JP2913885B2 - Lithium-manganese paper battery and conductive coating composition used therefor - Google Patents
Lithium-manganese paper battery and conductive coating composition used thereforInfo
- Publication number
- JP2913885B2 JP2913885B2 JP3091453A JP9145391A JP2913885B2 JP 2913885 B2 JP2913885 B2 JP 2913885B2 JP 3091453 A JP3091453 A JP 3091453A JP 9145391 A JP9145391 A JP 9145391A JP 2913885 B2 JP2913885 B2 JP 2913885B2
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- conductive coating
- paper battery
- terminal plate
- lithium
- 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
Description
【０００１】[0001]
【産業上の利用分野】本発明は、リチウム・マンガンペ
ーパー電池における正極端子板と正極合剤間の密着性を
高め、集電効果を向上してなるリチウム・マンガンペー
パー電池およびそれを使用する導電性塗料に関するもの
である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithium manganese paper battery having improved adhesion between a positive electrode terminal plate and a positive electrode mixture in a lithium manganese paper battery to improve a current collecting effect, and a conductive material using the same. It is related to a water-soluble paint.
【０００２】[0002]
【従来の技術】一般に、リチウム・マンガンペーパー電
池の構造は、図１に示すように、正極端子板１と正極合
剤２、セパレータ３、リチウム負極４、負極端子板５を
順次積層し、端子板の周縁部を封口剤６により封止密封
した電池である。2. Description of the Related Art In general, as shown in FIG. 1, a lithium manganese paper battery has a structure in which a positive electrode terminal plate 1, a positive electrode mixture 2, a separator 3, a lithium negative electrode 4, and a negative electrode terminal plate 5 are sequentially laminated. This is a battery in which the periphery of the plate is sealed and sealed with a sealing agent 6.
【０００３】しかしながら、この種のペーパー電池で
は、正極合剤と正極端子板との密着性が十分に得られ
ず、電池の内部抵抗が高くなるのが現状であった。However, in this type of paper battery, sufficient adhesion between the positive electrode mixture and the positive electrode terminal plate cannot be obtained, and the internal resistance of the battery has been increased at present.
【０００４】この密着性を改善するための従来の技術で
は、例えば導電性塗料を塗布することによって得られる
塗膜を正極合剤と正極端子板との間に介在させ、これを
介して両者を接着させ、その塗膜の導電性を利用して両
者間の電気的な導電性を高める方法が提案されている。
具体的な例としては、前記導電性塗料のバインダーとし
て、水ガラス系、フッ素系樹脂、ポリイミド系樹脂が用
いられ、これに導電性フィラーとして黒鉛を分散混合さ
せた塗料が用いられてきた。In a conventional technique for improving the adhesion, a coating film obtained by applying a conductive paint, for example, is interposed between a positive electrode mixture and a positive electrode terminal plate. A method has been proposed in which the film is adhered and the electric conductivity between the two is increased by utilizing the conductivity of the coating film.
As a specific example, a water glass-based, fluorine-based resin, or polyimide-based resin is used as a binder for the conductive paint, and a paint in which graphite is dispersed and mixed as a conductive filler has been used.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、これま
で提案されてきた導電性塗膜、特に水ガラス系導電性塗
料を用いた場合には、電池の屈曲が繰り返されたり、高
温で長期保存すると固着性が低下し、正極合剤と正極端
子板との剥離が発生し電池の内部抵抗が増加する等問題
があった。また、前記問題の改良としてポリイミド系樹
脂より成る導電性塗料（特開平２−２１３０５２号公
報）を用いた場合には、硬化処理時間が１８０〜２００
℃で５時間真空乾燥と高温、長時間の硬化条件が必要と
なり生産性に劣り、且つ正極端子板の材質を限定すると
いう問題点があった。However, in the case of using a conductive coating film that has been proposed so far, particularly a water glass-based conductive paint, the battery is repeatedly bent, or sticks when stored for a long time at a high temperature. However, there has been a problem in that, for example, the positive electrode mixture and the positive electrode terminal plate are separated and the internal resistance of the battery is increased. In order to solve the above problem, when a conductive paint made of a polyimide resin (Japanese Patent Application Laid-Open No. 2-130552) is used, the curing time is 180 to 200.
This requires vacuum drying at 5 ° C. for 5 hours and high-temperature and long-time curing conditions, resulting in poor productivity and limited material of the positive electrode terminal plate.
