JP2000149997A - Nonaqueous electrolyte secondary battery and its manufacture - Google Patents

Nonaqueous electrolyte secondary battery and its manufacture

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Publication number
JP2000149997A
JP2000149997A JP10361021A JP36102198A JP2000149997A JP 2000149997 A JP2000149997 A JP 2000149997A JP 10361021 A JP10361021 A JP 10361021A JP 36102198 A JP36102198 A JP 36102198A JP 2000149997 A JP2000149997 A JP 2000149997A
Authority
JP
Japan
Prior art keywords
aqueous electrolyte
secondary battery
separator
negative electrode
electrolyte secondary
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP10361021A
Other languages
Japanese (ja)
Other versions
JP3471238B2 (en
Inventor
Norio Takami
則雄 高見
Hiroyuki Hasebe
裕之 長谷部
Takahisa Osaki
隆久 大崎
Motoi Kanda
基 神田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toshiba Corp
Original Assignee
Toshiba Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toshiba Corp filed Critical Toshiba Corp
Priority to JP36102198A priority Critical patent/JP3471238B2/en
Publication of JP2000149997A publication Critical patent/JP2000149997A/en
Application granted granted Critical
Publication of JP3471238B2 publication Critical patent/JP3471238B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

PROBLEM TO BE SOLVED: To provide a nonaqueous electrolyte secondary battery and its manufacturing method capable of having a thin structure of thickness not more than 3 mm, while maintaining an excellent capacity, cycle performance, large electric current discharging characteristic and low-temperature discharging characteristic. SOLUTION: In this nonaqueous electrolyte secondary battery including an electrode group 2 comprising a stack of a positive electrode 5, a negative electrode 8 and a separator 10 arranged therebetween, and a nonaqueous electrolytic solution, porous adhesion layers 9a, 9b are respectively interposed at least between the positive electrode 5 and the separator 10, and between the negative electrode 8 and the separator 10, while at least, one end of the separator 10 extends from the electrode 5 and the negative electrode 8.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明は、非水電解液二次電
池及び非水電解液二次電池の製造方法に係わる。The present invention relates to a non-aqueous electrolyte secondary battery and a method of manufacturing a non-aqueous electrolyte secondary battery.

【０００２】[0002]

【従来の技術】現在、携帯電話などの携帯機器向けの非
水電解液二次電池として、薄型リチウムイオン二次電池
が商品化されている。この電池は、正極にリチウムコバ
ルト酸化物（ＬｉＣｏＯ２）、負極に黒鉛質材料や炭素
質材料、電解液にリチウム塩を溶解した有機溶媒、セパ
レータに多孔質膜が用いられている。2. Description of the Related Art At present, a thin lithium ion secondary battery has been commercialized as a nonaqueous electrolyte secondary battery for portable equipment such as a mobile phone. This battery uses a lithium cobalt oxide (LiCoO 2 ) for a positive electrode, a graphite material or a carbonaceous material for a negative electrode, an organic solvent in which a lithium salt is dissolved in an electrolytic solution, and a porous film for a separator.

【０００３】携帯機器の薄型化に伴って電池の厚さを薄
くすることが要望されているものの、厚さ４ｍｍ以下の
薄型リチウムイオン二次電池の実用化は困難である。こ
のため、従来ポリマー電解質を用いたカードタイプのリ
チウム二次電池が提案され、実用化開発が進められてい
る。[0003] Although there is a demand for a reduction in the thickness of a battery along with a reduction in the thickness of a portable device, it is difficult to put a thin lithium ion secondary battery having a thickness of 4 mm or less into practical use. For this reason, a card-type lithium secondary battery using a polymer electrolyte has been conventionally proposed, and its practical development has been promoted.

【０００４】しかしながら、ポリマー電解質を用いたリ
チウム二次電池は、ポリマーに非水電解液が保持された
ゲル状ポリマーであるため、非水電解液を用いるリチウ
ム二次電池に比べて電極界面のインピーダンスが大き
く、かつリチウムイオン伝導度が低いという問題点があ
る。また、リチウムイオン移動度を高めるために厚さを
薄くすると、正負極の活物質量が減少するため、エネル
ギー密度が低下するという問題点を生じる。However, since a lithium secondary battery using a polymer electrolyte is a gel polymer in which a non-aqueous electrolyte is held in a polymer, the impedance at the electrode interface is higher than that of a lithium secondary battery using a non-aqueous electrolyte. And the lithium ion conductivity is low. In addition, when the thickness is reduced in order to increase the mobility of lithium ions, the amount of active materials of the positive and negative electrodes decreases, which causes a problem that the energy density decreases.

【０００５】従って、ポリマー電解質を用いたリチウム
二次電池は、非水電解液が溶液・液状の状態で含浸され
ている薄型リチウム二次電池に比べて体積エネルギー密
度及び大電流特性および低温特性が劣るという問題点が
ある。Accordingly, a lithium secondary battery using a polymer electrolyte has a higher volume energy density, a larger current characteristic, and a lower temperature characteristic than a thin lithium secondary battery in which a non-aqueous electrolyte is impregnated in a solution / liquid state. There is a problem that it is inferior.

【０００６】[0006]

【発明が解決しようとする課題】本発明の目的は、容
量、大電流特性、低温特性及びサイクル性能を満足しつ
つ薄型化を図ることが可能な非水電解液二次電池及びそ
の製造方法を提供しようとするものである。電極群に非
水電解液が溶液・液状の状態で含浸されている非水電解
液二次電池において、薄型化を図ることが可能で、容
量、大電流特性およびサイクル性能が向上された非水電
解液二次電池を提供しようとするものである。SUMMARY OF THE INVENTION An object of the present invention is to provide a non-aqueous electrolyte secondary battery capable of achieving a small thickness while satisfying capacity, large current characteristics, low-temperature characteristics and cycle performance, and a method of manufacturing the same. It is something to offer. In a non-aqueous electrolyte secondary battery in which the electrode group is impregnated with a non-aqueous electrolyte in a solution / liquid state, the non-aqueous electrolyte can be made thinner, and has improved capacity, large current characteristics and cycle performance. An object is to provide an electrolyte secondary battery.

【０００７】[0007]

【課題を解決するための手段】本発明は、正極と、負極
と、正極及び負極の間に配置されるセパレータが積層さ
れた電極群及び非水電解液を具備する非水電解液二次電
池において、少なくとも正極及びセパレータ間と、負極
及びセパレータ間に多孔質の接着層がそれぞれ介在さ
れ、かつセパレータの少なくとも一端が正極及び負極よ
り延出していることを特徴とする非水電解液二次電池で
ある。SUMMARY OF THE INVENTION The present invention provides a non-aqueous electrolyte secondary battery comprising a non-aqueous electrolyte and a positive electrode, a negative electrode, an electrode group in which a separator is interposed between the positive electrode and the negative electrode. Wherein a porous adhesive layer is interposed at least between the positive electrode and the separator, and between the negative electrode and the separator, and at least one end of the separator extends from the positive electrode and the negative electrode. It is.

【０００８】また本発明は、接着剤が溶解された溶液を
正極及び負極の片面もしくは両面に塗付する工程と、前
記正極の前記溶液が塗布された面と前記負極の前記溶液
が塗布された面の間にセパレータを配置し、積層物を作
製する工程と、前記積層物中の前記溶液に含まれる溶媒
を蒸発させる工程とを具備する方法により電極群を作製
することを特徴とする非水電解液二次電池の製造方法で
ある。Further, the present invention provides a step of applying a solution in which an adhesive is dissolved to one or both surfaces of a positive electrode and a negative electrode, and a step of applying the solution of the positive electrode and the solution of the negative electrode. Non-aqueous method characterized by producing a group of electrodes by a method comprising the steps of: placing a separator between surfaces, producing a laminate, and evaporating a solvent contained in the solution in the laminate. This is a method for manufacturing an electrolyte secondary battery.

【０００９】[0009]

【発明の実施の形態】以下、本発明に係わる非水電解液
二次電池（例えば、薄型リチウムイオン二次電池）を図
１及び図２を参照して詳細に説明する。図１は本発明に
係わる非水電解液二次電池（例えば、薄型リチウムイオ
ン二次電池）を示す断面図、図２は図１のＡ部を示す拡
大図である。DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a non-aqueous electrolyte secondary battery (for example, a thin lithium ion secondary battery) according to the present invention will be described in detail with reference to FIGS. FIG. 1 is a cross-sectional view showing a non-aqueous electrolyte secondary battery (for example, a thin lithium ion secondary battery) according to the present invention, and FIG. 2 is an enlarged view showing part A of FIG.

【００１０】図１に示すように、例えばラミネートフィ
ルムからなる外装材１は、電極群２を包囲している。電
極群２は、例えば多孔質導電性基板からなる集電体３に
正極層４が担持された構造を有する正極５と、例えば多
孔質導電性基板からなる集電体６に負極層７がそれぞれ
担持された構造を有する負極８と、正極層４及び負極層
７にそれぞれ接着された多孔質の接着層９ａ、９ｂと両
面に多孔質の接着層９ａ、９ｂが接着されているセパレ
ータ１０とから構成される。As shown in FIG. 1, an exterior material 1 made of, for example, a laminate film surrounds an electrode group 2. The electrode group 2 includes, for example, a positive electrode 5 having a structure in which a positive electrode layer 4 is supported on a current collector 3 formed of a porous conductive substrate, and a negative electrode layer 7 on a current collector 6 formed of, for example, a porous conductive substrate. A negative electrode 8 having a supported structure, a porous adhesive layers 9a and 9b bonded to the positive electrode layer 4 and the negative electrode layer 7, respectively, and a separator 10 having porous adhesive layers 9a and 9b bonded to both surfaces. Be composed.

【００１１】非水電解液は、外装材１内に収容されてい
る。帯状の正極リード１１は、一端が電極群２の正極集
電体５に接続され、かつ他端が外装材１から延出されて
いる。一方、帯状の負極リード１２は、一端が電極群２
の負極集電体７に接続され、かつ他端が外装材１から延
出されている。The non-aqueous electrolyte is contained in the outer package 1. One end of the strip-shaped positive electrode lead 11 is connected to the positive electrode current collector 5 of the electrode group 2, and the other end is extended from the exterior material 1. On the other hand, one end of the strip-shaped negative electrode lead 12 is
, And the other end extends from the exterior material 1.

【００１２】セパレータ１０は少なくとも一端が正極及
び負極より延出している。それにより、外部からの衝撃
が加わったり過充電時であっても短絡が生じにくく、安
全性に優れている。また、延出したセパレータにも接着
剤を保持していることが望ましい。それにより延出した
セパレータの強度はより強くなり、特に電池に外部から
の衝撃が加わったときの短絡がより生じにくくなる。さ
らに電池が１００℃以上の高温条件下にあったときもセ
パレータの収縮が抑制され、正極と負極の短絡を防止す
ることが出来、安全性が確保される。そのとき接着剤は
多孔質であることがより望ましい。At least one end of the separator 10 extends from the positive electrode and the negative electrode. Thereby, short circuit hardly occurs even when an external impact is applied or during overcharging, and the safety is excellent. It is desirable that the extended separator also holds the adhesive. As a result, the strength of the extended separator is further increased, and short-circuiting is less likely to occur particularly when an external impact is applied to the battery. Further, even when the battery is under a high temperature condition of 100 ° C. or more, the contraction of the separator is suppressed, and a short circuit between the positive electrode and the negative electrode can be prevented, thereby ensuring safety. At that time, the adhesive is more preferably porous.

【００１３】次に、正極５、負極８、セパレータ１０、
接着層９ａ、９ｂ及び非水電解液について詳しく説明す
る。Next, a positive electrode 5, a negative electrode 8, a separator 10,
The adhesive layers 9a and 9b and the non-aqueous electrolyte will be described in detail.

【００１４】１）正極 この正極５は、活物質を含む正極層４が集電体３の片面
もしくは両面に担持された構造を有する。1) Positive Electrode The positive electrode 5 has a structure in which a positive electrode layer 4 containing an active material is supported on one or both sides of a current collector 3.

【００１５】正極層は、正極活物質、さらには導電剤や
正極活物質粒子を結着する結着剤を含んでいてもよい。
正極５は、例えば、正極活物質に導電剤及び結着剤を適
当な溶媒に懸濁し、この懸濁物を集電体に塗布、乾燥し
て薄板状にすることにより作製される。The positive electrode layer may contain a positive electrode active material, a conductive agent and a binder for binding the positive electrode active material particles.
The positive electrode 5 is produced, for example, by suspending a conductive agent and a binder in a suitable solvent in a positive electrode active material, applying the suspension to a current collector, and drying the resultant to form a thin plate.

【００１６】正極活物質としては、種々の酸化物、例え
ば二酸化マンガン、リチウムマンガン複合酸化物、リチ
ウム含有ニッケル酸化物、リチウム含有コバルト化合
物、リチウム含有ニッケルコバルト酸化物、リチウム含
有鉄酸化物、リチウムを含むバナジウム酸化物や、二硫
化チタン、二硫化モリブデンなどのカルコゲン化合物な
どを挙げることができる。中でも、リチウム含有コバル
ト酸化物（例えば、ＬｉＣｏＯ２ ）、リチウム含有ニ
ッケルコバルト酸化物（例えば、ＬｉＮｉ０．８Ｃｏ
０．２Ｏ２ ）、リチウムマンガン複合酸化物（例え
ば、ＬｉＭｎ２Ｏ４ 、ＬｉＭｎＯ２ ）を用いると、高
電圧が得られるために好ましい。Examples of the positive electrode active material include various oxides such as manganese dioxide, lithium manganese composite oxide, lithium-containing nickel oxide, lithium-containing cobalt compound, lithium-containing nickel-cobalt oxide, lithium-containing iron oxide, and lithium. Vanadium oxides and chalcogen compounds such as titanium disulfide and molybdenum disulfide. Among them, lithium-containing cobalt oxides (for example, LiCoO 2 ), Lithium-containing nickel cobalt oxide (eg, LiNi 0.8 Co
0.2 O 2 ), Lithium manganese composite oxide (for example, LiMn 2 O 4 , LiMnO 2 ) Is preferable because a high voltage can be obtained.

