JP2003132875A - Lithium secondary battery - Google Patents
Lithium secondary batteryInfo
- Publication number
- JP2003132875A JP2003132875A JP2001325797A JP2001325797A JP2003132875A JP 2003132875 A JP2003132875 A JP 2003132875A JP 2001325797 A JP2001325797 A JP 2001325797A JP 2001325797 A JP2001325797 A JP 2001325797A JP 2003132875 A JP2003132875 A JP 2003132875A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- electrode plate
- adhesive tape
- negative electrode
- active material
- 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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、非水電解液を用い
たリチウム二次電池に関し、特に正極リードを被覆する
為の粘着テープに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithium secondary battery using a non-aqueous electrolytic solution, and more particularly to an adhesive tape for coating a positive electrode lead.
【０００２】[0002]
【従来の技術】近年、携帯電話、携帯情報端末等の携帯
電子機器の性能は、搭載される半導体素子、電子回路だ
けでなく、充放電可能な二次電池の性能に大きく依存し
ており、搭載される二次電池の容量アップと共に、軽量
・コンパクト化をも同時に実現することが望まれてい
る。これらの要望に答える二次電池として、ニッケルカ
ドミウム蓄電池の約２倍のエネルギー密度を有する、ニ
ッケル水素蓄電池が開発され、次いで、これを上回るリ
チウム二次電池が開発され、脚光を浴びている。2. Description of the Related Art In recent years, the performance of mobile electronic devices such as mobile phones and personal digital assistants largely depends not only on the performance of semiconductor elements and electronic circuits, but also on the performance of rechargeable secondary batteries. It is desired to increase the capacity of the rechargeable battery to be mounted, and at the same time, realize weight reduction and compactness. As a secondary battery that meets these demands, a nickel-hydrogen storage battery having an energy density about twice that of a nickel-cadmium storage battery has been developed, and then a lithium secondary battery that exceeds this has been developed and is in the limelight.
【０００３】このリチウム二次電池は、非水電解液中
に、正極及び負極を配設し、各々の極板には、集電体表
面に正極活物質が結着され、或いは集電体表面に負極活
物質が結着された構成となっている。この電池に用いら
れる電池用極板は、一般的に活物質（正極活物質または
負極活物質）、導電材、結着材（バインダー）等を溶剤
に混練分散したペースト状合剤を、集電体の片面もしく
は両面に塗着、乾燥し、圧延して所定の厚みにしたもの
を、所定の形状に切断することにより作製されている。In this lithium secondary battery, a positive electrode and a negative electrode are arranged in a non-aqueous electrolyte, and a positive electrode active material is bound to the surface of the current collector or the surface of the current collector is attached to each electrode plate. It has a structure in which the negative electrode active material is bound to. The battery electrode plate used in this battery generally collects a pasty mixture prepared by kneading and dispersing an active material (positive electrode active material or negative electrode active material), a conductive material, a binder (binder), etc. in a solvent. It is produced by coating one side or both sides of a body, drying it, rolling it to a predetermined thickness, and cutting it into a predetermined shape.
【０００４】これらの正極板と負極板とをセパレータを
介して渦巻状に巻回されている極板群をケースに収納
し、非水電解液を注液した後、封口板にて封口すること
によって、リチウム二次電池が作製されている。そのた
め、この極板群がケースに収納されるまでの群圧の低下
に伴う極板群径の増大、それによってケースに収納でき
なくなるのを回避するために、極板群の巻き終端部を粘
着テープで貼着することによって群を固定する方法が採
用されている。A positive electrode plate and a negative electrode plate are housed in a case in which a spirally wound electrode plate group is housed in a case, a nonaqueous electrolytic solution is injected, and then the plate is sealed with a sealing plate. A lithium secondary battery is manufactured by Therefore, in order to prevent the electrode group diameter from increasing due to a decrease in the group pressure until the electrode group is housed in the case, which prevents the electrode group from being housed in the case, the winding end portion of the electrode group is adhered. A method of fixing the group by attaching with tape is adopted.
【０００５】また、リチウム二次電池の正極板は、図４
（ａ）に示すように正極板１の正極活物質無地部１１に
正極リード２の一端側が接続され、他端側が正極端子に
接続されており、負極板は、図４（ｂ）に示すように負
極板３の負極活物質無地部１３に負極リード４の一端側
が接続され、他端側が負極端子に接続されている。そし
て、正極リード２、負極リード４には、それぞれ正極粘
着テープ１２、負極粘着テープ１４が貼着されている。The positive electrode plate of the lithium secondary battery is shown in FIG.
As shown in FIG. 4A, one end side of the positive electrode lead 2 is connected to the positive electrode active material uncoated portion 11 of the positive electrode plate 1 and the other end side is connected to the positive electrode terminal, and the negative electrode plate is as shown in FIG. 4B. One end side of the negative electrode lead 4 is connected to the negative electrode active material uncoated portion 13 of the negative electrode plate 3, and the other end side is connected to the negative electrode terminal. The positive electrode adhesive tape 12 and the negative electrode adhesive tape 14 are attached to the positive electrode lead 2 and the negative electrode lead 4, respectively.
【０００６】[0006]
【発明が解決しようとする課題】極板群やリード端子に
貼着される粘着テープは、そのままケース内に収納され
るため、非水電解液に浸漬された状態となる。この粘着
テープが長期間非水電解液に浸漬されると粘着テープの
基材および／または粘着剤が非水電解液中に溶出し、非
水電解液のイオン伝導度を低下させ、電池容量の低下を
引き起こすという課題があった。この課題を生じる要因
は、粘着テープの基材および／または粘着剤が非水電解
液中の有機溶媒に溶出しやすい材料を用いた場合、有機
溶媒が不適切であった場合、これら両方に起因する場合
が考えられる。そこで、粘着テープの基材にポリイミド
またはポリオレフィンを主体とし、粘着剤がアクリル系
粘着剤を用い、特定の有機溶剤を用いる方法が特開平７
−１４２０８９号公報、特開平１０−１２２７７号公報
に、特定の不飽和度を有する粘着剤を用いる方法が特開
平１０−２４７４８９号公報に提案されている。The adhesive tape adhered to the electrode plate group and the lead terminals is stored in the case as it is, so that it is immersed in the non-aqueous electrolyte. When this adhesive tape is immersed in the non-aqueous electrolyte for a long period of time, the base material of the adhesive tape and / or the adhesive is eluted into the non-aqueous electrolyte to lower the ionic conductivity of the non-aqueous electrolyte and reduce the battery capacity. There was a problem of causing a decrease. The cause of this problem is caused by both the base material of the pressure-sensitive adhesive tape and / or the pressure-sensitive adhesive using a material that easily elutes into the organic solvent in the non-aqueous electrolyte, and the inappropriate organic solvent. It is possible that Therefore, there is a method of mainly using polyimide or polyolefin as the base material of the adhesive tape, using an acrylic adhesive as the adhesive, and using a specific organic solvent.
No. 142089 and Japanese Unexamined Patent Publication No. 10-12277 propose methods of using an adhesive having a specific degree of unsaturation in Japanese Unexamined Patent Publication No. 10-247489.
【０００７】しかしながら、これらの基材および／また
は粘着剤を用いた粘着テープを極板群および負極リード
に貼着した場合には問題がないが、正極リードに貼着し
た場合には、正極活物質、粘着テープ、セパレータが接
触する部分において、正極板と粘着テープとの電位差が
生じ、粘着テープと正極活物質との反応により、正極活
物質中に含まれるコバルトをはじめとする金属還元体が
溶出して、セパレータに目詰まりを生じさせ、微小ショ
ートによる電圧不良を発生させる。However, there is no problem when the adhesive tape using these base materials and / or adhesives is attached to the electrode plate group and the negative electrode lead, but when it is attached to the positive electrode lead, the positive electrode active material is used. In the portion where the substance, the adhesive tape, and the separator come into contact with each other, a potential difference between the positive electrode plate and the adhesive tape occurs, and the reaction between the adhesive tape and the positive electrode active material causes a metal reductant such as cobalt contained in the positive electrode active material. Elution causes the separator to be clogged, causing a voltage failure due to a minute short circuit.
【０００８】正極板と粘着テープとの間に電位差が生じ
る理由は、リチウムイオンを放出する正極活物質領域に
対向する負極活物質領域中に不可逆容量としてリチウム
量が残存するのに対して、正極無地部領域に対向する負
極活物質領域では存在しない為に、リチウムイオンを放
出する正極活物質領域に対向する負極活物質領域の方が
対リチウム酸化還元電位で約０．１V低くなるからであ
る。The reason why a potential difference occurs between the positive electrode plate and the adhesive tape is that the amount of lithium remains as irreversible capacity in the negative electrode active material region facing the positive electrode active material region that releases lithium ions, whereas Because it does not exist in the negative electrode active material region facing the uncoated region, the negative electrode active material region facing the positive electrode active material region that releases lithium ions has a lower lithium oxidation-reduction potential with respect to lithium by about 0.1V. .
