JP3272937B2 - Non-aqueous electrolyte secondary battery - Google Patents
Non-aqueous electrolyte secondary batteryInfo
- Publication number
- JP3272937B2 JP3272937B2 JP05476896A JP5476896A JP3272937B2 JP 3272937 B2 JP3272937 B2 JP 3272937B2 JP 05476896 A JP05476896 A JP 05476896A JP 5476896 A JP5476896 A JP 5476896A JP 3272937 B2 JP3272937 B2 JP 3272937B2
- Authority
- JP
- Japan
- Prior art keywords
- thin plate
- sealing body
- secondary battery
- aqueous electrolyte
- cut groove
- 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
-
- 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
Landscapes
- Secondary Cells (AREA)
- Gas Exhaust Devices For Batteries (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明、安全弁機構を有する
非水電解液二次電池に関する。The present invention relates to a non-aqueous electrolyte secondary battery having a safety valve mechanism.
【０００２】[0002]
【従来の技術】最近、携帯電話やビデオカメラ等の電子
機器や、コンピュータ等の小型化、軽量化、高性能化に
伴い、これらの電子機器などの電源となる二次電池につ
いても、軽量で、エネルギー密度が高く、さらに繰り返
し充放電が可能である等の要求が高まっている。2. Description of the Related Art In recent years, as electronic devices such as mobile phones and video cameras and computers and the like have become smaller, lighter, and more sophisticated, secondary batteries serving as power sources for these electronic devices have also become lighter. There is a growing demand for high energy density and the ability to repeatedly charge and discharge.
【０００３】水の分解電圧以上の高電圧化が可能な非水
電解液二次電池は、従来から使用されてきた鉛二次電池
やニッケルカドミウム二次電池に代わる二次電池として
開発が進んでいる。このような非水電解液二次電池は、
負極材料としてコークス、黒鉛、有機物焼結体等のリチ
ウムを吸蔵・放出することが可能な炭素材料を用い、正
極活物質としてＬｉＣｏＯ2 、ＬｉＮｉＯ2 などのリチ
ウムイオンを吸蔵・放出することが可能な金属酸化物を
用いたリチウムイオン二次電池が提案されている。A non-aqueous electrolyte secondary battery capable of increasing the voltage higher than the decomposition voltage of water has been developed as a secondary battery that replaces conventionally used lead secondary batteries and nickel cadmium secondary batteries. I have. Such a non-aqueous electrolyte secondary battery,
A carbon material capable of occluding and releasing lithium such as coke, graphite, and an organic sintered body is used as a negative electrode material, and lithium ions such as LiCoO 2 and LiNiO 2 can be inserted and released as a positive electrode active material. A lithium ion secondary battery using a metal oxide has been proposed.
【０００４】しかしながら、前記非水電解液二次電池は
上述した利点を有する反面、信頼性が乏しいという問題
があった。その一つとして、外装缶内に収納された正極
および負極を有する電極体が化学変化を起こして内圧が
高くなり、発火、破裂を生じる場合がある。例えば、リ
チウムイオン二次電池のような非水電解液電池に通常以
上の電流を与える、いわゆる過充電状態にしたり、誤使
用により短絡状態になって大電流が流れたりすると前記
電極体の中の非水電解液が分解されてガスが発生する場
合がある。このようなガスが前記外装缶内に次第に充満
し、外装缶内の内圧が上昇すると、最後には電池が破裂
する。[0004] However, the above-mentioned non-aqueous electrolyte secondary battery has the above-mentioned advantages, but has a problem of poor reliability. As one of them, there is a case where an electrode body having a positive electrode and a negative electrode housed in an outer can undergoes a chemical change to increase the internal pressure, thereby causing ignition and rupture. For example, applying a current higher than normal to a non-aqueous electrolyte battery such as a lithium ion secondary battery, or in a so-called overcharged state, or when a large current flows due to a short circuit due to misuse, the inside of the electrode body The non-aqueous electrolyte may be decomposed to generate gas. Such a gas gradually fills the outer can, and when the internal pressure in the outer can increases, the battery eventually bursts.
【０００５】このようなことから、従来では前述した電
池の破裂を防止するために外装缶の内圧が一定値以上に
達した場合、発生ガスを外装缶の外に放出し、破裂を防
止するための安全弁機構が設けられている。このような
安全弁機構を備えた非水電解液二次電池は、次のような
構造のものが知られている。すなわち、この非水電解液
二次電池は有底筒状の外装缶と、前記外装缶内に収納さ
れ、正極、セパレータおよび負極を渦巻き状に巻回した
電極体と、前記外装缶内に収容された非水電解液と、前
記外装缶の上端開口部に設けられた封口体とを備え、前
記封口体に圧力開放用孔を開口し、かつ前記封口体（例
えばその下面）の前記孔を塞ぐように設けられた切り込
み溝を有する金属薄板を取り付けた構造になっている。
前記切り込み溝は、例えば直線部およびこの両端をＶ字
型にした形状を有する。前記封口体の圧力開放用孔およ
び前記切り込み溝を有する薄板からなる安全便機構を有
する二次電池において、その内圧が過電流等により上昇
すると、前記切り込み溝部分から薄板が破断されて孔が
形成される。この孔および前記圧力開放用孔を通して前
記外装缶内に充満したガスが放出され、爆発が未然に防
止される。なお、前記内圧上昇に伴う爆発を防止するた
めには前記安全弁機構の作動圧は１５±５ｋｇｆ／ｃｍ
2 であることが好ましい。In view of the above, conventionally, when the internal pressure of the outer can reaches a certain value or more, the generated gas is discharged to the outside of the outer can to prevent the rupture of the battery. Is provided. A non-aqueous electrolyte secondary battery having such a safety valve mechanism is known to have the following structure. That is, this non-aqueous electrolyte secondary battery is a cylindrical outer can with a bottom, housed in the outer can, an electrode body in which a positive electrode, a separator and a negative electrode are spirally wound, and housed in the outer can. A non-aqueous electrolyte solution, and a sealing body provided at an upper end opening of the outer can, a pressure release hole is opened in the sealing body, and the hole of the sealing body (for example, the lower surface) is closed. It has a structure in which a thin metal plate having a cut groove provided so as to close it is attached.
The cut groove has, for example, a shape in which a straight portion and both ends thereof are V-shaped. In a secondary battery having a safety convenience mechanism comprising a thin plate having a pressure releasing hole and the cut groove of the sealing body, when the internal pressure increases due to overcurrent or the like, the thin plate is broken from the cut groove portion to form a hole. Is done. The gas filled in the outer can is released through the hole and the pressure release hole, thereby preventing explosion. In order to prevent the explosion caused by the rise of the internal pressure, the operating pressure of the safety valve mechanism is 15 ± 5 kgf / cm.
It is preferably 2 .
【０００６】しかしながら、前記切り込み溝を形成し、
その底部が前記作動圧で確実に破断される金属薄板を有
する安全弁機構を付設した非水電解液二次電池におい
て、落下衝撃、とりわけ前記安全弁機構が付設された封
口体に直接に落下衝撃を受けると、所定の作動圧以下で
あるにもかかわらず、前記薄板の切り込み溝が破断され
て開放状態になり、電池機能を喪失するか、外装缶内に
収容された電解液が外部に漏れだし周辺機器を損傷する
という問題があった。However, the cut groove is formed,
In a non-aqueous electrolyte secondary battery provided with a safety valve mechanism having a metal sheet whose bottom is reliably broken by the operating pressure, a drop impact, particularly, a drop impact is directly received by a sealing body provided with the safety valve mechanism. In spite of being below the predetermined operating pressure, the cut groove of the thin plate is broken to open, and the battery function is lost or the electrolyte contained in the outer can leaks out and leaks around. There was a problem that the equipment was damaged.