【００１７】導電剤としては、例えばアセチレンブラッ
ク、カーボンブラック、黒鉛等を挙げることができる。Examples of the conductive agent include acetylene black, carbon black, graphite and the like.

【００１８】結着剤としては、例えばポリテトラフルオ
ロエチレン（ＰＴＦＥ）、ポリフッ化ビニリデン（ＰＶ
ｄＦ）、エチレン−プロピレン−ジエン共重合体（ＥＰ
ＤＭ）、スチレン−ブタジエンゴム（ＳＢＲ）等を用い
ることができる。Examples of the binder include polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PV).
dF), ethylene-propylene-diene copolymer (EP
DM), styrene-butadiene rubber (SBR), and the like.

【００１９】正極活物質、導電剤および結着剤の配合割
合は、正極活物質８０〜９５重量％、導電剤３〜２０重
量％、結着剤２〜７重量％の範囲にすることが好まし
い。集電体としては、多孔質構造の導電性基板か、ある
いは無孔の導電性基板を用いることができる。これら導
電性基板は、例えば、アルミニウム、ステンレス、また
はニッケルから形成することができる。The compounding ratio of the positive electrode active material, the conductive agent and the binder is preferably in the range of 80 to 95% by weight of the positive electrode active material, 3 to 20% by weight of the conductive agent, and 2 to 7% by weight of the binder. . As the current collector, a conductive substrate having a porous structure or a non-porous conductive substrate can be used. These conductive substrates can be formed from, for example, aluminum, stainless steel, or nickel.

【００２０】中でも、直径３ｍｍ以下の孔が１０ｃｍ２
当たり１個以上の割合で存在する二次元的な多孔質構
造を有する導電性基板を用いることが好ましい。すなわ
ち、導電性基板に開口された孔の直径が３ｍｍよりも大
きくなると、十分な正極強度が得られなくなる恐れがあ
る。一方、直径３ｍｍ以下の孔の存在割合が範囲よりも
少なくなると、電極群に非水電解液を均一に浸透させる
ことが困難になるため、十分なサイクル寿命が得られな
くなる恐れがある。孔の直径は、０．１〜１ｍｍの範囲
にすることがより好ましい。また、孔の存在割合は、１
０ｃｍ２ 当たり１０〜２０個の範囲にすることがより
好ましい。Among them, a hole having a diameter of 3 mm or less has a size of 10 cm 2.
It is preferable to use a conductive substrate having a two-dimensional porous structure existing at a ratio of one or more per unit. That is, if the diameter of the hole formed in the conductive substrate is larger than 3 mm, sufficient positive electrode strength may not be obtained. On the other hand, when the proportion of the holes having a diameter of 3 mm or less is smaller than the range, it becomes difficult to uniformly infiltrate the non-aqueous electrolyte into the electrode group, so that a sufficient cycle life may not be obtained. More preferably, the diameter of the holes is in the range of 0.1 to 1 mm. In addition, the existence ratio of holes is 1
0cm 2 More preferably, the number is in the range of 10 to 20 pieces.

【００２１】前述した直径３ｍｍ以下の孔が１０ｃｍ２
当たり１個以上の割合で存在する二次元的な多孔質構
造を有する導電性基板は、厚さを１５〜１００μｍの範
囲にすることが好ましい。厚さを１５μｍ未満にする
と、十分な正極強度が得られなくなる恐れがある。一
方、厚さが１００μｍを超えると、電池重量および電極
群の厚さが増加し、薄型二次電池の重量エネルギー密度
や、体積エネルギー密度を十分に高くすることが困難に
なる恐れがある。厚さのより好ましい範囲は、３０〜８
０μｍである。The above-mentioned hole having a diameter of 3 mm or less has a size of 10 cm 2.
It is preferable that the thickness of the conductive substrate having a two-dimensional porous structure existing at a ratio of one or more per unit is 15 to 100 μm. If the thickness is less than 15 μm, sufficient positive electrode strength may not be obtained. On the other hand, when the thickness exceeds 100 μm, the weight of the battery and the thickness of the electrode group increase, and it may be difficult to sufficiently increase the weight energy density and the volume energy density of the thin secondary battery. A more preferable range of the thickness is 30 to 8
0 μm.

【００２２】２）負極８ 負極は、負極層７が集電体６の片面もしくは両面に担持
された構造を有する。2) Negative Electrode 8 The negative electrode has a structure in which the negative electrode layer 7 is supported on one side or both sides of the current collector 6.

【００２３】負極８は、負極材料、さらには結着剤を含
んでいてもよい。負極材料として例えば、リチウムイオ
ンを吸蔵・放出する炭素質物と結着剤とを溶媒の存在下
で混練し、得られた懸濁物を集電体に塗布し、乾燥した
後、所望の圧力で１回プレスもしくは２〜５回多段階プ
レスすることにより作製することができる。The negative electrode 8 may contain a negative electrode material and a binder. As a negative electrode material, for example, a carbonaceous material that occludes and releases lithium ions and a binder are kneaded in the presence of a solvent, and the obtained suspension is applied to a current collector, dried, and then dried at a desired pressure. It can be produced by pressing once or multi-stage pressing 2 to 5 times.

【００２４】炭素質物としては、黒鉛、コークス、炭素
繊維、球状炭素などの黒鉛質材料もしくは炭素質材料、
熱硬化性樹脂、等方性ピッチ、メソフェーズピッチ、メ
ソフェーズピッチ系炭素繊維、メソフェーズ小球体など
（特に、メソフェーズピッチ系炭素繊維が好ましい）に
５００〜３０００℃で熱処理を施すことにより得られる
黒鉛質材料または炭素質材料等を挙げることができる。
中でも、熱処理の温度を２０００℃以上にすることによ
り得られ、（００２）面の面間隔ｄ００２ が０．３４
０ｎｍ以下である黒鉛結晶を有する黒鉛質材料を用いる
のが好ましい。このような黒鉛質材料を炭素質物として
含む負極を備えた非水電解液二次電池は、電池容量およ
び大電流特性を大幅に向上することができる。面間隔ｄ
００２は、０．３３６ｎｍ以下であることが更に好まし
い。Examples of the carbonaceous material include graphite materials such as graphite, coke, carbon fiber, and spherical carbon or carbonaceous materials;
A graphitic material obtained by subjecting a thermosetting resin, isotropic pitch, mesophase pitch, mesophase pitch-based carbon fiber, mesophase small spheres, and the like (particularly, mesophase pitch-based carbon fiber is preferable) to a heat treatment at 500 to 3000 ° C. Alternatively, a carbonaceous material or the like can be used.
Among them, obtained by the temperature of the heat treatment 2000 ° C. or more, (002) plane of the plane spacing d 002 Is 0.34
It is preferable to use a graphitic material having graphite crystals of 0 nm or less. A non-aqueous electrolyte secondary battery including a negative electrode containing such a graphite material as a carbonaceous material can significantly improve battery capacity and large current characteristics. Surface distance d
002 is more preferably 0.336 nm or less.

【００２５】結着剤としては、例えばポリテトラフルオ
ロエチレン（ＰＴＦＥ）、ポリフッ化ビニリデン（ＰＶ
ｄＦ）、エチレン−プロピレン−ジエン共重合体（ＥＰ
ＤＭ）、スチレン−ブタジエンゴム（ＳＢＲ）、カルボ
キシメチルセルロース（ＣＭＣ）等を用いることができ
る。As the binder, for example, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PV
dF), ethylene-propylene-diene copolymer (EP
DM), styrene-butadiene rubber (SBR), carboxymethyl cellulose (CMC) and the like can be used.

【００２６】炭素質物及び結着剤の配合割合は、炭素質
物９０〜９８重量％、結着剤２〜２０重量％の範囲であ
ることが好ましい。特に、炭素質物は負極を作製した状
態で５〜２０ｇ／ｍ２の範囲にすることが好ましい。The mixing ratio of the carbonaceous material and the binder is preferably in the range of 90 to 98% by weight of the carbonaceous material and 2 to 20% by weight of the binder. In particular, the carbonaceous material is preferably in the range of 5 to 20 g / m 2 in a state where the negative electrode is manufactured.

【００２７】集電体としては、多孔質構造の導電性基板
か、あるいは無孔の導電性基板を用いることができる。
これら導電性基板は、例えば、銅、ステンレス、または
ニッケルから形成することができる。As the current collector, a conductive substrate having a porous structure or a non-porous conductive substrate can be used.
These conductive substrates can be formed from, for example, copper, stainless steel, or nickel.

【００２８】中でも、直径３ｍｍ以下の孔が１０ｃｍ２
当たり１個以上の割合で存在する二次元的な多孔質構
造を有する導電性基板を用いることが好ましい。すなわ
ち、導電性基板の孔の直径が３ｍｍよりも大きくなる
と、十分な負極強度が得られなくなる恐れがある。一
方、直径３ｍｍ以下の孔の存在割合が範囲よりも少なく
なると、電極群に非水電解液を均一に浸透させることが
困難になるため、十分なサイクル寿命が得られなくなる
恐れがある。孔の直径は、０．１〜１ｍｍの範囲にする
ことがより好ましい。また、孔の存在割合は、１０ｃｍ
２ 当たり１０〜２０個の範囲にすることがより好まし
い。Among them, a hole having a diameter of 3 mm or less has a size of 10 cm 2.
It is preferable to use a conductive substrate having a two-dimensional porous structure existing at a ratio of one or more per unit. That is, if the diameter of the hole in the conductive substrate is larger than 3 mm, sufficient negative electrode strength may not be obtained. On the other hand, when the proportion of the holes having a diameter of 3 mm or less is smaller than the range, it becomes difficult to uniformly infiltrate the non-aqueous electrolyte into the electrode group, so that a sufficient cycle life may not be obtained. More preferably, the diameter of the holes is in the range of 0.1 to 1 mm. In addition, the existence ratio of holes is 10 cm
2 More preferably, the number is in the range of 10 to 20 pieces.

【００２９】前述した直径３ｍｍ以下の孔が１０ｃｍ２
当たり１個以上の割合で存在する二次元的な多孔質構
造を有する導電性基板は、厚さを１０〜５０μｍの範囲
にすることが好ましい。厚さを１０μｍ未満にすると、
十分な負極強度が得られなくなる恐れがある。一方、厚
さが５０μｍを超えると、電池重量および電極群の厚さ
が増加し、薄型二次電池の重量エネルギー密度や、体積
エネルギー密度を十分に高くすることが困難になる恐れ
がある。The above-mentioned hole having a diameter of 3 mm or less has a size of 10 cm 2.
It is preferable that the thickness of the conductive substrate having a two-dimensional porous structure existing at a ratio of one or more per unit is in the range of 10 to 50 μm. If the thickness is less than 10 μm,
There is a possibility that sufficient negative electrode strength cannot be obtained. On the other hand, when the thickness exceeds 50 μm, the weight of the battery and the thickness of the electrode group increase, and it may be difficult to sufficiently increase the weight energy density and the volume energy density of the thin secondary battery.

【００３０】負極材料としては、前述したリチウムイオ
ンを吸蔵・放出する炭素質物の他に、金属酸化物か、金
属硫化物か、もしくは金属窒化物を含むものや、リチウ
ム金属またはリチウム合金からなるものを用いることが
できる。As the negative electrode material, in addition to the above-mentioned carbonaceous materials that occlude and release lithium ions, those containing metal oxides, metal sulfides, or metal nitrides, and those made of lithium metal or lithium alloy Can be used.

【００３１】金属酸化物としては、例えば、スズ酸化
物、ケイ素酸化物、リチウムチタン酸化物、ニオブ酸化
物、タングステン酸化物等を挙げることができる。Examples of the metal oxide include tin oxide, silicon oxide, lithium titanium oxide, niobium oxide, and tungsten oxide.

【００３２】金属硫化物としては、例えば、スズ硫化
物、チタン硫化物等を挙げることができる。Examples of the metal sulfide include tin sulfide and titanium sulfide.

【００３３】金属窒化物としては、例えば、リチウムコ
バルト窒化物、リチウム鉄窒化物、リチウムマンガン窒
化物等を挙げることができる。Examples of the metal nitride include lithium cobalt nitride, lithium iron nitride, lithium manganese nitride and the like.

【００３４】リチウム合金としては、例えば、リチウム
アルミニウム合金、リチウムスズ合金、リチウム鉛合
金、リチウムケイ素合金等を挙げることができる。Examples of the lithium alloy include a lithium aluminum alloy, a lithium tin alloy, a lithium lead alloy, and a lithium silicon alloy.

【００３５】３）セパレータ１０ セパレータとしては、例えば、ポリエチレン、ポリプロ
ピレンまたはポリフッ化ビニリデン（ＰＶｄＦ）を含む
多孔質フィルム、合成樹脂製不織布等を用いることがで
きる。中でも、ポリエチレンか、あるいはポリプロピレ
ン、または両者からなる多孔質フィルムは、二次電池の
安全性を向上できるため、好ましい。3) Separator 10 As the separator, for example, a porous film containing polyethylene, polypropylene, or polyvinylidene fluoride (PVdF), a nonwoven fabric made of synthetic resin, or the like can be used. Among them, a porous film made of polyethylene, polypropylene, or both is preferable because the safety of the secondary battery can be improved.