【０００９】特に、電池の高容量化を図るために正極活
物質の充填密度を増加させ、極板群の緊縛率を増加させ
た場合には、より顕著となり、電池の高容量化や小型化
の進展を阻害する課題となっていた。In particular, when the packing density of the positive electrode active material is increased to increase the capacity of the battery and the binding rate of the electrode plate group is increased, it becomes more remarkable, and the capacity and size of the battery are reduced. Was a problem that hinders the progress of the.
【００１０】本発明は、上記の課題に鑑み、充放電サイ
クルや高温保存をしても、微小ショートによる電圧不良
や電池容量の低下を引き起こさないリチウム二次電池を
提供することを目的とする。In view of the above problems, it is an object of the present invention to provide a lithium secondary battery which does not cause a voltage defect or a decrease in battery capacity due to a minute short even when it is charged and discharged or stored at high temperature.
【００１１】[0011]
【課題を解決するための手段】これらの課題を解決する
ための本発明は、正極板と負極板とがセパレータを介し
て渦巻状に巻回されている極板群をケースに収納してな
る電池において、前記正極板の正極リードが粘着テープ
で被覆されており、この粘着テープがフッ素系の樹脂か
らなる基材と、天然ゴム、イソブチルゴム、スチレンブ
タジエンゴムから選ばれた少なくとも一種からなる粘着
剤から構成されていることを特徴とするリチウム二次電
池であり、前記粘着テープが、前記正極板の活物質層と
接触しないようにして正極リードを被覆していることが
好ましく、前記粘着テープに着色するための顔料が、フ
タロシアニンを成分とする有機物、チタン及びアルミニ
ウムの金属粉や酸化物から選ばれた一種であることが好
ましい。そして、前記負極板の負極リードおよび／また
は前記極板群の巻き終端部も前記粘着テープで被覆され
ていることがより好ましい。According to the present invention for solving these problems, an electrode plate group in which a positive electrode plate and a negative electrode plate are spirally wound via a separator is housed in a case. In the battery, the positive electrode lead of the positive electrode plate is covered with an adhesive tape, and the adhesive tape is composed of a base material made of a fluorine resin and an adhesive made of at least one selected from natural rubber, isobutyl rubber, and styrene butadiene rubber. It is preferable that the pressure-sensitive adhesive tape covers the positive electrode lead so as not to come into contact with the active material layer of the positive electrode plate. It is preferable that the pigment for coloring is a kind selected from organic materials containing phthalocyanine as a component, metal powders and oxides of titanium and aluminum. It is more preferable that the negative electrode lead of the negative electrode plate and / or the winding terminal end of the electrode plate group is also covered with the adhesive tape.
【００１２】フッ素系の樹脂からなる基材と、天然ゴ
ム、イソブチルゴム、スチレンブタジエンゴムから選ば
れた少なくとも一種からなる粘着剤、及びフタロシアニ
ンを成分とする有機物、チタン及びアルミニウムの金属
粉や酸化物から選ばれた一種である顔料によって着色さ
れている粘着テープを用いることにより、電位差のある
正極板の正極リードに用いても粘着テープの基材、粘着
剤及び顔料の成分中にハロゲンまたはアゾ基などの二重
結合を有する官能基がないので、正極活物質との反応に
よる金属還元体の生成を抑制することができる。A base material made of a fluorine-based resin, an adhesive made of at least one selected from natural rubber, isobutyl rubber and styrene-butadiene rubber, and an organic substance containing phthalocyanine as a component, metal powder or oxide of titanium and aluminum. By using an adhesive tape that is colored with a pigment, which is one type selected from among the following, even if it is used for the positive electrode lead of a positive electrode plate having a potential difference, halogen or azo groups are contained in the components of the adhesive tape base material, adhesive and pigment. Since there is no functional group having a double bond such as, it is possible to suppress the production of a metal reductant due to the reaction with the positive electrode active material.
【００１３】チタン及びアルミニウムの金属粉や酸化物
は、電気伝導性はあるが、対リチウム酸化還元電位４．
５Vまで電位走査させてもチタンは安定挙動を示し、ア
ルミニウムは不動態膜が形成され、安定化するので顔料
として使用するのに適する。Although metal powders and oxides of titanium and aluminum are electrically conductive, they have a redox potential with respect to lithium.
Titanium shows stable behavior even when the potential is scanned up to 5 V, and aluminum is suitable for use as a pigment because a passive film is formed and stabilized.
【００１４】そして、正極板の正極活物質の無い無地部
に溶接した正極リードを被覆するための粘着テープを正
極活物質層と接触しないように貼着することにより、粘
着テープの基材や粘着剤の成分と正極活物質との反応に
よる金属還元体の生成をさらに抑制することができる。
従って、正極活物質層の充填密度や極板群の緊縛率を増
加させて電池の高容量化を図った電池を充放電サイクル
や高温保存をしても、微小ショートによる電圧不良や電
池容量の低下を引き起こさないリチウム二次電池が得ら
れる。Then, an adhesive tape for covering the positive electrode lead, which is welded to the uncoated portion of the positive electrode plate where the positive electrode active material is absent, is attached so as not to come into contact with the positive electrode active material layer. It is possible to further suppress the formation of a metal reductant due to the reaction between the components of the agent and the positive electrode active material.
Therefore, even if the battery, which has a higher capacity by increasing the packing density of the positive electrode active material layer and the binding rate of the electrode plate group, is subjected to charge / discharge cycles or high temperature storage, voltage shortages and battery capacity A lithium secondary battery that does not cause deterioration can be obtained.
【００１５】[0015]
【発明の実施の形態】以下、図面を参照して本発明の実
施の形態について説明する。BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below with reference to the drawings.
【００１６】図２は、円筒型リチウム二次電池の断面図
である。FIG. 2 is a sectional view of a cylindrical lithium secondary battery.
【００１７】上部が開口している有底の電池ケース８内
に正極板１と負極板３とをセパレータ５を介して絶縁さ
れた状態で渦巻状に巻回された極板群が収容され、正極
板１に接続された正極リード２の他端部が、電池ケース
８の開口部をガスケット９を介して封口する封口板に接
続され、負極板に接続された負極リード４の他端部が、
電池ケース８の底部に接続されており、極板群上下部に
はそれぞれ絶縁板６、７が配設されている。A positive electrode plate 1 and a negative electrode plate 3 are housed in a bottomed battery case 8 having an open top, and a group of spirally wound electrode plates are insulated from each other via a separator 5. The other end of the positive electrode lead 2 connected to the positive electrode plate 1 is connected to a sealing plate that seals the opening of the battery case 8 through a gasket 9, and the other end of the negative electrode lead 4 connected to the negative electrode plate is ,
It is connected to the bottom of the battery case 8, and insulating plates 6 and 7 are arranged on the upper and lower parts of the electrode plate group, respectively.
【００１８】前記正極板１の平面図を図１（ａ）に示
す。A plan view of the positive electrode plate 1 is shown in FIG.
【００１９】アルミニウム製の箔やラス加工やエッチン
グ処理された厚み１０μｍ〜６０μｍの箔からなる集電
体の片側または両面に正極活物質と結着剤、必要に応じ
て導電剤、増粘剤を溶剤に混練分散させたペーストを塗
着、乾燥、圧延して活物質層を作製し、この活物質層に
無地部を設け、正極リードを溶接したものである。A positive electrode active material, a binder, and if necessary, a conductive agent and a thickener are provided on one side or both sides of a current collector made of an aluminum foil or a foil having a thickness of 10 μm to 60 μm that has been lathed or etched. A paste obtained by kneading and dispersing in a solvent is applied, dried, and rolled to form an active material layer, a plain portion is provided on the active material layer, and a positive electrode lead is welded.
【００２０】正極活物質としては、特に限定されるもの
ではないが、例えば、リチウムイオンをゲストとして受
け入れ得るリチウム含有遷移金属化合物が使用される。
例えば、コバルト、マンガン、ニッケル、クロム、鉄お
よびバナジウムから選ばれる少なくとも一種類の金属と
リチウムとの複合金属酸化物、ＬｉＣｏＯ2、ＬｉＭｎ
Ｏ2、ＬｉＮｉＯ2、ＬｉＣｏxＮｉ(1-x)Ｏ2（０＜ｘ＜
１）、ＬｉＣｒＯ2、αＬｉＦｅＯ2、ＬｉＶＯ2等が好
ましい。The positive electrode active material is not particularly limited, but for example, a lithium-containing transition metal compound that can accept lithium ions as a guest is used.
For example, a composite metal oxide of at least one metal selected from cobalt, manganese, nickel, chromium, iron and vanadium and lithium, LiCoO 2 , LiMn.
O 2 , LiNiO 2 , LiCo x Ni (1-x) O 2 (0 <x <
1), LiCrO 2 , αLiFeO 2 , LiVO 2 and the like are preferable.
【００２１】結着剤としては、溶剤に混練分散できるも
のであれば特に限定されるものではないが、例えば、フ
ッ素系結着材やアクリルゴム、変性アクリルゴム、スチ
レンーブタジエンゴム（ＳＢＲ）、アクリル系重合体、
ビニル系重合体等を単独、或いは二種類以上の混合物ま
たは共重合体として用いることができる。フッ素系結着
剤としては、例えば、ポリフッ化ビニリデン、フッ化ビ
ニリデンと六フッ化プロピレンの共重合体やポリテトラ
フルオロエチレン樹脂のディスパージョンが好ましい。The binder is not particularly limited as long as it can be kneaded and dispersed in a solvent. For example, a fluorine-based binder, acrylic rubber, modified acrylic rubber, styrene-butadiene rubber (SBR), Acrylic polymer,
A vinyl polymer or the like can be used alone, or as a mixture or copolymer of two or more kinds. As the fluorine-based binder, for example, polyvinylidene fluoride, a copolymer of vinylidene fluoride and propylene hexafluoride, or a dispersion of polytetrafluoroethylene resin is preferable.