【０００７】すなわち、落下試験に際し、外装缶内に収
容された非水電解液が大きな加速度をもって外装缶の落
下面に衝撃を与える。特に、落下面が安全弁機構が付設
された封口体表面であると、前記衝撃は前記封口体に取
り付けられた薄板を凸状に変形するように加わる。この
時、前記落下衝撃によって前記薄板の切り込み溝を広げ
るように引き裂き応力が加わるため、前記切り込み溝が
形成された薄板の強度が低下する。その結果、前記薄板
が所定の作動圧未満で破断されて開放状態になる。That is, in the drop test, the non-aqueous electrolyte contained in the outer can impacts the falling surface of the outer can with a large acceleration. In particular, when the falling surface is the surface of the sealing body provided with the safety valve mechanism, the impact is applied so as to deform the thin plate attached to the sealing body into a convex shape. At this time, a tearing stress is applied so as to widen the cut groove of the thin plate by the drop impact, so that the strength of the thin plate formed with the cut groove is reduced. As a result, the thin plate is broken below a predetermined operating pressure, and becomes open.
【０００８】このような落下衝撃に対しては、安全弁機
構の作動圧を高めることが考えられるが、作動圧を高め
ると当初の目的である過充電や短絡減少による電池の内
圧上昇を防止する効果が著しく損なわれる。It is conceivable to increase the operating pressure of the safety valve mechanism against such a drop impact. However, if the operating pressure is increased, the effect of preventing an increase in the internal pressure of the battery due to the initial purpose of overcharging and short circuit reduction is considered. Is significantly impaired.
【０００９】[0009]
【発明が解決しようとする課題】本発明は、所定の作動
圧で確実に破断され、かつ落下衝撃に対して良好な強度
を保持した安全弁機構を備えた非水電解液二次電池を提
供しようとするものである。SUMMARY OF THE INVENTION The present invention is to provide a non-aqueous electrolyte secondary battery provided with a safety valve mechanism which is reliably broken at a predetermined operating pressure and has good strength against a drop impact. It is assumed that.
【００１０】[0010]
【課題を解決するための手段】本発明に係わる非水電解
液二次電池は、有底筒状の外装缶と、前記外装缶内に収
納され、正極、セパレータおよび負極を渦巻き状に巻回
した電極体と、前記外装缶内に収容された非水電解液
と、前記外装缶の上端開口部に設けられ、圧力開放用孔
が開口された封口体と、前記封口体に前記圧力開放用孔
を塞ぐように取り付けられ、切り込み溝が形成された薄
板と、前記封口体に前記薄板上面を覆うように取り付け
られたゴム弾性を有する高分子材料被膜とを具備したこ
とを特徴とするものである。A non-aqueous electrolyte secondary battery according to the present invention comprises a cylindrical outer can having a bottom and a positive electrode, a separator and a negative electrode which are housed in the outer can and are spirally wound. Electrode body, a non-aqueous electrolyte contained in the outer can, a sealing body provided at the upper end opening of the outer can, and having a pressure opening hole, and a pressure releasing hole for the sealing body. A thin plate attached to close the hole and formed with a notch groove, and a polymer material film having rubber elasticity attached to the sealing body so as to cover the upper surface of the thin plate. is there.
【００１１】[0011]
【発明の実施の形態】以下、本発明を図１および図２に
示す角形の非水電解液二次電池を例にして詳細に説明す
る。図１は、本発明に係わる非水電解液二次電池の要部
斜視図、図２は同電池の縦断面図である。例えばステン
レスからなる負極端子を兼ねる有底矩形筒状の外装缶１
内には、電極体２が収納されている。前記電極体２は、
正極３、セパレータ４および負極５の積層物を渦巻状に
巻回して構成されている。なお、前記電極体２は籠形の
電極カバー６に収納されている。非水電解液は、前記外
装缶１内に収容されている。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described below in detail with reference to a prismatic nonaqueous electrolyte secondary battery shown in FIGS. FIG. 1 is a perspective view of a main part of a non-aqueous electrolyte secondary battery according to the present invention, and FIG. 2 is a longitudinal sectional view of the battery. For example, a bottomed rectangular cylindrical outer can 1 also serving as a negative electrode terminal made of stainless steel
The electrode body 2 is housed inside. The electrode body 2 is
A laminate of the positive electrode 3, the separator 4, and the negative electrode 5 is spirally wound. The electrode body 2 is housed in a basket-shaped electrode cover 6. The non-aqueous electrolyte is contained in the outer can 1.
【００１２】中央に円形穴７およびこの穴７に隣接した
個所に矩形状の圧力開放用孔８がそれぞれ開口された例
えばステンレスからなる封口体９は、前記外装缶１の上
端開口部にレーザ溶接により気密に取り付けられてい
る。例えばステンレスからなる正極端子ピン１０は、前
記封口体９の前記穴７内にその上下端が前記封口体９の
上下面から突出するように挿入されていると共に、前記
穴７に充填されたガラス製絶縁材１１によりハーメティ
クシールされている。前記正極端子ピン１０は、リード
１２により前記電極体２の正極３と接続されている。A sealing body 9 made of, for example, stainless steel having a circular hole 7 in the center and a rectangular pressure release hole 8 at a position adjacent to the hole 7 is laser-welded to the upper end opening of the outer can 1. More airtight. For example, the positive electrode terminal pin 10 made of stainless steel is inserted into the hole 7 of the sealing body 9 so that the upper and lower ends thereof protrude from the upper and lower surfaces of the sealing body 9, and the glass filled in the hole 7. Hermetically sealed by the insulating material 11. The positive electrode terminal pin 10 is connected to the positive electrode 3 of the electrode body 2 by a lead 12.
【００１３】例えばステンレスからなる矩形状の薄板１
３は、前記封口体９の下面に前記圧力開放用孔８を塞ぐ
ようにレーザ溶接により気密に取り付けられている。直
線部およびこの両端をＶ字型にした形状を有する切り込
み溝１４は、前記薄板１３の上面に形成され、この切り
込み溝１４により溝部分は薄膜化されている。なお、前
記切り込み溝１４は、前記薄板１３の下面に前記形状の
パンチでプレス加工するか、もしくはエッチングを行う
ことにより形成される。前記封口体９の圧力開放用孔８
および前記切り込み溝１４を有する薄板１３とにより安
全弁機構を構成している。For example, a rectangular thin plate 1 made of stainless steel
Reference numeral 3 is hermetically attached to the lower surface of the sealing body 9 by laser welding so as to cover the pressure release hole 8. A straight portion and a cut groove 14 having a V-shaped shape at both ends are formed on the upper surface of the thin plate 13, and the groove portion is thinned by the cut groove 14. The cut groove 14 is formed by pressing or etching the lower surface of the thin plate 13 with a punch having the above-described shape. Pressure release hole 8 of the sealing body 9
The thin plate 13 having the cut groove 14 constitutes a safety valve mechanism.
【００１４】ゴム弾性を有する高分子材料被膜１５は、
前記封口体９の前記圧力開放用孔８内に前記薄板１３の
切り込み溝１４を覆うように充填されている。次に、前
記正極３、負極５及び非水電解液について説明する。The polymer material film 15 having rubber elasticity is
The pressure releasing hole 8 of the sealing body 9 is filled so as to cover the cut groove 14 of the thin plate 13. Next, the positive electrode 3, the negative electrode 5, and the non-aqueous electrolyte will be described.
