JPH087913A - Full vanadium redox cell - Google Patents
Full vanadium redox cellInfo
- Publication number
- JPH087913A JPH087913A JP6140359A JP14035994A JPH087913A JP H087913 A JPH087913 A JP H087913A JP 6140359 A JP6140359 A JP 6140359A JP 14035994 A JP14035994 A JP 14035994A JP H087913 A JPH087913 A JP H087913A
- Authority
- JP
- Japan
- Prior art keywords
- thickness
- plate
- cell
- battery
- packing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
Landscapes
- Fuel Cell (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、二次電池に関し、さら
に詳しくは、バナジウム（II/III）とバナジウム（V/I
V）をレドックス対とするレドックスフロー型二次電池
（略して、「レドックス電池」と呼ぶことがある）に関
するものであり、特に高電流密度で使用可能な全バナジ
ウムレドックス電池のセル構造に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a secondary battery, and more specifically to vanadium (II / III) and vanadium (V / I).
V) is a redox flow type secondary battery (sometimes abbreviated as "redox battery" for short), especially the cell structure of all vanadium redox batteries that can be used at high current density. is there.
【０００２】[0002]
【発明の背景】現在、化石燃料の大量使用による大気中
の炭酸ガス濃度の増加が著しく、地球の温暖化が大きな
問題となっている。このために、クリーンなエネルギー
源である太陽電池の開発が活発に行われているが、太陽
電池は、夜間や雨天時は発電できないため適切な２次電
池の開発が待たれている。一方、従来の発電設備に於い
ても夜と昼、ピーク時の需要の差が激しく発電設備の負
荷率は低下しており、大型の電力貯蔵電池による運転の
平滑化は省エネルギーの面で大きな意味を持っている。
電気エネルギーを貯蔵することは電力関係者の長年の夢
であるが、現在のところ揚水発電以外は実用化されてお
らず、大型の電力貯蔵電池の必要性は大きなものであ
る。レドックス電池はタッピングによって太陽電池の出
力電圧に合わせて充電できることや、構造が比較的シン
プルで大型化しやすい等の特徴を持つために、新型の２
次電池として大きな可能性を秘めている。BACKGROUND OF THE INVENTION At present, the concentration of carbon dioxide in the atmosphere is remarkably increased due to the large use of fossil fuels, and the global warming is a serious problem. For this reason, solar cells, which are clean energy sources, are being actively developed. However, since the solar cells cannot generate power at night or in rainy weather, the development of appropriate secondary batteries is awaited. On the other hand, even in the conventional power generation equipment, the load difference of the power generation equipment is decreasing due to the large difference in demand between night, daytime, and peak hours, and smoothing the operation with a large power storage battery is significant in terms of energy saving. have.
Storing electrical energy has been a dream of electric power companies for many years, but at present, there is no practical application other than pumped storage power generation, and there is a great need for large power storage batteries. The redox battery can be charged according to the output voltage of the solar cell by tapping, and the structure is relatively simple and easy to increase in size.
It has great potential as a secondary battery.
【０００３】レドックス型二次電池とは、電池活物質が
液状であり、正、負極の電池活物質を液透過型の電解槽
に流通せしめ、酸化還元反応を利用して充放電を行うも
のである。従来の二次電池と比べレドックス型二次電池
は 次の利点を有する。 (1) 蓄電容量を大きくするためには、貯蔵容器の容量を
大きくし、活物質量を増加させるだけでよく、出力を大
きくしない限り、電解槽自体はそのままでよい。 (2) 正、負極活物質は容器に完全に分離して貯蔵できる
ので、活物質が電極に接しているような電池と異なり、
自己放電の可能性が小さい。 (3) この電池で使用される液透過型炭素多孔質電極にお
いては、活物質イオンの充放電反応(電極反応)は、単
に、電極表面で電子の交換を行うのみで、亜鉛ー臭素電
池における、亜鉛イオンのように電極に析出することは
ないので、電池の反応が単純である。A redox type secondary battery is a battery in which the battery active material is liquid, and the positive and negative battery active materials are circulated in a liquid permeation type electrolytic cell and charged and discharged by utilizing an oxidation-reduction reaction. is there. Redox type secondary batteries have the following advantages over conventional secondary batteries. (1) In order to increase the storage capacity, it is sufficient to increase the capacity of the storage container and increase the amount of the active material, and the electrolytic cell itself can be used as long as the output is not increased. (2) Since the positive and negative electrode active materials can be completely separated and stored in a container, unlike a battery in which the active material is in contact with the electrodes,
The possibility of self-discharge is low. (3) In the liquid-permeable carbon porous electrode used in this battery, the charge / discharge reaction of the active material ions (electrode reaction) is simply carried out by exchanging electrons on the electrode surface. Since it does not deposit on the electrode like zinc ions, the reaction of the battery is simple.
【０００４】[0004]
【従来の技術】レドックスフロー型二次電池として、鉄
−クロム系電池が知られているが、該電池はエネルギー
密度が小さいこと、イオン交換膜を介して鉄とクロムが
混合することなどの欠点があるために、これに代わるも
のとして全バナジウム系電池が提案されている（特開昭
62-186473号公報)。この電池は、起電力、電池容量など
に優れており、電解液が一金属系であるため隔膜を介し
て正、負極液が相互に混合しても充電によって簡単に再
生することができ、電池容量が低下せず、電解液を完全
にクローズド化できる等の利点を持っている。しかし、
従来の全バナジウム系電池では、使用可能な高電流密度
は高々６０mA/cm2程度であり、さらに高い電流密度での
使用は不可能であった。2. Description of the Related Art Iron-chromium batteries are known as redox flow type secondary batteries, but they have drawbacks such as low energy density and mixing of iron and chromium through an ion exchange membrane. Therefore, an all-vanadium-based battery has been proposed as an alternative to this (Japanese Patent Application Laid-Open No. Sho-06-1999).
