JPH07114911A - Organic electrolytic battery - Google Patents
Organic electrolytic batteryInfo
- Publication number
- JPH07114911A JPH07114911A JP28198093A JP28198093A JPH07114911A JP H07114911 A JPH07114911 A JP H07114911A JP 28198093 A JP28198093 A JP 28198093A JP 28198093 A JP28198093 A JP 28198093A JP H07114911 A JPH07114911 A JP H07114911A
- Authority
- JP
- Japan
- Prior art keywords
- battery
- resin
- gasket
- negative electrode
- heat resistance
- 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.)
- Granted
Links
Classifications
-
- Y02E60/12—
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Primary Cells (AREA)
- Battery Mounting, Suspending (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、非プロトン性の有機溶
媒液を電解液とするコイン型（ボタン型）有機電解質電
池に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coin type (button type) organic electrolyte battery using an aprotic organic solvent solution as an electrolytic solution.
【０００２】[0002]
【従来の技術】本願の出願人の出願にかかる特開昭６０
−１７０１６３号公報にはポリアセン系骨格構造を有す
る有機半導体を正極及び負極とし、非プロトン性の有機
溶媒液を電解液とする有機電解質電池が開示されてい
る。2. Description of the Related Art Japanese Unexamined Patent Application Publication No. Sho 60 (1999)
JP-A-170163 discloses an organic electrolyte battery in which an organic semiconductor having a polyacene skeleton structure is used as a positive electrode and a negative electrode, and an aprotic organic solvent solution is used as an electrolytic solution.
【０００３】該電池においては、電池の気密、液密、お
よび正・負極缶の絶縁を保つガスケットの材質が極めて
重要である。従来ガスケット材質としては、耐薬品性、
弾力性、耐クリープ性にすぐれ、成形性がよく、射出成
形可能で安価なポリプロピレンが用いられてきた。In the battery, the material of the gasket that keeps the airtightness, the liquidtightness of the battery and the insulation of the positive and negative electrode cans is extremely important. Conventional gasket materials have chemical resistance,
Polypropylene, which has excellent elasticity and creep resistance, has good moldability, can be injection-molded, and is inexpensive, has been used.
【０００４】該電池の正・負極缶、セパレータ、ポリア
セン系骨格構造を有する有機半導体および電解液は、融
点あるいは沸点がいずれも高く耐熱性がすぐれている。
しかし、ガスケットに用いているポリプロピレンは耐熱
温度が低く、そのため従来の電池は耐熱性が劣るという
欠点を有していた。The positive and negative electrode cans, separators, organic semiconductors having a polyacene-based skeleton structure and electrolytes of the battery have high melting points or boiling points and excellent heat resistance.
However, the polypropylene used for the gasket has a low heat resistance temperature, so that the conventional battery has a drawback that the heat resistance is inferior.
【０００５】コイン型（ボタン型）有機電解質電池は、
主にメモリーバックアップ電源として用いられている。
その場合、該電池にハンダ付用の端子を溶接した後、メ
モリー素子とともにプリント基板上にハンダ付されるこ
とが多い。従来、プリント基板上へのハンダ付は、ハン
ダこてを用いて行なわれていたが、機器の小型化あるい
は高機能化にともない、プリント基板の同一面積内に搭
載される電子部品を多くする必要が生じハンダ付のため
にハンダこてを挿入する隙間を確保することが困難とな
ってきた。The coin type (button type) organic electrolyte battery is
Mainly used as a memory backup power supply.
In that case, after soldering the terminals for soldering to the battery, it is often soldered on the printed circuit board together with the memory element. Conventionally, soldering onto a printed circuit board has been performed using a soldering iron, but with the downsizing and higher functionality of equipment, it is necessary to increase the number of electronic components mounted in the same area of the printed circuit board. It has become difficult to secure a gap for inserting a soldering iron due to soldering.
