solution in which the silica powder is suspended for a predetermined time and then taking it out. Or it can obtain by making the nonwoven fabric which consists of glass fiber double, and filling a silica powder in the meantime.
In addition, the electrolyte solution which suspended the silica powder which immersed the nonwoven fabric is not used as an electrolyte solution of a battery.

図１に示す電力用二次電池では、臭素吸着遮断層１６の内側に、黒鉛粉末が充填されて成る導電性の臭素蓄積層１８が形成されており、臭素蓄積層１８の中心部近傍には、棒状の黒鉛から成る正極２０が挿入されている。棒状の正極２０の一端部は、円筒電槽１０の上面から突出されて突出正極２０ａが形成されている。
かかる臭素蓄積層１８を形成する黒鉛粒子では、臭素と黒鉛との層間化合物（Ｃ8Ｂｒ）を形成するため、臭素をよく吸収できる。
更に、臭素の層間化合物は、アクセプタの性質を持ち、よく電子を伝導するため、黒鉛粒子間の電気抵抗が低いことと相俟って、充放電の際に、内部抵抗を低下できる。従って、正極２０と黒鉛粒子から成る臭素蓄積層１８とは、全体で正極を形成する。
尚、黒鉛粒子から成る臭素蓄積層１８中を、電解液中の亜鉛イオンや臭素イオンは容易に移動できる。 In the secondary battery for electric power shown in FIG. 1, a conductive bromine storage layer 18 filled with graphite powder is formed inside the bromine adsorption blocking layer 16, and in the vicinity of the center of the bromine storage layer 18. A positive electrode 20 made of rod-like graphite is inserted. One end of the rod-shaped positive electrode 20 protrudes from the upper surface of the cylindrical battery case 10 to form a protruding positive electrode 20a.
The graphite particles forming the bromine storage layer 18 form an intercalation compound (C 8 Br) of bromine and graphite, and therefore can absorb bromine well.
Furthermore, since the intercalation compound of bromine has acceptor properties and conducts electrons well, coupled with the low electrical resistance between graphite particles, the internal resistance can be reduced during charging and discharging. Therefore, the positive electrode 20 and the bromine storage layer 18 made of graphite particles form a positive electrode as a whole.
Incidentally, zinc ions and bromine ions in the electrolytic solution can easily move in the bromine storage layer 18 made of graphite particles.

この負極１２、活性炭素繊維層１４、臭素吸着遮断層１６、臭素蓄積層１８及び正極２０を含浸する電解液としては、臭化亜鉛を含有する電解液を用いる。かかる電解液には、電気伝導性を向上する塩化カリウム等の電気伝導度向上剤を添加してもよい。
但し、塩化カリウム等の電気伝導度向上剤を添加した場合には、充放電の際に、少量の水素が発生することがあるため、ガラス製の円筒電槽１０に、水素パージ用の小孔２２，２２・・を開口しておくことが好ましい。
図１に示す電力用二次電池では、充電の際に、正極２０で発生した臭素は、臭素蓄積層１８によって吸収し蓄積され、この臭素蓄積層１８を通過した臭素も臭素吸着遮断層１６によって吸着されるため、臭素の通過を阻止して負極１２への到達を阻止している。このため、図１に示す電力用二次電池では、臭素との錯塩を形成する錯塩形成剤を添加した電解液を用い、臭素との錯塩の通過を阻止するセパレータを設けることを要せず、一種類の電解液を用いる一液性の電力用電解液静止型亜鉛―臭素二次電池とすることができ、その構造を簡単なものにできる。
更に、図１に示す電力用二次電池では、無機材料から形成されるため、環境に対してもやさしいものである。 As the electrolytic solution impregnating the negative electrode 12, the activated carbon fiber layer 14, the bromine adsorption blocking layer 16, the bromine storage layer 18 and the positive electrode 20, an electrolytic solution containing zinc bromide is used. An electrical conductivity improver such as potassium chloride that improves electrical conductivity may be added to the electrolytic solution.
However, when an electrical conductivity improver such as potassium chloride is added, a small amount of hydrogen may be generated during charging / discharging, so a small hole for purging hydrogen is formed in the glass cylindrical battery case 10. It is preferable to open 22, 22,.
In the power secondary battery shown in FIG. 1, bromine generated at the positive electrode 20 during charging is absorbed and accumulated by the bromine accumulation layer 18, and bromine that has passed through the bromine accumulation layer 18 is also absorbed by the bromine adsorption blocking layer 16. Since it is adsorbed, the passage of bromine is blocked to reach the negative electrode 12. For this reason, in the secondary battery for electric power shown in FIG. 1, it is not necessary to use an electrolytic solution to which a complex salt forming agent that forms a complex salt with bromine is added, and to provide a separator that prevents passage of the complex salt with bromine. It is possible to obtain a one-component power-use electrolytic solution static zinc-bromine secondary battery using one type of electrolytic solution, and the structure can be simplified.
Furthermore, since the secondary battery for electric power shown in FIG. 1 is formed from an inorganic material, it is friendly to the environment.

