JPH0682759U - Current collector for zinc-bromine battery - Google Patents
Current collector for zinc-bromine batteryInfo
- Publication number
- JPH0682759U JPH0682759U JP022985U JP2298593U JPH0682759U JP H0682759 U JPH0682759 U JP H0682759U JP 022985 U JP022985 U JP 022985U JP 2298593 U JP2298593 U JP 2298593U JP H0682759 U JPH0682759 U JP H0682759U
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- Prior art keywords
- electrode
- frame member
- packing
- zinc
- plate
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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
- Y02E60/10—Energy storage using batteries
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- Cell Electrode Carriers And Collectors (AREA)
- Hybrid Cells (AREA)
Abstract
(57)【要約】
【目的】 熱応力及び外力に起因する集電電極の「反
り」を防止するとともに、集電電極自体の機械的強度を
大きくし、疲労破断を低減した亜鉛−臭素電池の集電電
極を提供することを目的とする。
【構成】 電極部が挿入される孔部17を有する絶縁枠
材16と、鉄板又はステンレス板22の適宜位置に開口
された多数の穴部22a内に充填、溶着された絶縁体で
なる金属−絶縁物一体型枠部材18と、この金属−絶縁
物一体型枠部材18とカーボンプラスチック電極15
a,15b,15c及び集電メッシュ6の積層体をヒー
トプレス手段により一体成形した電極部30とを具備し
て成り、前記絶縁枠材16の孔部17にパッキン19及
び補助シール機構31を介在して電極部30を挿入した
亜鉛−臭素電池の集電電極を提供する。
(57) [Abstract] [Purpose] A zinc-bromine battery that prevents "warpage" of the collecting electrode due to thermal stress and external force and increases the mechanical strength of the collecting electrode itself to reduce fatigue rupture. It is intended to provide a collecting electrode. An insulating frame member 16 having a hole 17 into which an electrode part is inserted, and a metal made of an insulator filled and welded in a large number of holes 22a opened at appropriate positions of an iron plate or a stainless plate 22- Insulator integrated frame member 18, the metal-insulator integrated frame member 18 and carbon plastic electrode 15
a, 15b, 15c, and an electrode portion 30 integrally formed of a laminated body of the current collecting mesh 6 by a heat pressing means, and a packing 19 and an auxiliary sealing mechanism 31 are provided in the hole portion 17 of the insulating frame member 16. Thus, the current collecting electrode of the zinc-bromine battery having the electrode part 30 inserted therein is provided.
Description
【0001】[0001]
本考案は電解液循環型積層二次電池、特に亜鉛−臭素電池の構成部材である集 電電極に関するものである。 The present invention relates to a collecting electrode which is a constituent member of an electrolyte circulating type laminated secondary battery, particularly a zinc-bromine battery.
【0002】[0002]
亜鉛−臭素電池は正極活物質に臭素、負極活物質に亜鉛を用いた2次電池であ り、この電池は例えば電力の昼と夜のアンバランスを解決させるために、電力需 要が少ない夜間に電力を貯蔵して、昼間に放出させるため等に使用される。 Zinc-bromine batteries are secondary batteries that use bromine as the positive electrode active material and zinc as the negative electrode active material. For example, this battery is used at night when power demand is low to solve the imbalance between day and night. It is used to store electricity and discharge it in the daytime.
【0003】 充電時に正極電極側で発生した臭素は、電解液に添加した臭素錯化剤と反応し 、オイル状の沈殿物となって貯蔵タンクへ戻され、放電時はポンプで単電池内へ 送り込まれ還元される。電解液の成分はZnBr2水溶液と、抵抗を下げるため のNH4Cl等の塩と、負極亜鉛側のデンドライトを防止し、均一な電着を促進 させるためのPb,Sn,4級アンモニウム塩類と、臭素錯化剤とである。正極 電極と負極電極の間にはセパレータを介挿してあり、正極電極で発生した臭素が 負極電極へ拡散して亜鉛と反応することによる自己放電を防止している。Bromine generated on the positive electrode side at the time of charging reacts with the bromine complexing agent added to the electrolytic solution to be returned as an oily precipitate to the storage tank, and at the time of discharging it is pumped into the unit cell. It is sent and returned. The components of the electrolytic solution are a ZnBr 2 aqueous solution, a salt such as NH 4 Cl for reducing the resistance, and Pb, Sn, and quaternary ammonium salts for preventing dendrite on the negative electrode zinc side and promoting uniform electrodeposition. , With a bromine complexing agent. A separator is inserted between the positive electrode and the negative electrode to prevent self-discharge due to the bromine generated in the positive electrode diffusing into the negative electrode and reacting with zinc.
【0004】 この亜鉛−臭素電池の化学反応は、The chemical reaction of this zinc-bromine battery is
【0005】[0005]
【化1】 充電時……正極:2Br-→Br2+2e-,負極:Zn+++2e-→Zn 放電時……正極:2Br-←Br2+2e-,負極:Zn+++2e-←Zn で表される。[Chemical Formula 1] During charging: Positive electrode: 2Br − → Br 2 + 2e − , Negative electrode: Zn ++ + 2e − → Zn During discharging: Positive electrode: 2Br − ← Br 2 + 2e − , Negative electrode: Zn ++ + 2e − ← Zn It is represented by.
【0006】 この亜鉛−臭素電池は、主に電極をバイポーラ型とし、複数個の単電池(単セ ル)を電気的に直列に積層した電池本体と、電解液貯蔵槽と、これらの間に電解 液を循環させるポンプおよび配管系とで構成されている。This zinc-bromine battery is mainly of a bipolar type and has a battery main body in which a plurality of cells (cells) are electrically stacked in series, an electrolytic solution storage tank, and a space between them. It consists of a pump and a piping system that circulates the electrolyte.