【０００６】そこであらかじめプリント基板上のハンダ
付を行なう部分にハンダを塗布しておきその部分に部品
を載置するか、あるいは、部品を載置後ハンダ小球をハ
ンダ付部分に供給し、ハンダ付部分がハンダの融点以
上、例えば、２００〜２３０℃となるように設定された
高温雰囲気の炉内に部品を搭載したプリント基板を通過
させることにより、ハンダを溶融させてハンダ付を行な
う方法が用いられている（以下リフローハンダ付とい
う）。従来のポリプロピレンからなるガスケットを用い
たコイン型（ボタン型）有機電解質電池では、リフロー
ハンダ付時にポリプロピレンが融解あるいは変形し、ス
テンレス鋼あるいはアルミニウムからなる正・負極缶が
接して短絡するという問題点があった。Therefore, solder is applied in advance to the portion to be soldered on the printed circuit board and the component is placed on the portion, or after the component is placed, solder globules are supplied to the soldered portion and solder is applied. A method of melting the solder by passing the printed board on which the parts are mounted through a printed circuit board in a furnace in a high temperature atmosphere set so that the soldered portion has a melting point of the solder or higher, for example, 200 to 230 ° C. Used (hereinafter referred to as with reflow solder). The problem with coin-type (button-type) organic electrolyte batteries using gaskets made of conventional polypropylene is that polypropylene is melted or deformed when reflow soldering is applied, and positive and negative electrode cans made of stainless steel or aluminum come into contact and short-circuit. there were.
【０００７】耐熱性の改善のためには、耐熱性にすぐれ
たポリアミド系樹脂からなるガスケットを使用すること
が有効であるが、ポリアミド系樹脂は吸湿性が高く、有
機電解質電池の耐湿性が低下するという問題点があっ
た。In order to improve the heat resistance, it is effective to use a gasket made of a polyamide resin having excellent heat resistance, but the polyamide resin has a high hygroscopic property and the moisture resistance of the organic electrolyte battery is lowered. There was a problem to do.
【０００８】[0008]
【発明が解決しようとする課題】本発明者等は、上記し
た問題点を解決するために、従来のポリプロピレンから
なるガスケットの替りに、ポリアミド系樹脂からなるガ
スケットを、正極及び／又は負極がポリアセン系骨格構
造を有する有機半導体からなるコイン型（ボタン型）有
機電解質電池に用いるとともに、該電池を連続使用温度
100℃以上の熱可塑性樹脂のケース内で熱硬化性樹脂に
てモールドすることにより耐熱性が向上してリフローハ
ンダ付が可能となるとともに耐湿性が改善されることを
見出した。SUMMARY OF THE INVENTION In order to solve the above-mentioned problems, the present inventors have used a gasket made of polyamide resin instead of the conventional gasket made of polypropylene, and a positive electrode and / or a negative electrode made of polyacene. Used in coin-type (button-type) organic electrolyte batteries made of organic semiconductors having a system skeleton structure
It was found that by molding with a thermosetting resin in a thermoplastic resin case of 100 ° C or higher, heat resistance is improved, reflow soldering is possible and moisture resistance is improved.
【０００９】[0009]
【課題を解決するための手段】すなわち、本発明は、正
極、負極、セパレータ、ガスケットを備えて非プロトン
性の有機溶媒液を電解液に用いた有機電解質電池におい
て、正極及び／又は負極がポリアセン系骨格構造を有す
る有機半導体からなるとともにガスケットがポリアミド
系樹脂からなり、かつ連続使用温度 100℃以上の熱可塑
性樹脂のケース内に熱硬化性にてモールドすることを特
徴とするコイン型（ボタン型）有機電解質電池である。Means for Solving the Problems That is, the present invention provides an organic electrolyte battery comprising a positive electrode, a negative electrode, a separator and a gasket and using an aprotic organic solvent solution as an electrolytic solution, wherein the positive electrode and / or the negative electrode is polyacene. Coin type (button type) characterized by being made of an organic semiconductor having a system skeleton structure, a gasket made of polyamide type resin, and thermosetting in a case of a thermoplastic resin with a continuous use temperature of 100 ° C or higher ) An organic electrolyte battery.
【００１０】本発明の電池は、第１図に示すように、正
極缶１と負極缶６の内底部に導電性ペースト３，３’が
塗布され、ポリアセン系有機半導体からなるシート２，
２’が該導電性ペースト３，３’と接触するように正極
缶１と負極缶６に挿入されセパレータ５を介して相対向
している。ガスケット４は正極缶１と負極缶６とにより
圧縮され、気密性、液密性および正・負極缶の絶縁を保
持し、電解液は一部は、ポリアセン系有機半導体からな
るシート２，２’中の空隙にあり、一部は空間７にあっ
てもよい。In the battery of the present invention, as shown in FIG. 1, the conductive pastes 3, 3'are applied to the inner bottom portions of the positive electrode can 1 and the negative electrode can 6 to form a sheet 2 made of a polyacene-based organic semiconductor.
