JP2010277810A - Electrode plate of redox flow battery - Google Patents

Electrode plate of redox flow battery Download PDF

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JP2010277810A
JP2010277810A JP2009128606A JP2009128606A JP2010277810A JP 2010277810 A JP2010277810 A JP 2010277810A JP 2009128606 A JP2009128606 A JP 2009128606A JP 2009128606 A JP2009128606 A JP 2009128606A JP 2010277810 A JP2010277810 A JP 2010277810A
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film
base sheet
electrode plate
redox flow
flow battery
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Yoshiaki Tezuka
美章 手塚
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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
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    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrode plate suitable for a redox flow type inexpensively, capable of solving a problem of permeability while using a carbon material system film. <P>SOLUTION: A whole surface of a synthetic resin sheet 1 formed in an electrode plate shape for a redox flow battery in which its outer shape has a desired one with its thickness of about 0.2 to 0.5 mm, is covered with a film 2 containing a carbon material mainly composed of carbon or a carbonaceous material with its thickness of 0.5 to 0.2 mm and an electric resistance value of 1.0 to 0.5 Ω/cm<SP>2</SP>or less. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

本発明はレドックスフロー電池の電極板に関する。   The present invention relates to an electrode plate for a redox flow battery.

レドックスフロー電池の電極板については、従来より特許文献１〜５などにより、多数の提案がなされている。
従来のレドックスフロー電池用の電極には、白金鍍金電極や炭素混練樹脂フィルムを使用したものがある。
しかし、白金鍍金電極は、低抵抗で耐酸性が高いため有用ではあるものの高価に付くという難点がある。一方、炭素混練樹脂製フィルムを用いた電極は、比較的安価に作製できるが、電気抵抗値が1.0Ω／cm２以上あるため、大電流が流れる大型電池では抵抗による発熱対策をとり易いが、小電流の小型電池では電流に対する内部抵抗が大きくなって小型のレドックスフロー電池用の電極としては実用性に乏しかった。
小電流の小型電池に用いる電極板としては、抵抗値が1.0Ω／cm２以下、好ましくは0.5Ω／cm２以下であることが必要と考えられている。 Many proposals have been made on electrode plates of redox flow batteries according to Patent Documents 1 to 5 and the like.
Conventional electrodes for redox flow batteries include those using a platinum plated electrode or a carbon kneaded resin film.
However, the platinum-plated electrode is useful because it has low resistance and high acid resistance, but has a drawback of being expensive. On the other hand, an electrode using a carbon kneaded resin film can be produced at a relatively low cost. However, since the electrical resistance value is 1.0 Ω / cm 2 or more, it is easy to take a countermeasure against heat generation due to resistance in a large battery in which a large current flows. A small battery with a small current has a large internal resistance with respect to the current, and is not practical as an electrode for a small redox flow battery.
The electrode plate used in the small cell of the small current, the resistance value is 1.0 [Omega] / cm 2 or less, preferably is believed required to be 0.5 .OMEGA / cm 2 or less.

特開平１１−１６２４９６号公報Japanese Patent Laid-Open No. 11-162496 特公平６−５６７６７号公報Japanese Patent Publication No. 6-56767 特開２００４−２６５８２１号公報JP 2004-265821 A 特許第３９９６７６２号公報Japanese Patent No. 3996762 特許第３９７１４３７号公報Japanese Patent No. 3971437

そこで本発明では、コスト的に有利な炭素材系フィルムを使用するが、電気抵抗値を低く抑えることができ、また、炭素材系のみで形成したフィルムには電解液の浸透性の問題がある点を解消できるレドックスフロータイプの小型電池に用いて好適な電極板を低コストで提供することを課題として完成されたものである。   Therefore, in the present invention, a carbon material-based film advantageous in terms of cost is used, but the electric resistance value can be kept low, and the film formed only of the carbon material system has a problem of electrolyte permeability. The present invention has been completed with the object of providing a suitable electrode plate at a low cost for use in a redox flow type small battery capable of eliminating the problem.

