JP2869355B2 - Organic electrolyte battery - Google Patents

Organic electrolyte battery

Info

Publication number
JP2869355B2
JP2869355B2 JP6330721A JP33072194A JP2869355B2 JP 2869355 B2 JP2869355 B2 JP 2869355B2 JP 6330721 A JP6330721 A JP 6330721A JP 33072194 A JP33072194 A JP 33072194A JP 2869355 B2 JP2869355 B2 JP 2869355B2
Authority
JP
Japan
Prior art keywords
lithium
negative electrode
battery
positive electrode
pas
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.)
Expired - Fee Related
Application number
JP6330721A
Other languages
Japanese (ja)
Other versions
JPH08162162A (en
Inventor
信雄 安東
肇 木下
正起 山口
之規 羽藤
静邦 矢田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kanebo Ltd
Original Assignee
Kanebo Ltd
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Filing date
Publication date
Application filed by Kanebo Ltd filed Critical Kanebo Ltd
Priority to JP6330721A priority Critical patent/JP2869355B2/en
Publication of JPH08162162A publication Critical patent/JPH08162162A/en
Application granted granted Critical
Publication of JP2869355B2 publication Critical patent/JP2869355B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Classifications

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

Description

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

【０００１】[0001]

【産業上の利用分野】本発明は、負極にポリアセン系骨
格構造を有する不溶不融性基体、正極に金属酸化物を用
いた、高容量かつ高電圧を有する有機電解質電池に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic electrolyte battery having a high capacity and a high voltage using an insoluble and infusible substrate having a polyacene skeleton structure for a negative electrode and a metal oxide for a positive electrode.

【０００２】[0002]

【従来の技術】近年、導電性高分子、遷移金属酸化物等
を正極とし、負極にリチウム金属あるいはリチウム合金
を用いた二次電池がエネルギー密度が高いことから、Ｎ
ｉ−Ｃｄ電池、鉛電池に代る電池として提案されてい
る。しかし、これら二次電池は繰り返し充放電を行うと
正極、あるいは負極の劣化による容量低下が大きく実用
に問題が残されている。特に負極の劣化はデントライト
と呼ばれるこけ状のリチウム結晶の生成を伴い、充放電
の繰り返しにより終局的にはデントライトがセパレータ
を貫通し、電池内部でショートを引き起こし、場合によ
っては電池が破裂する等、安全面においても問題があっ
た。2. Description of the Related Art In recent years, a secondary battery using a conductive polymer, a transition metal oxide or the like as a positive electrode and a lithium metal or a lithium alloy as a negative electrode has a high energy density.
It has been proposed as a battery replacing i-Cd batteries and lead batteries. However, when these secondary batteries are repeatedly charged and discharged, the capacity is greatly reduced due to deterioration of the positive electrode or the negative electrode, and there is a problem in practical use. In particular, the deterioration of the negative electrode involves the formation of moss-like lithium crystals called dentite, and the repetition of charging and discharging eventually causes the dentite to penetrate the separator, causing a short circuit inside the battery, and in some cases, the battery exploding There was also a problem in terms of safety.

