JPH09283112A - Sealed nonaqueous secondary battery - Google Patents

Sealed nonaqueous secondary battery

Info

Publication number
JPH09283112A
JPH09283112A JP8094497A JP9449796A JPH09283112A JP H09283112 A JPH09283112 A JP H09283112A JP 8094497 A JP8094497 A JP 8094497A JP 9449796 A JP9449796 A JP 9449796A JP H09283112 A JPH09283112 A JP H09283112A
Authority
JP
Japan
Prior art keywords
battery
insulator
annular wall
secondary battery
electrode
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
Application number
JP8094497A
Other languages
Japanese (ja)
Other versions
JP3692605B2 (en
Inventor
Osamu Takahashi
修 高橋
Hisashi Suzuki
久 鈴木
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Holdings Corp
Original Assignee
Fuji Photo Film Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Priority to JP09449796A priority Critical patent/JP3692605B2/en
Publication of JPH09283112A publication Critical patent/JPH09283112A/en
Application granted granted Critical
Publication of JP3692605B2 publication Critical patent/JP3692605B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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

PROBLEM TO BE SOLVED: To shorten the electrolyte filling time, and prevent the generation of short-circuiting when dropped, and provide a sealed nonaqueous secondary battery having high safety by forming a stage difference between an outer peripheral part and an inner peripheral part of an insulating body, and forming plural holes for communicating the outer peripheral part and the inner peripheral part with each other, SOLUTION: An insulating body 3 of a top surface of a spiral group is provided with an annular wall part 31 near the outer peripheral part thereof, and this outer peripheral part is formed with an inclined part, which is inclined and projected from a lower part of the annular wall part toward an electrode group side, and a flange part 32, which is formed of a horizontal part extended in the horizontal direction and which is formed in the periphery of the inclined part. An inner peripheral side of the annular wall is formed with a central flat surface 33, and formed with a lead insertion through hole 35 and four through holes 34, which are arranged in the periphery of the through hole 35. A bottom surface of the annular wall 31 is formed in the same surface with a bottom surface of the central flat surface 33. The flange part 32 is provided with plural through holes 34. With this structure, a sealed nonaqueous secondary battery, which can shorten the time required for filling electrolyte and which can prevent the generation of short-circuiting when dropped and which has high assembling workability and high safety, is obtained.

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【発明の属する技術分野】本発明は、落下時の内部短絡
を防止すると共に、電池組立時に電解液注入が短時間で
行うことができる密閉型非水二次電池に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sealed non-aqueous secondary battery capable of preventing an internal short circuit at the time of dropping and injecting an electrolytic solution in a short time when assembling a battery.

【０００２】[0002]

【従来の技術】近年、電子機器の高性能化、小型化、ポ
ータブル化により、その電源として使用される電池に、
従来のニッケルカドミウム電池や鉛蓄電池等に代わる高
エネルギー密度の二次電池が要求されるようになってい
る。そこで、最近では負極に水素吸蔵合金を用いたニッ
ケル水素電池や、軽金属を挿入放出可能な物質を正極及
び負極に用いた非水二次電池が使用されるようになって
きている。特にリチウムの挿入放出を応用した密閉型非
水二次電池は電池電圧が３．６Ｖと高く、高エネルギー
密度を有するため、電池の小型軽量化が可能であり、ま
た自己放電も少なくサイクル特性にも優れていることか
ら、ポータブル機器用の電源として急速にその需要が伸
びてきている。一般にこの種の電源としては、帯状の電
極を渦巻き状に巻回したシリンダー形や角形の密閉型電
池が用いられているため、高電流での充放電が可能であ
り、よって安全性には十分配慮された構成となってい
る。電池外装缶に収納された電極群と電池蓋との間に配
置される絶縁体もその一つであり、電池落下時の内部短
絡を防止するのに効果的なものである。2. Description of the Related Art In recent years, due to the high performance, miniaturization, and portability of electronic devices, the batteries used as the power source have been
Secondary batteries with high energy density have been required to replace conventional nickel-cadmium batteries and lead-acid batteries. Therefore, recently, a nickel hydrogen battery using a hydrogen storage alloy for the negative electrode and a non-aqueous secondary battery using a substance capable of inserting and releasing a light metal for the positive electrode and the negative electrode have been used. In particular, the sealed non-aqueous secondary battery that applies the insertion and release of lithium has a high battery voltage of 3.6 V and a high energy density, so the battery can be made smaller and lighter, and self-discharge is less and cycle characteristics are improved. Since it is also excellent, the demand for it as a power source for portable devices is rapidly increasing. Generally, as a power source of this type, a cylindrical or prismatic sealed battery in which a strip-shaped electrode is spirally wound is used, so charging / discharging at high current is possible, and therefore safety is not sufficient. It has been designed with consideration. One of them is an insulator disposed between the electrode group housed in the battery outer can and the battery lid, which is effective in preventing an internal short circuit when the battery is dropped.

【０００３】絶縁体としては、ニッケルカドミウム電池
やニッケル水素電池等では、図３に示すように、中央に
貫通孔を有する円盤状のもので、厚さ０．５ｍｍ以下の
樹脂製のものや不織布といったもの、また図４に示すよ
うに、外周部近傍に環状壁を有する樹脂成形体のものが
広く使用されてきた。非水二次電池においてもその構成
はニッケルカドミウム電池やニッケル水素電池とほぼ同
様であるため、同様の絶縁体が使用されているのがほと
んどである。しかし非水二次電池の場合は、上記電池の
場合より薄くしかも長い帯状電極が用いられていること
が多いため、電池落下時に電極群の中心部が容易にずれ
易く、内部短絡も起こり易いといった問題がある。これ
を解決するために、特開平５−４１２４８号公報による
電池では、図３と同様形状で厚さ２．０〜２．３ｍｍの
肉厚の円盤状隔離板を用いるものが提案されている。こ
の場合は、電池落下時に電極群が上方にずれるのを効果
的に防止することができる。As the insulator, a nickel cadmium battery, a nickel hydride battery, or the like is a disk-shaped insulator having a through hole in the center as shown in FIG. Such a resin molded body having an annular wall in the vicinity of the outer peripheral portion as shown in FIG. 4 has been widely used. Since the structure of the non-aqueous secondary battery is almost the same as that of the nickel-cadmium battery or the nickel-hydrogen battery, the same insulator is mostly used. However, in the case of a non-aqueous secondary battery, a strip-shaped electrode that is thinner and longer than that of the above-mentioned battery is often used, so that the center part of the electrode group is easily displaced when the battery is dropped, and an internal short circuit is likely to occur. There's a problem. In order to solve this problem, a battery according to JP-A-5-41248 has been proposed in which a disk-shaped separator having a shape similar to that of FIG. 3 and a thickness of 2.0 to 2.3 mm is used. In this case, it is possible to effectively prevent the electrode group from being displaced upward when the battery is dropped.

【０００４】一方、非水二次電池の場合は、前記したよ
うに、薄くしかも長い帯状電極が用いられているため、
巻回された電極群の電解液浸透性が非常に悪く、電池組
立時の電解液注入時間が長くかかり、よって注液装置が
とても大きなものとなるだけでなく、非水電解液である
がゆえにその揮発性の高さから注液量の精度管理が難し
いという問題がある。これは円筒形のリチウム二酸化マ
ンガン電池である非水一次電池の場合も同様であり、こ
の問題を解決するための一手段として、電極群の上面に
配置する絶縁体の形状に工夫を凝らすという提案がいく
つかなされており、非水二次電池の場合にも用いること
ができる。実開平４−４６３６０号公報による電池で
は、図５に示すように、円盤状の絶縁体の外周部に少な
くとも１ケ所の切り欠きが形成されているものが提案さ
れており、また実開昭６２−１０３１６９号公報による
電池では、図６に示すように、外周部近傍に環状壁を有
しその外周部の鍔部に貫通孔を設けた絶縁体が提案され
ている。いずれの場合も、電解液注入時に電池外装缶内
のエアーあるいは不活性ガスが電極群の外周部から絶縁
体の切り欠き部、または外周部鍔部の貫通孔を通って抜
け易くなり、電解液が電極群に浸透し易くするのに効果
的である。On the other hand, in the case of a non-aqueous secondary battery, as described above, since a thin and long strip electrode is used,
Electrolyte permeability of the wound electrode group is very poor, it takes a long time to inject the electrolyte when assembling the battery, which makes the injection device very large and also because it is a non-aqueous electrolyte. Due to its high volatility, there is a problem that it is difficult to control the accuracy of the liquid injection amount. This is also the case with non-aqueous primary batteries, which are cylindrical lithium manganese dioxide batteries, and as a means to solve this problem, a proposal was made to devise the shape of the insulator placed on the upper surface of the electrode group. Have been made, and can also be used in the case of non-aqueous secondary batteries. As a battery according to Japanese Utility Model Laid-Open No. 4-46360, as shown in FIG. 5, it is proposed that at least one notch is formed in the outer peripheral portion of a disk-shaped insulator, and in Japanese Utility Model Laid-Open No. 62-62360. In the battery according to Japanese Patent Laid-Open No. -103169, as shown in FIG. 6, there has been proposed an insulator having an annular wall in the vicinity of an outer peripheral portion and a through hole provided in a flange portion of the outer peripheral portion. In either case, during injection of the electrolyte, the air or inert gas inside the battery outer can easily escapes from the outer periphery of the electrode group through the notch of the insulator or through the through hole of the outer collar. Is effective in facilitating penetration into the electrode group.