上記課題を解決することを目的としてなされた本発明電極板の構成は、炭素乃至炭素質材料を主成分とした厚さが0.5mm〜0.2mm、電気抵抗値が1.0Ω〜0.5Ω／cm２以下の炭素質材料を含有するフィルムによって、厚さが約0.2mm〜0.5mmであり外形を所望形状のレドックスフロー電池用の電極板形状に形成した合成樹脂シートの全面を被覆したことを特徴とするものである。 The structure of the electrode plate of the present invention made for the purpose of solving the above problems is a thickness of 0.5 mm to 0.2 mm mainly composed of carbon or carbonaceous material, and an electric resistance value of 1.0 Ω to 0.5 Ω / cm 2. It is characterized by covering the entire surface of a synthetic resin sheet having a thickness of about 0.2 mm to 0.5 mm and having an outer shape formed into an electrode plate shape for a redox flow battery with a film containing the following carbonaceous material. To do.

上記の本発明電極板において、ベースシートを被覆するフィルムに含有させる炭素質材料は、天然黒鉛，人造黒鉛，炭素繊維，気相成長法炭素繊維，ピッチ系炭素質材料，ニードルコークス，石油コークス，ポリアクリルニトリル系炭素繊維，カーボンブラックの中から選ばれた少なくとも一つであればよい。好ましくは、製造乃至は入手が容易かつ低価格のものが選択される。   In the above electrode plate of the present invention, the carbonaceous material to be included in the film covering the base sheet is natural graphite, artificial graphite, carbon fiber, vapor grown carbon fiber, pitch-based carbonaceous material, needle coke, petroleum coke, It may be at least one selected from polyacrylonitrile-based carbon fiber and carbon black. Preferably, those that are easy to manufacture or obtain and that are inexpensive are selected.

また、上記の炭素質材料を含むフィルムで全面被覆される合成樹脂製ベースシートは、レドックスフロー電池に用いられる正極液，負極液、すなわち電解液、例えば硫酸バナジウムなどの酸性溶液に冒されないか冒され難い耐酸性の高い合成樹脂を原料としたものが好ましい。   Further, the synthetic resin base sheet that is entirely covered with the film containing the carbonaceous material described above is not affected by the positive electrode solution and the negative electrode solution used in the redox flow battery, that is, the electrolytic solution, for example, an acidic solution such as vanadium sulfate. A material made of a synthetic resin that is difficult to be treated and has high acid resistance is preferable.

上記の本発明電極板の製造方法の構成は、耐酸性の高い合成樹脂製で0.2mm〜0.5mmの厚さを有するベースシートを正方形に形成し、該ベースシートの表裏両面と全外周端面を被覆するため炭素質材料を含み厚さを0.2mm〜0.5mmに形成した一枚の炭素材系フィルムを、前記ベースシートの２倍の面積を有する正方形に形成し、前記ベースシートの表面に接着剤を塗布して当該ベースシートと炭素材系フィルムとの中心を合せると共に両シートとフィルムを45度の回転中心角を以て重ね、ベースシートからはみ出した前記フィルムの三角形状部を当該ベースシートの内側に折畳み、前記ベースシートの全表面を炭素材系フィルムで被覆して接着することを特徴とするものである。   The structure of the manufacturing method of the above-mentioned electrode plate of the present invention is that a base sheet made of synthetic resin having high acid resistance and having a thickness of 0.2 mm to 0.5 mm is formed in a square, and both the front and back surfaces of the base sheet and the entire outer peripheral end surface are A single carbon-based film containing carbonaceous material and having a thickness of 0.2 mm to 0.5 mm for coating is formed into a square having twice the area of the base sheet and adhered to the surface of the base sheet Apply the agent to align the center of the base sheet and the carbon-based film, and overlap the sheet and film with a rotation center angle of 45 degrees so that the triangular portion of the film protruding from the base sheet is inside the base sheet. And the whole surface of the base sheet is covered with a carbon material film and bonded.