The positive electrode can 1 and the negative electrode can 6 are inserted so that 2 ′ is in contact with the conductive pastes 3, 3 ′ and face each other via the separator 5. The gasket 4 is compressed by the positive electrode can 1 and the negative electrode can 6 to maintain airtightness, liquid tightness, and insulation of the positive and negative electrode cans, and the electrolytic solution is a sheet 2, 2 ′ partially made of a polyacene-based organic semiconductor. It may be in the void inside and partly in the space 7.
【００１１】熱硬化性樹脂８は、正・負極缶表面を完全
に被覆しており、これがケース11に収容されている。正
極端子９と負極端子10は、正極缶１、負極缶６にそれぞ
れ抵抗溶接あるいはレーザー溶接され、一部は熱硬化性
樹脂８の外部に露出している。正極缶及び負極缶は慣用
のものであり、例えば、ステンレス又はアルミニウム製
である。セパレータは電池あるいはコンデンサーにおい
て慣用のもので、例えば多孔性合成樹脂フイルム、無機
繊維を樹脂で固めたもの、紙などであり、好ましくはガ
ラス繊維不織布からなる。The thermosetting resin 8 completely covers the surface of the positive and negative electrode cans, and this is housed in the case 11. The positive electrode terminal 9 and the negative electrode terminal 10 are resistance-welded or laser-welded to the positive electrode can 1 and the negative electrode can 6, respectively, and are partially exposed to the outside of the thermosetting resin 8. The positive electrode can and the negative electrode can are conventional ones, for example, stainless steel or aluminum. The separator is commonly used in batteries or capacitors, and is, for example, a porous synthetic resin film, a resin obtained by hardening inorganic fibers with a resin, paper or the like, and preferably made of glass fiber nonwoven fabric.
【００１２】有機電解液は、非プロトン性の有機溶媒に
よってイオンを生成する塩を溶解させた溶液である。通
常この種の有機電解質電池の電解液としては、溶媒とし
て、プロピレンカーボネート、γ−ブチロラクトン等の
非プロトン性有機溶媒が好ましく用いられまた塩として
テトラアルキルアンモニウム塩、例えば、The organic electrolytic solution is a solution in which a salt which produces ions is dissolved in an aprotic organic solvent. Usually, as an electrolytic solution of this type of organic electrolyte battery, aprotic organic solvents such as propylene carbonate and γ-butyrolactone are preferably used as a solvent, and a tetraalkylammonium salt as a salt, for example,
【化１】 （Ｒ1 ，Ｒ2 ，Ｒ3 及びＲ4 はアルキル基を示し、Ｒ1
〜Ｒ4 は同一でも異なっていてもよい。ＸはＣｌＯ4 又
はＢＦ4 を示す）が好ましく用いられる。塩は通常0.5
〜1.5 モル／ｌの濃度範囲で上記した溶媒に溶解し、電
解液として供される。[Chemical 1] (R1, R2, R3 and R4 represent an alkyl group, R1
~ R4 may be the same or different. X is ClO 4 or BF 4 ) is preferably used. Salt is usually 0.5
It is dissolved in the above-mentioned solvent in a concentration range of up to 1.5 mol / l and used as an electrolytic solution.
【００１３】端子は、電池あるいはコンデンサーにおい
て慣用のものであり例えばステンレス鋼ニッケルなどで
あり、好ましくは正・負極缶と同材質のステンレス鋼か
らなる。本発明で用いるポリアセン系骨格構造を有する
有機半導体自体は公知であり、例えば特開昭６１−２１
８０６０号公報に記載されている。該有機半導体を、ボ
ールミル等を用いて粉砕して粉末とし、この粉末に結着
材と導電材を加え、混合した後、加圧成形してポリアセ
ンシートとし正極あるいは／かつ負極とする。The terminal is commonly used in batteries or capacitors, and is, for example, stainless steel nickel or the like, and is preferably made of stainless steel of the same material as the positive and negative electrode cans. The organic semiconductor itself having a polyacene skeleton structure used in the present invention is known, and is disclosed in, for example, JP-A 61-21.
No. 8060. The organic semiconductor is pulverized using a ball mill or the like to obtain powder, and a binder and a conductive material are added to the powder, mixed, and then pressure-molded to form a polyacene sheet to be a positive electrode and / or a negative electrode.