【００３６】セパレータの厚さは、３０μｍ以下にする
ことが好ましい。厚さが３０μｍを越えると、正負極間
の距離が大きくなって内部抵抗が大きくなる恐れがあ
る。また、厚さの下限値は、５μｍにすることが好まし
い。厚さを５μｍ未満にすると、セパレータの強度が著
しく低下して内部ショートが生じやすくなる恐れがあ
る。厚さの上限値は、２５μｍにすることがより好まし
く、また、下限値は１０μｍにすることがより好まし
い。The separator preferably has a thickness of 30 μm or less. If the thickness exceeds 30 μm, the distance between the positive electrode and the negative electrode may increase, and the internal resistance may increase. The lower limit of the thickness is preferably set to 5 μm. If the thickness is less than 5 μm, the strength of the separator may be significantly reduced and an internal short circuit may easily occur. The upper limit of the thickness is more preferably 25 μm, and the lower limit is more preferably 10 μm.

【００３７】セパレータは、１２０℃の条件で１時間の
存在したときの熱収縮率が２０％以下であることが好ま
しい。熱収縮率が２０％を超えると、正負極およびセパ
レータの接着強度を十分なものにすることが困難になる
恐れがある。熱収縮率は、１５％以下にすることがより
好ましい。It is preferable that the separator has a heat shrinkage of 20% or less when the separator is present at 120 ° C. for one hour. If the heat shrinkage exceeds 20%, it may be difficult to increase the adhesive strength between the positive and negative electrodes and the separator. More preferably, the heat shrinkage is 15% or less.

【００３８】セパレータは、多孔度が３０〜６０％の範
囲であることが好ましい。これは次のような理由による
ものである。多孔度を３０％未満にすると、セパレータ
において高い電解液保持性を得ることが困難になる恐れ
がある。一方、多孔度が６０％を超えると、十分なセパ
レータ強度を得られなくなる恐れがある。多孔度のより
好ましい範囲は、３５〜５０％である。The porosity of the separator is preferably in the range of 30 to 60%. This is due to the following reasons. If the porosity is less than 30%, it may be difficult to obtain high electrolyte retention in the separator. On the other hand, if the porosity exceeds 60%, sufficient separator strength may not be obtained. A more preferred range of porosity is 35-50%.

【００３９】セパレータは、空気透過率が６００秒／１
００ｃｍ３ 以下であることが好ましい。空気透過率が
６００秒／１００ｃｍ３ を超えると、セパレータにお
いて高いリチウムイオン移動度を得ることが困難になる
恐れがある。また、空気透過率の下限値は、１００秒／
１００ｃｍ３ にすることが好ましい。空気透過率を１
００秒／１００ｃｍ３ 未満にすると、十分なセパレー
タ強度を得られなくなる恐れがあるからである。空気透
過率の上限値は５００秒／１００ｃｍ３ にすることよ
り好ましく、また、下限値は１５０秒／１００ｃｍ３
にすることより好ましい。The separator has an air permeability of 600 seconds / 1.
00cm 3 The following is preferred. Air permeability is 600 seconds / 100cm 3 When it exceeds, it may be difficult to obtain high lithium ion mobility in the separator. The lower limit of the air permeability is 100 seconds /
100cm 3 Is preferable. 1 air permeability
00 seconds / 100cm 3 If it is less than this, there is a possibility that sufficient separator strength may not be obtained. The upper limit of the air permeability is 500 seconds / 100 cm 3 More preferably, the lower limit is 150 seconds / 100 cm 3
Is more preferable.

【００４０】本発明においてはセパレータ１０は少なく
とも一端が正極及び負極より延出していることを特徴と
している。延出されるセパレータは前記負極端より０．
２５ｍｍ以上延出されることが望ましい。少なすぎると
内部ショートが生じ易くなる。また、セパレータの延出
した部分にも多孔質の接着層が存在していることが望ま
しい。セパレータは全ての辺か延出していることが内部
ショートを防止する点で望ましい。The present invention is characterized in that at least one end of the separator 10 extends from the positive electrode and the negative electrode. The extended separator is 0.1 mm from the negative electrode end.
It is desirable that the extension is 25 mm or more. If the amount is too small, an internal short circuit is likely to occur. In addition, it is desirable that a porous adhesive layer also exists in the extended portion of the separator. It is desirable that the separator extends from all sides in order to prevent internal short circuit.

【００４１】４）多孔質の接着層９ａ、９ｂ この多孔質の接着層９ａ、９ｂは非水電解液に溶解せ
ず、また非水電解液を保持した状態で高い接着性を維持
できる高分子材料から形成されていることが望ましい。
さらにかかる高分子材料はリチウムイオン伝導性が高い
となお好ましい。具体的な高分子材料はポリアクリロニ
トリル（ＰＡＮ）、ポリアクリレート（ＰＭＭＡ）、ポ
リフッ化ビニリデン（ＰＶｄＦ）、ポリ塩化ビニル（Ｐ
ＶＣ）、またはポリエチレンオキサイド（ＰＥＯ）等を
挙げることができる。特に、ポリフッ化ビニリデン（Ｐ
ＶｄＦ）が好ましい。ポリフッ化ビニリデン（ＰＶｄ
Ｆ）は、非水電解液を保持することができ、非水電解液
を含むと一部ゲル化を生じるため、正極中のイオン伝導
性をより向上することができる。4) Porous Adhesive Layers 9a and 9b The porous adhesive layers 9a and 9b do not dissolve in the non-aqueous electrolyte, and can maintain high adhesiveness while holding the non-aqueous electrolyte. Desirably, it is formed from a material.
Further, it is more preferable that such a polymer material has high lithium ion conductivity. Specific polymer materials are polyacrylonitrile (PAN), polyacrylate (PMMA), polyvinylidene fluoride (PVdF), polyvinyl chloride (P
VC) or polyethylene oxide (PEO). In particular, polyvinylidene fluoride (P
VdF) is preferred. Polyvinylidene fluoride (PVd
F) can hold a non-aqueous electrolyte, and if it contains a non-aqueous electrolyte, gelation occurs partially, so that the ionic conductivity in the positive electrode can be further improved.

【００４２】５）非水電解液 非水電解液は、非水溶媒に電解質を溶解することにより
調製される液体状電解液である。5) Non-aqueous electrolyte The non-aqueous electrolyte is a liquid electrolyte prepared by dissolving an electrolyte in a non-aqueous solvent.

【００４３】非水溶媒としては、リチウム二次電池の溶
媒として公知の非水溶媒を用いることができ、特に限定
はされないが、プロピレンカーボネート（ＰＣ）やエチ
レンカーボネート（ＥＣ）とＰＣやＥＣより低粘度であ
り且つドナー数が１８以下である１種以上の非水溶媒
（以下第２溶媒と称す）との混合溶媒を主体とする非水
溶媒を用いることが好ましい。As the non-aqueous solvent, a known non-aqueous solvent as a solvent for a lithium secondary battery can be used, and is not particularly limited. However, propylene carbonate (PC) or ethylene carbonate (EC) is lower than PC or EC. It is preferable to use a non-aqueous solvent mainly composed of a mixed solvent with one or more non-aqueous solvents having viscosity and a donor number of 18 or less (hereinafter, referred to as a second solvent).

【００４４】第２溶媒としては、例えば鎖状カーボンが
好ましく、中でもジメチルカーボネート（ＤＭＣ）、メ
チルエチルカーボネート（ＭＥＣ）、ジエチルカーボネ
ート（ＤＥＣ）、プロピオン酸エチル、プロピオン酸メ
チル、γ−ブチロラクトン（γ−ＢＬ）、アセトニトリ
ル（ＡＮ）、酢酸エチル（ＥＡ）、トルエン、キシレン
または、酢酸メチル（ＭＡ）などが挙げられる。これら
の第２溶媒は、単独または２種以上の混合物の形態で用
いることができる。特に、第２溶媒はドナー数が１６．
５以下であることがより好ましい。As the second solvent, for example, chain carbon is preferable. Among them, dimethyl carbonate (DMC), methyl ethyl carbonate (MEC), diethyl carbonate (DEC), ethyl propionate, methyl propionate, γ-butyrolactone (γ- BL), acetonitrile (AN), ethyl acetate (EA), toluene, xylene or methyl acetate (MA). These second solvents can be used alone or in the form of a mixture of two or more. In particular, the second solvent has a donor number of 16.
More preferably, it is 5 or less.

【００４５】第２溶媒の粘度は、２５℃において２８ｍ
ｐ以下であることが好ましい。混合溶媒中のエチレンカ
ーボネートまたはプロピレンカーボネートの配合量は、
体積比率で１０〜８０％であることが好ましい。より好
ましいエチレンカーボネートまたはプロピレンカーボネ
ートの配合量は体積比率で２０〜７５％である。The viscosity of the second solvent is 28 m at 25 ° C.
It is preferably at most p. The blending amount of ethylene carbonate or propylene carbonate in the mixed solvent,
The volume ratio is preferably 10 to 80%. A more preferred blending amount of ethylene carbonate or propylene carbonate is 20 to 75% by volume.

【００４６】混合溶媒のより好ましい組成は、ＥＣとＭ
ＥＣ、ＥＣとＰＣとＭＥＣ、ＥＣとＭＥＣとＤＥＣ、Ｅ
ＣとＭＥＣとＤＭＣ、ＥＣとＭＥＣとＰＣとＤＥＣの混
合溶媒で、ＭＥＣの体積比率は３０〜８０％とすること
が好ましい。より好ましいＭＥＣの体積比率は、４０〜
７０％の範囲である。The more preferable composition of the mixed solvent is EC and M
EC, EC and PC and MEC, EC and MEC and DEC, E
In a mixed solvent of C, MEC, and DMC, and EC, MEC, PC, and DEC, the volume ratio of MEC is preferably 30 to 80%. A more preferred volume ratio of MEC is 40 to
It is in the range of 70%.

【００４７】非水電解液に含まれる電解質としては、例
えば過塩素酸リチウム（ＬｉＣｌＯ ４）、六フッ化リン
酸リチウム（ＬｉＰＦ６）、ホウフッ化リチウム（Ｌｉ
ＢＦ ４）、六フッ化砒素リチウム（ＬｉＡｓＦ６）、ト
リフルオロメタスルホン酸リチウム（ＬｉＣＦ３Ｓ
Ｏ３）、ビストリフルオロメチルスルホニルイミドリチ
ウム［ＬｉＮ（ＣＦ３ＳＯ２）２］などのリチウム塩
（電解質）が挙げられる。中でもＬｉＰＦ６、ＬｉＢＦ
４を用いるのが好ましい。Examples of the electrolyte contained in the non-aqueous electrolyte include:
For example, lithium perchlorate (LiClO 4), Phosphorus hexafluoride
Lithium oxide (LiPF6), Lithium borofluoride (Li
BF 4), Lithium arsenic hexafluoride (LiAsF)6), To
Lithium trifluorometasulfonate (LiCF3S
O3), Bistrifluoromethylsulfonyl imidolithic
[LiN (CF3SO2)2] And other lithium salts
(Electrolyte). Among them, LiPF6, LiBF
4It is preferable to use

【００４８】電解質の非水溶媒に対する溶解量は、０．
５〜２．０モル／１とすることが望ましい。The amount of the electrolyte dissolved in the non-aqueous solvent is 0.1.
It is desirable to set it as 5 to 2.0 mol / 1.

【００４９】非水電解液の量は、電池単位容量１００ｍ
Ａｈ当たり０．２〜０．６ｇにすることが好ましい。こ
れは次のような理由によるものである。非水電解液量を
０．２ｇ／１００ｍＡｈ未満にすると、正極と負極のイ
オン伝導度を十分に保つことができなくなる恐れがあ
る。一方、非水電解液量が０．６ｇ／１００ｍＡｈを超
えると、電解液量が多量になってフィルム状外装材によ
る封止が困難になる恐れがある。非水電解液量のより好
ましい範囲は、０．４〜０．５５ｇ／１００ｍＡｈであ
る。The amount of the non-aqueous electrolyte is 100 m
It is preferable to set the amount to 0.2 to 0.6 g per Ah. This is due to the following reasons. If the amount of the non-aqueous electrolyte is less than 0.2 g / 100 mAh, the ion conductivity of the positive electrode and the negative electrode may not be able to be sufficiently maintained. On the other hand, if the amount of the non-aqueous electrolyte exceeds 0.6 g / 100 mAh, the amount of the electrolyte may become large and it may be difficult to seal with the film-shaped exterior material. A more preferable range of the amount of the non-aqueous electrolyte is 0.4 to 0.55 g / 100 mAh.

【００５０】６）外装材１ この外装材１は、例えば、可撓性を有する合成樹脂や金
属からなる薄膜を用いることができる。特に非水電解液
系電池の場合には合成樹脂からなる層にアルミニウム等
のバリア層を挿入したラミネート膜（多層膜）が好まし
い。アルミの層を含ませることにより、特に非水電解質
電池の場合、電解質への水分の混入を防止できるため電
池寿命を長くすることが可能となることから好ましい。6) Exterior Material 1 As the exterior material 1, for example, a thin film made of a flexible synthetic resin or metal can be used. In particular, in the case of a nonaqueous electrolyte battery, a laminate film (multilayer film) in which a barrier layer made of aluminum or the like is inserted in a layer made of a synthetic resin is preferable. It is preferable to include an aluminum layer, particularly in the case of a non-aqueous electrolyte battery, since it is possible to prevent water from being mixed into the electrolyte and to extend the battery life.

