JP2001176558A - Non-aqueous electrolyte secondary battery - Google Patents
Non-aqueous electrolyte secondary batteryInfo
- Publication number
- JP2001176558A JP2001176558A JP36159899A JP36159899A JP2001176558A JP 2001176558 A JP2001176558 A JP 2001176558A JP 36159899 A JP36159899 A JP 36159899A JP 36159899 A JP36159899 A JP 36159899A JP 2001176558 A JP2001176558 A JP 2001176558A
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- aqueous electrolyte
- active material
- material layer
- groove
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、非水電解液二次電
池に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-aqueous electrolyte secondary battery.
【０００２】[0002]
【従来の技術】非水電解液二次電池、例えば円筒形リチ
ウムイオン二次電池は、帯状の集電体の片面または両面
に正極活物質層が形成されてなる正極と、同じく帯状の
集電体の片面または両面に負極活物質層が形成されてな
る負極とをセパレータを介して積重し、この積重体を渦
巻状に巻いた電極群を円筒状の電池缶に収納した後、非
水電解液を注液し、封口することにより構成される。2. Description of the Related Art A non-aqueous electrolyte secondary battery, for example, a cylindrical lithium ion secondary battery, has a positive electrode having a positive electrode active material layer formed on one or both sides of a band-like current collector, and a similar band-like current collector. A negative electrode having a negative electrode active material layer formed on one or both sides of the body is stacked via a separator, and the stacked body is spirally wound, and the electrode group is stored in a cylindrical battery can. It is constituted by injecting an electrolyte solution and sealing it.
【０００３】前記円筒形リチウムイオン電池において
は、積重された電極群が渦巻状に密に巻かれた状態であ
り、かつ、非水電解液にはある程度の粘性があるため、
非水電解液は電極群内部へ浸透しにくい。さらに、充放
電により電池内ではリチウムイオン吸蔵・脱離に伴う活
物質の膨張・収縮により非水電解液の移動が起こるが、
充放電サイクルを繰り返すと前記非水電解液の移動に起
因して電極群の各部で非水電解液の分布の不均一が生じ
る。つまり円筒形リチウムイオン電池の底面または上底
面付近には非水電解液が集中し、中腹部においては液枯
れが生じやすくなる。この非水電解液の不均一な分布は
充放電サイクルの繰り返しによる電池容量の低下および
電池電圧の低下の原因となる。[0003] In the cylindrical lithium ion battery, the stacked electrode group is in a spirally densely wound state, and the nonaqueous electrolyte has a certain degree of viscosity.
The non-aqueous electrolyte does not easily penetrate into the electrode group. In addition, the non-aqueous electrolyte moves due to expansion and contraction of the active material due to lithium ion occlusion and desorption in the battery due to charge and discharge.
When the charge / discharge cycle is repeated, the non-aqueous electrolyte is unevenly distributed in each part of the electrode group due to the movement of the non-aqueous electrolyte. That is, the non-aqueous electrolyte concentrates near the bottom or upper bottom of the cylindrical lithium ion battery, and the middle abdomen tends to wither. The non-uniform distribution of the non-aqueous electrolyte causes a reduction in battery capacity and a reduction in battery voltage due to repeated charge and discharge cycles.
【０００４】さらに近年の高容量二次電池への需要の高
まりに基づいて、電池の高容量化のために電極サイズを
大型化したり、または、電極の密度が高くすると、前述
した非水電解液の分布の不均一およびそれに起因する電
池特性の低下はより顕著となるという問題が発生してい
る。[0004] Further, in response to the recent increase in demand for high capacity secondary batteries, if the size of the electrodes is increased or the density of the electrodes is increased in order to increase the capacity of the batteries, the above-mentioned nonaqueous electrolytic solution is used. Has a problem that the distribution of non-uniformity and the deterioration of battery characteristics caused by the uneven distribution become more remarkable.
【０００５】従来非水電解液の浸透性の向上のために、
帯状電極の長手方向に対して平行に連続的な浅い溝を形
成する方法(特開平１０−２７００１６号公報)等が提案
されているが、この技術は電池製造時の非水電解液を注
入工程において、非水電解液の電池内部への浸透性を良
くして電池の初期容量の向上を図ることを目的としたも
ので、充放電サイクルの繰り返しにより生じる非水電解
液の分布の不均一およびそれに起因する電池特性の低下
は十分に改善されない。Conventionally, in order to improve the permeability of a non-aqueous electrolyte,
A method of forming a continuous shallow groove parallel to the longitudinal direction of the strip-shaped electrode (Japanese Patent Laid-Open No. Hei 10-270016) has been proposed, but this technique involves a process of injecting a non-aqueous electrolyte during battery production. In the purpose of improving the initial capacity of the battery by improving the permeability of the non-aqueous electrolyte into the battery, uneven distribution of the non-aqueous electrolyte caused by repeated charge and discharge cycles and Deterioration of the battery characteristics resulting therefrom is not sufficiently improved.
【０００６】[0006]
【発明が解決しようとする課題】本発明の課題は、前述
した問題を解決するために、充放電サイクルの繰り返し
による容量の低下および電池電圧の低下が少ない長寿命
の非水電解液二次電池を提供することである。SUMMARY OF THE INVENTION An object of the present invention is to provide a long-life non-aqueous electrolyte secondary battery in which a decrease in capacity and a decrease in battery voltage due to repetition of charge / discharge cycles are small. It is to provide.
【０００７】[0007]
【課題を解決するための手段】本発明は、集電体の表面
に帯状の正極活物質層が形成されてなる正極、集電体の
表面に負極活物質層が形成されてなる帯状の負極、及び
前記正極及び前記負極との間に介在するセパレータが積
層されて渦巻状に捲回されてなる電極群と、非水電解液
とが容器に収納されてなる非水電解液二次電池におい
て、前記正極及び前記負極の少なくとも一方は前記活物
質層に溝を有し、前記溝の少なくとも一端が前記活物質
層の長辺上で終止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 positive electrode comprising a current collector having a band-shaped positive electrode active material layer formed thereon, and a band-shaped negative electrode comprising a current collector having a negative electrode active material layer formed thereon. And a non-aqueous electrolyte secondary battery in which a separator interposed between the positive electrode and the negative electrode is stacked and spirally wound, and a non-aqueous electrolyte is contained in a container. Wherein at least one of the positive electrode and the negative electrode has a groove in the active material layer, and at least one end of the groove terminates on a long side of the active material layer. Battery.
【０００８】前記溝の幅は前記溝の長さの５０％以下で
あり、前記溝の深さが前記活物質層の厚さ８０％以下で
あることが望ましい。The width of the groove is preferably 50% or less of the length of the groove, and the depth of the groove is preferably 80% or less of the thickness of the active material layer.
【０００９】本発明において電極に設けられる溝は、非
水電解液が電極へ浸透する速度を増すとともに、溝の壁
面において電極活物質層の深部と非水電解液が接触する
ことにより電極の面方向および厚み方向の非水電解液の
分布の均一性を高めるように作用する。In the present invention, the groove provided in the electrode increases the speed at which the non-aqueous electrolyte penetrates into the electrode, and the surface of the electrode is brought into contact with the deep portion of the electrode active material layer on the wall surface of the groove. It acts to increase the uniformity of distribution of the non-aqueous electrolyte in the direction and thickness direction.
【００１０】また、非水電解液二次電池においては充放
電に伴い活物質が膨張・収縮するため、非水電解液が電
極中から電極群の外へ浸出し、また浸入するというサイ
クルが繰り返される。In a non-aqueous electrolyte secondary battery, since the active material expands and contracts with charging and discharging, a cycle in which the non-aqueous electrolyte leaches from the inside of the electrode to the outside of the electrode group, and enters again is repeated. It is.
【００１１】本発明の如く電極が積層されて捲回されて
なる電池において、溝の少なくとも一端が活物質層の長
辺上に達していることにより、この非水電解液の浸出・
浸入が電極群内で偏ることなく主に捲回軸方向において
スムーズかつ均一に行われ、非水電解液の分布の均一性
が保たれる。In the battery in which the electrodes are stacked and wound as in the present invention, since at least one end of the groove reaches the long side of the active material layer, the leaching of the nonaqueous electrolyte is prevented.