【００１４】ガスケットは、正・負極缶の間にあり、正
・負極缶の絶縁を保つとともに、電池の気密、液密を保
持するために用いられている。その材質としては、非プ
ロトン性の有機溶媒液に対する耐薬品性があること、お
よび正・負極缶の間に載置されて圧縮されるために、弾
力性、耐クリープ性がすぐれている必要がある。さら
に、成形性がよく大量生産に適する射出成形可能である
ことがより好ましい。The gasket is located between the positive and negative electrode cans, and is used to maintain the insulation of the positive and negative electrode cans and to keep the battery air-tight and liquid-tight. As its material, it must have chemical resistance to an aprotic organic solvent liquid, and it must be excellent in elasticity and creep resistance because it is placed between the positive and negative electrode cans and compressed. is there. Furthermore, it is more preferable that injection molding is possible, which has good moldability and is suitable for mass production.
【００１５】本発明におけるポリアミド系樹脂とは、一
般にナイロン樹脂といわれる主鎖中にアミド結合−ＣＯ
−ＮＨ−をもつ高分子である。代表的には、ジカルボン
酸とジアミンの重縮合、ω−アミノカルボン酸の重縮
合、またはラクタムの開環重合によって合成される樹脂
であり、該樹脂は、耐熱性に優れるだけでなく、耐薬品
性、耐クリープ性弾力性に優れ、成形性がよく射出成形
可能でかつ安価であり、電池のガスケットに適してい
る。なかでも、ナイロン46、が耐熱性の点でより好まし
い。The polyamide resin in the present invention is generally referred to as a nylon resin and has an amide bond --CO in the main chain.
It is a polymer having -NH-. Typically, it is a resin synthesized by polycondensation of dicarboxylic acid and diamine, polycondensation of ω-aminocarboxylic acid, or ring-opening polymerization of lactam, and the resin not only has excellent heat resistance but also chemical resistance. , Excellent in creep resistance and elasticity, good in moldability, injection-moldable and inexpensive, and suitable for battery gaskets. Of these, nylon 46 is more preferable in terms of heat resistance.
【００１６】本発明における連続使用温度とは、材料が
１０万時間の連続使用で５０％の強度を保持している温
度のことをいい、樹脂の耐熱性を表す一般的な特性の一
つである。本発明における熱可塑性樹脂とは、加熱によ
って軟化・溶融し冷却によって固化する現象が可逆的に
起こる性質をもつ樹脂のことであるが、該電池はリフロ
ーハンダ付時における炉内の熱および実装された機器使
用時における周辺の部品からの放熱を受けるため、該電
池の外装ケース材としては特に耐熱性に優れている必要
があり、連続使用温度にして 100℃以上の特性が必要で
ある。The continuous use temperature in the present invention refers to the temperature at which the material retains 50% strength after 100,000 hours of continuous use, and is one of the general characteristics representing the heat resistance of resins. is there. The thermoplastic resin in the present invention is a resin having a property of reversibly undergoing a phenomenon of softening / melting by heating and solidifying by cooling, but the battery is not heated by the heat in the furnace when mounted with reflow solder and mounted. In order to receive heat from peripheral parts when the device is used, it is necessary for the outer case material of the battery to have particularly excellent heat resistance, and it is necessary to have a characteristic of 100 ° C. or higher in continuous use temperature.
【００１７】このような樹脂として、ポリエステル、ポ
リアミド、ポリカーボネート、ポリアセタール、変性ポ
リフェニレンエーテル等が挙げられるが、ポリフェニレ
ンスルフィド、ポリエーテルケトン、ポリエーテルエー
テルケトン、ポリエーテルスルホン、ポリスルホン、ポ
リエーテルイミド、ポリイミド、ポリアミドイミド、ポ
リアリレート、全芳香族ポリエステル、エチレンテレフ
タレート／パラヒドロキシ安息香酸共重合体が特に好ま
しい。また、これらの樹脂にカーボンブラック等の炭素
系フィラー、ガラス繊維、アルミナ等の無機質フィラ
ー、滑剤・カップリング剤等の添加剤あるいは各種金属
フィラーおよびこれらの混合物フィラーを混入したもの
も使用することができる。Examples of such resins include polyester, polyamide, polycarbonate, polyacetal, modified polyphenylene ether, and the like. Polyphenylene sulfide, polyether ketone, polyether ether ketone, polyether sulfone, polysulfone, polyether imide, polyimide, Polyamideimide, polyarylate, wholly aromatic polyester and ethylene terephthalate / parahydroxybenzoic acid copolymer are particularly preferred. It is also possible to use a mixture of these resins with a carbon-based filler such as carbon black, glass fiber, an inorganic filler such as alumina, an additive such as a lubricant / coupling agent, or various metal fillers and a mixture filler thereof. it can.
