JPH0554868A - Nonaqueous electrolyte battery - Google Patents
Nonaqueous electrolyte batteryInfo
- Publication number
- JPH0554868A JPH0554868A JP3216924A JP21692491A JPH0554868A JP H0554868 A JPH0554868 A JP H0554868A JP 3216924 A JP3216924 A JP 3216924A JP 21692491 A JP21692491 A JP 21692491A JP H0554868 A JPH0554868 A JP H0554868A
- Authority
- JP
- Japan
- Prior art keywords
- thermoplastic resin
- gasket
- case
- aqueous electrolyte
- electrolyte battery
- 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.)
- Pending
Links
Classifications
-
- Y02E60/12—
Landscapes
- Sealing Battery Cases Or Jackets (AREA)
- Primary Cells (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、例えばリチウム、ナト
リウム、マグネシウムなどの軽金属単体、あるいはこれ
らの合金を負極とし、金属ハロゲン化物、硫化物、酸化
物、あるいは固体状フッ化炭素などを正極とし、非水系
有機電解質を用いる非水電解質電池に関するものであ
る。BACKGROUND OF THE INVENTION The present invention uses a light metal element such as lithium, sodium and magnesium or an alloy thereof as a negative electrode, and a metal halide, sulfide, oxide, or solid carbon fluoride as a positive electrode. , A non-aqueous electrolyte battery using a non-aqueous organic electrolyte.
【０００２】[0002]
【従来の技術】従来よりリチウム電池で代表される非水
電解質電池は高エネルギー密度且つ軽量であるといった
特徴のある電池として広く用いられており、最近では民
生用の機器の一部品としての利用ならびに高温下での連
続したバックアップ用の電源としての用途が増加してい
る。この種の電池は従来より発電要素を内蔵したケース
と封口板の間にポリプロピレン（ＰＰ）やポリエチレン
（ＰＥ）樹脂製のガスケットを介して絶縁封口してい
た。2. Description of the Related Art Conventionally, non-aqueous electrolyte batteries typified by lithium batteries have been widely used as batteries having high energy density and light weight, and recently, they have been used as a component of consumer equipment and The use as a power supply for continuous backup under high temperature is increasing. This type of battery has conventionally been insulated and sealed via a gasket made of polypropylene (PP) or polyethylene (PE) resin between a case containing a power generating element and a sealing plate.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、前記の
ＰＰやＰＥ樹脂製のガスケットは結晶質性の熱可塑性樹
脂であり、高温雰囲気、および急激な温度変化に対して
結晶が収縮しやすいという欠点がある。このため電池組
み立て後に高温雰囲気および急激な温度変化の条件下に
さらされると電池の封口かしめ部、即ち、ガスケットと
ケースと封口板とのかしめ部にわずかな間隙ができ、そ
こから電池内部の電解液が気化したり、漏出するという
問題がある。本発明は、これら従来の問題を解消し、高
温保存特性に優れた非水電解質電池を提供することを目
的とする。However, the above-mentioned gasket made of PP or PE resin is a crystalline thermoplastic resin, and has a drawback that the crystal tends to shrink in a high temperature atmosphere and in a rapid temperature change. is there. For this reason, if the battery is exposed to a high temperature atmosphere and conditions of rapid temperature changes after assembly, a slight gap is created in the battery caulking part, that is, the caulking part between the gasket, the case, and the sealing plate, from which the electrolysis inside the battery occurs. There is a problem that the liquid vaporizes and leaks. An object of the present invention is to solve these conventional problems and provide a non-aqueous electrolyte battery having excellent high temperature storage characteristics.
【０００４】[0004]
【課題を解決するための手段】本発明の非水電解質電池
は負極と、正極と、セパレータと非水系電解質からなる
発電要素を内蔵したケースの開口を、ガスケットを介し
て封口板で密封してなる電池であって、前記ガスケット
の素材として非晶質性の耐熱性熱可塑性樹脂を用いたこ
とを特徴とする。The non-aqueous electrolyte battery of the present invention comprises a negative electrode, a positive electrode, an opening of a case containing a power generating element composed of a separator and a non-aqueous electrolyte, and a sealing plate which seals the opening of the case. And a heat-resistant amorphous thermoplastic resin is used as a material of the gasket.