【0007】 図6は上記亜鉛−臭素電池を構成する電池本体の一例を示す分解斜視図であり 、矩形平板状のバイポーラ型中間電極1の電極部1aの外周に絶縁性の枠体1b が配置され、同様に矩形平板状のセパレータ板2は、セパレータ3の外周に枠体 2aが形成されている。そして上記中間電極1にセパレータ板2及び必要に応じ てパッキン4,スペーサメッシュ5を重ねて単セルを構成し、この単セルを複数 個積層して電池本体が構成されている。FIG. 6 is an exploded perspective view showing an example of a battery body constituting the above zinc-bromine battery, in which an insulating frame 1b is arranged on the outer periphery of an electrode portion 1a of a bipolar plate-shaped intermediate electrode 1 having a rectangular flat plate shape. Similarly, in the separator plate 2 having a rectangular flat plate shape, the frame body 2 a is formed on the outer periphery of the separator 3. The separator plate 2 and, if necessary, the packing 4 and the spacer mesh 5 are stacked on the intermediate electrode 1 to form a single cell, and a plurality of the single cells are laminated to form a battery body.
【0008】 積層された電池本体の両端部には、集電メッシュ6を有する集電電極7と、一 対の締付端板8と、その内側に位置する押さえ用の積層端板9とが配置されてい る。そして両締付端板8,8間に図示しないボルトを通して、このボルトを締め 付けることにより、一体的に積層固定された電池本体が構成される。A collector electrode 7 having a collector mesh 6, a pair of tightening end plates 8 and a stacking end plate 9 for pressing, which is located inside the collector electrodes 7, are provided at both ends of the stacked battery bodies. It is arranged. Then, a bolt (not shown) is passed between both the tightening end plates 8 and 8 to fasten the bolt to form a battery body integrally laminated and fixed.
【0009】 上記のように構成された電池本体の各単セル内には、各中間電極1及びセパレ ータ板2の枠体2aの上下2箇所の隅角部に形成した正極マニホールド10と、 負極マニホールド11より、セパレータ板2の枠体2aに設けられたチャンネル 12及びマイクロチャンネル13を介して電解液が夫々流入排出する。In each unit cell of the battery main body configured as described above, a positive electrode manifold 10 formed at two upper and lower corners of the intermediate electrode 1 and the frame body 2 a of the separator plate 2, The electrolyte solution flows in and out from the negative electrode manifold 11 through the channels 12 and the microchannels 13 provided in the frame body 2a of the separator plate 2, respectively.
【0010】 このように構成された亜鉛−臭素電池は、50KW級電池における電池効率と して約80%、総合エネルギー効率として約70%が確認されている。It has been confirmed that the zinc-bromine battery configured as described above has a battery efficiency of about 80% in a 50 KW class battery and an overall energy efficiency of about 70%.
【0011】 上記の集電電極7は、図7,図8に示したようにシート状絶縁枠材16に形成 された孔部17内にカーボンプラスチック電極15を組み込み、図外の金型を利 用して所定の温度と圧力条件下でのヒートプレス手段に基づいて一体化して製造 される。このヒートプレスの条件として、例えば150℃,55kg/cm2が 採用される。カーボンプラスチック電極15は、ポリエチレンとカーボングラフ ァイトを混合して成形した部材であり、臭素に対する耐腐食性を有している。As shown in FIGS. 7 and 8, the current collecting electrode 7 has a carbon plastic electrode 15 incorporated in a hole 17 formed in a sheet-shaped insulating frame member 16, and a metal mold not shown is used. It is manufactured integrally by using a heat pressing means under predetermined temperature and pressure conditions. As conditions for this heat press, for example, 150 ° C. and 55 kg / cm 2 are adopted. The carbon plastic electrode 15 is a member formed by mixing polyethylene and carbon graphite, and has corrosion resistance against bromine.
【0012】 6はカーボンプラスチック電極15中に一体に組み込まれた真ちゅう製の集電 メッシュであり、該集電メッシュ6から導出された電力取出用の端子片6aは、 絶縁枠材16に形成されたスリット14を通って外方に導き出され、図外の集電 ブスバーに連結されている。図中の矢印Aは電池本体における背面側を、矢印B は接液側を夫々示している。Reference numeral 6 denotes a brass current collecting mesh integrally incorporated in the carbon plastic electrode 15, and the terminal piece 6 a for extracting electric power, which is derived from the current collecting mesh 6, is formed on the insulating frame member 16. It is led out through the slit 14 and is connected to a current collecting bus bar (not shown). Arrow A in the figure indicates the back side of the battery body, and arrow B indicates the liquid contact side.
【0013】[0013]
しかしながらこのような従来の亜鉛−臭素電池に用いられている集電電極7の 場合、電解液に対する背面側Aと接液側Bとの材質の相違に基づいて熱収縮率と か線膨張係数に差が生じてしまうことが避けられず、特に温度低下時には、上記 熱収縮率の差によってシート状絶縁枠材16に「そり」が生じてしまい、集電電 極の平面性が低下する惧れが生じる。 However, in the case of the current collecting electrode 7 used in such a conventional zinc-bromine battery, the thermal contraction rate and the linear expansion coefficient are determined based on the difference in material between the back side A and the liquid contact side B with respect to the electrolytic solution. It is unavoidable that a difference occurs, and especially when the temperature decreases, the sheet-like insulating frame member 16 may "warp" due to the difference in the heat shrinkage ratio, which may reduce the flatness of the current collector electrode. Occurs.