【００１８】本発明におけるケースとは、電池が熱硬化
性樹脂でモールドされた状態において、正負極端子の一
部を除く電池全体を収容できる大きさであれば良く、ケ
ース材がモールド表面全体を被覆していても、一部熱硬
化性樹脂が露出していても良い。またケースの肉厚、形
状は適宜選択することができる。本発明における熱硬化
性樹脂とは、加熱によって重合体中に残存する未反応基
が反応して重合度が高くなり架橋が進んで網状構造が生
ずることにより硬化する性質をもつ樹脂のことであり、
エポキシ樹脂、フェノール樹脂がより好ましい。該樹脂
は、耐熱性、耐溶剤性に優れ、コイン型（ボタン型）有
機電解質電池のモールドに適している。The case in the present invention may be any size as long as it can accommodate the entire battery except a part of the positive and negative terminals when the battery is molded with a thermosetting resin, and the case material covers the entire mold surface. It may be covered or a part of the thermosetting resin may be exposed. Further, the thickness and shape of the case can be appropriately selected. The thermosetting resin in the present invention is a resin having the property of being cured by heating, whereby unreacted groups remaining in the polymer react to increase the degree of polymerization and promote crosslinking to form a network structure. ,
Epoxy resin and phenol resin are more preferable. The resin has excellent heat resistance and solvent resistance and is suitable for molding a coin-type (button-type) organic electrolyte battery.
【００１９】正極あるいは／かつ負極に用いるポリアセ
ン系骨格構造を有する有機半導体は、熱縮合重合反応に
より製造され耐熱性にすぐれている。正極缶あるいは負
極缶に用いるステンレスあるいはアルミニウムは耐熱性
にすぐれた金属である。セパレータに好ましく用いられ
るガラス繊維不織布はガラスの融点が高く、耐熱性にす
ぐれている。電解液は、電解液の溶媒として用いられる
非プロトン性の有機溶媒、たとえばプロピレンカーボネ
ートは沸点が高く、水溶液系電池に用いられる電解液に
比べて大幅に耐熱性がすぐれている。したがって、もっ
とも耐熱性に劣るガスケットに耐熱性にすぐれたポリア
ミド系樹脂を用いることにより、本発明電池の耐熱性が
改善された。他の電池、例えば水溶液系電池では電解液
の耐熱性が劣っているため、ガスケットの耐熱性を改善
しても電池の耐熱性は改善されない。The organic semiconductor having a polyacene skeleton structure used for the positive electrode and / or the negative electrode is manufactured by a thermal condensation polymerization reaction and has excellent heat resistance. Stainless steel or aluminum used for the positive electrode can or the negative electrode can is a metal having excellent heat resistance. The glass fiber nonwoven fabric preferably used for the separator has a high melting point of glass and is excellent in heat resistance. An aprotic organic solvent used as a solvent for the electrolytic solution, such as propylene carbonate, has a high boiling point, and has significantly higher heat resistance than the electrolytic solution used for an aqueous battery. Therefore, the heat resistance of the battery of the present invention was improved by using a polyamide resin having excellent heat resistance for the gasket having the lowest heat resistance. In other batteries, for example, an aqueous battery, the heat resistance of the electrolytic solution is inferior, so even if the heat resistance of the gasket is improved, the heat resistance of the battery is not improved.
【００２０】[0020]
【発明の効果】上述した、ポリアミド系樹脂からなるガ
スケットを、従来のポリプロピレンからなるガスケット
のかわりに、正極あるいは／かつ負極にポリアセン系骨
格構造を有する有機半導体を用いた有機電解質電池に用
い、かつ上述した連続使用温度100℃以上の熱可塑性樹
脂のケース内に熱硬化性樹脂にてモールドすることによ
り該電池の耐熱性が向上し、リフローハンダ付が可能と
なるとともに耐湿性が改善される。The above-mentioned gasket made of polyamide resin is used for an organic electrolyte battery using an organic semiconductor having a polyacene skeleton structure for the positive electrode and / or the negative electrode, instead of the gasket made of conventional polypropylene, and By molding with a thermosetting resin in the case of a thermoplastic resin having a continuous use temperature of 100 ° C. or higher, the heat resistance of the battery is improved, reflow soldering becomes possible, and moisture resistance is improved.