【０００５】しかし、実開平４−４６３６０号公報、実
開昭６２−１０３１６９号公報による絶縁体では、電池
落下時に電極群の中心部がずれ易く内部短絡し易い問題
に対しては、絶縁体の強度また構造において不十分であ
り、また特開平５−４１２４８号公報による絶縁体で
は、電解液注入時の液浸透性が悪いという問題に対して
は、何の手助けもすることができないばかりか、電極群
収納体積が大きくできないといった別の問題が発生す
る。However, in the insulators according to Japanese Utility Model Laid-Open No. 4-46360 and Japanese Utility Model Laid-Open No. 62-103169, when the battery is dropped, the center portion of the electrode group is easily displaced and an internal short circuit is easily caused. The strength and the structure are insufficient, and the insulator according to JP-A-5-41248 cannot provide any help to the problem of poor liquid permeability at the time of injecting the electrolyte. Another problem occurs in that the electrode group storage volume cannot be increased.

【０００６】[0006]

【発明が解決しようとする課題】本発明は、これらの事
情に鑑みてなされたもので、電池落下時の内部短絡を防
止すると共に、電池組立時に電解液注入が短時間で行う
ことができる密閉型非水二次電池を提供することを目的
とするものである。SUMMARY OF THE INVENTION The present invention has been made in view of these circumstances, and it is possible to prevent an internal short circuit when a battery is dropped and to seal the battery so that the electrolyte can be injected in a short time when the battery is assembled. An object of the present invention is to provide a type non-aqueous secondary battery.

【０００７】[0007]

【課題を解決するための手段】本発明の課題は、軽金属
を挿入放出可能な正極及び負極と、セパレータとで構成
された電極群が、有底電池外装缶内に収納され、該電極
群の上面に絶縁体が配置され、該絶縁体の上部で該外装
缶の一部が細く絞り加工され、非水電解液が注入された
後、該外装缶の開口部が絶縁性ガスケットを介して電池
蓋で閉塞されてなる密閉型非水二次電池において、該絶
縁体が、絶縁体の外周部近傍に形成される環状壁と、該
環状壁の内部の中央平面部と、該環状壁の外周部に形成
される鍔部とから構成され、該中央平面部はその中央部
に電極リードが挿通する貫通孔と周辺部に複数の貫通孔
を有し、該鍔部は、複数の貫通孔を有し、該鍔部底面は
該中央平面部底面より電極群側に位置しており、該環状
壁の底面部は中央平面部の底面部と同一平面、又は鍔部
底面部と中央平面部の底面部の中間に位置することを特
徴とする密閉型非水二次電池により達成された。An object of the present invention is to provide an electrode group composed of a positive electrode and a negative electrode capable of inserting and releasing a light metal and a separator, housed in a bottomed battery outer can, and An insulator is arranged on the upper surface, and a part of the outer can is thinly drawn on the upper part of the insulator, and after the non-aqueous electrolyte is injected, the opening of the outer can is inserted into the battery via an insulating gasket. In a sealed non-aqueous secondary battery closed with a lid, the insulator comprises an annular wall formed in the vicinity of an outer peripheral portion of the insulator, a central plane portion inside the annular wall, and an outer periphery of the annular wall. The central plane portion has a through hole through which the electrode lead is inserted and a plurality of through holes in the peripheral portion, and the collar portion has a plurality of through holes. The bottom surface of the collar portion is located closer to the electrode group than the bottom surface of the central plane portion, and the bottom surface portion of the annular wall is at the center. Surface of the bottom portion flush, or was achieved by sealed non-aqueous secondary battery, characterized in that located in the middle of the bottom surface portion of the flange bottom surface portion and the central flat portion.

【０００８】[0008]

【発明の実施の形態】本発明で使用できる絶縁体は、材
質として、ポリオレフィン系ポリマーが好ましく、特に
ポリプロピレン主体の合成ポリマーであることが好まし
い。さらに高分子量または高曲げ弾性率を有する、ポリ
プロピレン含有率７０％以上の合成ポリマーであること
が好ましい。外周部鍔部の底面と中央平面部の底面との
段差は０．３〜１ｍｍであることが好ましい。また外周
部鍔部の厚みは、０．３ｍｍ以上であることが好まし
く、中央平面部の厚みが０．５ｍｍ以上であることが好
ましい。外周部鍔部は、環状壁部との間に、電池外装缶
の縮径部内壁に沿うような傾斜部を有することが好まし
く、外周部鍔部の貫通孔が前記傾斜部に設けられている
ことが好ましい。さらに、中央平面部には中央部にリー
ド挿通孔と電解液の注入孔を兼ねる貫通孔、その周辺部
に複数の貫通孔があることが望ましい。以下に本発明の
好ましい形態を示すが、本発明はこれらに限定されるも
のではない。 （１）軽金属を挿入放出可能な正極及び負極と、セパレ
ータとで構成された電極群が、有底電池外装缶内に収納
され、該電極群の上面に絶縁体が配置され、該絶縁体の
上部で該外装缶の一部が細く絞り加工され、非水電解液
が注入された後、該外装缶の開口部が絶縁性ガスケット
を介して電池蓋で閉塞されてなる密閉型非水二次電池に
おいて、該絶縁体が、絶縁体の外周部近傍に形成される
環状壁と、該環状壁の内部の中央平面部と、該環状壁の
外周部に形成される鍔部とから構成され、該中央平面部
はその中央部に電極リードが挿通する貫通孔と周辺部に
複数の貫通孔を有し、該鍔部は、複数の貫通孔を有し、
該鍔部底面は該中央平面部底面より電極群側に位置して
おり、該環状壁の底面部は中央平面部の底面部と同一平
面、又は鍔部底面部と中央平面部の底面部の中間に位置
することを特徴とする密閉型非水二次電池により達成さ
れた。 （２）該中央平面部底面より電極群側に位置している該
鍔部底面と、該中央平面部底面の段差が０．３〜１ｍｍ
であることを特徴とする項１に記載の密閉型非水二次電
池。 （３）該鍔部の厚みが０．３〜１ｍｍであることを特徴
とする項１または２に記載の密閉型非水二次電池。 （４）該中央平面部の厚みが０．５〜１．５ｍｍである
ことを特徴とする項１〜３のいずれか１項に記載の密閉
型非水二次電池。 （５）該鍔部は、該環状壁部との間に、電池外装缶の縮
径部内壁に沿うような傾斜部を有することを特徴とする
項１〜４のいずれか１項に記載の密閉型非水二次電池。 （６）項５に記載の鍔部の傾斜部が貫通孔を有すること
を特徴とする項５に記載の密閉型非水二次電池。 （７）該絶縁体がポリオレフィンポリマーにより作製さ
れたものであることを特徴とする項１〜４のいずれか１
項に記載の密閉型非水二次電池。BEST MODE FOR CARRYING OUT THE INVENTION The insulator which can be used in the present invention is preferably made of a polyolefin polymer as a material, and particularly preferably a synthetic polymer mainly composed of polypropylene. Further, a synthetic polymer having a high molecular weight or a high bending elastic modulus and a polypropylene content of 70% or more is preferable. The step between the bottom surface of the outer peripheral flange portion and the bottom surface of the central plane portion is preferably 0.3 to 1 mm. Further, the thickness of the outer peripheral flange portion is preferably 0.3 mm or more, and the thickness of the central plane portion is preferably 0.5 mm or more. The outer peripheral flange portion preferably has an inclined portion between the annular wall portion and the inner wall of the reduced diameter portion of the battery outer can, and the through hole of the outer peripheral flange portion is provided in the inclined portion. It is preferable. Further, it is desirable that the central plane portion has a through hole that also serves as a lead insertion hole and an electrolyte injection hole in the central portion and a plurality of through holes in the peripheral portion. The preferred embodiments of the present invention are shown below, but the present invention is not limited thereto. (1) An electrode group composed of a positive electrode and a negative electrode capable of inserting and releasing light metal, and a separator is housed in a bottomed battery outer can, and an insulator is arranged on the upper surface of the electrode group. A hermetically sealed non-aqueous secondary battery in which a part of the outer can is thinly drawn at the upper part and a non-aqueous electrolyte is injected, and then the opening of the outer can is closed by a battery lid through an insulating gasket. In the battery, the insulator is composed of an annular wall formed in the vicinity of the outer peripheral portion of the insulator, a central plane portion inside the annular wall, and a collar portion formed on the outer peripheral portion of the annular wall, The central plane portion has a through hole through which the electrode lead is inserted in the central portion and a plurality of through holes in the peripheral portion, and the collar portion has a plurality of through holes,
The bottom surface of the collar portion is located closer to the electrode group side than the bottom surface of the central flat surface portion, and the bottom surface portion of the annular wall is flush with the bottom surface portion of the central flat surface portion, or the bottom surface portion of the flange portion and the central flat surface portion. It was achieved by a sealed non-aqueous secondary battery characterized by being located in the middle. (2) The step difference between the bottom surface of the flange located on the electrode group side of the bottom surface of the central flat surface and the bottom surface of the central flat surface is 0.3 to 1 mm.
2. The sealed nonaqueous secondary battery according to item 1, which is (3) The sealed nonaqueous secondary battery according to item 1 or 2, wherein the collar portion has a thickness of 0.3 to 1 mm. (4) The sealed nonaqueous secondary battery according to any one of items 1 to 3, wherein the central plane portion has a thickness of 0.5 to 1.5 mm. (5) The collar portion has an inclined portion that extends along the inner wall of the reduced diameter portion of the battery outer can between the collar portion and the annular wall portion. Sealed non-aqueous secondary battery. (6) The sealed nonaqueous secondary battery according to item 5, wherein the inclined portion of the collar portion according to item 5 has a through hole. (7) Any one of Items 1 to 4, wherein the insulator is made of a polyolefin polymer.
The sealed nonaqueous secondary battery according to item.