【００５１】外装材の厚さは５０〜３００μｍの範囲内
であることが好ましい。薄すぎると変形や破損し易くな
り、厚すぎると薄型化の効果が小さくなる。The thickness of the exterior material is preferably in the range of 50 to 300 μm. If it is too thin, it will be easily deformed or damaged, and if it is too thick, the effect of thinning will be reduced.

【００５２】本発明に係る非水電解液二次電池（例えば
前述した図１，２に示す構造を有する薄型リチウムイオ
ン二次電池の製造方法）の製造方法には以下の２種の製
造方法が挙げられる。ただし本発明に係る非水電解液二
次電池の製造方法は本発明の範囲にあるものであれば以
下の形態に限定されるものではない。The following two types of manufacturing methods are used for manufacturing the non-aqueous electrolyte secondary battery according to the present invention (for example, a method for manufacturing a thin lithium ion secondary battery having the structure shown in FIGS. 1 and 2). No. However, the method for producing a nonaqueous electrolyte secondary battery according to the present invention is not limited to the following embodiments as long as it is within the scope of the present invention.

【００５３】＜第１の製造方法＞ （第１工程）まず、正極及び負極の間にセパレータとし
て多孔質シートを介在させて電極群を作製する。<First Manufacturing Method> (First Step) First, an electrode group is manufactured by interposing a porous sheet as a separator between a positive electrode and a negative electrode.

【００５４】前記正極は、例えば、正極活物質に導電剤
および結着剤を適当な溶媒に懸濁し、この懸濁物を集電
体に塗布、乾燥して薄板状にすることにより作製され
る。前記正極活物質、導電剤、結着剤及び集電体として
は、前述した（１）正極の欄で説明したのと同様なもの
を挙げることができる。The positive electrode is manufactured by, for example, suspending a conductive agent and a binder in a positive electrode active material in an appropriate solvent, applying the suspension to a current collector, and drying the resultant to form a thin plate. . Examples of the positive electrode active material, the conductive agent, the binder, and the current collector include those similar to those described in the section of (1) Positive electrode described above.

【００５５】前記負極は、例えば、リチウムイオンを吸
蔵・放出する炭素質物等の負極材料と結着剤とを溶媒の
存在下で混練し、得られた懸濁物を集電体に塗布し、乾
燥した後、所望の圧力で１回プレスもしくは２〜５回多
段階プレスすることにより作製される。For the negative electrode, for example, a negative electrode material such as a carbonaceous material that occludes / releases lithium ions and a binder are kneaded in the presence of a solvent, and the resulting suspension is applied to a current collector. After drying, it is produced by pressing once at a desired pressure or multi-stage pressing 2 to 5 times.

【００５６】前記炭素質物、結着剤及び集電体として
は、前述した（２）負極の欄で説明したのと同様なもの
を挙げることができる。The carbonaceous material, the binder and the current collector may be the same as those described in the section of (2) Negative electrode.

【００５７】前記セパレータの多孔質シートとしては、
前述した（３）セパレータの欄で説明したのと同様なも
のを用いることができる。 （第２工程）袋状に加工された外装材内に前記電極群を
積層面が開口部から収納する。溶媒に接着剤を溶解させ
ることにより得られた溶液を開口部から前記外装材内の
電極群に注入し、前記溶液を前記電極群に含浸させる。As the porous sheet of the separator,
The same one as described in the section of (3) Separator described above can be used. (Second step) The above-mentioned electrode group is housed through an opening in an exterior material processed into a bag shape. A solution obtained by dissolving the adhesive in a solvent is injected into an electrode group in the exterior material through an opening, and the solution is impregnated into the electrode group.

【００５８】前記外装材としては、前述した（７）外装
材の欄で説明したのと同様なものを挙げることができ
る。Examples of the exterior material include those similar to those described in the section of (7) Exterior material above.

【００５９】前記接着剤としては、前述した（４）多孔
質の接着層の欄で説明した高分子材料と同様なものを挙
げることができる。特に、ポリフッ化ビニリデン（ＰＶ
ｄＦ）が好ましい。Examples of the adhesive include those similar to the polymer materials described in the section of (4) Porous adhesive layer described above. In particular, polyvinylidene fluoride (PV
dF) is preferred.

【００６０】前記溶媒には、沸点が２００℃以下の有機
溶媒を用いることが望ましい。かかる有機溶媒として
は、例えば、ジメチルフォルムアミド（沸点１５３℃）
を挙げることができる。有機溶媒の沸点が２００℃を越
えると、後述する真空乾燥の温度を１００℃以下にした
際、乾燥時間が長く掛かる恐れがある。また、有機溶媒
の沸点の下限値は、５０℃にすることが好ましい。有機
溶媒の沸点を５０℃未満にすると、前記溶液を電極群に
注入している間に前記有機溶媒が蒸発してしまう恐れが
ある。沸点の上限値は、１８０℃にすることがさらに好
ましく、また、沸点の下限値は１００℃にすることがさ
らに好ましい。It is desirable to use an organic solvent having a boiling point of 200 ° C. or less as the solvent. Examples of such an organic solvent include dimethylformamide (boiling point: 153 ° C.)
Can be mentioned. When the boiling point of the organic solvent exceeds 200 ° C., when the temperature for vacuum drying described below is set to 100 ° C. or lower, the drying time may take a long time. The lower limit of the boiling point of the organic solvent is preferably set to 50 ° C. If the boiling point of the organic solvent is lower than 50 ° C., the organic solvent may evaporate while the solution is being injected into the electrode group. The upper limit of the boiling point is more preferably 180 ° C, and the lower limit of the boiling point is more preferably 100 ° C.

【００６１】前記溶液中の接着剤の濃度は、０．０５〜
２．５重量％の範囲にすることが好ましい。これは次の
ような理由によるものである。前記濃度を０．０５重量
％未満にすると、正負極及びセパレータを十分な強度で
接着することが困難になる恐れがある。一方、前記濃度
が２．５重量％を越えると、非水電解液を保持できるだ
けの十分な多孔度を得ることが困難になって電極の界面
インピーダンスが著しく大きくなる恐れがある。界面イ
ンピーダンスが増大すると、容量及び大電流放電特性が
大幅に低下する。濃度のより好ましい範囲は、０．１〜
１．５重量％である。The concentration of the adhesive in the solution is 0.05 to
It is preferred to be in the range of 2.5% by weight. This is due to the following reasons. If the concentration is less than 0.05% by weight, it may be difficult to bond the positive and negative electrodes and the separator with sufficient strength. On the other hand, if the concentration exceeds 2.5% by weight, it is difficult to obtain sufficient porosity to hold the non-aqueous electrolyte, and the interface impedance of the electrode may be significantly increased. When the interface impedance increases, the capacity and the large-current discharge characteristics are significantly reduced. A more preferable range of the concentration is 0.1 to
1.5% by weight.

【００６２】前記溶液の注入量は、前記溶液の接着剤の
濃度が０．１〜２．５重量％である場合、電池容量１０
０ｍＡｈ当たり０．１〜２ｍｌの範囲にすることが好ま
しい。これは次のような理由によるものである。前記注
入量を０．１ｍｌ未満にすると、正極、負極及びセパレ
ータの密着性を十分に高めることが困難になる恐れがあ
る。一方、前記注入量が２ｍｌを越えると、二次電池の
リチウムイオン伝導度の低下や、内部抵抗の上昇を招く
恐れがあり、放電容量、大電流放電特性及び充放電サイ
クル特性を改善することが困難になる恐れがある。前記
注入量のより好ましい範囲は、電池容量１００ｍＡｈ当
たり０．１５〜１ｍｌである。 （第３工程）前記電極群に真空乾燥を施すことにより前
記溶液中の溶媒を蒸発させ、前記正極、負極及びセパレ
ータ間に多孔質の接着剤層を形成できる。また、正極、
負極及びセパレータ間の微細な空隙内に接着性を有する
高分子を存在せしめる。また、セパレータの延出部分に
もまた多孔質の接着剤層を形成できる。また、この真空
乾燥により前記電極群中に含まれる水分の除去を同時に
行うことができる。When the concentration of the adhesive in the solution is 0.1 to 2.5% by weight, the battery capacity is 10
It is preferable to set the range of 0.1 to 2 ml per 0 mAh. This is due to the following reasons. If the injection amount is less than 0.1 ml, it may be difficult to sufficiently increase the adhesion between the positive electrode, the negative electrode, and the separator. On the other hand, if the injection amount exceeds 2 ml, the lithium ion conductivity of the secondary battery may decrease, or the internal resistance may increase, and the discharge capacity, large current discharge characteristics, and charge / discharge cycle characteristics may be improved. It can be difficult. A more preferable range of the injection amount is 0.15 to 1 ml per 100 mAh of battery capacity. (Third step) By subjecting the electrode group to vacuum drying, the solvent in the solution is evaporated, and a porous adhesive layer can be formed between the positive electrode, the negative electrode and the separator. Also, the positive electrode,
An adhesive polymer is present in the minute gap between the negative electrode and the separator. Also, a porous adhesive layer can be formed on the extended portion of the separator. In addition, the moisture contained in the electrode group can be simultaneously removed by the vacuum drying.

【００６３】なお、前記多孔質な接着剤層は、微量の溶
媒を含むことを許容する。Note that the porous adhesive layer is allowed to contain a trace amount of solvent.

【００６４】前記真空乾燥は、１００℃以下で行うこと
が好ましい。これは次のような理由によるものである。
真空乾燥の温度が１００℃を越えると、前記セパレータ
が大幅に熱収縮する恐れがある。熱収縮が大きくなる
と、セパレータが反るため、正極、負極及びセパレータ
を強固に接着することが困難になる。また、前述した熱
収縮は、ポリエチレンまたはポリプロピレンを含む多孔
質フィルムをセパレータとして用いる場合に顕著に生じ
やすい。真空乾燥の温度が低くなるほどセパレータの熱
収縮を抑制できるものの、真空乾燥の温度を４０℃未満
にすると、十分に溶媒を蒸発させることが困難になる恐
れがある。このため、真空乾燥温度は、４０〜１００℃
にすることがより好ましい。 （第４工程）前記外装材内の電極群に非水電解液を注入
した後、前記外装材の開口部を封止することにより薄型
非水電解液二次電池を組み立てる。The vacuum drying is preferably performed at 100 ° C. or lower. This is due to the following reasons.
If the temperature of the vacuum drying exceeds 100 ° C., the separator may be significantly shrunk by heat. When the heat shrinkage becomes large, the separator warps, and it becomes difficult to firmly bond the positive electrode, the negative electrode, and the separator. Further, the above-mentioned heat shrinkage tends to occur remarkably when a porous film containing polyethylene or polypropylene is used as a separator. Although the heat shrinkage of the separator can be suppressed as the vacuum drying temperature becomes lower, if the vacuum drying temperature is lower than 40 ° C., it may be difficult to sufficiently evaporate the solvent. For this reason, the vacuum drying temperature is 40 to 100 ° C.
Is more preferable. (Fourth step) After injecting the non-aqueous electrolyte into the electrode group in the exterior material, the opening of the exterior material is sealed to assemble a thin non-aqueous electrolyte secondary battery.

【００６５】前記非水電解液としては、前述した（５）
非水電解液の欄で説明したものと同様なものを用いるこ
とができる。As the non-aqueous electrolyte, the aforementioned (5)
The same one as described in the section of the non-aqueous electrolyte can be used.

【００６６】前述した製造方法においては、接着剤が溶
解された溶液の注入を外装材に電極群を収納してから行
ったが、外装材に収納せずに注入を行っても良い。この
場合、まず、正極と負極の間にセパレータを介在させて
電極群を作製する。前記電極群に前記溶液を含浸させた
後、前記電極群に真空乾燥を施すことにより前記溶液の
溶媒を蒸発させ、前記正極、負極及びセパレータの間に
多孔質の接着剤層を存在せしめる。このような電極群を
外装材に収納した後、非水電解液を注入し、封口等を行
うことにより薄型の非水電解液二次電池を製造すること
ができる。収納前に電極群外周に接着剤を塗布してもよ
い。それにより電極群と外装材との間に接着がなされ
る。 ＜第２の製造方法＞ （第１工程）まず、正極、負極及びセパレータを準備す
る。正極、負極、セパレータについては第１製造方法の
第１工程と同様に得ることができる。 （第２工程）接着剤を溶媒に溶解させることにより得ら
れた溶液を正極の正極層及び負極の負極層表面に塗布す
る。前記溶液が塗布された正負極層の間にセパレータを
配置し、積層物を作製する。In the above-described manufacturing method, the solution in which the adhesive is dissolved is injected after the electrode group is housed in the exterior material, but the solution may be injected without being housed in the exterior material. In this case, first, an electrode group is prepared by interposing a separator between the positive electrode and the negative electrode. After the electrode group is impregnated with the solution, the solvent of the solution is evaporated by subjecting the electrode group to vacuum drying, thereby leaving a porous adhesive layer between the positive electrode, the negative electrode, and the separator. After storing such an electrode group in an exterior material, a nonaqueous electrolyte solution is injected, and sealing is performed. Thus, a thin nonaqueous electrolyte secondary battery can be manufactured. An adhesive may be applied to the outer periphery of the electrode group before storage. As a result, adhesion is made between the electrode group and the exterior material. <Second Manufacturing Method> (First Step) First, a positive electrode, a negative electrode, and a separator are prepared. The positive electrode, the negative electrode, and the separator can be obtained in the same manner as in the first step of the first manufacturing method. (Second step) A solution obtained by dissolving the adhesive in a solvent is applied to the surfaces of the positive electrode layer of the positive electrode and the negative electrode layer of the negative electrode. A separator is arranged between the positive and negative electrode layers to which the solution has been applied, to produce a laminate.