図１に示す電力用二次電池では、臭素吸着遮断層１６及び臭素蓄積層１８によって臭素を吸収・吸着するため、臭素が円筒電槽１０に形成された小孔２２，２２・・を経由して外部に放出されることはない。
但し、急激に臭素が発生して臭素吸着遮断層１６及び臭素蓄積層１８での吸収・吸着能力を上回った場合は、腐食性の高い臭素が小孔２２，２２・・を経由して外部に放出されるおそれがある。
このため、図１に示す電力用二次電池では、急激に臭素が発生して臭素吸着遮断層１６及び臭素蓄積層１８での吸収・吸着能力を上回った場合でも、外部に臭素が放出されないように、臭素吸着遮断層１６及び臭素蓄積層１８と円筒電槽１０との空間部１０ａには、臭素密閉分離遮断層２４が形成されている。この臭素密閉分離遮断層２４は、ガラス繊維の粉砕物、シリカ粉末及び電解液の混合物から成り、水素その他の気体を通すが、臭素を補足して臭素の通過を阻止できる。 In the secondary battery for electric power shown in FIG. 1, bromine is absorbed and adsorbed by the bromine adsorption blocking layer 16 and the bromine storage layer 18, so that bromine passes through the small holes 22, 22. Are not released to the outside.
However, if bromine is suddenly generated and exceeds the absorption / adsorption capacity of the bromine adsorption blocking layer 16 and the bromine storage layer 18, highly corrosive bromine is exposed to the outside via the small holes 22, 22. May be released.
For this reason, in the power secondary battery shown in FIG. 1, even when bromine is suddenly generated and exceeds the absorption / adsorption capacity of the bromine adsorption blocking layer 16 and the bromine storage layer 18, bromine is not released to the outside. In addition, a bromine sealed separation blocking layer 24 is formed in the space portion 10 a between the bromine adsorption blocking layer 16 and the bromine storage layer 18 and the cylindrical battery case 10. This bromine sealing separation blocking layer 24 is made of a mixture of pulverized glass fiber, silica powder, and electrolyte, and allows hydrogen and other gases to pass therethrough, but it can capture bromine and block the passage of bromine.

