JPH06260183A - Diaphragm for aqueous solvent electrochemical device and battery with aqueous solvent using same - Google Patents
Diaphragm for aqueous solvent electrochemical device and battery with aqueous solvent using sameInfo
- Publication number
- JPH06260183A JPH06260183A JP5043469A JP4346993A JPH06260183A JP H06260183 A JPH06260183 A JP H06260183A JP 5043469 A JP5043469 A JP 5043469A JP 4346993 A JP4346993 A JP 4346993A JP H06260183 A JPH06260183 A JP H06260183A
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- Japan
- Prior art keywords
- diaphragm
- battery
- negative electrode
- positive electrode
- pores
- Prior art date
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Classifications
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- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、水溶媒系電気化学装置
用隔膜およびそれを用いた水溶媒系電池に関し、特に十
分低い内部抵抗と電解液の分離能に優れた水溶媒系電気
化学装置用隔膜、および該隔膜を用いた高効率かつ高容
量の水溶媒系電池に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a membrane for a water-solvent type electrochemical device and a water-solvent type battery using the same, and particularly to a water-solvent type electrochemical device excellent in sufficiently low internal resistance and separability of an electrolytic solution. The present invention relates to a diaphragm for use, and a high-efficiency and high-capacity water-solvent battery using the diaphragm.
【０００２】[0002]
【従来の技術】揚水発電に代わる電力貯蔵用電池装置と
して、種々の新型電池が開発されている。2. Description of the Related Art Various new types of batteries have been developed as a battery device for storing electric power, which replaces pumped-storage power generation.
【０００３】このような新型電池のうち、たとえば、レ
ドックスフロー型電池や、亜鉛臭素電池等の電解液流通
型電池は特に注目されている。Among such new batteries, for example, redox flow type batteries and electrolyte flow type batteries such as zinc bromine batteries have received particular attention.
【０００４】電解液流通型電池装置の構造と、動作原理
をレドックスフロー型電池を例にとり、以下に説明す
る。The structure and operating principle of the electrolyte flow type battery device will be described below by taking a redox flow type battery as an example.
【０００５】図１は、レドックスフロー型電池の一具体
例を概略的に示す構成図である。図１を参照して、この
レドックスフロー型電池１は、電池反応セル２、正極液
タンク３、および、負極液タンク４を備える。FIG. 1 is a schematic diagram showing a specific example of a redox flow battery. With reference to FIG. 1, the redox flow battery 1 includes a battery reaction cell 2, a positive electrode liquid tank 3, and a negative electrode liquid tank 4.
【０００６】電池反応セル２内は、たとえば、イオン交
換膜等からなる隔膜５により仕切られており、一方側が
正極セル２ａ、他方側が負極セル２ｂを構成する。The inside of the battery reaction cell 2 is partitioned by a diaphragm 5 made of, for example, an ion exchange membrane, and one side constitutes a positive electrode cell 2a and the other side constitutes a negative electrode cell 2b.
【０００７】正極セル２ａ内には、正極６が収容され、
また、負極セル２ｂ内には負極７が収容される。A positive electrode 6 is housed in the positive electrode cell 2a,
Further, the negative electrode 7 is accommodated in the negative electrode cell 2b.
【０００８】正極セル２ａと正極液タンク３とは、正極
液を正極液タンク３から正極セル２ａに供給する正極液
供給用管路８と、正極液を正極セル２ａから正極液タン
ク３に回収する正極液回収用管路９とにより連結され
る。The positive electrode cell 2a and the positive electrode liquid tank 3 are a positive electrode liquid supply line 8 for supplying the positive electrode liquid from the positive electrode liquid tank 3 to the positive electrode cell 2a, and the positive electrode liquid is recovered from the positive electrode cell 2a to the positive electrode liquid tank 3. It is connected to the positive electrode liquid recovery conduit 9 for
【０００９】また、正極液供給用管路８には、正極液の
流通循環手段として、ポンプ１０が設けられており、正
極セル２ａと正極液タンク３との間において、正極液が
流通循環できるようになっている。Further, a pump 10 is provided in the positive electrode liquid supply conduit 8 as a positive and negative liquid circulating means for circulating the positive electrode liquid between the positive electrode cell 2a and the positive electrode liquid tank 3. It is like this.
【００１０】他方、負極セル２ｂと負極液タンク４と
は、負極液を負極液タンク４から負極セル２ｂに供給す
る負極液供給用管路１１と、負極液を負極セル２ｂから
負極液タンク４に回収する負極液回収用管路１２とによ
り連結される。On the other hand, the negative electrode cell 2b and the negative electrode liquid tank 4 include a negative electrode liquid supply line 11 for supplying the negative electrode liquid from the negative electrode liquid tank 4 to the negative electrode cell 2b, and the negative electrode liquid from the negative electrode cell 2b to the negative electrode liquid tank 4. It is connected to the negative electrode liquid recovery conduit 12 for recovering the negative electrode.
【００１１】また、負極液供給用管路１１には、負極液
の流通循環手段としてポンプ１３が設けられており、負
極セル２ｂと負極液タンク４との間において、負極液が
流通循環できるようになっている。A pump 13 is provided in the negative electrode liquid supply conduit 11 as a means for circulating and circulating the negative electrode liquid so that the negative electrode liquid can be circulated and circulated between the negative electrode cell 2b and the negative electrode liquid tank 4. It has become.
【００１２】正極液タンク３内には、電解液として正極
電解液が蓄えられており、また、負極液タンク４内に
は、電解液として負極電解液が蓄えられる。A positive electrode electrolytic solution is stored as an electrolytic solution in the positive electrode solution tank 3, and a negative electrode electrolytic solution is stored as an electrolytic solution in the negative electrode solution tank 4.
