JPH09320639A - Spiral type non-aqueous secondary battery and manufacture thereof - Google Patents
Spiral type non-aqueous secondary battery and manufacture thereofInfo
- Publication number
- JPH09320639A JPH09320639A JP8156319A JP15631996A JPH09320639A JP H09320639 A JPH09320639 A JP H09320639A JP 8156319 A JP8156319 A JP 8156319A JP 15631996 A JP15631996 A JP 15631996A JP H09320639 A JPH09320639 A JP H09320639A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- width
- secondary battery
- electrode lead
- lead
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】製造時の電池性能のばらつき
を少なくした渦巻型非水二次電池に関し、特に中心部に
おける渦巻状の電極群の均一性を改良した渦巻電極の製
造法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a spiral non-aqueous secondary battery in which variations in battery performance during manufacturing are reduced, and more particularly to a method for manufacturing a spiral electrode in which uniformity of a spiral electrode group in a central portion is improved.
【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電極群を用いた円筒型の電池が
用いられている。高エネルギー密度を達成するために
は、巻き込む電極シートの長さをできるだけ長くすると
ともに均一な渦巻電極を作ることが必要である。しかし
ながら、電池の正負極端子に接続する電極リードは、集
電体そのものや活物質が塗布された電極部分とは厚みや
剛性が異なるため、電極リード溶接部が他の部分とは違
う曲率になったり、折れ曲がりが生じたりする。こうし
た問題を解決するためにあらかじめ電極リードを所定の
曲率に加工しておくことが特開平２−１３２７５８号等
に記載されている。しかしながらこの方法では、電極リ
ードに曲率を与える工程が必要となり巻回機のパス長が
長くなったり、曲率を与えたリードを溶接した集電体を
搬送するため、巻きずれや引っかかり等のトラブルを発
生しやすい。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. In general, as a power source of this type, a cylindrical battery using an electrode group in which a band-shaped electrode is spirally wound is used. In order to achieve a high energy density, it is necessary to make the length of the wound electrode sheet as long as possible and to make a uniform spiral electrode. However, since the electrode leads connected to the positive and negative terminals of the battery have different thickness and rigidity from the current collector itself and the electrode part coated with the active material, the electrode lead weld has a different curvature from other parts. Or it may bend. To solve these problems, it is described in JP-A-2-132758 that the electrode leads are previously processed to have a predetermined curvature. However, in this method, a step of giving curvature to the electrode lead is required, and the path length of the winding machine becomes long, and since the current collector in which the lead having a curvature is welded is conveyed, troubles such as winding misalignment and catching occur. Likely to happen.
【０００３】[0003]
【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、渦巻状の電極群の真円度を
良化させ、電池性能のばらつきを少なくした非水二次電
池とその製造方法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 is a non-aqueous secondary battery in which the circularity of a spiral electrode group is improved and the variation in battery performance is reduced. And its manufacturing method.
【０００４】[0004]
【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シート及び負極シートと、セパレ
ータを巻回してなる電極群と非水電解液を有底電池外装
缶内に収納した渦巻型非水二次電池において、該正極シ
ートを構成する正極集電体に溶接する正極リードの幅と
厚みの関係が下記一般式（１）で表されることを特徴と
する渦巻型非水二次電池により達成された。 １０００＜Ｂ／２ｔ3 ＜１００００ （１） ここで、Ｂは正極リードの幅（ｍｍ）、ｔは正極リード
の厚み（ｍｍ）を表す。An object of the present invention is to store a positive electrode sheet and a negative electrode sheet capable of inserting and releasing a light metal, an electrode group formed by winding a separator, and a non-aqueous electrolyte in a bottomed battery outer can. In the spiral non-aqueous secondary battery described above, the relationship between the width and the thickness of the positive electrode lead welded to the positive electrode current collector that constitutes the positive electrode sheet is represented by the following general formula (1). Achieved with a water secondary battery. 1000 <B / 2t 3 <10000 (1) Here, B represents the width (mm) of the positive electrode lead, and t represents the thickness (mm) of the positive electrode lead.