Penetration is performed smoothly and uniformly mainly in the direction of the winding axis without unevenness in the electrode group, and the uniformity of the distribution of the non-aqueous electrolyte is maintained.
【００１２】従って、本発明によれば、充放電サイクル
の繰り返しによる容量の低下および電池電圧の低下が少
ない長寿命の非水電解液二次電池を提供することができ
る。Therefore, according to the present invention, it is possible to provide a long-life non-aqueous electrolyte secondary battery in which a decrease in capacity and a decrease in battery voltage due to repeated charge / discharge cycles are small.
【００１３】[0013]
【発明の実施の形態】以下、本発明の望ましい実施の形
態について詳細に説明する。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, preferred embodiments of the present invention will be described in detail.
【００１４】図１は本発明に関わる非水電解液二次電池
の一構成例を示す斜視図である。FIG. 1 is a perspective view showing an example of the configuration of a non-aqueous electrolyte secondary battery according to the present invention.
【００１５】非水電解液二次電池は、正極６と、負極７
とがセパレータ８を介して積層され、前記積層体が渦巻
状に捲回され電極群９が形成されており、この電極群９
と、非水電解液とが缶からなる容器１０に収納され密閉
された構造を有する。正極６および負極７のうち少なく
とも一方６には溝４が設けられている。本発明の電池に
おいて正極あるいは負極にかかる捲回圧力は０．２〜２
０ｋｇ／ｃｍ２の範囲であることが望ましい。この範囲
にある電池に対し本発明の構成は特に有効である。The non-aqueous electrolyte secondary battery comprises a positive electrode 6 and a negative electrode 7.
Are laminated with a separator 8 interposed therebetween, and the laminate is spirally wound to form an electrode group 9.
And a non-aqueous electrolyte are housed in a can 10 made of a can and hermetically sealed. A groove 4 is provided in at least one of the positive electrode 6 and the negative electrode 7. In the battery of the present invention, the winding pressure applied to the positive electrode or the negative electrode is 0.2 to 2
It is desirable to be in the range of 0 kg / cm 2 . The configuration of the present invention is particularly effective for batteries in this range.
【００１６】次に上記正極６あるいは負極７の構造につ
いてさらに詳細に説明する。Next, the structure of the positive electrode 6 or the negative electrode 7 will be described in more detail.
【００１７】図２は本発明の正極または負極を示す斜視
図である。FIG. 2 is a perspective view showing a positive electrode or a negative electrode of the present invention.
【００１８】図２（ａ）は正極あるいは負極（以下電極
とする）を示す斜視図であり、図２（ｂ）は電極の側面
（図２（ａ）の四角で囲った部分）を示す断面図であ
る。図２（ａ）、（ｂ）において非水電解液二次電池用
の電極１は、活物質を含む活物質層２が集電体３の片面
もしくは両面（図２においては両面）に形成されて構成
されている。活物質層の平面の形状は帯状すなわち長方
形をなしている。活物質層２には溝４が設けられてい
る。溝４の少なくとも一端は帯状の活物質層の長辺上で
終止している。また、集電体３には集電用タブ５が接続
されている。FIG. 2A is a perspective view showing a positive electrode or a negative electrode (hereinafter referred to as an electrode), and FIG. 2B is a cross-sectional view showing a side surface of the electrode (a portion surrounded by a square in FIG. 2A). FIG. 2 (a) and 2 (b), an electrode 1 for a non-aqueous electrolyte secondary battery has an active material layer 2 containing an active material formed on one or both sides of a current collector 3 (both sides in FIG. 2). It is configured. The planar shape of the active material layer has a band shape, that is, a rectangular shape. A groove 4 is provided in the active material layer 2. At least one end of the groove 4 terminates on the long side of the strip-shaped active material layer. Further, a current collecting tab 5 is connected to the current collector 3.
【００１９】溝４は複数形成されていることが非水電解
液の分布の均一性を高めるために望ましい。活物質層に
占める全溝の比率は活物質層の面積に対して、溝部分の
合計の面積が１％以上１５％以下の範囲であることが本
発明の効果を十分に得るために望ましい。It is desirable that a plurality of grooves 4 be formed in order to improve the uniformity of distribution of the non-aqueous electrolyte. The ratio of the total groove to the active material layer is preferably such that the total area of the groove portions is in the range of 1% to 15% with respect to the area of the active material layer in order to sufficiently obtain the effects of the present invention.
【００２０】また、複数の溝４を形成する場合は、溝と
溝の間隔は電極の幅方向の長さ以下とすることが電極全
体に均一な効果を及ぼすことができるため望ましい。こ
こで幅方向とは電極の捲回軸に平行な方向、すなわち捲
回した電極コイルの高さとなる方向とする。複数の溝４
は一点以上の箇所で互いに交差していてもよい。溝４は
直線でも曲線でもよい。溝４の配列は何らかの規則性を
有しているのが好ましいが、ランダムでもよい。When a plurality of grooves 4 are formed, it is desirable that the distance between the grooves be equal to or less than the length in the width direction of the electrode because a uniform effect can be exerted on the entire electrode. Here, the width direction is a direction parallel to the winding axis of the electrode, that is, a direction that becomes the height of the wound electrode coil. Multiple grooves 4
May cross each other at one or more points. The groove 4 may be straight or curved. The arrangement of the grooves 4 preferably has some regularity, but may be random.
【００２１】溝４の断面の形状は、Ｖ字形、Ｕ字形、半
円状、コの字形の他、どのような形状でもよい。The cross-sectional shape of the groove 4 may be V-shaped, U-shaped, semicircular, U-shaped, or any other shape.
【００２２】溝４の深さは活物質層３の厚さの５％以上
８０％以下であることが電極の郷土を保つために望まし
い。また、溝４の幅は、電極の幅の０．１％以上２％以
下であることが好ましい。この範囲であると良好な改善
効果が得られるとともに、溝形成による容量の低下を最
小限に抑えることができる。It is desirable that the depth of the groove 4 is not less than 5% and not more than 80% of the thickness of the active material layer 3 in order to maintain the locality of the electrode. The width of the groove 4 is preferably 0.1% or more and 2% or less of the width of the electrode. Within this range, a good improvement effect can be obtained, and a decrease in capacitance due to the formation of the groove can be minimized.
【００２３】溝４の壁面の表面粗さは、電極表面に比較
して、より高くなっているものがよい。このような深さ
・壁面粗さの溝４を形成した電極では、非水電解液の浸
透性および均一性の保持力の改善効果がより大きくな
る。また、負極に溝を形成する場合においては、充電時
に溝４が形成された部分にリチウムが析出しやすくなる
恐れがあるが、溝の幅を極力小さくすることによりリチ
ウムの析出を抑えることができる。The surface roughness of the wall surface of the groove 4 is preferably higher than that of the electrode surface. In the electrode in which the groove 4 having the depth and the wall surface roughness is formed, the effect of improving the permeability of the nonaqueous electrolyte and the holding power of the uniformity is further increased. Further, in the case where a groove is formed in the negative electrode, lithium may easily precipitate at a portion where the groove 4 is formed at the time of charging, but the precipitation of lithium can be suppressed by minimizing the width of the groove. .
【００２４】本発明においては上記の如く活物質層に溝
を形成した電極を少なくとも正極あるいは負極の少なく
とも一方に使用する。特に電極の多孔度は正極の方が負
極に比べて低くなることが多いため、正極の前記活物質
層に溝を形成したものを用いることが特に有効である
が、負極を高密度化し負極の多孔度が低下した場合にお
いては、正極・負極の両方、または負極のみにおける溝
の形成も有効である。In the present invention, an electrode having a groove formed in the active material layer as described above is used as at least one of a positive electrode and a negative electrode. In particular, since the porosity of the electrode is often lower in the positive electrode than in the negative electrode, it is particularly effective to use a material in which a groove is formed in the active material layer of the positive electrode. When the porosity is reduced, it is also effective to form a groove in both the positive electrode and the negative electrode or only the negative electrode.