【０００３】近時、上記問題点を解決すべく、グラファ
イト等の炭素材料を負極に用い、正極にＬｉＣｏＯ2 等
のリチウム含有金属酸化物を用いた電池が提案されてい
る。該電池は、電池組立後、充電する事により正極のリ
チウム含有金属酸化物より負極にリチウムを供給し、更
に放電では負極リチウムを正極に戻すという、いわゆる
ロッキングチェア型電池である。該電池は高電圧、高容
量を特長とするものの、その容量は最大８０〜９０ｍＡ
ｈ／ｃｃ（電極、セパレータ、集電材の総体積基準）程
度であり、リチウム電池の特徴である高エネルギ−密度
を得るに至っていない。一方、芳香族系縮合ポリマーの
熱処理物であって水素原子／炭素原子の原子比が０．５
〜０．０５であるポリアセン系骨格構造を有する不溶不
融性基体は、一般の炭素材料に比べ大量にリチウムをド
ープする事が可能であるが、該不溶不融性基体を負極、
正極にリチウム含有酸化物を用いた上記ロッキングチェ
ア型の電池を組み立てた場合、炭素材料に比べ高容量が
得られるものの、その容量には不満足な点が残されてい
た。上記問題点を解決する為に、本願と同一の出願人に
係る、特願平５−２５９４０３号は未だ未公開ながら、
正極，負極並びに電解液としてリチウム塩の非プロトン
性有機溶媒溶液を備えた有機電解質電池であって、
（１）正極が金属酸化物を含み（２）負極が芳香族系縮
合ポリマーの熱処理物であって水素原子／炭素原子の原
子比が０．５〜０．０５であるポリアセン系骨格構造を
有する不溶不融性基体（以下ＰＡＳ）であり、（３）負
極ＰＡＳに対し、電池内に含まれる総リチウム量が５０
０ｍＡｈ／ｇ以上であり、かつ負極由来のリチウムが１
００ｍＡｈ／ｇ以上である事を特徴とする有機電解質電
池が提案されている。該電池は高容量であるものの、円
筒型等の実用電池を組む場合、実用的かつ簡便な負極由
来のリチウムの担持法が求められている。In recent years, in order to solve the above-mentioned problems, a battery using a carbon material such as graphite for a negative electrode and using a lithium-containing metal oxide such as LiCoO 2 for a positive electrode has been proposed. The battery is a so-called rocking chair type battery in which lithium is supplied to the negative electrode from the lithium-containing metal oxide of the positive electrode by charging after the battery is assembled, and the negative electrode lithium is returned to the positive electrode in discharging. Although the battery features high voltage and high capacity, its capacity is up to 80 to 90 mA.
h / cc (based on the total volume of electrodes, separators, and current collectors), and the high energy density characteristic of lithium batteries has not been obtained. On the other hand, a heat-treated product of an aromatic condensation polymer having a hydrogen atom / carbon atom ratio of 0.5
The insoluble infusible substrate having a polyacene-based skeleton structure of about 0.05 to 0.05 can be doped with lithium in a larger amount than a general carbon material.
When assembling the rocking chair type battery using a lithium-containing oxide for the positive electrode, a higher capacity is obtained as compared with a carbon material, but the capacity is still unsatisfactory. In order to solve the above problems, Japanese Patent Application No. 5-259403, which relates to the same applicant as the present application, has not been published yet.
An organic electrolyte battery comprising a positive electrode, a negative electrode, and an aprotic organic solvent solution of a lithium salt as an electrolyte,
(1) the positive electrode contains a metal oxide; (2) the negative electrode is a heat-treated aromatic condensation polymer having a polyacene skeleton structure in which the atomic ratio of hydrogen atoms / carbon atoms is 0.5 to 0.05. (3) The total amount of lithium contained in the battery is 50% with respect to the negative electrode PAS.
0 mAh / g or more and lithium derived from the negative electrode is 1
An organic electrolyte battery characterized by being at least 00 mAh / g has been proposed. Although the battery has a high capacity, a practical and simple method of supporting lithium derived from the negative electrode is required when a practical battery such as a cylindrical battery is assembled.

【０００４】[0004]

【発明が解決しようとする課題】本発明者らは上記問題
点に鑑み、鋭意研究を続けた結果本発明を完成したもの
であって、本発明の目的は高容量かつ高電圧を有する二
次電池を提供するにある。本発明の他の目的は長期に亘
って充放電が可能で、安全性に優れた二次電池を提供す
るにある。本発明の更に他の目的は内部抵抗が低い二次
電池を提供するにある。本発明の更に他の目的は製造が
容易な二次電池を提供するにある。本発明の更に他の目
的は以下の説明から明らかにされよう。In view of the above problems, the present inventors have made intensive studies and completed the present invention. An object of the present invention is to provide a secondary battery having a high capacity and a high voltage. To provide batteries. Another object of the present invention is to provide a secondary battery which can be charged and discharged for a long period of time and is excellent in safety. Still another object of the present invention is to provide a secondary battery having a low internal resistance. Still another object of the present invention is to provide a secondary battery which is easy to manufacture. Further objects of the present invention will become clear from the description below.