【０００５】[0005]
【発明の実施の形態】本発明の好ましい形態には以下の
ものがあるが、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シート及び負極シー
トと、セパレータを巻回してなる電極群と非水電解液を
有底電池外装缶内に収納した渦巻型非水二次電池におい
て、該正極シートを構成する正極集電体に溶接する正極
リードの幅と厚みの関係が下記一般式（１）で表される
ことを特徴とする渦巻型非水二次電池。 １０００＜Ｂ／２ｔ3 ＜１００００ （１） ここで、Ｂは正極リードの幅（ｍｍ）、ｔは正極リード
の厚み（ｍｍ）を表す。 （２）該正極リードの幅と厚みの関係が下記一般式
（２）で表されることを特徴とする項１に記載の渦巻型
非水二次電池。 １５００＜Ｂ／２ｔ3 ＜７０００ （２） ここで、Ｂは正極リードの幅（ｍｍ）、ｔは正極リード
の厚み（ｍｍ）を表す。 （３）該正極リードの該正極集電体への溶接幅が、正極
リード幅の３／４以下であり、正極リードの幅端を溶接
しないことを特徴とする項１または２に記載の渦巻型非
水二次電池。 （４）該正極リードがアルミニウム又はアルミニウム合
金であることを特徴とする項１から３のいずれか１項に
記載の非水二次電池。 （５）該アルミニウム又はアルミニウム合金中のアルミ
ニウム含有率が９９．３％以上、９９．９９％以下であ
ることを特徴とする項１から４のいずれか１項に記載の
渦巻型非水二次電池。 （６）該アルミニウム又はアルミニウム合金が焼き鈍し
処理されたものであることを特徴とする項１から５のい
ずれか１項に記載の非水二次電池。 （７）軽金属を挿入放出可能な正極シート及び負極シー
トと、セパレータを巻回してなる電極群を用いた電池に
おいて、正極シートの活物質の存在しない集電体部分に
正極リードを溶接した後に、該正極シートとセパレータ
ー、負極シートとを巻回し、該正極リードに巻芯軸と概
ね同曲率を与えることを特徴とする渦巻型非水二次電池
の製造方法。 （８）該正極リードが上記一般式（１）で表されること
を特徴とする項７に記載の渦巻型非水二次電池の製造方
法。 （９）該正極リードが上記一般式（２）で表されること
を特徴とする項８に記載の渦巻型非水二次電池の製造方
法。 （１０）該正極リードの該正極集電体への溶接幅が、正
極リード幅の３／４以下であり、正極リードの幅端を溶
接しないことを特徴とする項８または９に記載の渦巻型
非水二次電池の製造方法。 （１１）該正極リードがアルミニウム又はアルミニウム
合金であることを特徴とする項８から１０のいずれか１
項に記載の渦巻型非水二次電池の製造方法。 （１２）該アルミニウム又はアルミニウム合金中のアル
ミニウム含有率が９９．３％以上、９９．９９％以下で
あることを特徴とする項８から１１のいずれか１項に記
載の渦巻型非水二次電池の製造方法。 （１３）該アルミニウム又はアルミニウム合金が焼き鈍
し処理されたものであることを特徴とする項８から１２
のいずれか１項に記載の渦巻型非水二次電池の製造方
法。DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention include the following, but the present invention is not limited thereto. (1) A spiral non-aqueous secondary battery in which a positive electrode sheet and a negative electrode sheet capable of inserting and releasing a light metal, an electrode group formed by winding a separator, and a non-aqueous electrolyte are housed in a bottomed battery outer can. A spiral non-aqueous secondary battery, wherein the relationship between the width and the thickness of the positive electrode lead welded to the positive electrode current collector that constitutes the sheet is represented by the following general formula (1). 1000 <B / 2t 3 <10000 (1) Here, B represents the width (mm) of the positive electrode lead, and t represents the thickness (mm) of the positive electrode lead. (2) The spiral nonaqueous secondary battery according to item 1, wherein the relationship between the width and the thickness of the positive electrode lead is represented by the following general formula (2). 1500 <B / 2t 3 <7000 (2) Here, B represents the width (mm) of the positive electrode lead, and t represents the thickness (mm) of the positive electrode lead. (3) The swirl according to item 1 or 2, wherein the welding width of the positive electrode lead to the positive electrode current collector is 3/4 or less of the positive electrode lead width, and the width end of the positive electrode lead is not welded. Type non-aqueous secondary battery. (4) The nonaqueous secondary battery according to any one of items 1 to 3, wherein the positive electrode lead is aluminum or an aluminum alloy. (5) The spiral non-aqueous secondary according to any one of items 1 to 4, wherein the aluminum content in the aluminum or aluminum alloy is 99.3% or more and 99.99% or less. battery. (6) The non-aqueous secondary battery according to any one of items 1 to 5, wherein the aluminum or aluminum alloy is annealed. (7) In a battery using a positive electrode sheet and a negative electrode sheet capable of inserting and releasing a light metal, and an electrode group formed by winding a separator, after welding a positive electrode lead to a current collector portion of the positive electrode sheet where the active material does not exist, A method for producing a spiral non-aqueous secondary battery, which comprises winding the positive electrode sheet, a separator, and a negative electrode sheet, and giving the positive electrode lead substantially the same curvature as a winding core axis. (8) The method for manufacturing a spiral non-aqueous secondary battery according to item 7, wherein the positive electrode lead is represented by the general formula (1). (9) The method for manufacturing a spiral non-aqueous secondary battery according to item 8, wherein the positive electrode lead is represented by the general formula (2). (10) The swirl according to item 8 or 9, wherein a welding width of the positive electrode lead to the positive electrode current collector is 3/4 or less of a width of the positive electrode lead, and a width end of the positive electrode lead is not welded. Type non-aqueous secondary battery manufacturing method. (11) Any one of the items 8 to 10, wherein the positive electrode lead is aluminum or an aluminum alloy.