【００１５】１）正極３ この正極３は、アルミニウム箔、アルミニウム製メッシ
ュ、アルミニウム製パンチドメタル、アルミニウム製ラ
スメタルのような集電体３ａの両面に例えばＬｉx ＭＯ
2 （ただし、ＭはＣｏ、Ｎｉのような遷移金属、ｘは
０．０５≦ｘ≦１．１０を示す）で表される活物質を含
む正極合剤３ｂを形成した構造を有する。前記活物質
は、具体的にはＬｉＣｏ2 、ＬｉＮｉＯ2 、ＬｉＮｉy
ＣＯ(1-y) Ｏ2 （ただし、ｘは０．０５≦ｘ≦１．１
０、ｙは０＜ｙ，１を示す）で表される複合酸化物が挙
げられる。1) Positive Electrode 3 The positive electrode 3 is formed on both sides of a current collector 3a such as an aluminum foil, an aluminum mesh, an aluminum punched metal, or an aluminum lath metal by, for example, Li x MO.
2 (where M represents a transition metal such as Co or Ni, and x represents 0.05 ≦ x ≦ 1.10.) The positive electrode mixture 3b containing the active material is formed. The active material is specifically LiCo 2 , LiNiO 2 , LiNi y
CO (1-y) O 2 (where x is 0.05 ≦ x ≦ 1.1
0 and y represent 0 <y, 1).
【００１６】前記複合酸化物は、例えばリチウム、コバ
ルト、ニッケルの炭酸塩を出発原料とし、これらの炭酸
塩を所定量混合し、酸素雰囲気中、６００〜１０００℃
で焼成することにより得られる。また、前記出発原料は
炭酸塩に限らず、水酸化物、酸化物からも同様に合成可
能である。The composite oxide is prepared, for example, by using carbonates of lithium, cobalt and nickel as starting materials, mixing these carbonates in predetermined amounts, and heating at 600 to 1000 ° C. in an oxygen atmosphere.
It is obtained by baking. The starting materials are not limited to carbonates, but can be synthesized from hydroxides and oxides.
【００１７】２）負極５ この負極５は、銅箔、銅製メッシュ、銅製パンチドメタ
ル、銅製ラスメタルのような集電体５ａの両面にリチウ
ムを吸蔵・放出する材料を活物質として含む負極合剤５
ｂを形成した構造を有する。前記活物質としては、具体
的には熱分解炭素類；ピッチコークス、ニードルコーク
ス、石油コークスのようなコークス類；グラファイト
類；ガラス状炭素類；フェノール樹脂、フラン樹脂のよ
うな適当な温度で焼成化する有機高分子化合物焼成体；
炭素繊維；活性炭などの炭素材料、または金属リチウ
ム、リチウム−アルミニウム合金のようなリチウム合
金、ポリアセチレン、ポリピロールなどのポリマーを用
いることができる。2) Negative Electrode 5 The negative electrode 5 is a negative electrode mixture containing, as an active material, a material that absorbs and releases lithium on both surfaces of a current collector 5a such as copper foil, copper mesh, copper punched metal, and copper lath metal. 5
b. Specific examples of the active material include pyrolytic carbons; cokes such as pitch coke, needle coke and petroleum coke; graphites; glassy carbons; Organic polymer compound fired body to be converted;
Carbon fiber; a carbon material such as activated carbon; a lithium alloy such as lithium metal or a lithium-aluminum alloy; or a polymer such as polyacetylene or polypyrrole can be used.
【００１８】３）非水電解液 この非水電解液は、リチウム塩のような電解質を有機溶
媒で溶解したものである。3) Non-aqueous electrolyte This non-aqueous electrolyte is obtained by dissolving an electrolyte such as a lithium salt in an organic solvent.
【００１９】前記電解質としては、例えばＬｉＣｌＯ
4 、ＬｉＰＦ6 、ＬｉＡｓＦ6 、ＬｉＢＦ4 、ＬｉＣＦ
3 ＳＯ3 、ＬｉＢ（Ｃ6 Ｈ5 ）4 、ＬｉＣｌ、ＬｉＢ
ｒ、ＬｉＣＨ3 ＳＯ3 から選ばれる１種または２種以上
のリチウム塩を挙げることができる。As the electrolyte, for example, LiClO
4, LiPF 6, LiAsF 6, LiBF 4, LiCF
3 SO 3 , LiB (C 6 H 5 ) 4 , LiCl, LiB
r, one or more lithium salts selected from LiCH 3 SO 3 .
【００２０】前記有機溶媒としては、例えばプロピレン
カーボネート、エチレンカーボネート、１，２−ジメト
キシエタン、γ−ブチルラクトン、テトラヒドロフラ
ン、２−メチルテトラヒドロフラン、１，３−ジオキソ
ラン、スルホラン、アセトニトリル、ジエチレンカーボ
ネート、ジプロピルカーボネートから選ばれる１種また
は２種以上の混合物を挙げることができる。Examples of the organic solvent include propylene carbonate, ethylene carbonate, 1,2-dimethoxyethane, γ-butyllactone, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolan, sulfolane, acetonitrile, diethylene carbonate, dipropyl One type or a mixture of two or more types selected from carbonates can be mentioned.
【００２１】前記電解質の非水溶媒に対する溶解量は、
０．５〜１．５モル／ｌとすることが望ましい。前記ゴ
ム弾性を有する高分子材料は、この被膜が設けられる前
記薄板の素材であるステンレスに対して接着強度が低い
性質を有することが好ましい。このような性質は、ステ
ンレスに接着された時の引張り弾性率で定義することが
できる。すなわち、前記ゴム弾性を有する高分子材料は
前記引張り弾性率が４００ｋｇｆ／ｍｍ2 以下であるこ
とが好ましく、具体的にはシリコーン樹脂、フッ素樹脂
等を用いることができる。前記引張り弾性率が４００ｋ
ｇｆ／ｍｍ2 を越える高分子材料を用いると、前記高分
子材料被膜と前記薄板との接着強度が大きくなって内圧
上昇による電池の破裂、発火を防ぐ前記弁膜の破断が所
定の作動圧で行われなく恐れがある。The amount of the electrolyte dissolved in the non-aqueous solvent is as follows:
It is desirably 0.5 to 1.5 mol / l. The polymer material having rubber elasticity preferably has low adhesive strength to stainless steel, which is a material of the thin plate on which the coating is provided. Such properties can be defined by the tensile modulus of elasticity when bonded to stainless steel. That is, the polymer material having rubber elasticity preferably has a tensile modulus of 400 kgf / mm 2 or less, and specifically, a silicone resin, a fluororesin, or the like can be used. The tensile modulus is 400k
When a polymer material exceeding gf / mm 2 is used, the adhesive strength between the polymer material film and the thin plate is increased, so that the battery membrane is prevented from being ruptured due to an increase in internal pressure and the valve membrane is prevented from being broken at a predetermined operating pressure. There is fear that it is not done.
【００２２】前記ゴム弾性を有する高分子材料被膜、例
えば液状もしくはゲル状の高分子材料を封口体の所定の
部位に塗布、乾燥することにより形成される。以上説明
した本発明に係わる非水電解液二次電池によれば、外装
缶１の上端開孔部に設けられた封口体９の下面に切り込
み溝１４が形成された薄板１３を前記封口体９の圧力開
放用孔８を塞ぐように取り付け、かつ前記圧力開放用孔
８内にゴム弾性を有する高分子材料被膜１５を前記薄板
１３上面の少なくとも切り込み溝１４を覆うように充填
している。このため、過充電や短絡に起因して電池内の
温度上昇が生じ、前記外装缶１内に収納された電解液が
分解し、ガスが発生して内圧が上昇すると、前記薄板１
３が押上られて変形するため、所定の内圧以上に達する
と前記薄板１３の溝部分が破断し、同時にその上面の前
記高分子材料被膜１５が前記薄板１３から剥離し、前記
圧力開放用孔８が開放される。その結果、前記前記外装
缶１内に充満したガスを破断した薄板１３および前記封
口体９の圧力開放用孔８を通して外部に放出することが
できるため、前記外装缶１の破裂、変形を防止すること
ができる。The polymer material film having rubber elasticity, for example, a liquid or gel polymer material is applied to a predetermined portion of the sealing body and dried. According to the non-aqueous electrolyte secondary battery according to the present invention described above, the thin plate 13 in which the notch groove 14 is formed on the lower surface of the sealing body 9 provided at the upper opening of the outer can 1 is connected to the sealing body 9. The pressure releasing hole 8 is mounted so as to close the pressure releasing hole 8, and the polymer material film 15 having rubber elasticity is filled in the pressure releasing hole 8 so as to cover at least the cut groove 14 on the upper surface of the thin plate 13. For this reason, the temperature inside the battery rises due to overcharging or short-circuit, and the electrolytic solution contained in the outer can 1 is decomposed, and gas is generated to increase the internal pressure.
