JP2002170597A - Nonaqueous electrolyte solution secondary battery - Google Patents
Nonaqueous electrolyte solution secondary batteryInfo
- Publication number
- JP2002170597A JP2002170597A JP2000368725A JP2000368725A JP2002170597A JP 2002170597 A JP2002170597 A JP 2002170597A JP 2000368725 A JP2000368725 A JP 2000368725A JP 2000368725 A JP2000368725 A JP 2000368725A JP 2002170597 A JP2002170597 A JP 2002170597A
- Authority
- JP
- Japan
- Prior art keywords
- active material
- positive electrode
- lithium
- battery
- electrode active
- 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.)
- Abandoned
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
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
に係り、特に、所定圧で内圧を開放する内圧開放機構を
有する電池容器に、正極、負極及びセパレータを有する
電極群と該電極群から各極端子へ接続するための接続部
と非水電解液とを内蔵し、リチウムマンガン複酸化物と
導電材とを含む活物質合剤が箔状集電体の両面に塗着さ
れた正極を用いた非水電解液二次電池に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-aqueous electrolyte secondary battery, and more particularly, to a battery container having an internal pressure releasing mechanism for releasing an internal pressure at a predetermined pressure, an electrode group having a positive electrode, a negative electrode, and a separator, and the electrode group. A connection part for connecting from the group to each pole terminal and a non-aqueous electrolyte were built in, and an active material mixture containing a lithium manganese double oxide and a conductive material was applied to both surfaces of the foil-shaped current collector The present invention relates to a non-aqueous electrolyte secondary battery using a positive electrode.
【０００２】[0002]
【従来の技術】非水電解液二次電池を代表するリチウム
イオン二次電池は、高エネルギー密度であるメリットを
活かして、主にＶＴＲカメラやノートパソコン、携帯電
話等のポータブル機器の電源に使用されている。この電
池の内部構造は、通常以下に示されるような捲回式構造
とされている。電極は正極、負極共に活物質が金属箔に
塗着された帯状であり、セパレータを挟んで正極、負極
が直接接触しないように断面が渦巻状に捲回され、捲回
群が形成されている。この捲回群が電池容器となる円筒
形の電池缶に収納され、電解液注液後、封口されてい
る。2. Description of the Related Art Lithium ion secondary batteries, which represent non-aqueous electrolyte secondary batteries, are mainly used for powering portable devices such as VTR cameras, notebook computers, and mobile phones, taking advantage of their high energy density. Have been. The internal structure of this battery is usually a wound structure as shown below. Each of the electrodes has a positive electrode and a negative electrode in a band shape in which an active material is applied to a metal foil, and a cross section is spirally wound so that the positive electrode and the negative electrode do not come into direct contact with each other with a separator interposed therebetween, thereby forming a wound group. . The wound group is housed in a cylindrical battery can serving as a battery container, and is sealed after the electrolyte is injected.
【０００３】一般的な円筒形リチウムイオン二次電池の
外径寸法は、１８６５０型と呼ばれる、直径１８ｍｍ、
高さ６５ｍｍであり、小形民生用リチウムイオン電池と
して広く普及している。１８６５０型リチウムイオン二
次電池の正極活物質には、高容量、長寿命を特徴とする
コバルト酸リチウムが主として用いられており、電池容
量は、おおむね１．３Ａｈ〜１．７Ａｈ、出力はおよそ
１０Ｗ程度である。[0003] The outer diameter of a general cylindrical lithium ion secondary battery is called 18650 type, having a diameter of 18 mm.
It has a height of 65 mm and is widely used as a small consumer lithium ion battery. As the positive electrode active material of the 18650 type lithium ion secondary battery, lithium cobalt oxide having high capacity and long life is mainly used. The battery capacity is approximately 1.3 Ah to 1.7 Ah, and the output is about 10 W. It is about.
【０００４】一方、自動車産業界においては環境問題に
対応すべく、排出ガスのない、動力源を完全に電池のみ
とした電気自動車と、内燃機関エンジンと電池との両方
を動力源とするハイブリッド（電気）自動車の開発が加
速され、一部実用化の段階に到達している。電気自動車
の電源となる電池には当然高出力、高エネルギーが得ら
れる特性が要求され、この要求にマッチした電池として
リチウムイオン電池が注目されている。On the other hand, in the automobile industry, in order to cope with environmental problems, an electric vehicle having no exhaust gas and having only a battery as a power source, and a hybrid (using both an internal combustion engine and a battery as a power source) have been proposed. The development of electric vehicles has been accelerated and some of them have reached the stage of practical use. A battery serving as a power source for an electric vehicle is required to have characteristics capable of obtaining high output and high energy, and a lithium ion battery has attracted attention as a battery that meets these requirements.
【０００５】これらの電気自動車の普及のためには、電
池の低価格化が必須であり、そのためには、低コスト電
池材料の使用が求められ、例えば、正極活物質であれ
ば、資源的に豊富なマンガンの酸化物が特に注目され、
電池の高性能化を狙った改善がなされてきた。また、電
気自動車用電池には、高容量だけではなく、加速性能な
どを左右する高出力化、つまり電池の内部抵抗の低減が
求められる。電極反応面積の増大を狙って、正極活物質
として比表面積の大きいマンガン酸リチウムとすること
でこの要求に対応することができる。In order to spread these electric vehicles, it is essential to reduce the price of the battery. For this purpose, it is required to use a low-cost battery material. Abundant manganese oxides are of particular interest,
Improvements have been made to improve the performance of batteries. In addition, batteries for electric vehicles are required to have not only high capacity but also high output that affects acceleration performance and the like, that is, reduction of internal resistance of the battery. This requirement can be met by using lithium manganate having a large specific surface area as the positive electrode active material for the purpose of increasing the electrode reaction area.
【０００６】[0006]
【発明が解決しようとする課題】しかしながら、リチウ
ムイオン電池の場合、高容量、高出力になればなるほど
安全性が低下する傾向にあり、特に上述したような、高
出力化を狙ったマンガン酸リチウムを用いた場合には、
電池が異常状態に陥ったときの現象がやや激しくなる傾
向が見られる。電気自動車用電源に用いられるような高
容量、高出力の電池ともなると、大電流充電、大電流放
電がなされるので、１８６５０型リチウムイオン電池に
一般に採用されているような、異常時の電池内圧上昇に
応じて作動する電流遮断機構（一種の切断スイッチ）を
電池構造内に設けることは実質的に難しい。人を乗せて
走る電気自動車の場合、充電制御システムが故障してし
まった場合の過充電時、不慮の衝突事故の場合に遭遇す
る可能性のある電池のクラッシュ時あるいは、異物突き
刺し時、外部短絡時等の電池自体の安全性を確保するこ
とは、最低限必要な、非常に重要な電池特性である。However, in the case of lithium ion batteries, the higher the capacity and the higher the output, the lower the safety tends to be. Particularly, as described above, lithium manganate aiming at high output If you use
The phenomenon when the battery falls into an abnormal state tends to be slightly intense. When a high-capacity, high-output battery used in an electric vehicle power supply is used, a large current is charged and a large current is discharged. It is substantially difficult to provide a current cutoff mechanism (a kind of disconnect switch) that operates in response to the rise in the battery structure. In the case of an electric vehicle that runs with people, when the charge control system breaks down, the battery is overcharged, the battery may crash in the event of an accidental collision, the object is pierced, or an external short circuit occurs. Ensuring the safety of the battery itself at times is a very necessary and very important battery characteristic.
【０００７】本発明は上記事案に鑑み、高容量、高出力
でありながらも、極めて安全性の高い非水電解液二次電
池を提供することを課題とする。SUMMARY OF THE INVENTION In view of the above-mentioned problems, an object of the present invention is to provide a non-aqueous electrolyte secondary battery which has a high capacity and a high output, but is extremely safe.
【０００８】[0008]
【課題を解決するための手段】上記課題を解決するため
に、本発明の第１態様は、所定圧で内圧を開放する内圧
開放機構を有する電池容器に、正極、負極及びセパレー
タを有する電極群と該電極群から各極端子へ接続するた
めの接続部と非水電解液とを内蔵し、リチウムマンガン
複酸化物と導電材とを含む活物質合剤が箔状集電体の両
面に塗着された正極を用いた非水電解液二次電池におい
て、金属リチウムに対する電極電位が４．８Ｖ以上の領
域で、前記非水電解液中へのマンガンの溶出量が、リチ
ウムマンガン複酸化物を基準として５％以下であるリチ
ウムマンガン複酸化物を正極活物質に用い、充放電によ
りリチウムイオンを吸蔵、放出可能な黒鉛を負極活物質
に用いたことを特徴とする。In order to solve the above problems, a first aspect of the present invention is to provide a battery container having an internal pressure releasing mechanism for releasing an internal pressure at a predetermined pressure, an electrode group having a positive electrode, a negative electrode, and a separator. And a connecting portion for connecting the electrode group to each electrode terminal and a non-aqueous electrolyte, and an active material mixture containing a lithium manganese double oxide and a conductive material is applied to both surfaces of the foil-shaped current collector. In a non-aqueous electrolyte secondary battery using the positive electrode attached, in a region where the electrode potential with respect to metallic lithium is 4.8 V or more, the amount of manganese eluted into the non-aqueous electrolyte is lithium manganese double oxide. It is characterized in that a lithium manganese double oxide of 5% or less is used as a positive electrode active material as a reference, and graphite capable of occluding and releasing lithium ions by charging and discharging is used as a negative electrode active material.