【０００６】本発明は以上の問題点を解決するものであ
って、リチウム・マンガンペーパー電池における正極合
剤と正極端子板が剥離せず、電池の内部抵抗が高くな
く、塗膜の可撓性、耐溶剤性に優れ、また生産性の良い
導電性塗料を提供するものである。The present invention has been made to solve the above problems, and the positive electrode mixture and the positive electrode terminal plate in the lithium manganese paper battery do not peel off, the internal resistance of the battery is not high, and the flexibility of the coating film is low. An object of the present invention is to provide a conductive paint having excellent solvent resistance and good productivity.
【０００７】[0007]
【課題を解決するための手段】本発明は、正極集電体を
兼用する金属端子板に、熱硬化性樹脂であるノボラック
型エポキシ樹脂、アミン系硬化剤をバインダーとし、導
電性カーボンを導電フィラーとして構成されているとこ
ろの導電性塗料を塗布し、熱により硬化させ、この上に
正極合剤を塗布させるものである。According to the present invention, a metal terminal plate also serving as a positive electrode current collector is provided with a novolak type epoxy resin as a thermosetting resin, an amine type curing agent as a binder, and a conductive carbon as a conductive filler. Is applied, and cured by heat, and a positive electrode mixture is applied thereon.
【０００８】本発明に係る導電性塗料組成物において、
カーボンとしては、導電性を与えるものとして、アセチ
レンブラック、ケッチェンブラック、ファーネスブラッ
ク等の導電性カーボンがあり、望ましくはケッチェンブ
ラックが好ましい。また、このカーボン量としては、有
機溶剤を除く全組成物１００重量部に対し４０〜５５重
量部の範囲が好ましい。カーボンの含有率が４０重量部
未満の場合、導電性が下がり、内部抵抗が大きくなる。
５５重量部より多いと、分散状態が悪くなり、塗膜とし
て形成しづらくなり、塗膜自身にひび割れが入るなどし
て正極端子板との密着性が悪くなる傾向にある。[0008] In the conductive coating composition according to the present invention,
Examples of carbon that impart conductivity include conductive carbon such as acetylene black, Ketjen black, and furnace black, and Ketjen black is preferable. The amount of carbon is preferably in the range of 40 to 55 parts by weight based on 100 parts by weight of the total composition excluding the organic solvent. If the carbon content is less than 40 parts by weight, the conductivity will decrease and the internal resistance will increase.
If the amount is more than 55 parts by weight, the dispersion state is deteriorated, it is difficult to form a coating film, and the coating film itself tends to be cracked and the adhesion to the positive electrode terminal plate tends to be poor.
【０００９】本発明の組成物を構成するバインダー用ノ
ボラック型エポキシ樹脂としては、重量平均分子量の範
囲として６００〜３０００の範囲が好ましい。また、こ
のバインダー用ノボラック型エポキシ樹脂は、全組成物
中有機溶剤を除く３０〜４０重量部の範囲で使用するの
が好ましい。このノボラック型エポキシ樹脂として、ク
レゾールノボラック型エポキシ樹脂、フェノールノボラ
ック型エポキシ樹脂が使用できる。The novolak type epoxy resin for a binder constituting the composition of the present invention preferably has a weight average molecular weight in the range of 600 to 3000. The novolak type epoxy resin for a binder is preferably used in the range of 30 to 40 parts by weight excluding the organic solvent in the whole composition. As the novolak epoxy resin, a cresol novolak epoxy resin or a phenol novolak epoxy resin can be used.
【００１０】また、アミン系硬化剤としては、メタフェ
ニレンジアミン、ジアミノジフェニルメタン、ジアミノ
ジフェニルスルフォン等が挙げられる。これらは、有機
溶剤を除く全組成物中１０〜２０重量部の範囲で使用す
ることが好ましい。この量が１０重量部未満であると、
硬化不足となり、２０重量部をこえると塗膜強度が弱く
なり、耐溶剤性、可撓性が悪くなる傾向にある。[0010] Examples of the amine-based curing agent include metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone and the like. These are preferably used in the range of 10 to 20 parts by weight in the total composition except for the organic solvent. If this amount is less than 10 parts by weight,
If the curing is insufficient, and if the amount exceeds 20 parts by weight, the strength of the coating film becomes weak, and the solvent resistance and the flexibility tend to deteriorate.
【００１１】分散剤としては、燐−窒素、燐−ホウ素、
ホウ素−窒素複合型または、アニオン活性剤、芳香族
系、アミン変成型樹脂、酸型顔料、アルカリ性顔料等が
挙げられ、全組成中５〜１０重量部の範囲で使用するの
が好ましい。As dispersants, phosphorus-nitrogen, phosphorus-boron,
Examples thereof include a boron-nitrogen composite type, an anionic activator, an aromatic type, an amine-modified resin, an acid type pigment, and an alkaline pigment, and it is preferable to use 5 to 10 parts by weight of the total composition.