3 is pushed up and deformed, so that when a predetermined internal pressure or more is reached, the groove portion of the thin plate 13 is broken, and at the same time, the polymer material coating 15 on the upper surface of the thin plate 13 is peeled off from the thin plate 13 and the pressure release hole 8 is formed. Is released. As a result, the gas filled in the outer can 1 can be released to the outside through the ruptured thin plate 13 and the pressure release hole 8 of the sealing body 9, so that the rupture and deformation of the outer can 1 are prevented. be able to.
【００２３】また、前記封口体９の下面に切り込み溝１
４が形成された薄板１３を前記封口体９の圧力開放用孔
８を塞ぐように取り付け、かつ前記圧力開放用孔８内に
ゴム弾性を有する高分子材料被膜１５を前記薄板１３上
面の少なくとも切り込み溝１４を覆うように充填するこ
とによって、落下等の衝撃を受けても前記薄板が所定の
作動圧未満で破断されて開放状態になるのを阻止して電
池機能の喪失や外装缶内に収容された電解液の外部への
漏れだしを防止できる。Further, the cut groove 1 is formed on the lower surface of the sealing body 9.
The thin plate 13 on which the seal 4 is formed is attached so as to cover the pressure releasing hole 8 of the sealing body 9, and a polymer material film 15 having rubber elasticity is cut into the pressure releasing hole 8 at least in the upper surface of the thin plate 13. By filling the groove 14 so as to cover it, even if it receives an impact such as dropping, the thin plate is prevented from breaking under a predetermined operating pressure to be in an open state. The leaked electrolyte solution can be prevented from leaking to the outside.
【００２４】すなわち、落下の際に、外装缶１内に収容
された非水電解液が大きな加速度をもって外装缶１の落
下面に衝撃を与える。特に、落下面が安全弁機構が付設
された封口体９表面であると、前記衝撃は前記封口体９
に取り付けられた薄板１３を凸状に変形するように加わ
る。この時、前記封口体９下面に取り付けられた前記薄
板１３上面の少なくとも切り込み溝１４をゴム弾性を有
する前記高分子材料被膜１５で覆っているため、前記高
分子材料被膜１５が前記薄板１３に対して重石のように
作用し、前記薄板１３の変形を抑制できる。その結果、
前記落下に伴う衝撃により前記薄板１３の切り込み溝１
４を広げるような引き裂き応力が加わるのを緩和でき
る。その結果、前記切り込み溝１４部分の強度低下を抑
制できる。したがって、前記薄板１３が所定の作動圧未
満で破断されて開放状態になるのを阻止して電池機能の
喪失や外装缶内に収容された電解液の外部への漏れだし
を防止できる。That is, when falling, the non-aqueous electrolyte contained in the outer can 1 impacts the falling surface of the outer can 1 with a large acceleration. In particular, when the falling surface is the surface of the sealing body 9 provided with the safety valve mechanism, the impact is applied to the sealing body 9.
Is applied so as to deform the thin plate 13 attached to the convex shape. At this time, since at least the cut groove 14 on the upper surface of the thin plate 13 attached to the lower surface of the sealing body 9 is covered with the polymer material coating 15 having rubber elasticity, the polymer material coating 15 Acting like a weight, the deformation of the thin plate 13 can be suppressed. as a result,
The cut groove 1 of the thin plate 13
4 can be alleviated by the application of a tearing stress. As a result, a decrease in the strength of the cut groove 14 can be suppressed. Therefore, it is possible to prevent the thin plate 13 from being broken and opened under a predetermined operating pressure, thereby preventing the loss of the battery function and the leakage of the electrolyte contained in the outer can to the outside.
【００２５】次に、本発明に係わる別の非水電解液二次
電池を図３、図４、図５および図６を参照して説明す
る。なお、前述した図１および図２と同様な部材は同符
号を付して説明を省略する。Next, another non-aqueous electrolyte secondary battery according to the present invention will be described with reference to FIGS. 3, 4, 5 and 6. FIG. The same members as those in FIGS. 1 and 2 described above are denoted by the same reference numerals, and description thereof will be omitted.
【００２６】図３に示す非水電解液二次電池は、切り込
み溝１４を下面に設け、その切り込み溝１４が形成され
た薄板１３を封口体９の下面に圧力開放用孔８を塞ぐよ
うにレーザ溶接により気密に取り付け、かつ前記圧力開
放用孔８内にゴム弾性を有する高分子材料被膜１５を前
記薄板１３上面を覆うように充填した構造を有する。The non-aqueous electrolyte secondary battery shown in FIG. 3 is provided with a cut groove 14 on the lower surface, and the thin plate 13 having the cut groove 14 is formed on the lower surface of the sealing body 9 so as to cover the pressure release hole 8. It has a structure in which a polymer material film 15 having rubber elasticity is filled in the pressure release hole 8 so as to cover the upper surface of the thin plate 13 by airtightly attaching by laser welding.
【００２７】このような図３に示す構成の非水電解液二
次電池によれば、前述した図１、図２に示す構造の非水
電解液二次電池と同様、過充電や短絡に起因して電池内
の温度上昇による外装缶１の破裂、変形を防止すること
ができ、かつ落下等の衝撃を受けても前記弁膜が所定の
作動圧未満で破断されて開放状態になるのを阻止して電
池機能の喪失や外装缶内に収容された電解液の外部への
漏れだしを防止することができる。According to the non-aqueous electrolyte secondary battery having the structure shown in FIG. 3, the non-aqueous electrolyte secondary battery having the structure shown in FIGS. As a result, it is possible to prevent the outer can 1 from being ruptured or deformed due to a rise in the temperature inside the battery, and to prevent the valve membrane from being broken below a predetermined operating pressure and being opened even when subjected to an impact such as dropping. As a result, loss of the battery function and leakage of the electrolyte contained in the outer can to the outside can be prevented.
【００２８】図４および図５に示す非水電解液二次電池
は、切り込み溝１４を上面に設け、その切り込み溝１４
が形成された薄板１３を封口体９の上面に圧力開放用孔
８を塞ぐようにレーザ溶接により気密に取り付け、かつ
前記薄板１３を含む前記封口体９の上面に弾性を有する
高分子材料被膜１６を被覆した構造を有する。In the non-aqueous electrolyte secondary battery shown in FIGS. 4 and 5, a cut groove 14 is provided on the upper surface.