【０００９】また、本発明の第２態様は、所定圧で内圧
を開放する内圧開放機構を有する電池容器に、正極、負
極及びセパレータを有する電極群と該電極群から各極端
子へ接続するための接続部と非水電解液とを内蔵し、リ
チウムマンガン複酸化物と導電材とを含む活物質合剤が
箔状集電体の両面に塗着された正極を用いた非水電解液
二次電池において、金属リチウムに対する電極電位が
４．８Ｖ以上の領域で、前記非水電解液中へのマンガン
の溶出量が、リチウムマンガン複酸化物を基準として７
％以下であるリチウムマンガン複酸化物を正極活物質に
用い、充放電によりリチウムイオンを吸蔵、放出可能な
非晶質炭素を負極活物質に用いたことを特徴とする。A second aspect of the present invention is to connect an electrode group having a positive electrode, a negative electrode and a separator to a battery container having an internal pressure releasing mechanism for releasing an internal pressure at a predetermined pressure, and to connect the electrode group to each electrode terminal. Non-aqueous electrolyte solution using a positive electrode in which an active material mixture containing a lithium manganese double oxide and a conductive material is applied to both sides of a foil current collector. In the secondary battery, the elution amount of manganese into the non-aqueous electrolyte was 7% based on the lithium manganese double oxide in a region where the electrode potential with respect to metallic lithium was 4.8 V or more.
% Or less as a positive electrode active material, and amorphous carbon capable of occluding and releasing lithium ions by charging and discharging is used as a negative electrode active material.
【００１０】本発明では、高容量、高出力の非水電解液
二次電池を確保するために、正極活物質にリチウムマン
ガン複酸化物が、負極活物質に黒鉛又は非晶質炭素がそ
れぞれ用いられている。高容量、高出力の非水電解液二
次電池では、異常状態に陥ったときに、大電流充電又は
大電流放電状態が維持され、非水電解液と活物質合剤と
の化学反応により電池容器内で急激かつ大量のガスが発
生し、電池容器の内圧を上昇させる。一般に、非水電解
液二次電池では、電池容器内の内圧上昇を防止するため
に、電池容器に所定圧で内圧を開放する内圧開放機構を
有しているが、金属リチウムに対する電極電位が４．８
Ｖ以上の領域で、非水電解液中へのマンガンの溶出量
が、リチウムマンガン複酸化物を基準として５％以下で
あるリチウムマンガン複酸化物を正極活物質に用い、充
放電によりリチウムイオンを吸蔵、放出可能な黒鉛を負
極活物質に用いるか、又は、金属リチウムに対する電極
電位が４．８Ｖ以上の領域で、非水電解液中へのマンガ
ンの溶出量が、リチウムマンガン複酸化物を基準として
７％以下であるリチウムマンガン複酸化物を正極活物質
に用い、充放電によりリチウムイオンを吸蔵、放出可能
な非晶質炭素を負極活物質に用いることにより、内圧開
放機構からのガス放出が極めて穏やかに行われる。この
ため、本発明によれば、高容量、高出力でありながら
も、極めて安全性の高い非水電解液二次電池を実現する
ことができる。In the present invention, in order to secure a high capacity, high output non-aqueous electrolyte secondary battery, a lithium manganese double oxide is used as a positive electrode active material, and graphite or amorphous carbon is used as a negative electrode active material. Have been. In a high-capacity, high-output non-aqueous electrolyte secondary battery, when an abnormal state occurs, a large current charge or a large current discharge state is maintained, and the battery reacts due to a chemical reaction between the non-aqueous electrolyte and the active material mixture. A sudden and large amount of gas is generated in the container, which raises the internal pressure of the battery container. Generally, a non-aqueous electrolyte secondary battery has an internal pressure release mechanism for releasing the internal pressure at a predetermined pressure in the battery container in order to prevent an increase in the internal pressure in the battery container. .8
In the region above V, the amount of manganese eluted in the non-aqueous electrolyte is 5% or less based on the lithium manganese double oxide. Either occluding and releasing graphite can be used for the negative electrode active material, or the elution amount of manganese into the non-aqueous electrolyte in the region where the electrode potential with respect to metallic lithium is 4.8 V or more is based on lithium manganese double oxide. By using a lithium manganese compound oxide of 7% or less as a positive electrode active material and using an amorphous carbon capable of occluding and releasing lithium ions by charge and discharge as a negative electrode active material, gas release from an internal pressure release mechanism can be prevented. Very gentle. Therefore, according to the present invention, it is possible to realize a non-aqueous electrolyte secondary battery having extremely high safety while having high capacity and high output.
【００１１】この場合において、リチウムマンガン複酸
化物のＬｉ／Ｍｎの比を、０．５５以上、０．６以下と
すれば、初期容量及び充放電による容量維持率の高い非
水電解液二次電池とすることができる。このとき、負極
活物質に非晶質炭素を用い、リチウムマンガン複酸化物
の非水電解液中へのマンガンの溶出量を、該リチウムマ
ンガン複酸化物を基準として３．２％以下とすれば、非
水電解液二次電池が異常状態に陥ったときでも、非水電
解液と活物質合剤との化学反応により発生する発熱を低
く抑えることができ、非水電解液二次電池の安全性及び
信頼性を一層高めることができる。In this case, if the ratio of Li / Mn of the lithium manganese double oxide is 0.55 or more and 0.6 or less, the secondary capacity of the non-aqueous electrolyte solution having a high initial capacity and a high capacity retention rate due to charge and discharge. It can be a battery. At this time, if amorphous carbon is used as the negative electrode active material and the amount of manganese eluted into the non-aqueous electrolyte of the lithium manganese composite oxide is 3.2% or less based on the lithium manganese composite oxide, Even when the non-aqueous electrolyte secondary battery falls into an abnormal state, the heat generated by the chemical reaction between the non-aqueous electrolyte and the active material mixture can be kept low, and the safety of the non-aqueous electrolyte secondary battery can be reduced. Performance and reliability can be further improved.
【００１２】[0012]
【発明の実施の形態】以下、図面を参照して本発明に係
る非水電解液二次電池を電気自動車用電源として用いら
れる円筒形リチウムイオン電池に適用した実施の形態に
ついて説明する。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment in which a nonaqueous electrolyte secondary battery according to the present invention is applied to a cylindrical lithium ion battery used as a power supply for an electric vehicle will be described below with reference to the drawings.
【００１３】（正極板の作製）図１に示すように、正極
活物質としてのマンガン酸リチウム（ＬｉＭｎ２Ｏ４）
粉末と、導電材としての黒鉛粉末及びアセチレンブラッ
クと、結着剤としてポリフッ化ビニリデン（ＰＶＤＦ）
と、を質量比８３：１０：２：５で混合し、これに分散
溶媒のＮ−メチル−２−ピロリドン（ＮＭＰ）を添加、
混練したスラリを、厚さ２０μｍのアルミニウム箔Ｗ１
（正極集電体）の両面に塗布した。このとき、正極板長
寸方向の一方の側縁に幅３０ｍｍの未塗布部を残した。
その後乾燥、プレス、裁断して幅８２ｍｍ、長さ３４２
ｃｍ、活物質合剤塗布部Ｗ２厚さ１０９μｍの正極板を
得た。正極活物質合剤層Ｗ２のかさ密度は２．６５ｇ／
ｃｍ３とした。上記未塗布部に切り欠きを入れ、切り欠
き残部を正極リード片２とした。隣り合う正極リード片
２を５０ｍｍ間隔とし、正極リード片２の幅を５ｍｍと
した。(Preparation of positive electrode plate) As shown in FIG. 1, lithium manganate (LiMn 2 O 4 ) as a positive electrode active material
Powder, graphite powder and acetylene black as a conductive material, and polyvinylidene fluoride (PVDF) as a binder
Are mixed at a mass ratio of 83: 10: 2: 5, and N-methyl-2-pyrrolidone (NMP) as a dispersion solvent is added thereto,
The kneaded slurry is applied to an aluminum foil W1 having a thickness of 20 μm.
(Positive electrode current collector). At this time, an uncoated portion having a width of 30 mm was left on one side edge in the longitudinal direction of the positive electrode plate.
After drying, pressing and cutting, the width is 82 mm and the length is 342
cm, a positive electrode plate having an active material mixture application portion W2 and a thickness of 109 μm. The bulk density of the positive electrode active material mixture layer W2 is 2.65 g /
cm 3 . A cutout was made in the uncoated portion, and the remaining cutout was used as a positive electrode lead piece 2. Adjacent positive electrode lead pieces 2 were set at intervals of 50 mm, and the width of the positive electrode lead pieces 2 was set at 5 mm.
【００１４】（負極板の作製）所定の炭素粉末９２質量
部に結着剤として８質量部のポリフッ化ビニリデンを添
加し、これに分散溶媒のＮ−メチル−２−ピロリドンを
添加、混練したスラリを厚さ１０μｍの圧延銅箔Ｗ３
（負極集電体）の両面に塗布した。このとき、負極板長
寸方向の一方の側縁に幅３０ｍｍの未塗布部を残した。
その後乾燥、プレス、裁断して幅８６ｍｍ、後述する所
定長さ及び活物質塗布部Ｗ４所定厚さの負極板を得た。
負極活物質層Ｗ４の空隙率が約３５％となるように負極
板を圧縮した。上記未塗布部に正極板と同様に切り欠き
を入れ、切り欠き残部を負極リード片３とした。隣り合
う負極リード片３を５０ｍｍ間隔とし、負極リード片３
の幅を５ｍｍとした。(Preparation of Negative Electrode Plate) A slurry prepared by adding 8 parts by mass of polyvinylidene fluoride as a binder to 92 parts by mass of a predetermined carbon powder, adding N-methyl-2-pyrrolidone as a dispersion solvent thereto and kneading the mixture. Is rolled copper foil W3 having a thickness of 10 μm.