The method for manufacturing a spiral non-aqueous secondary battery according to item. (12) The spiral non-aqueous secondary according to any one of Items 8 to 11, wherein the aluminum content in the aluminum or aluminum alloy is 99.3% or more and 99.99% or less. Battery manufacturing method. (13) Item 8 to 12 wherein the aluminum or aluminum alloy is annealed
The method for manufacturing the spiral non-aqueous secondary battery according to any one of 1.
【０００６】以下本発明について詳述する。本発明の電
極群は、正極シート、セパレーター、負極シートを重ね
渦巻状に巻回したものであり、各正負極シートは、集電
体上に活物質合剤が塗布されているとともに電極リード
が接続されている。電極リードは、活物質合剤未塗布部
もしくは塗布後合剤を剥離した部分に接続されているこ
とが好ましい。電極リードは正負極の短絡を防ぐため、
相互に離れた位置にあることが好ましい。例えば、正極
リードは渦巻状の巻回群の中央部に、負極リードは外周
部に存在する形態が特に好ましい。また、正負極リード
の一方が電極シートの中央部に、他方が電極シートの端
部（渦巻電極群では中央部か外周部）に位置する形態で
あってもよい。Hereinafter, the present invention will be described in detail. The electrode group of the present invention comprises a positive electrode sheet, a separator, and a negative electrode sheet which are wound in a spiral shape, and each positive and negative electrode sheet has an active material mixture applied on a current collector and electrode leads. It is connected. It is preferable that the electrode lead is connected to a portion where the active material mixture has not been applied or a portion where the mixture has been peeled off after application. The electrode leads prevent short circuit between positive and negative electrodes,
It is preferable that they are located apart from each other. For example, it is particularly preferable that the positive electrode lead is present in the central portion of the spiral winding group and the negative electrode lead is present in the outer peripheral portion. Alternatively, one of the positive and negative electrode leads may be located in the central portion of the electrode sheet, and the other may be located in the end portion of the electrode sheet (in the spiral electrode group, the central portion or the outer peripheral portion).
【０００７】本発明を具体的にするため、正極リードは
渦巻状の巻回群の中央部に、負極リードは外周部に存在
する形態を例として説明する。塗布後、脱水乾燥した正
極シートの正極集電体の露出部（電極合剤未塗布部）に
正極リードを溶接する。このリードに関し、従来技術で
は巻回を行う前工程で概略巻き芯径と同じ曲率半径を持
つ型で正極リードにプレス成形し、次工程で巻回してい
る。これに対し本発明は、前工程での正極リードの成型
無しに、正極リードの形状と材質、溶接条件を規定する
ことで巻回することのみで真円度の高い巻回群を得るも
のである。本発明の正極リードは、正極リードの幅Ｂ
（ｍｍ）は１．５〜１０ｍｍが好ましく、２〜５ｍｍが
より好ましい。正極リードの厚みｔ（ｍｍ）は０．０３
〜１ｍｍが好ましく、０．０５〜０．３ｍｍがより好ま
しい。Ｂとｔは下記の関係を満たすことが好ましい。 １０００＜Ｂ／２ｔ3 ＜１００００ （１） Ｂ／２ｔ3 が１０００以下、１００００以上の場合は巻
回した渦巻電極群の真円度（変形度）が良くないものが
できた。特に１００００以上の場合はリードの端部で折
れ曲がりが発生していた。式（１）においてはＢ、ｔは
次の一般式（２）で表されるとより好ましい。 １５００＜Ｂ／２ｔ3 ＜７０００ （２） 更に、正極リードの該正極集電体への溶接幅が、正極リ
ード幅の３／４以下であり、かつ正極リードの幅端を溶
接しないことが望ましい。電極リードの端部はリード作
成時にバリが生じていたり他の部分より厚めになってい
たりするためこの部分を溶接することは巻回群の真円度
を高めるためには不利である。正極リードの材質として
は、軟性金属が好ましく、アルミニウム又はアルミニウ
ム合金がより好ましい。アルミニウム又はアルミニウム
合金中のアルミニウム含有率は９９．３％以上、９９．
９９％以下であると特に好ましい。アルミニウム合金中
のアルミニウム以外の元素としては、珪素、鉄、銅、マ
ンガン、マグネシウム、亜鉛などを挙げることができ
る。この中で、珪素と鉄は０．７％以下、銅は０．１％
以下、マンガン、亜鉛、マグネシウムは０．０５％以下
が好ましい。更に好ましいのは、これらのアルミニウム
又はアルミニウム合金の焼き鈍し品で、３４０℃〜４１
０℃で熱処理した後、空冷または炉冷したものである。
特に好ましいアルミニウム又はアルミニウム合金は、Ｊ
ＩＳ規格の番号で、ＪＩＳＨ４１６Ｏ，Ａ１Ｎ３０Ｈ−
Ｏである。これらのリードを正極集電体に溶接するに
は、超音波溶接、レーザー溶接、抵抗溶接等の手段を用
いることができる。例えば超音波溶接機で２０ｋＨｚま
たは４０ｋＨｚで溶接することができる。For the purpose of embodying the present invention, an example will be described in which the positive electrode lead is present in the central portion of the spiral winding group and the negative electrode lead is present in the outer peripheral portion. After the application, the positive electrode lead is welded to the exposed portion (the portion not coated with the electrode mixture) of the positive electrode current collector of the positive electrode sheet dehydrated and dried. Regarding this lead, in the prior art, the positive electrode lead is press-molded by a mold having a radius of curvature substantially the same as the winding core diameter in the previous step of winding, and is wound in the next step. On the other hand, the present invention is to obtain a winding group with high roundness only by winding by defining the shape and material of the positive electrode lead and welding conditions without molding the positive electrode lead in the previous step. is there. The positive electrode lead of the present invention has a width B of the positive electrode lead.