The thin plate 13 on which is formed is hermetically attached to the upper surface of the sealing body 9 by laser welding so as to cover the pressure release hole 8, and an elastic polymer film 16 on the upper surface of the sealing body 9 including the thin plate 13. Having a structure coated with
【００２９】このような図４および図５に示す構成の非
水電解液二次電池によれば、過充電や短絡に起因して電
池内の温度上昇が生じ、外装缶１内に収納された電解液
が分解し、ガスが発生して内圧が上昇すると、封口体９
の上面に圧力開放用孔８を塞ぐように取り付けられた薄
板１３が押上られて変形するため、所定の内圧以上に達
すると前記薄板１３の切り込み溝１４で破断し、同時に
前記薄板１３上面を覆う高分子材料被膜１６が前記薄板
１３から剥離し、前記圧力開放用孔８が開放される。そ
の結果、前記前記外装缶１内に充満したガスを前記封口
体９の圧力開放用孔８および破断した薄板１３を通して
外部に放出することができるため、前記外装缶１の破
裂、変形を防止することができる。According to the non-aqueous electrolyte secondary battery having the structure shown in FIGS. 4 and 5, the temperature inside the battery rises due to overcharging or short-circuit, and the battery is stored in the outer can 1. When the electrolytic solution is decomposed and gas is generated to increase the internal pressure, the sealing body 9
Since the thin plate 13 attached to the upper surface of the thin plate 13 so as to close the pressure releasing hole 8 is pushed up and deformed, when the internal pressure reaches a predetermined internal pressure or more, the thin plate 13 is broken by the cut groove 14 of the thin plate 13 and simultaneously covers the upper surface of the thin plate 13 The polymer material film 16 is peeled off from the thin plate 13, and the pressure release hole 8 is opened. As a result, the gas filled in the outer can 1 can be released to the outside through the pressure release hole 8 of the sealing body 9 and the broken thin plate 13, so that the rupture and deformation of the outer can 1 are prevented. be able to.
【００３０】また、図４および図５に示す構造の二次電
池が落下すると、外装缶１内に収容された非水電解液が
大きな加速度をもって外装缶１の落下面に衝撃を与え
る。特に、落下面が安全弁機構が付設された封口体９表
面であると、前記衝撃は前記封口体９に取り付けられた
薄板１３を凸状に変形するように加わる。この時、前記
封口体９上面に取り付けられた前記薄板１３はその上面
がゴム弾性を有する前記高分子材料被膜１６で覆われて
いるため、前記高分子材料被膜１６が前記薄板１３に対
して重石のように作用し、前記薄板１３の変形を抑制で
きる。その結果、前記落下に伴う衝撃により前記薄板１
３の切り込み溝１４を広げるような引き裂き応力が加わ
るのを緩和できるため、前記切り込み溝１４部分の強度
低下を抑制できる。したがって、前記薄板１３が所定の
作動圧未満で破断されて開放状態になるのを阻止して電
池機能の喪失や外装缶内に収容された電解液の外部への
漏れだしを防止できる。When the secondary battery having the structure shown in FIGS. 4 and 5 falls, the non-aqueous electrolyte contained in the outer can 1 impacts the falling surface of the outer can 1 with a large acceleration. In particular, if the falling surface is the surface of the sealing body 9 provided with the safety valve mechanism, the impact is applied so as to deform the thin plate 13 attached to the sealing body 9 into a convex shape. At this time, since the upper surface of the thin plate 13 attached to the upper surface of the sealing body 9 is covered with the polymer material film 16 having rubber elasticity, the polymer material film 16 And the deformation of the thin plate 13 can be suppressed. As a result, the thin plate 1
Since it is possible to alleviate the application of a tearing stress that widens the cut groove 14 of the third embodiment, it is possible to suppress a decrease in the strength of the cut groove 14 portion. Therefore, it is possible to prevent the thin plate 13 from being broken and opened under a predetermined operating pressure, thereby preventing the loss of the battery function and the leakage of the electrolyte contained in the outer can to the outside.
【００３１】図６に示す非水電解液二次電池は、切り込
み溝１４を下面に設け、その切り込み溝１４により溝部
分が薄膜化された薄板１３を封口体９の上面に圧力開放
用孔（図示せず）を塞ぐようにレーザ溶接により気密に
取り付け、かつ前記薄板１３を含む前記封口体９の上面
に弾性を有する高分子材料被膜１６を被覆した構造を有
する。In the non-aqueous electrolyte secondary battery shown in FIG. 6, a cut groove 14 is provided on the lower surface, and a thin plate 13 whose groove portion is thinned by the cut groove 14 is formed on the upper surface of the sealing body 9 with a pressure release hole ( (Not shown) is hermetically attached by laser welding so as to cover the upper surface of the sealing body 9 including the thin plate 13 with an elastic polymer film 16.
【００３２】このような図６に示す構成の非水電解液二
次電池によれば、前述した図４および図５に示す構造の
非水電解液二次電池と同様、過充電や短絡に起因して電
池内の温度上昇による外装缶１の破裂、変形を防止する
ことができ、かつ落下等の衝撃を受けても前記薄板が所
定の作動圧未満で破断されて開放状態になるのを阻止し
て電池機能の喪失や外装缶内に収容された電解液の外部
への漏れだしを防止することができる。According to the non-aqueous electrolyte secondary battery having the structure shown in FIG. 6, similar to the non-aqueous electrolyte secondary battery having the structure shown in FIGS. As a result, it is possible to prevent the outer can 1 from being ruptured or deformed due to a rise in the temperature inside the battery, and to prevent the thin plate from being broken below a predetermined operating pressure and being opened even when subjected to an impact such as dropping. As a result, loss of the battery function and leakage of the electrolyte contained in the outer can to the outside can be prevented.
【００３３】[0033]
【実施例】以下、本発明の実施例を前述した図１を参照
して詳細に説明する。 （実施例１） ＜正極の作製＞炭酸リチウムと炭酸コバルトをＬｉ／Ｃ
ｏのモル比で１になるように混合し、空気中、９００
℃、５時間焼成しての正極活物質である複合酸化物を合
成した。この複合酸化物について、Ｘ線回折測定を行っ
た。その結果、ＪＣＰＤカードのＬｉＣｏＯ2 とよく一
致していた。また、前記複合酸化物からなる試料を硫酸
で分解し、生成した二酸化炭素を塩化バリウムと水酸化
ナトリウムの溶液中に導入して吸収させた後、標準試料
で滴定することにより二酸化炭素を定量し、その二酸化
炭素量から換算して複合酸化物中の炭酸リチウムを定量
した。その結果、炭酸リチウムは殆ど検出されなかっ
た。この複合酸化物を自動乳鉢で粉砕してＬｉＣｏＯ2
を得た。An embodiment of the present invention will be described below in detail with reference to FIG. Example 1 <Preparation of Positive Electrode> Lithium carbonate and cobalt carbonate were Li / C
o and mixed in a molar ratio of 1 in air.
A composite oxide as a positive electrode active material was synthesized by firing at 5 ° C. for 5 hours. X-ray diffraction measurement was performed on the composite oxide. As a result, it was in good agreement with LiCoO 2 of the JCPD card. Further, the sample composed of the composite oxide is decomposed with sulfuric acid, and the generated carbon dioxide is introduced into a solution of barium chloride and sodium hydroxide and absorbed, and then the carbon dioxide is quantified by titration with a standard sample. The amount of lithium carbonate in the composite oxide was determined by converting the amount of carbon dioxide. As a result, lithium carbonate was hardly detected. This composite oxide is pulverized in an automatic mortar to form LiCoO 2
I got
【００３４】得られたＬｉＣｏＯ2 粉末（正極活物質）
９５重量％と炭酸リチウム５重量％とからなる混合物９
１重量部、導電材としてのグラファイト６重量部、結着
剤としてのポリフッ化ビニリデン３重量部とを混合し、
これをＮ−メチル−２−ピロリドンに分散させて正極合
剤を調製した。この正極合剤をアルミニウム箔の両面に
塗布し、乾燥した後、ローラプレス機で加圧成形するこ
とによりシート状の正極を作製した。Obtained LiCoO 2 powder (cathode active material)
Mixture 9 consisting of 95% by weight and 5% by weight of lithium carbonate
1 part by weight, 6 parts by weight of graphite as a conductive material, and 3 parts by weight of polyvinylidene fluoride as a binder,
This was dispersed in N-methyl-2-pyrrolidone to prepare a positive electrode mixture. This positive electrode mixture was applied to both sides of an aluminum foil, dried, and then pressed with a roller press to produce a sheet-shaped positive electrode.
