JP6925937B2 - Flow battery - Google Patents

Flow battery Download PDF

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JP6925937B2
JP6925937B2 JP2017210854A JP2017210854A JP6925937B2 JP 6925937 B2 JP6925937 B2 JP 6925937B2 JP 2017210854 A JP2017210854 A JP 2017210854A JP 2017210854 A JP2017210854 A JP 2017210854A JP 6925937 B2 JP6925937 B2 JP 6925937B2
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electrolytic solution
negative electrode
positive electrode
accommodating portion
flow battery
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JP2019083160A (en
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西原　雅人
雅人 西原
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Kyocera Corp
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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
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Description

開示の実施形態は、フロー電池に関する。 The disclosed embodiment relates to a flow battery.

従来、正極と負極との間に、テトラヒドロキシ亜鉛酸イオン（［Ｚｎ（ＯＨ）４］２−）を含有する電解液を循環させるフロー電池が知られている（例えば、非特許文献１参照）。 Conventionally, a flow battery in which an electrolytic solution containing tetrahydroxyzincate ion ([Zn (OH) 4 ] 2- ) is circulated between a positive electrode and a negative electrode is known (see, for example, Non-Patent Document 1). ..

また、亜鉛種などの活物質を含む負極を、選択的イオン電導性を有するイオン電導層で覆うことでデンドライトの成長を抑制する技術が提案されている（例えば、特許文献１参照）。 Further, a technique has been proposed in which a negative electrode containing an active material such as zinc type is covered with an ion conductive layer having selective ion conductivity to suppress the growth of dendrites (see, for example, Patent Document 1).

特開２０１５−１８５２５９号公報Japanese Unexamined Patent Publication No. 2015-185259

Y. Ito. et al.: Zinc morphology in zinc-nickel flow assisted batteries and impact on performance, Journal of Power Sources, Vol. 196, pp. 2340-2345, 2011Y. Ito. Et al .: Zinc morphology in zinc-nickel flow assisted batteries and impact on performance, Journal of Power Sources, Vol. 196, pp. 2340-2345, 2011

しかしながら、上記に記載の電池では、電極反応で生成した気体が滞留することで電池性能が劣化する懸念があった。 However, in the above-mentioned battery, there is a concern that the battery performance may be deteriorated due to the retention of the gas generated by the electrode reaction.

実施形態の一態様は、上記に鑑みてなされたものであって、性能劣化を低減することができるフロー電池を提供することを目的とする。 One aspect of the embodiment is made in view of the above, and an object of the present invention is to provide a flow battery capable of reducing performance deterioration.

実施形態の一態様に係るフロー電池は、正極および負極と、電解液と、収容部と、流動装置とを備える。電解液は、前記正極および前記負極に接触する。収容部は、前記正極または前記負極を覆うように収容する。流動装置は、前記電解液を流動させる。前記収容部は、上部に複数の開口部を備える。 The flow battery according to one aspect of the embodiment includes a positive electrode and a negative electrode, an electrolytic solution, an accommodating portion, and a flow device. The electrolytic solution comes into contact with the positive electrode and the negative electrode. The accommodating portion is accommodating so as to cover the positive electrode or the negative electrode. The flow device flows the electrolytic solution. The housing portion is provided with a plurality of openings at the top.

実施形態の一態様のフロー電池によれば、性能劣化を低減することができる。 According to the flow battery of one aspect of the embodiment, performance deterioration can be reduced.

図１は、第１の実施形態に係るフロー電池の概略を示す図である。FIG. 1 is a diagram showing an outline of a flow battery according to the first embodiment. 図２は、図１のＩ−Ｉ断面図である。FIG. 2 is a cross-sectional view taken along the line II of FIG. 図３は、第１の実施形態に係るフロー電池の電極間の接続の一例について説明する図である。FIG. 3 is a diagram illustrating an example of connection between electrodes of the flow battery according to the first embodiment. 図４は、第１の実施形態の第１変形例に係るフロー電池の概略を示す断面図である。FIG. 4 is a cross-sectional view showing an outline of a flow battery according to a first modification of the first embodiment. 図５は、第１の実施形態の第２変形例に係るフロー電池の概略を示す断面図である。FIG. 5 is a cross-sectional view showing an outline of a flow battery according to a second modification of the first embodiment. 図６は、第１の実施形態の第３変形例に係るフロー電池の概略を示す断面図である。FIG. 6 is a cross-sectional view showing an outline of a flow battery according to a third modification of the first embodiment. 図７は、第１の実施形態の第４変形例に係るフロー電池の概略を示す断面図である。FIG. 7 is a cross-sectional view showing an outline of a flow battery according to a fourth modification of the first embodiment. 図８は、第１の実施形態の第５変形例に係るフロー電池の概略を示す断面図である。FIG. 8 is a cross-sectional view showing an outline of a flow battery according to a fifth modification of the first embodiment. 図９は、第２の実施形態に係るフロー電池の概略を示す図である。FIG. 9 is a diagram showing an outline of the flow battery according to the second embodiment.

以下、添付図面を参照して、本願の開示するフロー電池の実施形態を詳細に説明する。なお、以下に示す実施形態によりこの発明が限定されるものではない。 Hereinafter, embodiments of the flow battery disclosed in the present application will be described in detail with reference to the accompanying drawings. The present invention is not limited to the embodiments shown below.

＜第１の実施形態＞
図１は、第１の実施形態に係るフロー電池の概略を示す図である。図１に示すフロー電池１は、正極２と、負極３と、収容部４と、電解液６と、粉末７と、発生部９と、隔膜１０，１１と、供給部１４と、筐体１７と、上板１８とを備える。フロー電池１は、発生部９で発生した気泡８を浮上させることにより電解液６を流動させる装置である。発生部９は、流動装置の一例である。 <First Embodiment>
FIG. 1 is a diagram showing an outline of a flow battery according to the first embodiment. The flow battery 1 shown in FIG. 1 includes a positive electrode 2, a negative electrode 3, an accommodating portion 4, an electrolytic solution 6, a powder 7, a generating portion 9, diaphragms 10 and 11, a supply portion 14, and a housing 17. And the upper plate 18. The flow battery 1 is a device for flowing the electrolytic solution 6 by floating the bubbles 8 generated in the generating unit 9. The generation unit 9 is an example of a flow device.

なお、説明を分かりやすくするために、図１には、鉛直上向きを正方向とし、鉛直下向きを負方向とするＺ軸を含む３次元の直交座標系を図示している。かかる直交座標系は、後述の説明に用いる他の図面でも示す場合がある。 For the sake of clarity, FIG. 1 illustrates a three-dimensional Cartesian coordinate system including a Z-axis having a vertically upward direction as a positive direction and a vertically downward direction as a negative direction. Such a Cartesian coordinate system may also be shown in other drawings used in the description below.

正極２は、例えば、ニッケル化合物、マンガン化合物またはコバルト化合物を正極活物質として含有する導電性の部材である。ニッケル化合物は、例えば、オキシ水酸化ニッケル、水酸化ニッケル、コバルト化合物含有水酸化ニッケル等が使用できる。マンガン化合物は、例えば、二酸化マンガン等が使用できる。コバルト化合物は、例えば、水酸化コバルト、オキシ水酸化コバルト等が使用できる。また、正極２は、黒鉛、カーボンブラック、導電性樹脂等を含んでもよい。電解液６が分解される酸化還元電位の観点からは、正極２はニッケル化合物を含有してもよい。また、正極２は、ニッケル金属、コバルト金属またはマンガン金属、あるいはそれらの合金であってもよい。 The positive electrode 2 is, for example, a conductive member containing a nickel compound, a manganese compound, or a cobalt compound as a positive electrode active material. As the nickel compound, for example, nickel oxyhydroxide, nickel hydroxide, cobalt hydroxide-containing nickel hydroxide and the like can be used. As the manganese compound, for example, manganese dioxide or the like can be used. As the cobalt compound, for example, cobalt hydroxide, cobalt oxyhydroxide and the like can be used. Further, the positive electrode 2 may contain graphite, carbon black, a conductive resin, or the like. From the viewpoint of the redox potential at which the electrolytic solution 6 is decomposed, the positive electrode 2 may contain a nickel compound. Further, the positive electrode 2 may be a nickel metal, a cobalt metal, a manganese metal, or an alloy thereof.

また、正極２は、例えば、上記した正極活物質や導電体その他の添加剤を複数の粒状体として含む。具体的には、正極２は、例えば、予め定められた割合で配合された粒状の活物質および導電体を、保形性に寄与するバインダとともに含有するペースト状の正極材料を発泡ニッケルなどの導電性を有する発泡金属へ圧入し、所望の形状に成形し、乾燥させたものである。 Further, the positive electrode 2 contains, for example, the above-mentioned positive electrode active material, a conductor, and other additives as a plurality of granules. Specifically, the positive electrode 2 contains, for example, a paste-like positive electrode material containing a granular active material and a conductor mixed in a predetermined ratio together with a binder that contributes to shape retention, and is conductive such as nickel foam. It is press-fitted into a foam metal having a property, formed into a desired shape, and dried.

負極３は、負極活物質を金属として含む。負極３は、例えば、ステンレスや銅などの金属板や、ステンレスや銅板の表面をニッケルやスズ、亜鉛でメッキ処理したものを使用することができる。また、メッキ処理された表面が一部酸化されたものを負極３として使用してもよい。 The negative electrode 3 contains a negative electrode active material as a metal. As the negative electrode 3, for example, a metal plate such as stainless steel or copper, or a stainless steel or copper plate whose surface is plated with nickel, tin, or zinc can be used. Further, the one whose plated surface is partially oxidized may be used as the negative electrode 3.