図１に示す電力用二次電池では、充電の際には、負極１２でＺｎ2+＋２ｅ→Ｚｎの電気化学反応が生じ、正極２０で２Ｂｒ-→Ｂｒ2＋２ｅの電気化学反応が生じる。正極２０での反応によって生じた臭素の一部分は電解液中に溶解するが、大部分は臭素蓄積層１８を形成する黒鉛粒子中に吸収され、電解液中に溶解した臭素も、臭素吸着遮断層１６を形成するガラス繊維に吸着される。このため、負極１２への臭素の到達を阻止し、負極１２に析出している亜鉛と反応して生じる電力ロスを防止できる。
一方、臭素吸着遮断層１６及び臭素蓄積層１８は、亜鉛イオンや臭素イオンが通過でき、負極１２及び正極２０での反応をスムーズに進行し、負極１２に亜鉛を析出させることができる。
しかも、臭素吸着遮断層１６に吸着された臭素は、負極１２に析出して侵入した亜鉛を溶解するため、一液性の電力用電解液静止型亜鉛―臭素二次電池において問題となる負極１２での亜鉛のデントライトの生成・成長を防止でき、充分に充電できる。 In the power secondary battery shown in FIG. 1, during charging, an electrochemical reaction of Zn 2+ + 2e → Zn occurs at the negative electrode 12, and an electrochemical reaction of 2 Br − → Br 2 + 2e occurs at the positive electrode 20. Although a part of bromine generated by the reaction at the positive electrode 20 is dissolved in the electrolytic solution, most of the bromine is absorbed in the graphite particles forming the bromine accumulating layer 18, and bromine dissolved in the electrolytic solution is also a bromine adsorption blocking layer. Adsorbed on the glass fiber forming 16. Therefore, it is possible to prevent bromine from reaching the negative electrode 12 and to prevent power loss caused by reaction with zinc deposited on the negative electrode 12.
On the other hand, the bromine adsorption blocking layer 16 and the bromine accumulating layer 18 can pass zinc ions and bromine ions, and the reaction at the negative electrode 12 and the positive electrode 20 can proceed smoothly to deposit zinc on the negative electrode 12.
In addition, bromine adsorbed on the bromine adsorption blocking layer 16 dissolves zinc that has been deposited and invaded into the negative electrode 12, so that the negative electrode 12, which is a problem in a one-component power electrolyte static zinc-bromine secondary battery. It can prevent the formation and growth of zinc dentite in the battery, and can be fully charged.

図１に示す電力用二次電池では、充電終了後に放置しておいても、電解液に溶解している臭素は、臭素吸着遮断層１６に吸着されるため、負極１２への臭素の到達を阻止し、負極１２に析出している亜鉛と反応して生じる電力ロスを防止でき、充電後の蓄電容量の低下を可及的に防止できる。
また、図１に示す電力用二次電池の放電の際には、負極１２でＺｎ→Ｚｎ2+＋２ｅの電気化学反応が生じ、正極２０でＢｒ2＋２ｅ→２Ｂｒ-の電気化学反応が生じる。この正極２０での反応に用いられる臭素は、電解液に溶解されている臭素も用いられるが、大部分は臭素蓄積層１８から供給される。
更に、臭素吸着遮断層１６及び臭素蓄積層１８は、亜鉛イオンや臭素イオンが通過でき、負極１２及び正極２０での反応をスムーズに進行し、充分に放電できる。 In the secondary battery for power shown in FIG. 1, bromine dissolved in the electrolytic solution is adsorbed by the bromine adsorption blocking layer 16 even if it is left after charging, and therefore bromine reaches the negative electrode 12. The power loss caused by the reaction with the zinc deposited on the negative electrode 12 can be prevented, and the reduction of the storage capacity after charging can be prevented as much as possible.
In addition, when the power secondary battery shown in FIG. 1 is discharged, an electrochemical reaction of Zn → Zn 2+ + 2e occurs at the negative electrode 12, and an electrochemical reaction of Br 2 + 2e → 2Br − occurs at the positive electrode 20. Bromine used for the reaction at the positive electrode 20 is also bromine dissolved in the electrolytic solution, but most is supplied from the bromine storage layer 18.
Further, the bromine adsorption blocking layer 16 and the bromine accumulation layer 18 can pass zinc ions and bromine ions, and the reaction at the negative electrode 12 and the positive electrode 20 can proceed smoothly and can be sufficiently discharged.