【００３５】＜負極の作製＞石油ピッチに酸素架橋した
後、Ａｒガス雰囲気中、１０００℃で焼成してガラス状
炭素に近似した難黒鉛炭素材料を得た。この炭素材料に
ついて、Ｘ線回折測定を行った。その結果（００２）面
の面間隔は３．７６オングストロームであった。また、
前記難黒鉛炭素材料の真密度は１．５８であった。<Preparation of Negative Electrode> After oxygen cross-linking was performed on petroleum pitch, it was baked at 1000 ° C. in an Ar gas atmosphere to obtain a non-graphitic carbon material similar to glassy carbon. X-ray diffraction measurement was performed on the carbon material. As a result, the spacing between the (002) planes was 3.76 angstroms. Also,
The true density of the non-graphite carbon material was 1.58.
【００３６】得られた炭素材料９０重量部と結着剤とし
てのポリフッ化ビニリデン１０重量部とを混合し、これ
をＮ−メチル−２−ピロリドンに分散させて負極合剤を
調製した。この負極合剤を銅箔の両面に塗布し、乾燥し
た後、ローラプレス機で加圧成形することによりシート
状の負極を作製した。90 parts by weight of the obtained carbon material and 10 parts by weight of polyvinylidene fluoride as a binder were mixed, and this was dispersed in N-methyl-2-pyrrolidone to prepare a negative electrode mixture. This negative electrode mixture was applied to both sides of a copper foil, dried, and then pressed with a roller press to produce a sheet-shaped negative electrode.
【００３７】＜電極体の作製＞前記シート状の正極、厚
さ２５μｍの微孔性ポリプロピレンフィルムからなるセ
パレータおよび前記負極をこの順序で積層し、この積層
物を前記負極が外側に位置するように渦巻状に巻回した
後、この巻回物を１０ｋｇｆ／ｃｍ2 の圧力で圧縮して
偏平状の電極体を作製した。<Preparation of Electrode Assembly> The sheet-shaped positive electrode, the separator made of a microporous polypropylene film having a thickness of 25 μm, and the negative electrode are laminated in this order, and the laminate is placed so that the negative electrode is positioned outside. After being spirally wound, the wound product was compressed at a pressure of 10 kgf / cm 2 to produce a flat electrode body.
【００３８】次いで、ステンレスからなる有底矩形筒状
の外装缶内に前記電極体を銅製の電極カバーで覆った状
態で収納し、プロピレンカーボネートとジメトキシエタ
ンとの混合溶媒（体積比率５０：５０）に六フッ化リン
酸リチウム（ＬｉＰＦ6 ）を１モル／ｌ溶解した電解液
を収容した。つづいて、中央に円形穴およびこの穴に隣
接した個所に矩形状の圧力開放用孔がそれぞれ開口され
たステンレスからなる矩形状の封口体の前記穴に正極端
子ピンをハーメティクシールし、さらに直線部およびこ
の両端をＶ字型にした形状を有する深さ３５μｍの切り
込み溝が形成された厚さ５０μｍのステンレス薄板を封
口体の下面に前記圧力開放用孔を塞ぐように、かつ前記
切り込み溝が前記封口体の前記圧力開放用孔の側に向く
ようにレーザ溶接した後、前記封口体の前記圧力開放用
孔内にシリコン樹脂溶液（東芝シリコン社製商品名；Ｔ
ＳＥ３８９−Ｃ）を塗布し、１２時間乾燥させることに
より前記薄板上面を覆う厚さ３ｍｍのゴム弾性を有する
高分子材料被膜を形成した。ひきつづき、前記封口体の
前記正極端子ピンの下端を前記外装缶内の正極とリード
を介して接続した後、前記封口体を前記外装缶の上端開
口部にレーザ溶接することにより前述した図１および図
２に示す構造の角型非水電解液二次電池を製造した。Next, the electrode body was housed in a rectangular bottomed outer can made of stainless steel with the electrode body covered with a copper electrode cover, and a mixed solvent of propylene carbonate and dimethoxyethane (volume ratio: 50:50). An electrolyte in which lithium hexafluorophosphate (LiPF 6 ) was dissolved at 1 mol / l was accommodated. Subsequently, a positive electrode terminal pin is hermetically sealed in the hole of the rectangular sealing body made of stainless steel in which a circular hole in the center and a rectangular pressure release hole are respectively opened at locations adjacent to the hole, and further, A 50 μm-thick stainless steel plate having a 35 μm deep cut groove having a straight portion and both ends formed in a V-shape is formed on the lower surface of the sealing body so as to cover the pressure release hole, and the cut groove is formed. Is laser-welded so as to face the pressure release hole side of the sealing body, and then a silicone resin solution (trade name; T;
SE389-C) was applied and dried for 12 hours to form a 3 mm-thick rubbery polymer film covering the upper surface of the thin plate. Subsequently, after the lower end of the positive electrode terminal pin of the sealing body is connected to the positive electrode in the outer can via a lead, the sealing body is laser-welded to the upper end opening of the outer can and FIG. A rectangular non-aqueous electrolyte secondary battery having the structure shown in FIG. 2 was manufactured.
【００３９】（実施例２）前述した図３に示すように直
線部およびこの両端をＶ字型にした形状を有する深さ３
５μｍの切り込み溝１４が形成された厚さ５０μｍのス
テンレス薄板１３を封口体９の下面にその圧力開放用孔
８を塞ぐように、かつ前記切り込み溝１４が前記封口体
９の前記圧力開放用孔８と反対側に向くようにレーザ溶
接した後、前記封口体９の前記圧力開放用孔８内にシリ
コン樹脂溶液（東芝シリコン社製商品名；ＴＳＥ３８９
−Ｃ）を塗布し、１２時間乾燥させることにより前記薄
板１３上面を覆う厚さ３ｍｍのゴム弾性を有する高分子
材料被膜１５を形成した以外、実施例１と同様な構成の
角型非水電解液二次電池を製造した。Example 2 As shown in FIG. 3 described above, a straight part and a depth 3 having a V-shaped shape at both ends.
A 50 μm-thick stainless steel plate 13 having a 5 μm cut groove 14 is formed on the lower surface of the sealing body 9 so as to cover the pressure release hole 8, and the cut groove 14 is formed in the pressure release hole of the sealing body 9. After laser welding so as to face the side opposite to the side 8, a silicone resin solution (trade name: TSE389, manufactured by Toshiba Silicon Corporation) is placed in the pressure release hole 8 of the sealing body 9.
-C) was applied and dried for 12 hours to form a 3 mm-thick rubber elastic polymer material coating 15 covering the upper surface of the thin plate 13, except that a square nonaqueous electrolytic solution having the same configuration as in Example 1 was formed. A liquid secondary battery was manufactured.
【００４０】（実施例３）前述した図４および図５に示
すように直線部およびこの両端をＶ字型にした形状を有
する深さ３５μｍの切り込み溝１４が形成された厚さ５
０μｍのステンレス薄板１３を封口体９の上面にその圧
力開放用孔８を塞ぐように、かつ前記切り込み溝１４が
前記封口体９の前記圧力開放用孔８と反対側に向くよう
にレーザ溶接した後、前記薄板１３を含む封口体９の上
面にシリコン樹脂溶液（東芝シリコン社製商品名；ＴＳ
Ｅ３８９−Ｃ）を塗布し、１２時間乾燥させることによ
り前記薄板１３上面を覆う厚さ０．５ｍｍのゴム弾性を
有する高分子材料被膜１６を形成した以外、実施例１と
同様な構成の角型非水電解液二次電池を製造した。(Example 3) As shown in FIGS. 4 and 5 described above, a linear portion and a thickness 5 having a V-shaped cut-off groove 14 with a depth of 35 μm are formed.
