JP3168777B2 - Zinc-bromine battery electrodes - Google Patents
Zinc-bromine battery electrodesInfo
- Publication number
- JP3168777B2 JP3168777B2 JP20737093A JP20737093A JP3168777B2 JP 3168777 B2 JP3168777 B2 JP 3168777B2 JP 20737093 A JP20737093 A JP 20737093A JP 20737093 A JP20737093 A JP 20737093A JP 3168777 B2 JP3168777 B2 JP 3168777B2
- Authority
- JP
- Japan
- Prior art keywords
- carbon paper
- fiber
- carbon
- electrode
- zinc
- 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
-
- 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
Landscapes
- Inert Electrodes (AREA)
- Secondary Cells (AREA)
- Hybrid Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Fibers (AREA)
- Multicomponent Fibers (AREA)
- Paper (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は電力貯蔵用新型電池のＺ
ｎ−Ｂｒ2（亜鉛−臭素）２次電池の構成部材である、
正極活性層の構造に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a new type of power storage battery Z.
a constituent member of an n-Br 2 (zinc-bromine) secondary battery,
The present invention relates to a structure of a positive electrode active layer.
【０００２】[0002]
【従来の技術】亜鉛−臭素電池において、正極活性層は
電池効率に影響を与える重要なパーツの一つであり、従
来から多くの種類の材料が検討されてきた。その中で、
活性炭素繊維を素材としてアレンジされた成形体は、活
性炭素繊維の電気化学的触媒活性作用の効果で分極特性
が優れ、また、活性炭素繊維自体は炭化物のため耐薬性
が有るので、亜鉛−臭素電池には良く利用されてきた。
その中で活性炭クロスは現状最も使用されている材料で
ある。2. Description of the Related Art In a zinc-bromine battery, a positive electrode active layer is one of the important parts that affect battery efficiency, and many types of materials have been studied. inside that,
A molded article arranged using activated carbon fiber as a material has excellent polarization characteristics due to the effect of the electrochemical catalytic activity of the activated carbon fiber, and since activated carbon fiber itself has a chemical resistance due to carbides, zinc-bromine It has been widely used for batteries.
Among them, activated carbon cloth is currently the most used material.
【０００３】[0003]
【発明が解決しようとする課題】前記活性炭クロスは出
発原料となる樹脂繊維を紡糸、繊織して織布にし、それ
を賦活炉に通して炭化賦活させて作製されるために、繊
維強度が低下し、引っ張り、及び圧縮に対して非常に弱
く、押し出しラミネーションのような活性炭クロスをカ
ーボンプラスチック板に熱圧着して電極を成形する電極
製造工程においては、しばしば活性炭素粉が発生して作
業環境に悪影響を及ぼすばかりでなく、電極の残留炭素
粉が電池作動中に電解液循環に伴って電池内部に浮遊し
てマイクロチャンネルに滞留し、局部的に電解液流路を
遮断するトラブルが発生している。The activated carbon cloth is produced by spinning and weaving a resin fiber as a starting material into a woven fabric, which is passed through an activation furnace and activated by carbonization. In the electrode manufacturing process in which activated carbon cloth, such as extruded lamination, is thermocompressed to a carbon plastic plate to form an electrode, the active carbon powder is often generated due to the occurrence of activated carbon powder. In addition to the adverse effects on the battery, the residual carbon powder on the electrode floats inside the battery as the electrolyte circulates during battery operation and stays in the microchannel, causing a problem that the electrolyte flow path is locally blocked. ing.
【０００４】そこで、このような状況を打開するために
活性炭クロスの代替品としてカーボンペーパーを使用し
始めることになった。カーボンペーパーは活性炭素繊維
のチョップとバインダー樹脂繊維チョップを素材に用い
て妙紙されており、織布ではないので圧縮力には強く、
電極製造時の押し出しラミネーション工程においても炭
素粉の発生が少ない利点が有る。また、カーボンペーパ
ーには織布製造工程がないのでコストが安くなる利点も
ある。[0004] In order to overcome such a situation, carbon paper has begun to be used as a substitute for activated carbon cloth. Carbon paper is made using activated carbon fiber chops and binder resin fiber chops as materials.It is not a woven fabric, so it is strong against compressive force.
There is an advantage that the generation of carbon powder is small even in the extrusion lamination process at the time of manufacturing the electrode. In addition, carbon paper does not have a woven fabric manufacturing process, and thus has the advantage of reducing costs.