【０００５】[0005]

【課題を解決するための手段】本発明者らは、正極に金
属酸化物、負極にポリアセン系骨格構造を有する不溶不
融性基体を用い、かつ、電池内のリチウム量を適切に制
御すると共に、負極由来の担持法（ドープ法）を選択す
ることにより本発明を完成した。すなわち、本発明は、
正極，負極並びに電解液としてリチウム塩の非プロトン
性有機溶媒溶液を備えた有機電解質電池であって、
（１）正極がリチウム含有金属酸化物を含み（２）負極
が芳香族系縮合ポリマーの熱処理物であって水素原子／
炭素原子の原子比が０．５〜０．０５であるポリアセン
系骨格構造を有する不溶不融性基体（ＰＡＳ）であり、
（３）負極ＰＡＳに対し、電池内に含まれる総リチウム
量が５００ｍＡｈ／ｇ以上であり、かつ負極由来のリチ
ウムが１００ｍＡｈ／ｇ以上であり負極由来のリチウム
が、電池組立後に正極リチウム含有金属酸化物よりＰＡ
Ｓに担持されたものであり、かつ正極にはＰＡＳにリチ
ウムを供給した後、リチウムとの電気化学的接触により
リチウムを担持させる事を特徴とする有機電解質電池で
ある。Means for Solving the Problems The present inventors have used a metal oxide for the positive electrode, an insoluble infusible substrate having a polyacene-based skeleton structure for the negative electrode, and appropriately controlling the amount of lithium in the battery. The present invention was completed by selecting a supporting method (dope method) derived from the negative electrode. That is, the present invention
An organic electrolyte battery comprising a positive electrode, a negative electrode, and an aprotic organic solvent solution of a lithium salt as an electrolyte,
(1) the positive electrode contains a lithium-containing metal oxide; and (2) the negative electrode is a heat-treated aromatic condensed polymer and has a hydrogen atom /
An insoluble infusible substrate (PAS) having a polyacene-based skeleton structure in which the atomic ratio of carbon atoms is 0.5 to 0.05,
(3) With respect to the negative electrode PAS, the total amount of lithium contained in the battery is 500 mAh / g or more, and the lithium derived from the negative electrode is 100 mAh / g or more. PA over things
An organic electrolyte battery supported on S and supplying lithium to the PAS on the positive electrode, and then supporting lithium by electrochemical contact with lithium.

【０００６】本発明における芳香族系縮合ポリマーと
は、芳香族炭化水素化合物とアルデヒド類との縮合物で
ある。芳香族炭化水素化合物としては、例えば、フェノ
ール，クレゾール，キシレノール等の如き、いわゆるフ
ェノール類が好適である。例えば、下記式The aromatic condensation polymer in the present invention is a condensate of an aromatic hydrocarbon compound and an aldehyde. As the aromatic hydrocarbon compound, for example, so-called phenols such as phenol, cresol, and xylenol are preferable. For example,

【化１】 （ここで、ｘおよびｙはそれぞれ独立に、０、１又は２
である）で表されるメチレン・ビスフェノール類である
ことができ、或いはヒドロキシ・ビフェニル類、ヒドロ
キシナフタレン類であることもできる。これらの内、実
用的にはフェノール類、特にフェノールが好適である。
本発明における芳香族系縮合ポリマ−として、上記のフ
ェノール性水酸基を有する芳香族炭化水素化合物の１部
をフェノール性水酸基を有さない芳香族炭化水素化合
物、例えば、キシレン、トルエン、アニリン等で置換し
た変成芳香族系縮合ポリマー例えばフェノールとキシレ
ンとホルムアルデヒドとの縮合物を用いることもでき、
また、メラミン、尿素で置換した変成芳香族系ポリマー
を用いることもできる。また、フラン樹脂も好適であ
る。また、アルデヒドとしては、ホルムアルデヒド、ア
セトアルデヒド、フルフラール等のアルデヒドを使用す
ることができるが、ホルムアルデヒドが好適である。フ
ェノールホルムアルデヒド縮合物としては、ノボラック
型又はレゾール型或はそれらの混合物のいずれであって
もよい。Embedded image (Where x and y are each independently 0, 1 or 2
Methylene bisphenols represented by the formula: or hydroxy biphenyls or hydroxynaphthalenes. Of these, phenols, particularly phenol, are practically preferred.
As the aromatic condensation polymer in the present invention, a part of the aromatic hydrocarbon compound having a phenolic hydroxyl group is replaced with an aromatic hydrocarbon compound having no phenolic hydroxyl group, such as xylene, toluene, or aniline. It is also possible to use a modified aromatic condensation polymer such as a condensate of phenol, xylene and formaldehyde,
Further, a modified aromatic polymer substituted with melamine or urea can also be used. Furan resins are also suitable. As the aldehyde, aldehydes such as formaldehyde, acetaldehyde, and furfural can be used, but formaldehyde is preferred. The phenol formaldehyde condensate may be any of a novolak type, a resol type, or a mixture thereof.