【００１３】正極電解液としては、たとえば、鉄イオン
のような原子価の変化するイオンの水溶液が用いられ、
また、負極電解液としては、たとえば、クロムイオンの
ような原子価の変化するイオンの水溶液が用いられる。As the positive electrode electrolyte, for example, an aqueous solution of ions whose valence changes, such as iron ions, is used.
Further, as the negative electrode electrolyte, for example, an aqueous solution of ions whose valence changes such as chromium ions is used.
【００１４】たとえば、そのような正極電解液として、
正極活物質Ｆｅ3+／Ｆｅ2+を含む塩酸水溶液を用い、負
極電解液として、負極活物質Ｃｒ2+／Ｃｒ3+を含む塩酸
水溶液を用いることができる。For example, as such a positive electrode electrolyte,
A hydrochloric acid aqueous solution containing the positive electrode active material Fe 3+ / Fe 2+ can be used, and a hydrochloric acid aqueous solution containing the negative electrode active material Cr 2+ / Cr 3+ can be used as the negative electrode electrolyte.
【００１５】このような電解液を用いたレドックスフロ
ー型電池１を用いて、充電時においては、負極液タンク
４に蓄えられたＣｒ3+イオンを含む塩酸水溶液がポンプ
１３により、負極セル２ｂに送られ、負極７において電
子を受け取り、Ｃｒ2+イオンに還元され、負極液タンク
４に回収される。When the redox flow type battery 1 using such an electrolytic solution is used, the hydrochloric acid aqueous solution containing Cr 3+ ions stored in the negative electrode solution tank 4 is charged by the pump 13 into the negative electrode cell 2b during charging. The electrons are sent and received by the negative electrode 7, reduced to Cr 2+ ions, and collected in the negative electrode liquid tank 4.
【００１６】他方、正極液タンク３に蓄えられたＦｅ2+
イオンを含む塩酸水溶液がポンプ１０により正極セル２
ａに送られ、正極６において外部回路に電子を放出し
て、Ｆｅ3+に酸化され、正極液タンク３に回収される。On the other hand, Fe 2+ stored in the cathode liquid tank 3
A hydrochloric acid aqueous solution containing ions is pumped by the pump 10 to the positive electrode cell 2
Then, the electrons are sent to the external circuit in the positive electrode 6, are oxidized to Fe 3+, and are collected in the positive electrode liquid tank 3.
【００１７】また、放電時においては、負極液タンク４
に蓄えられたＣｒ2+イオンを含む塩酸水溶液が、ポンプ
１３により負極セル２ｂに送られ、負極７において外部
回路に電子を放出して、Ｃｒ3+イオンに酸化され、負極
液タンク４に回収される。During discharge, the negative electrode liquid tank 4
The hydrochloric acid aqueous solution containing Cr 2+ ions stored in the negative electrode cell 2b is sent to the negative electrode cell 2b by the pump 13 and emits electrons to the external circuit at the negative electrode 7 to be oxidized into Cr 3+ ions and collected in the negative electrode liquid tank 4. To be done.
【００１８】他方、正極液タンク３に蓄えられたＦｅ3+
イオンを含む塩酸水溶液は、ポンプ１０により正極セル
２ａに送られ、正極６において外部回路から電子を受け
取り、Ｆｅ2+イオンに還元され、正極液タンク３に回収
される。On the other hand, Fe 3+ stored in the positive electrode liquid tank 3
The aqueous hydrochloric acid solution containing ions is sent to the positive electrode cell 2a by the pump 10, receives electrons from the external circuit at the positive electrode 6, is reduced to Fe 2+ ions, and is collected in the positive electrode liquid tank 3.
【００１９】このようなレドックスフロー型電池におい
ては、正極６および負極７における充放電反応は、下記
の式のようになる。In such a redox flow type battery, the charge / discharge reaction at the positive electrode 6 and the negative electrode 7 is expressed by the following equation.
【００２０】[0020]
【化１】 [Chemical 1]
【００２１】[0021]
【発明が解決しようとする課題】しかしながら、上記し
たレドックスフロー型電池１は、通常の電池とは異な
り、正極液と負極液との構成の異なる２液型電池構成で
あるため、両電解液の混合を阻止する必要があり、その
ため選択性の強いイオン交換膜が隔膜５として用いられ
ている。隔膜５としてイオン交換膜を用いた場合、レド
ックスフロー型電池１の内部抵抗を低減することができ
ず、したがって、高い充放電効率を達成することができ
ないという問題があった。すなわち、イオン交換膜は、
機械的強度の問題から、膜厚として約１００μｍ〜２０
０μｍ必要であり、このため内部抵抗を１．０Ω・ｃｍ
2 以下にするのは困難であった。However, unlike the normal battery, the redox flow type battery 1 described above has a two-component type battery configuration in which the positive electrode solution and the negative electrode solution are different from each other. Since it is necessary to prevent the mixing, an ion exchange membrane having a strong selectivity is used as the diaphragm 5. When an ion exchange membrane is used as the diaphragm 5, there is a problem that the internal resistance of the redox flow battery 1 cannot be reduced, and thus high charge / discharge efficiency cannot be achieved. That is, the ion exchange membrane is
Due to the problem of mechanical strength, the film thickness is about 100 μm to 20 μm.
0 μm is required, so the internal resistance is 1.0 Ω · cm.
It was difficult to make it less than 2 .