【０００５】前記耐熱性熱可塑性樹脂としては、例えば
変成ポリフェニレンオキシド、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、変成ポリフェニレ
ンエーテルなどが挙げられる。Examples of the heat-resistant thermoplastic resin include modified polyphenylene oxide, polyether sulfone,
Examples thereof include polysulfone, polyetherimide, and modified polyphenylene ether.
【０００６】[0006]
【作用】この構成により本発明の非水電解質電池は、従
来から使用されている結晶質性の熱可塑性樹脂であるポ
リプロピレンなどに比べ、熱安定性がよく、電池組み立
て後、高温雰囲気、および急激な温度変化の条件下にお
いても熱ストレスによる体積収縮が小さいため寸法変化
がなく、ガスケットと封口板とケースのかしめ部の密封
度を長期に渡って維持することとなる。With this structure, the non-aqueous electrolyte battery of the present invention has better thermal stability than polypropylene or the like, which is a crystalline thermoplastic resin that has been conventionally used, and after the battery is assembled, it is exposed to a high temperature atmosphere and abruptly. Since the volume shrinkage due to heat stress is small even under the condition of a large temperature change, there is no dimensional change, and the sealing degree of the caulked portion of the gasket, the sealing plate, and the case is maintained for a long time.
【０００７】[0007]
【実施例】以下に本発明の実施例を示す非水電解質電池
として、図１に示すコイン形フッ化黒鉛リチウム電池を
参照しながら説明する。EXAMPLE A coin-type lithium graphite fluoride battery shown in FIG. 1 will be described below as a non-aqueous electrolyte battery showing an example of the present invention.
【０００８】図１において、１はＳＵＳ材よりなるケー
スで、この内部にはフッ化黒鉛を主成分とする正極板２
と金属リチウムを活物質とする負極板３とを電解液を含
浸したセパレータ４を介して積層してなる発電要素５が
内蔵されている。そしてケース１の開口部１ａに、金属
性の封口板６の周縁部に本発明による耐熱性に優れ結晶
構造が非晶質性の熱可塑性樹脂である変成ポリフェニレ
ンオキシド、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、変成ポリフェニレンエーテルよりな
る各樹脂製ガスケット７を取り付けたものを嵌合させ、
その後該ケース１の開口部１ａの周縁を金型で内方に折
り曲げて、ケース１の開口部１ａを密封し、電池Ａ、
Ｂ、Ｃ、Ｄ、Ｅとした。In FIG. 1, reference numeral 1 is a case made of SUS material, inside of which a positive electrode plate 2 whose main component is fluorinated graphite is used.
A power generation element 5 is built in which a negative electrode plate 3 having metallic lithium as an active material are laminated via a separator 4 impregnated with an electrolytic solution. The modified polyphenylene oxide, polyether sulfone, polysulfone, polysulfone, polysulfone, and polysulfone, which are thermoplastic resins excellent in heat resistance according to the present invention and having an amorphous crystal structure, are formed in the opening 1a of the case 1 and in the peripheral portion of the metallic sealing plate 6. The resin gaskets 7 made of ether imide and modified polyphenylene ether are attached and fitted.
Thereafter, the periphery of the opening 1a of the case 1 is bent inward by a mold to seal the opening 1a of the case 1, and the battery A,
It was set to B, C, D, and E.
【０００９】次に、本実施例電池Ａ、Ｂ、Ｃ、Ｄ、Ｅに
用いた非晶質性の耐熱性熱可塑性樹脂について説明する
と、変成ポリフェニレンオキシド（ＰＰＯ）樹脂は、芳
香族ポリエーテル樹脂であるポリフェニレンオキシドを
スチレン系の樹脂によって改質したプラスチックで、ポ
リフェニレンオキシドはフェノール系モノマーである
２，６−ジメチルフェノールを触媒の存在下で酸化重合
することによって得られるエーテル結合を持つポリマー
である。Next, the amorphous heat-resistant thermoplastic resin used in the batteries A, B, C, D and E of this embodiment will be described. The modified polyphenylene oxide (PPO) resin is an aromatic polyether resin. Is a plastic obtained by modifying polyphenylene oxide, which is a styrene resin, with polyphenylene oxide being a polymer having an ether bond obtained by oxidative polymerization of 2,6-dimethylphenol, which is a phenolic monomer, in the presence of a catalyst. ..
【００１０】ポリエーテルスルホン（ＰＥＳＦ）樹脂
は、分子内に下記（化１）で示す繰り返し単位を含むプ
ラスチックである。Polyethersulfone (PESF) resin is a plastic containing a repeating unit represented by the following (formula 1) in the molecule.
【００１１】[0011]
【化１】 [Chemical 1]
【００１２】ポリスルホン（ＰＳＦ）樹脂は、分子内に
下記（化２）で示す繰り返し単位を含むプラスチックで
ある。The polysulfone (PSF) resin is a plastic containing a repeating unit represented by the following chemical formula 2 in the molecule.
【００１３】[0013]
【化２】 [Chemical 2]
【００１４】ポリエーテルイミド（ＰＥＩ）樹脂は分子
内に（化３）に示す芳香族イミドとエーテル結合を繰り
返し単位として含むプラスチックである。The polyetherimide (PEI) resin is a plastic containing an aromatic imide represented by the chemical formula (3) and an ether bond as a repeating unit.
【００１５】[0015]
【化３】 [Chemical 3]
【００１６】変成ポリフェニレンエーテル（ＰＰＥ）樹
脂は、分子内に（化４）に示すようにポリマー主鎖がベ
ンゼン環とエーテル結合を繰り返し単位として含むプラ
スチックで２，６ジメチルー１，４ーフェニレンエーテ
ルをスチレン樹脂によって改質したプラスチックであ
る。The modified polyphenylene ether (PPE) resin is a plastic whose polymer main chain contains a benzene ring and an ether bond as a repeating unit in the molecule as shown in (Chemical Formula 4), and is 2,6 dimethyl-1,4-phenylene ether. It is a plastic modified with styrene resin.
【００１７】[0017]
【化４】 [Chemical 4]
【００１８】以上述べた本発明の実施例に使用した樹脂
は熱変形温度が１２０〜２１０℃の高い値を有する非晶
質性の耐熱性熱可塑性樹脂であり、且つ有機電解液に対
しても強い抵抗を示すエンジニアリングプラスチックで
ある。The resin used in the examples of the present invention described above is an amorphous heat-resistant thermoplastic resin having a high heat distortion temperature of 120 to 210 ° C., and also for organic electrolytes. An engineering plastic with strong resistance.
【００１９】次に本発明のガスケットと従来の結晶質性
熱可塑性樹脂であるポリプロピレンよりなるガスケット
について、寸法安定性を比較するために、これらガスケ
ットを１００℃の雰囲気中に１２０時間放置し、その後
常温で２４時間放置し熱ストレスを与えた。この結果、
本実施例の非水電解質電池に用いたガスケットは熱スト
レスを与える前後の寸法変化率（収縮率）が０．０１％
以下であるのに対し、従来のものは０．５２％と大き
く、本発明のガスケットの高温保存下での寸法安定性が
極めて高いことがわかる。Next, in order to compare the dimensional stability of the gasket of the present invention and the conventional gasket made of polypropylene, which is a crystalline thermoplastic resin, these gaskets were left in an atmosphere of 100 ° C. for 120 hours, and thereafter, It was left at room temperature for 24 hours to be subjected to heat stress. As a result,
The gasket used in the non-aqueous electrolyte battery of this example has a dimensional change rate (shrinkage rate) of 0.01% before and after applying thermal stress.
In contrast to the following, the conventional one is as large as 0.52%, which shows that the gasket of the present invention has extremely high dimensional stability under high temperature storage.
【００２０】次に本実施例のガスケットの実効を確認す
るため、これらガスケットを用いた電池Ａ〜Ｅと、従来
の電池としてポリプロピレンよりなるガスケットを用い
たコイン形のリチウム電池ＢＲ３０３２をそれぞれ５０
０個作成した。これらリチウム電池を１００℃の中で４
週間保存した後取り出して電池特性として開路電圧、内
部抵抗、電解液の飛散による電池重量減少量、負荷抵抗
２０ｋΩでの放電時の容量比を評価した。その結果を表
１に示す。開路電圧は顕著な特性差は認められないが、
内部抵抗の推移では初期１２Ωであったものが従来構成
の電池Ｆでは１６０Ωに上昇していた。又、放電特性で
は従来構成の電池Ｆは初期放電容量を１００としたとき
２９に劣化していた。一方本発明による電池Ａ〜Ｅは開
路電圧は初期と殆ど変化は無かった。この結果から明ら
かなように本実施例による構成は高温保存の点で優れた
効果が得られることがわかる。Next, in order to confirm the effectiveness of the gasket of this embodiment, batteries A to E using these gaskets and coin-type lithium battery BR3032 using a gasket made of polypropylene as a conventional battery are respectively used.