(Mm) is preferably 1.5 to 10 mm, more preferably 2 to 5 mm. The thickness t (mm) of the positive electrode lead is 0.03
-1 mm is preferable, and 0.05-0.3 mm is more preferable. It is preferable that B and t satisfy the following relationship. 1000 <B / 2t 3 <10000 (1) When B / 2t 3 was 1000 or less and 10000 or more, the roundness (deformation) of the wound spirally wound electrode group was not good. In particular, in the case of 10,000 or more, bending occurred at the end of the lead. In the formula (1), B and t are more preferably represented by the following general formula (2). 1500 <B / 2t 3 <7000 (2) Further, it is desirable that the welding width of the positive electrode lead to the positive electrode current collector is 3/4 or less of the positive electrode lead width, and the width end of the positive electrode lead is not welded. . Since the ends of the electrode leads have burrs at the time of making the leads or are thicker than other parts, welding this part is disadvantageous for increasing the roundness of the winding group. The material of the positive electrode lead is preferably a soft metal, more preferably aluminum or an aluminum alloy. The aluminum content in aluminum or aluminum alloy is 99.3% or more, 99.
It is particularly preferably 99% or less. Examples of elements other than aluminum in the aluminum alloy include silicon, iron, copper, manganese, magnesium and zinc. Of these, 0.7% or less for silicon and iron, 0.1% for copper
Hereinafter, manganese, zinc, and magnesium are preferably 0.05% or less. More preferable is an annealed product of these aluminum or aluminum alloy, and the temperature is from 340 ° C to 41 ° C.
After being heat-treated at 0 ° C., it is air-cooled or furnace-cooled.
Particularly preferred aluminum or aluminum alloy is J
IS standard number, JIS 416O, A1N30H-
O. To weld these leads to the positive electrode current collector, ultrasonic welding, laser welding, resistance welding or the like can be used. For example, it is possible to weld with an ultrasonic welder at 20 kHz or 40 kHz.
【０００８】本発明の電極に用いる集電体としては、構
成された電池において化学変化を起こさない電子伝導体
であれば何でもよい。例えば、正極には、材料としてス
テンレス鋼、ニッケル、アルミニウム、チタン、炭素な
どの他に、アルミニウムやステンレス鋼の表面にカーボ
ン、ニッケル、チタンあるいは銀を処理させたものが用
いられるが、アルミニウムあるいはアルミニウム合金が
特に好ましい。負極には、材料としてステンレス鋼、ニ
ッケル、銅、チタン、アルミニウム、炭素などの他に、
銅やステンレス鋼の表面にカーボン、ニッケル、チタン
あるいは銀を処理させたもの、Ａｌ−Ｃｄ合金などが用
いられるが、銅あるいは銅合金が特に好ましい。これら
の材料の表面を酸化することも用いられる。また、表面
処理により集電体表面に凹凸を付けることが望ましい。
形状は、フォイルの他、フィルム、シート、ネット、パ
ンチされたもの、ラス体、多孔質体、発泡体、繊維群の
成形体などが用いられる。厚みは１〜５００μｍのもの
が用いられる。本発明の正極に用いる集電体とリードは
同一の材質であることが好ましく、アルミニウムの含有
率の高いものが好ましい。The current collector used for the electrode of the present invention may be any electron conductor that does not undergo a chemical change in the constructed battery. For example, for the positive electrode, in addition to stainless steel, nickel, aluminum, titanium, carbon, etc. as the material, aluminum or stainless steel whose surface is treated with carbon, nickel, titanium or silver is used. Alloys are particularly preferred. In addition to stainless steel, nickel, copper, titanium, aluminum, carbon, etc. as the material for the negative electrode,
The surface of copper or stainless steel treated with carbon, nickel, titanium or silver, or an Al-Cd alloy is used, but copper or copper alloy is particularly preferable. Oxidizing the surface of these materials is also used. In addition, it is desirable to make the current collector surface uneven by surface treatment.
As the shape, in addition to a foil, a film, a sheet, a net, a punched material, a lath body, a porous body, a foamed body, a molded body of a fiber group, and the like are used. A thickness of 1 to 500 μm is used. The current collector and the lead used for the positive electrode of the present invention are preferably made of the same material, and those having a high aluminum content are preferable.