図１に示す電力用二次電池は、単一セルから成る小容量の小型電池であるが、複数セルから成る大容量の電力用大型二次電池としては、図２に示す電力用二次電池を採用できる。この図２に示す電力用二次電池は、矩形型の電池であって、図２（ａ）は電池の正面部分断面図であり、図２（ｂ）は電池の側面断面図である。
図２に示す電力用二次電池は、図２（ｂ）に示す様に、二個の単一セルＡ，Ｂがプラスチック製の矩形容器３０内に収容されている。かかる単一セルＡ，Ｂでは、図２（ｂ）に示す様に、矩形容器３０の中央部に配設された亜鉛板から成る負極３２と、矩形容器３０の内壁面に設けられた帯状の黒鉛板から成る正極４０とが設けられている。この負極３２と正極４０との間には、負極３２から正極４０の方向に多孔質炭素板３４、ガラス繊維から成る不織布から成り、ガラス繊維間にシリカ粉末が充填された非導電性の臭素吸着遮断層３６、及び黒鉛板から成る臭素蓄積層３８が配設されている。
かかる負極３２を形成する亜鉛板の一部が矩形容器３０から突出して突出負極３２ａが形成され、正極４０を形成する帯状の黒鉛板の一端部が矩形容器３０から突出して突出正極４０ａが形成されている。
尚、図２に示す電力用二次電池を形成する負極３２、臭素吸着遮断層３６、臭素蓄積層３８及び正極４０の各々を形成する材料は、図１に示す電力二次電池を形成する負極１２、臭素吸着遮断層１６、臭素蓄積層１８及び正極２０と同一材料を用いることができる。 The power secondary battery shown in FIG. 1 is a small battery having a small capacity consisting of a single cell, but the power secondary battery shown in FIG. 2 may be used as a large capacity power secondary battery consisting of a plurality of cells. Can be adopted. The power secondary battery shown in FIG. 2 is a rectangular battery, FIG. 2 (a) is a front partial sectional view of the battery, and FIG. 2 (b) is a side sectional view of the battery.
In the power secondary battery shown in FIG. 2, as shown in FIG. 2B, two single cells A and B are accommodated in a rectangular container 30 made of plastic. In such single cells A and B, as shown in FIG. 2 (b), a negative electrode 32 made of a zinc plate disposed in the center of the rectangular container 30 and a strip-shaped provided on the inner wall surface of the rectangular container 30. A positive electrode 40 made of a graphite plate is provided. Between this negative electrode 32 and the positive electrode 40, the non-conductive bromine adsorption | suction which consists of the nonwoven fabric which consists of the porous carbon plate 34 and the glass fiber in the direction of the negative electrode 32 from the positive electrode 40 was filled with the silica powder between glass fibers. A blocking layer 36 and a bromine accumulating layer 38 made of a graphite plate are disposed.
A part of the zinc plate forming the negative electrode 32 protrudes from the rectangular container 30 to form a protruding negative electrode 32a, and one end of a strip-shaped graphite plate forming the positive electrode 40 protrudes from the rectangular container 30 to form the protruding positive electrode 40a. ing.
The material forming each of the negative electrode 32, the bromine adsorption blocking layer 36, the bromine storage layer 38, and the positive electrode 40 forming the power secondary battery shown in FIG. 2 is the negative electrode forming the power secondary battery shown in FIG. 12, the same material as the bromine adsorption blocking layer 16, the bromine storage layer 18, and the positive electrode 20 can be used.