【００２２】また、隔膜５は、上記したような選択性の
強いイオン交換膜、すなわち電極活物質の通過を防止す
ることができ、しかもＨ+ およびＣｌ- のようなイオン
移動担体を通過させ得るという特殊機能を有しなければ
ならないため、隔膜５を構成する材料のコストが高くつ
くという欠点があった。Further, the diaphragm 5 can prevent the ion exchange membrane having a strong selectivity as described above, that is, the electrode active material from passing therethrough, and can pass the ion transfer carrier such as H + and Cl −. Therefore, there is a drawback that the cost of the material forming the diaphragm 5 is high because it must have a special function.
【００２３】このような問題を解決するための技術とし
て、本発明者らは、特開昭６１−２２５７５号公報にお
いて、隔膜５として、イオン交換膜の代わりに多孔質膜
を用いた電池を開示している。As a technique for solving such a problem, the inventors of the present invention have disclosed a battery using a porous membrane instead of an ion exchange membrane as the diaphragm 5 in Japanese Patent Laid-Open No. 61-22575. is doing.
【００２４】特開昭６１−２２５７５号公報に記載され
る多孔質膜は、たとえば、セルロース系樹脂、ポリエチ
レンやポリプロピレン等のポリオレフィン系樹脂、フッ
素樹脂等の材料からなり、多孔質膜の複数の孔の孔径が
０．０５μｍ以上０．５μｍ以下に適切に選ばれ、ま
た、気孔率を約３０％〜９０％、膜厚を約２０μｍ〜３
００μｍ程度とすることにより、隔膜５の内部抵抗をイ
オン交換膜を用いた場合に比べ低減することができる。
多孔質膜を用いた場合の内部抵抗は０．２Ω・ｃｍ2 以
上２Ω・ｃｍ2 以下程度である。さらに、特開昭６１−
２２５７５号公報に記載される多孔質膜は、材料の原料
コストがイオン交換膜に比べ安いため、製造コストの低
減を図れるという効果もある。The porous membrane described in Japanese Patent Laid-Open No. 61-22575 is made of, for example, a material such as a cellulose resin, a polyolefin resin such as polyethylene or polypropylene, or a fluororesin, and has a plurality of pores in the porous membrane. Is appropriately selected from 0.05 μm to 0.5 μm, the porosity is about 30% to 90%, and the film thickness is about 20 μm to 3 μm.
By setting the thickness to about 00 μm, the internal resistance of the diaphragm 5 can be reduced as compared with the case where an ion exchange membrane is used.
The internal resistance in the case of using the porous membrane is on the order 0.2 [Omega] · cm 2 or more 2 [Omega · cm 2 or less. Furthermore, JP-A-61-1
The porous membrane described in Japanese Patent No. 22575 has a raw material cost lower than that of the ion exchange membrane, and thus has an effect of reducing manufacturing cost.
【００２５】しかしながら、特開昭６１−２２５７５号
公報に記載される多孔質膜は、隔膜としての内部抵抗を
十分に低減することができ、電圧損失（電圧損失は、電
圧効率で評価される）は、イオン交換膜に比べ低減でき
る一方、正極液と負極液が隔膜５として用いている多孔
質膜を介して、互いに混合される結果、その自己放電に
より、電池効率（電池効率は、電流効率で評価される）
の低下を招来することは免れ得なかった。However, the porous membrane described in Japanese Patent Application Laid-Open No. 61-22575 can sufficiently reduce the internal resistance as a diaphragm, and voltage loss (voltage loss is evaluated by voltage efficiency). Can be reduced as compared with the ion exchange membrane, but the positive electrode liquid and the negative electrode liquid are mixed with each other through the porous membrane used as the diaphragm 5, and as a result, the self-discharge causes the battery efficiency (the battery efficiency to be the current efficiency Evaluated by)
It was unavoidable that it would lead to a decline in.
【００２６】また、本発明者らは、特開昭６１−２２５
７４号公報において、隔膜５として、イオン交換膜の代
わりに膨潤膜を用いた電池を開示している。The inventors of the present invention have also disclosed in JP-A-61-225.
Japanese Patent Publication No. 74 discloses a battery using a swelling membrane instead of an ion exchange membrane as the diaphragm 5.
【００２７】特開昭６１−２２５７４号公報に記載され
る膨潤膜は、たとえば、セルロース系樹脂、ポリ酢酸ビ
ニル、ポリビニルアルコール、シリコン樹脂、およびこ
れらを含む共重合体、あるいはブレンド品などの材料か
らなり、含水率が１ｗｔ％〜５０ｗｔ％に適切に選ば
れ、膜厚を１０μｍ〜２００μｍ程度とすることによ
り、隔膜５の内部抵抗をイオン交換膜を用いた場合に比
べ低減することができる。膨潤膜を用いた場合の内部抵
抗は、０．２Ω・ｃｍ2 以上５Ω・ｃｍ2 以下程度であ
る。また、このような膨潤膜は、高温環境下において
も、特性が変化しないので高温環境下でのエネルギー効
率を上昇させることができるという長所がある。さら
に、特開昭６１−２２５７４号公報に記載される膨潤膜
は、材料がイオン交換膜に比べ比較的安価であるため、
イオン交換膜に比べ、製造コストの低減を図れるという
効果もある。The swelling film described in JP-A-61-2574 is made of, for example, a material such as a cellulosic resin, polyvinyl acetate, polyvinyl alcohol, a silicone resin, a copolymer containing them, or a blended product. By properly selecting the water content to 1 wt% to 50 wt% and setting the film thickness to about 10 μm to 200 μm, the internal resistance of the diaphragm 5 can be reduced as compared with the case where the ion exchange membrane is used. The internal resistance in the case of using the swelling film is the degree 0.2 [Omega] · cm 2 or more 5 [Omega · cm 2 or less. In addition, such a swollen film has the advantage that the energy efficiency can be increased in a high temperature environment because the characteristics do not change even in a high temperature environment. Further, the swelling membrane described in JP-A-61-2574 is relatively inexpensive as compared with the ion exchange membrane,
There is also an effect that the manufacturing cost can be reduced as compared with the ion exchange membrane.