正極２は、正極２Ａおよび正極２Ｂを含む。負極３は、負極３Ａ、負極３Ｂおよび負極３Ｃを含む。正極２および負極３は、負極３Ａと、正極２Ａと、負極３Ｂと、正極２Ｂと、負極３Ｃとが予め定められた間隔でＹ軸方向に沿って順に並ぶように配置されている。このように隣り合う正極２と負極３との間隔をそれぞれ設けることにより、正極２と負極３との間に電解液６および気泡８の流通経路が確保される。 The positive electrode 2 includes a positive electrode 2A and a positive electrode 2B. The negative electrode 3 includes a negative electrode 3A, a negative electrode 3B, and a negative electrode 3C. The positive electrode 2 and the negative electrode 3 are arranged so that the negative electrode 3A, the positive electrode 2A, the negative electrode 3B, the positive electrode 2B, and the negative electrode 3C are arranged in order along the Y-axis direction at predetermined intervals. By providing the intervals between the positive electrode 2 and the negative electrode 3 adjacent to each other in this way, the flow paths of the electrolytic solution 6 and the bubbles 8 are secured between the positive electrode 2 and the negative electrode 3.

収容部４は、正極２Ａを収容する。収容部４は、正極２Ａの厚み方向、すなわちＹ軸方向の両側を挟むように配置された第１シート部材４ａおよび第２シート部材４ｂを含む。収容部４は、第１シート部材４ａおよび第２シート部材４ｂで覆うように正極２Ａを収容する。収容部４は、第１シート部材４ａと第２シート部材４ｂとの間に挟まれるように配置された正極２ＡをＹ軸方向に沿って両側から押圧するように保持する。これにより、収容部４は、電解液６の流動状態の変化や、粉末７や気泡８との接触から正極２Ａを防護し、正極２Ａの保形性を向上させる。 The accommodating portion 4 accommodates the positive electrode 2A. The accommodating portion 4 includes a first sheet member 4a and a second sheet member 4b arranged so as to sandwich both sides of the positive electrode 2A in the thickness direction, that is, in the Y-axis direction. The accommodating portion 4 accommodates the positive electrode 2A so as to be covered with the first sheet member 4a and the second sheet member 4b. The accommodating portion 4 holds the positive electrode 2A arranged so as to be sandwiched between the first sheet member 4a and the second sheet member 4b so as to be pressed from both sides along the Y-axis direction. As a result, the accommodating portion 4 protects the positive electrode 2A from changes in the flow state of the electrolytic solution 6 and contact with the powder 7 and the bubbles 8, and improves the shape retention of the positive electrode 2A.

また、収容部４は、上部に開口部５を備える。ここで収容部４について、図１、図２を用いてさらに説明する。図２は、図１に示すフロー電池１のＩ−Ｉ断面図である。図２は、正極２Ａおよびその近傍を断面視したものに相当する。なお、正極２Ｂおよびその近傍の構成については、図２に示す正極２Ａおよびその近傍の構成と同様である。このため、正極２Ｂに関する図示および説明は省略する。 Further, the accommodating portion 4 is provided with an opening 5 at the upper portion. Here, the accommodating portion 4 will be further described with reference to FIGS. 1 and 2. FIG. 2 is a cross-sectional view taken along the line II of the flow battery 1 shown in FIG. FIG. 2 corresponds to a cross-sectional view of the positive electrode 2A and its vicinity. The configuration of the positive electrode 2B and its vicinity is the same as the configuration of the positive electrode 2A and its vicinity shown in FIG. Therefore, the illustration and description of the positive electrode 2B will be omitted.

図２に示すように、開口部５は、複数の開口部５ａ〜５ｃを含む。開口部５ａ〜５ｃのうち、開口部５ｃは、収容部４に収容された正極２Ａと電気的に接続される板状または棒状のタブ２Ａ１を収容部４の外部に延出させるための延出口を兼ねている。なお、図２に示す例では、開口部５は、３つの開口部５ａ〜５ｃを含むが、これに限らず、２つまたは４つ以上の開口部５を有してもよい。また、タブ２Ａ１を複数とし、開口部５ａ〜５ｃのうちタブ２Ａ１の延出口を兼ねるものを複数にしてもよい。また、延出口を兼ねていない１または複数の開口部５ａ〜５ｃ（図２では、開口部５ａ，５ｂに相当）を設ければ、後述する副反応で生じる気体の開口部５ａ〜５ｃからの排出性をよくできる。 As shown in FIG. 2, the opening 5 includes a plurality of openings 5a to 5c. Of the openings 5a to 5c, the opening 5c is an extension outlet for extending a plate-shaped or rod-shaped tab 2A1 electrically connected to the positive electrode 2A housed in the housing part 4 to the outside of the housing part 4. Also serves as. In the example shown in FIG. 2, the opening 5 includes three openings 5a to 5c, but is not limited to this, and may have two or four or more openings 5. Further, the number of tabs 2A1 may be a plurality, and the number of openings 5a to 5c that also serve as the extension / outlet of the tab 2A1 may be a plurality. Further, if one or a plurality of openings 5a to 5c (corresponding to openings 5a and 5b in FIG. 2) that do not also serve as extension outlets are provided, gas openings 5a to 5c generated by side reactions described later can be provided. The discharge can be improved.

第２シート部材４ｂは、Ｚ−Ｘ平面に沿うように形成された矩形部４ｂ１と、矩形部４ｂ１から上方に突出するように形成された複数の突出部４ｂ２とを含む。矩形部４ｂ１は、正極２Ａが収容および保持される部分に対応し、突出部４ｂ２は、開口部５に対応する。また、第１シート部材４ａは、第２シート部材４ｂと同じ形状を有している。 The second sheet member 4b includes a rectangular portion 4b1 formed along the ZX plane and a plurality of protruding portions 4b2 formed so as to project upward from the rectangular portion 4b1. The rectangular portion 4b1 corresponds to a portion in which the positive electrode 2A is housed and held, and the protruding portion 4b2 corresponds to the opening 5. Further, the first sheet member 4a has the same shape as the second sheet member 4b.

開口部５を備える収容部４は、重ね合わせるように配置した第１シート部材４ａおよび第２シート部材４ｂの外縁部分を互いに接合することで形成される。具体的には、例えば、突出部４ｂ２の側縁部３５〜４０と、矩形部４ｂ１の外縁部３１〜３４のうち、下縁部３３を除く部分、すなわち側縁部３１，３２および上縁部３４とを、例えば熱圧着等により接合する。そして、矩形部４ｂ１の下縁部３３側からタブ２Ａ１および正極２Ａを挿入した後で下縁部３３を接合することで、正極２Ａが収容された収容部４が形成される。なお、収容部４の作製方法は上記したものに限らず、例えば矩形部４ｂ１の側縁部３１，３２および下縁部３３を接合し、正極２Ａを収容した後で突出部４ｂ２の側縁部３５〜４０と、矩形部４ｂ１の上縁部３４とをそれぞれ接合してもよい。 The accommodating portion 4 provided with the opening 5 is formed by joining the outer edge portions of the first sheet member 4a and the second sheet member 4b arranged so as to overlap each other. Specifically, for example, of the side edge portions 35 to 40 of the protruding portion 4b2 and the outer edge portions 31 to 34 of the rectangular portion 4b1, the portions excluding the lower edge portion 33, that is, the side edge portions 31, 32 and the upper edge portion. The 34 is joined by, for example, thermal pressure bonding. Then, by inserting the tab 2A1 and the positive electrode 2A from the lower edge 33 side of the rectangular portion 4b1 and then joining the lower edge 33, the accommodating portion 4 in which the positive electrode 2A is accommodated is formed. The method for manufacturing the accommodating portion 4 is not limited to the above. 35-40 and the upper edge portion 34 of the rectangular portion 4b1 may be joined to each other.

ここで、第１シート部材４ａおよび第２シート部材４ｂの材料としては、例えば、ポリエチレンまたはポリプロピレン等の耐電解液性を有する繊維を含む不織布を使用することができる。また、第１シート部材４ａおよび第２シート部材４ｂの厚みはそれぞれ、例えば、乾燥時には１００μｍ程度、電解液６中では５００〜１０００μｍ程度となるものを使用することができるが、これに限らない。また、図２に示す第１シート部材４ａおよび第２シート部材４ｂの接合部分の幅Ｌ４は、例えば０．５μｍ程度とすることができるが、これに限らず、第１シート部材４ａおよび第２シート部材４ｂの材質等に応じて適宜設定することができる。なお電解液６の流通が可能であって、かつ正極２Ａを保持することができるものであれば第１シート部材４ａおよび第２シート部材４ｂの材料に制限はなく、例えば織布であってもよい。 Here, as the material of the first sheet member 4a and the second sheet member 4b, for example, a non-woven fabric containing fibers having electrolytic solution resistance such as polyethylene or polypropylene can be used. Further, the thicknesses of the first sheet member 4a and the second sheet member 4b can be, for example, about 100 μm when dried and about 500 to 1000 μm in the electrolytic solution 6, but are not limited thereto. Further, the width L4 of the joint portion between the first sheet member 4a and the second sheet member 4b shown in FIG. 2 can be, for example, about 0.5 μm, but is not limited to this, and the first sheet member 4a and the second sheet member 4a and the second sheet member 4a It can be appropriately set according to the material of the sheet member 4b and the like. The materials of the first sheet member 4a and the second sheet member 4b are not limited as long as the electrolytic solution 6 can be circulated and the positive electrode 2A can be held. For example, a woven fabric may be used. good.