図２に示す電力用二次電池では、負極３２、多孔質炭素板３４、臭素吸着遮断層３６、臭素蓄積層３８及び正極４０は、層状に形成されているため、その端面が露出する矩形容器３０の内壁面で短絡するおそれがある場合がある。かかる場合には、矩形容器３０の内壁面では、図２（ａ）に示す様に、ガラス繊維等の絶縁材料から成る絶縁層４４を設けることによって、板状に形成された層同士の短絡を確実に防止できる。
また、図２に示す電力用二次電池では、図１に示す電力用二次電池に用いる電解液と同一組成の電解液を用いることができる。
但し、電解液に電気伝導性を向上する塩化カリウム等の電気伝導度向上剤を添加した場合には、充放電の際に、少量の水素が発生することがあるため、矩形容器３０に水素パージ用の小孔４２を開口しておくことが好ましい。
更に、図２に示す電力用二次電池でも、急激に臭素が発生して臭素吸着遮断層３６及び臭素蓄積層３８での吸収・吸着能力を上回った場合でも、外部に臭素が放出されないように、臭素吸収遮断層３６及び臭素蓄積層３８と矩形容器３０との空間部３０ａには、臭素密閉分離遮断層４６が形成されている。この臭素密閉分離遮断層４６は、ガラス繊維の粉砕物、シリカ粉末及び電解液の混合物から成り、水素その他の気体を通すが、臭素を補足して臭素の通過を阻止できる。
以上、説明してきた電力用二次電池では、負極１２、３２は、亜鉛板を用いて形成しているが、亜鉛よりも耐食性に優れた黒鉛等の導電性材料を用いて形成してもよい。
また、図２に示す電力用二次電池では、矩形容器３０を用いているが、円筒形容器を用いてもよい。 In the power secondary battery shown in FIG. 2, the negative electrode 32, the porous carbon plate 34, the bromine adsorption blocking layer 36, the bromine storage layer 38, and the positive electrode 40 are formed in layers, and thus a rectangular container with exposed end faces. There is a possibility that a short circuit may occur on the inner wall surface of 30. In such a case, the inner wall surface of the rectangular container 30 is provided with an insulating layer 44 made of an insulating material such as glass fiber as shown in FIG. It can be surely prevented.
In the power secondary battery shown in FIG. 2, an electrolytic solution having the same composition as the electrolytic solution used in the power secondary battery shown in FIG. 1 can be used.
However, when an electrical conductivity improver such as potassium chloride that improves electrical conductivity is added to the electrolytic solution, a small amount of hydrogen may be generated during charging and discharging. It is preferable to open a small hole 42 for use.
Further, in the power secondary battery shown in FIG. 2, even when bromine is suddenly generated and exceeds the absorption / adsorption capacity of the bromine adsorption blocking layer 36 and the bromine accumulation layer 38, bromine is not released to the outside. In the space 30 a between the bromine absorption blocking layer 36 and bromine storage layer 38 and the rectangular container 30, a bromine hermetic separation blocking layer 46 is formed. This bromine sealing separation blocking layer 46 is made of a mixture of pulverized glass fiber, silica powder, and electrolyte, and allows hydrogen and other gases to pass through. However, it can capture bromine and block the passage of bromine.
As described above, in the power secondary battery described above, the negative electrodes 12 and 32 are formed by using a zinc plate, but may be formed by using a conductive material such as graphite that has better corrosion resistance than zinc. .
In the power secondary battery shown in FIG. 2, the rectangular container 30 is used, but a cylindrical container may be used.

図１に示す電力用二次電池を作成した。かかる電力用二次電池を形成する際には、先ず、ガラス製の円筒電槽１０の内周面に沿って厚さ０．２５ｍｍの亜鉛板から成る負極１２を配置し、その一部を円筒電槽１０の上面から突出して突出負極１２ａを形成した後、負極１２の内周面に沿って活性炭素繊維フェルトを配置し、活性炭素繊維層１４を形成した。
この活性炭素繊維層１４の内側に、ＢＥＴ法で測定した表面積が１．５ｍ2／ｇのガラス繊維から成る厚さ１．９ｍｍの不織布［日本無機(株)製］を、シリカ粉末が縣濁されてい
る電解液に所定時間浸漬してから取り出すことによって、ガラス繊維間にシリカ粉末が充填され不織布から成る臭素吸着遮断層１６を形成した。この不織布は、圧力２０ｋｇ／ｄｍ2で加圧して得られたものである。
更に、臭素吸着遮断層１６の内側に、黒鉛粉末を充填して臭素蓄積層１８を形成した後、臭素蓄積層１８の中心部近傍に棒状の黒鉛を挿入して正極２０を形成した。この臭素蓄積層１８を形成した黒鉛粉末は、トップサイズが０．９ｍｍの粗粒人造黒鉛［昭和電工(株)製の「ショーカライザ−整粒Ｓ−」］と、トップサイズが３０μｍの黒鉛粉末［昭和電工(株)製の「ＵＦＧ−３０」］とを重量比５：１で混合したものを用いた。
この様に形成した臭素蓄積層１８等に電解液を注ぎ込んだ。この電解液としては、臭化亜鉛（２mol／Ｌ）を含有する臭化亜鉛水溶液に、電気伝導性を向上する塩化カリウム（２mol／Ｌ）含有の塩化カリウム水溶液を体積比２０％添加して得た電解液を用いた。
その後、臭素吸着遮断層１６及び臭素蓄積層１８と円筒電槽１０との空間部１０ａには、ガラス繊維の粉砕物、シリカ粉末及び電解液の混合物から成る臭素密閉分離遮断層２４を形成した後、小孔２２，２２・・が形成された蓋を円筒電槽１０に被着して電池を完成した。 The power secondary battery shown in FIG. 1 was prepared. When forming such a secondary battery for electric power, first, a negative electrode 12 made of a zinc plate having a thickness of 0.25 mm is arranged along the inner peripheral surface of a glass cylindrical battery case 10, and a part of the negative electrode 12 is cylindrical. After protruding from the upper surface of the battery case 10 to form the protruding negative electrode 12 a, activated carbon fiber felt was arranged along the inner peripheral surface of the negative electrode 12 to form the activated carbon fiber layer 14.
Inside this activated carbon fiber layer 14, a 1.9 mm-thick nonwoven fabric [manufactured by Nippon Mineral Co., Ltd.] made of glass fiber having a surface area of 1.5 m 2 / g measured by the BET method is used, and silica powder is suspended. The bromine adsorption blocking layer 16 made of a nonwoven fabric in which silica powder was filled between the glass fibers was formed by immersing in the electrolytic solution for a predetermined time and then taking out. This nonwoven fabric is obtained by pressurizing at a pressure of 20 kg / dm 2 .
Further, after the bromine adsorption blocking layer 16 was filled with graphite powder to form the bromine accumulation layer 18, rod-like graphite was inserted near the center of the bromine accumulation layer 18 to form the positive electrode 20. The graphite powder on which the bromine accumulation layer 18 is formed is composed of coarse artificial graphite having a top size of 0.9 mm (“Showcalizer-sized S-” manufactured by Showa Denko KK) and graphite powder having a top size of 30 μm [ A mixture of “UFG-30” manufactured by Showa Denko KK at a weight ratio of 5: 1 was used.
An electrolytic solution was poured into the bromine storage layer 18 and the like thus formed. This electrolytic solution is obtained by adding a potassium chloride aqueous solution containing potassium chloride (2 mol / L) containing 20% by volume to a zinc bromide aqueous solution containing zinc bromide (2 mol / L). An electrolytic solution was used.
Then, after forming the bromine hermetic separation / blocking layer 24 made of a mixture of pulverized glass fiber, silica powder and electrolyte in the space 10a between the bromine adsorption blocking layer 16 and the bromine storage layer 18 and the cylindrical battery case 10, The battery with the small holes 22, 22... Was attached to the cylindrical battery case 10 to complete the battery.