【００２５】また、活物質層における溝の形成は、例え
ば金属またはセラミックスなどを用いた活物質層の切除
または研磨、溶剤を用いた除去などの活物質層の掘削に
よるのが好ましい。溝の製造工程は、集電体上に活物質
層を形成した後、乾燥及び圧延後に行うのが好ましい
が、乾燥の前後、圧延の前後のいずれの段階で行っても
よい。The formation of the groove in the active material layer is preferably performed by excavation or polishing of the active material layer using a metal or ceramics, or excavation of the active material layer such as removal using a solvent. The manufacturing process of the groove is preferably performed after forming the active material layer on the current collector and then drying and rolling, but may be performed before or after drying or before and after rolling.
【００２６】次に前記正極、前記負極、前記セパレータ
及び、前記非水電解液について詳細に説明する。 １）正極 正極は、活物質を含む正極活物質層が正極集電体の片面
もしくは両面に担持された構造を有する。Next, the positive electrode, the negative electrode, the separator, and the non-aqueous electrolyte will be described in detail. 1) Positive Electrode The positive electrode has a structure in which a positive electrode active material layer containing an active material is supported on one or both surfaces of a positive electrode current collector.
【００２７】前記正極活物質層の片面の厚さは１０〜１
５０μｍの範囲であることが望ましい。従って正極集電
体の両面に担持されている場合は正極活物質層の合計の
厚さは２０〜３００μmの範囲となることが望ましい。
片面のより好ましい範囲は３０〜１２０μｍである。こ
の範囲であると大電流放電特性とサイクル寿命は向上す
る。The thickness of one side of the positive electrode active material layer is 10 to 1
It is desirable that the thickness be in the range of 50 μm. Therefore, when it is carried on both surfaces of the positive electrode current collector, the total thickness of the positive electrode active material layer is desirably in the range of 20 to 300 μm.
A more preferable range on one side is 30 to 120 μm. Within this range, large current discharge characteristics and cycle life are improved.
【００２８】正極活物質層は、正極活物質の他に導電剤
を含んでいてもよい。The positive electrode active material layer may include a conductive agent in addition to the positive electrode active material.
【００２９】また、正極活物質層は正極材料同士を結着
する結着剤を含んでいてもよい。Further, the positive electrode active material layer may contain a binder for binding the positive electrode materials to each other.
【００３０】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
ウム含有ニッケルコバルト酸化物（例えば、ＬｉＣｏＯ
２）、リチウム含有ニッケルコバルト酸化物（例えばＬ
ｉＮｉ０．８Ｃｏ０．２Ｏ２）、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。As the positive electrode active material, various oxides, for example, manganese dioxide, lithium manganese composite oxide, lithium-containing nickel cobalt oxide (for example, LiCoO 2
2 ), lithium-containing nickel cobalt oxide (for example, L
It is preferable to use iNi 0.8 Co 0.2 O 2 ) or a lithium manganese composite oxide (eg, LiMn 2 O 4 or LiMnO 2 ) because a high voltage can be obtained.
【００３１】導電剤としてはアセチレンブラック、カー
ボンブラック、黒鉛などを挙げることができる。Examples of the conductive agent include acetylene black, carbon black, graphite and the like.
【００３２】結着材の具体例としては例えばポリテトラ
フルオロエチレン（ＰＴＦＥ）、ポリ弗化ビニリデン
（ＰＶｄＦ）、エチレン−プロピレン−ジエン共重合体
（ＥＰＤＭ）、スチレン−ブタジエンゴム（ＳＢＲ）等
を用いることができる。Specific examples of the binder include, for example, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), ethylene-propylene-diene copolymer (EPDM), and styrene-butadiene rubber (SBR). be able to.
【００３３】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
％、結着剤２〜７重量％の範囲にすることが好ましい。The mixing ratio of the positive electrode active material, the conductive agent and the binder is 80 to 95% by weight of the positive electrode active material, 3 to 20% of the conductive agent.
%, And a binder in a range of 2 to 7% by weight.
【００３４】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。集
電体の厚さは５〜２０μｍであることが望ましい。この
範囲であると電極強度と軽量化のバランスがとれるから
である。 ２）負極 負極は、負極材料を含む負極活物質が負極集電体の片面
もしくは両面に担持された構造を有する。As the current collector, a conductive substrate having a porous structure or a non-porous conductive substrate can be used. The current collector preferably has a thickness of 5 to 20 μm. This is because in this range, the balance between electrode strength and weight reduction can be achieved. 2) Negative electrode The negative electrode has a structure in which a negative electrode active material containing a negative electrode material is supported on one or both surfaces of a negative electrode current collector.
【００３５】前記負極活物質層の厚さは１０〜１５０μ
ｍの範囲であることが望ましい。従って負極集電体の両
面に担持されている場合は負極活物質層の合計の厚さは
２０〜３００μｍの範囲となる。片面の厚さのより好ま
しい範囲は３０〜１００μｍである。この範囲であると
大電流放電特性とサイクル寿命は大幅に向上する。The thickness of the negative electrode active material layer is 10 to 150 μm.
m is desirable. Therefore, when it is carried on both surfaces of the negative electrode current collector, the total thickness of the negative electrode active material layer is in the range of 20 to 300 μm. The more preferable range of the thickness on one side is 30 to 100 μm. Within this range, large current discharge characteristics and cycle life are significantly improved.
【００３６】また、負極活物質層は負極材料同士を結着
する結着剤を含んでいてもよい。The negative electrode active material layer may contain a binder for binding the negative electrode materials to each other.
【００３７】負極材料としてはリチウムイオンを吸蔵・
放出する炭素質物が挙げられる。炭素質物としては、黒
鉛、コークス、炭素繊維、球状炭素等の黒鉛質材料もし
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ｄ
００２が０．３４０nｍ以下である黒鉛結晶を有する黒
鉛質材料を用いることが好ましい。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、電池容量及び大電流特性を大幅に向上することが
できる。面間隔ｄ００２は０．３３６ｎｍ以下であるこ
とがさらに好ましい。As a negative electrode material, occludes lithium ions.
Emitted carbonaceous materials. Examples of the carbonaceous material include graphite, coke, carbon fiber, graphite material or carbonaceous material such as spherical carbon, thermosetting resin, isotropic pitch, mesophase pitch, mesophase pitch-based carbon fiber, mesophase sphere, etc. Graphite material or carbonaceous material obtained by subjecting mesophase pitch-based carbon fiber to heat treatment at 500 to 3000 ° C. can be used. Above all, it can be obtained by setting the temperature of the heat treatment to 2000 ° C. or higher, and the plane distance d of the (002) plane
It is preferable to use a graphitic material having graphite crystals whose 002 is 0.340 nm or less. A non-aqueous electrolyte secondary battery provided with a negative electrode containing such a graphite material as a carbonaceous material can significantly improve battery capacity and large current characteristics. More preferably, the plane distance d 002 is 0.336 nm or less.
【００３８】また、前記炭素質物としては特に２０００
℃以上で熱処理されたメソフェーズピッチ系炭素繊維が
好ましい。これを用いると電極密度を１．３ｇ／ｃｍ３
以上の高密度にしても負極とセパレータ間の界面インピ
ーダンスが小さいため、大電流放電特性、急速充放電サ
イクル性能に優れる。Further, the carbonaceous material is particularly 2,000
Mesophase pitch-based carbon fibers heat-treated at a temperature of not less than ° C are preferred. When this is used, the electrode density is 1.3 g / cm 3
Even at the above-mentioned high density, the interface impedance between the negative electrode and the separator is small, so that it is excellent in large current discharge characteristics and rapid charge / discharge cycle performance.
【００３９】結着剤としては、例えばポリテトラフルオ
ロエチレン（ＰＴＦＥ）、ポリ弗化ビニリデン（ＰＶｄ
Ｆ）、エチレン−プロピレン−ジエン共重合体（ＥＰＤ
Ｍ）、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 (PVd).
F), ethylene-propylene-diene copolymer (EPD)
M), styrene-butadiene rubber (SBR) and the like can be used.
【００４０】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。集電体の厚さは５〜
２０μｍであることが望ましい。この範囲であると電極
強度と軽量化のバランスがとれるからである。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. The thickness of the current collector is 5
Preferably, it is 20 μm. This is because in this range, the balance between electrode strength and weight reduction can be achieved.