図１に戻り、第１の実施形態に係るフロー電池１についてさらに説明する。隔膜１０，１１は、収容部４の厚み方向、すなわちＹ軸方向の両側を挟むように配置される。隔膜１０，１１は、電解液６に含まれるイオンの移動を許容する材料で構成される。具体的には、隔膜１０，１１の材料として、例えば、隔膜１０，１１が水酸化物イオン伝導性を有するように、陰イオン伝導性材料が挙げられる。陰イオン伝導性材料としては、例えば、有機ヒドロゲルのような三次元構造を有するゲル状の陰イオン伝導性材料、または固体高分子型陰イオン伝導性材料などが挙げられる。固体高分子型陰イオン伝導性材料は、例えば、ポリマーと、周期表の第１族〜第１７族より選択された少なくとも一種類の元素を含有する、酸化物、水酸化物、層状複水酸化物、硫酸化合物およびリン酸化合物からなる群より選択された少なくとも一つの化合物とを含む。 Returning to FIG. 1, the flow battery 1 according to the first embodiment will be further described. The diaphragms 10 and 11 are arranged so as to sandwich both sides of the accommodating portion 4 in the thickness direction, that is, in the Y-axis direction. The diaphragms 10 and 11 are made of a material that allows the movement of ions contained in the electrolytic solution 6. Specifically, examples of the material of the diaphragms 10 and 11 include an anion conductive material so that the diaphragms 10 and 11 have hydroxide ion conductivity. Examples of the anion conductive material include a gel-like anion conductive material having a three-dimensional structure such as an organic hydrogel, a solid polymer type anion conductive material, and the like. The solid polymer anion conductive material contains, for example, a polymer and at least one element selected from Groups 1 to 17 of the Periodic Table, such as oxides, hydroxides, and layered compound hydroxides. Includes at least one compound selected from the group consisting of compounds, sulfate compounds and phosphate compounds.

隔膜１０，１１は、好ましくは、水酸化物イオンよりも大きいイオン半径を備えた［Ｚｎ（ＯＨ）４］２−等の金属イオン錯体の透過を抑制するように緻密な材料で構成されると共に所定の厚さを有する。緻密な材料としては、例えば、アルキメデス法で算出された９０％以上、より好ましくは９２％以上、さらに好ましくは９５％以上の相対密度を有する材料が挙げられる。所定の厚さは、例えば、１０μｍ〜１０００μｍ、より好ましくは５０μｍ〜５００μｍである。 The diaphragms 10 and 11 are preferably made of a dense material so as to suppress the permeation of a metal ion complex such as [Zn (OH) 4 ] 2- having an ionic radius larger than that of hydroxide ions. It has a predetermined thickness. Examples of the dense material include a material having a relative density of 90% or more, more preferably 92% or more, still more preferably 95% or more calculated by the Archimedes method. The predetermined thickness is, for example, 10 μm to 1000 μm, more preferably 50 μm to 500 μm.

この場合には、充電の際に、負極３Ａ〜３Ｃにおいて析出する亜鉛がデンドライト（針状結晶）として成長し、隔膜１０，１１を貫通することを低減することができる。その結果、互いに向かい合う負極３と正極２との間の導通をそれぞれ低減することができる。 In this case, it is possible to reduce the growth of zinc precipitated in the negative electrodes 3A to 3C as dendrites (needle-shaped crystals) during charging and penetrating the diaphragms 10 and 11. As a result, the conduction between the negative electrode 3 and the positive electrode 2 facing each other can be reduced.

電解液６は、亜鉛種を含有するアルカリ水溶液である。電解液６中の亜鉛種は、［Ｚｎ（ＯＨ）４］２−として電解液６中に溶存している。電解液６は、例えば、Ｋ＋やＯＨ−を含むアルカリ水溶液に亜鉛種を飽和させたものを使用することができる。なお、電解液６は、後述する粉末７とともに調製すれば、充電容量を大きくできる。ここで、アルカリ水溶液としては、例えば、６．７ｍｏｌｄｍ−３の水酸化カリウム水溶液を使用することができる。また、１ｄｍ−３の水酸化カリウム水溶液に対し、０．５ｍｏｌの割合でＺｎＯを添加し、必要に応じて後述する粉末７を追加することにより電解液６を調製することができる。さらに、酸素発生抑制を目的に、水酸化リチウムや水酸化ナトリウムなどのアルカリ金属を添加してもよい。 The electrolytic solution 6 is an alkaline aqueous solution containing zinc species. The zinc species in the electrolytic solution 6 are dissolved in the electrolytic solution 6 as [Zn (OH) 4 ] 2-. As the electrolytic solution 6, for example, an alkaline aqueous solution containing K + or OH − saturated with zinc species can be used. If the electrolytic solution 6 is prepared together with the powder 7 described later, the charging capacity can be increased. Here, as the alkaline aqueous solution, for example, a 6.7 moldm- 3 potassium hydroxide aqueous solution can be used. Further, the electrolytic solution 6 can be prepared by adding ZnO at a ratio of 0.5 mol to 1 dm-3 potassium hydroxide aqueous solution and adding powder 7 described later as necessary. Further, an alkali metal such as lithium hydroxide or sodium hydroxide may be added for the purpose of suppressing oxygen evolution.

粉末７は、亜鉛を含む。具体的には、粉末７は、例えば粉末状に加工または生成された酸化亜鉛、水酸化亜鉛等である。粉末７は、アルカリ水溶液中には容易に溶解するが、亜鉛種の飽和した電解液６中には溶解せずに分散または浮遊し、一部が沈降した状態で電解液６中に混在する。電解液６が長時間静置されていた場合、ほとんどの粉末７が、電解液６の中で沈降した状態になることもあるが、電解液６に対流等を生じさせれば、沈降していた粉末７の一部は、電解液６に分散または浮遊した状態になる。つまり、粉末７は、電解液６中に移動可能に存在している。なお、ここで移動可能とは、粉末７が、周囲の他の粉末７の間にできた局所的な空間の中のみを移動できることではなく、電解液６の中を別の位置に粉末７が移動することにより、当初の位置以外の電解液６に粉末７が晒されるようになっていることを表す。さらに、移動可能の範疇には、正極２を収容する収容部４および負極３の両方の近傍まで粉末７が移動できるようになっていることや、筐体１７内に存在する電解液６中の、ほぼどこにでも粉末７が移動できるようになっていることが含まれる。電解液６中に溶存する亜鉛種である［Ｚｎ（ＯＨ）４］２−が消費されると、電解液６中に混在する粉末７は、粉末７および電解液６が互いに平衡状態を維持するように電解液６中に溶存する亜鉛種が飽和するまで溶解する。 Powder 7 contains zinc. Specifically, the powder 7 is, for example, zinc oxide, zinc hydroxide, or the like processed or produced in the form of powder. The powder 7 is easily dissolved in the alkaline aqueous solution, but is dispersed or suspended in the zinc-type saturated electrolytic solution 6 without being dissolved, and is mixed in the electrolytic solution 6 in a partially precipitated state. When the electrolytic solution 6 is left to stand for a long time, most of the powder 7 may be in a state of being settled in the electrolytic solution 6, but if convection or the like is caused in the electrolytic solution 6, it is settled. A part of the powder 7 is dispersed or suspended in the electrolytic solution 6. That is, the powder 7 is movably present in the electrolytic solution 6. Note that the fact that the powder 7 can move here does not mean that the powder 7 can move only in the local space created between the other powders 7 around it, but that the powder 7 moves to another position in the electrolytic solution 6. By moving, it means that the powder 7 is exposed to the electrolytic solution 6 other than the initial position. Further, the movable category includes that the powder 7 can be moved to the vicinity of both the accommodating portion 4 accommodating the positive electrode 2 and the negative electrode 3, and that the powder 7 is contained in the electrolytic solution 6 existing in the housing 17. It is included that the powder 7 can be moved almost anywhere. When [Zn (OH) 4 ] 2-, which is a zinc species dissolved in the electrolytic solution 6, is consumed, the powder 7 mixed in the electrolytic solution 6 maintains an equilibrium state between the powder 7 and the electrolytic solution 6. As described above, the zinc species dissolved in the electrolytic solution 6 are dissolved until they are saturated.

気泡８は、例えば正極２Ａ，２Ｂ、負極３Ａ，３Ｂ，３Ｃおよび電解液６に対して不活性な気体で構成される。このような気体としては、例えば、窒素ガス、ヘリウムガス、ネオンガス、またはアルゴンガスなどが挙げられる。電解液６に不活性な気体の気泡８を発生させることにより、電解液６の変性を低減することができる。また、例えば、亜鉛種を含有するアルカリ水溶液である電解液６の劣化を低減し、電解液６のイオン伝導度を高く維持することができる。なお、気体は空気を含有してもよい。 The bubbles 8 are composed of, for example, positive electrodes 2A and 2B, negative electrodes 3A, 3B and 3C, and a gas that is inert to the electrolytic solution 6. Examples of such a gas include nitrogen gas, helium gas, neon gas, argon gas and the like. By generating bubbles 8 of an inert gas in the electrolytic solution 6, the denaturation of the electrolytic solution 6 can be reduced. Further, for example, deterioration of the electrolytic solution 6 which is an alkaline aqueous solution containing zinc species can be reduced, and the ionic conductivity of the electrolytic solution 6 can be maintained high. The gas may contain air.