62-186473). This battery is excellent in electromotive force, battery capacity, etc., and because the electrolyte is a single metal type, it can be easily regenerated by charging even if positive and negative electrode liquids are mixed with each other through the diaphragm. It has the advantage that the capacity does not decrease and the electrolyte can be completely closed. But,
In the conventional all-vanadium battery, the high current density that can be used is about 60 mA / cm 2 at most, and it is impossible to use it at a higher current density.
【０００５】例えば８０mA/cm2以上の高電流密度を採用
して、高い電力効率を維持するためには、セルの抵抗を
１．５Ω/ｃｍ2以下にしなければならず、電極の電気抵
抗、電解液の導電率を考慮すると正極室及び負極室のセ
ル厚は２．５ｍｍ以下にすることが望ましく、新たなる
セルの開発が必要となってきた。For example, in order to maintain a high power efficiency by adopting a high current density of 80 mA / cm 2 or more, the resistance of the cell must be 1.5 Ω / cm 2 or less. Considering the conductivity of the electrolytic solution, it is desirable that the cell thickness of the positive electrode chamber and the negative electrode chamber be 2.5 mm or less, and it has become necessary to develop a new cell.
【０００６】従来の鉄−クロム系レドックス電池のセル
構造の一例としては、バイポーラ板とマニホールドから
電解液をセル内に分液するスリットとが一体化された構
造になっている。詳しくは、厚さ３ｍｍ前後の樹脂製の
外枠に、マニホールド、スリット、液漏れと接着時ズレ
を防止するための溝を刻み込み、内側にカーボン板をは
め込み、その両側からスリット及び液漏れとズレ防止用
の溝を刻み込んだ樹脂製の板を接着剤で張り合わせて、
分液するスリットとバイポーラ板が一体化されている。
このために、非常に多くの人手による接着作業を要し、
量産化する事は難しく、不良品等の解体、修理にも多く
の手間がかかり、経済的に制作するには支障がある。ま
た、バイポーラ板やセルの厚みを薄くすることが出来
ず、セルの抵抗を下げることも難しい。As an example of a cell structure of a conventional iron-chromium redox battery, a bipolar plate and a slit for separating an electrolytic solution into a cell from a manifold are integrated. Specifically, a resin outer frame with a thickness of about 3 mm is engraved with a manifold, slits, and grooves to prevent liquid leakage and displacement during bonding, and a carbon plate is fitted inside, and slits and liquid leakage are provided from both sides. Glue a resin plate with grooves to prevent misalignment with an adhesive,
The slit for liquid separation and the bipolar plate are integrated.
This requires a great deal of manual bonding work,
Mass production is difficult, and dismantling and repair of defective products takes a lot of work, which hinders economical production. In addition, it is difficult to reduce the thickness of the bipolar plate and the cell, and it is difficult to reduce the resistance of the cell.
【０００７】特開昭63-298977号では、弾性体で作成さ
れた反応電極の支持枠の外部に、トンネル状のスリット
孔を有するマニホールド部を設け、これをバイポーラ板
と隔膜により押圧したレドックスフロー型セルが提案さ
れている。このセルは、弾性体による面シールにより接
着作業の大幅な削減ができるが、隔膜にイオン交換膜を
使用した場合、イオン交換膜の外側に取り付けられるマ
ニホールドスペーサをを０．１ｍｍ以下の弾性体で作ら
なければシールが完全にできず、現実的ではない。ま
た、多孔性電極、樹脂製の電解液流通配管、セルの製作
時に使用される接着剤等の劣化による電解液中のコンタ
ミがスリットに詰まるため、特開昭63-281362号では電
解液を濾過したり、特開昭63-291365では、電解液の通
液方向を逆転する事などが提案されている。しかし、フ
ィルターは、いずれ目詰まりし、スリット等の洗浄が必
要となるために、セルを解体しなければならなず、より
簡単に解体洗浄できるセル構造であることが必要とな
る。In Japanese Laid-Open Patent Publication No. 63-298977, a redox flow is provided in which a manifold portion having a tunnel-shaped slit hole is provided outside a supporting frame of a reaction electrode made of an elastic body and which is pressed by a bipolar plate and a diaphragm. Type cells have been proposed. This cell can greatly reduce the adhesive work by surface sealing with an elastic body, but when an ion exchange membrane is used for the diaphragm, the manifold spacer attached to the outside of the ion exchange membrane is made of an elastic body of 0.1 mm or less. If you do not make it, the seal cannot be completely created, which is not realistic. Also, since the porous electrode, the electrolytic solution flow pipe made of resin, the contamination in the electrolytic solution due to the deterioration of the adhesive used when manufacturing the cell, etc. are clogged in the slit, the electrolytic solution is filtered in JP-A-63-281362. In addition, Japanese Patent Laid-Open No. 63-291365 proposes to reverse the flow direction of the electrolytic solution. However, since the filter eventually becomes clogged and cleaning of slits and the like is required, the cell must be disassembled, and a cell structure that enables easier disassembly and cleaning is required.
【０００８】[0008]
【発明が解決しようとする課題】本発明の目的は、バナ
ジウムレドックス電池の内部抵抗を低減させて高電流密
度に適応することができ、且つ量産が可能なセル構造を
持った、高出力の新規なバナジウムレドックス電池セル
を開発することである。本発明における高電流密度と
は、８０〜１２０mA/cm2である。電流密度をあげて、高
い効率を維持するためには、セルの内部抵抗を出来るだ
け小さくしなければならない。従来のレドックスセル
は、セルの構造上の問題から４０〜６０mA/cm2までの低
電流密度用に設計されており、上記目的を達成すること
は困難である。SUMMARY OF THE INVENTION An object of the present invention is to reduce the internal resistance of vanadium redox batteries to adapt to high current densities, and to have a cell structure capable of mass production and having a high output. Is to develop a new vanadium redox battery cell. The high current density in the present invention is 80 to 120 mA / cm 2 . In order to increase the current density and maintain high efficiency, the internal resistance of the cell must be minimized. The conventional redox cell is designed for a low current density of 40 to 60 mA / cm 2 due to a structural problem of the cell, and it is difficult to achieve the above object.