【００２２】必要に応じて導電剤、増粘剤を加えること
ができ、導電剤としてはアセチレンブラック、グラファ
イト、炭素繊維等を単独、或いは二種類以上の混合物が
好ましく、増粘剤としてはエチレン−ビニルアルコール
共重合体、カルボキシメチルセルロース、メチルセルロ
ースなどが好ましい。If desired, a conductive agent and a thickener can be added. As the conductive agent, acetylene black, graphite, carbon fiber or the like is preferably used alone, or a mixture of two or more kinds thereof is preferable. Vinyl alcohol copolymer, carboxymethyl cellulose, methyl cellulose and the like are preferable.
【００２３】溶剤としては、結着剤が溶解可能な溶剤が
適切で、有機系結着剤の場合は、Ｎ−メチル−２−ピロ
リドン、Ｎ，Ｎ−ジメチルホルムアミド、テトラヒドロ
フラン、ジメチルアセトアミド、ジメチルスルホキシ
ド、ヘキサメチルスルホルアミド、テトラメチル尿素、
アセトン、メチルエチルケトン等の有機溶剤を単独また
はこれらを混合した混合溶剤が好ましく、水系結着剤の
場合は水や温水が好ましい。As the solvent, a solvent capable of dissolving the binder is suitable, and in the case of an organic binder, N-methyl-2-pyrrolidone, N, N-dimethylformamide, tetrahydrofuran, dimethylacetamide, dimethylsulfoxide. , Hexamethylsulforamide, tetramethylurea,
An organic solvent such as acetone or methyl ethyl ketone is preferably used alone or as a mixed solvent thereof, and in the case of an aqueous binder, water or warm water is preferred.
【００２４】ところで、本発明における活物質、結着
剤、必要に応じて加える導電剤を溶剤に混練分散させて
ペースト状合剤を作製する方法は、特に限定されるもの
ではなく、例えば、プラネタリーミキサー、ホモミキサ
ー、ピンミキサー、ニーダー、ホモジナイザー等を用い
ることができる。これらを単独、或いは組み合わせて使
用することも可能である。By the way, the method of kneading and dispersing the active material, the binder, and the conductive agent, which is added as necessary, in the present invention to prepare the pasty mixture is not particularly limited. A Lee mixer, a homomixer, a pin mixer, a kneader, a homogenizer, etc. can be used. These may be used alone or in combination.
【００２５】また、上記ペースト状合剤の混練分散時
に、各種分散剤、界面活性剤、安定剤等を必要に応じて
添加することも可能である。It is also possible to add various dispersants, surfactants, stabilizers, etc., when necessary, at the time of kneading and dispersing the above-mentioned paste mixture.
【００２６】塗着乾燥は、特に限定されるものではな
く、上記のように混錬分散させたペースト状合剤を、例
えば、スリットダイコーター、リバースロールコータ
ー、リップコーター、ブレードコーター、ナイフコータ
ー、グラビアコーター、ディップコーター等を用いて、
容易に塗着することができ、自然乾燥に近い乾燥が好ま
しいが、生産性を考慮すると７０℃〜３００℃の温度で
５時間〜１分間乾燥させるのが好ましい。The coating and drying are not particularly limited, and the paste mixture prepared by kneading and dispersing as described above may be used, for example, a slit die coater, a reverse roll coater, a lip coater, a blade coater, a knife coater, Using a gravure coater, dip coater, etc.
Although it is easy to apply and drying close to natural drying is preferable, in consideration of productivity, drying at a temperature of 70 ° C. to 300 ° C. for 5 hours to 1 minute is preferable.
【００２７】圧延は、ロールプレス機によって所定の厚
みになるまで、線圧１０００〜２０００ｋｇ／ｃｍで数
回圧延を行うか、線圧を変えて圧延するのが好ましい。The rolling is preferably carried out by a roll pressing machine at a linear pressure of 1000 to 2000 kg / cm several times or at different linear pressures.
【００２８】この正極板１の正極リード２を接続する位
置には、図１（ａ）に示すように、正極活物質層を剥
離、除去した正極活物質無地部１１が形成され、この無
地部の寸法は、幅方向の寸法が５ｍｍ〜全幅いっぱい
で、長手方向の寸法は正極リード２の幅寸法より２ｍｍ
〜３ｍｍ広い範囲がスポット溶接や抵抗溶接等の溶接性
の観点から好ましく、この無地部１１には、正極リード
２の一端側が溶接され、この正極リード２を覆い正極活
物質層１８と接触しないように正極粘着テープ１２が貼
着される。At the position where the positive electrode lead 2 of the positive electrode plate 1 is connected, as shown in FIG. 1A, a positive electrode active material uncoated portion 11 is formed by peeling and removing the positive electrode active material layer, and this uncoated portion is formed. The dimension in the width direction is 5 mm to the full width, and the dimension in the longitudinal direction is 2 mm from the width dimension of the positive electrode lead 2.
A wide range of 3 mm is preferable from the viewpoint of weldability such as spot welding and resistance welding. One end side of the positive electrode lead 2 is welded to the uncoated portion 11 so as to cover the positive electrode lead 2 and prevent contact with the positive electrode active material layer 18. The positive electrode adhesive tape 12 is attached to.
【００２９】正極粘着テープ１２は、基材、粘着層およ
び着色するための顔料から構成され、基材は、ポリテト
ラフルオロエチレン（ＰＴＦＥ）、四フッ化エチレン・
六フッ化プロピレン共重合体（ＦＥＰ）、四フッ化エチ
レン・パーフルオロアルコキシエチレン共重合体（ＰＦ
Ａ）などのフッ素系の樹脂、粘着層は、天然ゴム、イソ
ブチルゴム、スチレンブタジエンゴムから選ばれた少な
くとも一種からなる粘着層、顔料は、フタロシアニンを
成分とするフタロシアニンブルー（銅フタロシアニン錯
体）の有機系顔料、チタン及びアルミニウムの金属粉や
酸化物から選ばれた一種の顔料を用いて着色する。チタ
ン及びアルミニウムの金属粉や酸化物の粒径は特に限定
されるものではないが、０．５μｍ〜５μｍの範囲が好
ましい。このような構成からなる正極粘着テープ１２を
用いることにより、電位差のある正極板１の正極リード
２に用いても正極粘着テープ１２の基材や粘着剤の成分
中にハロゲンまたはアゾ基などの二重結合を有する官能
基がないので、正極活物質との反応による金属還元体の
生成を抑制することができる。The positive electrode adhesive tape 12 is composed of a base material, an adhesive layer and a pigment for coloring. The base material is polytetrafluoroethylene (PTFE), tetrafluoroethylene.
Hexafluoropropylene copolymer (FEP), tetrafluoroethylene / perfluoroalkoxyethylene copolymer (PF
Fluorine-based resin such as A), the adhesive layer is an adhesive layer made of at least one selected from natural rubber, isobutyl rubber, and styrene-butadiene rubber, and the pigment is an organic compound of phthalocyanine blue (copper phthalocyanine complex) containing phthalocyanine as a component. Coloring is performed by using one type of pigment selected from metal-based pigments, titanium and aluminum metal powders and oxides. The particle size of the metal powder or oxide of titanium and aluminum is not particularly limited, but is preferably in the range of 0.5 μm to 5 μm. By using the positive electrode pressure-sensitive adhesive tape 12 having such a structure, even when it is used for the positive electrode lead 2 of the positive electrode plate 1 having a potential difference, the base material of the positive electrode pressure-sensitive adhesive tape 12 or the component of the pressure-sensitive adhesive contains a halogen or azo group or the like. Since there is no functional group having a heavy bond, generation of a metal reductant due to reaction with the positive electrode active material can be suppressed.
【００３０】そして、正極板１の正極活物質の無い無地
部１１に溶接した正極リード２を被覆するための正極粘
着テープ１２の寸法を正極リード２と同じ幅〜無地部１
１より１ｍｍ〜２ｍｍ狭く、基材の厚みを２０μｍ〜６
０μｍ、粘着剤の厚みを２０μｍ〜８０μｍの範囲で、
活物質層の厚みより薄い粘着テープを用いることによ
り、正極リード２の絶縁被覆性と粘着強度を確保し、正
極活物質層と接触しないように貼着することができるの
で、正極粘着テープ１２の基材や粘着剤の成分と正極活
物質との反応による金属還元体の生成をさらに抑制する
ことができると共に、均一な巻き状態の極板群が得られ
る。従って、正極活物質層の充填密度や極板群の緊縛率
を増加させて電池の高容量化を図っても、微小ショート
による電圧不良や電池容量の低下を引き起こさないリチ
ウム二次電池が得られる。The size of the positive electrode adhesive tape 12 for covering the positive electrode lead 2 welded to the uncoated region 11 of the positive electrode plate 1 having no positive electrode active material is the same as the width of the positive electrode lead 2 to the uncoated region 1.