発生部９から電解液６中に供給された気体により発生した気泡８は、所定の間隔で配置された電極間、より具体的には、負極３Ａと正極２Ａを収容する収容部４との間、正極２Ａを収容する収容部４と負極３Ｂとの間、負極３Ｂと正極２Ｂを収容する収容部４との間、正極２Ｂを収容する収容部４と負極３Ｃとの間において、それぞれ電解液６中を浮上する。電解液６中を気泡８として浮上した気体は、電解液６の液面６ａで消滅し、上板１８と電解液６の液面６ａとの間に気体層１３を構成する。 The bubbles 8 generated by the gas supplied from the generating unit 9 into the electrolytic solution 6 are between the electrodes arranged at predetermined intervals, more specifically, between the negative electrode 3A and the accommodating unit 4 accommodating the positive electrode 2A. , Between the accommodating portion 4 accommodating the positive electrode 2A and the negative electrode 3B, between the accommodating portion 4 accommodating the negative electrode 3B and the positive electrode 2B, and between the accommodating portion 4 accommodating the positive electrode 2B and the negative electrode 3C, respectively. Ascend in 6. The gas that floats as bubbles 8 in the electrolytic solution 6 disappears at the liquid level 6a of the electrolytic solution 6, and forms a gas layer 13 between the upper plate 18 and the liquid level 6a of the electrolytic solution 6.

ここで、フロー電池１における電極反応について、正極活物質として水酸化ニッケルを適用したニッケル亜鉛電池を例に挙げて説明する。充電時における正極２および負極３での反応式はそれぞれ、以下のとおりである。 Here, the electrode reaction in the flow battery 1 will be described by taking a nickel-zinc battery to which nickel hydroxide is applied as the positive electrode active material as an example. The reaction formulas for the positive electrode 2 and the negative electrode 3 during charging are as follows.

正極：Ｎｉ（ＯＨ）２ ＋ ＯＨ− → ＮｉＯＯＨ ＋ Ｈ２Ｏ ＋ ｅ−
負極：［Ｚｎ（ＯＨ）４］２− ＋ ２ｅ− → Ｚｎ ＋４ＯＨ− Positive electrode: Ni (OH) 2 + OH − → NiOOH + H 2 O + e −
The negative electrode: [Zn (OH) 4] 2- + 2e - → Zn + 4OH -

一般的には、この反応に伴って負極３で生成したデンドライトが正極２側へ成長し、正極２と負極３とが導通する懸念がある。反応式から明らかなように、負極３では、充電により亜鉛が析出するのに伴い、負極３の近傍における［Ｚｎ（ＯＨ）４］２−の濃度が低下する。そして、析出した亜鉛の近傍で［Ｚｎ（ＯＨ）４］２−の濃度が低下する現象が、デンドライトとして成長する一因である。すなわち、充電時に消費される電解液６中の［Ｚｎ（ＯＨ）４］２−を補給することにより、電解液６中の亜鉛種である［Ｚｎ（ＯＨ）４］２−の濃度が飽和状態に保持される。これにより、デンドライトの成長が低減され、正極２と負極３との導通が低減される。 In general, there is a concern that the dendrites generated in the negative electrode 3 grow toward the positive electrode 2 side with this reaction, and the positive electrode 2 and the negative electrode 3 become conductive. As is clear from the reaction formula, in the negative electrode 3, the concentration of [Zn (OH) 4 ] 2- in the vicinity of the negative electrode 3 decreases as zinc is precipitated by charging. The phenomenon that the concentration of [Zn (OH) 4 ] 2- decreases in the vicinity of the precipitated zinc is one of the causes for the growth as dendrite. That is, by replenishing [Zn (OH) 4 ] 2- in the electrolytic solution 6 consumed during charging, the concentration of [Zn (OH) 4 ] 2- , which is a zinc species in the electrolytic solution 6, is saturated. Is held in. As a result, the growth of dendrites is reduced, and the conduction between the positive electrode 2 and the negative electrode 3 is reduced.

第１の実施形態に係るフロー電池１では、電解液６中に亜鉛を含む粉末７を混在させるとともに、発生部９の吐出口９ａから電解液６中に気体を供給して気泡８を発生させる。気泡８は、負極３Ａと正極２Ａを収容する収容部４との間、正極２Ａを収容する収容部４と負極３Ｂとの間、負極３Ｂと正極２Ｂを収容する収容部４との間、正極２Ｂを収容する収容部４と負極３Ｃとの間のそれぞれにおいて筐体１７の下方から上方に向かって電解液６中を浮上する。 In the flow battery 1 according to the first embodiment, the powder 7 containing zinc is mixed in the electrolytic solution 6, and gas is supplied into the electrolytic solution 6 from the discharge port 9a of the generating unit 9 to generate bubbles 8. .. The bubbles 8 are between the negative electrode 3A and the accommodating portion 4 accommodating the positive electrode 2A, between the accommodating portion 4 accommodating the positive electrode 2A and the negative electrode 3B, and between the accommodating portion 4 accommodating the negative electrode 3B and the positive electrode 2B, and the positive electrode. The electrolytic solution 6 floats from the lower side to the upper side of the housing 17 between the accommodating portion 4 accommodating the 2B and the negative electrode 3C, respectively.

また、電極間における上記した気泡８の浮上に伴い、電解液６には上昇液流が発生し、負極３Ａと正極２Ａを収容する収容部４との間、正極２Ａを収容する収容部４と負極３Ｂとの間、負極３Ｂと正極２Ｂを収容する収容部４との間、正極２Ｂを収容する収容部４と負極３Ｃとの間では筐体１７の内底側から上方に向かって電解液６が流動する。そして、電解液６の上昇液流に伴い、主に筐体１７の内壁１７ａと負極３Ａとの間、および内壁１７ｂと負極３Ｃとの間で下降液流が発生し、電解液６が筐体１７の上方から下方に向かって流動する。 Further, as the bubbles 8 float between the electrodes, an ascending liquid flow is generated in the electrolytic solution 6, and between the negative electrode 3A and the accommodating portion 4 accommodating the positive electrode 2A, and the accommodating portion 4 accommodating the positive electrode 2A. Electrolyte liquid between the negative electrode 3B, between the negative electrode 3B and the accommodating portion 4 accommodating the positive electrode 2B, and between the accommodating portion 4 accommodating the positive electrode 2B and the negative electrode 3C from the inner bottom side of the housing 17 upward. 6 flows. Then, along with the rising liquid flow of the electrolytic solution 6, a falling liquid flow is mainly generated between the inner wall 17a and the negative electrode 3A of the housing 17 and between the inner wall 17b and the negative electrode 3C, and the electrolytic solution 6 is transferred to the housing. It flows from the upper side to the lower side of 17.

これにより、充電によって電解液６中の［Ｚｎ（ＯＨ）４］２−が消費されると、これに追従するように粉末７中の亜鉛が溶解することで［Ｚｎ（ＯＨ）４］２−が電解液６中に補給される。このため、電解液６中の［Ｚｎ（ＯＨ）４］２−の濃度を飽和状態に保つことができ、デンドライトの成長に伴う正極２と負極３との導通を低減することができる。 As a result, when [Zn (OH) 4 ] 2- in the electrolytic solution 6 is consumed by charging, zinc in the powder 7 is dissolved so as to follow this, and [Zn (OH) 4 ] 2- Is replenished in the electrolytic solution 6. Therefore, the concentration of [Zn (OH) 4 ] 2- in the electrolytic solution 6 can be kept saturated, and the conduction between the positive electrode 2 and the negative electrode 3 due to the growth of dendrite can be reduced.

なお、粉末７としては、酸化亜鉛および水酸化亜鉛以外に、金属亜鉛、亜鉛酸カルシウム、炭酸亜鉛、硫酸亜鉛、塩化亜鉛などが挙げられ、酸化亜鉛および水酸化亜鉛が好ましい。 Examples of the powder 7 include metallic zinc, calcium zincate, zinc carbonate, zinc sulfate, zinc chloride and the like in addition to zinc oxide and zinc hydroxide, and zinc oxide and zinc hydroxide are preferable.

また、負極３では、放電によりＺｎが消費され、［Ｚｎ（ＯＨ）４］２−を生成するが、電解液６はすでに飽和状態であるため、電解液６中では、過剰となった［Ｚｎ（ＯＨ）４］２−からＺｎＯが析出する。このとき負極３で消費される亜鉛は、充電時に負極３の表面に析出した亜鉛である。このため、元来亜鉛種を含有する負極を用いて充放電を繰り返す場合とは異なり、負極３の表面形状が変化するいわゆるシェイプチェンジが生じない。これにより、第１の実施形態に係るフロー電池１によれば、負極３の経時劣化を低減することができる。なお、電解液６の状態によっては、過剰となった［Ｚｎ（ＯＨ）４］２−から析出するのは、Ｚｎ（ＯＨ）２や、ＺｎＯとＺｎ（ＯＨ）２とが混合したものになる。 Further, in the negative electrode 3, Zn is consumed by the discharge to generate [Zn (OH) 4 ] 2- , but since the electrolytic solution 6 is already saturated, it becomes excessive in the electrolytic solution 6 [Zn]. (OH) 4 ] ZnO is precipitated from 2-. The zinc consumed by the negative electrode 3 at this time is zinc deposited on the surface of the negative electrode 3 during charging. Therefore, unlike the case where charging and discharging are repeated using a negative electrode originally containing a zinc type, so-called shape change in which the surface shape of the negative electrode 3 changes does not occur. As a result, according to the flow battery 1 according to the first embodiment, the deterioration of the negative electrode 3 with time can be reduced. Depending on the state of the electrolytic solution 6, the excess [Zn (OH) 4 ] 2- precipitates is Zn (OH) 2 or a mixture of ZnO and Zn (OH) 2. ..