【０００９】本発明の非水二次電池に用いられる正・負
極は、正極合剤あるいは負極合剤を集電体上に塗設、成
形して作ることができる。正極あるいは負極合剤には、
それぞれ正極活物質あるいは負極材料の他、それぞれに
導電剤、結着剤、分散剤、フィラー、イオン導電剤、圧
力増強剤や各種添加剤を含むことができる。The positive and negative electrodes used in the non-aqueous secondary battery of the present invention can be prepared by coating and molding a positive electrode mixture or a negative electrode mixture on a current collector. For the positive electrode or negative electrode mixture,
In addition to the positive electrode active material or the negative electrode material, a conductive agent, a binder, a dispersant, a filler, an ionic conductive agent, a pressure enhancer or various additives may be contained in each.

【００１０】本発明で使用できる正極中の活物質は、軽
金属を挿入放出できるものであれば良いが、好ましくは
リチウム含有遷移金属酸化物であり、更に好ましくはＬ
ｉxＣｏＯ2、ＬｉxＮｉＯ2、ＬｉxＣｏaＮｉ1-aＯ2、Ｌ
ｉxＣｏbＶ1-bＯz、 ＬｉxＣｏbＦｅ1ーbＯz、ＬｉxＭｎ
2Ｏ4、ＬｉxＭｎＯ2、ＬｉＭｎ2Ｏ3、ＬｉxＭｎbＣｏ
2ーbＯz、ＬｉxＭｎbＮｉ2ーbＯz、ＬｉxＭｎbＶ2ーbＯz、
ＬｉxＭｎbＦｅ1ーbＯz（ここでｘ＝０．０５〜１．２、
ａ＝０．１〜０．９、ｂ＝０．８〜０．９８、ｚ＝１．
５〜５）である。以下、本発明で言う軽金属とは、周期
律表第１Ａ族（水素を除く）及び第２Ａ族に属する元素
であり、好ましくはリチウム、ナトリウム、カリウムで
あり、特にリチウムであることが好ましい。The active material in the positive electrode which can be used in the present invention may be any material capable of inserting and releasing a light metal, but is preferably a lithium-containing transition metal oxide, more preferably L.
i x CoO 2 , Li x NiO 2 , Li x Co a Ni 1-a O 2 , L
i x Co b V 1-b O z , Li x Co b Fe 1-b O z , Li x Mn
2 O 4 , Li x MnO 2 , LiMn 2 O 3 , Li x Mn b Co
2-b O z, Li x Mn b Ni 2 over b O z, Li x Mn b V 2 over b O z,
Li x Mn b Fe 1 over b O z (where x = 0.05 to 1.2,
a = 0.1 to 0.9, b = 0.8 to 0.98, z = 1.
5-5). Hereinafter, the light metal referred to in the present invention is an element belonging to Group 1A (excluding hydrogen) and Group 2A of the periodic table, preferably lithium, sodium, and potassium, and particularly preferably lithium.

【００１１】本発明で使用できる負極中の活物質は、軽
金属を挿入放出できるものであれば良いが、好ましくは
黒鉛（天然黒鉛、人造黒鉛、気相成長黒鉛）、コークス
（石炭または石油系）、有機ポリマー焼成物（ポリアク
リロニトリルの樹脂または繊維、フラン樹脂、クレゾー
ル樹脂、フェノール樹脂）、メゾフェースピッチ焼成
物、金属酸化物、金属カルコゲナイド、リチウム含有遷
移金属酸化物及びカルコゲナイドである。特に，Ｇｅ，
Ｓｎ，Ｐｂ，Ｂｉ，Ａｌ，Ｇａ，Ｓｉ、Ｓｂの単独ある
いはこれらの組み合わせからなる酸化物、カルコゲナイ
ドが好ましい。更に、これらに網目形成剤として知られ
ているＳｉＯ2，Ｂ2Ｏ3，Ｐ2Ｏ5，Ａｌ2Ｏ3，Ｖ2Ｏ5な
どを加えて非晶質化させたものが特に好ましい。これら
は化学量論組成のものであっても、不定比化合物であっ
ても良い。これらの化合物の好ましい例として以下のも
のを上げることができるが本発明はこれらに限定される
ものではない。The active material in the negative electrode that can be used in the present invention may be one that can insert and release light metals, but is preferably graphite (natural graphite, artificial graphite, vapor-grown graphite), coke (coal or petroleum-based). , Organic polymer fired products (polyacrylonitrile resin or fiber, furan resin, cresol resin, phenol resin), mesoface pitch fired products, metal oxides, metal chalcogenides, lithium-containing transition metal oxides and chalcogenides. In particular, Ge,
Oxides and chalcogenides composed of Sn, Pb, Bi, Al, Ga, Si and Sb alone or in combination thereof are preferred. Further, it is particularly preferable to add SiO 2 , B 2 O 3 , P 2 O 5 , Al 2 O 3 , V 2 O 5 and the like, which are known as network forming agents, to make them amorphous. These may be of stoichiometric composition or non-stoichiometric compounds. Preferred examples of these compounds include the following, but the present invention is not limited thereto.

【００１２】ＧｅＯ、ＧｅＯ2、ＳｎＯ、ＳｎＯ2、Ｓｎ
ＳｉＯ3、ＰｂＯ、ＳｉＯ、Ｓｂ2Ｏ5、Ｂｉ2Ｏ3、 Ｌｉ
2ＳｉＯ3、Ｌｉ4Ｓｉ2Ｏ7、Ｌｉ2ＧｅＯ3、ＳｎＡｌ0.4
Ｂ0.5Ｐ0.5Ｋ0.1Ｏ3.65、ＳｎＡｌ0.4Ｂ0.5Ｐ0.5Ｃｓ
0.1Ｏ3.65、 ＳｎＡｌ0.4Ｂ0.5Ｐ0.5Ｋ0.1Ｇｅ0 .05Ｏ
3.85、ＳｎＡｌ0.4Ｂ0.5Ｐ0.5Ｋ0.1Ｍｇ0.1Ｇｅ0.02Ｏ
3.83、ＳｎＡｌ0.4Ｂ0.4Ｐ0.4Ｂａ0.08Ｏ3.28、ＳｎＡ
ｌ0. 5Ｂ0.4Ｐ0.5Ｍｇ0.1Ｆ0.2Ｏ3.65、ＳｎＡｌ0.4Ｂ
0.5Ｐ0 .5Ｃｓ0.1Ｍｇ0.1Ｆ0.2Ｏ3.65、 ＳｎＢ0.5Ｐ0.5
Ｃｓ0. 05Ｍｇ0.05Ｆ0.1Ｏ3.03、Ｓｎ1.1Ａｌ0.4Ｂ0.4Ｐ
0.4Ｂａ0 .08Ｏ3.34、 Ｓｎ1.2Ａｌ0.5Ｂ0.3Ｐ0.4Ｃｓ
0.2Ｏ3.5、ＳｎＳｉ0.5Ａｌ0.2Ｂ0.1Ｐ0.1Ｍｇ
0.1Ｏ2.8、ＳｎＳｉ0 .5Ａｌ0.3Ｂ0.4Ｐ0.5Ｏ4.30、 Ｓ
ｎＳｉ0.6Ａｌ0.1Ｂ0. 1Ｐ0.1Ｂａ0.2Ｏ2.95、ＳｎＳｉ
0.6Ａｌ0.4Ｂ0.2Ｍｇ0.1Ｏ3.2、 Ｓｎ0.9Ｍｎ0.3Ｂ0.4
Ｐ0.4Ｃａ0.1Ｒｂ0.1Ｏ2 .95、Ｓｎ0.9Ｆｅ0.3Ｂ0.4Ｐ
0.4Ｃａ0.1Ｒｂ0.1Ｏ2.95、Ｓｎ0.3Ｇｅ0.7Ｂａ0.1Ｐ
0.9Ｏ3.35、Ｓｎ0.9Ｍｎ0.1Ｍｇ0.1Ｐ0.9Ｏ3.35、Ｓｎ
0.2Ｍｎ0.8Ｍｇ0.1Ｐ0.9Ｏ3.35。GeO, GeO 2 , SnO, SnO 2 , Sn
SiO 3 , PbO, SiO, Sb 2 O 5 , Bi 2 O 3 , Li
2 SiO 3 , Li 4 Si 2 O 7 , Li 2 GeO 3 , SnAl 0.4
B 0.5 P 0.5 K 0.1 O 3.65 , SnAl 0.4 B 0.5 P 0.5 Cs
0.1 O 3.65, SnAl 0.4 B 0.5 P 0.5 K 0.1 Ge 0 .05 O
3.85 , SnAl 0.4 B 0.5 P 0.5 K 0.1 Mg 0.1 Ge 0.02 O
3.83 , SnAl 0.4 B 0.4 P 0.4 Ba 0.08 O 3.28 , SnA
l 0. 5 B 0.4 P 0.5 Mg 0.1 F 0.2 O 3.65, SnAl 0.4 B
0.5 P 0 .5 Cs 0.1 Mg 0.1 F 0.2 O 3.65, SnB 0.5 P 0.5
Cs 0. 05 Mg 0.05 F 0.1 O 3.03, Sn 1.1 Al 0.4 B 0.4 P
0.4 Ba 0 .08 O 3.34, Sn 1.2 Al 0.5 B 0.3 P 0.4 Cs
0.2 O 3.5 , SnSi 0.5 Al 0.2 B 0.1 P 0.1 Mg
0.1 O 2.8, SnSi 0 .5 Al 0.3 B 0.4 P 0.5 O 4.30, S
nSi 0.6 Al 0.1 B 0. 1 P 0.1 Ba 0.2 O 2.95, SnSi
0.6 Al 0.4 B 0.2 Mg 0.1 O 3.2 , Sn 0.9 Mn 0.3 B 0.4
P 0.4 Ca 0.1 Rb 0.1 O 2 .95, Sn 0.9 Fe 0.3 B 0.4 P
0.4 Ca 0.1 Rb 0.1 O 2.95 , Sn 0.3 Ge 0.7 Ba 0.1 P
0.9 O 3.35 , Sn 0.9 Mn 0.1 Mg 0.1 P 0.9 O 3.35 , Sn
0.2 Mn 0.8 Mg 0.1 P 0.9 O 3.35 .