【０００９】バナジウムレドックス電池の内部抵抗は、
バイポーラ板の抵抗、多孔性電極の抵抗、電解液の抵
抗、イオン交換膜の抵抗、及び各部材の接触抵抗の総和
である。本発明者らは、先に、ポリスルホン系のイオン
交換膜を採用して、イオン交換膜の抵抗を大幅に下げ、
高電流密度に適応しうるバナジウムレドックス電池を提
案したが（特願平４−４０４３号）、８０mA/cm2以上の
電流を流して、高い効率を出すバナジウムレドックス電
池とするには、バイポーラ板の抵抗、多孔性電極の抵抗
および電解液の抵抗を共に低減し、なおかつ、量産が可
能なセル構造にしなければならない。レドックス電池に
おいては、電流は厚さ方向に流れるため出来るだけ薄い
方が抵抗は小さくなる。しかしながら、カーボン板やセ
ルの厚さを薄くしようとすると、バイポーラ板、パッキ
ン等のセルの構成部材を制作する上で種々の問題にぶつ
かる。The internal resistance of a vanadium redox battery is
It is the sum of the resistance of the bipolar plate, the resistance of the porous electrode, the resistance of the electrolytic solution, the resistance of the ion exchange membrane, and the contact resistance of each member. The present inventors previously adopted a polysulfone-based ion exchange membrane to significantly reduce the resistance of the ion exchange membrane,
We proposed a vanadium redox battery that can adapt to high current densities (Japanese Patent Application No. 4-4043), but in order to make a vanadium redox battery with a high efficiency by passing a current of 80 mA / cm 2 or more, a bipolar plate It is necessary to reduce the resistance, the resistance of the porous electrode, and the resistance of the electrolytic solution, and to make the cell structure capable of mass production. In the redox battery, the electric current flows in the thickness direction, so that the resistance becomes smaller as thin as possible. However, when trying to reduce the thickness of the carbon plate or the cell, various problems are encountered in manufacturing the cell constituent members such as the bipolar plate and the packing.
【００１０】[0010]
【課題を解決するための手段】本発明は、セルの厚み、
殊にバイポーラ板の厚みを出来るだけ薄くして、抵抗を
下げ、なおかつ、面シールによってセルの接着作業を大
幅に低減し、量産が可能なセル構造とすることにより上
記問題点を解決した。即ち、本発明の全バナジウム系レ
ドックス電池は、樹脂製の外枠の内部に導電性の板を嵌
め込んだバイポーラ板と、電解液をセルに循環させるた
めのマニホールド及びスリットを有し且つ内部に電極が
装入保持されるくりぬき部を有する分液板と、隔膜と
を、適度な剛性を有するパッキンを介して面シールによ
り集層させて厚さ２．５ｍｍ以下の正極室又は負極室を
形成し、その際該スリットは該マニホールドと該くりぬ
き部の間に穿設された分液穴を境に表と裏に凹設されて
いることを特徴とするものである。SUMMARY OF THE INVENTION The present invention provides a cell thickness,
In particular, the above problems have been solved by making the thickness of the bipolar plate as thin as possible to reduce the resistance, and by significantly reducing the cell bonding work by the face seal, and by providing a cell structure that enables mass production. That is, the all-vanadium redox battery of the present invention has a bipolar plate in which a conductive plate is fitted inside a resin-made outer frame, and a manifold and a slit for circulating the electrolytic solution into the cell and having the inside. A separator plate having a hollow portion into which an electrode is charged and held, and a diaphragm are layered by a face seal through a packing having an appropriate rigidity to form a positive electrode chamber or a negative electrode chamber having a thickness of 2.5 mm or less. At this time, the slit is characterized by being formed on the front and the back with a liquid separation hole formed between the manifold and the hollow portion as a boundary.
【００１１】[0011]
【発明の具体的説明】本発明のレドックス電池の構成に
ついて、図面を参考にしてに詳しく説明する。 （１）セル構成部材 (1) バイポーラ板 本発明の新規なセルに使用されるバイポーラ板１は、樹
脂性の外枠２の内部に、導電性の板３を嵌め込んだもの
である。外枠２に用いられる樹脂は、適度の耐薬品性と
剛性を有するものであれば良く、例えば、ポリ塩化ビニ
ル、高密度ポリエチレン、ポリプロピレン，ＡＳ樹脂，
ＡＢＳ樹脂、ポリスルフォン、ポリエーテルスルフォ
ン、ポリエーテルエーテルケトン、テフロン等を用いる
ことができ、各成型法により最適の物を適宜使用するこ
とができる。DETAILED DESCRIPTION OF THE INVENTION The structure of the redox battery of the present invention will be described in detail with reference to the drawings. (1) Cell Constituent Members (1) Bipolar Plate The bipolar plate 1 used in the novel cell of the present invention has a conductive outer plate 2 and a conductive plate 3 fitted therein. The resin used for the outer frame 2 may be one having appropriate chemical resistance and rigidity, and examples thereof include polyvinyl chloride, high density polyethylene, polypropylene, AS resin,
ABS resin, polysulfone, polyethersulfone, polyetheretherketone, Teflon, etc. can be used, and the most suitable one can be appropriately used according to each molding method.
【００１２】導電性板３としては、導電性が良く、加工
性と剛性が適度なものであれば特に制限されないが、グ
ラッシーカーボン、フェノール結着カーボン、プラスチ
ックカーボン等が使用できる。バイポーラ板１は、電気
抵抗を少なくするために、出来るだけ薄くすることが好
ましいが、内部に導電性板３、例えばカーボン板を加工
装着する必要性から、０．５〜１．５ｍｍの厚さである
ことが好ましい。樹脂性の外枠２の内部にくり貫かれた
部分に、同じ厚さのカーボン板を完全に密着させ、外枠
２とカーボン板３が同一平面になるようにする。カーボ
ン板は加工性が悪く、通常の切削工具では割れてしまう
ため、水流ジェットにより切削することが好ましい。こ
れによりバイポーラ板１は、特注品でなく、従来リン酸
型燃料電池に用いらているカーボン材料を使って自由に
作ることが出来る。The conductive plate 3 is not particularly limited as long as it has good conductivity, workability and rigidity, but glassy carbon, phenol-bonded carbon, plastic carbon or the like can be used. The bipolar plate 1 is preferably made as thin as possible in order to reduce the electric resistance, but it is necessary to process and mount the conductive plate 3, for example, a carbon plate, so that the bipolar plate 1 has a thickness of 0.5 to 1.5 mm. Is preferred. A carbon plate having the same thickness is completely adhered to a portion which is hollowed out inside the resinous outer frame 2 so that the outer frame 2 and the carbon plate 3 are flush with each other. Since the carbon plate has poor workability and breaks with an ordinary cutting tool, it is preferable to cut with a water jet. As a result, the bipolar plate 1 can be freely made by using a carbon material conventionally used for phosphoric acid fuel cells, not a custom-made product.