(Negative electrode current collector). At this time, an uncoated portion having a width of 30 mm was left on one side edge in the longitudinal direction of the negative electrode plate.
Thereafter, drying, pressing, and cutting were performed to obtain a negative electrode plate having a width of 86 mm, a predetermined length described later, and a predetermined thickness of the active material application portion W4.
The negative electrode plate was compressed such that the porosity of the negative electrode active material layer W4 was about 35%. A cutout was made in the uncoated portion in the same manner as the positive electrode plate, and the remaining cutout was used as a negative electrode lead piece 3. Adjacent negative electrode lead pieces 3 are set at intervals of 50 mm.
Was 5 mm in width.
【００１５】（電池の作製）上記作製した正極板と負極
板とを、これら両極板が直接接触しないように幅９０ｍ
ｍ、厚さ４０μｍのポリエチレン製セパレータＷ５と共
に捲回した。捲回の中心には、ポリプロピレン製の中空
円筒状の軸芯１を用いた。このとき、正極リード片２と
負極リード片３とが、それぞれ捲回群６の互いに反対側
の両端面に位置するようにした。また、正極板、負極
板、セパレータの長さを調整し、捲回群６の直径を３８
±０．１ｍｍとした。(Preparation of Battery) The above-prepared positive electrode plate and negative electrode plate were 90 m wide so that these two electrode plates did not come into direct contact with each other.
m, together with a polyethylene separator W5 having a thickness of 40 μm. At the center of the winding, a hollow cylindrical shaft core 1 made of polypropylene was used. At this time, the positive electrode lead piece 2 and the negative electrode lead piece 3 were located on both end faces on the opposite side of the winding group 6, respectively. Further, the length of the positive electrode plate, the negative electrode plate, and the separator was adjusted, and the diameter of the winding group 6 was adjusted to 38.
± 0.1 mm.
【００１６】正極リード片２を変形させ、その全てを、
捲回群６の軸芯１のほぼ延長線上にある正極集電リング
４の周囲から一体に張り出した鍔部周面付近に集合、接
触させた後、正極リード片２と鍔部周面とを超音波溶接
して正極リード片２を鍔部周面に接続した。一方、負極
集電リング５と負極リード片３との接続操作も、正極集
電リング４と正極リード片２との接続操作と同様に実施
した。The positive electrode lead piece 2 is deformed, and all of the
After gathering and contacting the vicinity of the flange peripheral surface integrally projecting from the periphery of the positive electrode current collecting ring 4 substantially on the extension line of the shaft core 1 of the winding group 6, the positive electrode lead piece 2 and the flange peripheral surface are separated. The positive electrode lead piece 2 was connected to the flange peripheral surface by ultrasonic welding. On the other hand, the connection operation between the negative electrode current collector ring 5 and the negative electrode lead piece 3 was also performed in the same manner as the connection operation between the positive electrode current collector ring 4 and the positive electrode lead piece 2.
【００１７】その後、正極集電リング４の鍔部周面全周
に絶縁被覆を施した。この絶縁被覆には、基材がポリイ
ミドで、その片面にヘキサメタアクリレートからなる粘
着剤を塗布した粘着テープを用いた。この粘着テープを
鍔部周面から捲回群６外周面に亘って一重以上巻いて絶
縁被覆とし、捲回群６をニッケルメッキが施されたスチ
ール製の電池容器７内に挿入した。電池容器７の外形は
４０ｍｍ、内径は３９ｍｍである。Thereafter, an insulating coating was applied to the entire peripheral surface of the flange portion of the positive electrode current collecting ring 4. For this insulating coating, a pressure-sensitive adhesive tape was used in which the base material was polyimide and one side thereof was coated with a pressure-sensitive adhesive composed of hexamethacrylate. This adhesive tape was wound one or more times from the peripheral surface of the flange portion to the outer peripheral surface of the winding group 6 to form an insulating coating, and the winding group 6 was inserted into a nickel-plated steel battery container 7. The outer shape of the battery container 7 is 40 mm, and the inner diameter is 39 mm.
【００１８】負極集電リング５には予め電気的導通のた
めの負極リード板８が溶接されており、電池容器７に捲
回群６を挿入後、電池容器７の底部と負極リード板８と
を溶接した。A negative electrode lead plate 8 for electrical conduction is welded to the negative electrode current collecting ring 5 in advance. After the winding group 6 is inserted into the battery container 7, the bottom of the battery container 7 and the negative electrode lead plate 8 are connected to each other. Was welded.
【００１９】一方、正極集電リング４には、予め複数枚
のアルミニウム製のリボンを重ね合わせて構成した正極
リード９を溶接しておき、正極リード９の他端を、電池
容器７を封口するための電池蓋の下面に溶接した。電池
蓋には、円筒形リチウムイオン電池２０の内圧上昇に応
じて開裂する内圧開放機構としての開裂弁１１が設けら
れている。開裂弁１１の開裂圧は、約９×１０５Ｐａに
設定した。電池蓋は、蓋ケース１２と、蓋キャップ１３
と、気密を保つ弁押え１４と、開裂弁１１とで構成され
ており、これらが積層されて蓋ケース１２の周縁をカシ
メることによって組立てられている。On the other hand, a positive electrode lead 9 formed by laminating a plurality of aluminum ribbons is welded to the positive electrode current collecting ring 4 in advance, and the other end of the positive electrode lead 9 is sealed with the battery container 7. To the lower surface of the battery lid. The battery lid is provided with a cleavage valve 11 as an internal pressure release mechanism that is opened according to an increase in the internal pressure of the cylindrical lithium ion battery 20. The cleavage pressure of the cleavage valve 11 was set to about 9 × 10 5 Pa. The battery lid includes a lid case 12 and a lid cap 13.
, A valve retainer 14 for maintaining airtightness, and a cleavage valve 11, which are stacked and assembled by caulking the periphery of the lid case 12.
【００２０】非水電解液を所定量電池容器７内に注入
し、その後、正極リード９を折りたたむようにして電池
蓋で電池容器７に蓋をし、ＥＰＤＭ樹脂製ガスケット１
０を介してカシメて密封することにより円筒形リチウム
イオン電池２０を完成させた。A predetermined amount of a non-aqueous electrolyte is injected into the battery case 7, and then the battery case 7 is covered with the battery cover so that the positive electrode lead 9 is folded.
The cylindrical lithium-ion battery 20 was completed by caulking and sealing through the inside of the battery.
【００２１】非水電解液には、エチレンカーボネートと
ジメチルカーボネートとジエチルカーボネートの体積比
１：１：１の混合溶液中へ６フッ化リン酸リチウム（Ｌ
ｉＰＦ６）を１モル／リットル溶解したものを用いた。
なお、円筒形リチウムイオン電池２０には、電池内圧の
上昇に応じて電気的に作動する、例えば、ＰＴＣ(Posit
ive Temperature Coefficient) 素子等の電流遮断機構
は設けられていない。The non-aqueous electrolyte contains lithium hexafluorophosphate (L) in a mixed solution of ethylene carbonate, dimethyl carbonate and diethyl carbonate at a volume ratio of 1: 1: 1.
iPF 6 ) dissolved at 1 mol / liter was used.
The cylindrical lithium-ion battery 20 is electrically operated in response to an increase in battery internal pressure, for example, PTC (Posit).
ive Temperature Coefficient) There is no current interruption mechanism such as an element.
【００２２】ところで、本実施形態では、金属リチウム
に対する電極電位が４．８Ｖ以上の領域で、非水電解液
中へのマンガンの溶出量が、マンガン酸リチウムを基準
として５％以下であるマンガン酸リチウムを正極活物質
に用い、充放電によりリチウムイオンを吸蔵、放出可能
な黒鉛を負極活物質に用いるか、又は、非水電解液中へ
のマンガンの溶出量が、マンガン酸リチウムを基準とし
て７％以下であるマンガン酸リチウムを正極活物質に用
い、充放電によりリチウムイオンを吸蔵、放出可能な非
晶質炭素を負極活物質に用いた。In this embodiment, in the region where the electrode potential with respect to metallic lithium is 4.8 V or more, the amount of manganese eluted into the non-aqueous electrolyte is 5% or less based on lithium manganate. Lithium is used for the positive electrode active material, and graphite capable of occluding and releasing lithium ions by charge and discharge is used for the negative electrode active material, or the amount of manganese eluted in the non-aqueous electrolyte is 7% based on lithium manganate. % Or less of lithium manganate was used as a positive electrode active material, and amorphous carbon capable of inserting and extracting lithium ions by charge and discharge was used as a negative electrode active material.
【００２３】金属リチウムに対する電極電位が４．８Ｖ
以上の領域で、マンガンの非水電解液中への溶出量が、
マンガン酸リチウムを基準として上述した所定％以下で
あるマンガン酸リチウムを具体的に得るには、粒子径を
限定したり、比表面積を限定したり、マンガン酸リチウ
ムの合成原料や、合成条件を制御する等種々の因子があ
り、制御因子及びその他の因子が複雑に絡み合って溶出
量が変化しバラツキが大きくなるので、因子単独で全て
を特定することは難しい。本実施形態では、このため種
々の条件で数ロットのマンガン酸リチウムを調製し、そ
こから上記の要件を有するロットを選別して使用した。The electrode potential for metal lithium is 4.8 V
In the above region, the amount of manganese eluted into the non-aqueous electrolyte is
In order to specifically obtain lithium manganate having the above-mentioned predetermined percentage or less based on lithium manganate, the particle size is limited, the specific surface area is limited, and the raw materials and conditions for the synthesis of lithium manganate are controlled. There are various factors, such as control factors and other factors, which are complicatedly entangled with each other, changing the elution amount and increasing the variation. Therefore, it is difficult to specify all the factors alone. In this embodiment, for this purpose, several lots of lithium manganate were prepared under various conditions, and lots having the above requirements were selected therefrom and used.