【０００７】本発明における不溶不融性基体は、上記芳
香族系ポリマ−を熱処理する事により得られ、特公平１
−４４２１２号公報、特公平３−２４０２４号公報等に
記載されているポリアセン系骨格構造を有する不溶不融
性基体は全て用いることができ、例えば、次のようにし
て製造することもできる。該芳香族系縮合ポリマ−を、
非酸化性雰囲気下（真空も含む）中で、４００°Ｃ〜８
００°Ｃの適当な温度まで徐々に加熱する事により、水
素原子／炭素原子の原子比（以下Ｈ／Ｃと記す）が０．
５０〜０．０５、好ましくは０．３５〜０．１０の不溶
不融性基体を得ることができる。また、特公平３−２４
０２４号公報等に記載されている方法で、６００ｍ2 ／
ｇ以上のＢＥＴ法による比表面積を有する不溶不融性基
体を得ることもできる。例えば、芳香族系縮合ポリマー
の初期縮合物と無機塩、例えば塩化亜鉛を含む溶液を調
製し、該溶液を加熱して型内で硬化する。かくして得ら
れた硬化体を、非酸化性雰囲気化（真空も含む）中で、
３５０°Ｃ〜８００°Ｃの温度まで、好ましくは４００
°Ｃ〜７５０°Ｃの適当な温度まで徐々に加熱した後、
水あるいは希塩酸等によって充分に洗浄することによ
り、上記Ｈ／Ｃを有し、かつ、例えば６００ｍ2 ／ｇ以
上のＢＥＴ法による比表面積を有する不溶不融性基体を
得ることもできる。The insoluble and infusible substrate of the present invention can be obtained by heat-treating the above aromatic polymer.
All the insoluble and infusible substrates having a polyacene-based skeleton structure described in JP-A-44212, JP-B-3-24024 and the like can be used. For example, they can be produced as follows. The aromatic condensation polymer,
400 ° C-8 in a non-oxidizing atmosphere (including vacuum)
By gradually heating to an appropriate temperature of 00 ° C., the atomic ratio of hydrogen atoms / carbon atoms (hereinafter referred to as H / C) becomes 0.1.
An insoluble infusible substrate of 50 to 0.05, preferably 0.35 to 0.10. In addition, 3-24
No. 024/600 m 2 /
It is also possible to obtain an insoluble and infusible substrate having a specific surface area of at least g by the BET method. For example, a solution containing an initial condensate of an aromatic condensation polymer and an inorganic salt such as zinc chloride is prepared, and the solution is heated and cured in a mold. The cured product thus obtained is placed in a non-oxidizing atmosphere (including vacuum)
Up to a temperature of 350 ° C. to 800 ° C., preferably 400 ° C.
After gradually heating to a suitable temperature of
By washing sufficiently with water or diluted hydrochloric acid, an insoluble infusible substrate having the above H / C and a specific surface area of, for example, 600 m 2 / g or more by a BET method can be obtained.

【０００８】本発明に用いる不溶不融性基体は、Ｘ線回
折（ＣｕＫα）によれば、メイン・ピークの位置は２θ
で表して２４°以下に存在し、また該メイン・ピークの
他に４１〜４６°の間にブロードな他のピークが存在す
る。すなわち、上記不溶不融性基体は芳香族系多環構造
が適度に発達したポリアセン系骨格構造を有し、かつア
モルファス構造をとると示唆され、リチウムを安定にド
ーピングできることから電池用活物質として有用であ
る。Ｈ／Ｃが０．５０を越える場合、芳香族系多環構造
が充分に発達していないため、リチウムのドーピング、
脱ドーピングがスムーズに行うことができず、電池を組
んだ時、充放電効率が低下する。また、Ｈ／Ｃが０．０
５以下の場合、本発明の電池の容量が低下し好ましくな
い。The insoluble infusible substrate used in the present invention has a main peak at 2θ according to X-ray diffraction (CuKα).
And there are other broad peaks between 41 and 46 ° in addition to the main peak. That is, it is suggested that the insoluble infusible substrate has a polyacene skeleton structure in which an aromatic polycyclic structure is appropriately developed and has an amorphous structure, and is useful as an active material for a battery because lithium can be stably doped. It is. When H / C exceeds 0.50, doping of lithium,
Dedoping cannot be performed smoothly, and when a battery is assembled, the charge / discharge efficiency decreases. In addition, H / C is 0.0
If it is 5 or less, the capacity of the battery of the present invention decreases, which is not preferable.