【００１３】(2) 分液板 本発明のセルにおいては、電解液をマニホールド４から
カーボン板３の表面および電極へ通液し、ついで排出す
るためのスリット５を、従来のようにバイポーラ板１に
付設せずに、バイポーラ板１から独立した分液板６を使
用することが重要である。該分液板６の採用により、ス
リットの断面積と長さを変えて、使用目的により種々の
セルを作ることができ、セルの設計の自由度が大幅に向
上する。また、スリットの詰まり等が起こったときも簡
単に分解洗浄が可能となる。(2) Separation Plate In the cell of the present invention, the slit 5 for passing the electrolytic solution from the manifold 4 to the surface of the carbon plate 3 and the electrodes and then discharging it is provided with the bipolar plate 1 as in the conventional case. It is important to use the liquid separating plate 6 independent of the bipolar plate 1 without attaching it to the bipolar plate 1. By adopting the liquid separating plate 6, various cells can be produced by changing the cross-sectional area and length of the slit, depending on the purpose of use, and the degree of freedom in cell design is greatly improved. Further, even when the slit is clogged, the disassembly and cleaning can be easily performed.
【００１４】分液板６は、バイポーラ板内部のカーボン
板接合部１３の保護及びバイポーラ板側の面シールとイ
オン交換膜側の面シールをする役割がある。電解液を通
液させるスリット５が分液板６の片面にのみ刻設され、
特にスリット５の溝面積が大きい場合は、その面積に対
してパッキンと接触する分液板平面の面積が少なくな
り、十分な面シールが困難となることがある。このた
め、本発明の分液板６では、図２、図３および図４に示
すように、マニホールド４とくりぬき部７との間に分液
穴８を設け、この穴を境に分液板６の表と裏にスリット
５ａ及び５ｂを刻むことにより、完全な両面のシールを
可能にすることができる。分液板６の表側とは隔膜側の
面であり、裏側とはバイポーラ板の面を意味する。分液
板６の表側に凹設されるスリット５ａは分液穴とくりぬ
き部の間に設けられ、裏側に凹設されるスリット５ｂは
マニホールドと分液穴の間に設けられる。分液穴８およ
びスリット５は、分液板６の中心より対称の位置に２箇
所に設けられ、その一方が電解液の供給に、他方が電解
液の排出に寄与する。このようにスリット５を付設する
ことにより、スリット溝の面積に対してパッキンと接触
する分液板の表面の面積が大きくなり、パッキンが該溝
に食い込むことが防止されると共に、完全なシールが可
能となる。The liquid separating plate 6 has a role of protecting the carbon plate joint portion 13 inside the bipolar plate and performing a face seal on the bipolar plate side and a face seal on the ion exchange membrane side. The slit 5 for passing the electrolytic solution is engraved only on one surface of the liquid separating plate 6,
In particular, when the groove area of the slit 5 is large, the area of the plane of the liquid separating plate that comes into contact with the packing is smaller than that area, and it may be difficult to perform sufficient surface sealing. Therefore, in the liquid separating plate 6 of the present invention, as shown in FIGS. 2, 3 and 4, a liquid separating hole 8 is provided between the manifold 4 and the hollowed-out portion 7, and the liquid separating plate is bordered by this hole. By engraving slits 5a and 5b on the front and back of 6, it is possible to enable complete double-sided sealing. The front side of the liquid separating plate 6 is the surface on the diaphragm side, and the back side is the surface of the bipolar plate. The slit 5a recessed on the front side of the liquid separating plate 6 is provided between the liquid separating hole and the hollow portion, and the slit 5b recessed on the back side is provided between the manifold and the liquid separating hole. The liquid separating holes 8 and the slits 5 are provided at two positions symmetrical with respect to the center of the liquid separating plate 6, one of which contributes to the supply of the electrolytic solution and the other of which contributes to the discharging of the electrolytic solution. By providing the slit 5 in this way, the area of the surface of the liquid separating plate that comes into contact with the packing is larger than the area of the slit groove, the packing is prevented from biting into the groove, and a complete seal is provided. It will be possible.
