JP2967631B2 - Method for evaluating characteristics of carbon plastic electrode - Google Patents
Method for evaluating characteristics of carbon plastic electrodeInfo
- Publication number
- JP2967631B2 JP2967631B2 JP3322217A JP32221791A JP2967631B2 JP 2967631 B2 JP2967631 B2 JP 2967631B2 JP 3322217 A JP3322217 A JP 3322217A JP 32221791 A JP32221791 A JP 32221791A JP 2967631 B2 JP2967631 B2 JP 2967631B2
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- deformation
- carbon plastic
- battery
- amount
- 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.)
- Expired - Fee Related
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/96—Carbon-based electrodes
-
- 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
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Hybrid Cells (AREA)
- Inert Electrodes (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は亜鉛臭素電池等に用いら
れるカーボンプラスチック電極の特性評価方法に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for evaluating characteristics of a carbon plastic electrode used for a zinc bromine battery or the like.
【０００２】[0002]
【従来の技術】現在は電力貯蔵用電池として大容量の電
池が開発されている。電力貯蔵用電池のうち亜鉛臭素電
池は、正極活物質に臭素、負極活物質に亜鉛を用いた２
次電池である。電力の昼と夜の需要量のアンバランスを
解消させるために、夜間の予余電力を電池に貯蔵し、昼
間に放出するピークカット用の電池である。亜鉛臭素電
池の単セルの起電力は１．８Ｖであり、その電池反応は
次のように示される。2. Description of the Related Art At present, large capacity batteries are being developed as power storage batteries. Among power storage batteries, zinc bromine batteries use bromine for the positive electrode active material and zinc for the negative electrode active material.
Next battery. This is a peak-cut battery that stores nighttime surplus power in a battery and releases it during the day in order to eliminate the imbalance between daytime and nighttime power demands. The electromotive force of a single cell of the zinc bromine battery is 1.8 V, and the battery reaction is shown as follows.
【０００３】 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 この電池で使用している電極材料は、高密度ポリエチレ
ンをバインダーとして導電性をあたえる為にカーボンブ
ラック、グラファイトを混合して、シート化した電極を
用いている。また、正極表面は臭素の反応過電圧を減少
させるためにカーボンクロスを熱融着させて用いる。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 As the electrode material used in the battery, carbon black and graphite are mixed to give conductivity using high density polyethylene as a binder, and a sheeted electrode is used. In addition, a carbon cloth is heat-fused and used on the positive electrode surface in order to reduce the reaction overvoltage of bromine.
【０００４】電解液は、電池本体とは別置にして、充放
電時にポンプで循環させている。正極側で発生した臭素
は電解液中に添加してある臭素錯化合物（第４級アミ
ン）と反応してオイル状の沈澱物となり電解液タンクに
貯蔵され、放電時にポンプでセル内へ送り込まれ還元さ
れる。この電解液の成分としてはＺｎＢｒ2水溶液を用
い、この液抵抗を下げるためにＮＨ4Ｃｌ等の塩も含ま
れ、さらに負極側でのＺｎのデンドライドを抑制し、均
一なＺｎ電着を促進させるためにＰｂ，Ｓｎ，四級アン
モニウム塩，臭素錯化剤などが添加されている。なお、
正極と負極の間には、セパレータを用いて正極側で発生
した臭素が負極側へ拡散し、Ｚｎと自己放電するのを抑
制している。[0004] The electrolyte is circulated by a pump at the time of charging and discharging separately from the battery body. Bromine generated on the positive electrode side reacts with a bromine complex compound (quaternary amine) added to the electrolytic solution to form an oily precipitate, which is stored in the electrolytic solution tank, and pumped into the cell by a pump during discharging. Be reduced. As a component of the electrolytic solution, a ZnBr 2 aqueous solution is used, and a salt such as NH 4 Cl is also included to reduce the liquid resistance. Further, Zn dendride on the negative electrode side is suppressed, and uniform Zn electrodeposition is promoted. Therefore, Pb, Sn, a quaternary ammonium salt, a bromine complexing agent and the like are added. In addition,
Between the positive electrode and the negative electrode, a separator is used to suppress bromine generated on the positive electrode side from diffusing to the negative electrode side and self-discharging with Zn.