【００２４】また、マンガン酸リチウムのマンガン溶出
量の測定は、以下の手順で行った。上記のように作製し
た正極の一部を切り出し、金属リチウムを参照電極とし
て非水電解液中で４．８Ｖ以上の電位に２４時間以上保
持し、非水電解液中に溶出したマンガンと、対極に析出
したマンガンとを定量分析し、その総量をマンガン酸リ
チウム基準で算出した。なお、このマンガン溶出量の測
定において、６Ｖ以上の電位では非水電解液が分解する
ので、６Ｖ未満とすることが好ましい。The amount of manganese eluted from lithium manganate was measured according to the following procedure. A part of the positive electrode prepared as described above was cut out, and the potential was held at a potential of 4.8 V or more in a nonaqueous electrolyte for 24 hours or more in a nonaqueous electrolyte using metallic lithium as a reference electrode, and manganese eluted in the nonaqueous electrolyte and a counter electrode. Was quantitatively analyzed with respect to the manganese precipitated on the substrate, and the total amount was calculated on the basis of lithium manganate. In the measurement of the manganese elution amount, the non-aqueous electrolyte is decomposed at a potential of 6 V or more.
【００２５】[0025]
【実施例】次に、本実施形態に従って作製した円筒形リ
チウムイオン電池２０の実施例について説明する。比較
のために作製した比較例の電池についても併記する。Next, an example of the cylindrical lithium ion battery 20 manufactured according to this embodiment will be described. A battery of a comparative example produced for comparison is also described.
【００２６】（実施例１）下表１に示すように、実施例
１では、正極活物質にロットＮｏ．１のマンガン酸リチ
ウム（ＬｉＭｎ２Ｏ４）粉末を用い、負極活物質にメソ
フェーズ系球状黒鉛であるＭＣＭＢを用い、負極活物質
層（活物質塗布部）Ｗ４の厚さ（集電体厚さは含まな
い。）を７９μｍ、長さを３５４ｃｍとして電池を作製
した。この正極活物質のＬｉ／Ｍｎ比は、０．５２、マ
ンガン溶出量は、５．０％であった。Example 1 As shown in Table 1 below, in Example 1, lot No. 1 was used as the positive electrode active material. Using lithium manganate (LiMn 2 O 4 ) powder of No. 1 and MCMB which is a mesophase-based spherical graphite as the negative electrode active material, the thickness of the negative electrode active material layer (active material coated portion) W4 (the current collector thickness is (Not included)) and a length of 354 cm to produce a battery. The Li / Mn ratio of this positive electrode active material was 0.52, and the manganese elution amount was 5.0%.
【００２７】なお、作製した電極は、捲回したときに、
捲回最内周では捲回方向に正極が負極からはみ出すこと
がなく、また最外周でも捲回方向に正極が負極からはみ
出すことがないように負極長さは正極長さよりも１２ｃ
ｍ長くなるようにした。また、捲回方向と垂直方向にお
いても正極活物質塗布部が負極活物質塗布部からはみ出
すことがないように、負極活物質塗布部Ｗ４の幅は、正
極活物質塗布部Ｗ２の幅よりも４ｍｍ長くした（以下の
実施例及び比較例においても同じ。）。It should be noted that, when the manufactured electrode is wound,
The length of the negative electrode is 12 c longer than the length of the positive electrode so that the positive electrode does not protrude from the negative electrode in the winding direction at the innermost circumference of the winding and the positive electrode does not protrude from the negative electrode in the winding direction even at the outermost circumference.
m longer. Also, the width of the negative electrode active material application part W4 is 4 mm larger than the width of the positive electrode active material application part W2 so that the positive electrode active material application part does not protrude from the negative electrode active material application part even in the winding direction and the vertical direction. (The same applies to the following Examples and Comparative Examples.)
【００２８】[0028]
【表１】 [Table 1]
【００２９】（実施例２）表１に示すように、実施例２
では、正極活物質にロットＮｏ．２のマンガン酸リチウ
ム粉末を用い、負極活物質にＭＣＭＢを用い、負極活物
質層（活物質塗布部）Ｗ４の厚さ（集電体厚さは含まな
い。）を７９μｍ、長さを３５４ｃｍとして電池を作製
した。この正極活物質のＬｉ／Ｍｎ比は、０．５２、マ
ンガン溶出量は、３．３％であった。Example 2 As shown in Table 1, Example 2
In the positive electrode active material, lot No. The lithium manganate powder of No. 2 was used, MCMB was used as the negative electrode active material, and the thickness (excluding the thickness of the current collector) of the negative electrode active material layer (active material application portion) W4 was 79 μm and the length was 354 cm. A battery was manufactured. The Li / Mn ratio of this positive electrode active material was 0.52, and the manganese elution amount was 3.3%.
【００３０】（実施例３）表１に示すように、実施例３
では、正極活物質にロットＮｏ．３のマンガン酸リチウ
ム粉末を用い、負極活物質にＭＣＭＢを用い、負極活物
質層（活物質塗布部）Ｗ４の厚さ（集電体厚さは含まな
い。）を７９μｍ、長さを３５４ｃｍとして電池を作製
した。この正極活物質のＬｉ／Ｍｎ比は、０．５２、マ
ンガン溶出量は、１．６％であった。Example 3 As shown in Table 1, Example 3
In the positive electrode active material, lot No. The lithium manganate powder of No. 3 was used, MCMB was used as the negative electrode active material, and the thickness (excluding the thickness of the current collector) of the negative electrode active material layer (active material coated portion) W4 was 79 μm and the length was 354 cm. A battery was manufactured. The Li / Mn ratio of this positive electrode active material was 0.52, and the manganese elution amount was 1.6%.
【００３１】（実施例４）表１に示すように、実施例４
では、正極活物質にロットＮｏ．４のマンガン酸リチウ
ム粉末を用い、負極活物質にＭＣＭＢを用い、負極活物
質層（活物質塗布部）Ｗ４の厚さ（集電体厚さは含まな
い。）を７９μｍ、長さを３５４ｃｍとして電池を作製
した。この正極活物質のＬｉ／Ｍｎ比は、０．５２、マ
ンガン溶出量は、２．１％であった。(Embodiment 4) As shown in Table 1, Embodiment 4
In the positive electrode active material, lot No. The lithium manganate powder of No. 4 was used, MCMB was used as the negative electrode active material, and the thickness (not including the current collector thickness) of the negative electrode active material layer (active material coated portion) W4 was 79 μm and the length was 354 cm. A battery was manufactured. The Li / Mn ratio of this positive electrode active material was 0.52, and the manganese elution amount was 2.1%.
【００３２】（実施例５）表１に示すように、実施例５
では、正極活物質にロットＮｏ．５のマンガン酸リチウ
ム粉末を用い、負極活物質にＭＣＭＢを用い、負極活物
質層（活物質塗布部）Ｗ４の厚さ（集電体厚さは含まな
い。）を７９μｍ、長さを３５４ｃｍとして電池を作製
した。この正極活物質のＬｉ／Ｍｎ比は、０．５５、マ
ンガン溶出量は、３．２％であった。Example 5 As shown in Table 1, Example 5
In the positive electrode active material, lot No. The lithium manganate powder of No. 5 was used, MCMB was used as the negative electrode active material, and the thickness (excluding the thickness of the current collector) of the negative electrode active material layer (active material coated portion) W4 was 79 μm and the length was 354 cm. A battery was manufactured. The Li / Mn ratio of this positive electrode active material was 0.55, and the manganese elution amount was 3.2%.
【００３３】（実施例６）表１に示すように、実施例６
では、正極活物質にロットＮｏ．６のマンガン酸リチウ
ム粉末を用い、負極活物質にＭＣＭＢを用い、負極活物
質層（活物質塗布部）Ｗ４の厚さ（集電体厚さは含まな
い。）を７９μｍ、長さを３５４ｃｍとして電池を作製
した。この正極活物質のＬｉ／Ｍｎ比は、０．５８、マ
ンガン溶出量は、３．１％であった。(Embodiment 6) As shown in Table 1, Embodiment 6
In the positive electrode active material, lot No. The lithium manganate powder of No. 6 was used, MCMB was used as the negative electrode active material, and the thickness (excluding the thickness of the current collector) of the negative electrode active material layer (active material coated portion) W4 was 79 μm and the length was 354 cm. A battery was manufactured. The Li / Mn ratio of this positive electrode active material was 0.58, and the manganese elution amount was 3.1%.
【００３４】（実施例７）表１に示すように、実施例７
では、正極活物質にロットＮｏ．７のマンガン酸リチウ
ム粉末を用い、負極活物質にＭＣＭＢを用い、負極活物
質層（活物質塗布部）Ｗ４の厚さ（集電体厚さは含まな
い。）を７９μｍ、長さを３５４ｃｍとして電池を作製
した。この正極活物質のＬｉ／Ｍｎ比は、０．６０、マ
ンガン溶出量は、３．０％であった。(Embodiment 7) As shown in Table 1, the embodiment 7
In the positive electrode active material, lot No. The lithium manganate powder of No. 7 was used, MCMB was used as the negative electrode active material, and the thickness (excluding the thickness of the current collector) of the negative electrode active material layer (active material coated portion) W4 was 79 μm and the length was 354 cm. A battery was manufactured. The Li / Mn ratio of this positive electrode active material was 0.60, and the manganese elution amount was 3.0%.