【００１３】さらに本発明の負極材料は、軽金属、特に
リチウムを挿入して用いることができる。リチウムの挿
入方法は、電気化学的、化学的、熱的方法が好ましい。Further, the negative electrode material of the present invention can be used by inserting a light metal, particularly lithium. The method of inserting lithium is preferably an electrochemical, chemical or thermal method.

【００１４】本発明の負極材料へのリチウム挿入量は、
リチウムの析出電位に近似するまででよいが、上記の好
ましい負極材料当たり５０〜７００モル％が好ましい。
特に１００〜６００モル％が好ましい。The amount of lithium inserted into the negative electrode material of the present invention is
It may be up to approximation of the deposition potential of lithium, but is preferably 50 to 700 mol% per the above-mentioned preferable negative electrode material.
Particularly, 100 to 600 mol% is preferable.

【００１５】本発明で使用できる正極及び負極中の導電
剤は、グラファイト、アセチレンブラック、カーボンブ
ラック、ケッチェンブラック、炭素繊維や金属粉、金属
繊維やポリフェニレン誘導体であり、特にグラファイ
ト、アセチレンブラックが好ましい。本発明で使用でき
る正極及び負極中の結着剤は、ポリアクリル酸、カルボ
キシメチルセルロース、ポリテトラフルオロエチレン、
ポリフッ化ビニリデン、ポリビニルアルコール、澱粉、
再生セルロース、ジアセチルセルロース、ヒドロキシプ
ロピルセルロース、ポリビニルクロリド、ポリビニルピ
ロリドン、ポリエチレン、ポリプロピレン、ＳＢＲ，Ｅ
ＰＤＭ、スルホン化ＥＰＤＭ、フッ素ゴム、ポリブタジ
エン、ポリエチレンオキシドであり、特にポリアクリル
酸、カルボキシメチルセルロース、ポリテトラフルオロ
エチレン、ポリフッ化ビニリデンが好ましい。The conductive agent in the positive and negative electrodes usable in the present invention is graphite, acetylene black, carbon black, Ketjen black, carbon fiber or metal powder, metal fiber or polyphenylene derivative, and graphite or acetylene black is particularly preferable. . The binder in the positive electrode and the negative electrode that can be used in the present invention is polyacrylic acid, carboxymethylcellulose, polytetrafluoroethylene,
Polyvinylidene fluoride, polyvinyl alcohol, starch,
Regenerated cellulose, diacetyl cellulose, hydroxypropyl cellulose, polyvinyl chloride, polyvinyl pyrrolidone, polyethylene, polypropylene, SBR, E
PDM, sulfonated EPDM, fluororubber, polybutadiene, and polyethylene oxide, with polyacrylic acid, carboxymethylcellulose, polytetrafluoroethylene, and polyvinylidene fluoride being particularly preferred.

【００１６】本発明で使用できる正極及び負極の支持体
即ち集電体は、材質として、正極にはアルミニウム、ス
テンレス鋼、ニッケル、チタン、またはこれらの合金で
あり、負極には銅、ステンレス鋼、ニッケル、チタン、
またはこれらの合金であり、形態としては、箔、エキス
パンドメタル、パンチングメタル、金網である。特に、
正極にはアルミニウム箔、負極には銅箔が好ましい。本
発明で使用できるセパレータは、イオン透過度が大き
く、所定の機械的強度を持ち、絶縁性の薄膜であれば良
く、材質として、オレフィン系ポリマー、フッ素系ポリ
マー、セルロース系ポリマー、ポリイミド、ナイロン、
ガラス繊維、アルミナ繊維が用いられ、形態として、不
織布、織布、微孔性フィルムが用いられる。特に、材質
として、ポリプロピレン、ポリエチレン、ポリプロピレ
ンとポリエチレンの混合体、ポリプロピレンとテフロン
の混合体、ポリエチレンとテフロンの混合体が好まし
く、形態として微孔性フィルムであるものが好ましい。
特に、孔径が０．０１〜１μｍ、厚みが５〜５０μｍの
微孔性フィルムが好ましい。The positive electrode and negative electrode supports, ie, current collectors, which can be used in the present invention, are made of aluminum, stainless steel, nickel, titanium, or an alloy thereof for the positive electrode and copper, stainless steel for the negative electrode. Nickel, titanium,
Or, these are alloys, and are in the form of foil, expanded metal, punching metal, or wire mesh. Especially,
Aluminum foil is preferable for the positive electrode, and copper foil is preferable for the negative electrode. The separator that can be used in the present invention has a high ion permeability, a predetermined mechanical strength, and may be an insulating thin film. As the material, olefin polymer, fluorine polymer, cellulose polymer, polyimide, nylon,
Glass fibers and alumina fibers are used, and as a form, a nonwoven fabric, a woven fabric, or a microporous film is used. In particular, the material is preferably polypropylene, polyethylene, a mixture of polypropylene and polyethylene, a mixture of polypropylene and Teflon, a mixture of polyethylene and Teflon, and the form is preferably a microporous film.
In particular, a microporous film having a pore size of 0.01 to 1 μm and a thickness of 5 to 50 μm is preferable.

【００１７】本発明で使用できる電解液は、有機溶媒と
してプロピレンカーボネート、エチレンカーボネート、
ブチレンカーボネート、ジメチルカーボネート、ジエチ
ルカーボネート、１，２−ジメトキシエタン、γ−ブチ
ロラクトン、テトラヒドロフラン、２−メチルテトラヒ
ドロフラン、ジメチルスフォキシド、ジオキソラン、
１，３−ジオキソラン、ホルムアミド、ジメチルホルム
アミド、ニトロメタン、アセトニトリル、蟻酸メチル、
酢酸メチル、プロピオン酸メチル、燐酸トリエステル、
トリメトキシメタン、ジオキソラン誘導体、スルホラ
ン、３−メチル−２−オキサゾリジノン、プロピレンカ
ーボネート誘導体、テトラヒドロ誘導体、ジエチルエー
テル、１，３−プロパンサルトンの少なくとも１種以上
を混合したもの、また電解質として、ＬｉＣｌＯ4、Ｌ
ｉＢＦ4、ＬｉＰＦ6、ＬｉＣＦ3ＳＯ3、ＬｉＣＦ3Ｃ
Ｏ2、ＬｉＡｓＦ6、ＬｉＳｂＦ6、ＬｉＢ10Ｃｌ10、低
級脂肪族カルボン酸リチウム、ＬｉＡｌＣｌ4 、ＬｉＣ
ｌ、ＬｉＢｒ、ＬｉＩ、クロロボランリチウム、四フェ
ニルホウ酸リチウムの１種以上の塩を溶解したものが好
ましい。特にプロピレンカーボネートあるいはエチレン
カーボネートと１、２−ジメトキシエタン及び／あるい
はジエチルカーボネートとの混合溶媒にＬｉＣＦ3Ｓ
Ｏ3、ＬｉＣｌＯ4、ＬｉＢＦ4、及び／あるいはＬｉＰ
Ｆ6 を溶解したものが好ましく、特に、少なくともエチ
レンカーボネートとＬｉＰＦ6 を含むことが好ましい。The electrolytic solution which can be used in the present invention includes propylene carbonate, ethylene carbonate, and
Butylene carbonate, dimethyl carbonate, diethyl carbonate, 1,2-dimethoxyethane, γ-butyrolactone, tetrahydrofuran, 2-methyltetrahydrofuran, dimethylsulfoxide, dioxolane,
1,3-dioxolan, formamide, dimethylformamide, nitromethane, acetonitrile, methyl formate,
Methyl acetate, methyl propionate, phosphoric acid triester,
Trimethoxy methane, dioxolane derivatives, sulfolane, 3-methyl-2-oxazolidinone, propylene carbonate derivatives, tetrahydro derivative, diethyl ether, as a mixture of at least one or more kinds of 1,3-propane sultone, and as the electrolyte, LiClO 4 , L
iBF 4 , LiPF 6 , LiCF 3 SO 3 , LiCF 3 C
O 2 , LiAsF 6 , LiSbF 6 , LiB 10 Cl 10 , lower aliphatic lithium carboxylate, LiAlCl 4 , LiC
It is preferable to dissolve one or more salts of 1, 1, LiBr, LiI, lithium chloroborane, and lithium tetraphenylborate. In particular, LiCF 3 S is added to a mixed solvent of propylene carbonate or ethylene carbonate and 1,2-dimethoxyethane and / or diethyl carbonate.
O 3 , LiClO 4 , LiBF 4 , and / or LiP
It is preferable to dissolve F 6 , and it is particularly preferable to contain at least ethylene carbonate and LiPF 6 .