【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 、Ｌｉx ＮｉＯ2 、Ｌｉx Ｃｏa Ｎｉ1-a
Ｏ2 、Ｌｉx Ｃｏb Ｖ1-b Ｏz 、Ｌｉx Ｃｏb Ｆｅ1-b
Ｏz 、Ｌｉx Ｍｎ2 Ｏ4 、Ｌｉx ＭｎＯ2 、ＬｉＭｎ2
Ｏ3 、Ｌｉx Ｍｎb Ｃｏ2-b Ｏz 、Ｌｉx Ｍｎb Ｎｉ
2-b Ｏz 、Ｌｉx ＭｎbＶ2-b Ｏz 、Ｌｉx Ｍｎb Ｆｅ
1-b Ｏz （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 , Li 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-b Oz , Li x Mn b V 2-b O z , Li x Mn b Fe
1-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 to 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 ，Ｂ2 Ｏ3 ，Ｐ2 Ｏ5 ，Ａｌ2 Ｏ3 ，Ｖ
2Ｏ5 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. In addition, SiO 2 , B 2 O 3 , P 2 O 5 , Al 2 O 3 , V
Those made amorphous by adding 2 O 5 or the like are particularly preferable. 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 、Ｓ
ｎＳｉＯ3 、ＰｂＯ、ＳｉＯ、Ｓｂ2 Ｏ5 、Ｂｉ
2 Ｏ3 、Ｌｉ2 ＳｉＯ3 、Ｌｉ4 Ｓｉ2 Ｏ7 、Ｌｉ2 Ｇ
ｅＯ3 、ＳｎＡｌ0.4 Ｂ0.5 Ｐ0.5 Ｋ0.1 Ｏ3.65、Ｓｎ
Ａｌ0.4 Ｂ0.5 Ｐ0.5 Ｃｓ0.1 Ｏ3.65、ＳｎＡｌ0.4 Ｂ
0.5 Ｐ0.5 Ｋ0.1 Ｇｅ0.05Ｏ3.85、ＳｎＡｌ0.4 Ｂ0.5
Ｐ0.5 Ｋ0.1 Ｍｇ0.1 Ｇｅ0.02Ｏ3.83、ＳｎＡｌ0.4 Ｂ
0.4 Ｐ0.4 Ｂａ0.08Ｏ3.28、ＳｎＡｌ0.5 Ｂ0.4 Ｐ0.5
Ｍｇ0.1 Ｆ0.2 Ｏ3.65、ＳｎＡｌ0.4 Ｂ0.5 Ｐ0.5 Ｃｓ
0.1 Ｍｇ0.1 Ｆ0.2 Ｏ3.65、ＳｎＢ0.5 Ｐ0.5 Ｃｓ0.05
Ｍｇ0.05Ｆ0.1 Ｏ3.03、Ｓｎ1.1 Ａｌ0.4 Ｂ0.4 Ｐ0.4
Ｂａ0.08Ｏ3.34、Ｓｎ1.2 Ａｌ0.5 Ｂ0.3 Ｐ0.4 Ｃｓ
0.2 Ｏ3.5 、ＳｎＳｉ0.5 Ａｌ0.2 Ｂ0.1 Ｐ0.1 Ｍｇ
0.1 Ｏ2.8 、ＳｎＳｉ0.5 Ａｌ0.3 Ｂ0.4 Ｐ
0.5 Ｏ4.30、ＳｎＳｉ0.6 Ａｌ0.1 Ｂ0.1 Ｐ0.1 Ｂａ
0.2 Ｏ2.95、ＳｎＳｉ0.6 Ａｌ0.4 Ｂ0.2 Ｍｇ0.1 Ｏ
3.2 、Ｓｎ0.9 Ｍｎ0.3 Ｂ0.4 Ｐ0.4 Ｃａ0.1 Ｒｂ0.1
Ｏ2.95、Ｓｎ0.9 Ｆｅ0.3 Ｂ0.4 Ｐ0.4 Ｃａ0.1 Ｒｂ
0.1 Ｏ2.95、Ｓｎ0.3 Ｇｅ0.7 Ｂａ0.1 Ｐ0.9 Ｏ3.35、
Ｓｎ0.9 Ｍｎ0.1 Ｍｇ0.1 Ｐ0.9 Ｏ3.35、Ｓｎ0.2 Ｍｎ
0.8 Ｍｇ0.1 Ｐ0.9 Ｏ3.35。GeO, GeO 2 , SnO, SnO 2 , S
nSiO 3 , PbO, SiO, Sb 2 O 5 , Bi
2 O 3 , Li 2 SiO 3 , Li 4 Si 2 O 7 , Li 2 G
eO 3 , SnAl 0.4 B 0.5 P 0.5 K 0.1 O 3.65 , Sn
Al 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 , SnAl 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 , SnSi 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 、ＬｉＣＦ3 ＳＯ3 、ＬｉＣＦ3
ＣＯ2 、ＬｉＡｓＦ6 、ＬｉＳｂＦ6 、ＬｉＢ10Ｃ
ｌ10、低級脂肪族カルボン酸リチウム、ＬｉＡｌＣｌ
4 、ＬｉＣｌ、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Ｌｉ
ＣＦ3 ＳＯ3 、ＬｉＣｌＯ4 、ＬｉＢＦ4 、及び／ある
いはＬｉＰＦ6 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
CO 2, LiAsF 6, LiSbF 6 , LiB 10 C
l 10 , lithium lower aliphatic carboxylate, LiAlCl
4 , a solution in which one or more salts of LiCl, LiBr, LiI, lithium chloroborane, and lithium tetraphenylborate are dissolved. In particular, a mixed solvent of propylene carbonate or ethylene carbonate with 1,2-dimethoxyethane and / or diethyl carbonate
It is preferable to dissolve CF 3 SO 3 , LiClO 4 , LiBF 4 , and / or LiPF 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。EXAMPLES The present invention will be described in more detail with reference to specific examples below, but the present invention is not limited to the examples as long as the gist of the invention is not exceeded.