【００１５】スリットの口径（溝の幅と深さ）と長さ
は、シャント電流損失に関係し、口径は小さいほど、長
さは長い程、シャント電流損失は少なくなる。一方、電
解液の流動抵抗は小さければ小さい程、ポンプロスが少
なく望ましいが、スリットの口径が大きく、長さは短い
ほど小さくなる。従って、スリットの口径、本数及び長
さは、シャント電流損失と流動抵抗の両者を考慮して決
定される。各スリットの溝幅は１〜３ｍｍ、その深さは
０．５〜１．５ｍｍが好ましい。溝幅が３ｍｍ超過で
は、パッキンが溝に食い込み、１ｍｍ未満では電解液の
流動抵抗が高くなりすぎるので好ましくない。スリット
の深さが０．５ｍｍ未満では切削加工が困難であり、
１．５ｍｍ超過では分液板を厚くしなければならないの
で好ましくない。複数設けられたスリットの間隔は、自
由に取れるが、広く取ると電池が大きくなり、極端に狭
いと締め付け応力に樹脂板が耐えられず、スリット間隔
は１〜３ｍｍが適している。また、スリット全体の幅
（溝及び間隔の和）はスリットの本数により異なるが、
通常はマニホールドの径と一致させることが好ましい。
分液穴８は、表側スリット５ａから裏側スリット５ｂへ
の（またはその逆）の電解液の流通が支障なく行われる
のに適したサイズであればよく、例えば、長辺がマニホ
ールド径と同一で、短辺が２〜５ｍｍの長方形状または
楕円形状のものが適当である。The slit diameter (groove width and depth) and length are related to the shunt current loss. The smaller the diameter and the longer the length, the smaller the shunt current loss. On the other hand, the smaller the flow resistance of the electrolytic solution is, the smaller the pump loss is, which is desirable, but the smaller the diameter of the slit and the shorter the length, the smaller. Therefore, the diameter, the number and the length of the slits are determined in consideration of both the shunt current loss and the flow resistance. The groove width of each slit is preferably 1 to 3 mm and the depth thereof is preferably 0.5 to 1.5 mm. If the groove width exceeds 3 mm, the packing bites into the groove and if it is less than 1 mm, the flow resistance of the electrolytic solution becomes too high, which is not preferable. If the slit depth is less than 0.5 mm, it is difficult to cut,
If it exceeds 1.5 mm, the separating plate must be made thick, which is not preferable. A plurality of slits can be freely spaced, but if they are wide, the battery becomes large, and if they are extremely narrow, the resin plate cannot withstand the tightening stress, and a slit spacing of 1 to 3 mm is suitable. Also, the width of the entire slit (sum of grooves and intervals) varies depending on the number of slits,
Generally, it is preferable to match the diameter of the manifold.
The liquid separating hole 8 may be of any size suitable for allowing the flow of the electrolytic solution from the front side slit 5a to the back side slit 5b (or vice versa) without any hindrance, and for example, the long side is the same as the manifold diameter. A rectangular or elliptical shape having a short side of 2 to 5 mm is suitable.
【００１６】分液板６に用いる樹脂性の板は、適度の耐
薬品性と剛性を有するものであれば良く、バイポーラ板
１の外枠２に使用することのできる上記した材料から選
ぶことができる。The resin plate used for the liquid separating plate 6 may be any one having appropriate chemical resistance and rigidity, and is selected from the above-mentioned materials that can be used for the outer frame 2 of the bipolar plate 1. it can.
【００１７】(3) パッキン 本発明のセルに使用されるパッキン９は、その周縁部に
はマニホールド４が、その内部にはバイポーラ板の外枠
とカーボン板の境目１３を被うように、カーボン板のサ
イズより僅かに小さめにくり貫かれており（１０）、境
目からの液漏れを防いでいる。パッキン９は、その厚さ
が０．２〜１ｍｍで、デュ−ロ硬度（Ａタイプ）が８０
〜１２０のものであれば良く、低密度ポリエチレン、エ
チレン−プロピレンゴム、ポリプロピレン、ネオプレン
ゴム、バイトンゴム、テフロンシート等の樹脂またはゴ
ム質材料を使用することができる。パッキンの厚さが
０．２mm未満では面タッチシールが不可能であり、１ｍ
ｍ超過ではセルの厚さを薄くできない。また、デュ−ロ
硬度が８０未満では、スリットにパッキンが食い込み、
詰まったり、電解液の均等分配ができなくなり、硬度１
２０超過では面シールが困難となる。(3) Packing The packing 9 used in the cell of the present invention is made of carbon so that the manifold 4 is provided at the peripheral portion thereof and the outer frame of the bipolar plate and the boundary 13 of the carbon plate are covered therein. It is hollowed out slightly smaller than the size of the plate (10) to prevent liquid leakage from the border. The packing 9 has a thickness of 0.2 to 1 mm and a Duro hardness (A type) of 80.
As long as it is up to 120, a resin or rubber material such as low density polyethylene, ethylene-propylene rubber, polypropylene, neoprene rubber, viton rubber or Teflon sheet can be used. If the packing thickness is less than 0.2 mm, face touch seal is not possible and it is 1 m
If it exceeds m, the cell thickness cannot be reduced. If the Duro hardness is less than 80, the packing will dig into the slit,
Clogs, electrolyte cannot be evenly distributed, and hardness is 1
If it exceeds 20, face sealing becomes difficult.
【００１８】(4) 隔膜 正極室と負極室とを分離する隔膜１１は通常イオン交換
膜が使用される。イオン交換膜としては、５価のバナジ
ウムイオンの酸化力に耐性のあるものであれば、陽イオ
ン、陰イオンどちらのイオン交換膜でも良い。具体的に
は、ポリスルホン樹脂をベースにしたイオン交換膜やフ
ッ素樹脂をベースにしたイオン交換膜が使用できるが、
８０mA/cm2以上の高電流密度で使用するには、イオン交
換樹脂層の厚さが２０μｍ〜１５０μｍであることが好
ましい。これより薄い膜であればセル抵抗は低くなる
が、正極と負極の液移動が激しくて充放電をすることが
難しく、これ以上厚ければセル抵抗が高くなりすぎて所
定の効率を達成することが困難となる。(4) Separating Membrane 11 which normally separates the positive electrode chamber and the negative electrode chamber is usually an ion exchange membrane. The ion exchange membrane may be either a cation or anion ion exchange membrane as long as it is resistant to the oxidizing power of pentavalent vanadium ions. Specifically, an ion exchange membrane based on polysulfone resin or an ion exchange membrane based on fluororesin can be used,
For use at a high current density of 80 mA / cm 2 or more, the thickness of the ion exchange resin layer is preferably 20 μm to 150 μm. If the film is thinner than this, the cell resistance will be low, but it will be difficult to charge and discharge due to the strong liquid transfer between the positive and negative electrodes, and if it is thicker than this, the cell resistance will be too high to achieve the specified efficiency. Will be difficult.
【００１９】(5) 電極 本発明に使用される電極１２は、レドックスフロー型電
池に通常用いられる液透過性の多孔性電極であれば、い
ずれでも使用することができる。好ましい電極の例とし
ては、セルロース系の炭素繊維やＰＡＮ系の炭素繊維を
挙げることができる。(5) Electrode The electrode 12 used in the present invention may be any liquid-permeable porous electrode commonly used in redox flow type batteries. Examples of preferable electrodes include cellulose-based carbon fibers and PAN-based carbon fibers.