【００１８】電池の形状はシリンダー、角のいずれにも
適用できる。この場合、電極は、合剤を集電体上に塗
設、乾燥、脱水、プレスして用いる。電池は、セパレー
ターと共に巻回した電極を電池缶に挿入し、缶と電極を
電気的に接続し、電解液を注入し封口して形成する。こ
の時、安全弁を電池蓋として用いることができる。更に
電池の安全性を保証するためにＰＴＣ素子を用いるのが
好ましい。The shape of the battery can be applied to either a cylinder or a corner. In this case, the electrode is used by applying the mixture on the current collector, drying, dehydrating, and pressing. A battery is formed by inserting an electrode wound with a separator into a battery can, electrically connecting the can and the electrode, injecting an electrolyte, and sealing the battery. At this time, the safety valve can be used as a battery lid. Further, it is preferable to use a PTC element in order to guarantee the safety of the battery.

【００１９】本発明で使用できる有底電池外装缶は、材
質として、ニッケルメッキを施した鉄鋼板、ステンレス
鋼板（ＳＵＳ３０４、ＳＵＳ３０４Ｌ，ＳＵＳ３０４
Ｎ、ＳＵＳ３１６、ＳＵＳ３１６Ｌ、ＳＵＳ４３０、Ｓ
ＵＳ４４４等）、ニッケルメッキを施したステンレス鋼
板（同上）、アルミニウムまたはその合金、ニッケル、
チタン、銅であり、形状として、真円形筒状、楕円形筒
状、正方形筒状、長方形筒状である。特に、外装缶が負
極端子を兼ねる場合は、ステンレス鋼板、ニッケルメッ
キを施した鉄鋼板が好ましく、外装缶が正極端子を兼ね
る場合は、ステンレス鋼板、アルミニウムまたはその合
金が好ましい。The bottomed battery outer can that can be used in the present invention is made of nickel-plated iron and stainless steel plates (SUS304, SUS304L, SUS304).
N, SUS316, SUS316L, SUS430, S
US444, etc.), nickel-plated stainless steel plate (same as above), aluminum or its alloy, nickel,
They are titanium and copper, and have a shape of a perfect circular cylinder, an elliptical cylinder, a square cylinder, or a rectangular cylinder. In particular, when the outer can also serves as the negative electrode terminal, a stainless steel plate or a nickel-plated iron steel plate is preferable, and when the outer can also serves as the positive electrode terminal, a stainless steel plate, aluminum or an alloy thereof is preferable.

【００２０】本発明で使用できるガスケットは、材質と
して、オレフィン系ポリマー、フッ素系ポリマー、セル
ロース系ポリマー、ポリイミド、ポリアミドであり、耐
有機溶媒性及び低水分透過性から、オレフィン系ポリマ
ーが好ましく、特にプロピレン主体のポリマーが好まし
い。さらに、プロピレンとエチレンのブロック共重合ポ
リマーであることが好ましい。The gasket that can be used in the present invention is made of an olefin polymer, a fluorine polymer, a cellulosic polymer, a polyimide or a polyamide as a material, and the olefin polymer is preferable from the viewpoint of organic solvent resistance and low water permeability, and particularly, Polymers based on propylene are preferred. Further, it is preferably a block copolymer of propylene and ethylene.

【００２１】本発明の電池は必要に応じて外装材で被覆
される。外装材としては、熱収縮チューブ、粘着テー
プ、金属フィルム、紙、布、塗料、プラスチックケース
等がある。また、外装の少なくとも一部に熱で変色する
部分を設け、使用中の熱履歴がわかるようにしても良
い。本発明の電池は必要に応じて複数本を直列及び／ま
たは並列に組み電池パックに収納される。電池パックに
は正温度係数抵抗体、温度ヒューズ、ヒューズ及び／ま
たは電流遮断素子等の安全素子の他、安全回路（各電池
及び／または組電池全体の電圧、温度、電流等をモニタ
ーし、必要なら電流を遮断する機能を有す回路）を設け
ても良い。また電池パックには、組電池全体の正極及び
負極端子以外に、各電池の正極及び負極端子、組電池全
体及び各電池の温度検出端子、組電池全体の電流検出端
子等を外部端子として設けることもできる。また電池パ
ックには、電圧変換回路（ＤＣ−ＤＣコンバータ等）を
内蔵しても良い。また各電池の接続は、リード板を溶接
することで固定しても良いし、ソケット等で容易に着脱
できるように固定しても良い。さらには、電池パックに
電池残存容量、充電の有無、使用回数等の表示機能を設
けても良い。The battery of the present invention is optionally covered with an exterior material. Examples of the exterior material include a heat-shrinkable tube, an adhesive tape, a metal film, paper, cloth, paint, a plastic case, and the like. Further, at least a part of the exterior may be provided with a portion that changes color by heat so that the heat history during use can be recognized. A plurality of batteries of the present invention are assembled in series and / or in parallel and stored in a battery pack as needed. In addition to safety elements such as positive temperature coefficient resistors, thermal fuses, fuses and / or current interrupting elements, battery packs have safety circuits (voltage, temperature, current, etc. of each battery and / or assembled battery as a whole, Then, a circuit having a function of interrupting the current may be provided. In addition to the positive and negative terminals of the whole battery pack, the positive and negative terminals of each battery, the temperature detection terminals of the whole battery pack and each battery, the current detection terminals of the whole battery pack, etc. shall be provided as external terminals on the battery pack. Can also. The battery pack may have a built-in voltage conversion circuit (such as a DC-DC converter). The connection of each battery may be fixed by welding a lead plate, or may be fixed by a socket or the like so that it can be easily detached. Further, the battery pack may be provided with a display function of the remaining battery capacity, the presence / absence of charging, the number of times of use, and the like.

【００２２】本発明の電池は様々な機器に使用される。
特に、ビデオムービー、モニター内蔵携帯型ビデオデッ
キ、モニター内蔵ムービーカメラ、コンパクトカメラ、
一眼レフカメラ、使い捨てカメラ、レンズ付きフィル
ム、ノート型パソコン、ノート型ワープロ、電子手帳、
携帯電話、コードレス電話、ヒゲソリ、電動工具、電動
ミキサー、自動車等に使用されることが好ましい。The battery of the present invention is used in various devices.
In particular, video movies, portable VCRs with monitors, movie cameras with monitors, compact cameras,
SLR camera, disposable camera, film with lens, notebook computer, notebook word processor, electronic organizer,
It is preferably used for mobile phones, cordless phones, beards, electric tools, electric mixers, automobiles and the like.