ところで、第１の実施形態に係るフロー電池１では、正極２での副反応として酸素等の気体が発生する場合がある。正極２で発生した気体が収容部４に滞留すると、正極２の酸化や反応領域の減少により電池性能が劣化する可能性がある。 By the way, in the flow battery 1 according to the first embodiment, a gas such as oxygen may be generated as a side reaction at the positive electrode 2. If the gas generated in the positive electrode 2 stays in the accommodating portion 4, the battery performance may deteriorate due to the oxidation of the positive electrode 2 and the reduction of the reaction region.

そこで、第１の実施形態に係るフロー電池１では、収容部４の上部に複数の開口部５ａ〜５ｃを備えることとした。図１、図２に示すように、収容部４に収容された正極２で発生した気体は、開口部５ａ〜５ｃを介して収容部４の外部へ排出される。収容部４の外部へ排出された気体は、気泡８を発生させるために発生部９から供給された気体とともに筐体１７の外部へ排出される。これにより、発生した気体の滞留に伴う性能劣化が低減される。 Therefore, in the flow battery 1 according to the first embodiment, it is decided to provide a plurality of openings 5a to 5c in the upper part of the accommodating portion 4. As shown in FIGS. 1 and 2, the gas generated in the positive electrode 2 accommodated in the accommodating portion 4 is discharged to the outside of the accommodating portion 4 through the openings 5a to 5c. The gas discharged to the outside of the accommodating portion 4 is discharged to the outside of the housing 17 together with the gas supplied from the generating portion 9 in order to generate the bubbles 8. As a result, the performance deterioration due to the retention of the generated gas is reduced.

第１の実施形態に係るフロー電池１についてさらに説明する。発生部９は、筐体１７の下部、より具体的には正極２および負極３の下方に配置されている。 The flow battery 1 according to the first embodiment will be further described. The generating portion 9 is arranged below the housing 17, more specifically below the positive electrode 2 and the negative electrode 3.

発生部９は、後述する供給部１４から供給された気体を一時的に貯留するよう内部が中空となっており、Ｘ軸方向およびＹ軸方向に沿って並ぶ複数の吐出口９ａが発生部９の内部の中空部分に連通するように配置されている。 The generation unit 9 has a hollow interior so as to temporarily store the gas supplied from the supply unit 14, which will be described later, and has a plurality of discharge ports 9a arranged along the X-axis direction and the Y-axis direction. It is arranged so as to communicate with the hollow part inside the.

発生部９は、供給部１４から供給された気体を吐出口９ａから吐出することにより、電解液６中に気泡８を発生させる。吐出口９ａは、例えば０．０５ｍｍ以上０．５ｍｍ以下の直径を有する。吐出口９ａの直径をこのように規定することにより、吐出口９ａから発生部９の内部に電解液６や粉末７が進入する不具合を低減することができる。また、吐出口９ａから吐出される気体に対し、気泡８を発生させるのに適した圧力損失を与えることができる。 The generation unit 9 generates bubbles 8 in the electrolytic solution 6 by discharging the gas supplied from the supply unit 14 from the discharge port 9a. The discharge port 9a has, for example, a diameter of 0.05 mm or more and 0.5 mm or less. By defining the diameter of the discharge port 9a in this way, it is possible to reduce the problem that the electrolytic solution 6 or the powder 7 enters the inside of the generating portion 9 from the discharge port 9a. Further, it is possible to give a pressure loss suitable for generating bubbles 8 to the gas discharged from the discharge port 9a.

また、吐出口９ａのＸ軸方向に沿った間隔（ピッチ）は、例えば、２．５ｍｍ以上１０ｍｍ以下である。ただし、吐出口９ａは、発生した気泡８を互いに向かい合う正極２と負極３との間にそれぞれ適切に流動させることができるように配置されるものであれば、大きさや間隔に制限はない。 The spacing (pitch) of the discharge port 9a along the X-axis direction is, for example, 2.5 mm or more and 10 mm or less. However, the size and spacing of the discharge port 9a are not limited as long as they are arranged so that the generated bubbles 8 can be appropriately flowed between the positive electrode 2 and the negative electrode 3 facing each other.

筐体１７および上板１８は、例えば、ポリスチレン、ポリプロピレン、ポリエチレンテレフタレート、ポリテトラフルオロエチレン、ポリ塩化ビニルなど、耐アルカリ性および絶縁性を有する樹脂材料で構成される。筐体１７および上板１８は、好ましくは互いに同じ材料で構成されるが、異なる材料で構成されてもよい。 The housing 17 and the upper plate 18 are made of an alkali-resistant and insulating resin material such as polystyrene, polypropylene, polyethylene terephthalate, polytetrafluoroethylene, and polyvinyl chloride. The housing 17 and the top plate 18 are preferably made of the same material, but may be made of different materials.

供給部１４は、配管１６を介して筐体１７の内部から回収された気体を、配管１５を介して発生部９に供給する。供給部１４は、例えば気体を移送可能なポンプ（気体ポンプ）、コンプレッサまたはブロワである。供給部１４の気密性を高くすれば、気体や電解液６に由来する水蒸気を外部に漏出させることによるフロー電池１の発電性能の低下が起きにくい。なお、配管１６または１５、あるいは発生部９の内部に、開口部５から排出された酸素を吸収し、回収する脱酸素剤を配置してもよい。このように気体の流通経路上に脱酸素剤を配置することにより、正極２や負極３、電解液６の酸化に伴う電池性能の劣化を低減することができる。 The supply unit 14 supplies the gas recovered from the inside of the housing 17 via the pipe 16 to the generation unit 9 via the pipe 15. The supply unit 14 is, for example, a pump (gas pump), a compressor or a blower capable of transferring gas. If the airtightness of the supply unit 14 is increased, the power generation performance of the flow battery 1 is unlikely to deteriorate due to the leakage of water vapor derived from the gas or the electrolytic solution 6 to the outside. An oxygen scavenger that absorbs and recovers oxygen discharged from the opening 5 may be arranged inside the pipe 16 or 15 or the generating portion 9. By arranging the oxygen scavenger on the gas flow path in this way, it is possible to reduce the deterioration of the battery performance due to the oxidation of the positive electrode 2, the negative electrode 3, and the electrolytic solution 6.

次に、図２を参照し、開口部５を備える収容部４についてさらに説明する。正極２Ａの上端と収容部４の上部（矩形部４ｂ１の上縁部３４に対応）側の接合部分との間に設けられた空間の高さＬ１は、０ｍｍ以上１ｍｍ以下とすることができる。高さＬ１が１ｍｍ以下となるようにすることで、正極２での副反応により生成した酸素が開口部５の上部に滞留しにくくなり、例えばタブ２Ａ１の酸化に伴う劣化を低減することができる。 Next, with reference to FIG. 2, the accommodating portion 4 provided with the opening 5 will be further described. The height L1 of the space provided between the upper end of the positive electrode 2A and the joint portion on the upper side (corresponding to the upper edge portion 34 of the rectangular portion 4b1) of the accommodating portion 4 can be 0 mm or more and 1 mm or less. By setting the height L1 to 1 mm or less, oxygen generated by a side reaction at the positive electrode 2 is less likely to stay in the upper part of the opening 5, and deterioration due to oxidation of the tab 2A1 can be reduced, for example. ..

また、開口部５の高さＬ２は、例えば、１５．５ｍｍ以上２５．５ｍｍ以下とすることができる。高さＬ２を上記した範囲とすることにより、図１に示す電解液６の液面６ａが調整しやすくなる。なお、電解液６の液面６ａは、正極２および負極３の上端と開口部５の上端との間に位置するように調整される。液面６ａが正極２および負極３の上端以上の高さとなるように収容部４を配置させると、フロー電池１の能力を最大限に発揮することができる。また、開口部５の上端が電解液６の液面６ａから突出する、すなわち液面６ａが開口部５の上端よりも下となるように収容部４を配置させると、収容部４の内部には粉末７が混入せず、電解液６のみが含まれることとなる。このため、収容部４の内部に粉末７が滞留することに伴う電池性能の劣化を低減することができる。ただし、収容部４の内部に粉末７が混入する態様を完全に排除するものではなく、例えば予め所定量の粉末７が収容部４の内部の電解液６中に混在していてもよい。 Further, the height L2 of the opening 5 can be, for example, 15.5 mm or more and 25.5 mm or less. By setting the height L2 to the above range, the liquid level 6a of the electrolytic solution 6 shown in FIG. 1 can be easily adjusted. The liquid level 6a of the electrolytic solution 6 is adjusted so as to be located between the upper ends of the positive electrode 2 and the negative electrode 3 and the upper end of the opening 5. When the accommodating portion 4 is arranged so that the liquid level 6a is at a height equal to or higher than the upper ends of the positive electrode 2 and the negative electrode 3, the capacity of the flow battery 1 can be maximized. Further, when the accommodating portion 4 is arranged so that the upper end of the opening 5 protrudes from the liquid level 6a of the electrolytic solution 6, that is, the liquid surface 6a is below the upper end of the opening 5, the accommodating portion 4 is inside the accommodating portion 4. Does not contain the powder 7, but contains only the electrolytic solution 6. Therefore, it is possible to reduce the deterioration of the battery performance due to the accumulation of the powder 7 inside the accommodating portion 4. However, the mode in which the powder 7 is mixed inside the accommodating portion 4 is not completely excluded. For example, a predetermined amount of the powder 7 may be mixed in the electrolytic solution 6 inside the accommodating portion 4 in advance.