【００１２】本発明に係る導電性塗料組成物は、メチル
エチルケトン、トルエン、シクロヘキサノン等の非プロ
トン系の有機溶剤を用いて溶液とする。The conductive coating composition according to the present invention is made into a solution using an aprotic organic solvent such as methyl ethyl ketone, toluene and cyclohexanone.
【００１３】また、その塗膜の塗布厚みとしては、１〜
２μｍが望ましく、これ以上であると、電池発電要素と
して内部抵抗が高くなるため容量の低下をもたらし、ま
た、１μｍ未満であると十分な密着性が得られず、可撓
性低下をもたらすので好ましくない。The coating thickness of the coating is 1 to
A thickness of 2 μm is desirable, and if it is more than 2 μm, the internal resistance is increased as a battery power generation element, resulting in a decrease in capacity. Absent.
【００１４】[0014]
【作用】以上のリチウム・マンガンペーパー電池にあっ
て、導電性塗料を用いることにより正極端子板に対する
正極合剤の密着性が高くなり、しかも柔軟であるから屈
曲の繰り返しによっても容易に正極合剤と正極端子板が
剥離すること無く、更に高温保存しても電池の内部抵抗
の上昇が極めて小さい。また、硬化条件がマイルドなた
め、生産性が向上し、かつ正極端子板の外装部にプラス
ッチックフィルムを使用した場合の加工範囲が広がる。In the above lithium-manganese paper battery, the use of a conductive paint enhances the adhesiveness of the positive electrode mixture to the positive electrode terminal plate, and is flexible, so that the positive electrode mixture can be easily formed by repeated bending. And the positive electrode terminal plate does not peel off, and the internal resistance of the battery rises very little even when stored at a higher temperature. In addition, since the curing conditions are mild, the productivity is improved, and the processing range when a plastic film is used for the exterior of the positive electrode terminal plate is widened.
【００１５】[0015]
【実施例】以下、実施例にて本発明をさらに詳細に説明
する。 実施例 バインダーであるノボラック型エポキシ樹脂（ダウ・ケ
ミカル社製 商品名Ｄ．Ｅ．Ｎ．４３１）３４重量部、
ジアミノジフェニルメタン１２重量部、アミン変成型分
散剤（ＩＣＩ社製 ＳＯＬＳＰＥＲＳＥ ２４０００）
６重量部、導電性カーボン（ＣＡＢＯＴ社製 Ｖｕｌｃ
ａｎ ＸＣ−７２Ｒ）４８重量部を溶剤（トルエン：メ
チルエチルケトン：シクロヘキサノン＝２：２：１）４
００重量部に分散混合して塗料を作成した。この塗料を
２μｍの厚みで、ＳＵＳ３０４箔（厚さ３０μｍ）に塗
布し、１５０℃／６０分の条件で硬化させた。この塗膜
特性は、下記方法によって測定した。The present invention will be described in more detail with reference to the following examples. Example 34 parts by weight of a novolak type epoxy resin (DOW Chemical Co., Ltd., trade name: DEN.431) as a binder,
12 parts by weight of diaminodiphenylmethane, modified amine dispersant (SOLSPERSE 24000 manufactured by ICI)
6 parts by weight, conductive carbon (Vulc manufactured by CABOT)
an XC-72R) 48 parts by weight with a solvent (toluene: methyl ethyl ketone: cyclohexanone = 2: 2: 1) 4
The mixture was dispersed and mixed in 00 parts by weight to prepare a paint. This paint was applied to a SUS304 foil (thickness: 30 μm) with a thickness of 2 μm, and cured at 150 ° C./60 minutes. The characteristics of the coating film were measured by the following method.
【００１６】１．硬化度 硬化した塗膜を、メチルエチルケトンを含浸させＪＫワ
イパー（商品名 十条キンバリー社製）にて荷重１００
ｇにて５０回のラビング試験を実施したが何ら異常を生
じなっかた。1. Curing degree The cured coating film is impregnated with methyl ethyl ketone, and a load of 100 is applied with a JK wiper (trade name, manufactured by Jujo Kimberly).
The rubbing test was performed 50 times with g, but no abnormality occurred.
【００１７】２．耐溶剤性 プライマーを塗布したＳＵＳ箔をプロピレンカーボネー
ト中で６０℃、２４時間ディップした後、クロスカット
しセロテープ剥離試験を行った結果、少しも剥離しなっ
かた。2. Solvent resistance After the primer-coated SUS foil was dipped in propylene carbonate at 60 ° C. for 24 hours, it was cross-cut and subjected to a cellophane tape peeling test. As a result, no peeling was observed.