完成した図１に示す電力用二次電池に、２０℃の室内において、その電極面積に対する電流密度を２０ｍＡ／ｃｍ2で４０分間の定電流充電した後、直ちに充填時と同一電流密度で端子電圧が１Ｖとなるまで放電した。図３に図１に示す電力用二次電池の充電及び放電曲線Ｃを示す。
また、充電終了後に約１時間放置した後に放電を行なった。その放電曲線Ｄを図３に併せて示す。
図３から明らかな様に、図１に示す電力用二次電池では、充電終了後に約１時間放置した場合でも自己放電によるロスは約５％であった。
また、かかる充電放電を１０回繰り返して行なったが、負極１２に亜鉛のデントライトの発生は観察されなかった。 The completed power secondary battery shown in FIG. 1 was charged at a constant current density of 20 mA / cm 2 for 40 minutes in a room at 20 ° C. for 40 minutes, and immediately followed by the terminal voltage at the same current density as that during charging. Was discharged until 1V was reached. FIG. 3 shows a charging and discharging curve C of the power secondary battery shown in FIG.
In addition, the battery was discharged after being left for about 1 hour after the end of charging. The discharge curve D is also shown in FIG.
As is apparent from FIG. 3, the power secondary battery shown in FIG. 1 had a loss of about 5% due to self-discharge even when left for about 1 hour after the end of charging.
Moreover, although this charging / discharging was repeated 10 times, generation | occurrence | production of the zinc dentlite in the negative electrode 12 was not observed.