【００３５】（実施例８）表１に示すように、実施例８
では、正極活物質にロットＮｏ．８のマンガン酸リチウ
ム粉末を用い、負極活物質にＭＣＭＢを用い、負極活物
質層（活物質塗布部）Ｗ４の厚さ（集電体厚さは含まな
い。）を７９μｍ、長さを３５４ｃｍとして電池を作製
した。この正極活物質のＬｉ／Ｍｎ比は、０．６１、マ
ンガン溶出量は、３．０％であった。Example 8 As shown in Table 1, Example 8
In the positive electrode active material, lot No. The lithium manganate powder of No. 8 was used, MCMB was used as the negative electrode active material, and the thickness (excluding the thickness of the current collector) of the negative electrode active material layer (active material coated portion) W4 was 79 μm and the length was 354 cm. A battery was manufactured. The Li / Mn ratio of this positive electrode active material was 0.61, and the manganese elution amount was 3.0%.
【００３６】（実施例９）表１に示すように、実施例９
では、正極活物質にロットＮｏ．９のマンガン酸リチウ
ム粉末を用い、負極活物質に非晶質炭素を用い、負極活
物質層（活物質塗布部）Ｗ４の厚さ（集電体厚さは含ま
ない。）を７９μｍ、長さを３５４ｃｍとして電池を作
製した。この正極活物質のＬｉ／Ｍｎ比は、０．５２、
マンガン溶出量は、７．０％であった。Example 9 As shown in Table 1, Example 9
In the positive electrode active material, lot No. 9, a negative electrode active material layer (active material coated portion) W4 having a thickness (not including the current collector thickness) of 79 μm and a length of amorphous carbon as the negative electrode active material. Was set to 354 cm to produce a battery. The Li / Mn ratio of this positive electrode active material was 0.52,
The manganese elution amount was 7.0%.
【００３７】（実施例１０）表１に示すように、実施例
１０では、正極活物質にロットＮｏ．１０のマンガン酸
リチウム粉末を用い、負極活物質に非晶質炭素を用い、
負極活物質層（活物質塗布部）Ｗ４の厚さ（集電体厚さ
は含まない。）を７９μｍ、長さを３５４ｃｍとして電
池を作製した。この正極活物質のＬｉ／Ｍｎ比は、０．
５２、マンガン溶出量は、５．０％であった。Example 10 As shown in Table 1, in Example 10, lot No. was used as the positive electrode active material. Using lithium manganate powder of No. 10, using amorphous carbon as the negative electrode active material,
A battery was manufactured with a negative electrode active material layer (active material coated portion) W4 having a thickness (not including the current collector thickness) of 79 μm and a length of 354 cm. The Li / Mn ratio of this positive electrode active material is 0.1.
52, the manganese elution amount was 5.0%.
【００３８】（実施例１１）表１に示すように、実施例
１１では、正極活物質にロットＮｏ．１１のマンガン酸
リチウム粉末を用い、負極活物質に非晶質炭素を用い、
負極活物質層（活物質塗布部）Ｗ４の厚さ（集電体厚さ
は含まない。）を７９μｍ、長さを３５４ｃｍとして電
池を作製した。この正極活物質のＬｉ／Ｍｎ比は、０．
５２、マンガン溶出量は、３．２％であった。Example 11 As shown in Table 1, in Example 11, lot No. was used as the positive electrode active material. Using lithium manganate powder of No. 11, using amorphous carbon as the negative electrode active material,
A battery was manufactured with a negative electrode active material layer (active material coated portion) W4 having a thickness (not including the current collector thickness) of 79 μm and a length of 354 cm. The Li / Mn ratio of this positive electrode active material is 0.1.
52, the manganese elution amount was 3.2%.
【００３９】（実施例１２）表１に示すように、実施例
１２では、正極活物質にロットＮｏ．１２のマンガン酸
リチウム粉末を用い、負極活物質に非晶質炭素を用い、
負極活物質層（活物質塗布部）Ｗ４の厚さ（集電体厚さ
は含まない。）を７９μｍ、長さを３５４ｃｍとして電
池を作製した。この正極活物質のＬｉ／Ｍｎ比は、０．
５２、マンガン溶出量は、１．４％であった。Example 12 As shown in Table 1, in Example 12, lot No. 1 was used as the positive electrode active material. 12 lithium manganate powder, using amorphous carbon as the negative electrode active material,
A battery was manufactured with a negative electrode active material layer (active material coated portion) W4 having a thickness (not including the current collector thickness) of 79 μm and a length of 354 cm. The Li / Mn ratio of this positive electrode active material is 0.1.
52, the manganese elution amount was 1.4%.
【００４０】（実施例１３）表１に示すように、実施例
１３では、正極活物質にロットＮｏ．１３のマンガン酸
リチウム粉末を用い、負極活物質に非晶質炭素を用い、
負極活物質層（活物質塗布部）Ｗ４の厚さ（集電体厚さ
は含まない。）を７９μｍ、長さを３５４ｃｍとして電
池を作製した。この正極活物質のＬｉ／Ｍｎ比は、０．
５５、マンガン溶出量は、３．１％であった。Example 13 As shown in Table 1, in Example 13, lot No. 1 was used as the positive electrode active material. 13, using lithium manganate powder, using amorphous carbon as the negative electrode active material,
A battery was manufactured with a negative electrode active material layer (active material coated portion) W4 having a thickness (not including the current collector thickness) of 79 μm and a length of 354 cm. The Li / Mn ratio of this positive electrode active material is 0.1.
55, the manganese elution amount was 3.1%.
【００４１】（実施例１４）表１に示すように、実施例
１４では、正極活物質にロットＮｏ．１４のマンガン酸
リチウム粉末を用い、負極活物質に非晶質炭素を用い、
負極活物質層（活物質塗布部）Ｗ４の厚さ（集電体厚さ
は含まない。）を７９μｍ、長さを３５４ｃｍとして電
池を作製した。この正極活物質のＬｉ／Ｍｎ比は、０．
５８、マンガン溶出量は、３．２％であった。Example 14 As shown in Table 1, in Example 14, lot No. 1 was used as the positive electrode active material. Using lithium manganate powder of No. 14, using amorphous carbon as the negative electrode active material,
A battery was manufactured with a negative electrode active material layer (active material coated portion) W4 having a thickness (not including the current collector thickness) of 79 μm and a length of 354 cm. The Li / Mn ratio of this positive electrode active material is 0.1.
58, the manganese elution amount was 3.2%.
【００４２】（実施例１５）表１に示すように、実施例
１５では、正極活物質にロットＮｏ．１５のマンガン酸
リチウム粉末を用い、負極活物質に非晶質炭素を用い、
負極活物質層（活物質塗布部）Ｗ４の厚さ（集電体厚さ
は含まない。）を７９μｍ、長さを３５４ｃｍとして電
池を作製した。この正極活物質のＬｉ／Ｍｎ比は、０．
６０、マンガン溶出量は、３．０％であった。Example 15 As shown in Table 1, in Example 15, lot No. was used as the positive electrode active material. Using lithium manganate powder of No. 15, using amorphous carbon as the negative electrode active material,
A battery was manufactured with a negative electrode active material layer (active material coated portion) W4 having a thickness (not including the current collector thickness) of 79 μm and a length of 354 cm. The Li / Mn ratio of this positive electrode active material is 0.1.
60, the manganese elution amount was 3.0%.
【００４３】（実施例１６）表１に示すように、実施例
１６では、正極活物質にロットＮｏ．１６のマンガン酸
リチウム粉末を用い、負極活物質に非晶質炭素を用い、
負極活物質層（活物質塗布部）Ｗ４の厚さ（集電体厚さ
は含まない。）を７９μｍ、長さを３５４ｃｍとして電
池を作製した。この正極活物質のＬｉ／Ｍｎ比は、０．
６１、マンガン溶出量は、３．１％であった。Example 16 As shown in Table 1, in Example 16, lot No. 1 was used as the positive electrode active material. Using lithium manganate powder of No. 16, using amorphous carbon as the negative electrode active material,
A battery was manufactured with a negative electrode active material layer (active material coated portion) W4 having a thickness (not including the current collector thickness) of 79 μm and a length of 354 cm. The Li / Mn ratio of this positive electrode active material is 0.1.
61, the manganese elution amount was 3.1%.
【００４４】（比較例１）表１に示すように、比較例１
では、正極活物質にロットＮｏ．３１のマンガン酸リチ
ウム（ＬｉＭｎ２Ｏ４）粉末を用い、負極活物質にメソ
フェーズ系球状黒鉛であるＭＣＭＢを用い、負極活物質
層（活物質塗布部）の厚さ（集電体厚さは含まない。）
を７９μｍ、長さを３５４ｃｍとして電池を作製した。
この正極活物質のＬｉ／Ｍｎ比は、０．５８、マンガン
溶出量は、５．４％であった。Comparative Example 1 As shown in Table 1, Comparative Example 1
In the positive electrode active material, lot No. Using lithium manganate (LiMn 2 O 4 ) powder of No. 31 and MCMB which is a mesophase-based spherical graphite as the negative electrode active material, the thickness of the negative electrode active material layer (active material coated portion) (including the thickness of the current collector) Absent.)
Was 79 μm and the length was 354 cm to produce a battery.
The Li / Mn ratio of this positive electrode active material was 0.58, and the manganese elution amount was 5.4%.