【０００９】本発明の負極は上記不溶不融性基体（以下
ＰＡＳ）より成り、粉末状、粒状、短繊維状等の成形し
やすい形状にあるＰＡＳをバインダーで成形したもので
ある。バインダーとしては、ポリ四フッ化エチレン、ポ
リフッ化ビニリデン等の含フッ素系樹脂、ポリプロピレ
ン、ポリエチレン等の熱可塑性樹脂がを用いる事ができ
るが、好ましくフッ素系バインダ−が好ましく、更には
フッ素原子／炭素原子の原子比（以下、Ｆ／Ｃと記す）
が１．５未満０．７５以上であるフッ素系バインダーが
好ましく、特に、１．３未満０．７５以上のフッ素系バ
インダーが好ましい。上記フッ素系バインダーとして
は、例えば、ポリフッ化ビニリデン、フッ化ビニリデン
−３フッ化エチレン共重合体、エチレン−４フッ化エチ
レン共重合体、プロピレン−４フッ化エチレン共重合体
等が挙げられ、更に主鎖の水素をアルキル基で置換した
含フッ素系ポリマ−も用いることできる。ポリフッ化ビ
ニリデンの場合、Ｆ／Ｃは１であり、フッ化ビニリデン
−３フッ化エチレン共重合体の場合、フッ化ビニリデン
のモル分率が５０％の時、８０％の時それぞれＦ／Ｃは
１．２５、１．１となり、更にプロピレン−４フッ化エ
チレン共重合体の場合、プロピレンのモル分率が５０％
の時、Ｆ／Ｃは０．７５となる。中でも、ポリフッ化ビ
ニリデン、フッ化ビニリデンのモル分率が５０％以上の
フッ化ビニリデン−３フッ化エチレン共重合体が好まし
く、実用的にはポリフッ化ビニリデンが好ましい。これ
らバインダーを用いた場合、ＰＡＳの有するリチウムの
ドープ能（容量）を充分に利用することができる。The negative electrode of the present invention comprises the above-described insoluble and infusible substrate (hereinafter referred to as PAS), and is formed by molding a PAS having a shape such as powder, granules, short fibers, etc., which is easy to mold, with a binder. As the binder, a fluorinated resin such as polytetrafluoroethylene or polyvinylidene fluoride, or a thermoplastic resin such as polypropylene or polyethylene can be used, but a fluorinated binder is preferable, and a fluorine atom / carbon is preferable. Atomic ratio of atoms (hereinafter referred to as F / C)
Is preferably less than 1.5 and not less than 0.75, more preferably less than 1.3 and not less than 0.75. Examples of the fluorine-based binder include, for example, polyvinylidene fluoride, vinylidene fluoride-trifluoroethylene copolymer, ethylene-tetrafluoroethylene copolymer, propylene-tetrafluoroethylene copolymer, and the like. A fluorine-containing polymer in which hydrogen in the main chain is substituted with an alkyl group can also be used. In the case of polyvinylidene fluoride, the F / C is 1; in the case of the vinylidene fluoride-3fluoroethylene copolymer, when the molar fraction of the vinylidene fluoride is 50% and 80%, the F / C is respectively: 1.25, 1.1, and in the case of a propylene-tetrafluoroethylene copolymer, the propylene mole fraction is 50%.
In this case, F / C is 0.75. Among them, polyvinylidene fluoride and a vinylidene fluoride-3fluoroethylene copolymer having a molar fraction of vinylidene fluoride of 50% or more are preferable, and polyvinylidene fluoride is practically preferable. When these binders are used, the lithium doping ability (capacity) of PAS can be sufficiently utilized.