【００４１】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、金属酸化物をはじ
めとする金属カルコゲン化合物か、または金属窒化物
か、リチウム金属またはリチウム合金からなるものおよ
び、これらを炭素質物と複合させた材料などを用いるこ
とができる。Examples of the negative electrode material include, in addition to the above-mentioned carbonaceous materials that occlude and release lithium ions, metal chalcogen compounds such as metal oxides, metal nitrides, lithium metal or lithium alloys, and the like. A material obtained by combining these with a carbonaceous material can be used.
【００４２】金属カルコゲン化合物としては、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、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 chalcogen compound include tin oxide, silicon oxide, lithium titanium oxide, niobium oxide, tungsten oxide, tin sulfide, titanium sulfide and the like.
【００４３】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.
【００４４】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を挙げることができる。 ３）セパレータ セパレータは多孔質セパレータを用いる。セパレータの
材料としては、例えば、ポリエチレン、ポリプロピレ
ン、またはポリ弗化ピニリデン（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。Examples of the lithium alloy include a lithium aluminum alloy, a lithium tin alloy, a lithium lead alloy, and a lithium silicon alloy. 3) Separator A porous separator is used as the separator. As a material of the separator, for example, a porous film containing polyethylene, polypropylene, or poly (vinylidene fluoride) (PVdF), a synthetic resin nonwoven fabric, 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.
【００４５】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 thickness of the separator is preferably 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.
【００４６】セパレータは、１２０℃の条件で１時間お
い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、加熱により短絡が起
こる可能性が大きくなる。熱収縮率は、１５％以下にす
ることがより好ましい。The separator preferably has a heat shrinkage of 20% or less when left at 120 ° C. for one hour. If the heat shrinkage exceeds 20%, the possibility of short-circuiting due to heating increases. More preferably, the heat shrinkage is 15% or less.
【００４７】セパレータは、多孔度が３０〜７０％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
において高い電解質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、３５〜７０％である。The porosity of the separator is preferably in the range of 30 to 70%. 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 35-70%.
【００４８】セパレータは、空気透過率が５００秒／１
００ｃｍ３以下であると好ましい。空気透過率が５００
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、３０秒／１００ｃｍ
３である。空気透過率を３０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。The separator has an air permeability of 500 seconds / 1.
It is preferably at most 00 cm 3 . Air permeability 500
If it exceeds sec / 100 cm 3 , it may be difficult to obtain high lithium ion mobility in the separator. The lower limit of the air permeability is 30 seconds / 100 cm.
3 . If the air permeability is less than 30 seconds / 100 cm 3 , sufficient separator strength may not be obtained.
【００４９】空気透過率の上限値は３００秒／１００ｃ
ｍ３にすることがより好ましく、また、下限値は５０秒
／１００ｃｍ３にするとより好ましい。 ４）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
調製される液体状非水電解液で、電極群中の空隙に保持
される。The upper limit of the air permeability is 300 seconds / 100c.
m 3 is more preferable, and the lower limit is more preferably 50 seconds / 100 cm 3 . 4) Non-aqueous electrolyte The non-aqueous electrolyte is a liquid non-aqueous electrolyte prepared by dissolving an electrolyte in a non-aqueous solvent, and is held in a gap in the electrode group.
【００５０】非水溶媒としては、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Ｅ
Ｃより低粘度である非水溶媒（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, propylene carbonate (PC) or ethylene carbonate (EC) and PC or E
It is preferable to use a non-aqueous solvent mainly composed of a mixed solvent with a non-aqueous solvent having a lower viscosity than C (hereinafter, referred to as a second solvent).
【００５１】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（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）等が挙げられる。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 (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 more preferably has a donor number of 16.5 or less.
【００５２】第２溶媒の粘度は、２５℃において２．８
ｃｍｐ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 2.8 at 25 ° C.
cmp or less. The blending amount of ethylene carbonate or propylene carbonate in the mixed solvent is preferably 10 to 80% by volume. A more preferred blending amount of ethylene carbonate or propylene carbonate is 20 to 75% by volume.
【００５３】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）、六弗化リン酸
リチウム（ＬｉＰＦ６）、ホウ弗化リチウム（ＬｉＢＦ
４）、六弗化砒素リチウム（ＬｉＡｓＦ６）、トリフル
オロメタスルホン酸リチウム（ＬｉＣＦ３ＳＯ３）、ビ
ストリフルオロメチルスルホニルイミドリチウム［Ｌｉ
Ｎ（ＣＦ３ＳＯ２）２］等のリチウム塩（電解質）が挙
げられる。中でもＬｉＰＦ６、ＬｉＢＦ４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), Hexafluorophosphoric acid
Lithium (LiPF6), Lithium borofluoride (LiBF
4), Lithium arsenide hexafluoride (LiAsF)6), Trifle
Lithium olometasulfonate (LiCF3SO3), Bi
Lithium trifluoromethylsulfonylimide [Li
N (CF3SO2)2] And other lithium salts (electrolytes)
I can do it. Among them, LiPF6, LiBF4Is to use
preferable.
【００５４】電解質の非水溶媒に対する溶解量は、０．
５〜２．０ｍｏｌ／ｌ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 to 5 to 2.0 mol / l.
【００５５】[0055]
【実施例】（実施例１） ［正極の作製］リチウムコバルト酸化物(ＬｉｘＣｏＯ
２；ただしｘは０≦ｘ≦１である)粉末９１重量％をア
チセレンブラック２．５重量％及びグラファイト粉末
２．５重量％及びポリ弗化ビニリデン粉末４重量％とＮ
−メチルピロリドンを混合し、厚さが２０μｍのアルミ
ニウム箔からなる集電体の両面に塗布した後、乾燥し、
プレスすることにより電極密度を３．３ｇ／ｃｍ３とし
た。さらに電極をスリットし、活物質層の厚さが両面と
も０．１ｍｍあり、全長５６０ｍｍ、全幅５５．２５ｍ
ｍの長方形形状とした。EXAMPLES (Example 1) [Preparation of positive electrode] Lithium cobalt oxide (Li x CoO)
2 ; where x is 0 ≦ x ≦ 1) 91% by weight of the powder is mixed with 2.5% by weight of acetylene black, 2.5% by weight of graphite powder, 4% by weight of polyvinylidene fluoride powder and N
-Methylpyrrolidone was mixed, applied to both sides of a current collector made of aluminum foil having a thickness of 20 μm, and then dried,
The electrode density was adjusted to 3.3 g / cm 3 by pressing. The electrode is further slit, and the thickness of the active material layer is 0.1 mm on both sides, the total length is 560 mm, and the total width is 55.25 m.
m rectangular shape.
【００５６】次に前記活物質層に所定のサイズの金属製
の刃で削ることにより溝を形成した。Next, a groove was formed in the active material layer by shaving with a metal blade having a predetermined size.
【００５７】図３に実施例１に係る活物質層２の平面図
を示す。正極の両面の活物質層２表面に、図３に示すよ
うな活物質層２の長手方向に対して直角を成す、直線状
の深さ約０．０５ｍｍ、幅約０．５ｍｍの溝４を、電極
幅方向に互いに平行になるように７ｍｍ間隔で形成し
た。溝４の断面の形状はＶ字状とした。FIG. 3 is a plan view of the active material layer 2 according to the first embodiment. On the surface of the active material layer 2 on both surfaces of the positive electrode, a linear groove 4 having a depth of about 0.05 mm and a width of about 0.5 mm, which is perpendicular to the longitudinal direction of the active material layer 2 as shown in FIG. And formed at intervals of 7 mm so as to be parallel to each other in the electrode width direction. The cross section of the groove 4 was V-shaped.