実施例１において、臭素吸着遮断層１６に代えて、ＢＥＴ法で測定した表面積が０．１ｍ2／ｇのガラス繊維から成る厚さ１．９ｍｍの不織布と、細孔径が１μｍ以下のポリオレフィン系樹脂から成る厚さ１００μｍの多孔質フィルムとから成るセパレータを用いた他は実施例１と同様にして電力用二次電池を形成した。
この電力用二次電池に、２０℃の室内において、その電極面積に対する電流密度を２０ｍＡ／ｃｍ2で４０分間の定電流充電した後、直ちに充填時と同一電流密度で端子電圧が１Ｖとなるまで放電した。図４に、この電力用二次電池の充電及び放電曲線Ｅを示す。
また、充電終了後に約１時間放置した後に放電を行なった。その放電曲線Ｆを図４に併せて示す。
図４から明らかな様に、この電力二次電池では、充電終了後に約１時間放置した場合は、自己放電によるロスが約６０％にも達した。
また、かかる充電放電を繰り返して行なったところ、４サイクル目に負極に亜鉛のデントライトが発生した。 In Example 1, in place of the bromine adsorption blocking layer 16, a non-woven fabric having a thickness of 1.9 mm made of glass fibers having a surface area of 0.1 m 2 / g measured by the BET method, and a polyolefin resin having a pore diameter of 1 μm or less A secondary battery for electric power was formed in the same manner as in Example 1 except that a separator made of a porous film having a thickness of 100 μm was used.
This power secondary battery was charged at a constant current density of 20 mA / cm 2 for 40 minutes in a room at 20 ° C. for 40 minutes, and then immediately until the terminal voltage became 1 V at the same current density as that at the time of filling. Discharged. FIG. 4 shows a charge and discharge curve E of the power secondary battery.
In addition, the battery was discharged after being left for about 1 hour after the end of charging. The discharge curve F is also shown in FIG.
As is apparent from FIG. 4, in this power secondary battery, when left for about 1 hour after the end of charging, the loss due to self-discharge reached about 60%.
Further, when such charge and discharge were repeated, zinc dentlite was generated on the negative electrode in the fourth cycle.

本発明に係る電力用二次電池は、従来の電力用二次電池に比較して、充放電時の電荷保有時間は短いが、その構造及び動作システムが簡単であり、安価で且つ大容量の二次電池の製作が可能である。しかも、電力系統の電力を一次的に大量に貯蔵、放出できるため、電力系統の負荷平準化用二次電池、停電防止、非常用二次電池への適用が可能である。
例えば、本発明に係る電力用二次電池を、電力系統の負荷平準化用二次電池等に用いることによって、ニューヨークやカリフォルニアで発生した大停電を防止できることも可能である
更に、本発明に係る電力用二次電池は、鉛等の重金属を使用せず且つ電解液も中性であるため、自然にやさしい二次電池であり、自動車のバッテリーやソーラバッテリ、風力発電用にも適用できる。 The power secondary battery according to the present invention has a shorter charge retention time at the time of charging / discharging than the conventional power secondary battery, but its structure and operation system are simple, inexpensive and large capacity. Secondary batteries can be manufactured. In addition, since the power of the power system can be temporarily stored and released in large quantities, the power system can be applied to load leveling secondary batteries, power failure prevention, and emergency secondary batteries.
For example, the power secondary battery according to the present invention can be used as a secondary battery for leveling the load of an electric power system, etc., so that it is possible to prevent a major power failure occurring in New York or California. Since the secondary battery for electric power does not use heavy metals such as lead and the electrolyte is neutral, it is a secondary battery that is naturally friendly and can be applied to automobile batteries, solar batteries, and wind power generation.

本発明に係る電力用電解液静止型亜鉛―臭素二次電池の一例を説明するための断面図である。It is sectional drawing for demonstrating an example of the electrolyte solution stationary type zinc-bromine secondary battery for electric power which concerns on this invention. 本発明に係る電力用電解液静止型亜鉛―臭素二次電池の他の例を説明するための正面断面図及び側面断面図である。FIG. 4 is a front sectional view and a side sectional view for explaining another example of a power electrolyte stationary zinc-bromine secondary battery according to the present invention. 図１に示す電力用電解液静止型亜鉛―臭素二次電池の充電及び放電について説明するグラフである。2 is a graph illustrating charging and discharging of the power electrolyte static zinc-bromine secondary battery shown in FIG. 比較例として示す電力用電解液静止型亜鉛―臭素二次電池の充電及び放電について説明するグラフである。It is a graph explaining the charge and discharge of the electrolytic solution static type zinc-bromine secondary battery shown as a comparative example. 従来の電力用亜鉛―臭素二次電池の概要を説明する概略図である。It is the schematic explaining the outline | summary of the conventional zinc-bromine secondary battery for electric power. 従来の電解液静止型亜鉛―臭素二次電池の断面図である。It is sectional drawing of the conventional electrolyte solution static type zinc-bromine secondary battery.