【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
ＳｎＳｉ0.6 Ｍｇ0.2 Ｂ0.2 Ｏ2.7 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、負
極シートの未塗布部にはニッケル製のリード板を超音波
溶接した。さらに、正極シートの厚み２０μのアルミニ
ウム集電体の露出部にリード板を超音波溶接した。リー
ド板はアルミニウムの焼き鈍し品ＪＩＳ−ＩＮ３０Ｈ−
Ｏで、幅４ｍｍ、厚み０．１ｍｍ、長さ７５ｍｍのもの
を用いた。超音波溶接は表面に細かい凹凸部を多数設け
た鉄敷（アンビル）の上に、正極の集電体の露出部分を
位置決めし、短冊状のリードタブをその上に重ねて置
き、超音波溶接機（ブランソン製、２０ｋＨｚ、２００
０Ｗ）の超音波ホーンで０．５ＭＰａの圧力で加圧しな
がら７５ｍｓｅｃの間、振幅２２μｍの超音波振動を加
えて溶接した。超音波ホーンの加圧面は２．５ｍｍ×４
８ｍｍの長方形状で０．４ｍｍピッチで細かい凹凸面が
設けられている。溶接後、正極シートの長手方向の端面
付近に対応するリードの場所に幅１２ｍｍの絶縁テープ
を一周に渡って貼った。絶縁テープは基材がポリイミド
でシリコーン系粘着材を用いた粘着テープを使用した。In a low-humidity atmosphere (dew point: -50 ° C), the positive electrode and negative electrode obtained above were dehydrated and dried (far infrared heater, 150 ° C, 2 hours), and then cut into a predetermined size to prepare a negative electrode sheet. A lead plate made of nickel was ultrasonically welded to the uncoated portion. Further, a lead plate was ultrasonically welded to the exposed portion of the 20 μm thick aluminum current collector of the positive electrode sheet. The lead plate is an annealed aluminum product JIS-IN30H-
O, having a width of 4 mm, a thickness of 0.1 mm and a length of 75 mm was used. For ultrasonic welding, position the exposed part of the positive electrode current collector on an iron floor (anvil) with many fine irregularities on the surface, place a strip-shaped lead tab on top of it, and place it on an ultrasonic welding machine. (Branson, 20 kHz, 200
(0 W) while applying an ultrasonic horn at a pressure of 0.5 MPa for 75 msec, ultrasonic vibration with an amplitude of 22 μm was applied for welding. The pressure surface of the ultrasonic horn is 2.5 mm x 4
It has a rectangular shape of 8 mm and is provided with fine uneven surfaces at a pitch of 0.4 mm. After the welding, an insulating tape having a width of 12 mm was attached over the circumference at the position of the lead corresponding to the vicinity of the end face in the longitudinal direction of the positive electrode sheet. As the insulating tape, an adhesive tape having a polyimide base material and a silicone adhesive material was used.
【００２７】得られたリード付きの正極シート、セパレ
ーター、負極シートを用い、巻回機の巻き芯径を３．５
ｍｍとし、巻回張力がセパレーターでは１５０ｇ、正負
極シートでは３００ｇで巻回した。巻回張力を上げると
真円度は良化するが内部短絡が増加した。正極リードが
渦巻状電極の中心部、負極リードが外周部にくるように
巻回して渦巻状電極群Ａを作った。正極リードの材質と
形状を下表のように変更して電極群Ｂ〜Ｋを作った。こ
こで１Ｎ３０Ｈ−Ｏは焼き鈍し品を、１Ｎ３０Ｈは焼き
鈍していないものを表す。表中α値はＢ／２ｔ3 を表
す。リードの曲率加工は、半円柱状突起を有する上金型
と、対応する半円柱状くぼみを有する下金型に集電体に
溶接された正極リードを挟み加圧成形し、リードの幅方
向にＲ１．７５ｍｍの丸みを付けた。真円度評価は電極
群の最大径と最小径とをレーザー変位計で測定しその差
を見た。また、電極群を樹脂で固めた後切断して正極リ
ードの曲率のつき方を顕微鏡で観察し、官能評価した。
また、巻回適正は、正極リードつきの正極シートの巻回
時の搬送性を評価し５０個の電池を作製するときに引っ
かかりの生じた個数を示した。Using the obtained positive electrode sheet with a lead, separator and negative electrode sheet, the winding core diameter of the winding machine is 3.5.