【００６７】接着剤及び溶媒は、第１の製造方法の第２
工程の欄で説明したのと同様のものを用いればよい。The adhesive and the solvent are used in the second method of the first manufacturing method.
The same one as described in the step section may be used.

【００６８】前記溶液中の接着剤の濃度は、０．１〜５
重量％の範囲にすることが好ましい。これは次のような
理由によるものである。前記濃度を０．１重量％未満に
すると、正負極及びセパレータを十分な強度で接着する
ことが困難になる恐れがある。一方、前記濃度が５重量
％を越えると、非水電解液を保持できるだけの十分な多
孔度を得ることが困難になって電極の界面インピーダン
スが著しく大きくなる恐れがある。界面インピーダンス
が増大すると、容量及び大電流放電特性が大幅に低下す
る。濃度のより好ましい範囲は、０．２〜２重量％であ
る。 （第３工程）常圧または減圧下において前記積層物中の
前記溶液に含まれる溶媒を真空乾燥させることにより前
記正負極層とセパレータの間に多孔質の接着層を形成
し、電極群を得、前記電極群を袋状に加工した外装材内
に収納する。なお電極群は先に外装材内に収納された
後、真空乾燥を行ってもよい。収納前に電極群外周に接
着剤を塗布してもよい。それにより電極群と外装材との
間に接着がなされる。The concentration of the adhesive in the solution is 0.1 to 5
It is preferred to be in the range of weight%. This is due to the following reasons. If the concentration is less than 0.1% by weight, it may be difficult to bond the positive and negative electrodes and the separator with sufficient strength. On the other hand, if the concentration exceeds 5% by weight, it is difficult to obtain sufficient porosity to hold the non-aqueous electrolyte, and the interface impedance of the electrode may be significantly increased. When the interface impedance increases, the capacity and the large-current discharge characteristics are significantly reduced. A more preferred range of the concentration is 0.2 to 2% by weight. (Third step) A solvent contained in the solution in the laminate is vacuum-dried under normal pressure or reduced pressure to form a porous adhesive layer between the positive and negative electrode layers and the separator, thereby obtaining an electrode group. The electrode group is housed in a bag-shaped exterior material. The electrode group may be vacuum-dried after being stored in the exterior material first. An adhesive may be applied to the outer periphery of the electrode group before storage. As a result, adhesion is made between the electrode group and the exterior material.

【００６９】また、外装材としては、前述した（６）外
装材の欄で説明したのと同様なものを挙げることができ
る。Examples of the exterior material include those similar to those described in the section of (6) Exterior material described above.

【００７０】真空乾燥の条件は第１の製造方法の第３工
程の欄に記載した条件であればよい。 （第４工程）外装材内の電極群に非水電解液を注入した
後、外装材の開口部を封止することにより薄型非水電解
液二次電池を製造する。The conditions for the vacuum drying may be the conditions described in the column of the third step of the first manufacturing method. (Fourth Step) A non-aqueous electrolyte secondary battery is manufactured by injecting the non-aqueous electrolyte into the electrode group in the exterior material and then sealing the opening of the exterior material.

【００７１】非水電解液としては、前述した（５）非水
電解液の欄で説明したものと同様なものを用いることが
できる。As the non-aqueous electrolyte, those similar to those described in the section of (5) Non-aqueous electrolyte described above can be used.

【００７２】本発明においては、上記第１の製造方法に
よれば、セパレータの延出部分にもまた多孔質の接着剤
層を容易に形成できるためより好ましい。In the present invention, the first manufacturing method is more preferable because a porous adhesive layer can be easily formed also on the extended portion of the separator.

【００７３】[0073]

【実施例】以下、本発明の実施例を前述した図面を参照
して詳細に説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described below in detail with reference to the drawings.

【００７４】実施例１ ＜正極の作製＞まず、リチウムコバルト酸化物（Ｌｉｘ
ＣｏＯ２；但し、Ｘは０≦Ｘ≦１である）粉末９１重量
％をアセチレンブラック３．５重量％、グラファイト
３．５重量％及びエチレンプロピレンジエンモノマ粉末
２重量％とトルエンを加えて共に混合し、厚さが１５μ
ｍのアルミニウム箔からなる集電体の両面に塗布した
後、プレスすることにより電極密度が３ｇ／ｃｍ３で、
正極層が集電体の両面に担持された構造の正極を作製し
た。正極の大きさは縦が４５ｍｍ、横が７５ｍｍであっ
た。 ＜負極の作製＞炭素質材料として３０００℃で熱処理し
たメソフェーズピッチ系炭素繊維（繊維径が８μｍ、平
均繊維長が２０μｍ、平均面間隔（ｄ００２）が０．３
３６０ｎｍの粉末を９３重量％と、結着剤としてポリフ
ッ化ビニリデン（ＰＶｄＦ）７重量％とを混合し、これ
を厚さが１５μｍの銅箔らなる集電体の片面に塗布し、
乾燥し、プレスすることにより電極密度が１．３ｇ／ｃ
ｍ３で、負極層が集電体の片面に担持された構造の負極
を作製した。負極の大きさは縦が４６ｍｍ、横が７６ｍ
ｍであった。 ＜セパレータ＞厚さが２５μｍで、１２０℃、１時間で
の熱収縮が２０％で、多孔度が５０％のポリエチレン製
多孔質フィルムからなるセパレータを用意した。セパレ
ータの大きさは縦が４８ｍｍ、横が７８ｍｍとした。こ
の大きさは正極及び負極と積層したときに、４辺がすべ
て正極及び負極から延出する長さであり、正極の端から
それぞれ１．５ｍｍ幅、負極からそれぞれ１ｍｍの幅で
はみだす大きさである。 ＜電極群の作製＞接着剤としてポリアクリロニトリル
（ＰＡＮ）をジメチルフォルムアミド（沸点が１５３
℃）溶液に１重量％溶解させた。得られた溶液を正極の
正極層表面及び負極の負極層表面に塗布し、この正極層
表面と負極層表面の間にセパレータを配置した。セパレ
ータの４辺は正極の端からそれぞれ１．５ｍｍ幅、負極
からそれぞれ１ｍｍの幅ではみだすようにした。なお、
積層前に正極の集電体に帯状の正極リードを溶接し、負
極の集電体に帯状の負極リードを溶接した。得られた積
層物を８０℃で１２時間真空乾燥させてジメチルフォル
ムアミドを蒸発させることにより各電極層とセパレータ
の間に多孔質の接着層を形成し、電極群を得た。 ＜非水電解液の調製＞六フッ化リン酸リチウム（ＬｉＰ
Ｆ６）をエチレンカーボネート（ＥＣ）とメチルエチル
カーボネート（ＭＥＣ）の混合溶媒（混合体積比率１：
２）に１．４モル／１溶解して非水電解液を調製した。Example 1 <Preparation of Positive Electrode> First, lithium cobalt oxide (Li x
CoO 2 ; where X is 0 ≦ X ≦ 1) 91% by weight of powder is mixed with 3.5% by weight of acetylene black, 3.5% by weight of graphite and 2% by weight of ethylene propylene diene monomer powder and mixed with toluene And the thickness is 15μ
m is applied to both sides of a current collector made of aluminum foil, and then pressed to obtain an electrode density of 3 g / cm 3 .
A positive electrode having a structure in which a positive electrode layer was supported on both surfaces of a current collector was produced. The size of the positive electrode was 45 mm in length and 75 mm in width. <Preparation of Negative Electrode> A mesophase pitch-based carbon fiber heat-treated at 3000 ° C. as a carbonaceous material (fiber diameter: 8 μm, average fiber length: 20 μm, average plane distance (d 002 ): 0.3
A mixture of 93% by weight of a powder of 360 nm and 7% by weight of polyvinylidene fluoride (PVdF) as a binder is applied to one surface of a current collector made of a copper foil having a thickness of 15 μm.
After drying and pressing, the electrode density is 1.3 g / c.
In m 3, the negative electrode layer to prepare a negative electrode of the supported structure on one side of the current collector. The size of the negative electrode is 46 mm long and 76 m wide
m. <Separator> A separator made of a polyethylene porous film having a thickness of 25 μm, a heat shrinkage at 120 ° C. for 1 hour of 20%, and a porosity of 50% was prepared. The size of the separator was 48 mm in length and 78 mm in width. This size is the length that all four sides extend from the positive electrode and the negative electrode when laminated with the positive electrode and the negative electrode, and are 1.5 mm wide from the edge of the positive electrode and 1 mm from the negative electrode, respectively. is there. <Preparation of Electrode Group> Polyacrylonitrile (PAN) was used as an adhesive in dimethylformamide (boiling point: 153).
C) 1% by weight was dissolved in the solution. The obtained solution was applied to the surface of the positive electrode layer of the positive electrode and the surface of the negative electrode layer of the negative electrode, and a separator was disposed between the surfaces of the positive electrode layer and the negative electrode layer. The four sides of the separator were set so as to protrude 1.5 mm from the end of the positive electrode and 1 mm from the negative electrode, respectively. In addition,
Before lamination, a strip-shaped positive electrode lead was welded to the positive electrode current collector, and a strip-shaped negative electrode lead was welded to the negative electrode current collector. The obtained laminate was vacuum-dried at 80 ° C. for 12 hours to evaporate dimethylformamide, thereby forming a porous adhesive layer between each electrode layer and the separator to obtain an electrode group. <Preparation of non-aqueous electrolyte> Lithium hexafluorophosphate (LiP
F 6 ) in a mixed solvent of ethylene carbonate (EC) and methyl ethyl carbonate (MEC) (mixing volume ratio 1:
A non-aqueous electrolyte was prepared by dissolving 1.4 mol / 1 in 2).

【００７５】電極群及び非水電解液をアルミ箔の両面を
ポリプロピレンで覆った厚さ１００μｍのラミネートフ
ィルムを袋状に成形し、これに電極群を収納した。A 100 μm-thick laminated film in which the electrode group and the non-aqueous electrolyte were covered with polypropylene on both sides of an aluminum foil was formed into a bag, and the electrode group was housed in the bag.

【００７６】ラミネートフィルム内の電極群に非水電解
液を電池容量１Ａｈ当たりの量が５．０ｇとなるように
注入し封口して前述した図１、２に示す構造を有し、厚
さが０．５ｍｍ、縦が５４ｍｍ、横が８６ｍｍの薄型非
水電解液二次電池を組み立てた。A non-aqueous electrolyte was injected into the electrode group in the laminate film so that the amount per 5.0 Ah of battery capacity was 5.0 g, and the structure was closed as shown in FIGS. A thin nonaqueous electrolyte secondary battery having a size of 0.5 mm, a length of 54 mm, and a width of 86 mm was assembled.

【００７７】実施例２〜実施例５ 接着剤を下記表１に示す種類のポリマーにする以外は、
前述した実施例１と同様な構成の薄型非水電解液二次電
池を組み立てた。Examples 2 to 5 Except that the adhesive was a polymer of the type shown in Table 1 below,
A thin non-aqueous electrolyte secondary battery having the same configuration as that of Example 1 described above was assembled.

【００７８】実施例６ 厚さが０．１ｍｍのアルミニウム板からなる負極を用い
る以外は前述した実施例１と同様な構成の薄型非水電解
液二次電池を組み立てた。Example 6 A thin non-aqueous electrolyte secondary battery having the same structure as in Example 1 except that a negative electrode made of an aluminum plate having a thickness of 0.1 mm was used was assembled.

【００７９】実施例７ 電極群作成時の真空乾燥を１００℃で１２時間行うこと
以外は、前述した実施例１と同様にして薄型非水電解液
二次電池を組み立てた。Example 7 A thin non-aqueous electrolyte secondary battery was assembled in the same manner as in Example 1 except that vacuum drying at the time of preparing the electrode group was performed at 100 ° C. for 12 hours.

【００８０】実施例８ 電極群作成時の真空乾燥を１４０℃で１２時間行うこと
以外は、前述した実施例１と同様にして薄型非水電解液
二次電池を組み立てた。Example 8 A thin non-aqueous electrolyte secondary battery was assembled in the same manner as in Example 1 except that vacuum drying was performed at 140 ° C. for 12 hours when preparing the electrode group.

【００８１】実施例９ 実施例１で説明したのと同様にして作製された正極、負
極、セパレータを、正極層表面と負極層表面の間にセパ
レータを配置する形で積層した。セパレータの４辺は正
極の端からそれぞれ１．５ｍｍ幅、負極からそれぞれ１
ｍｍの幅ではみだすようにした。なお、積層前に正極の
集電体に帯状の正極リードを溶接し、負極の集電体に帯
状の負極リードを溶接した。ラミネートフィルムを袋状
に成形したものに電極群を前述した積層面が袋の開口部
から見えるように収納した。接着剤としてポリフッ化ビ
ニリデン（ＰＶｄＦ）を有機溶媒であるジメチルフォル
ムアミド（沸点が１５３℃）に０．３重量％溶解させ
た。得られた溶液をラミネートフィルム内の電極群に電
池容量１００ｍＡｈ当たりの量が例１と同様となるよう
に注入し、溶液を電極群の内部に浸透させると共に、電
極群の表面全体に付着させた。Example 9 A positive electrode, a negative electrode and a separator produced in the same manner as described in Example 1 were laminated in such a manner that the separator was arranged between the surface of the positive electrode layer and the surface of the negative electrode layer. The four sides of the separator are each 1.5 mm wide from the edge of the positive electrode and 1 mm each from the negative electrode.
It protruded in the width of mm. Before lamination, a band-shaped positive electrode lead was welded to the positive electrode current collector, and a band-shaped negative electrode lead was welded to the negative electrode current collector. The electrode group was accommodated in a bag formed from a laminated film so that the above-mentioned laminated surface could be seen from the opening of the bag. 0.3% by weight of polyvinylidene fluoride (PVdF) as an adhesive was dissolved in dimethylformamide (boiling point: 153 ° C.) as an organic solvent. The obtained solution was injected into the electrode group in the laminate film so that the amount per 100 mAh of battery capacity was the same as in Example 1, and the solution was permeated into the electrode group and adhered to the entire surface of the electrode group. .