【０００５】[0005]
【発明が解決しようとする課題】この亜鉛臭素電池のエ
ネルギー効率は約８０％以上であるが、寿命としては約
５００サイクルである。この寿命は現在市販されている
鉛電池と比較すると約１／４である。上記の亜鉛臭素電
池において、５００サイクル終了後の電池を解体すると
電極板の変形（ワーページ）が非常に認められたが、電
極板の表面状態の荒れは認められなかった。又、電極板
の過電圧を測定した結果、未使用品に比べて約１０％の
過電圧増加が認められた。しかし、５００サイクルの電
池効率は、過電圧増加による電圧効率の低下よりも、ク
ーロン効率の低下の方が大きいと考えられる。このため
電池の寿命が短い理由は、電極板の変形によりワレが発
生し、部分的に正負極液が漏れて、亜鉛の自己放電量が
増加するためと考えられる。以上のことより、亜鉛臭素
電池の寿命を長くするためには、電極板のワーページ量
を減少させる事が重要である。The energy efficiency of this zinc bromine battery is about 80% or more, but its life is about 500 cycles. This service life is about one-fourth of that of currently available lead batteries. In the above zinc bromine battery, when the battery was disassembled after 500 cycles, the electrode plate was very deformed (warpage), but the surface condition of the electrode plate was not rough. Further, as a result of measuring the overvoltage of the electrode plate, an overvoltage increase of about 10% was observed as compared with the unused product. However, it is considered that the 500-cycle battery efficiency has a greater decrease in coulomb efficiency than a decrease in voltage efficiency due to an increase in overvoltage. It is considered that the reason why the life of the battery is short is that cracks occur due to deformation of the electrode plate, the positive and negative electrode solutions partially leak, and the self-discharge amount of zinc increases. From the above, it is important to reduce the amount of work pages of the electrode plate in order to extend the life of the zinc bromine battery.
【０００６】ここで現在の電極の特性評価方法には、例
えば図４のように電極板を治具で拘束して電解液中に入
れて強制的に変形させその変形量を測定する方法があ
る。図４において、水槽１内の水中に容器２と撹拌器３
を設け、容器２を電解液４で満たしその中にチタンフレ
ーム５で拘束された電極６を浸漬し、撹拌器３で水を撹
拌しながら温調器７によって水槽１内を一定温度に保
つ。Here, as a current method of evaluating the characteristics of an electrode, there is a method of, for example, restraining an electrode plate with a jig, forcing the electrode plate into an electrolytic solution and forcibly deforming the electrode plate as shown in FIG. 4, and measuring the amount of deformation. . In FIG. 4, a container 2 and a stirrer 3 are placed in water in a water tank 1.
The container 2 is filled with the electrolytic solution 4, the electrode 6 restrained by the titanium frame 5 is immersed in the electrolytic solution 4, and the temperature of the water tank 1 is maintained at a constant temperature by the temperature controller 7 while stirring the water with the agitator 3.
【０００７】しかしながら図４の方法では約２週間も浸
漬させる必要があるため、特性評価結果が得られるのに
あまりにも時間がかかり過ぎるという欠点があった。However, the method shown in FIG. 4 has a drawback that it takes too long to obtain a characteristic evaluation result because it is necessary to immerse for about two weeks.
【０００８】本発明は上記の点に鑑みてなされたもので
その目的は、極めて短い時間で電極の特性を評価するこ
とができるカーボンプラスチック電極の特性評価方法を
提供することにある。[0008] The present invention has been made in view of the above points, and an object of the present invention is to provide a method for evaluating the characteristics of a carbon plastic electrode, which can evaluate the characteristics of the electrode in a very short time.
【０００９】[0009]
【課題を解決するための手段】本発明は、カーボンプラ
スチック電極をチタンフレームで拘束して二重恒温槽の
内側槽に配設し、該二重恒温槽の内側槽を１３０℃で１
時間加熱し、該加熱後前記電極を放冷して電極の変形量
を測定し、該測定結果に基づいてカーボンプラスチック
電極の特性を評価することを特徴としている。According to the present invention, a carbon plastic electrode is constrained by a titanium frame and disposed in an inner bath of a double thermostat.
After heating, the electrode is allowed to cool, the amount of deformation of the electrode is measured, and the characteristics of the carbon plastic electrode are evaluated based on the measurement result.