また、収容部４の側端部から開口部５側端部までの幅Ｌ３は０ｍｍ以上とすることができる。幅Ｌ３を０ｍｍ以上、すなわち正極２の直上に開口部５が有するように配置することにより、正極２で発生した気体が開口部５から排出されやすくなる。また、収容部４の側端部の外側で弾けた気泡８などから飛ばされた粉末７が、開口部５から混入しにくくなる。特に、幅Ｌ３を１５．５ｍｍ以上２５．５ｍｍ以下とすることにより、正極２のタブを収容部４の外部に延出させるための延出口として開口部５が機能しやすくなる。なお、図２ではＸ軸方向における開口部５の配置について図示しているが、Ｙ軸方向についても、開口部５が正極２の直上に配置されてもよい。 Further, the width L3 from the side end of the accommodating portion 4 to the side end of the opening 5 can be 0 mm or more. By arranging the width L3 to be 0 mm or more, that is, so that the opening 5 has the opening 5 directly above the positive electrode 2, the gas generated in the positive electrode 2 is easily discharged from the opening 5. Further, the powder 7 blown from the air bubbles 8 or the like that burst outside the side end portion of the accommodating portion 4 is less likely to be mixed through the opening 5. In particular, by setting the width L3 to 15.5 mm or more and 25.5 mm or less, the opening 5 can easily function as an extension outlet for extending the tab of the positive electrode 2 to the outside of the accommodating portion 4. Although FIG. 2 shows the arrangement of the opening 5 in the X-axis direction, the opening 5 may be arranged directly above the positive electrode 2 also in the Y-axis direction.

次に、フロー電池１における電極間の接続について説明する。図３は、第１の実施形態に係るフロー電池１の電極間の接続の一例について説明する図である。 Next, the connection between the electrodes in the flow battery 1 will be described. FIG. 3 is a diagram illustrating an example of connection between the electrodes of the flow battery 1 according to the first embodiment.

図３に示すように、負極３Ａ，３Ｂおよび３Ｃは、負極３Ａ，３Ｂおよび３Ｃがそれぞれ有するタブ３Ａ１，３Ｂ１，３Ｃ１を介して並列接続されている。また、正極２Ａおよび２Ｂは、正極２Ａおよび２Ｂがそれぞれ有するタブ２Ａ１，２Ｂ１を介して並列接続されている。このように負極３および正極２をそれぞれ並列に接続することにより、正極２および負極３の総数が異なる場合であってもフロー電池１の各電極間を適切に接続し、使用することができる。 As shown in FIG. 3, the negative electrodes 3A, 3B and 3C are connected in parallel via the tabs 3A1, 3B1, 3C1 each of the negative electrodes 3A, 3B and 3C, respectively. Further, the positive electrodes 2A and 2B are connected in parallel via the tabs 2A1 and 2B1 of the positive electrodes 2A and 2B, respectively. By connecting the negative electrode 3 and the positive electrode 2 in parallel in this way, even if the total number of the positive electrode 2 and the negative electrode 3 is different, the electrodes of the flow battery 1 can be appropriately connected and used.

なお、図１に示すフロー電池１では、合計５枚の電極が、負極３および正極２が交互に配置されるように構成されたが、これに限らず、３枚または６枚以上の電極を交互に配置するようにしてもよく、正極２および負極３をそれぞれ１枚ずつ配置させてもよい。また、図１に示すフロー電池１では、両端がともに負極（３Ａ，３Ｃ）となるように構成されたが、これに限らず、両端がともに正極となるように構成してもよい。 In the flow battery 1 shown in FIG. 1, a total of five electrodes are configured such that the negative electrode 3 and the positive electrode 2 are alternately arranged, but the present invention is not limited to this, and three or six or more electrodes are used. It may be arranged alternately, or one positive electrode 2 and one negative electrode 3 may be arranged. Further, in the flow battery 1 shown in FIG. 1, both ends are configured to be negative electrodes (3A, 3C), but the present invention is not limited to this, and both ends may be configured to be positive electrodes.

さらに、一方の端部が正極２、他方の端部が負極３となるように同枚数の負極３および正極２をそれぞれ交互に配置してもよい。かかる場合、電極間の接続は並列であってもよく、直列であってもよい。 Further, the same number of negative electrodes 3 and 2 may be alternately arranged so that one end is the positive electrode 2 and the other end is the negative electrode 3. In such a case, the connections between the electrodes may be in parallel or in series.

＜第１変形例＞
図４は、第１の実施形態の第１変形例に係るフロー電池１の概略を示す図である。図４に示す収容部４は、図２と同様に、正極２Ａおよびその近傍を断面視したものに相当する。なお、後述する図５〜図８についても、図４と同じ視点で図示する。 <First modification>
FIG. 4 is a diagram showing an outline of the flow battery 1 according to the first modification of the first embodiment. Similar to FIG. 2, the accommodating portion 4 shown in FIG. 4 corresponds to a cross-sectional view of the positive electrode 2A and its vicinity. Note that FIGS. 5 to 8 described later are also illustrated from the same viewpoint as in FIG.

図４に示す収容部４は、開口部５が積層構造を有することを除き、図２に示す収容部４と同様の構成を有している。図４に示すように、開口部５ａ〜５ｃは、それぞれ外層２１と内層２２とを含む。外層２１は、図２に示す収容部４と同じ材料で構成されているのに対し、内層２２は、例えばポリスチレンなど、外層２１よりも機械的強度が高く、保形性に優れた材料で構成される。このように第１変形例に係るフロー電池１によれば、収容部４で発生した気体が接触する内層２２を保形性に優れた材料で構成することにより、例えば電解液６の流動や気泡８の浮上に伴って開口部５が変形し、収容部４からの気体の排出が滞ることに伴う性能劣化を低減することができる。 The accommodating portion 4 shown in FIG. 4 has the same configuration as the accommodating portion 4 shown in FIG. 2, except that the opening 5 has a laminated structure. As shown in FIG. 4, the openings 5a to 5c include an outer layer 21 and an inner layer 22, respectively. The outer layer 21 is made of the same material as the accommodating portion 4 shown in FIG. 2, whereas the inner layer 22 is made of a material having higher mechanical strength and excellent shape retention than the outer layer 21, such as polystyrene. Will be done. As described above, according to the flow battery 1 according to the first modification, by forming the inner layer 22 with which the gas generated in the accommodating portion 4 comes into contact with a material having excellent shape retention, for example, the flow of the electrolytic solution 6 and bubbles. The opening 5 is deformed as the 8 floats, and the performance deterioration due to the delay in the discharge of gas from the accommodating portion 4 can be reduced.

＜第２変形例＞
図５は、第１の実施形態の第２変形例に係るフロー電池１の概略を示す図である。図５に示す収容部４は、開口部５に挿通された筒状部材２３を有することを除き、図２に示す収容部４と同様の構成を有している。 <Second modification>
FIG. 5 is a diagram showing an outline of the flow battery 1 according to the second modification of the first embodiment. The accommodating portion 4 shown in FIG. 5 has the same configuration as the accommodating portion 4 shown in FIG. 2 except that it has a tubular member 23 inserted through the opening 5.

筒状部材２３は、例えばポリスチレンなど、第２シート部材４ｂよりも機械的強度が高く、保形性に優れた材料で構成される。筒状部材２３は、開口部５と収容部４との連通を保持する保形部材の一例である。このように第２変形例に係るフロー電池１によれば、収容部４で発生した気体が接触する筒状部材２３を保形性に優れた材料で構成することにより、例えば電解液６の流動や気泡８の浮上に伴って開口部５が変形し、収容部４からの気体の排出が滞ることに伴う性能劣化を低減することができる。なお、筒状部材２３の下端と正極２Ａの上端とは離れていてもよく、また接していてもよい。 The tubular member 23 is made of a material having higher mechanical strength and excellent shape retention than the second sheet member 4b, such as polystyrene. The tubular member 23 is an example of a shape-retaining member that maintains communication between the opening 5 and the accommodating portion 4. As described above, according to the flow battery 1 according to the second modification, the tubular member 23 to which the gas generated in the accommodating portion 4 comes into contact is made of a material having excellent shape retention, so that, for example, the electrolytic solution 6 flows. The opening 5 is deformed due to the floating of the air bubbles 8 and the air bubbles 8, and the performance deterioration due to the delay in the discharge of gas from the accommodating portion 4 can be reduced. The lower end of the tubular member 23 and the upper end of the positive electrode 2A may be separated from each other or may be in contact with each other.

なお、図５に示すように開口部５ｃがタブ２Ａ１の延出口を兼ねる場合、開口部５ｃの寸法はタブ２Ａ１が延出できる程度の大きさを要する。図５に示す例では、開口部５ｃに筒状部材２３を挿通するとタブ２Ａ１の延出が困難となるため、開口部５ｃには筒状部材２３が挿通されていない。 When the opening 5c also serves as the extension / outlet of the tab 2A1 as shown in FIG. 5, the dimension of the opening 5c needs to be large enough to extend the tab 2A1. In the example shown in FIG. 5, when the tubular member 23 is inserted through the opening 5c, it becomes difficult to extend the tab 2A1, so that the tubular member 23 is not inserted through the opening 5c.

＜第３変形例＞
図６は、第１の実施形態の第３変形例に係るフロー電池１の概略を示す図である。図６に示す収容部４は、開口部５に挿通された網状部材２４を有することを除き、図２に示す収容部４と同様の構成を有している。 <Third modification example>
FIG. 6 is a diagram showing an outline of the flow battery 1 according to the third modification of the first embodiment. The accommodating portion 4 shown in FIG. 6 has the same configuration as the accommodating portion 4 shown in FIG. 2 except that it has a net-like member 24 inserted through the opening 5.