1 mm to 2 mm narrower than 1, and the thickness of the base material is 20 μm to 6
0 μm, the thickness of the adhesive in the range of 20 μm to 80 μm,
By using an adhesive tape thinner than the thickness of the active material layer, the insulation coverage and adhesive strength of the positive electrode lead 2 can be secured, and the positive electrode lead 2 can be attached without contact with the positive electrode active material layer. It is possible to further suppress the production of a metal reductant due to the reaction between the components of the base material or the pressure-sensitive adhesive and the positive electrode active material, and to obtain an electrode plate group in a uniformly wound state. Therefore, even if the capacity of the battery is increased by increasing the packing density of the positive electrode active material layer and the binding rate of the electrode plate group, a lithium secondary battery that does not cause a voltage defect or a decrease in battery capacity due to a minute short circuit can be obtained. .
【００３１】負極板３は、集電体の一面に、負極活物
質、結着剤、必要に応じて導電助剤を有機溶剤に混練分
散させたペースト状の合剤を塗着、乾燥し、集電体の他
面にも塗着、乾燥した後、圧延して作製される。The negative electrode plate 3 is coated on one surface of the current collector with a negative electrode active material, a binder, and a paste-like mixture in which a conductive auxiliary agent is kneaded and dispersed in an organic solvent, if necessary, and dried. It is prepared by coating the other surface of the current collector, drying and rolling.
【００３２】負極の集電体としては、銅製の箔、ラス加
工を施した箔、またはエッチング加工を施した箔からな
り、厚みは１０μｍ〜５０μｍの範囲が好ましい。The current collector of the negative electrode is made of copper foil, lath-processed foil, or etching-processed foil, and the thickness is preferably in the range of 10 μm to 50 μm.
【００３３】負極活物質としては、特に限定されるもの
ではないが、例えば、有機高分子化合物（フェノール樹
脂、ポリアクリロニトリル、セルロース等）を焼成する
ことにより得られる炭素材料、コークスやピッチを焼成
することにより得られる炭素材料、或いは人造グラファ
イト、天然グラファイト等を、その形状としては、球
状、鱗片状、塊状のものを用いることができる。The negative electrode active material is not particularly limited, but for example, a carbon material obtained by firing an organic polymer compound (phenol resin, polyacrylonitrile, cellulose, etc.), coke or pitch is fired. The carbon material thus obtained, artificial graphite, natural graphite, or the like can be used in the shape of a sphere, a scale, or a lump.
【００３４】結着剤、必要に応じて添加できる増粘剤と
しては、正極板と同様の結着剤を用いることができる。As the binder and the thickener which can be added if necessary, the same binder as used for the positive electrode plate can be used.
【００３５】セパレータ５としては、厚さ１５μｍ〜３
０μｍポリエチレン樹脂、ポリプロピレン樹脂などの微
多孔性ポリオレフイン系樹脂が好ましい。The separator 5 has a thickness of 15 μm to 3 μm.
A microporous polyolefin resin such as 0 μm polyethylene resin or polypropylene resin is preferable.
【００３６】このようにして得られた正極板１と負極板
３とをセパレータ５を介して渦巻き状に巻回して極板群
を作製するには、極板フープに一定のテンションを維持
しつつ正極リード２を溶接して取付け、粘着テープを貼
着した後、正極板１の正極リード２の位置が対向する負
極板３の負極活物質層領域内に配設されるように、渦巻
状に巻回し、負極板３の活物質無地部１３に溶接して取
付けられている負極リード４が前記正極活物質層１９の
領域外に配設されるように正極板１と負極板３を同時に
巻き始め極板群の巻き終わり部に負極リード４を配設す
るか、負極板３を先行して巻きはじめ極板群の巻き始め
部に負極リード４を配設して、極板群を構成することに
より、極板群の巻き状態が均一になり、正極粘着テープ
１２が剥れる危険性がなくなり、充放電サイクルや高温
保存をしても、微小ショートによる電圧不良や電池容量
の低下を生じることがない。The positive electrode plate 1 and the negative electrode plate 3 thus obtained are spirally wound with the separator 5 in between to form an electrode plate group, while maintaining a constant tension in the electrode plate hoop. After the positive electrode lead 2 is attached by welding and the adhesive tape is adhered, the positive electrode lead 2 is spirally formed so that the position of the positive electrode lead 2 of the positive electrode plate 1 is arranged in the negative electrode active material layer region of the negative electrode plate 3 facing the positive electrode lead 2. The positive electrode plate 1 and the negative electrode plate 3 are wound at the same time so that the negative electrode lead 4 wound around and attached to the active material uncoated portion 13 of the negative electrode plate 3 is disposed outside the region of the positive electrode active material layer 19. The negative electrode lead 4 is arranged at the winding end portion of the starting electrode plate group, or the negative electrode plate 3 is preceded and the negative electrode lead 4 is arranged at the winding start portion of the electrode plate group to form the electrode plate group. As a result, the winding state of the electrode plate group becomes uniform, and the positive electrode adhesive tape 12 may peel off. It is eliminated, even if the charge-discharge cycle and high-temperature storage, does not occur a lowering of the voltage failure and battery capacity due to micro-short circuit.
【００３７】なお、負極リード４を被覆する負極粘着テ
ープ１４と負極活物質とが反応して悪影響を及ぼす危険
性が無いので、負極粘着テープ１４が負極活物質層と接
触しても良いが、負極活物質層と接触するとその部分の
厚みが厚くなり、極板群が不均一になるので好ましくな
い。Since there is no risk that the negative electrode adhesive tape 14 covering the negative electrode lead 4 reacts with the negative electrode active material, the negative electrode adhesive tape 14 may come into contact with the negative electrode active material layer. When it comes into contact with the negative electrode active material layer, the thickness of that portion becomes large, and the electrode plate group becomes nonuniform, which is not preferable.
【００３８】さらに電池ケース８内には、非水電解液が
注液され、続いて安全機構を設けた封口板１０が絶縁パ
ッキン９を介して電池ケース８の開口部の周縁部を内方
にかしめ加工することにより密閉されている。Further, a non-aqueous electrolytic solution is injected into the battery case 8, and then a sealing plate 10 provided with a safety mechanism is inwardly directed to the inner edge of the opening of the battery case 8 via an insulating packing 9. It is sealed by caulking.
【００３９】電解液としては、非水溶媒に電解質を溶解
することにより、調整される。前記非水溶媒としては、
例えば、エチレンカーボネート、プロピレンカーボネー
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、γ−ブチロラクトン、１，２−ジ
メトキシエタン、１，２−ジクロロエタン、１，３−ジ
メトキシプロパン、４−メチル−２−ペンタノン、１，
４−ジオキサン、アセトニトリル、プロピオニトリル、
ブチロニトリル、バレロニトリル、ベンゾニトリル、ス
ルホラン、３−メチル−スルホラン、テトラヒドロフラ
ン、２−メチルテトラヒドロフラン、ジメチルホルムア
ミド、ジメチルスルホキシド、ジメチルホルムアミド、
リン酸トリメチル、リン酸トリエチル等を用いることが
でき、これらの非水溶媒は、単独或いは二種類以上の混
合溶媒として、使用することができる。The electrolytic solution is prepared by dissolving the electrolyte in a non-aqueous solvent. As the non-aqueous solvent,
For example, ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, γ-butyrolactone, 1,2-dimethoxyethane, 1,2-dichloroethane, 1,3-dimethoxypropane, 4-methyl-2-pentanone, 1 ，
4-dioxane, acetonitrile, propionitrile,
Butyronitrile, valeronitrile, benzonitrile, sulfolane, 3-methyl-sulfolane, tetrahydrofuran, 2-methyltetrahydrofuran, dimethylformamide, dimethylsulfoxide, dimethylformamide,
Trimethyl phosphate, triethyl phosphate and the like can be used, and these non-aqueous solvents can be used alone or as a mixed solvent of two or more kinds.
【００４０】非水電解液に含まれる電解質としては、例
えば、電子吸引性の強いリチウム塩を使用し、例えば、
ＬｉＰＦ6、ＬｉＢＦ4、ＬｉＣｌＯ4、ＬｉＡｓＦ6、Ｌ
ｉＣＦ3ＳＯ3、ＬｉＮ（ＳＯ2ＣＦ3）2、ＬｉＮ（ＳＯ2
Ｃ2Ｆ5）2、ＬｉＣ（ＳＯ2ＣＦ3）3等が挙げられる。こ
れらの電解質は、一種類で使用しても良く、二種類以上
組み合わせて使用しても良い。これらの電解質は、前記
非水溶媒に対して０．５〜１．５Ｍの濃度で溶解させる
ことが好ましい。As the electrolyte contained in the non-aqueous electrolyte, for example, a lithium salt having a strong electron-withdrawing property is used.