符号の説明Explanation of symbols

１０ 円筒電槽
１０ａ、３０ａ 空間部
１２ａ，３２ａ 突出負極
１２、３２ 負極
１４、３４ 活性炭素繊維層
１６、３６ 臭素吸着遮断層
１８、３８ 臭素蓄積層
２０、４０ 正極
２０ａ，４０ａ 突出正極
２４，４６ 臭素密閉分離遮断層
３０ 矩形容器
２２，４２ 小孔
４４ 絶縁層 10 cylindrical battery case 10a, 30a space 12a, 32a protruding negative electrode 12, 32 negative electrode 14, 34 activated carbon fiber layer 16, 36 bromine adsorption blocking layer 18, 38 bromine accumulation layer 20, 40 positive electrode 20a, 40a protruding positive electrode 24, 46 Bromine sealed separation blocking layer 30 Rectangular container 22, 42 Small hole 44 Insulating layer

Claims (5)

臭化亜鉛を含有する電解液に対して耐食性を有する正極と負極とを具備する一液性の電力用電解液静止型亜鉛―臭素二次電池であって、
該負極の正極側に、ＢＥＴ法で測定した表面積が０．５ｍ2／ｇ以上のガラス繊維から成る不織布によって形成され、前記電解液中の臭素を吸着して負極への臭素の到達を阻止する非導電性の臭素吸着遮断層と、
前記臭素吸着遮断層と正極との間に、無機材料によって形成され、充電の際に、前記正極で生じた臭素を吸収して蓄積する導電性の臭素蓄積層とが設けられていることを特徴とする電力用電解液静止型亜鉛―臭素二次電池。 A one-part liquid electrolyte-use zinc-bromine secondary battery for electric power comprising a positive electrode and a negative electrode having corrosion resistance to an electrolyte containing zinc bromide,
Formed on the positive electrode side of the negative electrode by a non-woven fabric made of glass fibers having a surface area measured by the BET method of 0.5 m 2 / g or more, adsorbs bromine in the electrolyte and prevents the bromine from reaching the negative electrode A non-conductive bromine adsorption blocking layer;
A conductive bromine storage layer is provided between the bromine adsorption blocking layer and the positive electrode, and is formed of an inorganic material and absorbs and accumulates bromine generated in the positive electrode during charging. Electrostatic solution static zinc-bromine secondary battery for power. 臭素吸着遮断層が、不織布を形成するガラス繊維間にシリカ粉末が充填されている請求項１記載の電力用電解液静止型亜鉛―臭素二次電池。   The electric power electrolyte stationary zinc-bromine secondary battery according to claim 1, wherein the bromine adsorption blocking layer is filled with silica powder between the glass fibers forming the nonwoven fabric. 臭素吸着遮断層を形成する不織布が、ＢＥＴ法で測定した表面積が３ｍ2／ｇ以下の不織布である請求項１又は請求項２記載の電力用電解液静止型亜鉛―臭素二次電池。 The electric power electrolyte stationary zinc-bromine secondary battery according to claim 1 or 2 , wherein the non-woven fabric forming the bromine adsorption blocking layer is a non-woven fabric having a surface area measured by BET method of 3 m 2 / g or less. 臭素蓄積層が、黒鉛粒子を主とする炭素材料から成る請求項１〜３のいずれか一項記載の電力用電解液静止型亜鉛―臭素二次電池。   The electric power electrolyte stationary zinc-bromine secondary battery according to any one of claims 1 to 3, wherein the bromine storage layer is made of a carbon material mainly composed of graphite particles. 臭素吸着遮断層と負極との間に、活性炭素繊維層又は多孔質炭素板が設けられている請求項１〜４のいずれか一項記載の電力用電解液静止型亜鉛―臭素二次電池。   The electrolytic solution static type zinc-bromine secondary battery for electric power according to any one of claims 1 to 4, wherein an activated carbon fiber layer or a porous carbon plate is provided between the bromine adsorption blocking layer and the negative electrode.
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