【0014】 集電電極7の平面性が低下すると、前記の図6で説明したように、電池本体を 構成する締付端板間8,8をボルトを用いて締め付けた際に、集電電極7の界面 から液漏れが生じ易くなり、蓄えられた電力の損失が生じてしまうという難点が 発生する。この液漏れをなくすためにボルトによる締付力を強力にすると、界面 に集中する応力によって構成部材に前記クラックが生じ易くなるという問題点が ある。When the flatness of the collector electrode 7 is reduced, as described in FIG. 6 above, when the clamp end plates 8, 8 constituting the battery body are tightened with bolts, the collector electrode 7 The liquid easily leaks from the interface of No. 7 and the stored electric power is lost. If the tightening force of the bolts is increased in order to eliminate this liquid leakage, there is a problem in that the stress concentrated on the interface easily causes the cracks in the constituent members.
【0015】 上記の対策として、通常ボルトに皿ばねを取り付けて荷重変化を最小限にする 手段が用いられているが、温度変化に基づく膨張変位を吸収することが出来ない ため、締付圧の上昇に伴うクリープにより、時間遅れの破断が生じる惧れがあり 、クラック防止対策として必ずしも充分であるとは言えないという問題が残って いる。As a countermeasure against the above, a means for attaching a disc spring to a bolt to minimize a load change is usually used. However, since the expansion displacement due to a temperature change cannot be absorbed, a tightening pressure There is a risk of time-delayed rupture due to creep associated with rising, and it remains a problem that it cannot be said to be sufficient as a crack prevention measure.
【0016】 上記絶縁枠材16は、通常ポリエチレン樹脂にタルクを混合したものが用いら れており、純粋のポリエチレン樹脂に比して破断時の「伸び」は小さく、これが 上記クラックが生じる原因ともなっている。The insulating frame member 16 is generally made of a mixture of polyethylene resin and talc, and has a smaller “elongation” at break than a pure polyethylene resin, which also causes the cracks. ing.
【0017】 更にカーボンプラスチック電極15は、導電性を高めるために前記したように ポリエチレンとカーボングラファイトを混合して成形した部材であるため、無機 フィラーが多量に含まれており、絶縁枠材16との溶着性が悪い上、電極自体が 固くてもろいという性質があって外力による機械歪に対する追従性に欠け、前記 クラックが発生したり、破断が生じ易い要因ともなっている。Further, since the carbon plastic electrode 15 is a member formed by mixing polyethylene and carbon graphite as described above in order to enhance the conductivity, it contains a large amount of inorganic filler, and the insulating frame member 16 and In addition to its poor weldability, the electrode itself has the property of being hard and brittle, so that it lacks followability to mechanical strain due to an external force, and is a factor that cracks and breaks easily occur.
【0018】 又、集電電極7には、ポンプの圧力によりカーボンプラスチック電極側から押 さえ付ける正圧と、電解液の液抜きの際に発生するカーボンプラスチックを引っ 張る負圧とが交互にかかるため、疲労破断に対する配慮が要求される。Further, the collector electrode 7 is alternately applied with a positive pressure which is pressed from the carbon plastic electrode side by the pressure of the pump and a negative pressure which is generated when the electrolytic solution is drained and which pulls the carbon plastic. Therefore, consideration for fatigue fracture is required.
【0019】 本考案は上記の点に鑑みてなされたものであり、集電電極の熱収縮に起因する そり現象と、このそり現象に起因する電解液の液洩れ等の特性不良を誘発する原 因をなくし、且つ抗疲労性を高めた亜鉛−臭素電池の集電電極を提供することを 目的とするものである。The present invention has been made in view of the above points, and causes a warp phenomenon caused by thermal contraction of a current collecting electrode and a characteristic defect such as electrolyte leakage caused by the warp phenomenon. It is an object of the present invention to provide a current collecting electrode for a zinc-bromine battery that eliminates the cause and has improved anti-fatigue properties.
【0020】[0020]
本考案は上記目的を達成するために、矩形平板状の中間電極にセパレータ板を 重ねて単セルを形成し、この単セルを複数個積層して電池本体を構成するととも に、該電池本体の両端部に、一対の集電電極と締付端板を配置し、両締付端板間 をボルト締めすることによって一体的に積層固定するようにした亜鉛−臭素電池 の集電電極において、電極部が挿入される孔部を有する絶縁枠材と、鉄板の適宜 位置に開口された多数の穴部内に充填、溶着された絶縁体でなる金属−絶縁物一 体型枠部材と、この金属−絶縁物一体型枠部材とカーボンプラスチック電極及び 集電メッシュの積層体をヒートプレス手段により一体成形した電極部とを具備し て成り、前記絶縁枠材の孔部にパッキン及び補助シール機構を介在して電極部を 挿入した亜鉛−臭素電池の集電電極の構成にしてある。上記鉄板に代えてステン レス板を用いることもできる。 In order to achieve the above object, the present invention forms a single cell by stacking a separator plate on a rectangular flat plate-shaped intermediate electrode, and stacks a plurality of the single cells to form a battery main body. A pair of collector electrodes and a clamp end plate are arranged at both ends, and the clamp electrodes are clamped together by bolts between the clamp end plates so that they are integrally laminated and fixed. Frame member having a hole into which a part is inserted, a metal-insulator integrated frame member made of an insulator filled and welded in a large number of holes opened at appropriate positions of an iron plate, and this metal-insulation And a carbon plastic electrode, and an electrode part integrally formed by a heat press means with a laminated body of a carbon plastic electrode, and a packing and an auxiliary seal mechanism interposed in the hole of the insulating frame material. Zinc with electrode inserted- It is the structure of the collecting electrode of the unit cell. A stainless plate may be used instead of the iron plate.