【０００５】しかしながら、カーボンペーパーは樹脂繊
維をバインダーに用いる分だけ全体に占める活性炭素繊
維の量が少ないので特性が低下し、またバインダーの種
類によっては臭素に攻撃され易く寿命が短いという欠点
がある。さらに大きな問題として、押し出しラミネーシ
ョン工程時のカーボンプラスチックがダイから押し出さ
れる高温度の環境で、その原形を保持するに十分耐えら
れ、尚且つ耐臭素性の有るバインダーが無い問題があ
る。[0005] However, carbon paper has a drawback that its properties are deteriorated because the amount of activated carbon fibers occupying in the whole is small because the resin fibers are used as a binder, and that the type of binder is susceptible to bromine depending on the type of binder and its life is short. . As a further big problem, there is a problem that there is no binder having sufficient resistance to retain its original shape in a high-temperature environment in which the carbon plastic is extruded from the die during the extrusion lamination process, and further has bromine resistance.
【０００６】本発明は上記の点に鑑みてなされたもので
その目的は、耐熱性と耐薬性を兼ね備えたカーボンペー
パーによって融着強度を高めた亜鉛−臭素電池の電極を
提供することにある。[0006] The present invention has been made in view of the above points, and an object of the present invention is to provide an electrode of a zinc-bromine battery in which the fusion strength is increased by using carbon paper having both heat resistance and chemical resistance.
【０００７】[0007]
【課題を解決するための手段】本発明はマトリックス樹
脂であるバインダーに、ポリエチレンテレフタレートを
芯とし、その外側をポリエチレンでコーティングした複
合樹脂繊維を用い、該複合樹脂繊維と活性炭素繊維とを
混合妙紙してカーボンペーパーを作製し、該カーボンペ
ーパーを正極活性層として用いたことを特徴としてい
る。According to the present invention, a composite resin fiber having a polyethylene terephthalate core as a core and a polyethylene coating on the outside thereof is used as a binder as a matrix resin, and the composite resin fiber and the activated carbon fiber are mixed. It is characterized in that carbon paper is produced by papermaking, and the carbon paper is used as a positive electrode active layer.
【０００８】[0008]
【作用】本発明のカーボンペーパーはポリエチレンテレ
フタレートの耐熱性とポリエチレンの耐薬性を両方兼ね
備えており、電極製造工程時に電極基板に均一にラミネ
ートされる。このため融着強度の高い正極活性層が成形
できる。The carbon paper of the present invention has both the heat resistance of polyethylene terephthalate and the chemical resistance of polyethylene, and is uniformly laminated on the electrode substrate during the electrode manufacturing process. For this reason, a positive electrode active layer having high fusion strength can be formed.
【０００９】[0009]
【実施例】本発明では当電池系における高濃度の臭素を
含む電解液に対して化学的に安定であり、尚且つ電極製
造工程の押し出しラミネーション時の熱圧着に耐えられ
るような、耐熱性があって耐臭素性のあるカーボンペー
パーを得るため、バインダーであるマトリックス樹脂の
材質を検討した。DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, the present battery system is chemically stable with respect to an electrolytic solution containing a high concentration of bromine and has heat resistance so as to withstand thermocompression bonding during extrusion lamination in an electrode manufacturing process. In order to obtain carbon paper with good bromine resistance, the material of the matrix resin as a binder was studied.
【００１０】その結果、ポリエチレンテレフタレート
（以下ＰＥＴと称する）を芯とし、その外側をポリエチ
レン（以下ＰＥと称する）で被服した複合合成繊維を用
いると良好であることが分かり、その複合合成繊維ファ
イバーと活性炭繊維を用いてペーパーに妙紙して、耐熱
及び耐臭素性のあるカーボンペーパーを得た。次にその
実施例を示す。[0010] As a result, it has been found that it is good to use a composite synthetic fiber having polyethylene terephthalate (hereinafter referred to as PET) as a core and the outside thereof coated with polyethylene (hereinafter referred to as PE). Activated carbon fiber was used to make paper, and carbon paper having heat and bromine resistance was obtained. Next, an embodiment will be described.