【００２０】（２）セルの構成 上記のバイポーラ板１、分液板６、パッキン９および隔
膜１１の各部材を、図１に示す順序の配列で集積して正
極室（または負極室）を構成し、一方、隔膜を挟んで対
称的に同様の構成の負極室（または正極室）を構成し
て、単位セルが形成される。さらに、該単位セルが複数
個、例えば２０〜３０個積層させることにより、電池の
内部抵抗を大幅に低減させ、高電流密度に最適で且つ量
産可能な積層型全バナジウムレドックス電池が提供され
る。(2) Structure of Cell A positive electrode chamber (or a negative electrode chamber) is formed by integrating the above-mentioned members of the bipolar plate 1, the liquid separating plate 6, the packing 9 and the diaphragm 11 in the order shown in FIG. On the other hand, a unit cell is formed by symmetrically forming a negative electrode chamber (or a positive electrode chamber) having the same structure with the diaphragm interposed therebetween. Further, by stacking a plurality of, for example, 20 to 30, the unit cells, it is possible to significantly reduce the internal resistance of the battery, provide a stacked all-vanadium redox battery that is suitable for high current density and can be mass-produced.
【００２１】本発明のセルでは、パッキン９によりバイ
ポーラ板１と分液板６と隔膜１１とがそれぞれ面タッチ
シールにより集積されるので、接着作業が不要である。
パッキン９の硬度とスリットの幅を上記範囲で適度に組
み合わせることにより、スリット５の内部にパッキンが
食い込んでスリットの径が変わるような事はなく、各セ
ルへの電解液の均等な配分を保証している。隔膜１１を
介しての正・負極液の混合は、分液板６の表と裏にスリ
ットを分けて刻み、分液板６の両面にフラットな面を必
ず残し、面シールする事によって完全に防いでいる。セ
ルの厚さは、パッキン９と分液板６の厚さの和であり、
これらを適宜組み合わせることにより、２．５ｍｍ以下
の最適のセル厚みを設定することができる。In the cell of the present invention, since the bipolar plate 1, the liquid separating plate 6 and the diaphragm 11 are integrated by the surface touch seal by the packing 9, the bonding work is unnecessary.
By appropriately combining the hardness of the packing 9 and the width of the slit within the above range, the packing will not bite into the inside of the slit 5 and the diameter of the slit will not change, and an even distribution of the electrolyte solution to each cell is guaranteed. are doing. Mixing the positive and negative electrode liquids through the diaphragm 11 is done by dividing the front and back of the liquid separating plate 6 into slits, leaving a flat surface on both surfaces of the liquid separating plate 6 and sealing the surfaces completely. It is preventing. The thickness of the cell is the sum of the thicknesses of the packing 9 and the liquid separating plate 6,
An optimum cell thickness of 2.5 mm or less can be set by appropriately combining these.
【００２２】[0022]
【実施例】以下、実施例及び比較例に基づいて、本発明
を具体的に説明する。 実施例１ 第１図に示したようなセル構成において、厚さ１００μ
ｍのポリスルホン系ポリマーから成るイオン交換膜１１
（旭硝子社製）、炭素繊維のフェルト状電極１２（面積
２０ｃｍ2）、ポリ塩化ビニルの外枠に同じ厚さのグラ
ッシーカーボン板から成るバイポーラ板１（厚さ１ｍ
ｍ）、エチレンープロピレンラバーのパッキン９（デュ
−ロ硬度Ａ９０，厚さ０．５ｍｍ）および厚さ１.５ｍ
ｍのポリ塩化ビニル製分液板６を集層して、セル厚さが
２.５ｍｍの電池セル（縦１５０ｍｍ及び横１１０ｍ
ｍ）を作製した。該分液板としては、図２〜４に示すよ
うに、外枠のコーナー部４箇所にマニホールド４（直径
１０ｍｍ）、その中央部にくりぬき部７（５０×５０ｍ
ｍ）、該マニホールドと該くりぬき部との中間に分液穴
８（２×１０ｍｍ）がそれぞれ穿設されており、さらに
３本のスリット５（深さ１．０ｍｍ、幅２.０ｍｍ、間
隔２．０ｍｍ）が、該分液板の表側には分液穴からくり
ぬき部へ向けて、及びその裏側には該マニホールドから
該分液穴へ向けて、それぞれ７ｍｍの長さで凹設されて
いるものを用いた。得られた電池セルを用いて８０mA/c
m2及び１００mA/cm2で充放電を実施した。その結果を表
−１に示す。EXAMPLES The present invention will be specifically described below based on Examples and Comparative Examples. Example 1 In the cell structure as shown in FIG.
ion-exchange membrane 11 composed of m polysulfone-based polymer
(Manufactured by Asahi Glass Co., Ltd.), a carbon fiber felt-like electrode 12 (area 20 cm 2 ), a bipolar plate 1 (thickness 1 m) made of a glassy carbon plate of the same thickness in an outer frame of polyvinyl chloride
m), ethylene-propylene rubber packing 9 (Duro hardness A90, thickness 0.5 mm) and thickness 1.5 m
m of polyvinyl chloride separator plates 6 are collected to form a battery cell having a cell thickness of 2.5 mm (length 150 mm and width 110 m).
m) was prepared. As the liquid separating plate, as shown in FIGS. 2 to 4, the manifold 4 (diameter 10 mm) is provided at four corners of the outer frame, and the hollow portion 7 (50 × 50 m) is provided at the center thereof.
m), a liquid separation hole 8 (2 × 10 mm) is provided in the middle between the manifold and the hollowed portion, and three slits 5 (depth 1.0 mm, width 2.0 mm, interval 2) are provided. 0.0 mm) is recessed on the front side of the liquid separating plate from the liquid separating hole to the hollowed-out portion and on the back side thereof from the manifold to the liquid separating hole with a length of 7 mm. I used one. 80mA / c using the obtained battery cell
Charge / discharge was performed at m 2 and 100 mA / cm 2 . The results are shown in Table-1.