【００１０】[0010]
【作用】従来のワーページ試験法における電極の変形の
主要因は電解液と温度であったが本発明による変形の要
因は温度のみに起因する。本発明のように加熱によるワ
ーページ試験を実施した場合でも、電極の変形度合いの
傾向は従来法と同様の傾向を示す。このため変形量の測
定結果から電極の特性（寿命等）を評価することができ
る。The main factors of the electrode deformation in the conventional warpage test method are the electrolyte and the temperature, but the factors of the deformation according to the present invention are caused only by the temperature. Even when a warpage test by heating is performed as in the present invention, the tendency of the degree of electrode deformation shows the same tendency as that of the conventional method. Therefore, the characteristics (lifetime and the like) of the electrode can be evaluated from the measurement result of the deformation amount.
【００１１】[0011]
【実施例】以下図面を参照しながら本発明の一実施例を
説明する。従来のワーページ試験（図４）での変形の主
要因としては、電解液と温度であったが、本発明による
新しいワーページ試験での主要因としては温度のみであ
る。この新ワーページ試験の方法は図２のように電極１
１をチタンフレーム１２で拘束したものを、図１に示す
二重恒温槽１３中で加熱するものである。図１において
二重恒温槽１３の外側槽１３ａ内には内側槽１３ｂ、ヒ
ータ１４、モータ１５により駆動されるファン１６が配
設されている。内側槽１３ｂには、前記チタンフレーム
付きの電極１１が収納されたビーカ１７が設けられてい
る。内側槽１３ｂの一方の側面はヒータ１４の熱がファ
ン１６の回転によりビーカ１７に伝達されやすいように
例えば格子状に形成されている。１８はビーカ１７のフ
タである。An embodiment of the present invention will be described below with reference to the drawings. The main factors of the deformation in the conventional warpage test (FIG. 4) were the electrolyte and the temperature, but the main factor in the new warpage test according to the present invention is only the temperature. The method of this new work page test is shown in FIG.
1 is restrained by a titanium frame 12, and is heated in a double thermostat 13 shown in FIG. In FIG. 1, an inner tank 13b, a heater 14, and a fan 16 driven by a motor 15 are disposed in an outer tank 13a of the double thermostat 13. The inner tank 13b is provided with a beaker 17 containing the electrode 11 with the titanium frame. One side surface of the inner tank 13b is formed, for example, in a lattice shape so that heat of the heater 14 is easily transmitted to the beaker 17 by rotation of the fan 16. Reference numeral 18 denotes a lid of the beaker 17.
【００１２】上記のように構成された装置において、ヒ
ータ１４，ファン１６を駆動させて二重恒温槽１３内を
１３０℃で１時間加熱する。そしてその後電極１１を二
重恒温槽１３から取り出して室温になるまで放冷する。
そのあとチタンフレーム１２を取外した後、電極１１の
変形量を計測する。ここで次の表１に示す組成の３つの
電極板（＃９０５０、＃９０６０、＃４３８３）を本実
施例により試験した結果、電極の変形量は表２のように
測定された。In the apparatus configured as described above, the heater 14 and the fan 16 are driven to heat the inside of the double thermostat 13 at 130 ° C. for one hour. Then, the electrode 11 is taken out of the double thermostat 13 and left to cool to room temperature.
Then, after removing the titanium frame 12, the deformation amount of the electrode 11 is measured. Here, three electrode plates (# 9050, # 9060, # 4383) having the compositions shown in the following Table 1 were tested according to the present example. As a result, the amount of deformation of the electrodes was measured as shown in Table 2.
【００１３】[0013]
【表１】 [Table 1]
【００１４】[0014]
【表２】 [Table 2]
【００１５】表２には３つの電極板について従来法（図
４の方法）によるワーページ試験を行った結果も記載さ
れているが、この表２によれば本実施例による測定結果
も従来法による測定結果も同様の傾向を示すことがわか
る。なお本実施例による方法では若干変形量が小さい
が、実用上問題はないと考えられる。前記電極の変形量
の測定は図３に示すように、カーボンプラスチック電極
１１をチタンフレーム１２より取り除き、ハイトゲージ
で電極の変形の一番高いところ（Ａ値）を測定し、その
一番高いところの電極の厚み（Ｂ値）を測定する。これ
ら測定値をもとに次の（１）式のように電極の変形量Ｃ
を求めるものである。Table 2 also shows the results of performing a warpage test on the three electrode plates by the conventional method (the method of FIG. 4). It can be seen that the measurement results of the above also show the same tendency. Although the amount of deformation is slightly small in the method according to the present embodiment, it is considered that there is no practical problem. As shown in FIG. 3, the amount of deformation of the electrode was measured by removing the carbon plastic electrode 11 from the titanium frame 12, measuring the highest point (A value) of the electrode deformation with a height gauge, and measuring the highest point. The thickness (B value) of the electrode is measured. Based on these measured values, the amount of electrode deformation C
Is what you want.