【００１１】ＰＥＴ製樹脂系にＰＥを塗布または浸漬に
よりコートした後、細断して得られた複合合成繊維ファ
イバーと比表面積１５００ｍ2／ｇの活性炭素繊維ファ
イバーを、重量比３０／７０で分散妙紙後乾燥熱プレス
して約０．６ｍｍ厚のカーボンペーパーＳを作製した。
このカーボンペーパーＳと、ＰＥ樹脂繊維をバインダー
に用いた従来のカーボンペーパーＵをそれぞれカーボン
プラスチック電極基板に押し出しラミネーションして電
極を作製した。After coating or dipping a PET resin system with PE, the composite synthetic fiber fiber obtained by shredding and activated carbon fiber fiber having a specific surface area of 1500 m 2 / g are dispersed at a weight ratio of 30/70. After the paper was dried and hot pressed, carbon paper S having a thickness of about 0.6 mm was produced.
The carbon paper S and the conventional carbon paper U using the PE resin fiber as a binder were respectively extruded and laminated on a carbon plastic electrode substrate to produce an electrode.
【００１２】これらのカーボンペーパーＳを用いた電極
ＳとカーボンペーパーＵを用いた電極Ｕの特性を比較し
た。表１はそれぞれのカーボンペーパーの電極基板から
の９０度引きはがし強度を比較したものである。The characteristics of the electrode S using the carbon paper S and the electrode U using the carbon paper U were compared. Table 1 compares the strength of peeling each carbon paper from the electrode substrate by 90 degrees.
【００１３】[0013]
【表１】 [Table 1]
【００１４】結果は、本発明の電極Ｓの方が電極Ｕより
も引きはがし強度が高い値を示している。カーボンペー
パーＳは、芯にＰＥＴを用いているために熱圧着時の熱
変形（熱収縮）が少なく、電極基板に均一に熱圧着され
るためである。一方、従来のカーボンペーパーＵはバイ
ンダーのＰＥ自体は電極基板に良く融着するが同時に熱
収縮も大きいので、電極基板に不均一にラミネートさ
れ、全体の融着強度としては小さくなったものである。The results show that the electrode S of the present invention has a higher peeling strength than the electrode U. This is because the carbon paper S uses PET for the core and therefore has little thermal deformation (thermal shrinkage) at the time of thermocompression bonding and is uniformly thermocompression bonded to the electrode substrate. On the other hand, in the conventional carbon paper U, the PE itself of the binder is fused well to the electrode substrate, but at the same time, the heat shrinkage is large, so that the laminate is unevenly laminated on the electrode substrate, and the overall fusion strength is reduced. .
【００１５】次に、耐臭素性を調べるためにこの２種類
の電極Ｕ，Ｓを高濃度電解液に浸漬させ、浸漬前後での
過電圧を測定した。測定電解液には、３Ｍ／ｌＺｎＢｒ
2＋０．１Ｍ／ｌＢｒ2を用いた。その結果を表２に示
す。Next, in order to examine the bromine resistance, the two types of electrodes U and S were immersed in a high-concentration electrolytic solution, and the overvoltage before and after immersion was measured. 3M / l ZnBr was used as the measurement electrolyte.
2 +0.1 M / lBr 2 was used. Table 2 shows the results.
【００１６】[0016]
【表２】 [Table 2]
【００１７】表２によれば４０℃、６０００時間の浸漬
前後で、両電極試料とも特に大きな変化は無く、耐薬的
にも問題が無いことが分かる。According to Table 2, before and after immersion at 40 ° C. for 6000 hours, there is no significant change in both electrode samples, and there is no problem in terms of chemical resistance.
【００１８】[0018]
【発明の効果】以上のように本発明によれば、マトリッ
クス樹脂であるバインダーに、ポリエチレンテレフタレ
ートを芯とし、その外側をポリエチレンでコーティング
した複合樹脂繊維を用い、該複合樹脂繊維と活性炭素繊
維とを混合妙紙してカーボンペーパーを作製し、該カー
ボンペーパーを正極活性層として用いたので、次のよう
な優れた効果が得られる。As described above, according to the present invention, a composite resin fiber having polyethylene terephthalate as a core and the outer side of which is coated with polyethylene is used as a binder which is a matrix resin. Was mixed to produce carbon paper, and the carbon paper was used as the positive electrode active layer, so that the following excellent effects were obtained.
【００１９】（１）本発明のカーボンペーパーは、ＰＥ
Ｔの耐熱性とＰＥの耐薬性を両方兼ね備えており、従来
のＰＥをバインダーに用いたカーボンペーパーの弱点で
あった、電極製造工程時の熱収縮性を解消して電極基板
に均一にラミネートされ、融着強度の高い正極活性層が
成形できるようになった。(1) The carbon paper of the present invention is made of PE
It has both the heat resistance of T and the chemical resistance of PE, and eliminates the weak point of carbon paper using conventional PE as a binder, eliminating the heat shrinkage during the electrode manufacturing process and uniformly laminating the electrode substrate. Thus, a positive electrode active layer having high fusion strength can be formed.