【００４５】（比較例２）表１に示すように、比較例２
では、正極活物質にロットＮｏ．３２のマンガン酸リチ
ウム粉末を用い、負極活物質にＭＣＭＢを用い、負極活
物質層（活物質塗布部）の厚さ（集電体厚さは含まな
い。）を７９μｍ、長さを３５４ｃｍとして電池を作製
した。この正極活物質のＬｉ／Ｍｎ比は、０．５８、マ
ンガン溶出量は、６．１％であった。Comparative Example 2 As shown in Table 1, Comparative Example 2
In the positive electrode active material, lot No. Using lithium manganate powder of No. 32 and MCMB as the negative electrode active material, the thickness of the negative electrode active material layer (active material coated portion) was 79 μm, and the length was 354 cm. Was prepared. The Li / Mn ratio of this positive electrode active material was 0.58, and the manganese elution amount was 6.1%.
【００４６】（比較例３）表１に示すように、比較例３
では、正極活物質にロットＮｏ．３３のマンガン酸リチ
ウム粉末を用い、負極活物質にＭＣＭＢを用い、負極活
物質層（活物質塗布部）の厚さ（集電体厚さは含まな
い。）を７９μｍ、長さを３５４ｃｍとして電池を作製
した。この正極活物質のＬｉ／Ｍｎ比は、０．５８、マ
ンガン溶出量は、７．２％であった。Comparative Example 3 As shown in Table 1, Comparative Example 3
In the positive electrode active material, lot No. Using lithium manganate powder of No. 33, MCMB as the negative electrode active material, the thickness of the negative electrode active material layer (active material coated portion) is 79 μm, and the length is 354 cm. Was prepared. The Li / Mn ratio of this positive electrode active material was 0.58, and the manganese elution amount was 7.2%.
【００４７】（比較例４）表１に示すように、比較例４
では、正極活物質にロットＮｏ．３４のマンガン酸リチ
ウム粉末を用い、負極活物質にＭＣＭＢを用い、負極活
物質層（活物質塗布部）の厚さ（集電体厚さは含まな
い。）を７９μｍ、長さを３５４ｃｍとして電池を作製
した。この正極活物質のＬｉ／Ｍｎ比は、０．５８、マ
ンガン溶出量は、９．６％であった。Comparative Example 4 As shown in Table 1, Comparative Example 4
In the positive electrode active material, lot No. Using lithium manganate powder of No. 34, MCMB as the negative electrode active material, the thickness (excluding the thickness of the current collector) of the negative electrode active material layer (active material coated portion) was 79 μm, and the length was 354 cm. Was prepared. The Li / Mn ratio of this positive electrode active material was 0.58, and the manganese elution amount was 9.6%.
【００４８】＜試験・評価＞次に、このようにして作製
した実施例及び比較例の各電池について、以下の一連の
試験を行った。<Test / Evaluation> Next, the following series of tests were performed on the batteries of the examples and the comparative examples thus manufactured.
【００４９】実施例及び比較例の各電池を、充電した後
放電し、放電容量を測定した。充電条件は、４．２Ｖ定
電圧、制限電流５Ａ、３．５時間とした。放電条件は、
５Ａ定電流、終止電圧２．７Ｖとした。The batteries of Examples and Comparative Examples were charged and then discharged, and the discharge capacities were measured. The charging conditions were a constant voltage of 4.2 V, a limited current of 5 A, and 3.5 hours. The discharge conditions are
The constant current was 5 A, and the final voltage was 2.7 V.
【００５０】また、上記条件で充電状態の電池の放電出
力を測定した。測定条件は、１Ａ、３Ａ、６Ａの各放電
電流で５秒目の電圧を読み取り、横軸電流値に対して縦
軸にプロットし、３点を結ぶ近似直線が、２．７Ｖと交
差するところの電流値と、２．７Ｖとの積を出力とし
た。The discharge output of the battery in the charged state under the above conditions was measured. The measurement conditions were as follows: the voltage at the 5th second was read at each discharge current of 1A, 3A, and 6A, plotted on the vertical axis against the horizontal axis current value, and the approximate line connecting the three points intersected 2.7 V And the product of the current value of 2.7 V and 2.7 V was used as the output.
【００５１】更に、実施例及び比較例の電池を、上記条
件で充放電を１００回繰り返した後、容量を測定し、初
期の出力に対する維持率を百分率で示した。当然のこと
ながら、この維持率が高いほうが寿命特性がよいことに
なる。Further, after repeating charging and discharging 100 times under the above-mentioned conditions, the capacities of the batteries of the examples and the comparative examples were measured, and the retention ratio to the initial output was shown as a percentage. Naturally, the higher the maintenance ratio, the better the life characteristics.
【００５２】これら充電、放電、出力の測定は、いずれ
も環境温度２５±１°Ｃの雰囲気で行った。The charge, discharge, and output measurements were all performed in an atmosphere at an environmental temperature of 25 ± 1 ° C.
【００５３】その後、作製した電池を、常温で、２０Ａ
定電流で連続充電し、電池挙動を観察した。その結果を
下表２に示す。現象は、開裂弁開裂の後、非水電解液の
揮発物からなるガス放出が起こる。このガス放出の程度
を比較するために、現象発生直後の電池表面温度を測定
した。また、ガス放出後、電池容器の変形の有無を確認
した。なお、表２において、「○」は電池容器の変形が
全く認められなかったもの、「△」は電池容器の若干の
変形が認められたもの、「×」は電池容器が大きく変形
したものを示している。After that, the produced battery was subjected to 20 A at room temperature.
The battery was continuously charged at a constant current, and the behavior of the battery was observed. The results are shown in Table 2 below. The phenomenon is that after the cleavage valve is cleaved, outgassing of volatiles of the non-aqueous electrolyte occurs. In order to compare the degree of this gas release, the battery surface temperature immediately after the occurrence of the phenomenon was measured. After gas release, the presence or absence of deformation of the battery container was confirmed. In Table 2, “○” indicates that the battery container was not deformed at all, “△” indicates that the battery container was slightly deformed, and “×” indicates that the battery container was significantly deformed. Is shown.
【００５４】[0054]
【表２】 [Table 2]
【００５５】表２に示すように、実施例１〜１６の電池
では、高容量、高出力な電池が得られ、かつ、連続充電
時の電池挙動も穏やかなものであった。これら実施例の
電池の表面温度は、９０°Ｃ〜１９０°Ｃであった。負
極に黒鉛を用い、正極活物質であるマンガン酸リチウム
のマンガンの溶出量が、５％を上回った比較例１及び比
較例２の電池、負極に非晶質炭素を用い、正極活物質で
あるマンガン酸リチウムのマンガンの溶出量が７％を上
回った比較例３及び比較例４の電池では、高容量、高出
力な電池が得られるものの、連続充電時の電池挙動は、
電池の変形を伴った激しいものとなり、電池表面温度
は、２００°Ｃをはるかに超える結果となった。As shown in Table 2, with the batteries of Examples 1 to 16, high-capacity, high-output batteries were obtained, and the battery behavior during continuous charging was moderate. The surface temperatures of the batteries of these examples were 90 ° C to 190 ° C. The batteries of Comparative Examples 1 and 2 in which graphite was used for the negative electrode, and the manganese elution amount of lithium manganate as the positive electrode active material exceeded 5%, and amorphous carbon was used for the negative electrode and the positive electrode active material was used. In the batteries of Comparative Examples 3 and 4 in which the manganese elution amount of lithium manganate exceeded 7%, although a high-capacity, high-output battery was obtained, the battery behavior during continuous charging was as follows:
The result was severe with deformation of the battery, and the battery surface temperature was much higher than 200 ° C.
【００５６】マンガン酸リチウムのＬｉ／Ｍｎ比が、
０．５５以上である実施例５〜７及び１３〜１５の電池
では、容量維持率が極めて高い。ところが０．６０を上
回る実施例８及び実施例１６の電池では、著しい容量の
低下を伴う結果となり、Ｌｉ／Ｍｎ比は、０．５５〜
０．６０の範囲が好ましいことが分かる。The Li / Mn ratio of lithium manganate is
In the batteries of Examples 5 to 7 and 13 to 15, which are 0.55 or more, the capacity retention ratio is extremely high. However, the batteries of Example 8 and Example 16 exceeding 0.60 resulted in a significant decrease in capacity, and the Li / Mn ratio was 0.55 to 0.55.
It turns out that the range of 0.60 is preferable.
【００５７】中でも、負極に非晶質炭素を用いた実施例
９〜１６の電池では、高出力、高放電容量維持率で、か
つ、連続充電時の電池表面温度も低い結果が得られた。
従って、実施例９〜１６の電池は、高容量、高出力で、
かつ、安全性に優れる、全体バランスの優れた電池であ
るということができる。特に、負極活物質に非晶質炭素
を用い、Ｌｉ／Ｍｎ比が０．５５〜０．６０、マンガン
溶出量が３．２％以下の実施例１３〜１５の電池は、連
続充電時の電池表面温度が９０°Ｃと最も低く、一層安
全な電池ということができる。In particular, in the batteries of Examples 9 to 16 using amorphous carbon for the negative electrode, high output, high discharge capacity retention ratio, and low battery surface temperature during continuous charging were obtained.
Therefore, the batteries of Examples 9 to 16 had high capacity and high output,
In addition, it can be said that the battery is excellent in safety and excellent in overall balance. In particular, the batteries of Examples 13 to 15 in which amorphous carbon was used as the negative electrode active material, the Li / Mn ratio was 0.55 to 0.60, and the manganese elution amount was 3.2% or less, were the batteries during continuous charging. It can be said that the battery has the lowest surface temperature of 90 ° C. and is safer.