【００２１】[0021]
【実施例 1】まず、ポリアセンシートを次のようにして
製造した。本発明の出願人に係る特開昭６１−２１８０
６０号公報の実施例１に記載している製造方法により、
不溶不融性のポリアセンのフィルムを合成した。該物質
の電気伝導度を室温で直流４端子法で測定したところ、
10-4Ω-1・cm-1であった。元素分析によると、水素原子
／炭素原子の原子比は0.27であった。ＢＥＴ法による比
表面積は、2100m2／gと極めて大きな値であった。次に
該ポリアセンフィルムを、ボールミルを用いて３時間粉
砕し粉末とした。この粉末にポリ四フッ化エチレン５重
量％，カーボンブラック10重量％を加え、混合した後、
加圧成形して厚さ0.2mm のポリアセンシートを得た。次
に、このポリアセンシート及び硼珪酸塩のガラス繊維不
織布からなるセパレータをディスク状に打ち抜き200 ℃
で３時間真空乾燥した後に、ジャムポットに入れて保管
した。Example 1 First, a polyacene sheet was manufactured as follows. Japanese Patent Application Laid-Open No. 61-2180 relating to the applicant of the present invention
According to the manufacturing method described in Example 1 of Japanese Patent Publication No. 60,
A film of insoluble and infusible polyacene was synthesized. The electric conductivity of the substance was measured at room temperature by the direct current 4-terminal method,
It was 10 −4 Ω −1 · cm −1 . According to elemental analysis, the atomic ratio of hydrogen atoms / carbon atoms was 0.27. The specific surface area by the BET method was an extremely large value of 2100 m 2 / g. Next, the polyacene film was pulverized with a ball mill for 3 hours to obtain a powder. To this powder was added 5% by weight of polytetrafluoroethylene and 10% by weight of carbon black, and after mixing,
It was pressure-molded to obtain a 0.2 mm thick polyacene sheet. Next, a separator made of this polyacene sheet and borosilicate glass fiber non-woven fabric was punched into a disc shape at 200 ° C.
After vacuum drying for 3 hours, it was stored in a jam pot.
【００２２】本発明のポリアミド系樹脂であるナイロン
46を射出成形したガスケットを、100 ℃３時間の真空乾
燥で乾燥させジャムポットに保管した。次に、ステンレ
スからなる正極缶内底部に導電性ペ−ストを塗布した
後、前述したポリアセンシートを載置して、上部より圧
着した後、100 ℃で30分間乾燥した。同様に、ステンレ
スからなる負極缶内底面に導電性ペーストを塗布し、ポ
リアセンシートを載置し圧着後100 ℃で30分間乾燥し
た。Nylon which is the polyamide resin of the present invention
The gasket obtained by injection molding 46 was dried by vacuum drying at 100 ° C. for 3 hours and stored in a jam pot. Next, a conductive paste was applied to the inner bottom of the positive electrode can made of stainless steel, the above-mentioned polyacene sheet was placed on the bottom, pressure-bonded from above, and then dried at 100 ° C. for 30 minutes. Similarly, a conductive paste was applied to the inner bottom surface of a negative electrode can made of stainless steel, a polyacene sheet was placed thereon, pressure-bonded, and dried at 100 ° C. for 30 minutes.
【００２３】このようにして得た正極に、電解液として
ホウフッ化テトラエチルアンモニウムを含んでプロピレ
ンカーボネートの所定量を注入して、セパレータを載置
した。また、負極にも同様にして電解液の所定量を注入
した後、第１図に示すような直径6.8mm 高さ0.96mmのコ
イン型（ボタン型）有機電解質電池を組み立てた。尚、
上述した組立作業は全て除湿ルーム内で行なった。A predetermined amount of propylene carbonate containing tetraethylammonium borofluoride as an electrolytic solution was injected into the positive electrode thus obtained, and a separator was placed thereon. In addition, after injecting a predetermined amount of the electrolytic solution into the negative electrode in the same manner, a coin type (button type) organic electrolyte battery having a diameter of 6.8 mm and a height of 0.96 mm as shown in FIG. 1 was assembled. still,
All the above-mentioned assembly work was performed in the dehumidification room.