網状部材２４は、例えばポリエチレン、ポリプロピレン、ポリスチレン、ポリエチレンテレフタレート、ポリテトラフルオロエチレン、ポリ塩化ビニルなどの樹脂材料で構成された、第２シート部材４ｂよりも機械的強度が高く、保形性およびガス流通性に優れた不織布または織布である。網状部材２４は、開口部５と収容部４との連通を保持する保形部材の一例である。このように第３変形例に係るフロー電池１によれば、収容部４で発生した気体が接触する網状部材２４を保形性およびガス流通性に優れた材料で構成することにより、例えば電解液６の流動や気泡８の浮上に伴って開口部５が変形し、収容部４からの気体の排出が滞ることに伴う性能劣化を低減することができる。 The reticulated member 24 has higher mechanical strength than the second sheet member 4b, which is made of a resin material such as polyethylene, polypropylene, polystyrene, polyethylene terephthalate, polytetrafluoroethylene, and polyvinyl chloride, and has higher mechanical strength, shape retention, and gas. A non-woven fabric or woven fabric with excellent flowability. The net-like member 24 is an example of a shape-retaining member that maintains communication between the opening 5 and the accommodating portion 4. As described above, according to the flow battery 1 according to the third modification, the network member 24 to which the gas generated in the accommodating portion 4 comes into contact is made of a material having excellent shape retention and gas flowability, for example, an electrolytic solution. The opening 5 is deformed due to the flow of the 6 and the floating of the bubbles 8, and the performance deterioration due to the delay in the discharge of the gas from the accommodating portion 4 can be reduced.

なお、図５に示すように開口部５ｃがタブ２Ａ１の延出口を兼ねる場合、開口部５ｃの寸法はタブ２Ａ１が延出できる程度の大きさを要する。図６に示す例では、開口部５ａ，５ｂとは異なる形状を有する網状部材２４を開口部５ｃに挿通することにより、タブ２Ａ１の延出を可能にしている。 When the opening 5c also serves as the extension / outlet of the tab 2A1 as shown in FIG. 5, the dimension of the opening 5c needs to be large enough to extend the tab 2A1. In the example shown in FIG. 6, the tab 2A1 can be extended by inserting the mesh member 24 having a shape different from that of the openings 5a and 5b into the opening 5c.

＜第４、第５変形例＞
図７、図８はそれぞれ、第１の実施形態の第４、第５変形例に係るフロー電池１の概略を示す図である。図７に示す収容部４は、開口部５が断面視で台形状を有することを除き、図２に示す断面視で矩形状の開口部５を有する収容部４と同様の構成を有している。また、図８に示す収容部４は、開口部５が曲面状を有することを除き、図７に示す平面状の開口部５を有する収容部４と同様の構成を有している。 <Fourth and fifth modifications>
7 and 8 are diagrams showing an outline of the flow battery 1 according to the fourth and fifth modifications of the first embodiment, respectively. The accommodating portion 4 shown in FIG. 7 has the same configuration as the accommodating portion 4 having the rectangular opening 5 in the cross-sectional view shown in FIG. 2, except that the opening 5 has a trapezoidal shape in the cross-sectional view. There is. Further, the accommodating portion 4 shown in FIG. 8 has the same configuration as the accommodating portion 4 having the planar opening 5 shown in FIG. 7, except that the opening 5 has a curved surface shape.

第４、第５変形例に係るフロー電池１はいずれも、開口部５ａ〜５ｃが、例えば下端部の幅Ｄ１よりも上端部の幅Ｄ２の方が小さくなるように形成されることにより、開口部５ａ〜５ｃの開口面積は、下端よりも上端の方が小さくなるように形成されている。このように第４、第５変形例に係るフロー電池１によれば、収容部４で発生した気体は収容部４の外部へ速やかに排出される一方、開口部５ａ〜５ｃからは異物や粉末７等が進入しづらい。これにより、例えば収容部４からの気体の排出が滞る不具合や、開口部５ａ〜５ｃから侵入した異物等による電池反応の阻害に伴う性能劣化を低減することができる。なお、開口部５ａ〜５ｃの下端よりも上端の開口面積の方が小さいものであれば開口部５ａ〜５ｃの形状は図７、図８に図示したものに限らず、例えば半球状であってもよい。 In each of the flow batteries 1 according to the fourth and fifth modifications, the openings 5a to 5c are formed so that the width D2 of the upper end portion is smaller than the width D1 of the lower end portion, for example. The opening area of the portions 5a to 5c is formed so that the upper end is smaller than the lower end. As described above, according to the flow battery 1 according to the fourth and fifth modifications, the gas generated in the accommodating portion 4 is rapidly discharged to the outside of the accommodating portion 4, while foreign matter and powder are discharged from the openings 5a to 5c. It is difficult for 7th grade to enter. As a result, for example, it is possible to reduce the problem that the gas discharge from the housing portion 4 is delayed and the performance deterioration due to the inhibition of the battery reaction due to the foreign matter invading from the openings 5a to 5c. If the opening area at the upper end is smaller than the lower end of the openings 5a to 5c, the shape of the openings 5a to 5c is not limited to that shown in FIGS. 7 and 8, and is, for example, hemispherical. May be good.

＜第２の実施形態＞
図９は、第２の実施形態に係るフロー電池の概略を示す図である。図９に示すフロー電池１Ａは、図１に示す発生部９、供給部１４、配管１５，１６、に代えて、供給部１４ａ、配管１５ａ，１６ａを備えることを除き、第１の実施形態に係るフロー電池１と同様の構成を有している。 <Second embodiment>
FIG. 9 is a diagram showing an outline of the flow battery according to the second embodiment. The flow battery 1A shown in FIG. 9 has the first embodiment except that the supply unit 14a and the pipes 15a and 16a are provided in place of the generation unit 9, the supply unit 14, and the pipes 15 and 16 shown in FIG. It has the same configuration as the flow battery 1.

供給部１４ａは、配管１６ａを介して筐体１７の内部から回収された、粉末７が混在する電解液６を、配管１５ａを介して筐体１７の下部に供給する。供給部１４ａは、流動装置の一例である。 The supply unit 14a supplies the electrolytic solution 6 containing the powder 7 collected from the inside of the housing 17 via the pipe 16a to the lower part of the housing 17 via the pipe 15a. The supply unit 14a is an example of a flow device.

供給部１４ａは、例えば電解液６を移送可能なポンプである。供給部１４ａの気密性を高くすれば、粉末７および電解液６を外部に漏出させることによるフロー電池１Ａの発電性能の低下が起きにくい。そして、筐体１７の内部に送られた電解液６は、第１の実施形態に係るフロー電池１と同様に、各電極間を上方に流動する間に充放電反応に供されることとなる。 The supply unit 14a is, for example, a pump capable of transferring the electrolytic solution 6. If the airtightness of the supply unit 14a is increased, the power generation performance of the flow battery 1A is unlikely to deteriorate due to the leakage of the powder 7 and the electrolytic solution 6 to the outside. Then, the electrolytic solution 6 sent to the inside of the housing 17 is subjected to a charge / discharge reaction while flowing upward between the electrodes, as in the flow battery 1 according to the first embodiment. ..

このように発生部９を有しないフロー電池１Ａにおいても、正極２を収容する収容部４の上部に複数の開口部５ａ〜５ｃを配置することにより、正極２で酸素などの気体が発生した場合であっても、複数の開口部５ａ〜５ｃから排出させることで収容部４内部への気体の滞留を低減させることができる。このため、第２の実施形態に係るフロー電池１Ａによれば、例えば正極２や電解液６の酸化等に伴う性能劣化が低減される。 Even in the flow battery 1A that does not have the generating portion 9 as described above, when a gas such as oxygen is generated in the positive electrode 2 by arranging the plurality of openings 5a to 5c above the accommodating portion 4 accommodating the positive electrode 2. Even so, it is possible to reduce the retention of gas inside the accommodating portion 4 by discharging the gas from the plurality of openings 5a to 5c. Therefore, according to the flow battery 1A according to the second embodiment, performance deterioration due to, for example, oxidation of the positive electrode 2 and the electrolytic solution 6 is reduced.

なお、図９に示すフロー電池１Ａでは、配管１６ａに接続された開口が、各電極の主面と向かい合う内壁１７ｂ、すなわち筐体１７のＹ軸方向側の端部に設けられているが、これに限らず、Ｘ軸方向側の端部に設けられてもよい。 In the flow battery 1A shown in FIG. 9, an opening connected to the pipe 16a is provided at the inner wall 17b facing the main surface of each electrode, that is, at the end of the housing 17 on the Y-axis direction side. However, it may be provided at the end on the X-axis direction side.

また、図９に示すフロー電池１Ａでは、供給部１４ａは、粉末７が混在する電解液６を筐体１７に供給するとしたが、これに限らず、電解液６のみを供給することとしてもよい。かかる場合、例えば配管１６ａの途中に、粉末７が混在する電解液６を一時的に貯留するタンクを設け、タンク内部において電解液６中に溶解する［Ｚｎ（ＯＨ）４］２−の濃度を調整することとしてもよい。 Further, in the flow battery 1A shown in FIG. 9, the supply unit 14a is supposed to supply the electrolytic solution 6 in which the powder 7 is mixed to the housing 17, but the present invention is not limited to this, and only the electrolytic solution 6 may be supplied. .. In such a case, for example, a tank for temporarily storing the electrolytic solution 6 in which the powder 7 is mixed is provided in the middle of the pipe 16a, and the concentration of [Zn (OH) 4 ] 2-dissolved in the electrolytic solution 6 is adjusted inside the tank. It may be adjusted.