【００５８】以上のように、本実施形態の円筒形リチウ
ムイオン電池２０は、電池が異常な状態にさらされた場
合の挙動が極めて穏やかで、安全性に優れた電池であ
る。このように、高容量、高出力で、極めて安全性の高
い電池は、特に電気自動車の電源に適している。As described above, the cylindrical lithium-ion battery 20 of the present embodiment has a very gentle behavior when the battery is exposed to an abnormal state, and has excellent safety. Thus, a battery with high capacity, high output, and extremely high safety is particularly suitable for a power supply of an electric vehicle.
【００５９】なお、本実施形態では、電気自動車用電源
に用いられる大形の二次電池について例示したが、電池
の大きさ、電池容量には限定されず、電池容量としてお
おむね３〜１０Ａｈ程度の電池に対して本発明は効果を
著しく発揮することが確認されている。また、本実施形
態では円筒形電池について例示したが、本発明は電池の
形状についても限定されず、角形、その他の多角形の電
池にも適用可能である。更に、本発明の適用可能な形状
としては、上述した有底筒状容器（缶）に電池上蓋がカ
シメによって封口されている構造の電池以外であっても
構わない。このような構造の一例として正負外部端子が
電池蓋を貫通し電池容器内で軸芯を介して正負外部端子
が押し合っている状態の電池を挙げることができる。In this embodiment, a large secondary battery used as a power source for an electric vehicle has been described as an example. However, the present invention is not limited to the size and battery capacity of the battery, and the battery capacity is about 3 to 10 Ah. It has been confirmed that the present invention exerts remarkable effects on batteries. Further, in the present embodiment, the cylindrical battery is exemplified, but the present invention is not limited to the shape of the battery, and is applicable to a square battery and other polygon batteries. Furthermore, as a shape to which the present invention can be applied, a battery other than the battery having a structure in which the battery upper lid is sealed in the above-described bottomed cylindrical container (can) by caulking may be used. An example of such a structure is a battery in which the positive and negative external terminals penetrate the battery cover and the positive and negative external terminals press against each other via the shaft core in the battery container.
【００６０】また、本実施形態では、絶縁被覆に、基材
がポリイミドで、その片面にヘキサメタアクリレートか
らなる粘着剤を塗布した粘着テープを用いた例を示した
が、例えば、基材がポリプロピレンやポリエチレン等の
ポリオレフィンで、その片面又は両面にヘキサメタアク
リレートやブチルアクリレート等のアクリル系粘着剤を
塗布した粘着テープや、粘着剤を塗布しないポリオレフ
ィンやポリイミドからなるテープ等も好適に使用するこ
とができる。In this embodiment, an example is shown in which an adhesive tape is used in which the base material is polyimide and the adhesive agent made of hexamethacrylate is applied to one surface of the insulating coating. Or a polyolefin such as polyethylene, an adhesive tape coated with an acrylic adhesive such as hexamethacrylate or butyl acrylate on one or both sides thereof, or a tape made of a polyolefin or polyimide not coated with an adhesive can also be suitably used. it can.
【００６１】更に、本実施形態では、リチウムイオン電
池用の正極にマンガン酸リチウム、負極に非晶質炭素、
電解液にエチレンカーボネートとジメチルカーボネート
とジエチルカーボネートの体積比１：１：１の混合溶液
中へ６フッ化リン酸リチウムを１モル／リットル溶解し
たものを用いたが、本発明の電池には特に制限はなく、
また、導電材、結着剤も通常用いられているいずれのも
のも使用可能である。なお、一般に、マンガン酸リチウ
ムは、適当なリチウム塩と酸化マンガンとを混合、焼成
して合成することができるが、リチウム塩と酸化マンガ
ンの仕込み比を制御することによって所望のＬｉ／Ｍｎ
比とすることができる。Further, in this embodiment, lithium manganate is used for the positive electrode for lithium ion batteries, amorphous carbon is used for the negative electrode,
The electrolyte used was one in which lithium hexafluorophosphate was dissolved at 1 mol / l in a mixed solution of ethylene carbonate, dimethyl carbonate and diethyl carbonate in a volume ratio of 1: 1: 1. There are no restrictions,
In addition, any of commonly used conductive materials and binders can be used. In general, lithium manganate can be synthesized by mixing and baking an appropriate lithium salt and manganese oxide. However, by controlling the charging ratio of the lithium salt and manganese oxide, desired Li / Mn can be obtained.
It can be a ratio.
【００６２】また、本実施形態以外で用いることのでき
るリチウムイオン電池用極板活物質結着剤としては、テ
フロン（登録商標）、ポリエチレン、ポリスチレン、ポ
リブタジエン、ブチルゴム、ニトリルゴム、スチレン／
ブタジエンゴム、多硫化ゴム、ニトロセルロース、シア
ノエチルセルロース、各種ラテックス、アクリロニトリ
ル、フッ化ビニル、フッ化ビニリデン、フッ化プロピレ
ン、フッ化クロロプレン等の重合体及びこれらの混合体
などがある。The electrode active material binder for lithium ion batteries that can be used in other than this embodiment includes Teflon (registered trademark), polyethylene, polystyrene, polybutadiene, butyl rubber, nitrile rubber, styrene /
Examples thereof include butadiene rubber, polysulfide rubber, nitrocellulose, cyanoethylcellulose, various latexes, polymers such as acrylonitrile, vinyl fluoride, vinylidene fluoride, propylene fluoride, and chloroprene, and mixtures thereof.
【００６３】また更に、本実施形態以外で用いることの
できるリチウムイオン電池用正極活物質としては、リチ
ウムを挿入・脱離可能な材料であり、予め十分な量のリ
チウムを挿入したリチウムマンガン複酸化物が好まし
く、スピネル構造を有したマンガン酸リチウムや、結晶
中のマンガンやリチウムの一部をそれら以外の元素で置
換あるいはドープした材料を使用するようにしてもよ
い。Further, the positive electrode active material for lithium ion batteries that can be used in other than this embodiment is a material into which lithium can be inserted and desorbed, and a lithium manganese double oxide in which a sufficient amount of lithium has been inserted in advance. It is preferable to use lithium manganate having a spinel structure, or a material in which a part of manganese or lithium in the crystal is substituted or doped with another element.
【００６４】更にまた、本実施形態以外で用いることの
できるリチウムイオン電池用負極活物質も上記特許請求
範囲に記載した事項以外に特に制限はない。例えば、天
然黒鉛や、人造の各種黒鉛材、コークス、非晶質炭素な
どの炭素質材料等でよく、その粒子形状においても、鱗
片状、球状、繊維状、塊状等、特に制限されるものでは
ない。Further, the negative electrode active material for a lithium ion battery that can be used in other than this embodiment is not particularly limited except for the matters described in the claims. For example, natural graphite, artificial graphite materials, coke, carbonaceous materials such as amorphous carbon and the like may be used, and even in the particle shape thereof, flakes, spheres, fibers, lump, and the like are not particularly limited. Absent.
【００６５】また、非水電解液としては、一般的なリチ
ウム塩を電解質とし、これを有機溶媒に溶解した電解液
が用いられる。しかし、用いられるリチウム塩や有機溶
媒は特に制限されない。例えば、電解質としては、Ｌｉ
ＣｌＯ4、ＬｉＡｓＦ6、ＬｉＰＦ6、ＬｉＢＦ4、ＬｉＢ
（Ｃ6Ｈ5）4、ＣＨ3ＳＯ3Ｌｉ、ＣＦ3ＳＯ3Ｌｉ等やこ
れらの混合物を用いることができる。非水電解液有機溶
媒としては、プロピレンカーボネート、エチレンカーボ
ネート、１，２−ジメトキシエタン、１，２−ジエトキ
シエタン、γ−ブチロラクトン、テトラヒドロフラン、
１，３−ジオキソラン、４−メチル−１，３−ジオキソ
ラン、ジエチルエーテル、スルホラン、メチルスルホラ
ン、アセトニトリル、プロピオニトニル等またはこれら
２種類以上の混合溶媒を用いるようにしてもよく、混合
配合比についても限定されるものではない。As the non-aqueous electrolyte, an electrolyte obtained by dissolving a general lithium salt as an electrolyte in an organic solvent is used. However, the lithium salt or organic solvent used is not particularly limited. For example, as the electrolyte, Li
ClO 4 , LiAsF 6 , LiPF 6 , LiBF 4 , LiB
(C 6 H 5 ) 4 , CH 3 SO 3 Li, CF 3 SO 3 Li, and the like, and a mixture thereof can be used. Non-aqueous electrolyte organic solvents include propylene carbonate, ethylene carbonate, 1,2-dimethoxyethane, 1,2-diethoxyethane, γ-butyrolactone, tetrahydrofuran,
1,3-dioxolane, 4-methyl-1,3-dioxolane, diethyl ether, sulfolane, methylsulfolane, acetonitrile, propionitonyl, etc. or a mixed solvent of two or more of these may be used, and the mixing ratio is also limited. It is not something to be done.