【００５８】また、電極の表と裏で形成した溝の配列を
半周期ずらし、溝の位置が表面と裏面で重ならないよう
にした。活物質層の面積に占める全溝の合計の面積の割
合は約７％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 ７８重量％及び、グラファイト粉
末１９重量％、カルボキシメチルセルロース粉末を重量
１％、スチレンブタジエンゴムを重量２％と水を混合
し、厚さ１５μｍの銅箔からなる集電体の両面に塗付
し、乾燥し、プレスすることにより電極密度を１．３７
ｇ／ｃｍ３とした。電極をスリットし、活物質層の厚さ
が両面とも０．０８ｍｍ、全長が５７０ｍｍ、全幅が５
７．２５ｍｍとし、負極を作製した。 ［セパレータ］厚さ２５μｍのポリエチレン製多孔性セ
パレータを使用した。セパレータの多孔度は４０％、透
気度は１５０秒／１００ｃｍ３であった。 ［非水電解液］非水電解液として、六弗化リン酸リチウ
ム（ＬｉＰＦ６）をエチレンカーボネート（ＥＣ）とエ
チルメチルカーボネート（ＥＭＣ）の混合溶媒（混合体
積比率１：２）に１ｍｏｌ／ｌの濃度に溶解して非水電
解液を調整した。 ［電極群の作製］作製した正極及び負極とセパレータ
を、セパレータ、正極、セパレータ、負極の順に積層
し、渦巻状に捲回して電極群を作製した。 ［電池の作製］電極群および非水電解液をニッケルメッ
キした軟鋼製の有底円筒状容器内にそれぞれ収納して前
述した図１に示す非水電解液二次電池(１８６５０サイ
ズ)を組み立てた。電極にかかる捲回圧力は１ｋｇ／ｃ
ｍ２であった。 （実施例２） ［正極の作製］正極は、プレスおよびスリットまでの工
程を実施例１と同様に行い、さらに金属製の刃で削るこ
とによって溝を形成した。図４に実施例２に係る活物質
層２の平面図を示す。正極の両面の活物質層２表面に、
図４に示すような直線状の深さ約０．０５ｍｍ、幅約
０．５ｍｍの溝を、電極の長手方向に対して電極の上端
および下端からそれぞれ−４５°および４５°の角度に
７ｍｍ間隔で平行に形成した。溝４の断面の形状はＶ字
状とした。The arrangement of the grooves formed on the front and back of the electrode is shifted by a half cycle so that the positions of the grooves do not overlap on the front and back surfaces. The ratio of the total area of all the grooves to the area of the active material layer was about 7%. [Production 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 ): 0.3
(360 nm) powder, 78% by weight of graphite powder, 19% by weight of graphite powder, 1% by weight of carboxymethylcellulose powder, 2% by weight of styrene-butadiene rubber and water, and both sides of a current collector made of copper foil having a thickness of 15 μm. , Dried and pressed to obtain an electrode density of 1.37.
g / cm 3 . The electrode is slit, the thickness of the active material layer is 0.08 mm on both sides, the total length is 570 mm, and the total width is 5
The thickness was set to 7.25 mm to produce a negative electrode. [Separator] A polyethylene porous separator having a thickness of 25 μm was used. The porosity of the separator was 40%, and the air permeability was 150 seconds / 100 cm 3 . [Non-aqueous electrolyte] As a non-aqueous electrolyte, 1 mol / l of lithium hexafluorophosphate (LiPF 6 ) was mixed in a mixed solvent of ethylene carbonate (EC) and ethyl methyl carbonate (EMC) (mixing volume ratio 1: 2). To obtain a non-aqueous electrolyte solution. [Production of Electrode Group] The produced positive electrode, negative electrode and separator were laminated in the order of a separator, a positive electrode, a separator, and a negative electrode, and spirally wound to produce an electrode group. [Production of Battery] The non-aqueous electrolyte secondary battery (18650 size) shown in FIG. 1 described above was assembled by storing the electrode group and the non-aqueous electrolyte in nickel-plated mild steel bottomed cylindrical containers. . The winding pressure applied to the electrode is 1 kg / c
It was m 2. (Example 2) [Preparation of positive electrode] In the positive electrode, the steps up to pressing and slitting were performed in the same manner as in Example 1, and a groove was formed by shaving with a metal blade. FIG. 4 is a plan view of the active material layer 2 according to the second embodiment. On the surface of the active material layer 2 on both surfaces of the positive electrode,
Linear grooves having a depth of about 0.05 mm and a width of about 0.5 mm as shown in FIG. 4 are formed at intervals of 7 mm at angles of -45 ° and 45 ° from the upper and lower ends of the electrode with respect to the longitudinal direction of the electrode, respectively. And formed in parallel. The cross section of the groove 4 was V-shaped.
【００５９】また、電極の表と裏で形成した溝の配列を
半周期ずらし、溝の位置が表面と裏面で重ならないよう
にした。活物質層の面積に占める全溝の合計の面積の割
合は約１４％であった。 ［負極の作製］負極は実施例１と同様に作製した。 ［セパレータ］セパレータは実施例１と同様のものを使
用した。 ［非水電解液］非水電解液は実施例１と同様のものを使
用した。 ［電極群の作製］作製した正極及び負極とセパレータ
を、セパレータ、正極、セパレータ、負極の順に積層
し、渦巻状に捲回して電極群を作製した。 ［電池の作製］電極群および非水電解液をニッケルメッ
キした軟鋼製の有底円筒状容器内にそれぞれ収納して前
述した図１に示す非水電解液二次電池(１８６５０サイ
ズ)を組み立てた。電極にかかる捲回圧力は１ｋｇ／ｃ
ｍ２であった。 （実施例３） ［正極の作製］正極は実施例１と同様に作製した。 ［負極の作製］負極は、プレスおよびスリットまでの工
程を実施例１の負極と同様に行い、さらに金属製の刃に
よって削ることによって溝を形成した。図３に実施例３
に係る活物質層２の平面図を示す。負極の両面の活物質
層２表面に、図３に示すような活物質層２の長手方向に
対して直角を成す、直線状の深さ約０．０５ｍｍ、幅約
０．５ｍｍの溝４を、電極幅方向に互いに平行になるよ
うに７ｍｍ間隔で形成した。溝４の断面の形状はＶ字状
とした。The arrangement of the grooves formed on the front and back of the electrode is shifted by half a cycle so that the positions of the grooves do not overlap on the front and back surfaces. The ratio of the total area of all the grooves to the area of the active material layer was about 14%. [Production of Negative Electrode] A negative electrode was produced in the same manner as in Example 1. [Separator] The same separator as in Example 1 was used. [Non-Aqueous Electrolyte] The same non-aqueous electrolyte as used in Example 1 was used. [Production of Electrode Group] The produced positive electrode, negative electrode and separator were laminated in the order of a separator, a positive electrode, a separator, and a negative electrode, and spirally wound to produce an electrode group. [Production of Battery] The non-aqueous electrolyte secondary battery (18650 size) shown in FIG. 1 described above was assembled by storing the electrode group and the non-aqueous electrolyte in nickel-plated mild steel bottomed cylindrical containers. . The winding pressure applied to the electrode is 1 kg / c
It was m 2. (Example 3) [Production of positive electrode] A positive electrode was produced in the same manner as in Example 1. [Preparation of Negative Electrode] In the negative electrode, steps up to pressing and slitting were performed in the same manner as in the negative electrode of Example 1, and a groove was formed by shaving with a metal blade. FIG. 3 shows a third embodiment.
1 is a plan view of an active material layer 2 according to the first embodiment. On the surface of the active material layer 2 on both surfaces of the negative electrode, a linear groove 4 having a depth of about 0.05 mm and a width of about 0.5 mm, which is perpendicular to the longitudinal direction of the active material layer 2 as shown in FIG. And formed at intervals of 7 mm so as to be parallel to each other in the electrode width direction. The cross section of the groove 4 was V-shaped.