【００８２】次いで、ラミネートフィルム内の電極群に
４０℃で真空乾燥を２４時間施すことにより有機溶媒を
蒸発させ、正極、負極及びセパレータの空隙に電極群の
表面に多孔質な接着部を形成した。さらにセパレータの
正極及び負極からはみ出した部分にも接着剤を保持させ
ることが出来た。Next, the electrode group in the laminate film was subjected to vacuum drying at 40 ° C. for 24 hours to evaporate the organic solvent to form a porous bonded portion on the surface of the electrode group in the gap between the positive electrode, the negative electrode and the separator. . Further, the adhesive was able to be held at the portions of the separator protruding from the positive electrode and the negative electrode.

【００８３】ラミネートフィルム内の電極群に非水電解
液を電池容量１Ａｈ当たりの量が例１と同様となるよう
に注入し、前述した図１、２に示す構造を有し、厚さが
厚さが０．５ｍｍ、縦が５４ｍｍ、横が８６ｍｍの薄型
非水電解液二次電池を組み立てた。A non-aqueous electrolyte was injected into the electrode group in the laminate film so that the amount per 1 Ah of battery capacity was the same as in Example 1. The non-aqueous electrolyte had the structure shown in FIGS. A thin nonaqueous electrolyte secondary battery having a length of 0.5 mm, a length of 54 mm, and a width of 86 mm was assembled.

【００８４】比較例１ 実施例１で説明したのと同様な正極の正極層と実施例１
で説明したのと同様な負極の負極層との間に、実施例１
で説明したのと同様なセパレータを配置することにより
電極群を作製した。電極群及び実施例１で説明したのと
同様な非水電解液をラミネートフィルム内に収納し、電
池容量１Ａｈ当たりの非水電解液量が５．０ｇで厚さが
０．５ｍｍ、縦が５４ｍｍ、横が８６ｍｍの薄型非水電
解液二次電池を組み立てた。Comparative Example 1 The same positive electrode layer of the positive electrode as described in Example 1 was used.
Example 1 between the negative electrode layer of the negative electrode similar to that described in
An electrode group was produced by arranging the same separator as described in the above. The electrode group and the same non-aqueous electrolyte as described in Example 1 were accommodated in a laminate film, the amount of non-aqueous electrolyte per 1 Ah of battery capacity was 5.0 g, the thickness was 0.5 mm, and the length was 54 mm. A thin non-aqueous electrolyte secondary battery having a width of 86 mm was assembled.

【００８５】比較例２ ポリアクリロニトリルにＬｉＰＦ６、ＥＣ及びＰＣを添
加し混合することにより得られたゲル電解質を、厚さが
６０μｍで、多孔度が６５％の不織布からなるセパレー
タに含浸させた。このようなセパレータを実施例１で説
明したのと同様な負極の負極層との間に配置することに
より電極群を作製した。電極群及び実施例1で説明した
のと同様な非水電解液をラミネートフィルム内に収納
し、前述した図1に示す構造を有し、電池容量1Ah当たり
の非水電解液量が０ｇ（PANに非水電解液が保持されて
いるため）で、厚さが０．５ｍｍ、幅が５４ｍｍ、高さ
が８ｍｍの薄型非水電解液二次電池を組み立てた。Comparative Example 2 A gel electrolyte obtained by adding and mixing LiPF 6 , EC and PC to polyacrylonitrile was impregnated into a separator made of a nonwoven fabric having a thickness of 60 μm and a porosity of 65%. An electrode group was manufactured by disposing such a separator between the negative electrode layer and the negative electrode similar to that described in Example 1. The electrode group and the same non-aqueous electrolyte as described in Example 1 were housed in a laminate film, and had the structure shown in FIG. 1 described above, and the amount of non-aqueous electrolyte per 1 Ah of battery capacity was 0 g (PAN , A thin nonaqueous electrolyte secondary battery having a thickness of 0.5 mm, a width of 54 mm, and a height of 8 mm was assembled.

【００８６】比較例３ セパレータの端が負極端と同じであること以外、実施例
１と同様な薄型非水電解液二次電池を組み立てた。Comparative Example 3 A thin non-aqueous electrolyte secondary battery similar to that of Example 1 was assembled except that the end of the separator was the same as the end of the negative electrode.

【００８７】得られた実施例１〜５、７〜９及び比較例
１〜３の二次電池について、充電電流４０ｍＡで４．２
Ｖまで５時間充電した後、４０ｍＡで２．７Ｖまで放電
する充放電サイクル試験を２０℃の雰囲気において実施
した。一方、実施例６の二次電池については、充電電流
４０ｍＡで４．０Ｖまで５時間充電した後、４０ｍＡで
２．７Ｖまで放電する充放電サイクル試験を２０℃の雰
囲気において実施した.各充放旭サイクル試験における1
サイクル目の放電容量（初期容量）及び３００サイクル
時における容量維持率（初期容量に対する）を下記表２
に示す。With respect to the obtained secondary batteries of Examples 1 to 5, 7 to 9 and Comparative Examples 1 to 3, a charge current of 40 mA was applied to 4.2.
After charging to V for 5 hours, a charge / discharge cycle test of discharging to 2.7 V at 40 mA was performed in an atmosphere at 20 ° C. On the other hand, the secondary battery of Example 6 was subjected to a charge / discharge cycle test in which the battery was charged to 4.0 V at a charging current of 40 mA for 5 hours, and then discharged to 2.7 V at 40 mA in an atmosphere of 20 ° C. 1 in Asahi cycle test
Table 2 shows the discharge capacity at the cycle (initial capacity) and the capacity retention rate at 300 cycles (relative to the initial capacity).
Shown in

【００８８】また、実施例１〜５、７〜９及び比較例１
〜３の二次電池について、充電電流４０ｍＡで４．２Ｖ
まで５時間電した後、２Ｃで２．７Ｖまで放電した際の
放電容量を測定し、２Ｃ放電レートでの容量維持率（２
Ｃでの放電容量の初期容量に対する比率）を算出し、そ
の結果を下記表２に併記する。一方、実施例６の二次電
池については、充電電流４０ｍＡで４．０Ｖまで５時間
充電した後、２Ｃで２．７Ｖまで放電した際の放電容量
を測定して２Ｃ放電レートでの容量維持率を算出し、そ
の結果を下記表２に併記する。Examples 1 to 5, 7 to 9 and Comparative Example 1
4.2 V at a charging current of 40 mA for the secondary batteries
After discharging for 5 hours, the discharge capacity at the time of discharging to 2.7 V at 2 C was measured, and the capacity retention rate at 2 C discharge rate (2
The ratio of the discharge capacity to the initial capacity at C) was calculated, and the results are also shown in Table 2 below. On the other hand, the secondary battery of Example 6 was charged at a charging current of 40 mA to 4.0 V for 5 hours, and then discharged at 2 C to 2.7 V to measure the discharge capacity. And the results are shown in Table 2 below.

【００８９】さらに、実施例１〜５、７〜９及び比較例
１〜３の二次電池について、２０℃の雰囲気において充
電電流４０ｍＡで４．２Ｖまで５時間充電した後、０℃
の雰囲気において４０ｍＡで２．７Ｖまで放電した際の
放電容量を測定し、０℃放電での容量維持率（０℃での
放電容量の初期容量に対する比率）を算出し、その結果
を下記表２に併記する。一方、実施例６の二次電池につ
いては、２０℃の雰囲気において充電電流４０ｍＡで
４．０Ｖまで５時間充電した後、０℃の雰囲気において
４０ｍＡで２．７Ｖまで放電した際の放電容量を測定し
て０℃放電での放電容量維持率を算出し、その結果を下
記表２に併記する。Further, the secondary batteries of Examples 1 to 5, 7 to 9 and Comparative Examples 1 to 3 were charged at a charging current of 40 mA to 4.2 V for 5 hours in an atmosphere of 20 ° C., and then charged at 0 ° C.
The discharge capacity was measured when the battery was discharged to 2.7 V at 40 mA in the atmosphere described above, and the capacity retention ratio at 0 ° C. discharge (ratio of the discharge capacity at 0 ° C. to the initial capacity) was calculated. It is described together. On the other hand, the secondary battery of Example 6 was charged to 4.0 V at a charging current of 40 mA in an atmosphere of 20 ° C. for 5 hours, and then the discharge capacity when discharged to 2.7 V at 40 mA in an atmosphere of 0 ° C. was measured. Then, the discharge capacity retention ratio at 0 ° C. discharge was calculated, and the results are also shown in Table 2 below.

【表１】 [Table 1]

【表２】 表１、２から明らかなように実施例１〜実施例９の二次
電池は初期容量、サイクル寿命、２Ｃの大電流で放電し
た際の放電容量及び０℃の低温での放電容量を同時に満
足できることがわかる。特に実施例１、実施例２、実施
例９の二次電池は他の二次電池に比べて性能が優れ定て
いることがわかる。[Table 2] As is clear from Tables 1 and 2, the secondary batteries of Examples 1 to 9 simultaneously satisfied the initial capacity, the cycle life, the discharge capacity when discharged with a large current of 2C, and the discharge capacity at a low temperature of 0 ° C. We can see that we can do it. In particular, it can be seen that the performance of the secondary batteries of Examples 1, 2 and 9 is superior to other secondary batteries.

【００９０】これに対し、比較例１の二次電池は、初期
容量に優れるものの、サイクル寿命、２Ｃの大電流で放
電した際の放電容量及び０℃の低温での放電容量が実施
例〜９の二次電池に比べて低いことがわかる。また、比
較例２の二次電池は、初期容量、２Ｃの大電流で放電し
た際の放電容量及び０℃の低温での放電容量が実施例１
〜９の二次電池に比べて低いことがわかる。On the other hand, although the secondary battery of Comparative Example 1 was excellent in initial capacity, the cycle capacity, the discharge capacity when discharged at a large current of 2 C, and the discharge capacity at a low temperature of 0 ° C. It can be seen that this is lower than that of the secondary battery. The secondary battery of Comparative Example 2 had an initial capacity of 2 C and a discharge capacity at the time of discharging with a large current and a discharge capacity at a low temperature of 0 ° C. in Example 1.
9 are lower than those of the secondary batteries of No. 9 to No. 9.

【００９１】比較例３は電池性能は実施例１と同様であ
るが、高さ１ｍからの落下試験において短絡し、電池作
動できなくなった。さらに３Ｃレートの過充電試験にお
いても短絡が早期に発生し、電池発熱が急激におきてガ
ス噴出、液もれが発生した。一方実施例１〜実施例８は
落下試験、過充電試験のいずれにおいても問題は発生せ
ず、特に実施例９は電池強度、安全性に優れていた。The battery performance of Comparative Example 3 was the same as that of Example 1, but a short circuit occurred in a drop test from a height of 1 m, and the battery could not be operated. Further, even in the 3C rate overcharge test, a short circuit occurred early, and the battery generated heat rapidly, causing gas ejection and liquid leakage. On the other hand, in Examples 1 to 8, no problem occurred in any of the drop test and the overcharge test, and particularly, Example 9 was excellent in battery strength and safety.

【００９２】実施例１０ 前述した実施例１で説明したのと同様な正極と.前述し
た実施例1で説明したのと同様な負極と、120℃、1時間
での熱収縮率が１０％で、厚さが２５μｍで、多孔度が
５０％であるポリエチレン・ポリプロピレンの多層構造
を有する多孔質フィルムからなるセパレータとを用いて
前述した実施例1で説明したのと同様にして電極群を作
製した.電極群及び実施例1で説明したのと同様な非水電
解液をラミネートフィルム内に収納し、前述した図1に
示す構造を有し、電池容量1Ah当たりの非水電解液が
４．５で、厚さが０．５ｍｍ、縦が５４ｍｍ、横が８６
ｍｍの薄型非水電解液二次電池を組み立てた。Example 10 A positive electrode similar to that described in Example 1 above, a negative electrode similar to that described in Example 1 above, and a heat shrinkage rate of 10% at 120 ° C. for 1 hour were obtained. And a separator made of a porous film having a multilayer structure of polyethylene / polypropylene having a thickness of 25 μm and a porosity of 50%, and an electrode group was prepared in the same manner as described in Example 1 above. The electrode group and the same non-aqueous electrolyte as described in Example 1 were housed in a laminate film, and had the structure shown in FIG. 1 described above, and the non-aqueous electrolyte per 1 Ah of battery capacity was 4.5. 0.5mm thick, 54mm long, 86 wide
mm thin non-aqueous electrolyte secondary battery was assembled.

【００９３】実施例１１〜実施例１５ セパレータにおける１２０℃、１時間での熱収縮率、厚
さ及び多孔度を下記表３に示す値にすること以外は、前
述した実施例１０と同様な構成の薄型非水電解液二次電
池を組み立てた。Examples 11 to 15 The same configuration as in Example 10 described above, except that the heat shrinkage, thickness and porosity of the separator at 120 ° C. for one hour were set to the values shown in Table 3 below. The thin non-aqueous electrolyte secondary battery was assembled.