【００２８】しかしながら、特開昭６１−２２５７４号
公報に記載される膨潤膜は、隔膜としての内部抵抗は十
分に低減させることができる一方、正極液と負極液が隔
膜５として用いている膨潤膜を介して、互いに混合され
る結果、その自己放電により電池効率の低下を招来する
ことは免れ得なかった。However, the swelling film described in JP-A-61-2574 can sufficiently reduce the internal resistance as a diaphragm, while the positive electrode liquid and the negative electrode liquid are used as the diaphragm 5. As a result of being mixed with each other through the, it was unavoidable that the self-discharge caused a decrease in battery efficiency.
【００２９】また、一般的に膨潤膜は、長期的に酸に耐
える材料が少なく、さらに、内部抵抗を小さくできる膨
潤膜は、耐酸性に優れず、また、機械的強度が十分でな
いという問題があった。このため、レドックスフロー型
電池の隔膜として用いることのできる膨潤膜は、材料が
限定されるという問題があった。In general, the swelling film has few materials capable of withstanding acid for a long period of time, and further, the swelling film capable of reducing the internal resistance is not excellent in acid resistance and has insufficient mechanical strength. there were. Therefore, there is a problem that the material of the swelling film that can be used as the diaphragm of the redox flow battery is limited.
【００３０】また、機械的特性に優れた多孔度の大きい
多孔質膜と、電解液の分離能を高めるための薄い膜とを
物理的に貼り合わせてなる膜と膜とが２層構造を有する
隔膜の研究が行なわれているが、いずれも、イオン交換
膜単独、多孔質膜単独、および膨潤膜単独を用いた隔膜
に比べ、内部抵抗および電解液の分離能の点において、
有意な差を示すに至っていない。Further, a porous membrane having excellent mechanical properties and high porosity, and a membrane formed by physically bonding a thin membrane for enhancing the separating ability of the electrolytic solution have a two-layer structure. Diaphragms have been studied, but in both cases, in terms of internal resistance and separability of electrolytic solution, compared to a diaphragm using an ion exchange membrane alone, a porous membrane alone, and a swelling membrane alone.
It has not reached a significant difference.
【００３１】水溶媒系電池用隔膜としては、プロトン導
電性が大きく、プロトン選択透過性が大きく、機械的・
化学的強度が大きく、また、電解液との濡れ性が大きい
隔膜が長年望まれていた。As a membrane for a water-solvent battery, the proton conductivity is high, the proton selective permeability is high, and
A diaphragm having high chemical strength and high wettability with an electrolytic solution has been desired for many years.
【００３２】本発明は、以上のような問題を解決するた
めになされたものであって、内部抵抗が十分小さく、か
つ、電解液の分離能に優れた水溶媒系電気化学装置用隔
膜およびそれを用いた水溶媒系電池を提供することを目
的とする。The present invention has been made in order to solve the above problems, and has a sufficiently small internal resistance and excellent separability of an electrolytic solution, and a membrane for a water-solvent electrochemical device. It is an object of the present invention to provide an aqueous solvent battery using
【００３３】[0033]
【課題を解決するための手段】本発明に従う水溶媒系電
気化学装置用隔膜は、複数の孔部を有する多孔質膜と、
多孔質膜の複数の孔部の少なくとも一部の空隙部内全体
にまたは部分的に設けられた親水性樹脂とを備える。A diaphragm for a water-solvent-based electrochemical device according to the present invention comprises a porous membrane having a plurality of pores,
And a hydrophilic resin provided entirely or partially in the voids of at least some of the plurality of pores of the porous membrane.
【００３４】親水性樹脂は、好ましくは、イオン交換樹
脂である。また、本発明に従う水溶媒系電池は、正極
と、負極と、正極と負極との間に設けられた隔膜とを含
む水溶媒系電池であって、隔膜は、複数の孔部を有する
多孔質膜と、多孔質膜の複数の孔部の少なくとも一部の
空隙部内全体にまたは部分的に設けられた親水性樹脂と
を備える。The hydrophilic resin is preferably an ion exchange resin. Further, the water-solvent battery according to the present invention is a water-solvent battery including a positive electrode, a negative electrode, and a diaphragm provided between the positive electrode and the negative electrode, and the diaphragm is a porous material having a plurality of pores. A membrane and a hydrophilic resin provided entirely or partially in the voids of at least some of the plurality of pores of the porous membrane.
【００３５】[0035]
【作用】レドックスフロー型電池を例にとり、隔膜とし
て要求される機能をさらに詳細に説明する。The function required as a diaphragm will be described in more detail by taking a redox flow battery as an example.
【００３６】図２は、隔膜に要求される機能を説明する
ためのものであり、図１に示すレドックスフロー型電池
１の電池反応セル２の隔膜５の近傍を拡大して示す断面
図である。FIG. 2 is for explaining the function required for the diaphragm, and is an enlarged sectional view showing the vicinity of the diaphragm 5 of the battery reaction cell 2 of the redox flow type battery 1 shown in FIG. .
【００３７】図２を参照して、隔膜５の両側には、正極
液と負極液がそれぞれ供給される。隔膜５には、特に以
下の２つの機能が要求される。With reference to FIG. 2, the positive electrode liquid and the negative electrode liquid are supplied to both sides of the diaphragm 5, respectively. The diaphragm 5 is required to have the following two functions.