【００６０】また、電極の表と裏で形成した溝の配列を
半周期ずらし、溝の位置が表面と裏面で重ならないよう
にした。活物質層の面積に占める全溝の合計の面積の割
合は約７％であった。 ［セパレータ］セパレータは実施例１と同様のものを使
用した。 ［非水電解液］非水電解液は実施例１と同様のものを使
用した。 ［電極群の作製］作製した正極及び負極とセパレータ
を、セパレータ、正極、セパレータ、負極の順に積層
し、渦巻状に捲回して電極群を作製した。 ［電池の作製］電極群および非水電解液をニッケルメッ
キした軟鋼製の有底円筒状容器内にそれぞれ収納して前
述した図１に示す非水電解液二次電池(１８６５０サイ
ズ)を組み立てた。電極にかかる捲回圧力は１ｋｇ／ｃ
ｍ２であった。 （比較例１）正極に圧延およびスリット後に溝の形成を
行わず、正極・負極ともに溝が形成されていない電極を
用いて、実施例１と同様にして円筒型非水電解液二次電
池を組み立てた。The arrangement of the grooves formed on the front and back of the electrode is shifted by half a cycle so that the positions of the grooves do not overlap on the front and back surfaces. The ratio of the total area of all the grooves to the area of the active material layer was about 7%. [Separator] The same separator as in Example 1 was used. [Non-Aqueous Electrolyte] The same non-aqueous electrolyte as used in Example 1 was used. [Production of Electrode Group] The produced positive electrode, negative electrode and separator were laminated in the order of a separator, a positive electrode, a separator, and a negative electrode, and spirally wound to produce an electrode group. [Production of Battery] The non-aqueous electrolyte secondary battery (18650 size) shown in FIG. 1 described above was assembled by storing the electrode group and the non-aqueous electrolyte in nickel-plated mild steel bottomed cylindrical containers. . The winding pressure applied to the electrode is 1 kg / c
It was m 2. (Comparative Example 1) A cylindrical non-aqueous electrolyte secondary battery was prepared in the same manner as in Example 1 except that no groove was formed on the positive electrode after rolling and slitting, and an electrode having no groove was formed on both the positive electrode and the negative electrode. Assembled.
【００６１】得られた実施例１〜３、比較例１の二次電
池について、２０℃の環境下で充電電流１．８Ａで４．
２Ｖまで３時間充電し、２．７Ｖまで１．８Ａで放電
し、充放電サイクル試験を行い比較した。それぞれの電
池の初期容量を表１に示す。The obtained secondary batteries of Examples 1 to 3 and Comparative Example 1 were charged at a charging current of 1.8 A under an environment of 20 ° C.
The battery was charged to 2 V for 3 hours, discharged to 2.7 V at 1.8 A, subjected to a charge / discharge cycle test, and compared. Table 1 shows the initial capacity of each battery.
【表１】 活物質量から計算した理論容量は各電池とも１．８Ａｈ
である。また、充放電サイクル試験の結果を図５に示
す。[Table 1] The theoretical capacity calculated from the amount of active material is 1.8 Ah for each battery.
It is. FIG. 5 shows the results of the charge / discharge cycle test.
【００６２】表１から明らかなように、実施例１〜３と
比較例１の非水電解液二次電池との間で、電池の初期容
量に有意な差は見られない。また、図５から明らかなよ
うに、実施例１〜３の非水電解液二次電池は５００サイ
クルで初期容量の８０％以上の容量を維持しており、非
常に優れた特性を示す。一方、比較例１の非水電解液二
次電池は５００サイクルで初期容量の６０％程度まで容
量が低下する。従って、実施例１〜３の非水電解液二次
電池は、サイクル特性が比較例１に比べて大幅に向上
し、かつ容量は維持したままである。As is evident from Table 1, there is no significant difference in the initial capacity of the battery between the non-aqueous electrolyte secondary batteries of Examples 1 to 3 and Comparative Example 1. Further, as is apparent from FIG. 5, the nonaqueous electrolyte secondary batteries of Examples 1 to 3 maintain a capacity of 80% or more of the initial capacity in 500 cycles, and exhibit extremely excellent characteristics. On the other hand, the capacity of the non-aqueous electrolyte secondary battery of Comparative Example 1 is reduced to about 60% of the initial capacity in 500 cycles. Therefore, in the nonaqueous electrolyte secondary batteries of Examples 1 to 3, the cycle characteristics are significantly improved as compared with Comparative Example 1, and the capacity is maintained.
【００６３】[0063]
【発明の効果】本発明によれば、電池容量を低下させる
ことなく非水電解液の浸透性および非水電解液の均一な
保持に優れた電極を提供し、さらにこの電極を使用する
ことにより充放電の繰り返しによる容量の低下および、
電池電圧の低下が少ない非水電解液二次電池を提供する
ことができる。According to the present invention, it is possible to provide an electrode having excellent permeability of a non-aqueous electrolyte and uniform holding of the non-aqueous electrolyte without lowering the battery capacity. Decrease in capacity due to repeated charge and discharge, and
It is possible to provide a non-aqueous electrolyte secondary battery in which a decrease in battery voltage is small.
【図１】 本発明の非水電解液二次電池の斜視図。FIG. 1 is a perspective view of a non-aqueous electrolyte secondary battery of the present invention.
【図２】 本発明の非水電解液二次電池の正極あるいは
負極を示す斜視図及び断面図。FIG. 2 is a perspective view and a sectional view showing a positive electrode or a negative electrode of the nonaqueous electrolyte secondary battery of the present invention.
【図３】 実施例１、３に係る電極の平面図。FIG. 3 is a plan view of an electrode according to the first and third embodiments.
【図４】 実施例２に係る電極の平面図。FIG. 4 is a plan view of an electrode according to a second embodiment.
【図５】 本発明の実施例および比較例のリチウム二次
電池のサイクル寿命を示す特性図。FIG. 5 is a characteristic diagram showing the cycle life of lithium secondary batteries of Examples and Comparative Examples of the present invention.
１…電極 ２…活物質層 ３…集電体 ４…溝 ５…集電用タブ ６…正極 ７…負極 ８…セパレータ ９…電極群 １０…電池缶 DESCRIPTION OF SYMBOLS 1 ... Electrode 2 ... Active material layer 3 ... Current collector 4 ... Groove 5 ... Current collecting tab 6 ... Positive electrode 7 ... Negative electrode 8 ... Separator 9 ... Electrode group 10 ... Battery can
───────────────────────────────────────────────────── フロントページの続き (72)発明者 門馬 旬 神奈川県川崎市幸区堀川町72番地 株式会 社東芝川崎事業所内 (72)発明者 小岩 馨 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 佐藤 麻子 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 高見 則雄 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 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 Ｆターム(参考） 5H014 AA02 AA04 BB04 CC04 CC07 EE08 EE10 HH06 5H029 AJ02 AJ03 AJ05 AJ14 AK03 AL02 AL04 AL07 AL12 AL18 AM03 AM04 AM05 AM07 BJ02 BJ14 CJ02 CJ03 CJ04 CJ07 CJ08 CJ22 DJ12 DJ14 HJ04 HJ12 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Shun Kadoma 72, Horikawa-cho, Saiwai-ku, Kawasaki-shi, Kanagawa Pref. Inside the Toshiba Kawasaki Office (72) Inventor Asako Sato 72 Horikawa-cho, Saiwai-ku, Kawasaki-shi, Kanagawa Pref. Inside the Kawasaki Plant (72) Inventor Takahisa Osaki 72 Horikawa-cho, Saiwai-ku, Kawasaki City, Kanagawa Prefecture F-term in the Toshiba Kawasaki Plant (Reference) 5H014 AA02 AA04 BB04 CC04 CC07 EE08 EE10 HH06 5H029 AJ02 AJ03 AJ05 AJ14 AK03 AL02 AL04 AL04 AL12 AL18 AM03 AM04 AM05 AM07 BJ02 BJ14 CJ02 CJ03 CJ04 CJ07 CJ08 CJ22 DJ12 DJ14 HJ04 HJ12
Claims (2)
されてなる正極、集電体の表面に負極活物質層が形成さ
れてなる帯状の負極、及び前記正極及び前記負極との間
に介在するセパレータが積層されて渦巻状に捲回されて
なる電極群と、非水電解液とが容器に収納されてなる非
水電解液二次電池において、前記正極及び前記負極の少
なくとも一方は前記活物質層に溝を有し、前記溝の少な
くとも一端が前記活物質層の長辺上で終止していること
を特徴とする非水電解液二次電池。1. A positive electrode comprising a current collector with a band-shaped positive electrode active material layer formed on a surface thereof, a band-shaped negative electrode comprising a current collector having a negative electrode active material layer formed on a surface thereof, and the positive electrode and the negative electrode. In a non-aqueous electrolyte secondary battery in which a separator interposed therebetween is laminated and spirally wound, and a non-aqueous electrolyte is contained in a container, at least the positive electrode and the negative electrode One has a groove in the active material layer, and at least one end of the groove terminates on a long side of the active material layer.