【００１８】３．正極端子板と正極合剤の密着性 正極端子板であるＳＵＳ箔（３０μｍ厚）に導電性塗膜
を塗布し、硬化後その上に正極合剤を塗布硬化させた塗
膜を、ＪＩＳ Ｋ５４００に基づいて最小径での屈曲試
験を行った結果、塗膜はＳＵＳ箔から剥がれず良好な接
着性を示した。3. Adhesion between positive electrode terminal plate and positive electrode mixture A conductive film is applied to a SUS foil (30 μm thick), which is a positive electrode terminal plate, and after curing, a positive electrode mixture is applied and cured. As a result of performing a bending test with the minimum diameter based on the results, the coating film showed good adhesion without peeling off from the SUS foil.
【００１９】[0019]
【発明の効果】以上のように、本発明の導電性塗料を使
用することにより、正極端子板と正極合剤との密着性を
高めることができ、この塗膜は耐溶剤性，可撓性に優
れ、内部抵抗も低く、かつ硬化時間の短縮により生産性
が向上するため、リチウム・マンガンペーパー電池の製
造上、その効果は極めて大である。As described above, by using the conductive paint of the present invention, the adhesion between the positive electrode terminal plate and the positive electrode mixture can be increased, and this coating film has solvent resistance and flexibility. And the internal resistance is low, and the productivity is improved by shortening the curing time. Therefore, the effect is extremely large in the production of a lithium manganese paper battery.
【００２０】[0020]
図１はリチウム・マンガンペーパー電池の断面図であ
る。 符号の説明 １ 正極集電体を兼ねる金属端子板 ２ 正極合剤 ３ セパレータ ４ 負極リチウム ５ 負極集電体を兼ねる金属端子板 ６ 封口剤FIG. 1 is a sectional view of a lithium manganese paper battery. DESCRIPTION OF SYMBOLS 1 Metal terminal plate also serving as positive electrode current collector 2 Positive electrode mixture 3 Separator 4 Negative lithium 5 Metal terminal plate also serving as negative electrode current collector 6 Sealing agent
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.6，ＤＢ名) H01M 2/20 - 2/34 ──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. 6 , DB name) H01M 2/20-2/34
Claims (2)
剤間とに導電性塗膜を介在してなるリチウム・マンガン
ペーパー電池において、その導電性塗膜がバインダーと
してノボラック型エポキシ樹脂、硬化剤としてアミン系
硬化剤、導電フィラーとしてカーボンブラックよりなる
ことを特徴とするリチウム・マンガンペーパー電池。1. A lithium manganese paper battery having a conductive coating interposed between a metal terminal plate also serving as a positive electrode current collector and a positive electrode mixture, wherein the conductive coating is a novolac epoxy resin as a binder, A lithium manganese paper battery comprising an amine-based curing agent as a curing agent and carbon black as a conductive filler.
端子板と正極合剤間に設けられる導電性塗膜のための、
バインダーとしてノボラック型エポキシ樹脂、硬化剤と
してアミン系硬化剤、導電フィラーとしてカーボンブラ
ックよりなることを特徴とする導電性塗料組成物。2. A conductive coating film provided between a metal terminal plate and a positive electrode mixture of a lithium manganese paper battery,
A conductive coating composition comprising a novolak epoxy resin as a binder, an amine-based curing agent as a curing agent, and carbon black as a conductive filler.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3091453A JP2913885B2 (en) | 1991-03-29 | 1991-03-29 | Lithium-manganese paper battery and conductive coating composition used therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3091453A JP2913885B2 (en) | 1991-03-29 | 1991-03-29 | Lithium-manganese paper battery and conductive coating composition used therefor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04303562A JPH04303562A (en) | 1992-10-27 |
| JP2913885B2 true JP2913885B2 (en) | 1999-06-28 |
Family
ID=14026786
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3091453A Expired - Fee Related JP2913885B2 (en) | 1991-03-29 | 1991-03-29 | Lithium-manganese paper battery and conductive coating composition used therefor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2913885B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0662728B1 (en) * | 1993-12-29 | 1998-04-29 | TDK Corporation | Lithium secondary cell |
| FR2824418B1 (en) * | 2001-05-04 | 2005-05-27 | Conservatoire Nat Arts | REALIZATION OF CURRENT COLLECTORS FOR ELECTROCHEMICAL GENERATORS IN ORGANIC MEDIA |
-
1991
- 1991-03-29 JP JP3091453A patent/JP2913885B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04303562A (en) | 1992-10-27 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |