JPH11260329A - Nonaqueous electrolyte battery - Google Patents
Nonaqueous electrolyte batteryInfo
- Publication number
- JPH11260329A JPH11260329A JP10057938A JP5793898A JPH11260329A JP H11260329 A JPH11260329 A JP H11260329A JP 10057938 A JP10057938 A JP 10057938A JP 5793898 A JP5793898 A JP 5793898A JP H11260329 A JPH11260329 A JP H11260329A
- Authority
- JP
- Japan
- Prior art keywords
- metal
- battery
- laser
- electrolyte battery
- sealing lid
- 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
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、発電要素が収納さ
れた金属製で有底筒状の外装缶と、この外装缶の開口部
を封口する金属製の封口蓋とを有し、この封口蓋と上記
外装缶とがレーザー溶接される非水電解質電池に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal-made bottomed cylindrical outer can containing a power generating element, and a metal sealing lid for closing an opening of the outer can. The present invention relates to a nonaqueous electrolyte battery in which a lid and the outer can are laser-welded.
【０００２】[0002]
【従来の技術】近年、携帯電話等の電子機器には非水電
解質電池が用いられるようになってきたが、この場合、
電池の重量エネルギー密度の向上を図るべく、比重の小
さなアルミニウム又はアルミニウム合金が電池の外装缶
及び封口蓋に用いられる。そして、当該電池における外
装缶と封口蓋とはレーザー溶接法により溶着されて、電
池が封口される。ここで、このようにしてレーザー溶接
法により、電池の封口を行った場合には、検査工程では
発見できないような微小なピンホールが生じる。このよ
うな微小なピンホールは通常の状態では何ら問題を生じ
ない。2. Description of the Related Art In recent years, non-aqueous electrolyte batteries have been used for electronic devices such as mobile phones.
In order to improve the weight energy density of the battery, aluminum or an aluminum alloy having a small specific gravity is used for an outer can and a sealing lid of the battery. Then, the outer can and the sealing lid in the battery are welded by a laser welding method, and the battery is sealed. Here, when the battery is sealed by the laser welding method in this way, minute pinholes that cannot be found in the inspection process are generated. Such a minute pinhole does not cause any problem in a normal state.
【０００３】しかしながら、このような微小なピンホー
ルを放置した状態で長期間使用したり長期間保存する
と、電池容量が低下する等電池の諸特性が低下する。こ
のように電池容量が低下するメカニズムは、以下に示す
理由によるものと考えられる。However, if such a minute pinhole is used for a long period of time or stored for a long period of time, various characteristics of the battery such as a decrease in battery capacity are deteriorated. It is considered that the mechanism for reducing the battery capacity is due to the following reason.
【０００４】即ち、非水電解質電池では電解質としてＬ
ｉＰＦ6 等が用いられるが、長期間保存等すると、微小
なピンホールから電池内に水分が侵入し、この水分とＬ
ｉＰＦ6 とが反応してフッ酸が生成される。この生成さ
れたフッ酸が、上記微小なピンホール周辺のアルミニウ
ムを腐食させて、ピンホールの径が大きくなる。そうす
ると更に多量の水分が電池内に侵入して、より多量のフ
ッ酸が生成される。このような悪循環を繰り返すことに
より、微小なピンホールが通常のリークホールとなり、
電解液が漏出する結果、電池容量が低下するのである。That is, in a non-aqueous electrolyte battery, L
iPF 6 or the like is used, but when stored for a long period of time, moisture penetrates into the battery through minute pinholes, and this moisture and L
Reaction with iPF 6 generates hydrofluoric acid. The generated hydrofluoric acid corrodes aluminum around the minute pinholes, and the diameter of the pinholes increases. Then, a larger amount of water penetrates into the battery to generate a larger amount of hydrofluoric acid. By repeating such a vicious cycle, minute pinholes become normal leak holes,
As a result of the leakage of the electrolyte, the battery capacity is reduced.
【０００５】そこで、特開平８−１０６９１９号公報に
示すように、外装缶の開口端部と端子部材との表出部分
が、ポリテトラフルオロエチレン（ＰＴＦＥ）、ポリフ
ッ化ビニリデン（ＰＶｄＦ）等の揮発性の樹脂膜で被覆
されるような電池が提案されている。しかしながら、こ
れらの樹脂では、レーザー溶接部を十分に保護すること
ができないという課題を有していた。Therefore, as shown in Japanese Patent Application Laid-Open No. 8-106919, the exposed portion of the open end of the outer can and the terminal member is made of a volatile material such as polytetrafluoroethylene (PTFE) or polyvinylidene fluoride (PVdF). A battery that is covered with a conductive resin film has been proposed. However, these resins have a problem that the laser weld cannot be sufficiently protected.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、以上の事情
に鑑みなされたものであって、例えフッ酸が発生した場
合であっても、アルミニウム等の金属が腐食するのを十
分に抑制することによって、電解液の漏出による電池容
量の低下等を長期間にわたって防止しうる非水電解質電
池の提供を目的とする。SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and sufficiently suppresses corrosion of metals such as aluminum even when hydrofluoric acid is generated. Accordingly, an object of the present invention is to provide a non-aqueous electrolyte battery capable of preventing a decrease in battery capacity or the like due to leakage of an electrolytic solution over a long period of time.
【０００７】[0007]
【課題を解決するための手段】上記目的を達成するため
に、本発明のうちで請求項１記載の発明は、発電要素が
収納された金属製で有底筒状の外装缶と、この外装缶の
開口部を封口する金属製の封口蓋とを有し、この封口蓋
と上記外装缶とがレーザー溶接される非水電解質電池に
おいて、上記レーザー溶接部がフッ素ゴム樹脂で被覆さ
れていることを特徴とする非水電解質電池。Means for Solving the Problems In order to achieve the above object, the invention according to claim 1 of the present invention provides a metal bottomed cylindrical outer can containing a power generating element, A non-aqueous electrolyte battery having a metal sealing lid for sealing the opening of the can and being laser-welded to the sealing lid and the outer can, wherein the laser-welded portion is coated with a fluororubber resin. Non-aqueous electrolyte battery characterized by the above-mentioned.
【０００８】上記の如く微小なピンホールを有するレー
ザー溶接部がフッ素ゴム樹脂で被覆されていれば、フッ
素ゴム樹脂は緻密でありフッ酸を透過し難いという性質
に起因して、例えフッ酸等の酸が発生した場合であって
も、微小なピンホール近傍のアルミニウム等から成る金
属が腐食するのを抑制することができる。したがって、
微小なピンホールが通常のリークホールとなるのを防止
できるので、電解液の漏出による電池容量の低下を抑制
することができる。また、フッ素ゴム樹脂は弾力性に富
んでいるので、レーザー溶接部から剥離するようなこと
もなく、上記効果が長期間にわたり持続されることにな
る。加えて、フッ素ゴム樹脂は水分を透過し難いという
ことから、電池内部に水が侵入することによるフッ酸等
の酸の生成自体を抑制することができるという効果もあ
る。If the laser-welded portion having fine pinholes is covered with a fluororubber resin as described above, the fluororubber resin is dense and hardly permeates hydrofluoric acid. Even when the acid is generated, it is possible to suppress corrosion of the metal such as aluminum near the minute pinhole. Therefore,
Since a fine pinhole can be prevented from becoming a normal leak hole, a decrease in battery capacity due to leakage of the electrolyte can be suppressed. Further, since the fluororubber resin is rich in elasticity, the above effect is maintained for a long time without peeling off from the laser welded portion. In addition, since the fluororubber resin hardly permeates moisture, there is also an effect that generation of an acid such as hydrofluoric acid due to intrusion of water into the battery can be suppressed.
【０００９】また、請求項２記載の発明は、発電要素が
収納された金属製で有底筒状の外装缶と、この外装缶の
開口部を封口する金属製の封口蓋とを有すると共に、上
記封口蓋には電解液を注液するための注液口が形成さ
れ、且つこの注液口は上記封口蓋にレーザー溶接された
金属製の蓋体により塞がれる非水電解質電池において、
上記レーザー溶接部がフッ素ゴム樹脂で被覆されている
ことを特徴とする。封口蓋と蓋体とのレーザー溶接部が
フッ素ゴム樹脂で被覆されていれば、やはり上記と同様
に、金属の腐食による電池容量の低下という問題を解決
することができる。According to a second aspect of the present invention, there is provided a metal-made bottomed cylindrical outer can containing a power generating element, a metal sealing lid for closing an opening of the outer can, In the non-aqueous electrolyte battery, a liquid injection port for injecting an electrolyte is formed in the sealing lid, and the liquid injection port is closed by a metal lid that is laser-welded to the sealing lid.
The laser welded portion is covered with a fluoro rubber resin. If the laser-welded portion between the sealing lid and the lid is covered with a fluororubber resin, the problem of a reduction in battery capacity due to metal corrosion can be solved similarly as described above.
【００１０】また、請求項３記載の発明は、発電要素が
収納された金属製で有底筒状の外装缶と、この外装缶の
開口部を封口する金属製の封口蓋とを有すると共に、上
記封口蓋には、当該封口蓋を貫通するガス排出孔と、当
該封口蓋にレーザー溶接されて通常の状態では上記ガス
排出孔を塞いでいる薄板状で金属製の弁体とからなる安
全弁が設けられた非水電解質電池において、上記レーザ
ー溶接部と上記弁体とがフッ素ゴム樹脂で被覆されてい
ることを特徴とする。According to a third aspect of the present invention, there is provided a metal-made, bottomed, cylindrical outer can in which a power generating element is housed, and a metal sealing lid for closing an opening of the outer can. The sealing lid has a gas discharge hole penetrating through the sealing lid, and a safety valve including a thin plate-shaped metal valve body which is laser-welded to the sealing lid and covers the gas discharging hole in a normal state. In the provided nonaqueous electrolyte battery, the laser welded portion and the valve body are coated with a fluororubber resin.
【００１１】封口蓋と安全弁の弁体とのレーザー溶接部
がフッ素ゴム樹脂で被覆されていれば、やはり上記と同
様に、金属の腐食による電池容量の低下という問題を解
決することができる。加えて、安全弁の弁体は封口蓋或
いは蓋体等と比べて厚みが非常に小さいため、フッ酸等
の酸により腐食し易いが、上記の如く弁体をフッ素ゴム
樹脂で被覆すれば、弁体が酸により侵されるのを防止で
きる。If the laser welding portion between the sealing lid and the valve element of the safety valve is covered with a fluororubber resin, the problem of a reduction in battery capacity due to corrosion of metal can be solved similarly as described above. In addition, since the valve body of the safety valve is very thin compared to the sealing lid or the lid body, the valve body is easily corroded by an acid such as hydrofluoric acid. It can prevent the body from being attacked by acid.
【００１２】また、請求項４記載の発明は、請求項１、
２又は３記載の発明において、上記金属がアルミニウム
又はアルミニウム合金であることを特徴とする。アルミ
ニウム又はアルミニウム合金はフッ酸等の酸により特に
腐食し易いので、金属としてアルミニウム又はアルミニ
ウム合金を用いた場合には、上記効果が一層発揮され
る。[0012] The invention described in claim 4 is based on claim 1,
4. The invention according to the item 2 or 3, wherein the metal is aluminum or an aluminum alloy. Aluminum or an aluminum alloy is particularly easily corroded by an acid such as hydrofluoric acid. Therefore, when aluminum or an aluminum alloy is used as the metal, the above-mentioned effect is further exhibited.
【００１３】また、請求項５記載の発明は、請求項１、
２、３又は４記載の発明において、電解質塩としてＬｉ
ＰＦ6 が用いられることを特徴とする。非水電解質電池
の電解質としては、ＬｉＰＦ6 、ＬｉＢＦ4 、ＬｉＡｓ
Ｆ6 、ＬｉＣｌＯ4 、ＬｉＣＦ3 ＳＯ3 等がある。電導
性等の見地からはＬｉＡｓＦ6が最適ではあるが、これ
には猛毒のＡｓ（砒素）が含まれているため、民生用の
電池には使用することができない。そこで、電導性等の
見地からはＬｉＡｓＦ6の次に優れたＬｉＰＦ6 を用い
るのが望ましい。但し、ＬｉＰＦ6 はＬｉＦとＰＦ5 と
から成る複塩であるため、一部は容易にＬｉＦとＰＦ5
とに解離する。そして解離したＬｉＦは空気中の水分と
反応してフッ酸を生成する。したがって、ＬｉＰＦ6 を
用いた電池に、上記のような処理を施すのが望ましい。[0013] The invention described in claim 5 is the first invention.
In the invention described in 2, 3 or 4, the electrolyte salt may be Li
Wherein the PF 6 is used. Examples of the electrolyte of the nonaqueous electrolyte battery include LiPF 6 , LiBF 4 , and LiAs.
F 6 , LiClO 4 , LiCF 3 SO 3 and the like. Although LiAsF 6 is optimal from the viewpoint of conductivity and the like, it contains highly toxic As (arsenic), and therefore cannot be used for consumer batteries. Therefore, it is desirable to use LiPF 6, which is superior to LiAsF 6 , from the viewpoint of conductivity and the like. However, since LiPF 6 is a double salt consisting of LiF, PF 5 Prefecture, some easily LiF, PF 5
And dissociate. The dissociated LiF reacts with moisture in the air to generate hydrofluoric acid. Therefore, it is desirable to perform the above-described treatment on the battery using LiPF 6 .
【００１４】[0014]
【発明の実施の形態】本発明の実施の形態を、図１〜図
４に基づいて、以下に説明する。図１は本発明に係る非
水電解質電池の斜視図、図２は封口蓋と外装缶とのレー
ザ溶接部の拡大断面図、図３は本発明に用いる安全弁の
拡大断面図、図４は本発明に用いる注液口の拡大断面図
である。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of the present invention will be described below with reference to FIGS. 1 is a perspective view of a nonaqueous electrolyte battery according to the present invention, FIG. 2 is an enlarged sectional view of a laser welded portion between a sealing lid and an outer can, FIG. 3 is an enlarged sectional view of a safety valve used in the present invention, and FIG. FIG. 3 is an enlarged sectional view of a liquid inlet used in the present invention.
【００１５】図１に示すように、本発明の非水電解質電
池は、アルミニウムから成る有底筒状の外装缶１を有し
ており、この外装缶１内には、アルミニウムから成る芯
体にＬｉＣｏＯ2 を主体とする活物質層が形成された正
極と、銅から成る芯体に天然黒鉛を主体とする活物質層
が形成された負極と、これら両電極を離間するセパレー
タとから成る発電要素（図示せず）が収納されている。
また、上記外装缶１内には、エチレンカーボネート（Ｅ
Ｃ）とジエチルカーボネート（ＤＥＣ）とが体積比で
４：６の割合で混合された混合溶媒に、ＬｉＰＦ6 が１
Ｍ（モル／リットル）の割合で溶解された電解液が注入
されている。更に、上記外装缶１の開口部には、アルミ
ニウムから成る封口蓋２がレーザー溶接されて、電池が
封口される。As shown in FIG. 1, the non-aqueous electrolyte battery of the present invention has a bottomed cylindrical outer can 1 made of aluminum. A power generating element comprising a positive electrode having an active material layer mainly composed of LiCoO 2 , a negative electrode having an active material layer mainly composed of natural graphite formed on a core made of copper, and a separator separating these electrodes. (Not shown) are stored.
In addition, ethylene carbonate (E
C) and diethyl carbonate (DEC) in a mixed solvent of 4: 6 in volume ratio, and LiPF 6 in an amount of 1
An electrolyte dissolved at a rate of M (mol / liter) is injected. Further, a sealing lid 2 made of aluminum is laser-welded to the opening of the outer can 1 to seal the battery.
【００１６】ここで、図２に示すように、上記封口蓋２
と外装缶１とのレーザー溶接部４は、三元系のフッ素ゴ
ム樹脂（商品名：昭和電工デュポン社製のバイトン）５
ａ（厚み：１０μｍ）により覆われている。上記三元系
のフッ素ゴム樹脂はフッ化ビニリデンと六フッ化プロピ
レンと四フッ化エチレンとの三元共重合体から成る。Here, as shown in FIG.
The laser welding portion 4 between the outer can 1 is made of a ternary fluororubber resin (trade name: Viton manufactured by Showa Denko DuPont) 5
a (thickness: 10 μm). The ternary fluororubber resin is composed of a terpolymer of vinylidene fluoride, propylene hexafluoride and ethylene tetrafluoride.
【００１７】また、上記封口蓋２には、アルミニウムか
ら成る安全弁の弁体６とアルミニウムから成り注液口を
塞ぐ蓋体８とがレーザー溶接されていると共に、外部電
極３が固定されている。上記弁体６は、図３に示すよう
に、封口蓋２を貫通するガス排出孔１０を塞いでおり、
弁体６と封口蓋２とのレーザー溶接部７と弁体６の全体
とが、上記と同様の三元系のフッ素ゴム樹脂５ｂ（厚
み：１０μｍ）により覆われている。一方、上記蓋体８
は、図４に示すように、封口蓋２を貫通する注液口１１
を塞いでおり、蓋体８と封口蓋２とのレーザー溶接部９
が、上記と同様の三元系のフッ素ゴム樹脂５ｃ（厚み：
１０μｍ）により覆われている。尚、上記非水電解質電
池の外寸は、厚さが８．１ｍｍ、幅が２２．５ｍｍ、高
さが４８．０ｍｍであり、また、公称容量は６００ｍＡ
ｈ、公称電圧は３．６Ｖである。The sealing lid 2 is laser-welded with a valve body 6 of a safety valve made of aluminum and a lid body 8 made of aluminum and closing a liquid injection port, and the external electrode 3 is fixed. As shown in FIG. 3, the valve body 6 closes a gas discharge hole 10 penetrating the sealing lid 2,
The laser welded portion 7 between the valve element 6 and the sealing lid 2 and the entire valve element 6 are covered with the same ternary fluororubber resin 5b (thickness: 10 μm) as described above. On the other hand, the lid 8
As shown in FIG. 4, the liquid inlet 11 penetrates the sealing lid 2.
And a laser weld 9 between the lid 8 and the sealing lid 2.
Is a ternary fluororubber resin 5c (thickness:
10 μm). The outer dimensions of the nonaqueous electrolyte battery were 8.1 mm in thickness, 22.5 mm in width, and 48.0 mm in height, and the nominal capacity was 600 mA.
h, the nominal voltage is 3.6V.
【００１８】ここで、上記構造の非水電解質電池を、以
下のようにして作製した。先ず、正負両極を作製した
後、上記正負両極とセパレータとから成る発電要素を外
装缶１内に収納する。次に、弁体６と封口蓋２とをレー
ザー溶接して、封口蓋２のガス抜き孔１０を弁体６で塞
ぐ。この後、上記三元系のフッ素ゴム樹脂を１０％のメ
チルエチルケトン溶液に溶かし、更にこの溶液をレーザ
ー溶接部７と弁体６の全体とをはけで塗り付けた後、自
然乾燥させて、これらをフッ素ゴム樹脂５ｂで覆う。Here, the non-aqueous electrolyte battery having the above structure was manufactured as follows. First, after forming the positive and negative electrodes, the power generating element including the positive and negative electrodes and the separator is housed in the outer can 1. Next, the valve 6 and the sealing lid 2 are laser-welded, and the gas vent hole 10 of the sealing lid 2 is closed with the valve 6. Thereafter, the ternary fluororubber resin was dissolved in a 10% methyl ethyl ketone solution, and the solution was further applied to the laser welded portion 7 and the entire valve body 6 with a brush. Is covered with a fluororubber resin 5b.
【００１９】しかる後、外装缶１と封口蓋２とをレーザ
ー溶接した後、注液口１１から電池内に電解液を注入
し、更に蓋体８と封口蓋２とをレーザー溶接して、封口
蓋２の注液口１１を蓋体８で塞ぐ。次に、外装缶１と封
口蓋２とのレーザー溶接部４と蓋体８と封口蓋２とレー
ザー溶接部９とに、上記と同一のメチルエチルケトン溶
液をはけで塗り付けた後、自然乾燥させて、これらをフ
ッ素ゴム樹脂５ａ・５ｃで覆う。これにより非水電解質
電池が作製される。Thereafter, after the outer can 1 and the lid 2 are laser-welded, an electrolytic solution is injected into the battery from the liquid inlet 11 and the lid 8 and the lid 2 are laser-welded. The liquid inlet 11 of the lid 2 is closed with the lid 8. Next, the same methyl ethyl ketone solution as described above was applied to the laser welding portion 4, the lid 8, the sealing lid 2, and the laser welding portion 9 of the outer can 1 and the sealing lid 2 by brush, and then naturally dried. Then, these are covered with fluororubber resins 5a and 5c. Thus, a non-aqueous electrolyte battery is manufactured.
【００２０】尚、フッ素ゴム樹脂としては、上記三元系
のフッ素ゴム樹脂に限定するものではなく、フッ化ビニ
リデンと六フッ化プロピレンとの二元共重合体から成る
二元系のフッ素ゴム樹脂等であっても良い。但し、フッ
化ビニリデンと六フッ化プロピレンと四フッ化エチレン
との三元共重合体から成る三元系のフッ素ゴム樹脂であ
れば、フッ化ビニリデンはアモルファス部分が６０％と
少なく堅くて緻密であるという性質、六フッ化プロピレ
ンはアモルファス部分が７５％と多く弾性に富むという
性質、四フッ化エチレン単独では弾性変形が非常に大き
くなるという性質を有している。したがって、三元共重
合体から成る三元系のフッ素ゴム樹脂を用いると、弾性
力が大きくて応力を吸収できるので剥離することがな
く、しかもアモルファス部分の存在により、結晶材料に
比べてガス透過性が小さくなるという利点がある。加え
て、有機溶媒に可溶で、温度変化による塗膜の厚み変化
を吸収することもできる。また、本発明にはポリテトラ
フルオロエチレン（ＰＴＦＥ）やポリフッ化ビニリデン
（ＰＶｄＦ）等のフッ素樹脂は含まれない。なぜなら、
ＰＴＦＥにおいては、有機溶媒に不溶で水に溶解させる
必要があるが、このような水性ディスパージョンから沈
降する塗膜は弾性力は有るが緻密性に劣るため、ガス透
過性が大きくなる一方、ＰＶｄＦにおいては、有機溶媒
に可溶で塗膜は緻密になるが、弾性力に劣るため剥離を
生じるという理由によるものである。The fluororubber resin is not limited to the above-mentioned ternary fluororubber resin, but may be a binary fluororubber resin comprising a binary copolymer of vinylidene fluoride and propylene hexafluoride. And so on. However, if the tertiary fluororubber resin is made of a terpolymer of vinylidene fluoride, propylene hexafluoride and ethylene tetrafluoride, the vinylidene fluoride is hard and dense with a small amorphous portion of 60%. Propylene hexafluoride has a property that the amorphous portion is as large as 75% and is rich in elasticity, and a property that elastic deformation is extremely large when tetrafluoroethylene alone is used. Therefore, when a tertiary fluororubber resin made of a terpolymer is used, the elastic force is large and the stress can be absorbed, so there is no peeling, and the presence of the amorphous portion allows gas permeation as compared with a crystalline material. There is an advantage that performance is reduced. In addition, it is soluble in an organic solvent and can absorb a change in thickness of a coating film due to a change in temperature. Further, the present invention does not include a fluororesin such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVdF). Because
In PTFE, it is necessary to dissolve in water without dissolving in an organic solvent. However, a coating film settled from such an aqueous dispersion has elasticity but is inferior in denseness, so that gas permeability becomes large, while PVdF Is soluble in an organic solvent, and the coating film becomes dense, but peels off due to poor elasticity.
【００２１】また、正極材料としては上記ＬｉＣｏＯ2
の他、例えば、ＬｉＮｉＯ2 、ＬｉＭｎ2 Ｏ4 或いはこ
れらの複合体等が好適に用いられ、また負極材料として
は天然黒鉛、グラファイト、カーボンブラック、コーク
ス、ガラス状炭素、炭素繊維或いはこれらの焼成体等が
好適に用いられる。加えて、電解質塩としては、上記Ｌ
ｉＰＦ6 に限定するものではなく、ＬｉＣｌＯ4 、Ｌｉ
ＢＦ4 、ＬｉＣＦ3 ＳＯ3 等を用いることも可能であ
が、上述した理由によりＬｉＰＦ6 を用いるのが望まし
い。The above-mentioned LiCoO 2 is used as a positive electrode material.
In addition, for example, LiNiO 2 , LiMn 2 O 4 or a composite thereof is preferably used, and as a negative electrode material, natural graphite, graphite, carbon black, coke, glassy carbon, carbon fiber, or a fired body thereof is used. Etc. are preferably used. In addition, as the electrolyte salt, the above L
It is not limited to iPF 6 , but may be LiClO 4 , Li
It is possible to use BF 4 , LiCF 3 SO 3 or the like, but it is preferable to use LiPF 6 for the above-described reason.
【００２２】[0022]
【実施例】〔実施例〕封口蓋と外装缶とのレーザー溶接
部のみを三元系のフッ素ゴム樹脂で覆い、弁体と封口蓋
とのレーザー溶接部、弁体の全体及び蓋体と封口蓋との
レーザー溶接部は三元系のフッ素ゴム樹脂で覆わない他
は、上記発明の実施の形態と同様にして電池を作製し
た。このようにして作製した電池を、以下、本発明電池
Ａと称する。[Example] [Example] Only the laser welding portion between the sealing lid and the outer can is covered with a ternary fluororubber resin, the laser welding portion between the valve body and the sealing lid, the entire valve body, and the lid and the sealing body. A battery was fabricated in the same manner as in the above embodiment of the invention except that the laser welded portion to the lid was not covered with a ternary fluororubber resin. The battery fabricated in this manner is hereinafter referred to as Battery A of the invention.
【００２３】〔比較例１〕封口蓋と外装缶とのレーザー
溶接部を三元系のフッ素ゴム樹脂ではなく、ＰＴＦＥか
ら成るフッ素樹脂で覆う他は、上記実施例１と同様にし
て電池を作製した。尚、具体的には、ＰＴＦＥ（三井フ
ロロケミカル社製のＰＴＦＥ−３０Ｊ）を水に溶解させ
て、ＰＴＦＥを１０％含む水性ディスパージョン溶液を
作製した後、この溶液をレーザー溶接部にはけで塗り付
け自然乾燥させることによりフッ素樹脂皮膜（厚さ：１
５μｍ）を形成した。このようにして作製した電池を、
以下、比較電池Ｘ１と称する。Comparative Example 1 A battery was fabricated in the same manner as in Example 1 except that the laser welded portion between the sealing lid and the outer can was covered with a fluororesin made of PTFE instead of a ternary fluororubber resin. did. In addition, specifically, PTFE (PTFE-30J manufactured by Mitsui Fluorochemicals Co., Ltd.) is dissolved in water to prepare an aqueous dispersion solution containing 10% of PTFE, and then this solution is applied to a laser welded portion. Fluorine resin film (thickness: 1)
5 μm). The battery fabricated in this way is
Hereinafter, it is referred to as a comparative battery X1.
【００２４】〔比較例２〕封口蓋と外装缶とのレーザー
溶接部を三元系のフッ素ゴム樹脂ではなく、ＰＶｄＦか
ら成るフッ素樹脂で覆う他は、上記実施例１と同様にし
て電池を作製した。尚、具体的には、ＰＶｄＦを５％含
むＮ−メチル−２−ピロリドン溶液を作製した後、この
溶液をレーザー溶接部にはけで塗り付け１００℃で２分
間乾燥させることによりフッ素樹脂皮膜（厚さ：１８μ
ｍ）を形成した。このようにして作製した電池を、以
下、比較電池Ｘ２と称する。Comparative Example 2 A battery was fabricated in the same manner as in Example 1 except that the laser welded portion between the sealing lid and the outer can was covered with a fluororesin made of PVdF instead of a ternary fluororubber resin. did. Specifically, after preparing an N-methyl-2-pyrrolidone solution containing 5% of PVdF, the solution was applied to a laser-welded portion with a brush and dried at 100 ° C. for 2 minutes to form a fluororesin film ( Thickness: 18μ
m) was formed. The battery fabricated in this manner is hereinafter referred to as Comparative Battery X2.
【００２５】〔比較例３〕封口蓋と外装缶とのレーザー
溶接部を三元系のフッ素ゴム樹脂で覆わない他は、上記
実施例１と同様にして電池を作製した。このようにして
作製した電池を、以下、比較電池Ｘ３と称する。Comparative Example 3 A battery was manufactured in the same manner as in Example 1 except that the laser welded portion between the sealing lid and the outer can was not covered with a ternary fluororubber resin. The battery fabricated in this manner is hereinafter referred to as Comparative Battery X3.
【００２６】〔実験１〕上記本発明電池Ａ及び比較電池
Ｘ１〜Ｘ３について、以下のような実験を行ったので、
その結果を表１に示す。先ず、下記の条件で充電した
後、下記の条件で放電することにより各電池の初期容量
を測定した。次に、下記の条件で充電した後、恒温槽内
で５０℃で３０日間電池を保存し、更に保存直後の電池
を下記の条件で放電して保存直後の電池容量を測定し
た。次いで、常温且つ下記の条件で充電した後、下記の
条件で放電することにより各電池の保存後の固有電池容
量を測定した。尚、電池の試料数は、各電池１０個ずつ
である。[Experiment 1] The following experiment was conducted on the battery A of the present invention and the comparative batteries X1 to X3.
Table 1 shows the results. First, the battery was charged under the following conditions and then discharged under the following conditions to measure the initial capacity of each battery. Next, after charging under the following conditions, the battery was stored in a thermostat at 50 ° C. for 30 days, and the battery immediately after storage was discharged under the following conditions to measure the battery capacity immediately after storage. Next, the battery was charged at room temperature and under the following conditions, and then discharged under the following conditions to measure the specific battery capacity of each battery after storage. The number of battery samples is 10 for each battery.
【００２７】充電条件：定電流、定電圧充電であり、具
体的には、６００ｍＡの電流で電池電圧が４．１Ｖにな
った後、電流値が２５ｍＡに低下した時点で充電を終了
する。 放電条件：定電流放電であり、具体的には、５００ｍＡ
の電流で電池電圧が２．７５Ｖになった時点で放電を終
了する。Charging conditions: Constant current and constant voltage charging. Specifically, after the battery voltage reaches 4.1 V at a current of 600 mA, the charging is terminated when the current value drops to 25 mA. Discharge conditions: constant current discharge, specifically, 500 mA
When the battery voltage reaches 2.75 V with the current of 2, the discharge is terminated.
【００２８】[0028]
【表１】 [Table 1]
【００２９】表１から明らかなように、本発明電池Ａ及
び比較電池Ｘ１〜Ｘ３は、初期容量においては差異が認
められない。しかしながら、比較電池Ｘ１〜Ｘ３では、
保存直後の電池容量及び保存後の固有電池容量が低下
し、しかもバラツキが大きくなっているのに対して、本
発明電池Ａでは、保存直後の電池容量及び保存後の固有
電池容量の低下が小さく、しかもバラツキも小さいこと
が認められる。したがって、レーザー溶接部を全く覆わ
ないか、或いは単にフッ素樹脂で覆うだけでは、アルミ
ニウム等の金属が腐食するのを十分に抑制することがで
きないことがわかる。As is evident from Table 1, there is no difference in the initial capacity between the battery A of the present invention and the comparative batteries X1 to X3. However, in the comparative batteries X1 to X3,
While the battery capacity immediately after storage and the specific battery capacity after storage are reduced and the variation is large, the battery A of the present invention has a small decrease in the battery capacity immediately after storage and the specific battery capacity after storage. Moreover, it is recognized that the variation is small. Therefore, it can be understood that corrosion of a metal such as aluminum cannot be sufficiently suppressed by not covering the laser welded portion at all or simply covering it with the fluororesin.
【００３０】尚、上記実験では、封口蓋と外装缶とのレ
ーザー溶接部のみを三元系のフッ素ゴム樹脂で覆い、弁
体と封口蓋とのレーザー溶接部、弁体の全体及び蓋体と
封口蓋とのレーザー溶接部は三元系のフッ素ゴム樹脂で
覆わなかったが、これらを三元系のフッ素ゴム樹脂で覆
った場合にも上記と同様の効果を有することを実験によ
り確認している。In the above experiment, only the laser welding portion between the sealing lid and the outer can was covered with a ternary fluororubber resin, and the laser welding portion between the valve body and the sealing lid, the entire valve body, and the lid were removed. Although the laser welded part with the sealing lid was not covered with the ternary fluororubber resin, it was confirmed by experiments that the same effect as above was obtained when these were covered with the ternary fluororubber resin. I have.
【００３１】[0031]
【発明の効果】以上説明したように、本発明によれば、
例えフッ酸が発生した場合であっても、アルミニウム等
の金属が腐食するのを十分抑制することによって、電解
液の漏出による電池容量が低下等を長期間にわたって防
止することができるといった優れた効果を奏する。As described above, according to the present invention,
Even if hydrofluoric acid is generated, excellent effects such as a reduction in battery capacity due to leakage of electrolyte can be prevented over a long period of time by sufficiently suppressing corrosion of metals such as aluminum. To play.
【図１】図１は本発明の実施の形態に係る非水電解質電
池の斜視図である。FIG. 1 is a perspective view of a nonaqueous electrolyte battery according to an embodiment of the present invention.
【図２】図２は封口蓋と外装缶とのレーザ溶接部の拡大
断面図である。FIG. 2 is an enlarged sectional view of a laser welded portion between a sealing lid and an outer can.
【図３】図３は本発明に用いる安全弁の拡大断面図であ
る。FIG. 3 is an enlarged sectional view of a safety valve used in the present invention.
【図４】図４は本発明に用いる注液口の拡大断面図であ
る。FIG. 4 is an enlarged sectional view of a liquid inlet used in the present invention.
１：外装缶 ２：封口蓋 ３：ラミネート外装体 ４：レーザー溶接部 ５ａ：三元系のフッ素ゴム樹脂 ５ｂ：三元系のフッ素ゴム樹脂 ５ｃ：三元系のフッ素ゴム樹脂 ６：弁体 ７：レーザー溶接部 ８：蓋体 ９：レーザー溶接部 １０：ガス排出孔 1: Exterior can 2: Sealing lid 3: Laminated exterior 4: Laser weld 5a: Ternary fluoro rubber resin 5b: Ternary fluoro rubber resin 5c: Ternary fluoro rubber resin 6: Valve body 7 : Laser weld 8: Lid 9: Laser weld 10: Gas exhaust hole
Claims (5)
の外装缶と、この外装缶の開口部を封口する金属製の封
口蓋とを有し、この封口蓋と上記外装缶とがレーザー溶
接される非水電解質電池において、 上記レーザー溶接部がフッ素ゴム樹脂で被覆されている
ことを特徴とする非水電解質電池。1. A metal-made cylindrical outer can having a bottom in which a power generating element is housed, and a metal sealing lid for closing an opening of the outer can. A non-aqueous electrolyte battery, wherein the laser-welded portion is coated with a fluororubber resin.
の外装缶と、この外装缶の開口部を封口する金属製の封
口蓋とを有すると共に、上記封口蓋には電解液を注液す
るための注液口が形成され、且つこの注液口は上記封口
蓋にレーザー溶接された金属製の蓋体により塞がれる非
水電解質電池において、 上記レーザー溶接部がフッ素ゴム樹脂で被覆されている
ことを特徴とする非水電解質電池。2. A metal-made bottomed cylindrical outer can containing a power-generating element, a metal sealing lid for closing an opening of the outer can, and an electrolytic solution is supplied to the sealing lid. A non-aqueous electrolyte battery in which a liquid injection port for liquid injection is formed, and the liquid injection port is closed by a metal lid that is laser-welded to the sealing lid, wherein the laser-welded portion is made of fluororubber resin. A nonaqueous electrolyte battery characterized by being coated.
の外装缶と、この外装缶の開口部を封口する金属製の封
口蓋とを有すると共に、上記封口蓋には、当該封口蓋を
貫通するガス排出孔と、上記封口蓋にレーザー溶接され
て通常の状態では上記ガス排出孔を塞いでいる薄板状で
金属製の弁体とからなる安全弁が設けられた非水電解質
電池において、 上記レーザー溶接部と上記弁体とがフッ素ゴム樹脂で被
覆されていることを特徴とする非水電解質電池。3. A metal-clad, bottomed cylindrical outer can containing a power generating element, and a metal sealing lid for closing an opening of the outer can. In a non-aqueous electrolyte battery provided with a gas discharge hole penetrating the lid, and a safety valve comprising a thin plate-shaped metal valve element which is laser-welded to the sealing lid in a normal state and covers the gas discharge hole. A nonaqueous electrolyte battery, wherein the laser welded portion and the valve body are covered with a fluororubber resin.
１、２又は３記載の非水電解質電池。4. The non-aqueous electrolyte battery according to claim 1, wherein the metal is aluminum.
る、請求項１、２、３又は４記載の非水電解質電池。5. The non-aqueous electrolyte battery according to claim 1, wherein LiPF 6 is used as an electrolyte salt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05793898A JP3902322B2 (en) | 1998-03-10 | 1998-03-10 | Non-aqueous electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05793898A JP3902322B2 (en) | 1998-03-10 | 1998-03-10 | Non-aqueous electrolyte battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11260329A true JPH11260329A (en) | 1999-09-24 |
| JP3902322B2 JP3902322B2 (en) | 2007-04-04 |
Family
ID=13069980
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP05793898A Expired - Fee Related JP3902322B2 (en) | 1998-03-10 | 1998-03-10 | Non-aqueous electrolyte battery |
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| Country | Link |
|---|---|
| JP (1) | JP3902322B2 (en) |
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| JP2011124156A (en) * | 2009-12-11 | 2011-06-23 | Kurita Water Ind Ltd | Material of nonaqueous electrolyte secondary battery |
| JP2011124202A (en) * | 2010-03-30 | 2011-06-23 | Kurita Water Ind Ltd | Nonaqueous electrolyte secondary battery |
| DE102015108530A1 (en) | 2014-05-30 | 2015-12-03 | Toyota Jidosha Kabushiki Kaisha | Composite battery |
| JP2018505517A (en) * | 2014-12-08 | 2018-02-22 | 東莞新能源科技有限公司Ｄｏｎｇｇｕａｎ Ａｍｐｅｒｅｘ Ｔｅｃｈｎｏｌｏｇｙ Ｌｉｍｉｔｅｄ | Electrochemical energy storage device |
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| JP2003168404A (en) * | 2001-11-30 | 2003-06-13 | Sanyo Electric Co Ltd | Nonaqueous electrolyte battery |
| JP2011124156A (en) * | 2009-12-11 | 2011-06-23 | Kurita Water Ind Ltd | Material of nonaqueous electrolyte secondary battery |
| JP2011124202A (en) * | 2010-03-30 | 2011-06-23 | Kurita Water Ind Ltd | Nonaqueous electrolyte secondary battery |
| DE102015108530A1 (en) | 2014-05-30 | 2015-12-03 | Toyota Jidosha Kabushiki Kaisha | Composite battery |
| JP2015228295A (en) * | 2014-05-30 | 2015-12-17 | トヨタ自動車株式会社 | Assembled battery |
| CN105280845A (en) * | 2014-05-30 | 2016-01-27 | 丰田自动车株式会社 | Assembled battery |
| US9564618B2 (en) | 2014-05-30 | 2017-02-07 | Toyota Jidosha Kabushiki Kaisha | Assembled battery |
| JP2018505517A (en) * | 2014-12-08 | 2018-02-22 | 東莞新能源科技有限公司Ｄｏｎｇｇｕａｎ Ａｍｐｅｒｅｘ Ｔｅｃｈｎｏｌｏｇｙ Ｌｉｍｉｔｅｄ | Electrochemical energy storage device |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3902322B2 (en) | 2007-04-04 |
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