本発明は、炭素乃至炭素質材料を主成分とした厚さが0.5mm〜0.2mm、電気抵抗値が0.5Ω／cm２以下の炭素質材料を含有するフィルムにより、厚さが約0.2mm〜0.5mmであって外形を所望形状のレドックスフロー電池用の電極板形状に形成した合成樹脂シートの全面を被覆としてレドックスフロー電池用の電極板を構成したので、電極の厚さを0.4mm〜1.0mm程度の極く薄い仕様に形成でき、しかも、電気抵抗値は悠に1.0Ω／cm２以下を容易に実現することができ、従って、小型のレドックスフロー電池用の電極としてきわめて有用である。 The present invention is a film containing a carbonaceous material having a thickness of 0.5 mm to 0.2 mm mainly composed of carbon or a carbonaceous material and having an electric resistance of 0.5 Ω / cm 2 or less. Since the electrode plate for the redox flow battery is configured by covering the entire surface of the synthetic resin sheet which is 0.5 mm and the outer shape is formed into the electrode plate shape for the desired shape of the redox flow battery, the thickness of the electrode is 0.4 mm to 1.0 mm. It can be formed to a very thin specification of about mm, and can easily realize an electrical resistance value of 1.0 Ω / cm 2 or less. Therefore, it is extremely useful as an electrode for a small redox flow battery.

本発明電極板の製造過程における構成部材の配置態様を示す正面図。The front view which shows the arrangement | positioning aspect of the structural member in the manufacture process of this invention electrode plate. 完成した本発明電極板の一例の正面図。The front view of an example of the completed this invention electrode plate.

まず、耐酸性が高く、好ましくは低価格で入手できる厚さ0.2mm〜0.5mm程度の合成樹脂板（又はシート）、例えば塩ビ系樹脂，アクリル系樹脂，フッ素樹脂，ポリカーボネイト，ポリプロピレン等の中から選んだ材料により形成した合成樹脂製のシート１を、製造されるレドックスフロー電池の電極板と同大の、ここでは正方形に形成する。以下、このシート１をベースシート１ともいう。   First of all, a synthetic resin plate (or sheet) having a high acid resistance and preferably available at a low price of about 0.2 mm to 0.5 mm, such as a vinyl resin, acrylic resin, fluororesin, polycarbonate, polypropylene, etc. The synthetic resin sheet 1 formed of the selected material is formed in the same size as the electrode plate of the manufactured redox flow battery, in this case a square. Hereinafter, this sheet 1 is also referred to as a base sheet 1.

次に、前記ベースシート１に対し、炭素質材料として天然黒鉛，人造黒鉛，炭素繊維，気相成長法炭素繊維，ピッチ系炭素質材料，ニードルコークス，石油コークス，ポリアクリルニトリル系炭素繊維，カーボンブラックの中の少なくとも一つを含有して形成された炭素質材料を主成分とするフィルムであって、厚さが0.2mm〜0.5mm，電気抵抗値が1.0Ω／cm２以下、好ましくは0.5Ω／cm２の炭素材系フィルム２をベースシート１の２倍の面積を有する大きさの正方形に形成する。 Next, with respect to the base sheet 1, natural graphite, artificial graphite, carbon fiber, vapor grown carbon fiber, pitch-based carbon material, needle coke, petroleum coke, polyacrylonitrile-based carbon fiber, carbon A film mainly composed of a carbonaceous material containing at least one of black, having a thickness of 0.2 mm to 0.5 mm and an electric resistance of 1.0 Ω / cm 2 or less, preferably 0.5 A carbon material film 2 of Ω / cm 2 is formed into a square having a size twice that of the base sheet 1.