【００９４】実施例１６〜実施例１７ セパレータとして、１２０℃、１時間での熱収縮率、厚
さ及び多孔度が下記表３に示す値であるポリプロピレン
製多孔質フィルムを用いること以外は、前述した例１０
と同様な構成の薄型非水電解液二次電池を組み立てた。Examples 16 to 17 The same procedures as described above were carried out except that a polypropylene porous film having a heat shrinkage at 120 ° C. for 1 hour, a thickness and a porosity as shown in Table 3 below was used as a separator. Example 10
A thin non-aqueous electrolyte secondary battery having the same configuration as that of was assembled.

【００９５】実施例１８ 負極の炭素質材料として、１１００℃で熱処理を施した
石油コークス（平均粒径が5μmで、平均面間隔（ｄ
００２）が０．３５５ｎｍ、BET法による比表面積が１
０ｍ２／ｇを用いること以外は前述した実施例１０と同
様な薄型非水電解液二次電池を組み立てた。Example 18 As a carbonaceous material for a negative electrode, petroleum coke heat-treated at 1100 ° C. (having an average particle size of 5 μm and an average plane spacing (d
002 ) is 0.355 nm and the specific surface area by the BET method is 1
A thin non-aqueous electrolyte secondary battery similar to that of Example 10 described above was used except that 0 m2 / g was used.

【００９６】実施例１９ 負極の炭素質材料として、天然黒鉛（平均粒径が7μm
で、平均面間隔（ｄ００ ２）が０．３３５５ｎｍ、BET
法による比表面積が３ｍ２／ｇを用いること以外は、前
述した実施例１０と同様な構成の薄型非水電解液二次電
池を組み立てた。Example 19 As a carbonaceous material for a negative electrode, natural graphite (having an average particle size of 7 μm
In the average spacing (d 00 2) is 0.3355Nm, BET
A thin non-aqueous electrolyte secondary battery having the same configuration as that of Example 10 described above except that the specific surface area by the method was 3 m 2 / g was assembled.

【００９７】得られた例１０〜１９の二次電池につい
て、充電電流４０ｍＡで４．２Ｖまで５時間充電した
後、４０ｍＡで２．７Ｖまで放電する充放電サイクル試
験を２０℃の雰囲気において実施した。１サイクル目の
放電容量（初期容量)及び３００サイクル時における容
量維持率（前記初期容量に対する)を下記表４に示す。The obtained secondary batteries of Examples 10 to 19 were charged at a charging current of 40 mA to 4.2 V for 5 hours and then discharged at 40 mA to 2.7 V in a 20 ° C. atmosphere. . Table 4 below shows the discharge capacity at the first cycle (initial capacity) and the capacity retention rate at 300 cycles (relative to the initial capacity).

【００９８】また、実施例１０〜１９の二次電池につい
て、充電電流４０ｍＡで4.2Vまで5時間充電した後、２
Ｃで２．７Ｖまで放電した際の放電容量を測定し、２Ｃ
放電レートでの容量維持率（２Ｃでの放電容量の前記初
期容量に対する比率）を算出し、その結果を下記表４に
併記する。Further, the secondary batteries of Examples 10 to 19 were charged at a charging current of 40 mA to 4.2 V for 5 hours, and then charged.
The discharge capacity at the time of discharging to 2.7 V at C was measured.
The capacity retention ratio at the discharge rate (the ratio of the discharge capacity at 2C to the initial capacity) was calculated, and the results are also shown in Table 4 below.

【００９９】さらに、例１０〜１９の二次電池につい
て、20℃の雰囲気において充電電流４０ｍＡで４．２Ｖ
まで５時間充電した後、０℃の雰囲気において４０ｍＡ
で２．７Ｖまで放電した際の放電容量を測定し、０℃放
電での放電容量維持率（０℃での放電容量の初期容量に
対する比率)を算出し、その結果を下記表４に併記す
る。なお、表４には、前述した比較例２の結果を併記す
る。Further, with respect to the secondary batteries of Examples 10 to 19, at a charging current of 40 mA and a charging current of 4.2 V in an atmosphere of 20 ° C.
After charging for 5 hours, it is 40 mA in an atmosphere of 0 ° C.
The discharge capacity at the time of discharging to 2.7 V was measured, and the discharge capacity retention ratio at 0 ° C. discharge (ratio of the discharge capacity at 0 ° C. to the initial capacity) was calculated. The results are also shown in Table 4 below. . Table 4 also shows the results of Comparative Example 2 described above.

【表３】 [Table 3]

【表４】 表3及び表4から明らかなように、実施例１０〜１９の二
次電池は、比較例２の二次電池に比べて初期容量、サイ
クル寿命及び2Cの大電流で放電した際の放電容量が優れ
ていることがわかる。特に実施例１０及び実施例１７の
二次電池は他の二次電池に比べて性能が優れていること
がわかる。[Table 4] As is clear from Tables 3 and 4, the secondary batteries of Examples 10 to 19 have an initial capacity, a cycle life, and a discharge capacity when discharged at a large current of 2 C as compared with the secondary batteries of Comparative Example 2. It turns out that it is excellent. In particular, it can be seen that the secondary batteries of Example 10 and Example 17 have better performance than other secondary batteries.

【０１００】実施例２０ ＜正極の作製＞まず、リチウムコバルト酸化物（Ｌｉｘ
ＣｏＯ２；但し、Ｘは０≦Ｘ≦１である)粉末９１重量
％をアセチレンブラック３．５重量％、グラファイト
３．５重量％及びエチレンプロピレンジエンモノマ粉末
２重量％とトルエンを加えて共に混合し、１０ｃｍ２当
たり１０個の割合で直径０．５ｍｍの孔が存在する多孔
質アルミニウム箔（厚さが20μｍ）からなる集電体の片
面に塗布した後、プレスすることにより電極密度が３ｇ
／ｃｍ３で、正極層が集電体に担持された構造の正極を
作製した。正極の大きさは縦が４５ｍｍ、横が７５ｍｍ
であった。 ＜負極の作製＞炭素質材料として３０００℃で熱処理し
たメソフェーズピッチ系炭素繊維（繊維径が8μｍ、平
均繊維長が20μｍ、平均面間隔（ｄ００２）が０．３３
６０ｎｍ、ＢＥＴ法による比表面積が２ｍ２／ｇ)の粉
末を９３重量％と、結着剤としてポリフッ化ビニリデン
（ＰＶｄＦ）７重量％とを混合し、これを集電体として
の１０ｃｍ２当たり１０個の割合で直径０．５ｍｍの孔
が存在する多孔質銅箔（厚さが１６μｍ)の片面に塗布
し、乾燥し、プレスすることにより電極密度が１．３ｇ
／ｃｍ３で、負極層が集電体に担持された構造の負極を
作製した。負極の大きさは縦が４６ｍｍ、横が７６ｍｍ
であった。 ＜セパレータ＞セパレータとして、厚さが２５μｍで、
120℃、1時間での熱収縮が１０％で、多孔度が５０％の
ポリエチレン製多孔質フィルムを用意した。セパレータ
の大きさは縦が４８ｍｍ、横が７８ｍｍとした。この大
きさは正極及び負極と積層したときに、４辺がすべて正
極及び負極から延出する長さであり、正極の端からそれ
ぞれ１．５ｍｍ幅、負極からそれぞれ１ｍｍの幅ではみ
だす大きさである。 ＜電極群の作製＞前記正極、負極及びセパレータを用い
ること以外は、前述した実施例1で説明したのと同様な
方法により電極群を作製した。Example 20 <Production of Positive Electrode> First, lithium cobalt oxide (Li x
CoO 2 ; where X is 0 ≦ X ≦ 1) 91% by weight of powder is mixed with 3.5% by weight of acetylene black, 3.5% by weight of graphite and 2% by weight of ethylene propylene diene monomer powder and mixed with toluene And applied to one side of a current collector made of a porous aluminum foil (thickness: 20 μm) having holes of 0.5 mm in diameter at a rate of 10 per 10 cm 2 , and then pressed to obtain an electrode density of 3 g.
/ Cm 3 , a positive electrode having a structure in which a positive electrode layer was supported on a current collector was produced. The size of the positive electrode is 45 mm long and 75 mm wide
Met. <Preparation of Negative Electrode> Mesophase pitch-based carbon fiber heat-treated at 3000 ° C. as a carbonaceous material (fiber diameter: 8 μm, average fiber length: 20 μm, average plane distance (d 002 ): 0.33
93% by weight of a powder having a specific surface area of 2 m 2 / g according to the BET method at 60 nm and 7% by weight of polyvinylidene fluoride (PVdF) as a binder were mixed, and this was mixed with 10% per 10 cm 2 as a current collector. The electrode density was 1.3 g by applying to one side of a porous copper foil (thickness: 16 μm) having holes of 0.5 mm in diameter, drying and pressing.
/ Cm 3 , a negative electrode having a structure in which a negative electrode layer was supported on a current collector was produced. The size of the negative electrode is 46 mm long and 76 mm wide
Met. <Separator> As a separator, the thickness is 25 μm,
A polyethylene porous film having a heat shrinkage of 10% at 120 ° C. for 1 hour and a porosity of 50% was prepared. The size of the separator was 48 mm in length and 78 mm in width. This size is the length that all four sides extend from the positive electrode and the negative electrode when laminated with the positive electrode and the negative electrode, and are 1.5 mm wide from the edge of the positive electrode and 1 mm from the negative electrode, respectively. is there. <Preparation of Electrode Group> An electrode group was prepared in the same manner as described in Example 1 except that the positive electrode, the negative electrode, and the separator were used.

【０１０１】前記電極群及び前述した実施例１で説明し
たのと同様な非水電解液をラミネートフィルム内に収納
し、前述した図1に示す構造を有し、電池容量１Ah当た
りの非水電解液量が５．０ｇで、厚さが０．５ｍｍ、幅
が５４ｍｍ、高さが８６ｍｍの薄型非水電解液二次電池
を組み立てた。The above-mentioned electrode group and the same non-aqueous electrolyte as described in the first embodiment were housed in a laminate film, and had the structure shown in FIG. 1 described above. A thin non-aqueous electrolyte secondary battery having a liquid amount of 5.0 g, a thickness of 0.5 mm, a width of 54 mm, and a height of 86 mm was assembled.

【０１０２】実施例２１ 正極集電体として１０ｃｍ２当たり５個の割合で直径
０．５ｍｍの孔が存在する多孔質アルミニウム箔(厚さ
が２３０μｍ)を用い、負極集電体として１０ｃｍ ２当
たり５個の割合で直径０．５ｍｍの孔が存在する多孔質
銅箔（厚さが20μm)を用いること以外は、前述した実施
例２０と同様な構成の薄型非水電解液二次電池を組み立
てた。Example 21 As a positive electrode current collector, 10 cm25 pieces per diameter
Porous aluminum foil with 0.5 mm holes (thickness
Is 230 μm), and 10 cm is used as a negative electrode current collector. 2This
Porous with 0.5 mm diameter holes at a ratio of 5 pieces
Except for using copper foil (thickness 20μm),
Assembling a thin non-aqueous electrolyte secondary battery having the same configuration as in Example 20
I was

【０１０３】実施例２２ 正極集電体として厚さが５０μｍの無孔のアルミニウム
箔を用い、負極集電体として１０ｃｍ２当たり１５個の
割合で直径０．３ｍｍの孔が存在する多孔質銅箔（厚さ
が20μｍ）を用いること以外は、前述した実施例２０と
同様な構成の薄型非水電解液二次電池を組み立てた。Example 22 A non-porous aluminum foil having a thickness of 50 μm was used as a positive electrode current collector, and a porous copper foil having 0.3 mm-diameter holes at a rate of 15 per 10 cm 2 was used as a negative electrode current collector. A thin non-aqueous electrolyte secondary battery having the same configuration as that of Example 20 described above except that the thickness was 20 μm was assembled.

【０１０４】実施例２３ 正極集電体として厚さが６０μｍの無孔のアルミニウム
箔を用い、負極集電体として１０ｃｍ２当たり５個の割
合で直径１ｍｍの孔が存在する多孔質銅箔(厚さが１６
μｍ)を用いること以外は、前述した実施例２０と同様
な構成の薄型非水電解液二次電池を組み立てた。Example 23 A non-porous aluminum foil having a thickness of 60 μm was used as a positive electrode current collector, and a porous copper foil (thickness: 5 mm / 10 cm 2 ) having holes having a diameter of 1 mm was used as a negative electrode current collector. Saga 16
A thin non-aqueous electrolyte secondary battery having the same configuration as that of Example 20 described above except that μm) was used was assembled.

【０１０５】実施例２４ 正極集電体として厚さが１５μｍの無孔のアルミニウム
箔を用い、負極集電体として１０ｃｍ２当たり1個の割
合で直径３ｍｍの孔が存在する多孔質銅箔（厚さが１６
μｍ）を用いること以外は.前述した実施例２０と同様
な構成の薄型非水電解液二次電池を組み立てた。Example 24 A non-porous aluminum foil having a thickness of 15 μm was used as a positive electrode current collector, and a porous copper foil (thickness: 3 mm in diameter per 1 cm 2 ) was used as a negative electrode current collector. Saga 16
A thin non-aqueous electrolyte secondary battery having the same structure as in Example 20 described above except that μm) was used was assembled.