LiPF 6 , LiBF 4 , LiClO 4 , LiAsF 6 , L
iCF 3 SO 3, LiN (SO 2 CF 3) 2, LiN (SO 2
C 2 F 5) 2, LiC (SO 2 CF 3) 3 and the like. These electrolytes may be used alone or in combination of two or more. These electrolytes are preferably dissolved in the non-aqueous solvent at a concentration of 0.5 to 1.5M.
【００４１】[0041]
【実施例】本発明を実施例および比較例を用いて、詳細
に説明するが、これらは本発明を何ら限定するものでは
ない。EXAMPLES The present invention will be described in detail with reference to Examples and Comparative Examples, but these do not limit the present invention in any way.
【００４２】（実施例１）まず、図１（ａ）に平面図を
示す正極板１の作製方法について説明する。Example 1 First, a method of manufacturing the positive electrode plate 1 whose plan view is shown in FIG.
【００４３】正極活物質としてコバルト酸リチウムを１
００重量部、導電剤としてアセチレンブラックを３重量
部、結着剤としてポリテトラフルオロエチレン（ＰＴＦ
Ｅ）樹脂を固形分で４重量部とカルボキシメチルセルロ
ースを０．８重量部を加え、水を溶剤として混練分散さ
せてペーストを作製した。このペーストを、厚さ２０μ
ｍの帯状のアルミニウム箔からなる集電体に連続的に間
欠塗着を行い乾燥した後、２５０℃で１０時間熱処理を
行い、厚み２９０μｍの正極板を作製し、線圧１０００
Ｋｇ／ｃｍで３回圧延を行うことにより、正極板厚みを
１８０μｍに圧延した。Lithium cobalt oxide was used as a positive electrode active material.
00 parts by weight, 3 parts by weight of acetylene black as a conductive agent, and polytetrafluoroethylene (PTF) as a binder.
E) 4 parts by weight of resin and 0.8 parts by weight of carboxymethyl cellulose were added, and the mixture was kneaded and dispersed with water as a solvent to prepare a paste. This paste is 20μ thick
m band-shaped aluminum foil current collector was continuously intermittently coated and dried, and then heat-treated at 250 ° C. for 10 hours to produce a positive electrode plate having a thickness of 290 μm and a linear pressure of 1000.
The positive electrode plate was rolled to 180 μm by rolling 3 times at Kg / cm.
【００４４】図１（ａ）に示すように、この正極板１の
中央部に正極リード２を溶接する為の無地部１１を、超
音波ホーンを有する活物質剥離装置を用いて正極活物質
を剥離し、真ちゅう製の回転ブラシにて正極活物質を除
去することにより、幅７．０ｍｍ、長さ３８．０ｍｍの
寸法にて作製した。この無地部１１にアルミニウム製で
幅４．５ｍｍ、長さ３８．０ｍｍのものをスポット溶接
して取付け、さらに基材がＰＴＦＥからなるフッ素樹脂
製で厚みが３０μｍ、粘着剤がスチレンブタジエンゴム
（ＳＢＲ）製で厚みが３０μｍで、顔料がフタロシアニ
ンブルーの顔料からなり、寸法が幅５．５ｍｍ、長さ３
４．０ｍｍの正極粘着テープ１２にて、前記正極リード
２を被覆し、正極活物質層と接触しないように貼着し
た。As shown in FIG. 1 (a), a plain portion 11 for welding the positive electrode lead 2 is formed in the central portion of the positive electrode plate 1 by using the active material peeling device having an ultrasonic horn to remove the positive electrode active material. The positive electrode active material was peeled off and the positive electrode active material was removed with a brass rotating brush to prepare a sample having a width of 7.0 mm and a length of 38.0 mm. An aluminum-made product having a width of 4.5 mm and a length of 38.0 mm is spot-welded and attached to the uncoated portion 11, and the base material is made of a fluororesin having a thickness of 30 μm. The adhesive is styrene-butadiene rubber (SBR). ), The thickness is 30 μm, the pigment is phthalocyanine blue pigment, and the dimensions are width 5.5 mm and length 3
The positive electrode lead 2 was covered with a 4.0 mm positive electrode pressure-sensitive adhesive tape 12 and attached so as not to contact the positive electrode active material layer.
【００４５】次に、図１（ｂ）に平面図を示す負極板３
の作製方法について説明する。Next, the negative electrode plate 3 whose plan view is shown in FIG.
The manufacturing method of will be described.
【００４６】負極活物質としてリチウムを吸蔵、放出可
能な鱗片状黒鉛を１００重量部、結着剤としてスチレン
ブタジエンゴム（ＳＢＲ）の水溶性デイスパージョンを
固形分として４重量部、増粘剤としてカルボキシメチル
セルロースを０．８重量部、溶剤として水を加え、混練
分散させてペースト状合剤を作製した。100 parts by weight of flake graphite capable of occluding and releasing lithium as a negative electrode active material, 4 parts by weight of a water-soluble dispersion of styrene-butadiene rubber (SBR) as a binder as a solid content, and a thickener as a thickener. 0.8 parts by weight of carboxymethyl cellulose and water as a solvent were added, kneaded and dispersed to prepare a paste mixture.
【００４７】このペーストを、厚さ１４μｍの帯状の銅
箔からなる集電体に連続的に間欠塗着を行い乾燥した
後、１１０℃で１０時間熱処理を行い、厚さ３００μｍ
の負極板を作製し、線圧１１０Ｋｇ／ｃｍで３回圧延を
行うことにより、負極板厚みを１９６μｍに圧延した。This paste was applied intermittently to a current collector made of a strip-shaped copper foil having a thickness of 14 μm and dried, and then heat-treated at 110 ° C. for 10 hours to give a thickness of 300 μm.
The negative electrode plate was prepared and rolled three times at a linear pressure of 110 Kg / cm to roll the negative electrode plate to a thickness of 196 μm.
【００４８】図１（ｂ）に示すように、この負極板３の
右端部に負極リード４を溶接する為の無地部１３を、正
極板１と同様にして幅６．０ｍｍ、長さ３８．０ｍｍの
寸法にて作製した。As shown in FIG. 1B, a plain portion 13 for welding the negative electrode lead 4 to the right end portion of the negative electrode plate 3 has a width of 6.0 mm and a length of 38. It was manufactured with a size of 0 mm.
【００４９】この無地部１３にニッケル製で幅４．０ｍ
ｍ、長さ３８ｍｍの負極リード４をスポット溶接して取
付け、さらに基材がＰＴＦＥからなるフッ素樹脂で厚み
が３０μｍ、粘着剤がイソブチルゴムで厚みが３０μｍ
で、顔料が平均粒径３．０μｍの二酸化チタン粉からな
り、寸法が幅５．０ｍｍ、長さ３４．０ｍｍの負極粘着
テープ１４を、前記負極リード４を被覆し、負極活物質
層１９と接触しないように貼着した。The plain portion 13 is made of nickel and has a width of 4.0 m.
A negative electrode lead 4 having a length of m and a length of 38 mm is attached by spot welding. Further, the base material is a fluororesin made of PTFE and has a thickness of 30 μm. The adhesive is isobutyl rubber and the thickness is 30 μm.
The pigment is made of titanium dioxide powder having an average particle size of 3.0 μm, and the negative electrode adhesive tape 14 having a width of 5.0 mm and a length of 34.0 mm is coated on the negative electrode lead 4 to form a negative electrode active material layer 19. It was attached so that it would not come into contact.
【００５０】このようにして作製した図１（ａ）に示す
ような正極板１と図１（ｂ）に示すような負極板３とが
厚さ２５μｍの微多孔性のポリエチレン樹脂製のセパレ
ータ５を介して絶縁され、正極板１の正極リード２の位
置が対向する負極板３の負極活物質層領域内に配設さ
れ、かつ負極板３の負極リード４の位置が対向する正極
板１の正極活物質層領域外の外側に配設されるように渦
巻状に巻回されている極板群の巻き終端部を正極板１で
用いた正極粘着テープ１２にて群固定した後、図２に示
すような上部が開口している有底の電池ケース８内に収
容し、正極板１に接続された正極リード２の他端部を封
口板１０に接続し、負極板３に接続された負極リード４
の他端部を、電池ケース８の底部に接続した。The positive electrode plate 1 as shown in FIG. 1 (a) and the negative electrode plate 3 as shown in FIG. 1 (b) thus produced were made of a microporous polyethylene resin separator 5 having a thickness of 25 μm. Of the positive electrode plate 1 which is insulated via the positive electrode plate 1 and is disposed in the negative electrode active material layer region of the negative electrode plate 3 where the position of the positive electrode lead 2 of the positive electrode plate 1 faces. After the winding terminal end of the electrode plate group that is spirally wound so as to be disposed outside the positive electrode active material layer region is group-fixed with the positive electrode adhesive tape 12 used in the positive electrode plate 1, FIG. The positive electrode lead 2 is housed in a bottomed battery case 8 having an open top as shown in FIG. 2, and the other end of the positive electrode lead 2 connected to the positive electrode plate 1 is connected to the sealing plate 10 and connected to the negative electrode plate 3. Negative electrode lead 4
The other end of was connected to the bottom of the battery case 8.
【００５１】この極板群の上下それぞれに上部絶縁板
６、下部絶縁板７を配した。An upper insulating plate 6 and a lower insulating plate 7 are arranged above and below the electrode plate group.