【００２３】上述したように、非水二次電池の場合、使
用する電極が、ニッケルカドミウム電池やニッケル水素
電池の場合より薄くしかも長い帯状である場合が多いた
め、巻回された電極群の電解液浸透性が非常に悪く、電
池組立時の電解液注入時間が長くかかり、よって注液装
置がとても大きなものとなるだけでなく、非水電解液で
あるがゆえにその揮発性の高さから注液量の精度管理が
難しい。これを解決するために、電極群の上面に配置さ
れる絶縁体に多くの貫通孔を設けようとすると、絶縁体
の強度が低下し、電池落下時の電極群のずれによる内部
短絡が起こり易くなってしまう。逆に、絶縁体に設ける
貫通孔をできるだけ少なくして厚みを大きくすれば、強
度は増すが、電極群の電解液浸透性が低下してしまう。
本発明の密閉型非水二次電池は、電極群の電解液浸透性
が良く、電池組立時の電解液注入を短時間で行うことが
可能であり、なおかつ電池落下時の内部短絡をも防止す
ることができる構成をなしている。つまり、電極群の上
面に配置される絶縁体において、環状壁の外周部に形成
される鍔部の底面より、環状壁の内周部に形成される中
央平面部の底面が上方に位置し、鍔部には複数の貫通孔
を有する。さらに中央平面部の中央部とその周辺に貫通
孔を有するため、電解液注入時に電池外装缶内のエアー
あるいは不活性ガスがこれらの貫通孔を通って抜け易く
なり、電解液が電極群に浸透し易くなる。また、絶縁体
中央部には平面部が存在するため、電池落下時の電極群
のずれを最小限に抑えることができる。したがって、組
立作業性が高く、しかも安全性の高い密閉型非水二次電
池とすることができる。As described above, in the case of the non-aqueous secondary battery, the electrodes used are often thinner and longer in strip shape than those of the nickel-cadmium battery or the nickel-hydrogen battery, and therefore the electrolysis of the wound electrode group is performed. The liquid permeability is very poor, and it takes a long time to inject the electrolyte solution when assembling the battery, which not only makes the injection device very large, but also because it is a non-aqueous electrolyte solution, it is highly volatile. It is difficult to control the accuracy of the liquid volume. In order to solve this, if many through holes are provided in the insulator arranged on the upper surface of the electrode group, the strength of the insulator is reduced, and an internal short circuit easily occurs due to the displacement of the electrode group when the battery is dropped. turn into. On the contrary, if the through holes provided in the insulator are made as small as possible and the thickness is increased, the strength is increased, but the electrolyte permeability of the electrode group is reduced.
INDUSTRIAL APPLICABILITY The sealed non-aqueous secondary battery of the present invention has good electrolyte permeability of the electrode group, can inject the electrolyte during battery assembly in a short time, and also prevents internal short circuit when the battery is dropped. It has a configuration that can. That is, in the insulator arranged on the upper surface of the electrode group, the bottom surface of the central plane portion formed on the inner peripheral portion of the annular wall is located above the bottom surface of the flange portion formed on the outer peripheral portion of the annular wall, The flange has a plurality of through holes. Furthermore, since there are through holes in the center of the central plane and its surroundings, air or inert gas inside the battery case can easily escape through these through holes when the electrolyte is injected, and the electrolyte penetrates into the electrode group. Easier to do. Further, since the flat portion exists in the central portion of the insulator, it is possible to minimize the displacement of the electrode group when the battery is dropped. Therefore, it is possible to obtain a sealed non-aqueous secondary battery that has high assembly workability and high safety.

【００２４】[0024]

【実施例】以下に具体例をあげ、本発明をさらに詳しく
説明するが、発明の主旨を越えない限り、本発明は実施
例に限定されるものではない。密閉型非水二次電池は、
図１に示すように、正極集電体に正極活物質を含む正極
合剤を塗布してなる正極と、負極集電体に負極材料を含
む負極合剤を塗布してなる負極とを、セパレータを介し
て巻回し構成した電極群を、その上下に絶縁体を配置し
た状態で外装缶に収納し、さらに、外装缶開口部に絶縁
性ガスケットを介して電池蓋を配置して密閉することに
より構成した。この時、電池蓋を正極より導き出された
リード板に接続し、また負極より導き出されたリード板
を外装缶に電気的に接続し、電池蓋及び外装缶がそれぞ
れ正極あるいは負極の端子として機能するように構成し
た。The present invention will be described in more detail with reference to specific examples, but the present invention is not limited to the examples unless it exceeds the gist of the invention. The sealed non-aqueous secondary battery is
As shown in FIG. 1, a positive electrode current collector is coated with a positive electrode mixture containing a positive electrode active material, and a negative electrode current collector is coated with a negative electrode mixture containing a negative electrode material. By accommodating the electrode group formed by winding through the outer casing with the insulators arranged above and below it in the outer can, and further by arranging the battery lid through the insulating gasket in the outer can opening and sealing it. Configured. At this time, the battery lid is connected to the lead plate led out from the positive electrode, and the lead plate led out from the negative electrode is electrically connected to the outer can, so that the battery lid and the outer can function as terminals of the positive electrode or the negative electrode, respectively. As configured.

【００２５】正極は、活物質としてＬｉＣｏＯ2 （８７
重量部）を用い、導電剤として鱗片状黒鉛（６重量部）
とアセチレンブラック（３重量部）を、結着剤としてポ
リテトラフルオロエチレン水分散物（３重量部）とポリ
アクリル酸ナトリウム（１重量部）を加え、水を媒体と
して混練して得られたスラリーをアルミニウム箔（集電
体：厚さ２０μｍ）の両面にエクストルージョン法によ
り塗布し、この塗布物を乾燥した後、カレンダープレス
機により圧縮成形して帯状の正極（厚さ２５０μｍ）と
した。負極においては、一酸化錫（７３．３重量部）、
二酸化珪素（１９．５重量部）、酸化マグネシウム
（３．５重量部）、酸化ほう素（３．７重量部）を乾式
混合し、アルゴン雰囲気下で１０時間（１２００℃）焼
成した後、冷却して粉砕して得た平均粒径４．５μｍの
ＳｎＳｉ0.6Ｍｇ0.2Ｂ0.2Ｏ2.7を負極材料として用い
た。負極は、上記の負極材料（８８重量部）と、導電剤
として燐片状黒鉛（６重量部）、結着剤としてポリフッ
化ビリニデンの水分散物（４重量部）とカルボキシメチ
ルセルロース（１重量部）及び酢酸リチウム（１重量
部）を加え、水を媒体として混練して得られたスラリー
を銅箔（集電体：厚さ１８μｍ）の両面にエクストルー
ジョン法により塗布し、正極と同様、乾燥、圧縮成形し
て帯状の負極（厚さ７８μｍ）とした。The positive electrode was made of LiCoO 2 (87) as an active material.
(Parts by weight) and flaky graphite (6 parts by weight) as a conductive agent
And acetylene black (3 parts by weight), polytetrafluoroethylene aqueous dispersion (3 parts by weight) as a binder and sodium polyacrylate (1 part by weight) were added, and the mixture was kneaded with water as a medium to obtain a slurry. Was applied to both sides of an aluminum foil (current collector: thickness 20 μm) by an extrusion method, and the applied material was dried and compression-molded by a calender press to obtain a strip-shaped positive electrode (thickness 250 μm). In the negative electrode, tin monoxide (73.3 parts by weight),
Silicon dioxide (19.5 parts by weight), magnesium oxide (3.5 parts by weight), and boron oxide (3.7 parts by weight) are dry-mixed and baked in an argon atmosphere for 10 hours (1200 ° C.) and then cooled. the average particle size 4.5μm in SnSi 0 obtained by grinding. 6 Mg 0.2 B 0.2 O 2.7 was used as a negative electrode material. The negative electrode was prepared by using the above negative electrode material (88 parts by weight), scaly graphite (6 parts by weight) as a conductive agent, polyvinylidene fluoride water dispersion (4 parts by weight) and carboxymethyl cellulose (1 part by weight) as a binder. ) And lithium acetate (1 part by weight) are added, and a slurry obtained by kneading with water as a medium is applied to both surfaces of a copper foil (current collector: thickness 18 μm) by an extrusion method and dried in the same manner as the positive electrode. Then, compression molding was carried out to obtain a strip-shaped negative electrode (thickness 78 μm).

【００２６】低湿度雰囲気中（露点：−５０℃）で、上
記で得られた正極と負極を脱水乾燥（遠赤外線ヒータ
ー、１５０℃、２時間）した後所定の寸法に裁断し、正
極及び負極のそれぞれの端部にアルミニウム及びニッケ
ル製のリード板を取り付け、正極と負極をポリエチレン
製微孔性フィルムセパレータを介して巻回し電極群を構
成した。さらにこの電極群を、エチレンカーボネートと
ジエチルカーボネートの２対８容積比混合溶媒に０．９
５ｍｏｌ／リットルのＬｉＰＦ6 と０．０５ｍｏｌ／リ
ットルのＬｉＢＦ4 を溶解した電解液と共に真円形筒状
有底外装缶（ニッケルメッキを施した鉄鋼板製）に収納
して、プロピレンとエチレンの共重合ポリマーからなる
ガスケットと共に、電池内圧が上昇した時に電池内での
電気的接続を遮断する機能を有する電池蓋を用いて封口
し、直径１６．３ｍｍ、高さ６７ｍｍの円筒型電池を構
成した。なお電池蓋は、特願平６−２９４６１１号記載
の防爆弁体と、特願平７−２４２８１６号記載の電流遮
断体、及びＰＴＣ素子と端子キャップとで構成し、また
巻回電極群の上面には後述する絶縁体を配置して構成し
た。The positive electrode and the negative electrode obtained above were dehydrated and dried (far infrared heater, 150 ° C., 2 hours) in a low humidity atmosphere (dew point: −50 ° C.) and then cut into a predetermined size to obtain the positive electrode and the negative electrode. A lead plate made of aluminum and nickel was attached to each end of the above, and the positive electrode and the negative electrode were wound with a polyethylene microporous film separator interposed therebetween to form an electrode group. Furthermore, 0.9% of this electrode group was mixed with a mixed solvent of ethylene carbonate and diethyl carbonate in a volume ratio of 2 to 8.
Copolymerization of propylene and ethylene by accommodating 5 mol / l of LiPF 6 and 0.05 mol / l of LiBF 4 together with an electrolytic solution in a true round tubular bottomed outer can (made of nickel-plated steel plate) A cylindrical battery having a diameter of 16.3 mm and a height of 67 mm was formed by using a gasket made of a polymer and a battery lid having a function of interrupting electrical connection in the battery when the internal pressure of the battery increased. The battery lid is composed of the explosion-proof valve element described in Japanese Patent Application No. 6-294611, the current interrupter described in Japanese Patent Application No. 7-242816, the PTC element and the terminal cap, and the upper surface of the wound electrode group. In this configuration, an insulator described later is arranged.