【００２０】（２）本発明のカーボンペーパーは、バイ
ンダー樹脂の外側がＰＥでコーティングされており、従
来のＰＥをバインダーに用いたカーボンペーパーと同様
に耐臭素性がある。高濃度電解液に長時間浸漬した後で
もその特性に変化は無く、当電池系の環境で充分に使用
可能である。(2) The carbon paper of the present invention is coated with PE on the outside of the binder resin, and has the same bromine resistance as conventional carbon paper using PE as a binder. Even after being immersed in a high-concentration electrolyte for a long time, there is no change in its characteristics, and it can be sufficiently used in the environment of this battery system.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平４−184868（ＪＰ，Ａ) 特開 平３−187158（ＪＰ，Ａ) 特開 平２−267866（ＪＰ，Ａ) 特開 昭62−211865（ＪＰ，Ａ) 特開 昭60−117559（ＪＰ，Ａ) 特開 平２−135668（ＪＰ，Ａ) 特開 平１−187772（ＪＰ，Ａ) 特開 平５−174839（ＪＰ，Ａ) 特開 平１−169876（ＪＰ，Ａ) 特開 昭59−163765（ＪＰ，Ａ) 特開 昭60−23963（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 4/86 - 4/98 D01F 8/14 D01F 9/14 512 D21H 13/50 H01M 12/08 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-4-184868 (JP, A) JP-A-3-187158 (JP, A) JP-A-2-267866 (JP, A) JP-A-62-162 211865 (JP, A) JP-A-60-117559 (JP, A) JP-A-2-135668 (JP, A) JP-A-1-187772 (JP, A) JP-A-5-174839 (JP, A) JP-A-1-169876 (JP, A) JP-A-59-163765 (JP, A) JP-A-60-23963 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) H01M 4/86-4/98 D01F 8/14 D01F 9/14 512 D21H 13/50 H01M 12/08
Claims (1)
ポリエチレンテレフタレートを芯とし、その外側をポリ
エチレンでコーティングした複合樹脂繊維を用い、該複
合樹脂繊維と活性炭素繊維とを混合妙紙してカーボンペ
ーパーを作製し、該カーボンペーパーを正極活性層とし
て用いたことを特徴とする亜鉛−臭素電池の電極。1. A binder which is a matrix resin,
Using a composite resin fiber having polyethylene terephthalate as a core and the outside coated with polyethylene, the composite resin fiber and activated carbon fiber were mixed to form a carbon paper to prepare a carbon paper, and the carbon paper was used as a positive electrode active layer. An electrode for a zinc-bromine battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20737093A JP3168777B2 (en) | 1993-08-23 | 1993-08-23 | Zinc-bromine battery electrodes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20737093A JP3168777B2 (en) | 1993-08-23 | 1993-08-23 | Zinc-bromine battery electrodes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0765841A JPH0765841A (en) | 1995-03-10 |
| JP3168777B2 true JP3168777B2 (en) | 2001-05-21 |
Family
ID=16538608
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20737093A Expired - Fee Related JP3168777B2 (en) | 1993-08-23 | 1993-08-23 | Zinc-bromine battery electrodes |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3168777B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8293390B2 (en) * | 2007-03-28 | 2012-10-23 | Redflow Pty Ltd | Cell stack for a flowing electrolyte battery |
| JP5443401B2 (en) * | 2011-01-21 | 2014-03-19 | 株式会社ノリタケカンパニーリミテド | Gas diffusion layer of polymer electrolyte fuel cell, membrane-electrode assembly including gas diffusion layer, method for producing gas diffusion layer, and slurry used for production of gas diffusion layer |
| JP5443413B2 (en) * | 2011-03-09 | 2014-03-19 | 株式会社ノリタケカンパニーリミテド | Gas diffusion layer of polymer electrolyte fuel cell, membrane-electrode assembly of polymer electrolyte fuel cell including gas diffusion layer, and slurry used for production of gas diffusion layer |
-
1993
- 1993-08-23 JP JP20737093A patent/JP3168777B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0765841A (en) | 1995-03-10 |
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| LAPS | Cancellation because of no payment of annual fees |