あり、前記溝の深さが前記活物質層の厚さ８０％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。2. The method according to claim 1, wherein the width of the groove is not more than 50% of the length of the groove, and the depth of the groove is not more than 80% of the thickness of the active material layer. Non-aqueous electrolyte secondary battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP36159899A JP2001176558A (en) | 1999-12-20 | 1999-12-20 | Non-aqueous electrolyte secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP36159899A JP2001176558A (en) | 1999-12-20 | 1999-12-20 | Non-aqueous electrolyte secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001176558A true JP2001176558A (en) | 2001-06-29 |
Family
ID=18474239
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP36159899A Pending JP2001176558A (en) | 1999-12-20 | 1999-12-20 | Non-aqueous electrolyte secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2001176558A (en) |
Cited By (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003197265A (en) * | 2001-12-27 | 2003-07-11 | Sanyo Electric Co Ltd | Nonaqueous electrolytic solution battery |
| WO2003088404A1 (en) * | 2002-04-12 | 2003-10-23 | Kabushiki Kaisha Toshiba | Nonaqueous electrolyte secondary battery |
| WO2004036670A1 (en) * | 2002-10-15 | 2004-04-29 | Kabushiki Kaisha Toshiba | Nonacqueous electrolyte secondary cell |
| JP2004303754A (en) * | 2003-03-28 | 2004-10-28 | Nissan Diesel Motor Co Ltd | Method and apparatus for manufacturing electric double layer capacitor |
| JP2005285607A (en) * | 2004-03-30 | 2005-10-13 | Matsushita Electric Ind Co Ltd | Nonaqueous secondary battery and manufacturing method thereof |
| JP2007066665A (en) * | 2005-08-30 | 2007-03-15 | Nissan Motor Co Ltd | Electrode structure, its manufacturing method, secondary battery, battery pack, composite battery pack and vehicle with these batteries mounted thereon |
| JP2007141622A (en) * | 2005-11-17 | 2007-06-07 | Sumitomo Electric Ind Ltd | Positive electrode for thin film battery and thin film battery |
| JP2007173178A (en) * | 2005-12-26 | 2007-07-05 | Sony Corp | Battery |
| JP2008243656A (en) * | 2007-03-28 | 2008-10-09 | Matsushita Electric Ind Co Ltd | Electrode for electrochemical element, and manufacturing method therefor |
| JP2008277242A (en) * | 2007-03-30 | 2008-11-13 | Sanyo Electric Co Ltd | Electrode for lithium secondary battery and lithium secondary battery |
| WO2009011123A1 (en) * | 2007-07-17 | 2009-01-22 | Panasonic Corporation | Secondary cell and secondary cell manufacturing method |
| WO2009157158A1 (en) * | 2008-06-23 | 2009-12-30 | パナソニック株式会社 | Nonaqueous electrolyte secondary battery |
| US7695864B2 (en) | 2007-07-20 | 2010-04-13 | Panasonic Corporation | Electrode plate for battery, electrode group for battery, lithium secondary battery, and method for producing electrode plate for battery |
| WO2010082257A1 (en) * | 2009-01-14 | 2010-07-22 | パナソニック株式会社 | Negative electrode plate for nonaqueous battery, electrode group for nonaqueous battery and method for producing same, and tubular nonaqueous secondary battery and method for manufacturing same |
| WO2010082258A1 (en) * | 2009-01-16 | 2010-07-22 | パナソニック株式会社 | Electrode group for nonaqueous battery and method for producing same, and tubular nonaqueous secondary battery and method for manufacturing same |
| WO2010082256A1 (en) * | 2009-01-13 | 2010-07-22 | パナソニック株式会社 | Negative electrode plate for nonaqueous battery, electrode group for nonaqueous battery and method for producing same, and tubular nonaqueous secondary battery and method for manufacturing same |
| US7806943B2 (en) | 2007-07-17 | 2010-10-05 | Panasonic Corporation | Secondary battery and method for producing the same |
| US7854773B2 (en) | 2003-09-30 | 2010-12-21 | Dai Nippon Printing Co., Ltd. | Method of producing an electrode plate for a nonaqueous electrolyte secondary battery |
| US7951487B2 (en) | 2009-01-16 | 2011-05-31 | Panasonic Corporation | Electrode group for nonaqueous battery and method for producing the same, and cylindrical nonaqueous secondary battery and method for producing the same |
| JP2011233357A (en) * | 2010-04-27 | 2011-11-17 | Nissan Motor Co Ltd | Method of manufacturing bipolar electrode for secondary battery and bipolar secondary battery |
| WO2018110655A1 (en) | 2016-12-15 | 2018-06-21 | 日産自動車株式会社 | Secondary battery electrode, and secondary battery |
| WO2020194376A1 (en) * | 2019-03-22 | 2020-10-01 | 株式会社 東芝 | Electrode, cell, and cell pack |
| JPWO2021038851A1 (en) * | 2019-08-30 | 2021-03-04 | ||
| WO2021106593A1 (en) | 2019-11-29 | 2021-06-03 | 三洋電機株式会社 | Non-aqueous electrolyte secondary cell and method for manufacturing non-aqueous electrolyte secondary cell |
| WO2023045418A1 (en) * | 2021-09-27 | 2023-03-30 | 宁德时代新能源科技股份有限公司 | Electrode assembly, battery cell, battery, and electric apparatus |
| CN116830282A (en) * | 2022-09-30 | 2023-09-29 | 宁德时代新能源科技股份有限公司 | Negative electrode plate, preparation method thereof, secondary battery and power utilization device |
| WO2023226671A1 (en) * | 2022-05-21 | 2023-11-30 | 宁德时代新能源科技股份有限公司 | Negative electrode sheet, electrode assembly, battery cell, battery and electrical device |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09298057A (en) * | 1996-04-30 | 1997-11-18 | Sanyo Electric Co Ltd | Lithium ion battery |
| WO1998048466A1 (en) * | 1997-04-23 | 1998-10-29 | Japan Storage Battery Co., Ltd. | Electrode and battery |
| JPH11154508A (en) * | 1997-11-19 | 1999-06-08 | Toshiba Corp | Nonaqueous electrolyte battery |
| JP2000195525A (en) * | 1998-12-28 | 2000-07-14 | Sanyo Electric Co Ltd | Nonaqueous electrolyte battery |
| JP2001023612A (en) * | 1999-07-09 | 2001-01-26 | Matsushita Electric Ind Co Ltd | Nonaqueous electrolyte secondary battery |
| JP2001035484A (en) * | 1999-05-19 | 2001-02-09 | Nec Corp | Nonaqueous electrolyte secondary battery |
-
1999
- 1999-12-20 JP JP36159899A patent/JP2001176558A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09298057A (en) * | 1996-04-30 | 1997-11-18 | Sanyo Electric Co Ltd | Lithium ion battery |
| WO1998048466A1 (en) * | 1997-04-23 | 1998-10-29 | Japan Storage Battery Co., Ltd. | Electrode and battery |
| JPH11154508A (en) * | 1997-11-19 | 1999-06-08 | Toshiba Corp | Nonaqueous electrolyte battery |
| JP2000195525A (en) * | 1998-12-28 | 2000-07-14 | Sanyo Electric Co Ltd | Nonaqueous electrolyte battery |
| JP2001035484A (en) * | 1999-05-19 | 2001-02-09 | Nec Corp | Nonaqueous electrolyte secondary battery |
| JP2001023612A (en) * | 1999-07-09 | 2001-01-26 | Matsushita Electric Ind Co Ltd | Nonaqueous electrolyte secondary battery |
Cited By (35)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003197265A (en) * | 2001-12-27 | 2003-07-11 | Sanyo Electric Co Ltd | Nonaqueous electrolytic solution battery |
| WO2003088404A1 (en) * | 2002-04-12 | 2003-10-23 | Kabushiki Kaisha Toshiba | Nonaqueous electrolyte secondary battery |
| US8530081B2 (en) | 2002-04-12 | 2013-09-10 | Kabushiki Kaisha Toshiba | Nonaqueous electrolyte secondary battery including positive electrode active material layers having parallel grooves |
| WO2004036670A1 (en) * | 2002-10-15 | 2004-04-29 | Kabushiki Kaisha Toshiba | Nonacqueous electrolyte secondary cell |
| JP2004303754A (en) * | 2003-03-28 | 2004-10-28 | Nissan Diesel Motor Co Ltd | Method and apparatus for manufacturing electric double layer capacitor |
| US7854773B2 (en) | 2003-09-30 | 2010-12-21 | Dai Nippon Printing Co., Ltd. | Method of producing an electrode plate for a nonaqueous electrolyte secondary battery |