A 0 μm thin stainless plate 13 was laser-welded on the upper surface of the sealing body 9 so as to cover the pressure releasing hole 8 and the cut groove 14 was directed to the opposite side of the sealing body 9 from the pressure releasing hole 8. Then, a silicon resin solution (trade name; TS, manufactured by Toshiba Silicon Corp.)
E389-C) was applied and dried for 12 hours to form a 0.5 mm-thick rubber-elastic polymer material film 16 covering the upper surface of the thin plate 13, except that the square shape was the same as in Example 1. A non-aqueous electrolyte secondary battery was manufactured.
【００４１】（実施例４）前述した図６に示すように直
線部およびこの両端をＶ字型にした形状を有する深さ３
５μｍの切り込み溝１４が形成された厚さ５０μｍのス
テンレス薄板１３を封口体９の上面にその圧力開放用孔
を塞ぐように、かつ前記切り込み溝１４が前記封口体９
の前記圧力開放用孔の側に向くようにレーザ溶接した
後、前記薄板１３を含む封口体９の上面にシリコン樹脂
溶液（東芝シリコン社製商品名；ＴＳＥ３８９−Ｃ）を
塗布し、１２時間乾燥させることにより前記薄板１３上
面を覆う厚さ０．５ｍｍのゴム弾性を有する高分子材料
被膜１６を形成した以外、実施例１と同様な構成の角型
非水電解液二次電池を製造した。(Embodiment 4) As shown in FIG. 6 described above, a straight portion and a depth 3 having a V-shaped shape at both ends.
A 50 μm-thick stainless steel plate 13 having a 5 μm cut groove 14 is formed on the upper surface of the sealing body 9 so as to cover the pressure release hole, and the cut groove 14 is formed in the sealing body 9.
After laser welding so as to face the pressure release hole side, a silicon resin solution (trade name: TSE389-C, manufactured by Toshiba Silicon Corporation) is applied to the upper surface of the sealing body 9 including the thin plate 13 and dried for 12 hours. A rectangular non-aqueous electrolyte secondary battery having the same configuration as in Example 1 was manufactured except that a 0.5 mm thick polymer film 16 having a rubber elasticity covering the upper surface of the thin plate 13 was formed.
【００４２】（実施例５）前述した図１および図２に示
すように直線部およびこの両端をＶ字型にした形状を有
する深さ３５μｍの切り込み溝１４が形成された厚さ５
０μｍのステンレス薄板１３を封口体９の下面にその圧
力開放用孔８を塞ぐように、かつ前記切り込み溝１４が
前記封口体９の前記圧力開放用孔８の側に向くようにレ
ーザ溶接した後、前記封口体の前記圧力開放用孔内にフ
ッ素樹脂溶液（旭硝子社製商品名；ＬＦ−１００）を塗
布し、１２時間乾燥させることにより前記薄板１３上面
を覆う厚さ３ｍｍのゴム弾性を有する高分子材料被膜１
５を形成した以外、実施例１と同様な構成の角型非水電
解液二次電池を製造した。(Example 5) As shown in FIGS. 1 and 2 described above, a linear portion and a cut-out groove 14 having a depth of 35 μm having a V-shaped shape at both ends are formed.
After laser welding a 0 μm thin stainless steel plate 13 on the lower surface of the sealing body 9 so as to cover the pressure releasing hole 8 and the cut groove 14 is directed toward the pressure releasing hole 8 of the sealing body 9. A fluororesin solution (trade name: LF-100, manufactured by Asahi Glass Co., Ltd.) is applied to the inside of the pressure release hole of the sealing body, and is dried for 12 hours to have a rubber elasticity of 3 mm in thickness covering the upper surface of the thin plate 13. Polymer material coating 1
A prismatic nonaqueous electrolyte secondary battery having the same configuration as that of Example 1 except that No. 5 was formed was manufactured.
【００４３】（比較例１）直線部およびこの両端をＶ字
型にした形状を有する深さ３５μｍの切り込み溝が形成
された厚さ５０μｍのステンレス薄板を封口体の下面に
その圧力開放用孔を塞ぐように、かつ前記切り込み溝が
前記封口体の前記圧力開放用孔の側に向くようにレーザ
溶接し、前記圧力開放用孔内へのゴム弾性を有する高分
子材料被膜の形成を行わない以外、実施例１と同様な構
成の角型非水電解液二次電池を製造した。(Comparative Example 1) A 50 μm-thick stainless steel plate having a straight portion and a V-shaped end formed with a cut groove having a depth of 35 μm was formed with a pressure releasing hole on the lower surface of the sealing body. Laser welding so as to close and the cut groove faces the pressure release hole side of the sealing body, except that a polymer material film having rubber elasticity is not formed in the pressure release hole. A prismatic nonaqueous electrolyte secondary battery having the same configuration as that of Example 1 was manufactured.
【００４４】得られた実施例１〜５および比較例１の各
二次電池１００個について、電流１Ａ、電圧４．２Ｖ、
３時間の条件で充電し、それら充電状態の電池を１ｍ、
１．２ｍおよび１．８ｍの高さから樫の木上に前記電池
の封口体の面が直接当たるように１０回それぞれ落下さ
せ、これら落下試験後の前記薄板（切り込み溝部分）の
破裂による非水電解液の漏洩状況を調べた。その結果を
下記表１に示す。For each of the 100 secondary batteries of Examples 1 to 5 and Comparative Example 1, a current of 1 A, a voltage of 4.2 V,
Charged under the condition of 3 hours, the charged battery was 1 m,
The battery was dropped 10 times from the height of 1.2 m and 1.8 m onto the oak tree so that the surface of the sealing body of the battery would directly hit the oak tree. The state of leakage of the water electrolyte was examined. The results are shown in Table 1 below.
【００４５】[0045]
【表１】 [Table 1]
【００４６】表１から明らかなように実施例１〜５の二
次電池では落下高さが１．８ｍと高くした場合でも前記
薄板の切り込み溝部分の破裂による非水電解液の漏洩が
防止されることがわかる。これに対し、比較例１の二次
電池では、落下高さが低い場合でも前記切り込み溝部分
の破裂による非水電解液の漏洩が生じることがわかる。As is clear from Table 1, in the secondary batteries of Examples 1 to 5, even when the drop height is as high as 1.8 m, leakage of the nonaqueous electrolyte due to the rupture of the cut groove portion of the thin plate is prevented. You can see that On the other hand, in the secondary battery of Comparative Example 1, even when the drop height is low, the nonaqueous electrolyte leaks due to the rupture of the cut groove portion.
【００４７】また、実施例１〜５および比較例１の各二
次電池１００個について、電流１Ａ、電圧４．２Ｖ、３
時間の条件で充電し、それら充電状態の電池を１ｍ、
１．２ｍおよび１．８ｍの高さからコンクリート上に前
記電池の封口体の面が直接当たるように１０回それぞれ
落下させ、これら落下試験後の前記薄板（切り込み溝部
分）の破裂による非水電解液の漏洩状況を調べた。その
結果を下記表２に示す。Further, for each of the 100 secondary batteries of Examples 1 to 5 and Comparative Example 1, a current of 1 A, a voltage of 4.2 V,
The battery is charged under the condition of time, and the charged battery is 1 m,
The battery was dropped 10 times from a height of 1.2 m and 1.8 m onto concrete so that the surface of the sealing body of the battery directly hit, and the non-aqueous electrolysis by rupture of the thin plate (cut groove portion) after these drop tests. The state of liquid leakage was examined. The results are shown in Table 2 below.