【００５２】さらに、エチレンカーボネート、エチルメ
チルカーボネートの混合溶媒中に、電解質としてヘキサ
フルオロリン酸リチウム（ＬｉＰＦ6）を１．３モル溶
かした電解液を所定量注液した後、ポリプロピレン樹脂
製のガスケット９を介して電池ケース８を封口板１０で
密封してＪＩＳ Ｃ８７１１に記載されているＩＣＲ１
７５００サイズで電池容量が８００ｍＡｈの電池を作製
し、実施例１の電池とした。Furthermore, a predetermined amount of an electrolytic solution prepared by dissolving 1.3 mol of lithium hexafluorophosphate (LiPF 6 ) as an electrolyte in a mixed solvent of ethylene carbonate and ethyl methyl carbonate was poured, and then a gasket made of polypropylene resin was used. The battery case 8 is sealed with the sealing plate 10 via the ICR 1 described in JIS C8711.
A battery having a size of 7500 and a battery capacity of 800 mAh was manufactured and used as a battery of Example 1.
【００５３】（実施例２）実施例１の正極板１で用いた
正極粘着テープ１２を用い、その寸法が幅８．０ｍｍ、
長さ３４．０ｍｍで、正極リード２を被覆し、正極活物
質層と接触する幅が１．０ｍｍになるように貼着した以
外は、実施例１と同様にして電池を作製し、実施例２の
電池とした。(Example 2) The positive electrode pressure-sensitive adhesive tape 12 used in the positive electrode plate 1 of Example 1 was used, and its dimensions were 8.0 mm in width,
A battery was prepared in the same manner as in Example 1 except that the positive electrode lead 2 having a length of 34.0 mm was coated and was attached so that the width in contact with the positive electrode active material layer was 1.0 mm. The battery was No. 2.
【００５４】（実施例３）基材がＦＥＰからなるフッ素
樹脂で厚みが４０μｍ、粘着剤が天然ゴム製で厚みが２
０μｍ、顔料が平均粒径２．５μｍの二酸化チタン粉で
構成される正極粘着テープ１２を用いた以外は実施例１
と同様にして作製した図３（ａ）に示すような正極板１
と、負極リード４の位置を左端に配設した以外は実施例
１と同様にして作製した図３（ｂ）に示すような負極板
３とを、厚さ２０μｍの微多孔性ポリプロピレン樹脂製
のセパレータ５を介して、負極板３を先行して巻きはじ
め極板群の巻き始め部に負極リード４が配設され、かつ
正極板１の正極リード２の位置が対向する負極板３の負
極活物質層領域内に配設されるように渦巻状に巻回した
以外は、実施例１と同様にして電池を作製し、実施例３
の電池とした。(Example 3) The base material is a fluororesin made of FEP and has a thickness of 40 μm, and the adhesive is made of natural rubber and has a thickness of 2
Example 1 except that the positive electrode adhesive tape 12 composed of titanium dioxide powder having a particle size of 0 μm and an average particle size of 2.5 μm was used.
A positive electrode plate 1 as shown in FIG.
And a negative electrode plate 3 as shown in FIG. 3 (b) prepared in the same manner as in Example 1 except that the position of the negative electrode lead 4 was arranged at the left end, and the negative electrode plate 3 was made of a microporous polypropylene resin having a thickness of 20 μm. Starting the negative electrode plate 3 through the separator 5 in advance, the negative electrode lead 4 is arranged at the winding start portion of the electrode plate group, and the position of the positive electrode lead 2 of the positive electrode plate 1 faces the negative electrode active surface of the negative electrode plate 3. A battery was manufactured in the same manner as in Example 1 except that the material was wound in a spiral shape so as to be arranged in the material layer region.
Battery.
【００５５】（実施例４）実施例３の正極板１で用いた
正極粘着テープ１２を用い、その寸法が幅８．０ｍｍ、
長さ３４．０ｍｍで、正極リード２を被覆し、正極活物
質層と接触する幅が１．０ｍｍになるように貼着した以
外は、実施例３と同様にして電池を作製し、実施例４の
電池とした。(Example 4) The positive electrode pressure-sensitive adhesive tape 12 used in the positive electrode plate 1 of Example 3 was used, and the size thereof was 8.0 mm.
A battery was produced in the same manner as in Example 3 except that the positive electrode lead 2 was covered with a length of 34.0 mm and was attached so that the width in contact with the positive electrode active material layer was 1.0 mm. The battery of No. 4 was used.
【００５６】（実施例５）基材がポリプロピレン樹脂製
で厚みが３０μｍ、粘着剤がブチルアクリレートを主成
分とするアクリル樹脂製で厚みが３０μｍ、顔料がジス
アゾイエローで構成される負極粘着テープ１４を用い、
その寸法が幅８．０ｍｍ、長さ３４．０ｍｍで、負極リ
ード４を被覆し、負極活物質層と接触する幅が２．０ｍ
ｍになるように貼着して作製した負極板３を用いた以外
は実施例４と同様にして極板群を作製し、この群の巻き
終端部を前記正極板１で用いた正極粘着テープ１２にて
群固定した以外は、実施例１と同様にして電池を作製
し、実施例５の電池とした。(Embodiment 5) A negative electrode adhesive tape 14 having a base material made of polypropylene resin and a thickness of 30 μm, an adhesive made of acrylic resin containing butyl acrylate as a main component and a thickness of 30 μm, and a pigment made of disazo yellow. Used,
The dimensions are width 8.0 mm and length 34.0 mm, and the width which covers the negative electrode lead 4 and contacts the negative electrode active material layer is 2.0 m.
A positive electrode adhesive tape was prepared in the same manner as in Example 4 except that the negative electrode plate 3 was attached so as to have a thickness of m, and the winding end of this group was used in the positive electrode plate 1. A battery was prepared in the same manner as in Example 1 except that the battery was fixed in group 12 to obtain a battery of Example 5.
【００５７】（実施例６）実施例５の負極板３で用いた
負極粘着テープ１４を用いた以外は、実施例２と同様に
して電池を作製し、実施例６の電池とした。Example 6 A battery of Example 6 was prepared in the same manner as in Example 2, except that the negative electrode adhesive tape 14 used in the negative electrode plate 3 of Example 5 was used.
【００５８】（実施例７）基材がＰＦＡからなるフッ素
樹脂で厚みが３０μｍ、粘着剤がイソブチルゴム製で厚
みが３０μｍ、顔料がフタロシアニンブルーで構成され
る正極粘着テープ１５を用い、実施例５の負極板３で用
いた負極粘着テープ１４を用いた以外は、実施例５と同
様にして電池を作製し、実施例７の電池とした。Example 7 A positive electrode pressure-sensitive adhesive tape 15 having a base material made of PFA and having a thickness of 30 μm, an adhesive agent made of isobutyl rubber and a thickness of 30 μm, and a pigment made of phthalocyanine blue was used. A battery was produced in the same manner as in Example 5 except that the negative electrode adhesive tape 14 used in the negative electrode plate 3 was used to obtain a battery of Example 7.
【００５９】（比較例１）基材がポリイミド樹脂製で厚
みが３０μｍ、粘着剤がシリコン樹脂製で厚みが３０μ
ｍ、顔料がフタロシアニンブルーで構成される正極粘着
テープ１２を用いた以外は、実施例１と同様にして電池
を作製し、比較例１の電池とした。(Comparative Example 1) The base material was made of polyimide resin and had a thickness of 30 μm, and the adhesive was made of silicone resin and had a thickness of 30 μm.
A battery of Comparative Example 1 was prepared in the same manner as in Example 1 except that the positive electrode adhesive tape 12 in which the pigment was phthalocyanine blue was used.
【００６０】（比較例２）基材がポリプロピレン樹脂製
で厚みが３０μｍ、粘着剤がブチルアクリレートを主成
分とするアクリル樹脂製で厚みが３０μｍ、顔料がフタ
ロシアニンブルーで構成される正極粘着テープ１２を用
いた以外は、実施例１と同様にして電池を作製し、比較
例２の電池とした。Comparative Example 2 A positive electrode adhesive tape 12 having a base material made of polypropylene resin and a thickness of 30 μm, an adhesive made of acrylic resin containing butyl acrylate as a main component and a thickness of 30 μm, and a pigment made of phthalocyanine blue. A battery was produced in the same manner as in Example 1 except that it was used, and was used as a battery of Comparative Example 2.
【００６１】（比較例３）正極粘着テープ１２の顔料に
ジスアゾイエローを用いた以外は、実施例１と同様にし
て電池を作製し、比較例３の電池とした。(Comparative Example 3) A battery was prepared in the same manner as in Example 1 except that disazo yellow was used as the pigment of the positive electrode adhesive tape 12 to obtain a battery of Comparative Example 3.
【００６２】（比較例４）粘着剤がシリコン樹脂製で厚
みが３０μｍで構成される正極粘着テープ１２を用いた
以外は、実施例１と同様にして電池を作製し、比較例４
の電池とした。(Comparative Example 4) A battery was prepared in the same manner as in Example 1 except that the positive electrode pressure-sensitive adhesive tape 12 having a silicon resin adhesive and a thickness of 30 μm was used.
Battery.