【００２３】実施例２ ポリ塩化ビニル製の分液板の厚さを１.０ｍｍ、スリッ
トの深さを０.５ｍｍに変える以外は、実施例１と同じ
セル構成でセルの厚さが２ｍｍの電池セルを作製し、８
０mA/cm2及び１００mA/cm2で充放電を実施した。結果を
表−１に示す。Example 2 The same cell construction as in Example 1 except that the thickness of the polyvinyl chloride separator was changed to 1.0 mm and the slit depth was changed to 0.5 mm, and the cell thickness was 2 mm. Make a battery cell,
Charge and discharge were performed at 0 mA / cm 2 and 100 mA / cm 2 . The results are shown in Table 1.
【００２４】実施例３ 図５に示した深さ１.０ｍｍ、幅２.０ｍｍのスリットを
３本刻み込んだ厚さ１.５ｍｍのポリ塩化ビニル製分液
板を用いた以外は、実施例１と同じく充放電を行った。
結果を表−１に示す。Example 3 Example 1 was repeated except that a polyvinyl chloride separator having a thickness of 1.5 mm in which three slits having a depth of 1.0 mm and a width of 2.0 mm shown in FIG. 5 were engraved was used. It was charged and discharged in the same manner as in.
The results are shown in Table 1.
【００２５】実施例４ 隔膜を厚さ６０μｍのフッ素系ポリマーから成るイオン
交換膜（デユポン社製）を使用した以外は、実施例１と
同様な電池セルを作製し、充放電を実施した。結果を表
−１に示す。Example 4 A battery cell similar to that of Example 1 was prepared except that an ion-exchange membrane (manufactured by Dyupon Co., Ltd.) having a thickness of 60 μm and made of a fluoropolymer was used as the diaphragm, and charging / discharging was carried out. The results are shown in Table 1.
【００２６】実施例５ 隔膜を厚さ１２０μｍのフッ素系ポリマーから成るイオ
ン交換膜（デユポン社製）を使用した以外は、実施例１
と同様な電池セルを作製し、充放電を実施した。結果を
表−１に示す。Example 5 Example 1 was repeated except that an ion exchange membrane (manufactured by Dyupon) having a thickness of 120 μm and made of a fluoropolymer was used as the diaphragm.
A battery cell similar to that was prepared and charged and discharged. The results are shown in Table 1.
【００２７】[0027]
【表１】 [Table 1]
【００２８】比較例１ 従来から鉄-クロム系で使用されている３枚のポリ塩化
ビニル製の板を接着剤で張り付けたスリット一体型のセ
ルを用いて、実施例１と同様な充放電実験を行った。結
果を表−２に示す。外枠に炭素板をはめ込んでいる境界
面がパッキンで覆われていないため、電解液に直接触れ
シリコンペーストが劣化して液漏れが生じた。Comparative Example 1 A charge / discharge experiment similar to that of Example 1 was carried out using a slit-integrated cell in which three polyvinyl chloride plates, which have been conventionally used in an iron-chromium system, are attached with an adhesive. I went. Table 2 shows the results. Since the boundary surface in which the carbon plate was fitted in the outer frame was not covered with the packing, the silicon paste was directly contacted with the electrolytic solution and the silicon paste was deteriorated to cause liquid leakage.
【００２９】比較例２ 厚さ１.０ｍｍのエチレンープロピレンラバーパッキン
用いて、セル厚３.０ｍｍのセルを作製して使用した以
外は、実施例１と同様に行った。結果を表−２に示す。
セル厚を３.０ｍｍにすると効率は低下する。Comparative Example 2 The procedure of Example 1 was repeated, except that a cell having a cell thickness of 3.0 mm was prepared by using an ethylene-propylene rubber packing having a thickness of 1.0 mm. Table 2 shows the results.
If the cell thickness is 3.0 mm, the efficiency will decrease.
【００３０】比較例３ エチレンープロピレンラバーパッキンのデュ−ロ硬度Ａ
を７０にする以外は実施例１と同様に行った。結果を表
−２に示す。パッキンがスリット内部に食い込み電解液
が均一に流れず効率が低下した。Comparative Example 3 Duro hardness A of ethylene-propylene rubber packing
The same procedure as in Example 1 was performed except that the value was changed to 70. Table 2 shows the results. The packing bite into the slit and the electrolyte did not flow uniformly, resulting in a decrease in efficiency.
【００３１】[0031]
【表２】 [Table 2]
【００３２】[0032]
【発明の効果】本発明によれば、以下の効果が達成でき
る。 （1）バイポーラ板及びセルの厚さを薄くして、電池セ
ルの内部抵抗を大幅に低減できる。 （2）セルの制作過程で接着作業が不要となり、量産化
が可能である。 （3）バイポーラ板とスリットを有する分液板を分離す
ることにより、セルの組立、解体が容易となり、セルの
破損、スリットの目詰まり等の対応が簡単に出来る。 （4）特殊な切削加工が不要である。 （5）分液板のみを取り替えることで、スリット径及び
長さの異なるセルを作ることができ、セルの設計におい
て大幅な自由度が得られる。According to the present invention, the following effects can be achieved. (1) The internal resistance of the battery cell can be significantly reduced by reducing the thickness of the bipolar plate and the cell. (2) Adhesive work is not required in the cell production process, and mass production is possible. (3) By separating the bipolar plate and the separating plate having slits, the cell can be easily assembled and disassembled, and the cell damage and slit clogging can be easily handled. (4) No special cutting process is required. (5) By exchanging only the separating plate, cells with different slit diameters and lengths can be made, and a great degree of freedom in cell design can be obtained.
【図１】本発明の単一セルの正極室を構成する部材を示
す斜視説明図である。FIG. 1 is a perspective explanatory view showing members constituting a positive electrode chamber of a single cell of the present invention.
【図２】本発明の分液板の一例を示す平面説明図であ
る。FIG. 2 is a plan view showing an example of the liquid separating plate of the present invention.