【００６６】[0066]
【発明の効果】以上説明したように、本発明によれば、
正極活物質にリチウムマンガン複酸化物、負極活物質に
黒鉛又は非晶質炭素を用いたので、高容量、高出力とす
ることができると共に、金属リチウムに対する電極電位
が４．８Ｖ以上の領域で、非水電解液中へのマンガンの
溶出量が、リチウムマンガン複酸化物を基準として５％
以下であるリチウムマンガン複酸化物を正極活物質に用
い、充放電によりリチウムイオンを吸蔵、放出可能な黒
鉛を負極活物質に用いるか、又は、非水電解液中へのマ
ンガンの溶出量が、リチウムマンガン複酸化物を基準と
して７％以下であるリチウムマンガン複酸化物を正極活
物質に用い、充放電によりリチウムイオンを吸蔵、放出
可能な非晶質炭素を負極活物質に用いたので、内圧開放
機構からのガス放出が極めて穏やかに行われるため、高
容量、高出力でありながらも、極めて安全性の高い非水
電解液二次電池を実現することができる、という効果を
得ることができる。As described above, according to the present invention,
Since lithium-manganese double oxide is used for the positive electrode active material and graphite or amorphous carbon is used for the negative electrode active material, high capacity and high output can be achieved, and in a region where the electrode potential with respect to metallic lithium is 4.8 V or more. The amount of manganese eluted into the non-aqueous electrolyte is 5% based on lithium manganese double oxide
The following lithium manganese double oxide is used for the positive electrode active material, and lithium ions can be occluded by charge and discharge, or graphite that can be released is used for the negative electrode active material, or the amount of manganese eluted into the non-aqueous electrolyte is Since lithium-manganese composite oxide, which is 7% or less based on lithium-manganese composite oxide, was used for the positive electrode active material, and amorphous carbon capable of occluding and releasing lithium ions by charge and discharge was used for the negative electrode active material, the internal pressure was low. Since the release of gas from the opening mechanism is performed very gently, it is possible to obtain an effect that a non-aqueous electrolyte secondary battery having a high capacity and a high output and a very high safety can be realized. .
【図１】本発明が適用可能な実施形態の円筒形リチウム
イオン電池の断面図である。FIG. 1 is a sectional view of a cylindrical lithium ion battery according to an embodiment to which the present invention can be applied.
１ 軸芯 ２ 正極リード片（正極の一部） ３ 負極リード片（負極の一部） ４ 正極集電リング（接続部の一部） ５ 負極集電リング（接続部の一部） ６ 捲回群（電極群） ７ 電池容器 ８ 負極リード板（接続部の一部） ９ 正極リード（接続部の一部） １０ ガスケット １１ 開裂弁（内圧開放機構） １２ 蓋ケース １３ 蓋キャップ １４ 弁押え ２０ 円筒形リチウムイオン電池（非水電解液二次電
池） Ｗ１ 正極集電体 Ｗ２ 正極活物質層 Ｗ３ 負極集電体 Ｗ４ 負極活物質層 Ｗ５ セパレータDESCRIPTION OF SYMBOLS 1 Shaft core 2 Positive electrode lead piece (part of positive electrode) 3 Negative electrode lead piece (part of negative electrode) 4 Positive electrode current collecting ring (part of connection part) 5 Negative electrode current collecting ring (part of connection part) 6 Winding Group (electrode group) 7 Battery container 8 Negative electrode lead plate (part of connection part) 9 Positive electrode lead (part of connection part) 10 Gasket 11 Cleavage valve (internal pressure release mechanism) 12 Lid case 13 Lid cap 14 Valve retainer 20 Cylindrical Lithium-ion battery (non-aqueous electrolyte secondary battery) W1 Positive electrode current collector W2 Positive electrode active material layer W3 Negative electrode current collector W4 Negative electrode active material layer W5 Separator
───────────────────────────────────────────────────── フロントページの続き (72)発明者 八木 陽心 東京都中央区日本橋本町二丁目８番７号 新神戸電機株式会社内 (72)発明者 弘中 健介 東京都中央区日本橋本町二丁目８番７号 新神戸電機株式会社内 Ｆターム(参考） 5H029 AJ02 AJ12 AK03 AL07 AL08 AM03 AM05 AM07 BJ02 HJ18 5H050 AA02 AA15 BA17 CA09 CB08 CB09 DA10 HA18 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Yoshin Yagi 2-8-7 Nihonbashi Honcho, Chuo-ku, Tokyo Inside Shin-Kobe Electric Machinery Co., Ltd. (72) Kensuke Hironaka 2-87 Nihonbashi Honcho, Chuo-ku, Tokyo No. Shin Kobe Electric Co., Ltd. F-term (reference) 5H029 AJ02 AJ12 AK03 AL07 AL08 AM03 AM05 AM07 BJ02 HJ18 5H050 AA02 AA15 BA17 CA09 CB08 CB09 DA10 HA18
Claims (4)
有する電池容器に、正極、負極及びセパレータを有する
電極群と該電極群から各極端子へ接続するための接続部
と非水電解液とを内蔵し、リチウムマンガン複酸化物と
導電材とを含む活物質合剤が箔状集電体の両面に塗着さ
れた正極を用いた非水電解液二次電池において、金属リ
チウムに対する電極電位が４．８Ｖ以上の領域で、前記
非水電解液中へのマンガンの溶出量が、リチウムマンガ
ン複酸化物を基準として５％以下であるリチウムマンガ
ン複酸化物を正極活物質に用い、充放電によりリチウム
イオンを吸蔵、放出可能な黒鉛を負極活物質に用いたこ
とを特徴とする非水電解液二次電池。1. A battery container having an internal pressure releasing mechanism for releasing an internal pressure at a predetermined pressure, an electrode group having a positive electrode, a negative electrode, and a separator, a connecting portion for connecting the electrode group to each electrode terminal, and a non-aqueous electrolyte. In a non-aqueous electrolyte secondary battery using a positive electrode in which an active material mixture containing a lithium manganese double oxide and a conductive material is applied to both sides of a foil-like current collector, an electrode for metallic lithium A lithium manganese double oxide having a potential of 4.8 V or more and in which the amount of manganese eluted into the non-aqueous electrolyte is 5% or less based on the lithium manganese double oxide is used as the positive electrode active material. A non-aqueous electrolyte secondary battery using graphite capable of occluding and releasing lithium ions by discharging as a negative electrode active material.
有する電池容器に、正極、負極及びセパレータを有する
電極群と該電極群から各極端子へ接続するための接続部
と非水電解液とを内蔵し、リチウムマンガン複酸化物と
導電材とを含む活物質合剤が箔状集電体の両面に塗着さ
れた正極を用いた非水電解液二次電池において、金属リ
チウムに対する電極電位が４．８Ｖ以上の領域で、前記
非水電解液中へのマンガンの溶出量が、リチウムマンガ
ン複酸化物を基準として７％以下であるリチウムマンガ
ン複酸化物を正極活物質に用い、充放電によりリチウム
イオンを吸蔵、放出可能な非晶質炭素を負極活物質に用
いたことを特徴とする非水電解液二次電池。2. A battery container having an internal pressure release mechanism for releasing an internal pressure at a predetermined pressure, an electrode group having a positive electrode, a negative electrode, and a separator, a connection portion for connecting the electrode group to each electrode terminal, and a non-aqueous electrolyte. In a non-aqueous electrolyte secondary battery using a positive electrode in which an active material mixture containing a lithium manganese double oxide and a conductive material is applied to both sides of a foil-like current collector, an electrode for metallic lithium A lithium manganese double oxide having a potential of 4.8 V or more and a manganese elution amount into the nonaqueous electrolyte of 7% or less based on the lithium manganese double oxide is used as a positive electrode active material. A non-aqueous electrolyte secondary battery using amorphous carbon capable of occluding and releasing lithium ions by discharging as a negative electrode active material.
Ｍｎの比が、０．５５以上、０．６以下であることを特
徴とする請求項1又は請求項２に記載の非水電解液二次
電池。3. The method according to claim 1, wherein the lithium / manganese double oxide has a Li /
3. The non-aqueous electrolyte secondary battery according to claim 1, wherein a ratio of Mn is 0.55 or more and 0.6 or less.
つ、前記リチウムマンガン複酸化物の前記非水電解液中
へのマンガンの溶出量が、該リチウムマンガン複酸化物
を基準として３．２％以下であることを特徴とする請求
項３に記載の非水電解液二次電池。4. An amorphous carbon is used as the negative electrode active material, and the amount of manganese eluted into the non-aqueous electrolyte of the lithium manganese double oxide is 3 to 3% based on the lithium manganese double oxide. The non-aqueous electrolyte secondary battery according to claim 3, wherein the content is not more than 0.2%.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000368725A JP2002170597A (en) | 2000-12-04 | 2000-12-04 | Nonaqueous electrolyte solution secondary battery |
| US09/977,214 US6803149B2 (en) | 2000-12-04 | 2001-10-16 | Non-aqueous electrolytic solution secondary battery |
| EP01308884A EP1211747A3 (en) | 2000-12-04 | 2001-10-19 | Non-aqueous electrolytic solution secondary battery |
| EP06000888A EP1650819A1 (en) | 2000-12-04 | 2001-10-19 | Non-aqueous electrolytic solution secondary battery |
| TW090126214A TW522596B (en) | 2000-12-04 | 2001-10-23 | Non-aqueous electrolytic solution secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000368725A JP2002170597A (en) | 2000-12-04 | 2000-12-04 | Nonaqueous electrolyte solution secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2002170597A true JP2002170597A (en) | 2002-06-14 |
Family
ID=18838888
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000368725A Abandoned JP2002170597A (en) | 2000-12-04 | 2000-12-04 | Nonaqueous electrolyte solution secondary battery |
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| Country | Link |
|---|---|
| JP (1) | JP2002170597A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005191003A (en) * | 2003-12-01 | 2005-07-14 | Shin Kobe Electric Mach Co Ltd | Lithium secondary battery and method of manufacturing lithium secondary battery |
-
2000
- 2000-12-04 JP JP2000368725A patent/JP2002170597A/en not_active Abandoned
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005191003A (en) * | 2003-12-01 | 2005-07-14 | Shin Kobe Electric Mach Co Ltd | Lithium secondary battery and method of manufacturing lithium secondary battery |
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