【００３８】（１） イオン隔離機能 すなわち、クロムイオン（Ｃｒ2+／Ｃｒ3+）と鉄イオン
（Ｆｅ3+／Ｆｅ2+）との隔離機能である。(1) Ion Separating Function That is, it is a separating function of chromium ions (Cr 2+ / Cr 3+ ) and iron ions (Fe 3+ / Fe 2+ ).
【００３９】（２） イオン透過機能 すなわち、水素イオンの透過機能である。(2) Ion permeation function, that is, a hydrogen ion permeation function.
【００４０】本発明に従う水溶媒系電気化学装置用隔膜
は、複数の孔部を有する多孔質膜と、多孔質膜の複数の
孔部の少なくとも一部の空隙部内全体にまたは部分的に
設けられた親水性樹脂とを備える。A water-solvent-based electrochemical device diaphragm according to the present invention is provided entirely or partially within a porous membrane having a plurality of pores and at least a part of the voids of the plurality of pores of the porous membrane. And a hydrophilic resin.
【００４１】複数の孔部を有する多孔質膜単体では、イ
オン透過機能は十分に優れているが、イオン隔離機能が
不十分である。A single porous membrane having a plurality of pores has a sufficiently excellent ion permeation function, but an insufficient ion isolation function.
【００４２】一方、本発明に従う水溶媒系電気化学装置
用隔膜は、多孔質膜の複数の孔部の少なくとも一部の空
隙部内全体にまたは部分的に設けられた親水性樹脂とを
備える。このため、多孔質膜の複数の孔部の孔径が実質
的に小さくなり、かつ孔部に親水性機能および／または
イオン交換機能が付与されるという孔部の機能的制御に
よりイオン隔離機能が向上する。また、親水性樹脂とし
て、イオン交換樹脂を用いた場合には、さらに、イオン
隔離機能が向上する。On the other hand, the water-solvent-based diaphragm for electrochemical device according to the present invention comprises a hydrophilic resin provided entirely or partially in the voids of at least some of the plurality of pores of the porous membrane. Therefore, the pore size of the plurality of pores of the porous membrane is substantially reduced, and the ion isolation function is improved by the functional control of the pores such that the pores have a hydrophilic function and / or an ion exchange function. To do. Further, when an ion exchange resin is used as the hydrophilic resin, the ion isolation function is further improved.
【００４３】[0043]
【実施例】以下、本発明について実施例および比較例を
挙げて、さらに具体的に説明するが、本発明は、これら
の実施例のみに限定されるものではない。EXAMPLES The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
【００４４】実施例１ ポリプロピレン製多孔質膜（平均孔径０．０５μｍ、厚
み約１００μｍ、気孔率５５％）の両面に、ナフィオン
溶液（５ｗｔ％）を極めて薄く（数μｍ厚）塗布した
後、乾燥させた。なお、ナフィオン溶液とは、ナフィオ
ン樹脂（デュポン社製）をメタノール等の溶剤に溶かし
た溶液をいう。Example 1 A Nafion solution (5 wt%) was applied very thinly (several μm thick) on both sides of a polypropylene porous membrane (average pore size 0.05 μm, thickness about 100 μm, porosity 55%), and then dried. Let The Nafion solution is a solution prepared by dissolving Nafion resin (manufactured by DuPont) in a solvent such as methanol.
【００４５】図１を参照して、レドックスフロー型電池
１の隔膜５として、上記隔膜を用いた、電極面積９ｃｍ
2 の小型電池セル（単セル）を構成し、充放電特性を調
べた。結果を表１に示す。なお、電解液としては、正極
液として、３ＮＨＣｌにＦｅＣｌ2 １モルを溶解させた
もの、負極液として、３ＮＨＣｌにＣｒＣｌ3 １モルを
溶解させたものを用いた。Referring to FIG. 1, as the diaphragm 5 of the redox flow battery 1, the above diaphragm is used and the electrode area is 9 cm.
2 small battery cells (single cell) were constructed and the charge / discharge characteristics were investigated. The results are shown in Table 1. As the electrolytic solution, a positive electrode solution in which 1 mol of FeCl 2 was dissolved in 3N HCl, and a negative electrode solution in which 1 mol of CrCl 3 was dissolved in 3N HCl were used.
【００４６】比較例１ 実施例１と同様の小型単セルに、一般的な陽イオン交換
膜（イオン透過性を付与するためスルフォン化処理（Ｓ
Ｏ3 - ）を行なったスチレン−ジビニルベンゼン共重合
体、膜厚１００〜２００μｍ）を用いて、実施例１と同
様の試験を行なった。結果を表１に示す。Comparative Example 1 A small single cell similar to that of Example 1 was added to a general cation exchange membrane (a sulfonation treatment (S for imparting ion permeability) (S
The same test as in Example 1 was conducted using a styrene-divinylbenzene copolymer subjected to O 3 − ) and a film thickness of 100 to 200 μm). The results are shown in Table 1.
【００４７】比較例２ 実施例１で用いたポリプロピレン製多孔質膜のみを用い
て、実施例１と同様の充放電特性を調べた。結果を表１
に示す。Comparative Example 2 The same charge / discharge characteristics as in Example 1 were examined using only the polypropylene porous film used in Example 1. The results are shown in Table 1.
Shown in.
【００４８】[0048]
【表１】 [Table 1]
【００４９】表１から明らかなように、実施例１は、電
流効率が、比較例２に比べ大きく改善されている。ま
た、実施例１は、比較例１および比較例２に比べ高いエ
ネルギー効率を示した。As is clear from Table 1, the current efficiency of Example 1 is greatly improved as compared with Comparative Example 2. Further, Example 1 showed higher energy efficiency than Comparative Examples 1 and 2.