【０１０６】実施例２５ 正極集電体として厚さが３０μｍの無孔のアルミニウム
箔を用い、負極集電1体として１０ｃｍ２当たり５個の
割合で直径４ｍｍの孔が存在する多孔質銅箔（厚さが１
６μｍ)を用いること以外は、前述した実施例２０と同
様な構成の薄型非水電解液二次電池を組み立てた。Example 25 A non-porous aluminum foil having a thickness of 30 μm was used as a positive electrode current collector, and a porous copper foil having 5 mm holes per 10 cm 2 was used as one negative electrode current collector ( Thickness 1
A thin non-aqueous electrolyte secondary battery having the same configuration as in Example 20 except that the thickness was 6 μm) was assembled.

【０１０７】実施例２６ 正極集電体として１０ｃｍ２当たり2個の割合で直径
０．３ｍｍの孔が存在する多孔質アルミニウム箔（厚さ
が20μｍ)を用い、負極集電体として厚さが１６μｍの
無孔の銅箔を用いること以外は、前述した実施例２０μ
と同様な構成の薄型非水電解液二次電池を組み立てた。Example 26 As a positive electrode current collector, a porous aluminum foil (thickness: 20 μm) having holes of 0.3 mm in diameter at a rate of two per 10 cm 2 was used, and a negative electrode current collector having a thickness of 16 μm was used. Except for using non-porous copper foil of
A thin non-aqueous electrolyte secondary battery having the same configuration as that of was assembled.

【０１０８】実施例２７ 正極集電体として10ｃｍ２当たり１０個の割合で直径１
ｍｍの孔が存在する多孔質アルミニウム箔（厚さが20μ
m)を用い、負極集電体として厚さが１６μｍの無孔の銅
箔を用いること以外は、前述した実施例２０と同様な構
成の薄型非水電解液二次電池を組み立て。Example 27 As a positive electrode current collector, the diameter of the current collector was 10 at a rate of 10 per 10 cm 2.
Porous aluminum foil with 20 mm holes (thickness of 20μ)
m), except that a nonporous copper foil having a thickness of 16 μm was used as the negative electrode current collector, to assemble a thin nonaqueous electrolyte secondary battery having the same configuration as in Example 20 described above.

【０１０９】実施例２８ 正極集電体として１０ｃｍ２当たり１個の割合で直径３
ｍｍの孔が存在する多孔質アルミニウム箔（厚さが20μ
ｍ)を用い、負極集電体として厚さが16μｍの無孔の銅
箔を用いること以外は、前述した実施例２０と同様な構
成の薄型非水電解液二次電池を組み立てた。Example 28 One positive electrode current collector having a diameter of 3 per 10 cm 2 was prepared.
Porous aluminum foil with 20 mm holes (thickness of 20μ)
m), and a thin non-aqueous electrolyte secondary battery having the same structure as in Example 20 described above was assembled except that a nonporous copper foil having a thickness of 16 μm was used as the negative electrode current collector.

【０１１０】実施例２９ 正極集電体として１０ｃｍ２当たり1個の割合で直径４
ｍｍの孔が存在する多孔質アルミニウム箔（厚さが15μ
ｍ)を用い、負極集電体として厚さが16μmの無孔の銅箔
を用いること以外は、前述した実施例２０と同様な構成
の薄型非水電解液二次電池を組み立てた。Example 29 One positive electrode current collector having a diameter of 4 per 10 cm 2 was prepared.
mm porous aluminum foil (thickness of 15μ)
m), and a thin non-aqueous electrolyte secondary battery having the same structure as in Example 20 described above was assembled except that a nonporous copper foil having a thickness of 16 μm was used as the negative electrode current collector.

【０１１１】実施例３０ 正極集電体として厚さが１５μｍの無孔のアルミニウム
箔を用い、負極集電体として厚さが１６μmの無孔の銅
箔を用いること以外は、前述した実施例２０と同様な構
成の薄型非水電解液二次電池を組み立てた。得られた実
施例２０〜３０の二次電池について正極集電体及び負極
集電体の形状を表５に示す。Example 30 The same procedure as described in Example 20 was carried out except that a nonporous aluminum foil having a thickness of 15 μm was used as the positive electrode current collector and a nonporous copper foil having a thickness of 16 μm was used as the negative electrode current collector. A thin non-aqueous electrolyte secondary battery having the same configuration as that of was assembled. Table 5 shows the shapes of the positive electrode current collector and the negative electrode current collector for the obtained secondary batteries of Examples 20 to 30.

【０１１２】得られた実施例２０〜３０の二次電池につ
いて、充電電流60mAで4.2Vまで３時間充電した後、60mA
で２．７Ｖまで放電する充放電サイクル試験を施し、1
サイクル目の放電容量（初期容量)及び500サイクル時に
おける容量維持率（前記初期容量に対する)を下記表６
に示す。The obtained secondary batteries of Examples 20 to 30 were charged at a charging current of 60 mA to 4.2 V for 3 hours, and then charged at 60 mA.
Charge / discharge cycle test to discharge to 2.7V
The discharge capacity at the cycle (initial capacity) and the capacity retention rate at 500 cycles (relative to the initial capacity) are shown in Table 6 below.
Shown in

【表５】 [Table 5]

【表６】 表５および表６から明らかなように実施例２０〜実施例
３０の二次電池は、初期容量およびサイクル寿命が優れ
ていることがわかる。とくに、実施例２０、実施例２２
の二次電池は、ほかの二次電池に比べて性能が優れてい
ることがわかる。[Table 6] As is clear from Tables 5 and 6, the secondary batteries of Examples 20 to 30 have excellent initial capacity and cycle life. In particular, Examples 20 and 22
It can be seen that the secondary battery has excellent performance as compared with other secondary batteries.

【０１１３】なお、前述した実施例においては、正極、
セパレータ及び負極を1枚ずつ用いて電極群を作製した
が、正極、セパレータ及び負極を複数枚用いて電極群を
作製しても良い。In the above-described embodiment, the positive electrode,
Although the electrode group is manufactured using one separator and one negative electrode, the electrode group may be manufactured using a plurality of positive electrodes, separators, and negative electrodes.

【０１１４】また、前述した実施例においては、金属製
の有底円筒形容器を備える円筒形非水電解液二次電池に
適用した例を説明したが、金属製の有底矩形筒状容器を
備える角形非水電解液二次電池にも同様に適用すること
ができる。In the above-described embodiment, an example in which the present invention is applied to a cylindrical non-aqueous electrolyte secondary battery having a bottomed cylindrical container made of metal has been described. The present invention can be similarly applied to a rectangular non-aqueous electrolyte secondary battery provided.

【０１１５】[0115]

【発明の効果】以上詳述したように、本発明によれば、
優れた容量、サイクル性能.大電流放電特性及び低温放
電特性維持しつつ、厚さ３ｍｍ以下の薄型構造にするこ
とが可能な非水電解液二次電池およびその製造方法を提
供することができる。As described in detail above, according to the present invention,
It is possible to provide a non-aqueous electrolyte secondary battery capable of achieving a thin structure with a thickness of 3 mm or less while maintaining excellent capacity, cycle performance, large current discharge characteristics and low-temperature discharge characteristics, and a method for manufacturing the same.

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

【図１】本発明に係わる非水電解液二次電池の一例を示
す断面図。FIG. 1 is a sectional view showing an example of a non-aqueous electrolyte secondary battery according to the present invention.

【図２】図１のA部を示す拡大断面図。FIG. 2 is an enlarged sectional view showing a portion A in FIG. 1;

【符号の説明】[Explanation of symbols]

１…外装材 ２…電極群 ３…正極集電体 ４…正極層 ５…正極 ６…負極集電体 ７…負極層 ８…負極 ９ａ、９ｂ…多孔質の接着層 １０…セパレータ １１…正極端子 １２…負極端子 DESCRIPTION OF SYMBOLS 1 ... Exterior material 2 ... Electrode group 3 ... Positive electrode collector 4 ... Positive electrode layer 5 ... Positive electrode 6 ... Negative electrode current collector 7 ... Negative electrode layer 8 ... Negative electrode 9a, 9b ... Porous adhesive layer 10 ... Separator 11 ... Positive electrode terminal 12 ... negative electrode terminal

───────────────────────────────────────────────────── フロントページの続き (72)発明者 大崎 隆久 神奈川県川崎市幸区堀川町72番地 株式会 社東芝川崎事業所内 (72)発明者 神田 基 神奈川県川崎市幸区堀川町72番地 株式会 社東芝川崎事業所内 Ｆターム(参考） 5H003 AA01 AA02 AA04 AA07 BA01 BA02 BB01 BC06 BD01 BD02 5H029 AJ00 AJ02 AJ03 AJ05 AK02 AK03 AK05 AL06 AL07 AM02 AM03 AM05 AM07 BJ04 BJ12 CJ01 CJ02 CJ13 CJ23 DJ01 DJ04 DJ08 DJ17 EJ11 EJ12 HJ00 HJ01 HJ04 HJ06 HJ09 HJ13 HJ14 HJ15  ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Takahisa Osaki 72 Horikawa-cho, Saiwai-ku, Kawasaki-shi, Kanagawa Pref. F-term at Toshiba Kawasaki Office (reference) HJ06 HJ09 HJ13 HJ14 HJ15

Claims (10)

【特許請求の範囲】[Claims] 【請求項１】 正極と、負極と、正極及び負極の間に配
置されるセパレータが積層された電極群及び非水電解液
を具備する非水電解液二次電池において、少なくとも正
極及びセパレータ間と、負極及びセパレータ間に多孔質
の接着層がそれぞれ介在され、かつセパレータの少なく
とも一端が正極及び負極より延出していることを特徴と
する非水電解液二次電池。A non-aqueous electrolyte secondary battery comprising a positive electrode, a negative electrode, an electrode group in which a separator disposed between the positive electrode and the negative electrode is laminated, and a non-aqueous electrolyte, wherein at least a portion between the positive electrode and the separator A non-aqueous electrolyte secondary battery, wherein a porous adhesive layer is interposed between the negative electrode and the separator, and at least one end of the separator extends from the positive electrode and the negative electrode. 【請求項２】 少なくともセパレータ延出部分に接着剤
を保持することを特徴とする請求項１記載の非水電解液
二次電池。2. The non-aqueous electrolyte secondary battery according to claim 1, wherein an adhesive is held at least at a portion where the separator extends. 【請求項３】 前記多孔質の接着層は、ポリフッ化ビニ
リデン、ポリアクリロニトリル、ポリアクリレート、ま
たはポリエチレンオキサイドから選ばれる少なくとも１
種から主に形成されていることを特徴とする請求項１記
載の非水電解液二次電池。3. The porous adhesive layer comprises at least one selected from the group consisting of polyvinylidene fluoride, polyacrylonitrile, polyacrylate, and polyethylene oxide.
2. The non-aqueous electrolyte secondary battery according to claim 1, wherein the non-aqueous electrolyte secondary battery is mainly formed from a seed. 【請求項４】 前記セパレータは厚さが３０μｍ以下で
あることを特徴とする請求項１記載の非水電解液二次電
池。4. The non-aqueous electrolyte secondary battery according to claim 1, wherein said separator has a thickness of 30 μm or less. 【請求項５】 前記セパレータは１２０℃の条件で１時
間存在したときの熱収縮率が２０％以下であることを特
徴とする請求項１記載の非水電解液二次電池。5. The non-aqueous electrolyte secondary battery according to claim 1, wherein the separator has a heat shrinkage of 20% or less when the separator is present at 120 ° C. for one hour. 【請求項６】 前記セパレータは多孔度が３０〜６０％
であることを特徴とする請求項１記載の非水電解液二次
電池。6. The separator has a porosity of 30 to 60%.
The non-aqueous electrolyte secondary battery according to claim 1, wherein 【請求項７】 前記負極はリチウムイオンを吸蔵・放出
する炭素質物を含むことを特徴とする請求項１記載の非
水電解液二次電池。7. The non-aqueous electrolyte secondary battery according to claim 1, wherein the negative electrode contains a carbonaceous material that stores and releases lithium ions. 【請求項８】 前記炭素質物は（００２）面の面間隔ｄ
００２が０．３４０ｎｍ以下である黒鉛結晶を有するこ
とを特徴とする請求項７記載の非水電解液二次電池。8. The carbonaceous material has a (002) plane distance d.
8. The non-aqueous electrolyte secondary battery according to claim 7, wherein the non-aqueous electrolyte secondary battery has graphite crystals whose 002 is 0.340 nm or less. 【請求項９】 前記正極及び前記負極のうち少なくとも
いずれか一方の電極は直径３ｍｍ以下の孔が１０ｃｍ２
あたり１個以上の割合で存在する多孔質構造を持つ導電
性基板を有することを特徴とする請求項１記載の非水電
解液二次電池。9. At least one of the positive electrode and the negative electrode has a hole having a diameter of 3 mm or less of 10 cm 2.
2. The non-aqueous electrolyte secondary battery according to claim 1, wherein the non-aqueous electrolyte secondary battery has a conductive substrate having a porous structure which is present in a ratio of one or more per substrate. 【請求項１０】 正極と負極の間にセパレータを介在さ
せて電極群を作製する工程と、 接着性を有する高分子が０．１〜２．５重量％溶解され
た溶液を前記電極群に含浸させる工程と、 前記電極群に真空乾燥を施す工程と、 前記電極群に非水電解液を含浸させる工程とを具備する
ことを特徴とする請求項１記載の非水電解液二次電池の
製造方法。10. A step of preparing an electrode group by interposing a separator between a positive electrode and a negative electrode; and impregnating the electrode group with a solution in which 0.1 to 2.5% by weight of an adhesive polymer is dissolved. 2. The method of claim 1, further comprising: a step of performing vacuum drying on the electrode group; and a step of impregnating the electrode group with a non-aqueous electrolyte. 3. Method.
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