I made 0. 4 these lithium batteries at 100 ℃
After being stored for a week, they were taken out and evaluated as the battery characteristics such as an open circuit voltage, an internal resistance, a weight reduction amount of the battery due to scattering of an electrolytic solution, and a capacity ratio at the time of discharging with a load resistance of 20 kΩ. The results are shown in Table 1. No significant difference in open circuit voltage is observed,
In the transition of the internal resistance, the initial value of 12Ω was increased to 160Ω in the battery F having the conventional configuration. Regarding the discharge characteristics, the battery F having the conventional configuration was deteriorated to 29 when the initial discharge capacity was 100. On the other hand, in the batteries A to E according to the present invention, the open circuit voltage was almost unchanged from the initial value. As is clear from this result, it can be seen that the structure of this example has an excellent effect in terms of high temperature storage.
【００２１】[0021]
【表１】 [Table 1]
【００２２】[0022]
【発明の効果】以上の実施例の説明で明らかなように、
本発明のガスケット素材を用いたものは、非晶質性の結
晶構造を有しているため熱ストレスに対して長期に渡っ
て寸法変化を起こさず、有機溶媒に対して強い抵抗性を
有するため、封口部の気密性を長期に渡って維持でき、
電池特性の安定した電池を提供できる。As is apparent from the above description of the embodiments,
Since the one using the gasket material of the present invention has an amorphous crystal structure, it does not cause a dimensional change for a long time due to thermal stress and has a strong resistance to an organic solvent. The airtightness of the sealing part can be maintained for a long time,
A battery with stable battery characteristics can be provided.
【図１】本発明の一実施例の非水電解質電池の断面図で
ある。FIG. 1 is a cross-sectional view of a non-aqueous electrolyte battery according to an embodiment of the present invention.
１ ケース １ａ ケースの開口部 ２ 正極 ３ 負極 ４ セパレータ ５ 発電要素 ６ 封口板 ７ ガスケット 1 case 1a case opening 2 positive electrode 3 negative electrode 4 separator 5 power generating element 6 sealing plate 7 gasket
Claims (6)
解質からなる発電要素を内蔵したケースの開口を、ガス
ケットを介して封口板で密封してなる電池であって、前
記ガスケットの素材として非晶質性の耐熱性熱可塑性樹
脂を用いたことを特徴とする非水電解質電池。1. A battery in which an opening of a case containing a negative electrode, a positive electrode, a separator and a power generating element composed of a non-aqueous electrolyte is sealed with a sealing plate via a gasket, and the non-material is used as a material of the gasket. A non-aqueous electrolyte battery comprising a crystalline heat-resistant thermoplastic resin.
ニレンオキシドである請求項１記載の非水電解質電池。2. The non-aqueous electrolyte battery according to claim 1, wherein the heat resistant thermoplastic resin is a modified polyphenylene oxide.
スルホンである請求項１記載の非水電解質電池。3. The non-aqueous electrolyte battery according to claim 1, wherein the heat-resistant thermoplastic resin is polyether sulfone.
である請求項１記載の非水電解質電池。4. The non-aqueous electrolyte battery according to claim 1, wherein the heat-resistant thermoplastic resin is polysulfone.
イミドである請求項１記載の非水電解質電池。5. The non-aqueous electrolyte battery according to claim 1, wherein the heat-resistant thermoplastic resin is polyetherimide.
ニレンエーテルである請求項１記載の非水電解質電池。6. The non-aqueous electrolyte battery according to claim 1, wherein the heat resistant thermoplastic resin is a modified polyphenylene ether.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3216924A JPH0554868A (en) | 1991-08-28 | 1991-08-28 | Nonaqueous electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3216924A JPH0554868A (en) | 1991-08-28 | 1991-08-28 | Nonaqueous electrolyte battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0554868A true JPH0554868A (en) | 1993-03-05 |
Family
ID=16696066
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3216924A Pending JPH0554868A (en) | 1991-08-28 | 1991-08-28 | Nonaqueous electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0554868A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010278455A (en) * | 2003-09-30 | 2010-12-09 | Tdk Corp | Electrochemical device |
-
1991
- 1991-08-28 JP JP3216924A patent/JPH0554868A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010278455A (en) * | 2003-09-30 | 2010-12-09 | Tdk Corp | Electrochemical device |
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