【0021】 上記補助シール機構は、絶縁枠材の孔部に沿って立ち上がるパッキンリブと、 このパッキンリブの上部に嵌合された側面パッキンと、該側面パッキンの上部に 配置された押え板とから構成され、上記パッキンリブ,側面パッキン及び押え板 の各接合部を断面V字形にしてある。更に前記鉄板の所定位置から背面側に突出 する複数本のボルトを設け、絶縁枠材の所定位置には上記ボルトが螺合可能なナ ット穴を穿設してある。The auxiliary seal mechanism includes a packing rib standing up along the hole of the insulating frame member, a side packing fitted to the upper part of the packing rib, and a holding plate arranged above the side packing. The packing rib, the side packing, and the pressing plate are connected to each other in a V-shaped cross section. Further, a plurality of bolts protruding from a predetermined position of the iron plate to the back side are provided, and a nut hole into which the bolt can be screwed is formed at a predetermined position of the insulating frame member.
【0022】[0022]
かかる集電電極によれば、カーボンプラスチックと金属−絶縁物一体型枠部材 を主体とする電極部と、絶縁枠材とが実質的に別体として構成されており、パッ キン及び補助シール機構を用いたボルトの締付力によって両者の液密性性が保持 される。従って熱収縮等に起因する集電電極の「そり」の発生が防止され、この ようなそりによる電解液の液漏れと、過度なボルト締め付けに基づくクラックの 発生及び電極部と絶縁枠材の破断が生じないという作用が得られる。 According to such a collecting electrode, the electrode part mainly composed of the carbon plastic and the metal-insulator integrated frame member and the insulating frame member are configured as substantially separate bodies, and the packing and the auxiliary seal mechanism are formed. The tightening force of the bolts used maintains the liquid tightness of both. Therefore, the occurrence of “warpage” of the collecting electrode due to heat shrinkage, etc. is prevented, the electrolyte leaks due to such warpage, the occurrence of cracks due to excessive bolt tightening and the breakage of the electrode part and insulating frame material. The effect of not occurring is obtained.
【0023】 補助シール機構として、パッキンリブと該パッキンリブの上部に嵌合された側 面パッキン及び押え板とを採用し、且つ各接合部は上下面ともに断面V字形とし たことにより、絶縁枠材と電極部との液密性をより高めることができる。As the auxiliary sealing mechanism, a packing rib and a side packing and a pressing plate fitted to the upper part of the packing rib are adopted, and the upper and lower surfaces of each joint are V-shaped in cross section. The liquid tightness between the material and the electrode portion can be further enhanced.
【0024】 又、電極部中に比較的厚みの大きな金属−絶縁物一体型枠部材が介在している ため、得られた集電電極自体の機械的強度が高くなり、集電電極に対する正圧と 負圧とが交互にかかることによる疲労破断を低減する作用がある。Further, since the metal-insulator integrated frame member having a relatively large thickness is interposed in the electrode part, the mechanical strength of the obtained current collecting electrode itself is increased, and the positive pressure to the current collecting electrode is increased. This has the effect of reducing fatigue rupture due to the alternating application of negative pressure and negative pressure.
【0025】 金属−絶縁物一体型枠部材を構成する鉄板に代えてステンレス板を用いたこと により、上記作用に加えてステンレス板自体の持つ耐腐食性によって電解液に含 まれる臭素による集電電極の腐食が効率的に防止される。By using a stainless steel plate in place of the iron plate that constitutes the metal-insulator integrated frame member, in addition to the above-mentioned action, the corrosion resistance of the stainless steel plate itself collects electricity due to bromine contained in the electrolytic solution. Corrosion of the electrodes is effectively prevented.
【0026】[0026]
以下図面を参照しながら本考案にかかる亜鉛−臭素電池の集電電極の具体的な 実施例を、前記図7,図8に示した構成部分と同一の構成部分に同一の符号を付 して詳述する。 Hereinafter, referring to the drawings, a specific embodiment of a current collecting electrode of a zinc-bromine battery according to the present invention will be described in which the same components as those shown in FIGS. Detailed description.
【0027】 図1は本実施例にかかる集電電極7の構造を示す要部分解断面図である。図中 の15a,15aは厚さ1mmのカーボンプラスチック電極であり、この2枚の カーボンプラスチック電極15a,15aの背面側Aに真ちゅう製の集電メッシ ュ6が配置され、更に該集電メッシュ6の背面側Aに厚さ1mmのカーボンプラ スチック電極15bが配置されている。FIG. 1 is an exploded cross-sectional view of an essential part showing the structure of the collector electrode 7 according to this embodiment. In the figure, 15a and 15a are carbon plastic electrodes having a thickness of 1 mm, and a brass current collecting mesh 6 is arranged on the back side A of these two carbon plastic electrodes 15a and 15a. A carbon plastic electrode 15b having a thickness of 1 mm is arranged on the back side A of the.
【0028】 そして上記カーボンプラスチック電極15bの背面側Aには、本考案の特徴的 構成部材の一つである金属−絶縁物一体型枠部材18が配置されており、且つ該 金属−絶縁物一体型枠部材18の背面側Aにカーボンプラスチック電極15cと テフロン製のパッキン19が配置されている。このパッキン19に代えてフッ素 ゴム製のOリングを用いることもできる。On the back side A of the carbon plastic electrode 15b, a metal-insulator integrated frame member 18, which is one of the characteristic constituent members of the present invention, is arranged, and A carbon plastic electrode 15c and a Teflon packing 19 are arranged on the back side A of the body frame member 18. An O-ring made of fluororubber can be used instead of the packing 19.