【００２７】（電池１）図１及び図２に示すように、巻
回群上面の絶縁体（図中の記号３）は、外周部近傍に環
状の壁部（３１）があり、その外周部には、環状壁部の
下部より電極群側へ傾斜し突出した傾斜部とさらにその
外周部に水平方向に延出する水平部からなる、鍔部（３
２）が形成されている。環状壁部の内周側には、中央平
面部（３３）があり、リード（４）の挿通用の貫通孔
（３５）とその周辺には４つの貫通孔（３４）が形成さ
れている。環状壁（３１）の底面と中央平面部（３３）
の底面とは本実施例では同一平面上にある。また、鍔部
（３２）には複数の貫通孔（３４）がある。上記絶縁体
は、材質はポリプロピレンを主体とする、ポリエチレン
とのブロック共重合ポリマーを用い、射出成形法により
形成した。鍔部の厚さは０．３ｍｍ、内周部平面部の厚
さは０．５ｍｍ、鍔部水平部の下面と内周部平面部の下
面との段差は０．３ｍｍとした。このように形成した絶
縁体を用いた電池を電池１とした。(Battery 1) As shown in FIGS. 1 and 2, the insulator (symbol 3 in the drawing) on the upper surface of the winding group has an annular wall portion (31) near the outer peripheral portion, and the outer peripheral portion thereof. Includes a flange portion (3) including an inclined portion that is inclined and protrudes from the lower portion of the annular wall portion toward the electrode group side, and a horizontal portion that extends horizontally in the outer peripheral portion.
2) is formed. A central plane portion (33) is provided on the inner peripheral side of the annular wall portion, and a through hole (35) for inserting the lead (4) and four through holes (34) are formed around the through hole (35). The bottom surface of the annular wall (31) and the central plane portion (33)
In the present embodiment, the bottom surface of is in the same plane. Further, the collar portion (32) has a plurality of through holes (34). The insulator was formed by injection molding using a block copolymer of polyethylene as a main material and polyethylene. The thickness of the flange portion was 0.3 mm, the thickness of the inner peripheral flat portion was 0.5 mm, and the step between the lower surface of the horizontal flange portion and the lower surface of the inner peripheral flat portion was 0.3 mm. A battery using the thus-formed insulator was designated as Battery 1.

【００２８】（電池２、３、４、５、６）電池１におけ
る絶縁体において、鍔部水平部の下面と内周部平面部の
下面との段差を、０．１ｍｍ、０．５ｍ、０．７ｍｍ、
１．０ｍｍ、１．３ｍｍとした電池を、それぞれ電池
２、電池３、電池４、電池５、電池６とした。(Batteries 2, 3, 4, 5, 6) In the insulator of the battery 1, the steps between the lower surface of the horizontal flange portion and the lower surface of the inner peripheral flat portion are 0.1 mm, 0.5 m, 0. 0.7 mm,
Batteries of 1.0 mm and 1.3 mm were referred to as Battery 2, Battery 3, Battery 4, Battery 5, and Battery 6, respectively.

【００２９】（電池７、８）電池１における絶縁体にお
いて、鍔部の厚さを、０．１ｍｍ、０．５ｍｍとした電
池を、それぞれ電池７、電池８とした。(Batteries 7 and 8) In the insulator of the battery 1, batteries having a flange thickness of 0.1 mm and 0.5 mm were designated as batteries 7 and 8, respectively.

【００３０】（電池９、１０）電池１における絶縁体に
おいて、内周部平面部の厚さを、０．３ｍｍ、０．７ｍ
ｍとした電池を、それぞれ電池９、電池１０とした。(Batteries 9 and 10) In the insulator of the battery 1, the thickness of the inner peripheral flat portion is 0.3 mm and 0.7 m.
The batteries with m were designated as Battery 9 and Battery 10, respectively.

【００３１】（電池１１、１２）図３に示すように、上
記絶縁体として、厚さ０．５ｍｍのポリプロピレン製の
円盤状のものを用いた電池を電池１１とし、また特開平
５−４１２４８号公報記載によるもの（厚さ２．０ｍｍ
のベークライト製の円盤状）を用いた電池を電池１２と
した。(Batteries 11 and 12) As shown in FIG. 3, a battery using a 0.5 mm-thick polypropylene disk-shaped insulator as the above-mentioned insulator is referred to as Battery 11, and is disclosed in JP-A-5-41248. According to the publication (thickness 2.0 mm
A battery using a bakelite disc-shaped) of No. 2 was used as a battery 12.

【００３２】（電池１３）図４に示すように、上記絶縁
体として、外周部近傍に環状壁部を有するもの（厚さ
０．５ｍｍのポリプロピレン製）を用いた電池を電池１
３とした。(Battery 13) As shown in FIG. 4, a battery using an insulator having an annular wall portion near the outer peripheral portion (made of polypropylene having a thickness of 0.5 mm) as a battery 1
It was set to 3.

【００３３】（電池１４）図５に示すように、上記絶縁
体として、実開平４−４６３６０号公報記載によるもの
（厚さ０．５ｍｍのポリプロピレン製）を用いた電池を
電池１４とした。(Battery 14) As shown in FIG. 5, a battery using the insulator described in Japanese Utility Model Publication No. 4-46360 (made of polypropylene having a thickness of 0.5 mm) as the insulator was used as a battery 14.

【００３４】（電池１５）図６に示すように、上記絶縁
体として、実開昭６２−１０３１６９号公報によるもの
（厚さ０．５ｍｍのポリプロピレン製）を用いた電池を
電池１５とした。(Battery 15) As shown in FIG. 6, a battery using the insulator according to Japanese Utility Model Laid-Open No. 62-103169 (made of polypropylene having a thickness of 0.5 mm) as the insulator was used as a battery 15.

【００３５】上述のように構成した本発明による実施例
及び従来例の電池に対し、高さ１ｍからコンクリート上
への落下試験を３０回行い、次いで室温にて５日間、電
池の開路電圧測定を継続して行った。なお、電池の落下
方向は、端子キャップ側、横側、電池外装缶底部側をそ
れぞれ下方にするものとし、３方向を各１回ずつ順番に
繰り返し行うという方法で行った（落下試験数は各２０
個）。落下試験で防爆弁体が変形して電流遮断体が作動
した電池数（Ａ）、落下後の放置時に開路電圧が異常に
低下した電池数（Ｂ）、電池組立時の電解液注入に要し
た時間（Ｃ：２０個の平均、単位は分）を表１に示す。The batteries of the examples according to the present invention and the conventional examples configured as described above were subjected to a drop test from a height of 1 m onto concrete 30 times, and then the open circuit voltage of the batteries was measured at room temperature for 5 days. I went on continuously. The battery was dropped in such a manner that the terminal cap side, the lateral side, and the bottom side of the battery outer can were set downward, and the three directions were repeated once in sequence (the number of drop tests was 20
Pieces). In the drop test, the number of batteries in which the explosion-proof valve body was deformed and the current interrupter operated (A), the number of batteries in which the open circuit voltage dropped abnormally after standing after falling (B), and the injection of the electrolyte solution during battery assembly were required. The time (C: average of 20 pieces, unit: minutes) is shown in Table 1.

【００３６】 [0036]

【００３７】上記結果表によれば、電池１１、電池１
３、電池１４、電池１５の場合は、電極群の中心部のず
れが大きく、これに対応する部分の絶縁体の強度が不足
していることが明らかである。一方電池１２の場合は、
絶縁体の強度が大きいため、落下試験での異常はみられ
なかったが、電解液注入時のエアー抜けが悪いことがは
っきりわかる。電池１から電池１０の本実施例の場合
は、絶縁体の鍔部の厚さが０．３ｍｍ以上、中央平面部
の厚さが０．５ｍｍ以上で、落下時の安全性が確保され
ており、また鍔部の下面と中央平面部の下面との段差が
０．３ｍｍ以上で、電解液注入時の時間を大幅に短縮で
きることがわかる。なお、前記段差寸法が１ｍｍを越え
てしまうと、電極群の中心部のずれを効果的に押さえ込
むことができなくなる。According to the above result table, battery 11 and battery 1
In the case of 3, battery 14, and battery 15, it is clear that the center portion of the electrode group is largely displaced and the strength of the insulator at the corresponding portion is insufficient. On the other hand, in the case of the battery 12,
Since the strength of the insulator was high, no abnormalities were found in the drop test, but it is clearly seen that the air escape during injection of the electrolyte was poor. In the case of the batteries 1 to 10 according to this embodiment, the collar portion of the insulator has a thickness of 0.3 mm or more, and the central plane portion has a thickness of 0.5 mm or more, so that safety at the time of dropping is ensured. Further, it is understood that the step between the lower surface of the collar portion and the lower surface of the central plane portion is 0.3 mm or more, and the time for injecting the electrolytic solution can be significantly shortened. If the step size exceeds 1 mm, it becomes impossible to effectively suppress the deviation of the central portion of the electrode group.