【００６３】このようにして作製した実施例１〜実施例
７、比較例１〜比較例４の電池について、充放電サイク
ル試験と高温保存試験を各２０のサンプルを用意して実
施した。With respect to the batteries of Examples 1 to 7 and Comparative Examples 1 to 4 produced in this way, a charge / discharge cycle test and a high temperature storage test were carried out by preparing 20 samples each.
【００６４】充放電サイクル試験は、充電は４．２Ｖで
２時間の定電流−定電圧充電を行った。電池電圧が４．
２Ｖに達するまでは８００ｍＡ（１ＣｍＡ）の定電流充
電を行い、その後、電流値が減衰して４０ｍＡ（０．０
５ＣｍＡ）になるまで充電した後、８００ｍＡの定電流
で３．０Ｖの放電終止電圧まで放電する充放電サイクル
を２０℃の環境下で、５００サイクル繰り返し、３サイ
クル目を１００％とした場合の５００サイクル目の容量
維持率を求めた平均値の結果を表1に示す。In the charge / discharge cycle test, charging was carried out at a constant current-constant voltage charge for 2 hours at 4.2V. Battery voltage is 4.
Constant current charging of 800mA (1CmA) is performed until reaching 2V, and then the current value decays to 40mA (0.0mA).
5 CmA), and then a charging / discharging cycle of discharging at a constant current of 800 mA to an end-of-discharge voltage of 3.0 V at a temperature of 20 ° C. is repeated for 500 cycles. Table 1 shows the results of the average values of the capacity retention rate at the cycle.
【００６５】高温保存特性はこの充放電サイクルを３サ
イクル繰り返した後、前記充電条件で充電状態にし、８
０℃の環境下で１６８時間放置後、２０℃に冷却し、前
記と同様の充放電条件で３サイクル繰り返した。この６
０℃保存前と保存後の容量比を高温保存後の容量回復率
として求めた平均値の結果を表１に示す。The high temperature storage characteristics were as follows: after repeating this charging / discharging cycle 3 times, the battery was charged under the above charging conditions.
After leaving it in an environment of 0 ° C. for 168 hours, it was cooled to 20 ° C., and 3 cycles were repeated under the same charge and discharge conditions as described above. This 6
Table 1 shows the results of the average value of the capacity ratio before and after storage at 0 ° C. as the capacity recovery rate after storage at high temperature.
【００６６】[0066]
【表１】 [Table 1]
【００６７】表１から明らかなように、フッ素系の樹脂
からなる基材と、天然ゴム、イソブチルゴム、スチレン
ブタジエンゴムから選ばれた少なくとも一種からなる粘
着剤から構成される粘着テープにて、正極リードを被覆
することにより、正極活物質との反応による金属還元体
の生成を抑制することができ、充放電サイクルや高温保
存をしても、微小ショートによる電圧不良や電池容量の
低下を引き起こさないリチウム二次電池が得られること
がわかった。As is clear from Table 1, the positive electrode was prepared by using a pressure-sensitive adhesive tape composed of a base material made of a fluorine-based resin and a pressure-sensitive adhesive made of at least one selected from natural rubber, isobutyl rubber and styrene-butadiene rubber. By coating the lead, it is possible to suppress the generation of metal reductant due to the reaction with the positive electrode active material, and it does not cause a voltage failure or a decrease in battery capacity due to a minute short circuit even during charge / discharge cycles or high temperature storage. It was found that a lithium secondary battery can be obtained.
【００６８】そして、粘着テープを正極板の活物質層と
接触しないように正極リードを被覆したり、粘着テープ
を着色するための顔料が、フタロシアニンを成分とする
有機物、チタン及びアルミニウムの金属粉や酸化物から
選ばれた一種を用いることにより、さらに充放電サイク
ルや高温保存特性に優れたリチウム二次電池が得られる
ことがわかったThe pigment for coating the positive electrode lead so that the adhesive tape does not come into contact with the active material layer of the positive electrode plate or for coloring the adhesive tape is formed of an organic substance containing phthalocyanine, metal powder of titanium and aluminum, or It was found that by using one selected from the oxides, a lithium secondary battery with excellent charge / discharge cycle and high temperature storage characteristics can be obtained.
【００６９】[0069]
【発明の効果】以上の説明の通り本発明による粘着テー
プを正極板の活物質層と接触しないように正極リードを
被覆することにより、正極活物質との反応による金属還
元体の生成を抑制することができ、充放電サイクルや高
温保存をしても、微小ショートによる電圧不良や電池容
量の低下を引き起こさないリチウム二次電池が得られ
る。As described above, by covering the positive electrode lead with the pressure-sensitive adhesive tape according to the present invention so as not to contact the active material layer of the positive electrode plate, generation of a metal reductant due to reaction with the positive electrode active material is suppressed. It is possible to obtain a lithium secondary battery that does not cause a voltage defect or a decrease in battery capacity due to a minute short circuit even after charge / discharge cycles or high temperature storage.
【図１】本発明の実施形態に係る（ａ）は正極板、
（ｂ）は負極板の平面図FIG. 1A is a positive electrode plate according to an embodiment of the present invention,
(B) is a plan view of the negative electrode plate
【図２】本発明の実施形態に係る電池の断面図FIG. 2 is a sectional view of a battery according to an embodiment of the present invention.
【図３】本発明の別の実施形態に係る（ａ）は正極板、
（ｂ）は負極板の平面図FIG. 3A is a positive electrode plate according to another embodiment of the present invention,
(B) is a plan view of the negative electrode plate
【図４】従来例に係る（ａ）は正極板、（ｂ）は負極板
の平面図FIG. 4A is a plan view of a positive electrode plate and FIG. 4B is a negative electrode plate of a conventional example.
１ 正極板 ２ 正極リード ３ 負極板 ４ 負極リード ５ セパレータ ６ 上部絶縁板 ７ 下部絶縁板 ８ 電池ケース ９ ガスケット １０ 封口板 １１ 正極活物質無地部 １２ 正極粘着テープ １３ 負極活物質無地部 １４ 負極粘着テープ 1 Positive plate 2 Positive lead 3 Negative electrode plate 4 Negative electrode lead 5 separator 6 Upper insulating plate 7 Lower insulation plate 8 battery case 9 gasket 10 Seal plate 11 Solid part of positive electrode active material 12 Positive electrode adhesive tape 13 Negative electrode active material plain area 14 Negative electrode adhesive tape
───────────────────────────────────────────────────── フロントページの続き (72)発明者 宮崎 洋一 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 (72)発明者 庄司 昌史 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 Ｆターム(参考） 5H022 AA09 AA18 BB11 CC19 EE06 EE07 KK03 5H029 AJ04 AJ05 AK03 AL06 AL07 AM02 AM03 AM04 AM05 AM07 BJ02 BJ13 DJ05 EJ12 5H050 AA07 AA10 BA17 CA07 CA08 CA09 CB07 CB08 DA20 EA23 EA24 EA28 FA04 FA05 FA18 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Yoichi Miyazaki 1006 Kadoma, Kadoma-shi, Osaka Matsushita Electric Sangyo Co., Ltd. (72) Inventor Masafumi Shoji 1006 Kadoma, Kadoma-shi, Osaka Matsushita Electric Sangyo Co., Ltd. F term (reference) 5H022 AA09 AA18 BB11 CC19 EE06 EE07 KK03 5H029 AJ04 AJ05 AK03 AL06 AL07 AM02 AM03 AM04 AM05 AM07 BJ02 BJ13 DJ05 EJ12 5H050 AA07 AA10 BA17 CA07 CA08 CA09 CB07 CB08 DA20 EA23 EA24 EA28 FA04 FA05 FA18
Claims (4)
渦巻状に巻回されている極板群をケースに収納してなる
電池において、前記正極板の正極リードが粘着テープで
被覆されており、この粘着テープがフッ素系の樹脂から
なる基材と、天然ゴム、イソブチルゴム、スチレンブタ
ジエンゴムから選ばれた少なくとも一種からなる粘着剤
から構成されていることを特徴とするリチウム二次電
池。1. A battery comprising a case in which a positive electrode plate and a negative electrode plate are spirally wound with a separator interposed between them, and a positive electrode lead of the positive electrode plate is covered with an adhesive tape. A lithium secondary battery, wherein the adhesive tape is composed of a base material made of a fluorine-based resin and an adhesive made of at least one selected from natural rubber, isobutyl rubber, and styrene-butadiene rubber.
層と接触しないようにして正極リードを被覆しているこ
とを特徴とする請求項１に記載のリチウム二次電池。2. The lithium secondary battery according to claim 1, wherein the adhesive tape covers the positive electrode lead so as not to contact the active material layer of the positive electrode plate.
が、フタロシアニンを成分とする有機物、チタン及びア
ルミニウムの金属粉や酸化物から選ばれた一種であるこ
とを特徴とする請求項１または請求項２に記載のリチウ
ム二次電池。3. The pigment for coloring the pressure-sensitive adhesive tape is one selected from an organic substance containing phthalocyanine as a component, and metal powders and oxides of titanium and aluminum. 2. The lithium secondary battery described in 2.