【００５０】なお、以上の実施例に関する開示は、本発
明の単なる具体例に過ぎず、本発明の技術的範囲を何ら
制限するものではない。It should be noted that the disclosure of the above embodiments is merely specific examples of the present invention and does not limit the technical scope of the present invention.
【００５１】この発明において、複数の孔部を有する多
孔質膜の材質としては、特に限定するものではないが、
たとえば、ポリエチレン、ポリプロピレン、フッ素樹脂
等の耐酸材料（酸性に強い材料）を用いることができ
る。In the present invention, the material of the porous membrane having a plurality of pores is not particularly limited,
For example, an acid resistant material (a material that is resistant to acidity) such as polyethylene, polypropylene or fluororesin can be used.
【００５２】また、複数の孔部を有する多孔質膜の孔部
の平均孔径は、０．０５μｍ以上１μｍ以下が好まし
い。０．０５μｍ未満の小孔径は製作するのが困難であ
り、また、１μｍより大きい孔径を有する場合は、電解
液が混合することになり好ましくない。The average pore diameter of the pores of the porous membrane having a plurality of pores is preferably 0.05 μm or more and 1 μm or less. It is difficult to manufacture a small pore size of less than 0.05 μm, and if the pore size is more than 1 μm, the electrolytic solution is mixed, which is not preferable.
【００５３】また、複数の孔部を有する多孔質膜の膜厚
は、１０μｍ以上２００μｍ以下が好ましい。１０μｍ
未満の場合は、機械的強度が十分でなく好ましくなく、
また、２００μｍを超える膜厚では、内部抵抗が大きく
なり好ましくない。また、複数の孔部を有する多孔質膜
の気孔率は、特に限定されることはないが３０％以上９
０％以下が好ましい。The thickness of the porous film having a plurality of pores is preferably 10 μm or more and 200 μm or less. 10 μm
If less than, mechanical strength is not sufficient and is not preferable,
Further, if the film thickness exceeds 200 μm, the internal resistance becomes large, which is not preferable. The porosity of the porous film having a plurality of pores is not particularly limited, but is 30% or more 9
0% or less is preferable.
【００５４】多孔質膜の複数の孔部の少なくとも一部の
空隙部内全体にまたは部分的に設ける親水性樹脂の材料
としては、特に限定されることはないが、たとえば、エ
チレンビニルアルコール樹脂、セルロース系樹脂、セル
ロース樹脂等を挙げることができる。このような親水性
樹脂の含水率としては、１ｗｔ％以上５０ｗｔ％以下の
ものが好ましい。含水率が１ｗｔ％未満の場合は、隔膜
の内部抵抗が大きくなり好ましくなく、また、５０ｗｔ
％を超える場合は、イオン隔離機能が低下し好ましくな
い。The material of the hydrophilic resin provided entirely or partially in the voids of at least a part of the plurality of pores of the porous membrane is not particularly limited, and examples thereof include ethylene vinyl alcohol resin and cellulose. Examples of the resin include a resin and a cellulose resin. The water content of such hydrophilic resin is preferably 1 wt% or more and 50 wt% or less. If the water content is less than 1 wt%, the internal resistance of the diaphragm becomes large, which is not preferable.
When it exceeds%, the ion segregation function is deteriorated, which is not preferable.
【００５５】また、多孔質膜の複数の孔部の少なくとも
一部の空隙部内全体にまたは部分的に親水性樹脂を設け
る工程は、特に限定されることはないが、たとえば、親
水性樹脂を、メタノール等の溶剤に溶かした後、多孔質
膜の少なくとも片方の表面に、溶剤に溶かした親水性樹
脂を塗布した後、乾燥させる方法、または、多孔質膜の
少なくとも片方の表面に、アクリル酸、メタクリル酸等
のモノマを塗布した後、電子線または化学的な方法によ
り重合させる方法等を挙げることができる。The step of providing the hydrophilic resin entirely or partially in the voids of at least a part of the plurality of pores of the porous membrane is not particularly limited, but, for example, the hydrophilic resin is After dissolving in a solvent such as methanol, on at least one surface of the porous membrane, after applying a hydrophilic resin dissolved in a solvent, a method of drying, or at least one surface of the porous membrane, acrylic acid, Examples include a method in which a monomer such as methacrylic acid is applied and then polymerized by an electron beam or a chemical method.
【００５６】多孔質膜の孔部の孔径を親水性樹脂を用い
て、制御する方法として、溶剤に溶かした親水性樹脂を
多孔質膜の少なくとも片方の表面に塗布した後、乾燥さ
せる方法を用いる場合は、塗布条件、たとえば、用いる
溶剤の量、塗布回数、樹脂濃度を変化させること等によ
り行なわれる。As a method for controlling the pore size of the pores of the porous membrane by using the hydrophilic resin, a method of applying the hydrophilic resin dissolved in a solvent to at least one surface of the porous membrane and then drying it is used. In this case, it is carried out by changing the coating conditions such as the amount of solvent used, the number of coatings, and the resin concentration.
【００５７】すなわち、本発明に従う隔膜では、溶剤に
溶かした親水性樹脂が、多孔質膜の複数の孔部の一部の
孔部に毛細管現象により導入された後、乾燥されること
により、多孔質膜の複数の孔部の少なくとも一部の空隙
部内全体にまたは部分的に親水性樹脂が設けられてい
る。That is, in the membrane according to the present invention, the hydrophilic resin dissolved in the solvent is introduced into some of the plurality of pores of the porous membrane by the capillary phenomenon and then dried to obtain the porous membrane. The hydrophilic resin is provided entirely or partially in the voids of at least some of the plurality of pores of the quality membrane.