【００２４】次に、コイン型（ボタン型）電池を２個重
ねたあと、一方の電池の正極缶および他方の電池の負極
缶にステンレス鋼製の端子をレーザー溶接し、ポリフェ
ニレンスルフィド（大日本インキ化学工業（株）製FZ=3
600 ）のケースおよびエポキシ樹脂（松下電工（株）社
製ＣＶ５０３２）にて、底面 8.5mm×8.5mm 高さ3.5mm
にモールド成形した。以上のようにして作製した本発明
有機電解質電池を、正・負極端子表面が図２に示す温度
推移となるようなリフローハンダ付を行なった時の交流
内部抵抗（1kHz,1mA) の変化を第１表に、リフローハン
ダ付後、60℃相対湿度93% の恒温恒湿中にて5.0 v の電
圧を５日間印加した後の内部抵抗を第２表に示す。Next, after stacking two coin type (button type) batteries, a stainless steel terminal is laser-welded to the positive electrode can of one battery and the negative electrode can of the other battery, and polyphenylene sulfide (Dainippon Ink Chemical Industry Co., Ltd. FZ = 3
600) case and epoxy resin (CV5032 manufactured by Matsushita Electric Works, Ltd.), bottom surface 8.5 mm × 8.5 mm height 3.5 mm
Was molded. The organic electrolyte battery of the present invention manufactured as described above was subjected to reflow soldering such that the surface of the positive and negative electrode terminals had the temperature transition shown in FIG. 2, and the change in AC internal resistance (1 kHz, 1 mA) Table 1 shows the internal resistance after reflow soldering and after applying a voltage of 5.0 v for 5 days in a constant temperature and constant humidity of 60 ° C and a relative humidity of 93%.
【００２５】[0025]
【実施例 2】実施例 1と同様にして製造したコイン型
（ボタン型）電池を２個重ねたあと、一方の電池の正極
缶および他方の電池の負極缶にステンレス鋼製の端子を
レ−ザ−溶接し、ポリエーテルエーテルケトン（住友化
学工業（株）製）のケースおよびエポキシ樹脂（松下電
工（株）社製ＣＶ５０３２）にて、底面 8.5mm×8.5mm
高さ3.5mm にモールド成形した。以上のようにして作製
した本発明有機電解質電池を、正・負極端子表面が図２
に示す温度推移となるようなリフローハンダ付を行なっ
た時の交流内部抵抗（1kHz,1mA) の変化を第１表に、リ
フローハンダ付後、60℃ 相対湿度93% の恒温恒湿中に
て5.0 v の電圧を５日間印加した後の内部抵抗を第２表
に示す。Example 2 Two coin-type (button-type) batteries manufactured in the same manner as in Example 1 were stacked, and then stainless steel terminals were mounted on the positive electrode can of one battery and the negative electrode can of the other battery. The welded, polyetheretherketone (Sumitomo Chemical Co., Ltd.) case and epoxy resin (Matsushita Electric Co., Ltd. CV5032), bottom 8.5 mm × 8.5 mm
Molded to a height of 3.5 mm. The organic electrolyte battery of the present invention produced as described above has the positive and negative electrode terminal surfaces shown in FIG.
Table 1 shows the changes in the AC internal resistance (1kHz, 1mA) when reflow soldering was used to achieve the temperature transition shown in Table 1. After reflow soldering, at 60 ° C and 93% relative humidity in constant temperature and humidity. Table 2 shows the internal resistance after applying a voltage of 5.0 v for 5 days.
【００２６】[0026]
【表１】 [Table 1]
【００２７】[0027]
【表２】 [Table 2]
【００２８】[0028]
【比較例１】ポリプロピレンを射出成形したガスケット
を用いて、実施例１と同様に、コイン型有機電解質電池
を組み立てて、樹脂モールドしリフローハンダ付を行な
った時の交流内部抵抗変化を第１表に示す。[Comparative Example 1] A coin-type organic electrolyte battery was assembled in the same manner as in Example 1 by using a gasket formed by injection molding of polypropylene, resin-molded, and reflow soldering was performed. Shown in.
【００２９】[0029]
【比較例２】ナイロン46を射出成形したガスケットを用
いて、実施例と同様のコイン型有機電解質電池を組み立
て、樹脂モールドを行なわずに、リフローハンダ付を行
なった時の交流内部抵抗変化を第１表に、リフローハン
ダ付後60℃相対湿度93% の恒温恒湿中にて、5.0 v の電
圧を５日間印加した後の内部抵抗を第２表に示す。[Comparative Example 2] A coin-type organic electrolyte battery similar to that of the embodiment was assembled using a gasket formed by injection molding of nylon 46, and the change in AC internal resistance was observed when reflow soldering was performed without resin molding. Table 1 shows the internal resistance after applying a voltage of 5.0 v for 5 days in a constant temperature and constant humidity of 60 ° C and a relative humidity of 93% after reflow soldering.