電極板の外形に沿った形の正方形に形成されていると共に、全面に接着剤を塗布したベースシート１と、当該シート１の２倍の面積を有する正方形状に形成した炭素系フィルム２とは、図１に示す態様で配置される。即ち、正方形のベースシート１と２倍の面積を有する正方形の炭素系フィルム２は、正面から見て45度の回転中心角で重ね、ベースシート１の外周からはみ出た炭素系フィルム２の４つの三角形状部分2a〜2dを、図２に示すようにベースシート１の内側に折曲げることにより、ベースシート１の全周囲の端面も含む外面のすべて（これをベースシート１の全面という）が炭素系フィルム２によって完全に覆われ、かつ、当該フィルム２がベースシート１の全表面に接着される。この接着においては、ベースシート１と炭素系フィルム２との密着度を確保するため、圧着することが望ましい。   A base sheet 1 that is formed into a square shape that conforms to the outer shape of the electrode plate, and an adhesive is applied to the entire surface, and a carbon-based film 2 that is formed in a square shape having an area twice that of the sheet 1. Are arranged in the manner shown in FIG. That is, the square base sheet 1 and the square carbon film 2 having a double area are overlapped at a rotation center angle of 45 degrees when viewed from the front, and the four carbon films 2 protruding from the outer periphery of the base sheet 1 are included. By folding the triangular portions 2a to 2d to the inside of the base sheet 1 as shown in FIG. 2, all of the outer surface including the entire peripheral surface of the base sheet 1 (this is called the entire surface of the base sheet 1) is made of carbon. The film 2 is completely covered with the system film 2, and the film 2 is adhered to the entire surface of the base sheet 1. In this bonding, it is desirable to press-bond in order to secure the adhesion between the base sheet 1 and the carbon film 2.

炭素系フィルム２がベースシート１の全周端面を含む前後両面を被覆して形成された本発明電極板は、全体の厚さが0.4mm〜1.0mm程度と薄く、また、薄くても電解液の浸透は皆無であり、さらに、電気抵抗値も1.0Ω／cm２以下、好ましくは、0.5Ω／cm２程度であるから、３〜５kw程度の小型のレドックスフロー電池の電極板としてきわめて好適である。なお、本発明電極板は、50A程度までの電流を流しても問題ない。 The electrode plate of the present invention in which the carbon-based film 2 is formed by covering both the front and rear surfaces including the entire peripheral end surface of the base sheet 1 has a thin total thickness of about 0.4 mm to 1.0 mm. the penetration is nil, further electrical resistance is also 1.0 [Omega] / cm 2 or less, preferably, because it is about 0.5 .OMEGA / cm 2, very suitable as an electrode plate of a redox flow battery of small about 3~5kw is there. In the electrode plate of the present invention, there is no problem even when a current of up to about 50 A is passed.

しかも、本発明電極の構成は至ってシンプルであるから、低コストで容易に製造することができる利点がある。   Moreover, since the configuration of the electrode of the present invention is very simple, there is an advantage that it can be easily manufactured at low cost.

１ ベースプレート
２ 炭素系フィルム
2a〜2d 炭素系フィルム２の三角形状部分
1 Base plate 2 Carbon film
2a-2d Triangular part of carbon film 2

Claims (4)