【００５８】同様に、多孔質膜の孔部の孔径を親水性樹
脂を用いて制御する方法として、モノマを塗布した後、
電子線または化学的な方法により重合させる方法を用い
る場合は、塗布条件、たとえば、用いる溶剤の量、塗布
回数、樹脂濃度、電子線の量、または、反応速度を変化
させることにより行なわれる。Similarly, as a method of controlling the pore size of the pores of the porous membrane by using a hydrophilic resin, after coating the monomer,
When a method of polymerizing by electron beam or a chemical method is used, it is carried out by changing coating conditions, for example, the amount of solvent used, the number of coatings, the resin concentration, the amount of electron beam, or the reaction rate.
【００５９】すなわち、本発明に従う隔膜では、親水性
樹脂の原料となるモノマが、多孔質膜の複数の孔部の一
部の孔部に毛細管現象により導入された後、電子線また
は化学的な方法により重合されることにより、多孔質膜
の複数の孔部の少なくとも一部の空隙部内全体に、また
は、部分的に親水性樹脂が設けられている。That is, in the diaphragm according to the present invention, the monomer as the raw material of the hydrophilic resin is introduced into some of the plural pores of the porous membrane by the capillary phenomenon, and then the electron beam or the chemical is used. By being polymerized by the method, the hydrophilic resin is provided entirely or partially in the voids of at least some of the plurality of pores of the porous membrane.
【００６０】本発明において特徴的な点は、多孔質膜の
複数の孔部の少なくとも一部の空隙部内全体にまたは部
分的に親水性樹脂を設けた後において、本発明に従う多
孔質膜と親水性樹脂とからなる隔膜は、多孔質膜の少な
くとも片面のすべての表面が一様に親水性樹脂によりま
んべんなく必ずしも覆われていない点において、従来の
性質の異なる膜と膜とを物理的に貼り合わせてなる２層
構造の隔膜と異なっている。A characteristic point of the present invention is that after the hydrophilic resin is provided entirely or partially in the voids of at least a part of the plurality of pores of the porous membrane, the porous membrane according to the present invention and the hydrophilic membrane are hydrophilic. A membrane composed of a hydrophobic resin is a physical membrane in which at least one surface of a porous membrane is not evenly covered with a hydrophilic resin evenly, and the conventional membranes having different properties are physically bonded to each other. It is different from the diaphragm having a two-layer structure.
【００６１】本発明においては、親水性樹脂として、イ
オン交換樹脂を用いることができる。In the present invention, an ion exchange resin can be used as the hydrophilic resin.
【００６２】イオン交換樹脂の材料としては、特に限定
されることはないが、たとえば、下記一般式で示される
ナフィオン樹脂の他、The material of the ion exchange resin is not particularly limited, but for example, in addition to the Nafion resin represented by the following general formula,
【００６３】[0063]
【化２】 [Chemical 2]
【００６４】一般的な公知のイオン交換樹脂、たとえ
ば、−ＳＯ3 Ｈ等の強酸性基等のイオン交換可能な酸性
基を有する不溶性樹脂を挙げることができる。イオン交
換樹脂の材料としては、特に限定されることはないが、
たとえば、スチレンとジビニルベンゼンの共重合体、ア
クリル酸、メタクリル酸、アクリルニトリル等を重合さ
せた公知の材料を用いることができる。There may be mentioned a generally known ion exchange resin, for example, an insoluble resin having an ion-exchangeable acidic group such as a strong acidic group such as —SO 3 H. The material of the ion exchange resin is not particularly limited,
For example, a known material obtained by polymerizing a copolymer of styrene and divinylbenzene, acrylic acid, methacrylic acid, acrylonitrile, or the like can be used.
【００６５】また、多孔質膜の複数の孔部の少なくとも
一部の空隙部内全体にまたは部分的にイオン交換樹脂を
設ける工程は、特に限定されることはないが、たとえ
ば、イオン交換樹脂を、メタノール等の溶剤に溶かした
後、多孔質膜の少なくとも片方の表面に、溶剤に溶かし
たイオン交換樹脂を塗布した後、乾燥させる方法を挙げ
ることができる。樹脂濃度は、特に限定されることはな
いが、たとえば、ナフィオン樹脂を用いる場合は、０．
１ｗｔ％〜５ｗｔ％の溶液を用いることができる。そし
て、溶媒に溶かしたイオン交換樹脂の塗布量は、多孔質
膜の少なくとも片方の表面に、膜厚１μｍ以上１０μｍ
以下塗布するのが好ましい。１μｍ以下の塗布量では、
イオン隔離機能が十分でなく好ましくなく、また、１０
μｍを超えると、内部抵抗が大きくなり好ましくない。The step of providing the ion exchange resin entirely or partially in the voids of at least a part of the plurality of pores of the porous membrane is not particularly limited, but, for example, A method may be mentioned in which, after being dissolved in a solvent such as methanol, at least one surface of the porous membrane is coated with the ion-exchange resin dissolved in the solvent and then dried. The resin concentration is not particularly limited, but for example, when Nafion resin is used, it is 0.
A solution of 1 wt% to 5 wt% can be used. Then, the coating amount of the ion exchange resin dissolved in the solvent is 1 μm or more and 10 μm or more on at least one surface of the porous membrane.
The following coating is preferred. With a coating amount of 1 μm or less,
The ion isolation function is not sufficient and is not preferable, and 10
If it exceeds μm, the internal resistance increases, which is not preferable.