The separator was wound at a tension of 150 g for the separator and 300 g for the positive and negative electrode sheets. When the winding tension was increased, the roundness was improved but the internal short circuit increased. The positive electrode lead was wound so that the central part of the spiral electrode and the negative electrode lead were located on the outer peripheral part to form a spiral electrode group A. Electrode groups B to K were prepared by changing the material and shape of the positive electrode lead as shown in the table below. Here, 1N30H-O represents an annealed product, and 1N30H represents an unannealed product. The α value in the table represents B / 2t 3 . Curvature processing of the lead is performed by sandwiching the positive electrode lead welded to the current collector in an upper die having a semi-cylindrical protrusion and a lower die having a corresponding semi-cylindrical depression, and pressurizing it in the width direction of the lead. A roundness of R 1.75 mm was added. In the roundness evaluation, the maximum diameter and the minimum diameter of the electrode group were measured by a laser displacement meter and the difference was observed. Further, the electrode group was solidified with a resin and then cut to observe the curvature of the positive electrode lead with a microscope for sensory evaluation.
Further, the winding appropriateness was evaluated by evaluating the transportability of the positive electrode sheet with the positive electrode lead at the time of winding and showing the number of catches when producing 50 batteries.
【００２８】 正極リードの変更 渦巻状電 リード 幅 厚み α値 曲率加 巻回 真円度 備考 極群Ｎｏ 材質 mm mm 工有無 不適 評価 Ａ 1N30H-O 4.0 0.10 2000 無し ０ ◎ 本発明 Ｂ 1N30H-O 4.0 0.10 2000 有 17 ○ 比較例 Ｃ 1N30H-O 3.0 0.10 1500 無し ０ ○ 本発明 Ｄ 1N30H-O 2.5 0.10 1250 無し ０ ○ 本発明 Ｅ 1N30H-O 4.5 0.10 2250 無し ０ ◎ 本発明 Ｆ 1N30H-O 4.0 0.09 2743 無し ０ ◎ 本発明 Ｇ 1N30H 3.0 0.12 868 無し ０ × 比較例 Ｈ 1N30H 3.0 0.12 868 有 13 × 比較例 Ｉ 1N30H-O 3.0 0.12 868 無し ０ × 比較例 Ｊ 1N30H-O 3.0 0.12 868 有 14 × 比較例 Ｋ 1N30H 3.0 0.10 1500 無し ０ × 比較例Change of positive electrode lead Swirl electric lead width Thickness α value Curvature winding Roundness Remark Pole group No Material mm mm Machining presence / absence A 1N30H-O 4.0 0.10 2000 None 0 ◎ Present invention B 1N30H-O 4.0 0.10 2000 Yes 17 ○ Comparative Example C 1N30H-O 3.0 0.10 1500 None 0 ○ Invention D 1N30H-O 2.5 0.10 1250 None 0 ○ Invention E 1N30H-O 4.5 0.10 2250 None 0 ◎ Invention F 1N30H-O 4.0 0.09 2743 None 0 ◎ Invention G 1N30H 3.0 0.12 868 None 0 × Comparative example H 1N30H 3.0 0.12 868 Yes 13 × Comparative example I 1N30H-O 3.0 0.12 868 None 0 × Comparative example J 1N30H-O 3.0 0.12 868 Yes 14 × Comparative example K 1N30H 3.0 0.10 1500 None 0 × Comparative example
【００２９】[0029]
【発明の効果】正極リードが溶着された正極シートを巻
回するときに搬送経路での引っかかり等のトラブルをな
くすことができる。リードを溶接後巻芯径に合わせて曲
率を持たせるためのプレス工程が省略できるのでパス長
が短くなり、巻ずれなどのトラブルを減少できる。巻回
群の真円度の向上により電池缶への巻回群の挿入や正負
極リードの端子溶接などでの故障が減少できる。更に巻
回群の極板距離の均一化により電池性能の均一性が向上
する。EFFECTS OF THE INVENTION When winding a positive electrode sheet having a positive electrode lead welded, it is possible to eliminate troubles such as getting caught in the conveying path. Since the pressing step for giving the lead a curvature corresponding to the winding core diameter after welding can be omitted, the path length can be shortened and troubles such as winding misalignment can be reduced. By improving the roundness of the winding group, it is possible to reduce troubles such as insertion of the winding group into the battery can and terminal welding of the positive and negative electrode leads. Further, the uniformity of the battery performance is improved by making the electrode plate distance of the winding group uniform.
【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.