【００３８】本発明の実施例の電池においては、絶縁体
の材質として、ポリプロピレンを主体とする、ポリエチ
レンとのブロック共重合ポリマーを用いたが、ポリプロ
ピレン単体のホモポリマー、ポリプロピレンとポリエチ
レンのランダム重合ポリマー、高分子量ポリエチレンポ
リマーを用いた場合でも、その効果は同様で変わりはな
かった。In the battery of the embodiment of the present invention, a block copolymer with polyethylene, which is mainly polypropylene, was used as the material of the insulator, but a homopolymer of polypropylene alone or a random polymer of polypropylene and polyethylene. Even when a high molecular weight polyethylene polymer was used, the effect was the same and remained unchanged.

【００３９】[0039]

【発明の効果】本発明による密閉型非水二次電池におい
ては、電極群の上面に配置される絶縁体が、環状の壁部
を境に外周部と内周部とで段差があり、外周部から内周
部へ通ずる孔が複数形成されていることから、電解液注
入が短時間で行え、また落下時の内部短絡も防止でき、
組立作業性が高くしかも安全性の高い密閉型非水二次電
池を提供することができる。In the sealed non-aqueous secondary battery according to the present invention, the insulator arranged on the upper surface of the electrode group has a step between the outer peripheral portion and the inner peripheral portion with the annular wall as a boundary, Since a plurality of holes leading from the part to the inner peripheral part are formed, the electrolytic solution can be injected in a short time, and an internal short circuit at the time of dropping can be prevented,
It is possible to provide a sealed non-aqueous secondary battery that has high assembly workability and high safety.

【図面の簡単な説明】[Brief description of drawings]

【図１】本発明の密閉型非水二次電池の実施例を示す縦
断面図FIG. 1 is a vertical sectional view showing an embodiment of a sealed non-aqueous secondary battery of the present invention.

【図２】本発明の密閉型非水二次電池の実施例における
絶縁体を示す上面図（ａ）及び縦断面図（ｂ、ｃ）FIG. 2 is a top view (a) and a longitudinal sectional view (b, c) showing an insulator in an embodiment of the sealed non-aqueous secondary battery of the present invention.

【図３】従来の密閉型電池における絶縁体を示す上面図FIG. 3 is a top view showing an insulator in a conventional sealed battery.

【図４】従来の密閉型電池における絶縁体を示す上面図
（ａ）及び縦断面図（ｂ）FIG. 4 is a top view (a) and a vertical sectional view (b) showing an insulator in a conventional sealed battery.

【図５】従来の密閉型電池における絶縁体を示す上面図FIG. 5 is a top view showing an insulator in a conventional sealed battery.

【図６】従来の密閉型電池における絶縁体を示す上面図
（ａ）及び縦断面図（ｂ）FIG. 6 is a top view (a) and a vertical sectional view (b) showing an insulator in a conventional sealed battery.

【符号の説明】[Explanation of symbols]

１ 電池外装缶 ２ 電極群 ３ 絶縁体 ３１ 環状壁部 ３２ 鍔部 ３３ 中央平面部 ３４ 貫通孔 ３５ リード挿通用の貫通孔 ４ リード板 ５ ガスケット ６ 電池蓋 ６１ 防爆弁体 ６２ 電流遮断体 ６３ ＰＴＣ素子 ６４ 端子キャップ DESCRIPTION OF SYMBOLS 1 Battery outer can 2 Electrode group 3 Insulator 31 Annular wall part 32 Collar part 33 Central plane part 34 Through hole 35 Through hole for lead insertion 4 Lead plate 5 Gasket 6 Battery lid 61 Explosion-proof valve body 62 Current breaker 63 PTC element 64 terminal cap

Claims (1)

【特許請求の範囲】[Claims] 【請求項１】 軽金属を挿入放出可能な正極及び負極
と、セパレータとで構成された電極群が、有底電池外装
缶内に収納され、該電極群の上面に絶縁体が配置され、
該絶縁体の上部で該外装缶の一部が細く絞り加工され、
非水電解液が注入された後、該外装缶の開口部が絶縁性
ガスケットを介して電池蓋で閉塞されてなる密閉型非水
二次電池において、該絶縁体が、絶縁体の外周部近傍に
形成される環状壁と、該環状壁の内部の中央平面部と、
該環状壁の外周部に形成される鍔部とから構成され、該
中央平面部はその中央部に電極リードが挿通する貫通孔
と周辺部に複数の貫通孔を有し、該鍔部は、貫通孔を有
し、鍔部底面は該中央平面部底面より電極群側に位置し
ており、該環状壁の底面部は中央平面部の底面部と同一
平面又は鍔部底面部と中央平面部の底面部の中間に位置
することを特徴とする密閉型非水二次電池。1. An electrode group composed of a positive electrode and a negative electrode capable of inserting and releasing a light metal, and a separator is housed in a bottomed battery outer can, and an insulator is arranged on the upper surface of the electrode group.
A part of the outer can is thinly drawn at the upper part of the insulator,
In a sealed non-aqueous secondary battery in which the opening of the outer can is closed with a battery lid through an insulating gasket after the non-aqueous electrolyte is injected, the insulator is near the outer periphery of the insulator. An annular wall formed in, and a central plane portion inside the annular wall,
And a flange portion formed on the outer peripheral portion of the annular wall, the central plane portion has a through hole through which the electrode lead is inserted in the central portion and a plurality of through holes in the peripheral portion, and the collar portion is It has a through hole, the bottom of the collar is located closer to the electrode group side than the bottom of the central plane, and the bottom of the annular wall is flush with the bottom of the center plane or the bottom and center plane of the collar. A sealed non-aqueous secondary battery, characterized in that it is located in the middle of the bottom surface of the.
JP09449796A 1996-04-16 1996-04-16 Sealed non-aqueous secondary battery Expired - Fee Related JP3692605B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP09449796A JP3692605B2 (en) 1996-04-16 1996-04-16 Sealed non-aqueous secondary battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP09449796A JP3692605B2 (en) 1996-04-16 1996-04-16 Sealed non-aqueous secondary battery

Publications (2)

Publication Number Publication Date
JPH09283112A true JPH09283112A (en) 1997-10-31
JP3692605B2 JP3692605B2 (en) 2005-09-07

Family

ID=14111952

Family Applications (1)

Application Number Title Priority Date Filing Date
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Country Status (1)

Country Link
JP (1) JP3692605B2 (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005149861A (en) * 2003-11-14 2005-06-09 Shin Kobe Electric Mach Co Ltd Nonaqueous electrolyte secondary battery
JP2006196292A (en) * 2005-01-13 2006-07-27 Sanyo Electric Co Ltd Nonaqueous electrolytic solution secondary battery and its manufacturing method
JP2008135263A (en) * 2006-11-28 2008-06-12 Matsushita Electric Ind Co Ltd Battery
JP2009289683A (en) * 2008-05-30 2009-12-10 Hitachi Vehicle Energy Ltd Sealed-type secondary battery
JP2010009841A (en) * 2008-06-25 2010-01-14 Panasonic Corp Cylindrical sealed battery
US8492022B2 (en) 2009-10-07 2013-07-23 Samsung Sdi Co., Ltd. Rechargeable battery with buffer sheet between electrode assembly and battery case

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005149861A (en) * 2003-11-14 2005-06-09 Shin Kobe Electric Mach Co Ltd Nonaqueous electrolyte secondary battery
JP4581378B2 (en) * 2003-11-14 2010-11-17 新神戸電機株式会社 Non-aqueous electrolyte secondary battery
JP2006196292A (en) * 2005-01-13 2006-07-27 Sanyo Electric Co Ltd Nonaqueous electrolytic solution secondary battery and its manufacturing method
US7687195B2 (en) 2005-01-13 2010-03-30 Sanyo Electric Co., Ltd. Nonaqueous electrolyte secondary battery and producing method thereof
JP2008135263A (en) * 2006-11-28 2008-06-12 Matsushita Electric Ind Co Ltd Battery
JP2009289683A (en) * 2008-05-30 2009-12-10 Hitachi Vehicle Energy Ltd Sealed-type secondary battery
JP2010009841A (en) * 2008-06-25 2010-01-14 Panasonic Corp Cylindrical sealed battery
US8492022B2 (en) 2009-10-07 2013-07-23 Samsung Sdi Co., Ltd. Rechargeable battery with buffer sheet between electrode assembly and battery case
US9577226B2 (en) 2009-10-07 2017-02-21 Samsung Sdi Co., Ltd. Rechargeable battery with buffer sheet between electrode assembly and battery case

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