【００４８】[0048]
【表２】 [Table 2]
【００４９】表２から明らかなように実施例１〜５の二
次電池では衝撃度合が前記樫の木より過酷なコンクリー
ト上に落下された場合でも前記薄板の切り込み溝部分の
破裂による非水電解液の漏洩が防止されることがわか
る。As is apparent from Table 2, in the secondary batteries of Examples 1 to 5, non-aqueous electrolysis due to the rupture of the cut groove portion of the thin plate even when the impact degree was dropped on the concrete which was more severe than the oak tree. It can be seen that liquid leakage is prevented.
【００５０】さらに、得られた実施例１〜５および比較
例１の各二次電池２０個について電流を２．０Ａに設定
し、電源電圧を１５Ｖ、２０Ｖ、３０Ｖに変化させて過
充電を行い、発火、破裂を生じる電池および薄板（切り
込み溝部分）の破断が生じた電池の発生率を調べた。そ
の結果を下記表３に示す。Further, the current was set to 2.0 A for each of the obtained 20 rechargeable batteries of Examples 1 to 5 and Comparative Example 1, and the power supply voltage was changed to 15 V, 20 V and 30 V to perform overcharging. The rate of occurrence of batteries that caused ignition, rupture, and rupture of thin plates (cut grooves) was examined. The results are shown in Table 3 below.
【００５１】[0051]
【表３】 [Table 3]
【００５２】前記表２から明らかなように実施例１〜５
および比較例１のいずれの二次電池においても、電源電
圧が１５Ｖと低い場合は薄板の切り込み溝部分の破断が
生じない。しかしながら、電源電圧を高くすると、弁膜
の破断が生じる頻度が高くなる。ただし、所定の動作圧
での薄板の切り込み溝部分の破断が確実に行われてお
り、電池の破裂、発火を確実に防止できることがわか
る。なお、前記実施例では角形の非水電解液電池に適用
した例を説明したが、円筒形など各種の形状の非水電解
液二次電池にも同様に適用することができる。As apparent from Table 2 above, Examples 1 to 5
Also, in any of the secondary batteries of Comparative Example 1, when the power supply voltage is as low as 15 V, the cut grooves of the thin plate do not break. However, when the power supply voltage is increased, the frequency of rupture of the valve membrane increases. However, it can be seen that the cut groove portion of the thin plate is reliably broken at a predetermined operating pressure, and the burst and ignition of the battery can be reliably prevented. In the above embodiment, an example in which the present invention is applied to a rectangular non-aqueous electrolyte battery is described. However, the present invention can be similarly applied to non-aqueous electrolyte secondary batteries having various shapes such as a cylindrical shape.
【００５３】[0053]
【発明の効果】以上詳述しように、本発明によれば所定
の作動圧で確実に破断され、かつ落下衝撃に対して良好
な強度を保持した安全弁機構を備えた信頼性の高い非水
電解液二次電池を提供できる。As described above in detail, according to the present invention, a highly reliable non-aqueous electrolysis provided with a safety valve mechanism which is reliably broken at a predetermined operating pressure and has good strength against a drop impact. A liquid secondary battery can be provided.
【図１】本発明に係わる角形非水電解液二次電池を示す
要部斜視図。FIG. 1 is a perspective view of a main part showing a prismatic nonaqueous electrolyte secondary battery according to the present invention.
【図２】図１の角形非水電解液二次電池を示す断面図。FIG. 2 is a sectional view showing the prismatic nonaqueous electrolyte secondary battery of FIG. 1;
【図３】本発明に係わる別の角形非水電解液二次電池を
示す要部斜視図。FIG. 3 is a perspective view of a main part showing another prismatic nonaqueous electrolyte secondary battery according to the present invention.
【図４】本発明に係わるさらに別の角形非水電解液二次
電池を示す要部斜視図。FIG. 4 is an essential part perspective view showing still another prismatic nonaqueous electrolyte secondary battery according to the present invention.
【図５】図４の角形非水電解液二次電池を示す断面図。FIG. 5 is a sectional view showing the prismatic nonaqueous electrolyte secondary battery of FIG. 4;
【図６】本発明に係わるさらに別の角形非水電解液二次
電池を示す要部斜視図。FIG. 6 is a main part perspective view showing still another prismatic nonaqueous electrolyte secondary battery according to the present invention.
１…外装缶、 ２…電極体、 ３…正極、 ５…負極、 ８…圧力開放用孔、 ９…封口体、 １３…薄板、 １４…切り込み溝、 １５、１６…ゴム弾性を有する高分子材料被膜。 DESCRIPTION OF SYMBOLS 1 ... Outer can, 2 ... Electrode body, 3 ... Positive electrode, 5 ... Negative electrode, 8 ... Hole for pressure release, 9 ... Sealing body, 13 ... Thin plate, 14 ... Cut groove, 15, 16 ... High polymer material having rubber elasticity Coating.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 大崎 隆久 神奈川県川崎市幸区堀川町72番地 株式 会社東芝川崎事業所内 (72)発明者 小里 建一郎 神奈川県川崎市川崎区日進町７番地１ 東芝電子エンジニアリング株式会社内 (56)参考文献 特開 平５−41204（ＪＰ，Ａ) 特開 平７−169452（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 2/12 101 H01M 10/40 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Takahisa Osaki 72 Horikawa-cho, Saiwai-ku, Kawasaki-shi, Kanagawa Prefecture Inside the Toshiba Kawasaki Office Co., Ltd. (56) References JP-A-5-41204 (JP, A) JP-A-7-169452 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) H01M 2 / 12 101 H01M 10/40
Claims (1)
を渦巻き状に巻回した電極体と、 前記外装缶内に収容された非水電解液と、 前記外装缶の上端開口部に設けられ、圧力開放用孔が開
口された封口体と、 前記封口体に前記圧力開放用孔を塞ぐように取り付けら
れ、切り込み溝が形成された薄板と、 前記封口体に前記薄板上面を覆うように取り付けられた
ゴム弾性を有する高分子材料被膜とを具備したことを特
徴とする非水電解液二次電池。1. A bottomed cylindrical outer can, an electrode body housed in the outer can, in which a positive electrode, a separator, and a negative electrode are spirally wound, and a non-aqueous electrolyte housed in the outer can. A sealing body provided at the upper end opening of the outer can and having an opening for pressure release, a thin plate attached to the sealing body so as to close the opening for pressure release, and having a cut groove formed therein, A non-aqueous electrolyte secondary battery, comprising: a polymer material film having rubber elasticity attached to the sealing member so as to cover an upper surface of the thin plate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05476896A JP3272937B2 (en) | 1996-03-12 | 1996-03-12 | Non-aqueous electrolyte secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05476896A JP3272937B2 (en) | 1996-03-12 | 1996-03-12 | Non-aqueous electrolyte secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09245837A JPH09245837A (en) | 1997-09-19 |
| JP3272937B2 true JP3272937B2 (en) | 2002-04-08 |
Family
ID=12979957
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP05476896A Expired - Fee Related JP3272937B2 (en) | 1996-03-12 | 1996-03-12 | Non-aqueous electrolyte secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3272937B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6190798B1 (en) | 1998-01-09 | 2001-02-20 | Kabushiki Kaisha Toshiba | Sealed battery and method of manufacturing the same |
| JP3902322B2 (en) * | 1998-03-10 | 2007-04-04 | 三洋電機株式会社 | Non-aqueous electrolyte battery |
| JP5114063B2 (en) * | 2007-02-02 | 2013-01-09 | Ｎｅｃエナジーデバイス株式会社 | Sealed battery |
| KR102019682B1 (en) | 2017-12-08 | 2019-09-09 | 주식회사 엘지화학 | Secondary Battery Case Having Vent Filled with Thermoplastic Resin |
-
1996
- 1996-03-12 JP JP05476896A patent/JP3272937B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09245837A (en) | 1997-09-19 |
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