６ 正極リード ７ 負極リード ８ 正極シート ９ 負極シート １０ セパレーター １１ 電池外装缶 １２ 端子キャップ １３ ガスケット １４ 安全弁 6 Positive electrode lead 7 Negative electrode lead 8 Positive electrode sheet 9 Negative electrode sheet 10 Separator 11 Battery outer can 12 Terminal cap 13 Gasket 14 Safety valve
Claims (7)
負極シートと、セパレータを巻回してなる電極群と非水
電解液を有底電池外装缶内に収納した渦巻型非水二次電
池において、該正極シートを構成する正極集電体に溶接
する正極リードの幅と厚みの関係が下記一般式（１）で
表されることを特徴とする渦巻型非水二次電池。 １０００＜Ｂ／２ｔ3 ＜１００００ （１） ここで、Ｂは正極リードの幅（ｍｍ）、ｔは正極リード
の厚み（ｍｍ）を表す。1. A spiral nonaqueous secondary battery in which a positive electrode sheet and a negative electrode sheet capable of inserting and releasing a light metal, an electrode group formed by winding a separator, and a nonaqueous electrolytic solution are housed in a bottomed battery outer can. A spiral non-aqueous secondary battery, wherein the relationship between the width and the thickness of the positive electrode lead welded to the positive electrode current collector that constitutes the positive electrode sheet is represented by the following general formula (1). 1000 <B / 2t 3 <10000 (1) Here, B represents the width (mm) of the positive electrode lead, and t represents the thickness (mm) of the positive electrode lead.
般式（２）で表されることを特徴とする請求項１に記載
の渦巻型非水二次電池。 １５００＜Ｂ／２ｔ3 ＜７０００ （２） ここで、Ｂは正極リードの幅（ｍｍ）、ｔは正極リード
の厚み（ｍｍ）を表す。2. The spiral non-aqueous secondary battery according to claim 1, wherein the relationship between the width and the thickness of the positive electrode lead is represented by the following general formula (2). 1500 <B / 2t 3 <7000 (2) Here, B represents the width (mm) of the positive electrode lead, and t represents the thickness (mm) of the positive electrode lead.
が、正極リード幅の３／４以下であり、正極リードの幅
端を溶接しないことを特徴とする請求項１または２に記
載の渦巻型非水二次電池。3. The welding width of the positive electrode lead to the positive electrode current collector is 3/4 or less of the positive electrode lead width, and the width end of the positive electrode lead is not welded. The described spiral non-aqueous secondary battery.
ニウム合金であることを特徴とする請求項１から３のい
ずれか１項に記載の非水二次電池。4. The non-aqueous secondary battery according to claim 1, wherein the positive electrode lead is aluminum or an aluminum alloy.
のアルミニウム含有率が９９．３％以上、９９．９９％
以下であることを特徴とする請求項１から４のいずれか
１項に記載の渦巻型非水二次電池。5. The aluminum content in the aluminum or aluminum alloy is 99.3% or more and 99.99%.
It is the following, The spiral nonaqueous secondary battery of any one of Claim 1 to 4 characterized by the following.
焼き鈍し処理されたものであることを特徴とする請求項
１から５のいずれか１項に記載の非水二次電池。6. The non-aqueous secondary battery according to claim 1, wherein the aluminum or aluminum alloy is annealed.
負極シートと、セパレータを巻回してなる電極群を用い
た電池において、正極シートの活物質の存在しない集電
体部分に正極リードを溶接した後に、該正極シートとセ
パレーター、負極シートとを巻回し、該正極リードに巻
芯軸と概ね同曲率を与えることを特徴とする渦巻型非水
二次電池の製造方法。7. In a battery using a positive electrode sheet and a negative electrode sheet capable of inserting and releasing a light metal, and an electrode group formed by winding a separator, a positive electrode lead is welded to a current collector portion of the positive electrode sheet where the active material does not exist. After that, the positive electrode sheet, the separator, and the negative electrode sheet are wound, and the positive electrode lead is provided with substantially the same curvature as that of the winding core, a method for manufacturing a spiral non-aqueous secondary battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15631996A JP3677873B2 (en) | 1996-05-29 | 1996-05-29 | Spiral type non-aqueous secondary battery and method for manufacturing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15631996A JP3677873B2 (en) | 1996-05-29 | 1996-05-29 | Spiral type non-aqueous secondary battery and method for manufacturing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09320639A true JPH09320639A (en) | 1997-12-12 |
| JP3677873B2 JP3677873B2 (en) | 2005-08-03 |
Family
ID=15625206
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15631996A Expired - Fee Related JP3677873B2 (en) | 1996-05-29 | 1996-05-29 | Spiral type non-aqueous secondary battery and method for manufacturing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3677873B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006324143A (en) * | 2005-05-19 | 2006-11-30 | Nissan Motor Co Ltd | Secondary battery |
| JP2009059487A (en) * | 2007-08-30 | 2009-03-19 | Panasonic Corp | Nonaqueous secondary battery |
| JP2009134971A (en) * | 2007-11-30 | 2009-06-18 | Furukawa Battery Co Ltd:The | Method of ultrasonic welding between positive electrode collector for storage battery and tab, and lithium ion battery |
-
1996
- 1996-05-29 JP JP15631996A patent/JP3677873B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006324143A (en) * | 2005-05-19 | 2006-11-30 | Nissan Motor Co Ltd | Secondary battery |
| JP2009059487A (en) * | 2007-08-30 | 2009-03-19 | Panasonic Corp | Nonaqueous secondary battery |
| JP2009134971A (en) * | 2007-11-30 | 2009-06-18 | Furukawa Battery Co Ltd:The | Method of ultrasonic welding between positive electrode collector for storage battery and tab, and lithium ion battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3677873B2 (en) | 2005-08-03 |
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