【００３０】[0030]
【比較例３】ポリスチレンのケースを使用し、実施例と
同様にコイン型有機電解質電池をモールド成型し、リフ
ローハンダ付を行なったところ、ケースが溶融・変形す
る異常がみられた。第１表および第２表において、本発
明品と従来品とを比較する。本発明品は、リフロ−ハン
ダ付において短絡することがなく、交流内部抵抗の変化
もみられず耐熱性が改善されてリフロ−ハンダ付が可能
となり、かつ、耐湿性も改善されている。[Comparative Example 3] When a coin type organic electrolyte battery was molded using a polystyrene case and subjected to reflow soldering, the case was found to be abnormally melted and deformed. In Tables 1 and 2, the product of the present invention and the conventional product are compared. The product of the present invention does not cause a short circuit during reflow soldering, has no change in alternating current internal resistance, has improved heat resistance and can be reflow soldered, and has improved moisture resistance.
【図１】本発明の一実施例によるコイン型（ボタン型）
電池の断面図。FIG. 1 is a coin type (button type) according to an embodiment of the present invention.
Sectional drawing of a battery.
【図２】リフロ−ハンダ付時の正・負極端子表面温度変
化。[Fig. 2] Change in surface temperature of positive and negative electrode terminals when reflow soldering is applied.
１：正極缶 ２，２’：ポリアセン系有機半導体からなるシ−ト ３，３’：導電性ペ−スト ４：ポリアミド系樹脂からなるガスケット ５：セパレ−タ ６：負極缶 ７：電解液 ８：モ−ルド樹脂 ９：正極端子 １０：負極端子 １１：ケース 1: Positive electrode can 2,2 ': Sheet made of polyacene organic semiconductor 3,3': Conductive paste 4: Gasket made of polyamide resin 5: Separator 6: Negative electrode can 7: Electrolyte 8 : Mold resin 9: Positive electrode terminal 10: Negative electrode terminal 11: Case
───────────────────────────────────────────────────── フロントページの続き (72)発明者 矢田 静邦 兵庫県加古郡播磨町宮西２丁目６番13号 (72)発明者 原田 豊郎 仙台市太白区西多賀５丁目30番１号 (72)発明者 篠田 勇 仙台市太白区西多賀５丁目30番１号 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shizukuni Yata 2-6-13 Miyanishi Harima-cho, Kako-gun, Hyogo Prefecture (72) Inventor Toyoro Harada 5-30-1 Nishitaga, Taihaku-ku, Sendai (72) Inventor Isamu Shinoda 5-30-1 Nishitaga, Taihaku-ku, Sendai City
Claims (1)
タ、ガスケットを備えた有機電解質電池において、正極
及び／又は、負極がポリアセン系骨格構造を有する有機
半導体からなるとともに、ガスケットがポリアミド系樹
脂からなり、かつ、連続使用温度 100℃以上の熱可塑性
樹脂のケース内に熱硬化性樹脂にてモールドすることを
特徴とするコイン型有機電解質電池。1. An organic electrolyte battery comprising a positive electrode can, a negative electrode can, a positive electrode, a negative electrode, a separator and a gasket, wherein the positive electrode and / or the negative electrode is made of an organic semiconductor having a polyacene skeleton structure, and the gasket is a polyamide resin. A coin-type organic electrolyte battery, which is made of a thermosetting resin and is molded in a case of a thermoplastic resin having a continuous use temperature of 100 ° C. or higher.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28198093A JP3482970B2 (en) | 1993-10-14 | 1993-10-14 | Organic electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28198093A JP3482970B2 (en) | 1993-10-14 | 1993-10-14 | Organic electrolyte battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07114911A true JPH07114911A (en) | 1995-05-02 |
| JP3482970B2 JP3482970B2 (en) | 2004-01-06 |
Family
ID=17646577
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28198093A Expired - Fee Related JP3482970B2 (en) | 1993-10-14 | 1993-10-14 | Organic electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3482970B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007165141A (en) * | 2005-12-14 | 2007-06-28 | Kitagawa Ind Co Ltd | Battery case and electronic apparatus |
-
1993
- 1993-10-14 JP JP28198093A patent/JP3482970B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007165141A (en) * | 2005-12-14 | 2007-06-28 | Kitagawa Ind Co Ltd | Battery case and electronic apparatus |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3482970B2 (en) | 2004-01-06 |
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