【図３】本発明の分液板の表側表面に設けたスリット近
傍の拡大斜視説明図である。FIG. 3 is an enlarged perspective explanatory view of the vicinity of a slit provided on the front surface of the liquid separating plate of the present invention.
【図４】本発明の分液板の裏側表面に設けたスリット近
傍の拡大斜視説明図である。FIG. 4 is an enlarged perspective view illustrating the vicinity of a slit provided on the back surface of the liquid separating plate of the present invention.
【図５】本発明の分液板の他の例を示す平面説明図であ
る。FIG. 5 is an explanatory plan view showing another example of the liquid separating plate of the present invention.
【符号の説明】 １ バイポーラ板 ２ バイポーラ板の外枠 ３ 導電性板 ４ マニホールド ５ スリット ６ 分液板 ７ くりぬき部 ８ 分液穴 ９ パッキン １０ くりぬき部 １１ 隔膜 １２ 電極[Explanation of symbols] 1 bipolar plate 2 outer frame of bipolar plate 3 conductive plate 4 manifold 5 slit 6 liquid separating plate 7 hollowing part 8 liquid separating hole 9 packing 10 hollowing part 11 diaphragm 12 electrode
───────────────────────────────────────────────────── フロントページの続き (72)発明者 佐藤 完二 茨城県稲敷郡阿見町中央８丁目３番１号 鹿島北共同発電株式会社Ｖ電池開発室内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kanji Sato 8-3-1 Chuo, Ami-cho, Inashiki-gun, Ibaraki Kashima Kita Kyodo Power Co., Ltd. V battery development room
Claims (7)
れ、該電極をその外側から挟持するバイポーラ板により
構成される正極室及び負極室からなるセルを、該バイポ
ーラ板を介して交互に複数個積層して電気的に直列に接
続し、該セル内に設けられたマニホールドを通して複数
個の正極室及び負極室に５価／４価バナジウムからなる
正極電解液および２価／３価バナジウムからなる負極電
解液を通液し、酸化還元反応により充放電する電解液循
環型の全バナジウムレドックス電池において、樹脂製の
外枠の内部に導電性の板を嵌め込んだバイポーラ板と、
電解液をセルに循環させるためのマニホールド及びスリ
ットを有し且つ内部に電極が装入保持されるくりぬき部
を有する分液板と、隔膜とを、適度な剛性を有するパッ
キンを介して面シールにより集層させて厚さ２．５ｍｍ
以下の正極室又は負極室を形成し、その際該スリットは
該マニホールドと該くりぬき部の間に穿設された分液穴
を境に表と裏に凹設されていることを特徴とする全バナ
ジウムレドックス電池。1. A cell comprising a positive electrode chamber and a negative electrode chamber, which are composed of a bipolar plate in which a positive electrode and a negative electrode are disposed with a diaphragm interposed therebetween, and which sandwich the electrode from outside, alternate cells are disposed through the bipolar plate. A plurality of positive electrode electrolytes made of vanadium pentavalent and tetravalent vanadium in a plurality of positive electrode chambers and negative electrode chambers through a manifold provided in the cells and electrically connected in series. In passing through the negative electrode electrolyte consisting of, the electrolyte circulation type all-vanadium redox battery to charge and discharge by the oxidation-reduction reaction, a bipolar plate in which a conductive plate is fitted inside a resin outer frame,
A partition plate having a manifold and a slit for circulating the electrolytic solution into the cell and having a hollow portion in which an electrode is inserted and held, and a diaphragm are provided by a face seal via a packing having an appropriate rigidity. 2.5mm thick
The following positive electrode chamber or negative electrode chamber is formed, in which case the slit is recessed on the front side and the back side with a liquid separation hole formed between the manifold and the hollow portion as a boundary. Vanadium redox battery.
外枠と同一平面となるようにその内部に嵌め込まれてお
り、０．５〜１．５ｍｍの厚さを有するものである請求
項１記載の電池。2. The bipolar plate has a carbon plate fitted therein such that the carbon plate is flush with the outer frame, and has a thickness of 0.5 to 1.5 mm. Batteries.
０．５〜１．５ｍｍの溝状スリットを複数本有し、該ス
リットが分液穴とくりぬき部との間では表側（膜側）
に、マニホールドと分液穴との間では裏側に凹設された
樹脂製の板からなるものである請求項１記載の電池。3. The liquid separating plate has a plurality of groove-shaped slits having a width of 1 to 3 mm and a depth of 0.5 to 1.5 mm, and the slits are on the front side between the liquid separating hole and the hollow portion. Membrane side)
The battery according to claim 1, wherein the battery is formed of a resin plate recessed on the back side between the manifold and the liquid separation hole.
ロ硬度Ａ（ＪＩＳＫ６３０１）を有し、その厚さが０．
２〜１ｍｍのものである請求項１記載の電池。4. The packing has a Duro hardness A (JISK6301) of 80 to 100 and a thickness of 0.
The battery according to claim 1, which has a length of 2 to 1 mm.
することにより、正極室または負極室の厚さを２．５ｍ
ｍ以下にする請求項１記載の電池。5. The thickness of the positive electrode chamber or the negative electrode chamber is 2.5 m by adjusting the thickness of the packing and the liquid separating plate.
The battery according to claim 1, which is not more than m.
する耐酸性イオン交換膜である請求項１記載の電池。6. The battery according to claim 1, wherein the diaphragm is an acid-resistant ion exchange membrane having a thickness of 20 to 150 μm.
行われる請求項１記載の電池。7. The battery according to claim 1, which is charged and discharged at a high current density of 80 mA / cm 2 or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6140359A JPH087913A (en) | 1994-06-22 | 1994-06-22 | Full vanadium redox cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6140359A JPH087913A (en) | 1994-06-22 | 1994-06-22 | Full vanadium redox cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH087913A true JPH087913A (en) | 1996-01-12 |
Family
ID=15266995
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6140359A Pending JPH087913A (en) | 1994-06-22 | 1994-06-22 | Full vanadium redox cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH087913A (en) |
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