炭素乃至炭素質材料を主成分とした厚さが0.5mm〜0.2mm、電気抵抗値が1.0Ω〜0.5Ω／cm２以下の炭素質材料を含有するフィルムによって、厚さが約0.2mm〜0.5mmであり外形を所望形状のレドックスフロー電池用の電極板形状に形成した合成樹脂シートの全面を被覆したことを特徴とするレドックスフロー電池の電極板。 By a film of carbon or the thickness mainly composed of carbonaceous material 0.5Mm～0.2Mm, electrical resistance containing 1.0Ω~0.5Ω / cm 2 or less of carbonaceous material, a thickness of about 0.2mm~0.5 An electrode plate for a redox flow battery, characterized in that the entire surface of a synthetic resin sheet that is mm and has an outer shape formed into an electrode plate shape for a redox flow battery having a desired shape is coated. フィルムに含有させる炭素質材料は、天然黒鉛，人造黒鉛，炭素繊維，気相成長法炭素繊維，ピッチ系炭素質材料，ニードルコークス，石油コークス，ポリアクリルニトリル系炭素繊維，カーボンブラックの中から選ばれた少なくとも一つである請求項１のレドックスフロー電池の電極板。   The carbonaceous material to be included in the film is selected from natural graphite, artificial graphite, carbon fiber, vapor grown carbon fiber, pitch carbonaceous material, needle coke, petroleum coke, polyacrylonitrile carbon fiber, and carbon black. The electrode plate of the redox flow battery according to claim 1, wherein the electrode plate is at least one of the above. 上記の炭素質材料を含むフィルムで全面被覆される合成樹脂シートは、レドックスフロー電池に用いられる正極液，負極液、すなわち電解液に冒されないか冒され難い耐酸性の高い合成樹脂を原料とした請求項１又は２のレドックスフロー電池の電極板。   The synthetic resin sheet that is entirely covered with the film containing the carbonaceous material is made from a high acid resistance synthetic resin that is not affected or hardly affected by the positive electrode solution and the negative electrode solution used in the redox flow battery, that is, the electrolyte solution. The electrode plate of the redox flow battery according to claim 1 or 2. 耐酸性の高い合成樹脂製で0.2mm〜0.5mmの厚さを有するベースシートを正方形に形成し、該ベースシートの表裏両面と全外周端面を被覆するため炭素質材料を含み厚さを0.2mm〜0.5mmに形成した一枚の炭素材系フィルムを、前記ベースシートの２倍の面積を有する正方形に形成し、前記ベースシートの表面に接着剤を塗布して当該ベースシートと炭素材系フィルムとの中心を合せると共に、前記シートとフィルムの中心を45度回転させた角度を以て重ね、ベースシートからはみ出した前記フィルムの三角形状部を当該ベースシートの内側に折畳み、前記ベースシートの全表面を炭素材系フィルムで被覆して接着することを特徴とするレドックスフロー電池用電極板の製造方法。
A base sheet made of synthetic resin with high acid resistance and having a thickness of 0.2 mm to 0.5 mm is formed in a square shape, and includes a carbonaceous material to cover both the front and back surfaces of the base sheet and the entire outer peripheral end surface, and the thickness is 0.2 mm. A single carbon material film formed in a thickness of ~ 0.5 mm is formed into a square having an area twice that of the base sheet, and an adhesive is applied to the surface of the base sheet to form the base sheet and the carbon material film. And the sheet and the center of the film are rotated at an angle of 45 degrees, the triangular portion of the film protruding from the base sheet is folded inside the base sheet, and the entire surface of the base sheet is A method for producing an electrode plate for a redox flow battery, characterized by covering and adhering with a carbon material film.
JP2009128606A 2009-05-28 2009-05-28 Electrode plate of redox flow battery Pending JP2010277810A (en)

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KR20140021661A (en) * 2011-04-11 2014-02-20 유나이티드 테크놀로지스 코포레이션 Flow battery having electrodes with a plurality of different pore sizes and/or different layers
US8785023B2 (en) 2008-07-07 2014-07-22 Enervault Corparation Cascade redox flow battery systems
US8906529B2 (en) 2008-07-07 2014-12-09 Enervault Corporation Redox flow battery system for distributed energy storage
US8916281B2 (en) 2011-03-29 2014-12-23 Enervault Corporation Rebalancing electrolytes in redox flow battery systems
US8980484B2 (en) 2011-03-29 2015-03-17 Enervault Corporation Monitoring electrolyte concentrations in redox flow battery systems
CN114072944A (en) * 2019-07-18 2022-02-18 住友电气工业株式会社 Redox flow battery cell, cell stack, and redox flow battery system

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8785023B2 (en) 2008-07-07 2014-07-22 Enervault Corparation Cascade redox flow battery systems
US8906529B2 (en) 2008-07-07 2014-12-09 Enervault Corporation Redox flow battery system for distributed energy storage
US8916281B2 (en) 2011-03-29 2014-12-23 Enervault Corporation Rebalancing electrolytes in redox flow battery systems
US8980484B2 (en) 2011-03-29 2015-03-17 Enervault Corporation Monitoring electrolyte concentrations in redox flow battery systems
KR20140021661A (en) * 2011-04-11 2014-02-20 유나이티드 테크놀로지스 코포레이션 Flow battery having electrodes with a plurality of different pore sizes and/or different layers
KR101940148B1 (en) * 2011-04-11 2019-01-18 유나이티드 테크놀로지스 코포레이션 Flow battery having electrodes with a plurality of different pore sizes and/or different layers
CN114072944A (en) * 2019-07-18 2022-02-18 住友电气工业株式会社 Redox flow battery cell, cell stack, and redox flow battery system
CN114072944B (en) * 2019-07-18 2024-01-09 住友电气工业株式会社 Redox flow battery cell, cell stack, and redox flow battery system

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