以上、本発明の実施形態について説明したが、本発明は上記実施形態に限定されるものではなく、その趣旨を逸脱しない限りにおいて種々の変更が可能である。例えば、図７または図８に示す開口部５に、図５に示す筒状部材２３または図６に示す網状部材２４に対応する保形部材を挿通させてもよい。 Although the embodiments of the present invention have been described above, the present invention is not limited to the above embodiments, and various modifications can be made without departing from the spirit of the present invention. For example, the shape-retaining member corresponding to the tubular member 23 shown in FIG. 5 or the network member 24 shown in FIG. 6 may be inserted through the opening 5 shown in FIG. 7 or FIG.

また、上記した各実施形態では、収容部４は重ね合わせた第１シート部材４ａおよび第２シート部材４ｂを接合し、作製するとして説明したが、これに限らず、例えば図２に示す側縁部３１，３２が連続する筒状の部材や、下縁部３３を挟んで対称となる一枚のシート部材を折り曲げたものを用意し、必要な部分を例えば熱溶着等により接合し、収容部４を作製してもよい。 Further, in each of the above-described embodiments, the accommodating portion 4 has been described as being manufactured by joining the first sheet member 4a and the second sheet member 4b that are overlapped with each other, but the present invention is not limited to this, and for example, the side edge shown in FIG. Prepare a tubular member in which the portions 31 and 32 are continuous, or a single sheet member that is symmetrical with the lower edge portion 33 in between, and join the necessary portions by, for example, heat welding to accommodate the accommodating portion. 4 may be produced.

また、図１に示すフロー電池１では、発生部９は、筐体１７の内部に配置させたが、これに限らず、例えば筐体１７の下方に配置させてもよい。かかる場合、発生部９は筐体１７の内底と一体化されることとなる。 Further, in the flow battery 1 shown in FIG. 1, the generating unit 9 is arranged inside the housing 17, but the present invention is not limited to this, and for example, the generating unit 9 may be arranged below the housing 17. In such a case, the generating portion 9 is integrated with the inner bottom of the housing 17.

また、上記した各実施形態では、電解液６中に粉末７が混在されているとして説明したが、これに限らず、粉末７を有しなくてもよい。かかる場合、負極３が含有する負極活物質を増量するとよい。また、図２に示す高さＬ２は０であってもよい。 Further, in each of the above-described embodiments, the powder 7 is described as being mixed in the electrolytic solution 6, but the present invention is not limited to this, and the powder 7 may not be provided. In such a case, it is advisable to increase the amount of the negative electrode active material contained in the negative electrode 3. Further, the height L2 shown in FIG. 2 may be 0.

また、上記した各実施形態では、隔膜１０，１１は収容部４の厚み方向の両側を挟むように配置されるとして説明したが、これに限らず、正極２と負極３との間に配置されていればよく、また、収容部４を被覆していてもよい。また、正極２と収容部４との間に隔膜１０，１１を配置してもよい。 Further, in each of the above-described embodiments, the diaphragms 10 and 11 have been described as being arranged so as to sandwich both sides of the accommodating portion 4 in the thickness direction, but the present invention is not limited to this, and the diaphragms 10 and 11 are arranged between the positive electrode 2 and the negative electrode 3. It may be covered, and the accommodating portion 4 may be covered. Further, the diaphragms 10 and 11 may be arranged between the positive electrode 2 and the accommodating portion 4.

また、上記した各実施形態では、収容部４は正極２を収容するとして説明したが、これに限らず、負極３を収容していてもよい。 Further, in each of the above-described embodiments, the accommodating portion 4 has been described as accommodating the positive electrode 2, but the present invention is not limited to this, and the negative electrode 3 may be accommodated.

なお、供給部１４，１４ａは、常時動作させてもよいが、電力消費を低減する観点から、放電時には充電時よりも気体または電解液６の供給レートを低下させてもよい。 The supply units 14 and 14a may be operated at all times, but from the viewpoint of reducing power consumption, the supply rate of the gas or the electrolytic solution 6 may be lowered at the time of discharging than at the time of charging.

さらなる効果や変形例は、当業者によって容易に導き出すことができる。このため、本発明のより広範な態様は、以上のように表しかつ記述した特定の詳細および代表的な実施形態に限定されるものではない。したがって、添付の特許請求の範囲およびその均等物によって定義される総括的な発明の概念の精神または範囲から逸脱することなく、様々な変更が可能である。 Further effects and variations can be easily derived by those skilled in the art. For this reason, the broader aspects of the invention are not limited to the particular details and representative embodiments expressed and described above. Therefore, various modifications can be made without departing from the spirit or scope of the general concept of the invention as defined by the appended claims and their equivalents.

１，１Ａ フロー電池
２，２Ａ，２Ｂ 正極
３，３Ａ，３Ｂ，３Ｃ 負極
４ 収容部
５，５ａ，５ｂ，５ｃ 開口部
６ 電解液
７ 粉末
８ 気泡
９ 発生部
９ａ 吐出口
１０，１１ 隔膜
１４，１４ａ 供給部
１７ 筐体
１８ 上板
２３ 筒状部材
２４ 網状部材 1,1A Flow battery 2,2A, 2B Positive electrode 3,3A, 3B, 3C Negative electrode 4 Storage part 5,5a, 5b, 5c Opening part 6 Electrolyte 7 Powder 8 Bubbles 9 Generation part 9a Discharge port 10, 11 Septum 14, 14a Supply part 17 Housing 18 Top plate 23 Cylindrical member 24 Net-like member

Claims (8)

正極および負極と、
前記正極および前記負極に接触する電解液と、
前記正極の少なくとも前記負極と向かい合う部分を覆うように収容し、前記正極を保持するとともに、前記電解液が流通可能である収容部と、
前記電解液を流動させる流動装置とを備え、
前記収容部は、上部に複数の開口部を備えることを特徴とするフロー電池。 With positive and negative electrodes
An electrolytic solution that comes into contact with the positive electrode and the negative electrode,
Accommodating the positive electrode so as to cover at least a portion facing the negative electrode, holding the positive electrode, and accommodating the accommodating portion through which the electrolytic solution can flow.
A flow device for flowing the electrolytic solution is provided.
The accommodating portion is a flow battery characterized by having a plurality of openings at the upper portion. 前記開口部に挿通され、前記開口部と前記収容部との連通を保持する保形部材
をさらに備えることを特徴とする請求項１に記載のフロー電池。 The flow battery according to claim 1, further comprising a shape-retaining member that is inserted through the opening and maintains communication between the opening and the accommodating portion. 前記開口部の少なくとも一つは、前記収容部に収容された前記正極と電気的に接続されるタブを前記収容部の外部に延出させるための延出口を兼ねることを特徴とする請求項１または２に記載のフロー電池。 The claim is characterized in that at least one of the openings also serves as an extension outlet for extending a tab electrically connected to the positive electrode housed in the housing part to the outside of the housing part. The flow battery according to 1 or 2. 前記延出口を兼ねていない前記開口部が存在することを特徴とする請求項３に記載のフロー電池。 The flow battery according to claim 3, wherein the opening that does not also serve as an extension outlet is present. 前記開口部の開口面積は、下端よりも上端の方が小さいことを特徴とする請求項１〜４のいずれか１つに記載のフロー電池。 The flow battery according to any one of claims 1 to 4, wherein the opening area of the opening is smaller at the upper end than at the lower end. 前記流動装置は、前記電解液中に気泡を発生させる発生部を含み、
前記気泡は、前記収容部の外部に配置された前記負極と、前記収容部との間を浮上することを特徴とする請求項１〜５のいずれか１つに記載のフロー電池。 The flow device includes a generator that generates bubbles in the electrolytic solution.
The bubble has a front SL negative electrode disposed outside of said housing portion, the flow cell according to any one of claims 1 to 5, characterized in that floats between the receiving portion. 前記負極は、前記正極を収容する前記収容部を挟んで向かい合う第１負極および第２負極を含み、
前記気泡は、前記第１負極と前記収容部との間、および前記収容部と前記第２負極との間を浮上し、
前記電解液は、前記電解液を収容する筐体の第１内壁と前記第１負極との間、および前記第１内壁と向かい合う前記筐体の第２内壁と前記第２負極との間を下降することを特徴とする請求項６に記載のフロー電池。 The negative electrode includes a first negative electrode and a second negative electrode that face each other with the accommodating portion accommodating the positive electrode.
The bubbles float between the first negative electrode and the accommodating portion, and between the accommodating portion and the second negative electrode.
The electrolytic solution descends between the first inner wall of the housing containing the electrolytic solution and the first negative electrode, and between the second inner wall of the housing facing the first inner wall and the second negative electrode. The flow battery according to claim 6, wherein the flow battery is characterized in that. 亜鉛を含み、前記収容部の外部を流動する前記電解液中を移動可能に混在する粉末
をさらに備え、
前記開口部の上端は、前記電解液の液面から突出するように配置されていることを特徴とする請求項１〜７のいずれか１つに記載のフロー電池。 Further comprising a powder containing zinc and movably mixed in the electrolytic solution flowing outside the accommodating portion.
The flow battery according to any one of claims 1 to 7, wherein the upper end of the opening is arranged so as to protrude from the liquid surface of the electrolytic solution.
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