【００６６】なお、本発明に従う水溶媒系電気化学装置
用隔膜は、多孔質膜の少なくとも片側表面に親水性樹
脂、イオン交換樹脂を導入してもよく、また、多孔質膜
の両側表面に親水性樹脂、イオン交換樹脂を導入しても
よい。また、本発明によれば、本発明に従う水溶媒系電
気化学装置用隔膜を、水溶媒系電池に用いることによ
り、該電池（単セル）の内部抵抗を０．２Ω・ｃｍ2 以
上１Ω・ｃｍ2 以下とすることができる。In the water-solvent system diaphragm for an electrochemical device according to the present invention, a hydrophilic resin or an ion exchange resin may be introduced into at least one surface of the porous membrane, or both surfaces of the porous membrane are hydrophilic. A resin or an ion exchange resin may be introduced. Further, according to the present invention, by using the membrane for a water-solvent electrochemical device according to the present invention in a water-solvent battery, the internal resistance of the battery (single cell) is 0.2 Ω · cm 2 or more and 1 Ω · cm. It can be 2 or less.
【００６７】[0067]
【発明の効果】以上詳細に説明したように、本発明に従
う水溶媒系電気化学装置用隔膜は、上記した構成を有す
る結果、イオン透過機能と、イオン隔離機能の双方が向
上されている。したがって、本発明に従う水溶媒系電気
化学装置用隔膜を用いた、レドックスフロー型電池等の
水溶媒系電池は、電池自体の内部抵抗を低減させること
ができ、内部抵抗に起因する容量低下を抑制できるとと
もに、隔膜を介して電解液が混合されるのを低減するこ
とができ、自己放電に起因する容量低下を抑制すること
ができる結果、水溶媒系電池の高効率化を実現できる。
また、本発明に従う水溶媒系電気化学装置用隔膜は、材
料が安価であり、レドックスフロー型電池の隔膜に用い
ると安価でかつ効率の高い電力貯蔵用電池装置を構築で
きる。As described in detail above, the membrane for a water-solvent electrochemical device according to the present invention has the above-mentioned structure, and as a result, has both an ion permeation function and an ion sequestration function. Therefore, a water-solvent battery such as a redox flow battery that uses the diaphragm for a water-solvent electrochemical device according to the present invention can reduce the internal resistance of the battery itself and suppress a decrease in capacity due to the internal resistance. In addition, it is possible to reduce the mixing of the electrolytic solution through the diaphragm and suppress the capacity decrease due to self-discharge. As a result, the efficiency of the water-solvent battery can be improved.
In addition, the water-solvent-based diaphragm for electrochemical device according to the present invention is inexpensive in material, and when used as a diaphragm for a redox flow battery, an inexpensive and highly efficient battery device for power storage can be constructed.
【００６８】なお、本発明に従う水溶媒系電気化学装置
用隔膜は、レドックスフロー型電池を中心に説明した
が、水溶媒系電解質を用いた電気化学装置であるなら
ば、適用可能である。The diaphragm for a water-solvent type electrochemical device according to the present invention has been mainly described for a redox flow battery, but it is applicable as long as it is an electrochemical device using a water-solvent type electrolyte.
【図１】レドックスフロー型電池の一具体例を概略的に
示す構成図である。FIG. 1 is a configuration diagram schematically showing a specific example of a redox flow battery.
【図２】図１に示すレドックスフロー型電池１の電池反
応セル２内の隔膜５の近傍を拡大して示す概略的な断面
図である。FIG. 2 is a schematic cross-sectional view showing an enlarged vicinity of a diaphragm 5 in a battery reaction cell 2 of the redox flow battery 1 shown in FIG.
１ レドックスフロー型電池 ２ 電池反応セル ３ 正極液タンク ４ 負極液タンク ５ 隔膜 ６ 正極 ７ 負極 ８ 正極液供給用管路 ９ 正極液回収用管路 １０、１３ ポンプ １１ 負極液供給用管路 １２ 負極液回収用管路 1 redox flow type battery 2 battery reaction cell 3 positive electrode liquid tank 4 negative electrode liquid tank 5 diaphragm 6 positive electrode 7 negative electrode 8 positive electrode liquid supply conduit 9 positive electrode liquid recovery conduit 10, 13 pump 11 negative electrode liquid supply conduit 12 negative electrode Liquid recovery line
Claims (3)
全体にまたは部分的に設けられた親水性樹脂とを備え
る、水溶媒系電気化学装置用隔膜。1. A water solvent comprising a porous membrane having a plurality of pores, and a hydrophilic resin provided entirely or partially in a void portion of at least a part of the plurality of pores of the porous membrane. Diaphragm for electrochemical system.
る請求項１に記載の水溶媒系電気化学装置用隔膜。2. The membrane for a water-solvent electrochemical device according to claim 1, wherein the hydrophilic resin is an ion exchange resin.
溶媒系電池であって、 前記隔膜は、複数の孔部を有する多孔質膜と、 前記多孔質膜の複数の孔部の少なくとも一部の空隙部内
全体にまたは部分的に設けられた親水性樹脂とを備え
る、水溶媒系電池。3. A water-solvent battery comprising a positive electrode, a negative electrode, and a diaphragm provided between the positive electrode and the negative electrode, wherein the diaphragm is a porous film having a plurality of pores, A water-solvent-based battery, comprising a hydrophilic resin provided entirely or partially in the voids of at least some of the plurality of pores of the porous membrane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5043469A JPH06260183A (en) | 1993-03-04 | 1993-03-04 | Diaphragm for aqueous solvent electrochemical device and battery with aqueous solvent using same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5043469A JPH06260183A (en) | 1993-03-04 | 1993-03-04 | Diaphragm for aqueous solvent electrochemical device and battery with aqueous solvent using same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06260183A true JPH06260183A (en) | 1994-09-16 |
Family
ID=12664583
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5043469A Withdrawn JPH06260183A (en) | 1993-03-04 | 1993-03-04 | Diaphragm for aqueous solvent electrochemical device and battery with aqueous solvent using same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06260183A (en) |
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