【００１６】Ｃ＝Ａ−Ｂ……（１）C = AB (1)
【００１７】[0017]
【発明の効果】以上のように本発明によればカーボンプ
ラスチック電極をチタンフレームで拘束して二重恒温槽
内で１３０℃、１時間加熱し、放冷後の電極の変形量を
測定するようにしたので、次のような優れた効果が得ら
れる。As described above, according to the present invention, a carbon plastic electrode is restrained by a titanium frame, heated at 130 ° C. for 1 hour in a double thermostat, and the amount of deformation of the electrode after cooling is measured. Therefore, the following excellent effects can be obtained.
【００１８】（１）従来法に比べて非常に短時間で特性
を評価することができる。例えば従来のように電解液中
に２週間浸漬する方法に比べると約３３６倍（２４ｈ×
１４＝３３６ｈ：１ｈ）速い。(1) The characteristics can be evaluated in a very short time as compared with the conventional method. For example, about 336 times (24 h ×
14 = 336h: 1h) Fast.
【００１９】（２）短時間評価であるため、品質管理等
に適用することができる。(2) Since it is a short-time evaluation, it can be applied to quality control and the like.
【００２０】（３）この新方法での主要因は１つ（温度
のみ）であるため特性解析がしやすい。(3) Since the main factor in this new method is one (only temperature), it is easy to analyze the characteristics.
【図１】本発明の方法を実施するための装置の一例を示
す構成図。FIG. 1 is a configuration diagram showing an example of an apparatus for performing a method of the present invention.
【図２】電極とチタンフレームの構成を示す説明図。FIG. 2 is an explanatory view showing a configuration of an electrode and a titanium frame.
【図３】電極の変形量の測定方法を示す説明図。FIG. 3 is an explanatory view showing a method for measuring the amount of deformation of an electrode.
【図４】従来の電極の特性評価方法を実施するための装
置の一例を示す構成図。FIG. 4 is a configuration diagram showing an example of an apparatus for implementing a conventional electrode characteristic evaluation method.
１１…カーボンプラスチック電極、１２…チタンフレー
ム、１３…二重恒温槽、１４…ヒータ、１５…モータ、
１６…ファン、１７…ビーカ、１８…フタ。11: carbon plastic electrode, 12: titanium frame, 13: double thermostat, 14: heater, 15: motor,
16 ... fan, 17 ... beaker, 18 ... lid.
Claims (1)
ームで拘束して二重恒温槽の内側槽に配設し、該二重恒
温槽の内側槽を１３０℃で１時間加熱し、該加熱後前記
電極を放冷して電極の変形量を測定し、該測定結果に基
づいてカーボンプラスチック電極の特性を評価すること
を特徴とするカーボンプラスチック電極の特性評価方
法。1. A carbon plastic electrode is restrained by a titanium frame and disposed in an inner bath of a double thermostat, and the inner bath of the double thermostat is heated at 130 ° C. for 1 hour. A method for evaluating the characteristics of a carbon plastic electrode, comprising allowing the electrode to cool, measuring the amount of deformation of the electrode, and evaluating the characteristics of the carbon plastic electrode based on the measurement result.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3322217A JP2967631B2 (en) | 1991-12-06 | 1991-12-06 | Method for evaluating characteristics of carbon plastic electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3322217A JP2967631B2 (en) | 1991-12-06 | 1991-12-06 | Method for evaluating characteristics of carbon plastic electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05159813A JPH05159813A (en) | 1993-06-25 |
| JP2967631B2 true JP2967631B2 (en) | 1999-10-25 |
Family
ID=18141260
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3322217A Expired - Fee Related JP2967631B2 (en) | 1991-12-06 | 1991-12-06 | Method for evaluating characteristics of carbon plastic electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2967631B2 (en) |
-
1991
- 1991-12-06 JP JP3322217A patent/JP2967631B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05159813A (en) | 1993-06-25 |
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