| JP2005285607A (en) * | 2004-03-30 | 2005-10-13 | Matsushita Electric Ind Co Ltd | Nonaqueous secondary battery and manufacturing method thereof |
| JP2007066665A (en) * | 2005-08-30 | 2007-03-15 | Nissan Motor Co Ltd | Electrode structure, its manufacturing method, secondary battery, battery pack, composite battery pack and vehicle with these batteries mounted thereon |
| JP2007141622A (en) * | 2005-11-17 | 2007-06-07 | Sumitomo Electric Ind Ltd | Positive electrode for thin film battery and thin film battery |
| JP2007173178A (en) * | 2005-12-26 | 2007-07-05 | Sony Corp | Battery |
| JP2008243656A (en) * | 2007-03-28 | 2008-10-09 | Matsushita Electric Ind Co Ltd | Electrode for electrochemical element, and manufacturing method therefor |
| JP2008277242A (en) * | 2007-03-30 | 2008-11-13 | Sanyo Electric Co Ltd | Electrode for lithium secondary battery and lithium secondary battery |
| US7806943B2 (en) | 2007-07-17 | 2010-10-05 | Panasonic Corporation | Secondary battery and method for producing the same |
| WO2009011123A1 (en) * | 2007-07-17 | 2009-01-22 | Panasonic Corporation | Secondary cell and secondary cell manufacturing method |
| US7695864B2 (en) | 2007-07-20 | 2010-04-13 | Panasonic Corporation | Electrode plate for battery, electrode group for battery, lithium secondary battery, and method for producing electrode plate for battery |
| WO2009157158A1 (en) * | 2008-06-23 | 2009-12-30 | パナソニック株式会社 | Nonaqueous electrolyte secondary battery |
| WO2010082256A1 (en) * | 2009-01-13 | 2010-07-22 | パナソニック株式会社 | Negative electrode plate for nonaqueous battery, electrode group for nonaqueous battery and method for producing same, and tubular nonaqueous secondary battery and method for manufacturing same |
| JP2010186736A (en) * | 2009-01-13 | 2010-08-26 | Panasonic Corp | Anode plate for nonaqueous battery, electrode group for nonaqueous battery and its manufacturing method, and cylindrical nonaqueous secondary battery and its manufacturing method |
| JP4672079B2 (en) * | 2009-01-14 | 2011-04-20 | パナソニック株式会社 | Non-aqueous battery negative electrode plate, non-aqueous battery electrode group and manufacturing method thereof, cylindrical non-aqueous secondary battery and manufacturing method thereof |
| WO2010082257A1 (en) * | 2009-01-14 | 2010-07-22 | パナソニック株式会社 | Negative electrode plate for nonaqueous battery, electrode group for nonaqueous battery and method for producing same, and tubular nonaqueous secondary battery and method for manufacturing same |
| JP2010186738A (en) * | 2009-01-14 | 2010-08-26 | Panasonic Corp | Anode plate for nonaqueous battery, electrode group for nonaqueous battery and its manufacturing method, and cylindrical nonaqueous secondary battery and its manufacturing method |
| WO2010082258A1 (en) * | 2009-01-16 | 2010-07-22 | パナソニック株式会社 | Electrode group for nonaqueous battery and method for producing same, and tubular nonaqueous secondary battery and method for manufacturing same |
| US7951487B2 (en) | 2009-01-16 | 2011-05-31 | Panasonic Corporation | Electrode group for nonaqueous battery and method for producing the same, and cylindrical nonaqueous secondary battery and method for producing the same |
| JP2010186740A (en) * | 2009-01-16 | 2010-08-26 | Panasonic Corp | Electrode group for nonaqueous battery, its manufacturing method, cylindrical nonaqueous secondary battery and its manufacturing method |
| JP2011233357A (en) * | 2010-04-27 | 2011-11-17 | Nissan Motor Co Ltd | Method of manufacturing bipolar electrode for secondary battery and bipolar secondary battery |
| WO2018110655A1 (en) | 2016-12-15 | 2018-06-21 | 日産自動車株式会社 | Secondary battery electrode, and secondary battery |
| US10790535B2 (en) | 2016-12-15 | 2020-09-29 | Nissan Motor Co., Ltd. | Electrode for secondary cell, and secondary cell |
| WO2020194376A1 (en) * | 2019-03-22 | 2020-10-01 | 株式会社 東芝 | Electrode, cell, and cell pack |
| JPWO2021038851A1 (en) * | 2019-08-30 | 2021-03-04 | ||
| JP7247353B2 (en) | 2019-08-30 | 2023-03-28 | 株式会社東芝 | Electrodes, batteries and battery packs |
| WO2021106593A1 (en) | 2019-11-29 | 2021-06-03 | 三洋電機株式会社 | Non-aqueous electrolyte secondary cell and method for manufacturing non-aqueous electrolyte secondary cell |
| WO2023045418A1 (en) * | 2021-09-27 | 2023-03-30 | 宁德时代新能源科技股份有限公司 | Electrode assembly, battery cell, battery, and electric apparatus |
| WO2023226671A1 (en) * | 2022-05-21 | 2023-11-30 | 宁德时代新能源科技股份有限公司 | Negative electrode sheet, electrode assembly, battery cell, battery and electrical device |
| CN116830282A (en) * | 2022-09-30 | 2023-09-29 | 宁德时代新能源科技股份有限公司 | Negative electrode plate, preparation method thereof, secondary battery and power utilization device |
| WO2024065764A1 (en) * | 2022-09-30 | 2024-04-04 | 宁德时代新能源科技股份有限公司 | Negative electrode sheet and preparation method therefor, and secondary battery and electric device |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2001176558A (en) | Non-aqueous electrolyte secondary battery | |
| KR100629545B1 (en) | Nonaqueous electrolyte secondary battery | |
| EP0991132B1 (en) | Nonaqueous electrolyte secondary battery and method of manufacturing nonaqueous electrolyte secondary battery | |
| JP3702318B2 (en) | Non-aqueous electrolyte battery electrode and non-aqueous electrolyte battery using the electrode | |
| JP2007329077A (en) | Nonaqueous electrolyte secondary battery and its manufacturing method | |
| JP2003282148A (en) | Thin lithium ion secondary battery | |
| JP2000149997A (en) | Nonaqueous electrolyte secondary battery and its manufacture | |
| JP3990107B2 (en) | Non-aqueous electrolyte secondary battery charging method | |
| JP2016157609A (en) | Power storage device | |
| JP2000082498A (en) | Nonaqueous electrolyte secondary battery | |
| JP2002367602A (en) | Nonaqueous electrolyte secondary cell | |
| JP2003115324A (en) | Nonaqueous electrolyte battery | |
| JP2007172879A (en) | Battery and its manufacturing method | |
| JP2004158441A (en) | Nonaqueous electrolyte secondary battery | |
| JP2004158213A (en) | Manufacturing method of nonaqueous electrolyte secondary battery | |
| JP2000048862A (en) | Charging method for nonaqueous secondary battery | |
| JPH10255818A (en) | Wound battery | |
| JP2007172878A (en) | Battery and its manufacturing method | |
| JP4240960B2 (en) | Lithium secondary battery and manufacturing method thereof | |
| JP4161396B2 (en) | Non-aqueous electrolyte secondary battery | |
| JP4560851B2 (en) | Method for producing solid electrolyte battery | |
| JP2002203606A (en) | Nonaqueous electrolyte solution battery | |
| JP2007172881A (en) | Battery and its manufacturing method | |
| JP2004200122A (en) | Manufacturing method of non-aqueous electrolyte secondary battery | |
| JPH05283107A (en) | Laminated battery and its manufacture |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Effective date: 20040330 Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20040401 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Year of fee payment: 4 Free format text: PAYMENT UNTIL: 20080416 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090416 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Year of fee payment: 6 Free format text: PAYMENT UNTIL: 20100416 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Year of fee payment: 7 Free format text: PAYMENT UNTIL: 20110416 |
|
| LAPS | Cancellation because of no payment of annual fees |