【0029】 16は該パッキン19の背面側Aに配置された絶縁枠材である。この絶縁枠材 16には電極部が挿入される孔部17が形成され、且つ該絶縁枠材16の所定位 置には、金属−絶縁物一体型枠部材18から突出するボルト24,24が螺合可 能なナット穴25,25が穿設されている。Reference numeral 16 is an insulating frame member arranged on the back side A of the packing 19. A hole 17 into which an electrode portion is inserted is formed in the insulating frame member 16, and bolts 24, 24 protruding from the metal-insulator integrated frame member 18 are provided at predetermined positions of the insulating frame member 16. Nut holes 25, 25 that can be screwed are provided.
【0030】 上記の集電メッシュ6から取り出された端子片6aは、カーボンプラスチック 電極15b、金属−絶縁物一体型枠部材18、カーボンプラスチック電極15c 及びパッキン19から絶縁枠材16に予め開口された孔を通過して該絶縁枠材1 6の外方にまで導かれている。The terminal piece 6 a taken out from the current collecting mesh 6 is preliminarily opened in the insulating frame member 16 from the carbon plastic electrode 15 b, the metal-insulator integrated frame member 18, the carbon plastic electrode 15 c and the packing 19. It passes through the hole and is guided to the outside of the insulating frame member 16.
【0031】 上記の金属−絶縁物一体型枠部材18の具体的な構造を、図2の接液側平面図 と図3の背面側平面図を併用して説明する。即ち、この金属−絶縁物一体型枠部 材18は、外周部分に位置する絶縁性の枠体21と、この枠体21によって包囲 された位置にあって、多数の穴部22aが開口された鉄板22と、上記穴部22 a内に充填された状態として一体に溶着された絶縁体23と、鉄板22の所定位 置から背面側A方向に突出する複数本のボルト24,24(図示例では4本)と によって構成されている。本実施例では、金属−絶縁物一体型枠部材18の厚さ は5mm以上となっている。又、鉄板22に代えてステンレス板を用いることも 可能である。A specific structure of the metal-insulator integrated frame member 18 will be described with reference to the liquid contact side plan view of FIG. 2 and the back side plan view of FIG. That is, the metal-insulator-integrated frame member 18 has an insulative frame member 21 located in the outer peripheral portion and a position surrounded by the frame member 21, and a large number of holes 22a are opened. The iron plate 22, the insulator 23 integrally welded in a state of being filled in the hole 22a, and a plurality of bolts 24, 24 protruding from a predetermined position of the iron plate 22 in the rear side A direction (illustrated example). 4) and. In this embodiment, the metal-insulator integrated frame member 18 has a thickness of 5 mm or more. Further, it is possible to use a stainless plate instead of the iron plate 22.
【0032】 この金属−絶縁物一体型枠部材18は、集電電極7の組付に先立って、予め枠 体21の内方に穴部22aが開口された鉄板22を配置し、この鉄板22の穴部 22a内に絶縁体23を充填し、金型を利用して150℃,55kg/cm2程 度のヒートプレスを実施することにより、一体に溶着して予備製作してある。In this metal-insulator integrated frame member 18, an iron plate 22 having holes 22 a opened in advance is arranged inside the frame body 21 prior to the assembling of the collector electrode 7. The hole 23a is filled with the insulator 23 and heat-pressed at 150 ° C. and about 55 kg / cm 2 by using a mold to integrally weld and prefabricate.
【0033】 集電電極7の組付時には、先ず電極部を製作するために図外の金型を利用して カーボンプラスチック電極15a,15a、集電メッシュ6、カーボンプラスチ ック電極15b、金属−絶縁物一体型枠部材18及びカーボンプラスチック15 cを積層して、ヒートプレス手段、例えば150℃〜180℃,プレス圧力55 kg/cm2の条件で一体的に成形する。At the time of assembling the collector electrode 7, first, a metal mold (not shown) is used to manufacture the electrode portion. The carbon plastic electrodes 15a, 15a, the collector mesh 6, the carbon plastic electrode 15b, the metal- The insulator-integrated frame member 18 and the carbon plastic 15c are laminated and integrally molded under the conditions of heat pressing means, for example, 150 ° C. to 180 ° C. and a pressing pressure of 55 kg / cm 2 .
【0034】 図4は上記絶縁枠材16と電極部30の間に設けた補助シール機構31の構造 を示しており、この補助シール機構31は絶縁枠材16から孔部17に沿って立 ち上がるパッキンリブ33と、このパッキンリブ33の上部に嵌合された側面パ ッキン34と、該側面パッキン34の上部に配置された押え板35とから構成さ れている。側面パッキン34としてはフッ素系のゴム材が用いられる。FIG. 4 shows the structure of an auxiliary seal mechanism 31 provided between the insulating frame member 16 and the electrode section 30. The auxiliary seal mechanism 31 stands up from the insulating frame member 16 along the hole 17. The packing rib 33 is raised, the side packing 34 is fitted to the upper part of the packing rib 33, and the pressing plate 35 is arranged above the side packing 34. A fluorine-based rubber material is used for the side packing 34.
【0035】 上記パッキンリブ33は絶縁枠材16と一体成形され、側面パッキン34と押 え板35は別途に用意する。これらパッキンリブ33,側面パッキン34及び押 え板35の各接合部は、上下面ともに断面V字形となっていて、液密性を高めた 構成となっている。The packing rib 33 is formed integrally with the insulating frame member 16, and the side packing 34 and the holding plate 35 are separately prepared. Each of the joints of the packing rib 33, the side packing 34, and the holding plate 35 has a V-shaped cross section on both the upper and lower surfaces, and is configured to enhance liquid tightness.
【0036】 そして電極部30から突出するボルト24を、前記パッキン19を介在してナ ット穴25に挿入し、該ナット穴25に配置したナット26を用いて螺合固定す ることによって電極部30が絶縁枠材16の孔部17内に螺合固定された集電電 極7が得られる。図5は得られた集電電極7の平面図であり、図示したように中 心部に位置するカーボンプラスチック電極15aと絶縁枠材16とが補助シール 機構31を介在して液密状態に接合されている。Then, the bolt 24 protruding from the electrode portion 30 is inserted into the nut hole 25 with the packing 19 interposed therebetween, and is screwed and fixed by using the nut 26 arranged in the nut hole 25. The current collector 7 having the portion 30 screwed and fixed in the hole 17 of the insulating frame member 16 is obtained. FIG. 5 is a plan view of the obtained current collecting electrode 7. As shown in the drawing, the carbon plastic electrode 15a located at the center and the insulating frame member 16 are joined in a liquid-tight state with the auxiliary seal mechanism 31 interposed. Has been done.
【0037】 得られた集電電極7を電池本体に組み付ける場合には、前記図6に示す一対の 積層端板9の外側に位置する締付端板8,8間に通した図示しないボルトを締め 付けることにより、電極部30と絶縁枠材16が補助シール機構31の存在下で 液密下にシールされ、電解液に対する密閉性が良好に保持される。When the obtained collector electrode 7 is assembled to the battery body, a bolt (not shown) inserted between the tightening end plates 8 located outside the pair of laminated end plates 9 shown in FIG. 6 is used. By tightening, the electrode portion 30 and the insulating frame member 16 are liquid-tightly sealed in the presence of the auxiliary sealing mechanism 31, and the hermeticity with respect to the electrolytic solution is maintained well.
【0038】 従って本実施例によれば、カーボンプラスチック電極15a,15b,15c 及び金属−絶縁物一体型枠部材18を主体とする電極部と、絶縁枠材16とが補 助シール機構31を介して液密下に組付けられ、且つパッキン19を用いたボル トの締付力によってシール性を保持したことが大きな特徴となっている。Therefore, according to the present embodiment, the electrode portion mainly composed of the carbon plastic electrodes 15a, 15b, 15c and the metal-insulator integrated frame member 18 and the insulating frame member 16 are provided with the auxiliary seal mechanism 31 interposed therebetween. It is characterized in that it is assembled in a liquid-tight manner and the sealing performance is maintained by the tightening force of the bolt using the packing 19.
【0039】 本実施例にかかる集電電極7によれば、熱膨張率の異なる電極部30と絶縁枠 材16とが別体となっているため、熱収縮等に起因する集電電極7の「そり」現 象の発生が防止され、このような「そり」による電解液の液漏れとか、過度なボ ルト締め付けに基づくクラックの発生及び電極部と絶縁枠材の破断が生じないと いう作用が得られる。又、パッキン19としてテフロン製のものを採用すること により、臭素を含む電解液に対する耐腐食性が高められる。According to the current collecting electrode 7 of the present embodiment, the electrode portion 30 having a different coefficient of thermal expansion and the insulating frame member 16 are separate bodies, so that the current collecting electrode 7 caused by thermal contraction or the like is not formed. The function of preventing the occurrence of "warpage" and preventing the leakage of electrolyte due to such "warpage", the occurrence of cracks due to excessive bolt tightening, and the breakage of the electrode part and insulating frame material Is obtained. Further, by adopting the packing made of Teflon as the packing 19, the corrosion resistance to the electrolytic solution containing bromine can be enhanced.
【0040】 又、金属−絶縁物一体型枠部材18は、枠体21の内方に配置された鉄板22 の穴部22aに絶縁体23が充填されて一体に溶着されているため、カーボンプ ラスチック電極との界面接着接着が高められる上、鉄板22の存在に伴ってカー ボンプラスチック15a,15bとの溶着性が良好となる。Further, since the metal-insulator-integrated frame member 18 has the holes 23 a of the iron plate 22 arranged inside the frame body 21 filled with the insulator 23 and welded together, the carbon plastic The interfacial adhesion with the electrode is enhanced, and the presence of the iron plate 22 improves the weldability with the carbon plastics 15a and 15b.
【0041】 更に電極部を構成するカーボンプラスチック15a,15b,15cと金属− 絶縁物一体型枠部材18を構成する鉄板22との熱膨張率の相違によって前記「 そり」が生じることが考慮されるが、このような場合には、鉄板22の厚みをカ ーボンプラスチック電極15a,15b,15cの厚みよりも大きくすることに より、該カーボンプラスチック電極15a,15b,15cの熱膨張分が鉄板2 2に吸収され、前記そりが発生することが防止される。Further, it is considered that the “warpage” occurs due to the difference in thermal expansion coefficient between the carbon plastics 15a, 15b, 15c forming the electrode portion and the iron plate 22 forming the metal-insulator integrated frame member 18. However, in such a case, by making the thickness of the iron plate 22 larger than the thickness of the carbon plastic electrodes 15a, 15b, 15c, the thermal expansion amount of the carbon plastic electrodes 15a, 15b, 15c is increased. 2, so that the warpage is prevented from occurring.
【0042】 又、電極部中に比較的厚みの大きな金属−絶縁物一体型枠部材18が介在して いるので、得られた集電電極7自体の厚みが8mm以上となり、この厚みの増大 に伴って機械的強度が高くなるとともに鉄板22の内蔵によって全体的に剛体構 造が得られ、集電電極7に対するポンプによる正圧と負圧とが交互にかかること による疲労破断を低減する面から考慮しても有用である。Further, since the metal-insulator-integrated frame member 18 having a relatively large thickness is interposed in the electrode portion, the thickness of the obtained collector electrode 7 itself becomes 8 mm or more, which increases the thickness. Accordingly, the mechanical strength is increased, and a rigid structure is obtained as a whole by the built-in iron plate 22, which reduces fatigue rupture due to alternating positive and negative pressures applied to the collector electrode 7 by the pump. It is useful to consider.
【0043】 尚、前記鉄板22に代えてステンレスを用いた場合には、このステンレス自体 が鉄板よりも耐腐食性が高いため、電解液に含まれる臭素による集電電極の腐食 が効率的に防止されるという特有の作用が得られる。When stainless steel is used instead of the iron plate 22, this stainless steel itself has higher corrosion resistance than the iron plate, so that corrosion of the current collecting electrode due to bromine contained in the electrolytic solution is effectively prevented. The unique effect of being performed is obtained.
【0044】[0044]
以上詳細に説明したように、本考案にかかる亜鉛−臭素電池の集電電極によれ ば、カーボンプラスチックと金属−絶縁物一体型枠部材を主体とする電極部と、 絶縁枠材とが実質的に別体として構成されており、パッキン及び補助シール機構 を介在して電極部を絶縁枠材に固定することによって両者のシール性が保持され 、しかも熱収縮等に起因する集電電極の「そり」の発生がなくなり、電解液の液 漏れと、過度なボルト締め付けに基づくクラックの発生及び絶縁枠材の破断が生 じないという効果が得られる。特に絶縁枠材と電極部との間に補助シール機構と してパッキンリブと該パッキンリブの上部に嵌合された側面パッキン及び押え板 とを採用し、且つ各接合部は上下面ともに断面V字形としたことにより、絶縁枠 材と電極部との液密性をより高めることができる。 As described in detail above, according to the current collecting electrode of the zinc-bromine battery according to the present invention, the electrode portion mainly composed of carbon plastic and the metal-insulator integrated frame member and the insulating frame material are substantially formed. The electrode part is fixed to the insulating frame material with the packing and the auxiliary seal mechanism interposed, so that the sealability between the two is maintained, and the “sledding” of the current collecting electrode caused by heat shrinkage is caused. It is possible to obtain the effect that the occurrence of “” does not occur, the leakage of the electrolytic solution, the occurrence of cracks due to excessive bolt tightening and the breakage of the insulating frame material do not occur. In particular, a packing rib and a side packing and a pressing plate fitted on the upper part of the packing rib are used as an auxiliary sealing mechanism between the insulating frame member and the electrode section, and each joint has a cross-section V on both the upper and lower surfaces. By forming the character shape, the liquid tightness between the insulating frame member and the electrode portion can be further enhanced.
【0045】 又、電極部中に比較的厚みの大きな金属−絶縁物一体型枠部材が介在している ため、得られた集電電極自体の機械的強度が高くなり、集電電極に対する正圧と 負圧とが交互にかかることによる疲労破断を低減するという効果を発揮する。Further, since the relatively thick metal-insulator integrated frame member is interposed in the electrode portion, the mechanical strength of the obtained collecting electrode itself is increased, and the positive pressure to the collecting electrode is increased. This has the effect of reducing fatigue rupture due to the alternating application of negative pressure and negative pressure.
【0046】 他方で金属−絶縁物一体型枠部材を構成する鉄板に代えてステンレス板を用い たことにより、ステンレス板自体がの持つ耐腐食性によって電解液に含まれる臭 素による集電電極の腐食が防止可能であり、更に鉄板の所定位置から背面側に突 出する複数本のボルトと、絶縁枠材の所定位置に穿設したナット穴とにより、電 極部をパッキンを介在して絶縁枠材の孔部内に挿入た後にボルトをナット穴に螺 合することにより、集電電極自体に所望のシール性が確保されるという効果が得 られる。On the other hand, by using a stainless steel plate instead of the iron plate that forms the metal-insulator integrated frame member, the corrosion resistance of the stainless steel plate itself causes the collector electrode of the collector electrode due to the bromine contained in the electrolytic solution. Corrosion can be prevented, and the bolts projecting from the specified position on the iron plate to the back side and the nut holes drilled at the specified positions of the insulating frame material insulate the electrode part with the packing interposed. By inserting the bolt into the nut hole after inserting it into the hole of the frame member, it is possible to obtain a desired sealing property of the collector electrode itself.
【0047】 従って本考案によれば、集電電極の熱収縮に起因するそり現象と、このそり現 象に起因する電解液の液洩れ等の特性不良を誘発する原因をなくし、且つ機械的 強度を高めた亜鉛−臭素電池の集電電極が提供される。Therefore, according to the present invention, the warping phenomenon caused by the heat shrinkage of the current collecting electrode and the cause of the characteristic failure such as the electrolyte leakage due to the warping phenomenon are eliminated, and the mechanical strength is eliminated. There is provided a zinc-bromine battery current collecting electrode having enhanced electrical characteristics.
【図1】本考案にかかる亜鉛−臭素電池の集電電極を示
す要部分解断面図。FIG. 1 is an exploded cross-sectional view of an essential part showing a collector electrode of a zinc-bromine battery according to the present invention.
【図2】図1の構成要素である金属−絶縁物一体型枠部
材の接液側平面図。FIG. 2 is a plan view of the metal-insulator integrated frame member, which is a component of FIG. 1, on the liquid contact side.
【図3】図1の構成要素である金属−絶縁物一体型枠部
材の背面側平面図。3 is a rear side plan view of the metal-insulator integrated frame member which is a component of FIG. 1. FIG.
【図4】本実施例で採用した補助シール機構の構造を示
す要部拡大断面図。FIG. 4 is an enlarged sectional view of an essential part showing the structure of an auxiliary seal mechanism adopted in this embodiment.
【図5】本実施例により得られた集電電極の平面図。FIG. 5 is a plan view of a current collecting electrode obtained in this example.
【図6】亜鉛−臭素電池の電池本体を示す要部分解斜視
図。FIG. 6 is an exploded perspective view of essential parts showing a battery body of a zinc-bromine battery.
【図7】従来の集電電極の構造例を示す平面図。FIG. 7 is a plan view showing a structural example of a conventional collector electrode.
【図8】従来の集電電極の構造例を示す要部断面図。FIG. 8 is a cross-sectional view of an essential part showing a structural example of a conventional collector electrode.
6…集電メッシュ 6a…端子片 7…集電電極 15a,15b,15c…カーボンプラスチック電極 16…絶縁枠材 17…孔部 18…金属−絶縁物一体型枠部材 19…パッキン 21…枠体 22…鉄板 22a…穴部 23…絶縁体 24…ボルト 25…ナット穴 30…電極部 31…補助シール機構 33…パッキンリブ 34…側面パッキン 35…押え板 6 ... Current collecting mesh 6a ... Terminal piece 7 ... Current collecting electrode 15a, 15b, 15c ... Carbon plastic electrode 16 ... Insulating frame material 17 ... Hole part 18 ... Metal-insulator integrated frame member 19 ... Packing 21 ... Frame body 22 ... Iron plate 22a ... Hole 23 ... Insulator 24 ... Bolt 25 ... Nut hole 30 ... Electrode 31 ... Auxiliary sealing mechanism 33 ... Packing rib 34 ... Side packing 35 ... Holding plate
Claims (4)
重ねて単セルを形成し、この単セルを複数個積層して電
池本体を構成するとともに、該電池本体の両端部に、一
対の集電電極と締付端板を配置し、両締付端板間をボル
ト締めすることによって一体的に積層固定するようにし
た亜鉛−臭素電池の集電電極において、 電極部が挿入される孔部を有する絶縁枠材と、鉄板の適
宜位置に開口された多数の穴部内に充填、溶着された絶
縁体でなる金属−絶縁物一体型枠部材と、この金属−絶
縁物一体型枠部材とカーボンプラスチック電極及び集電
メッシュの積層体をヒートプレス手段により一体成形し
た電極部とを具備して成り、前記絶縁枠材の孔部にパッ
キン及び補助シール機構を介在して電極部を挿入した構
成を有することを特徴とする亜鉛−臭素電池の集電電
極。1. A rectangular flat plate-shaped intermediate electrode is laminated with a separator plate to form a single cell, and a plurality of the single cells are laminated to form a battery main body, and a pair of collectors are provided at both ends of the battery main body. In the collector electrode of the zinc-bromine battery, in which the electrode electrode and the tightening end plate are arranged, and the tightening end plates are bolted together to integrally fix them in layers, the hole where the electrode part is inserted An insulating frame member having a metal-insulator integrated frame member made of an insulator filled and welded in a large number of holes opened at appropriate positions of an iron plate, and the metal-insulator integrated frame member and carbon A structure in which a laminated body of a plastic electrode and a current collecting mesh is integrally formed by heat pressing means, and the electrode portion is inserted into the hole of the insulating frame member with a packing and an auxiliary sealing mechanism interposed. Zinc characterized by having The collector electrode of bromine battery.
に沿って立ち上がるパッキンリブと、このパッキンリブ
の上部に嵌合された側面パッキンと、該側面パッキンの
上部に配置された押え板とから構成され、上記パッキン
リブ,側面パッキン及び押え板の各接合部を断面V字形
とした請求項1記載の亜鉛−臭素電池の集電電極。2. The auxiliary seal mechanism is a packing rib that rises along a hole of an insulating frame member, a side packing fitted to an upper part of the packing rib, and a holding plate arranged above the side packing. The current collecting electrode for a zinc-bromine battery according to claim 1, wherein each of the joints of the packing rib, the side packing, and the pressing plate has a V-shaped cross section.
る複数本のボルトを設ける一方、絶縁枠材の所定位置
に、上記ボルトが螺合可能なナット穴を穿設したことを
特徴とする請求項1,2記載の亜鉛−臭素電池の集電電
極。3. A plurality of bolts protruding from a predetermined position of the iron plate to the back side are provided, and a nut hole into which the bolt can be screwed is formed at a predetermined position of the insulating frame member. The current collecting electrode of the zinc-bromine battery according to claim 1.
ことを特徴とする請求項1,2,3記載の亜鉛−臭素電
池の集電電極。4. The current collecting electrode for a zinc-bromine battery according to claim 1, wherein a stainless plate is used instead of the iron plate.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP022985U JPH0682759U (en) | 1993-04-30 | 1993-04-30 | Current collector for zinc-bromine battery |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP022985U JPH0682759U (en) | 1993-04-30 | 1993-04-30 | Current collector for zinc-bromine battery |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH0682759U true JPH0682759U (en) | 1994-11-25 |
Family
ID=12097845
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP022985U Pending JPH0682759U (en) | 1993-04-30 | 1993-04-30 | Current collector for zinc-bromine battery |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0682759U (en) |
-
1993
- 1993-04-30 JP JP022985U patent/JPH0682759U/en active Pending
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