前記極板群の巻き終端部が請求項１〜請求項３のいずれ
かに記載の粘着テープで被覆されていることを特徴とす
るリチウム二次電池。4. The lithium secondary battery characterized in that the negative electrode lead of the negative electrode plate and / or the winding terminal end of the electrode plate group is covered with the adhesive tape according to any one of claims 1 to 3. Next battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001325797A JP4017376B2 (en) | 2001-10-24 | 2001-10-24 | Lithium secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001325797A JP4017376B2 (en) | 2001-10-24 | 2001-10-24 | Lithium secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2003132875A true JP2003132875A (en) | 2003-05-09 |
| JP4017376B2 JP4017376B2 (en) | 2007-12-05 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001325797A Expired - Fee Related JP4017376B2 (en) | 2001-10-24 | 2001-10-24 | Lithium secondary battery |
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| Country | Link |
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| JP (1) | JP4017376B2 (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003068271A (en) * | 2001-06-13 | 2003-03-07 | Matsushita Electric Ind Co Ltd | Lithium secondary battery and manufacturing method of positive plate used for lithium secondary battery |
| US6790557B2 (en) * | 2000-02-10 | 2004-09-14 | Ngk Spark Plug Co., Ltd. | Li-ion and/or Li-ion polymer battery with shielded leads |
| JP2006040812A (en) * | 2004-07-29 | 2006-02-09 | Sanyo Electric Co Ltd | Non-aqueous electrolyte battery |
| JP2009059487A (en) * | 2007-08-30 | 2009-03-19 | Panasonic Corp | Nonaqueous secondary battery |
| KR20090129343A (en) * | 2008-06-11 | 2009-12-16 | 소니 가부시끼가이샤 | Electrode with porous protective film, nonaqueous electrolyte secondary battery, and method for manufacturing electrode with porous protective film |
| JP2012099227A (en) * | 2010-10-29 | 2012-05-24 | Nitto Denko Corp | Adhesive tape for battery |
| WO2017038010A1 (en) * | 2015-08-31 | 2017-03-09 | パナソニックＩｐマネジメント株式会社 | Nonaqueous electrolytic secondary battery |
| WO2018020896A1 (en) * | 2016-07-28 | 2018-02-01 | パナソニックＩｐマネジメント株式会社 | Nonaqueous electrolyte secondary battery |
| WO2019049479A1 (en) * | 2017-09-11 | 2019-03-14 | パナソニックＩｐマネジメント株式会社 | Secondary battery |
| WO2020241410A1 (en) | 2019-05-28 | 2020-12-03 | 三洋電機株式会社 | Nonaqueous electrolyte secondary battery |
| EP3859820A4 (en) * | 2018-09-27 | 2022-06-15 | Zeon Corporation | Slurry for nonaqueous secondary battery adhesive layer, battery member for nonaqueous secondary battery with adhesive layer, method of manufacturing laminate for nonaqueous secondary battery, and method of manufacturing nonaqueous secondary battery |
| JP2022539769A (en) * | 2019-06-28 | 2022-09-13 | 寧徳時代新能源科技股▲分▼有限公司 | Electrode sheet, electrochemical device and its device |
| US11923498B2 (en) | 2014-01-17 | 2024-03-05 | Ningde Amperex Technology Limited | Lithium-ion battery having desirable safety performance |
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| JPH07142089A (en) * | 1993-11-17 | 1995-06-02 | Sanyo Electric Co Ltd | Lithium ion battery |
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| JP2000297259A (en) * | 1999-04-16 | 2000-10-24 | Nippon Kakoh Seishi Kk | Self-adhesive type simple adhesive sheet, and its production |
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| JPH01304172A (en) * | 1988-05-31 | 1989-12-07 | Nitto Denko Corp | Self-adhesive tape for battery |
| JPH0762302A (en) * | 1993-08-27 | 1995-03-07 | Nitto Denko Corp | Composite pressure-sensitive adhesive tape or sheet |
| JPH07142089A (en) * | 1993-11-17 | 1995-06-02 | Sanyo Electric Co Ltd | Lithium ion battery |
| JPH07150120A (en) * | 1993-12-01 | 1995-06-13 | Nitto Denko Corp | Composite pressure-sensitive adhesive tape or sheet |
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Cited By (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6790557B2 (en) * | 2000-02-10 | 2004-09-14 | Ngk Spark Plug Co., Ltd. | Li-ion and/or Li-ion polymer battery with shielded leads |
| JP2003068271A (en) * | 2001-06-13 | 2003-03-07 | Matsushita Electric Ind Co Ltd | Lithium secondary battery and manufacturing method of positive plate used for lithium secondary battery |
| JP2006040812A (en) * | 2004-07-29 | 2006-02-09 | Sanyo Electric Co Ltd | Non-aqueous electrolyte battery |
| JP2009059487A (en) * | 2007-08-30 | 2009-03-19 | Panasonic Corp | Nonaqueous secondary battery |
| KR101601690B1 (en) * | 2008-06-11 | 2016-03-09 | 소니 가부시끼가이샤 | 2 electrode with porous protective film nonaqueous electrolyte secondary battery and method for manufacturing electrode with porous protective film |
| JP2009301765A (en) * | 2008-06-11 | 2009-12-24 | Sony Corp | Electrode with porous protective membrane, nonaqueous electrolyte secondary battery, and method of manufacturing electrode with porous protective membrane |
| US9236606B2 (en) | 2008-06-11 | 2016-01-12 | Sony Corporation | Electrode with porous protective film, nonaqueous electrolyte secondary battery, and method for manufacturing electrode with porous protective film |
| US10020478B2 (en) | 2008-06-11 | 2018-07-10 | Murata Manufacturing Co., Ltd. | Electrode with porous protective film, nonaqueous electrolyte secondary battery, and method for manufacturing electrode with porous protective film |
| KR20090129343A (en) * | 2008-06-11 | 2009-12-16 | 소니 가부시끼가이샤 | Electrode with porous protective film, nonaqueous electrolyte secondary battery, and method for manufacturing electrode with porous protective film |
| JP2012099227A (en) * | 2010-10-29 | 2012-05-24 | Nitto Denko Corp | Adhesive tape for battery |
| US11923498B2 (en) | 2014-01-17 | 2024-03-05 | Ningde Amperex Technology Limited | Lithium-ion battery having desirable safety performance |
| US11139480B2 (en) | 2015-08-31 | 2021-10-05 | Panasonic Intellectual Property Management Co., Ltd. | Secondary battery |
| WO2017038010A1 (en) * | 2015-08-31 | 2017-03-09 | パナソニックＩｐマネジメント株式会社 | Nonaqueous electrolytic secondary battery |
| CN107851769A (en) * | 2015-08-31 | 2018-03-27 | 松下知识产权经营株式会社 | Rechargeable nonaqueous electrolytic battery |
| JPWO2017038010A1 (en) * | 2015-08-31 | 2018-06-14 | パナソニックＩｐマネジメント株式会社 | Nonaqueous electrolyte secondary battery |
| US11824202B2 (en) | 2015-08-31 | 2023-11-21 | Panasonic Intellectual Property Management Co., Ltd. | Secondary battery including insulating tape covering positive electrode |
| JP7026317B2 (en) | 2016-07-28 | 2022-02-28 | パナソニックＩｐマネジメント株式会社 | Non-aqueous electrolyte secondary battery |
| JPWO2018020896A1 (en) * | 2016-07-28 | 2019-05-16 | パナソニックＩｐマネジメント株式会社 | Non-aqueous electrolyte secondary battery |
| CN109478631A (en) * | 2016-07-28 | 2019-03-15 | 松下知识产权经营株式会社 | Non-aqueous electrolyte secondary battery |
| WO2018020896A1 (en) * | 2016-07-28 | 2018-02-01 | パナソニックＩｐマネジメント株式会社 | Nonaqueous electrolyte secondary battery |
| JPWO2019049479A1 (en) * | 2017-09-11 | 2020-10-22 | パナソニックＩｐマネジメント株式会社 | Rechargeable battery |
| JP6994664B2 (en) | 2017-09-11 | 2022-01-14 | パナソニックＩｐマネジメント株式会社 | Secondary battery |
| WO2019049479A1 (en) * | 2017-09-11 | 2019-03-14 | パナソニックＩｐマネジメント株式会社 | Secondary battery |
| EP3859820A4 (en) * | 2018-09-27 | 2022-06-15 | Zeon Corporation | Slurry for nonaqueous secondary battery adhesive layer, battery member for nonaqueous secondary battery with adhesive layer, method of manufacturing laminate for nonaqueous secondary battery, and method of manufacturing nonaqueous secondary battery |
| WO2020241410A1 (en) | 2019-05-28 | 2020-12-03 | 三洋電機株式会社 | Nonaqueous electrolyte secondary battery |
| JP2022539769A (en) * | 2019-06-28 | 2022-09-13 | 寧徳時代新能源科技股▲分▼有限公司 | Electrode sheet, electrochemical device and its device |
| EP3993110A4 (en) * | 2019-06-28 | 2023-08-02 | Contemporary Amperex Technology Co., Limited | Electrode sheet, electrochemical device and device thereof |
| JP7430737B2 (en) | 2019-06-28 | 2024-02-13 | 寧徳時代新能源科技股▲分▼有限公司 | Electrode sheets, electrochemical devices and their devices |
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