【００１０】本発明の有機電解質電池の正極としては、
ＬｉX ＣｏＯ2 、 ＬｉX ＮｉＯ2 、ＬｉX ＭｎＯ2 、Ｌ
ｉX ＦｅＯ2 等のＬｉX Ｍy ＯZ （Ｍは金属、二種以上
の金属でも良い）の一般式で表され得る、リチウムを電
気化学的にドープ、脱ドープが可能なリチウム含有金属
酸化物を用いる。特にリチウム金属に対し４Ｖ以上の電
圧を有するリチウム含有酸化物が好ましい。中でも、リ
チウム含有コバルト酸化物、リチウム含有ニッケル酸化
物が好ましい。本発明における正極は、上記活物質、及
び必要に応じて導電材、バインダーを加え成形したもの
であり、導電材、バインダーの種類、組成等は適宜設定
すればよい。As the positive electrode of the organic electrolyte battery of the present invention,
Li X CoO 2, Li X NiO 2, Li X MnO 2 , L
i X FeO 2, etc. Li X M y O Z (M is a metal, may also be in two or more metals) may be represented by the general formula, electrochemically doped, de-doped Lithium-containing metal oxide of lithium Use things. Particularly, a lithium-containing oxide having a voltage of 4 V or more with respect to lithium metal is preferable. Among them, lithium-containing cobalt oxide and lithium-containing nickel oxide are preferable. The positive electrode in the present invention is formed by adding the above-mentioned active material and, if necessary, a conductive material and a binder, and the type and composition of the conductive material and the binder may be appropriately set.

【００１１】導電剤の種類は、金属ニッケル等の金属粉
末でもよいが、例えば、活性炭、カーボンブラック、ア
セチレンブラック、黒鉛等の炭素系のものが特に好まし
い。混合比は活物質の電気伝導度、電極形状等により異
なるが、活物質に対して２〜４０％加えるのが適当であ
る。また、バインダーの種類は、後述の本発明にて用い
る電解液に不溶のものであればよく、例えば、ＳＢＲ等
のゴム系バインダー、ポリ四フッ化エチレン、ポリフッ
化ビニリデン等の含フッ素系樹脂、ポリプロピレン、ポ
リエチレン等の熱可塑性樹脂が好ましく、その混合比は
２０％以下とするのが好ましい。The type of the conductive agent may be a metal powder such as metallic nickel, but for example, a carbon-based material such as activated carbon, carbon black, acetylene black and graphite is particularly preferred. The mixing ratio varies depending on the electric conductivity of the active material, the shape of the electrode, and the like, but it is appropriate to add 2 to 40% to the active material. Further, the kind of the binder may be any one that is insoluble in the electrolytic solution used in the present invention described later, for example, a rubber-based binder such as SBR, polytetrafluoroethylene, a fluorinated resin such as polyvinylidene fluoride, Thermoplastic resins such as polypropylene and polyethylene are preferable, and the mixing ratio is preferably 20% or less.

【００１２】本発明に用いる正極、負極の電極形状は、
目的とする電池により、板状、フィルム状、円柱状、あ
るいは、金属箔上に成形するなど、種々の形状をとるこ
とが出来る。特に、金属箔上に成形したものは集電体一
体電極として、種々の電池に応用できることから好まし
い。The shapes of the positive electrode and the negative electrode used in the present invention are as follows.
Depending on the intended battery, various shapes such as a plate shape, a film shape, a column shape, or a shape formed on a metal foil can be adopted. In particular, those formed on a metal foil are preferable because they can be applied to various batteries as a current collector integrated electrode.

【００１３】本発明の電池は、上記ＰＡＳを負極に用
い、かつ電池内に含まれるリチウム量を適切に制御する
事により従来の電池に比べ、容量を大幅に向上すること
ができる。本発明において電池内の総リチウム量とは正
極由来のリチウム、電解液由来のリチウム、負極由来の
リチウムの総計である。正極由来のリチウムとは、（電
池組立時正極に含まれるリチウム）＋（リチウム源より
正極に供給されたリチウム）−（負極に供給されたリチ
ウム）である。また、電解液由来のリチウムとは、セパ
レータ、正極、負極等に含まれる電解液中のリチウムで
ある。また、負極由来のリチウムとは、本発明の負極Ｐ
ＡＳに、電池完成前に、正極からの供給により担持され
ているリチウムである（正極由来のリチウム、電解液由
来のリチウム以外のリチウムである）。本発明におい
て、負極由来のリチウムは、電池組立後に正極リチウム
含有金属酸化物より負極ＰＡＳに担持される。具体的に
は、例えば、円筒型電池を組む場合、正極と負極をセパ
レーターを介して、巻き取った後、電気化学的に正極リ
チウム含有酸化物より負極ＰＡＳに下記に記載の範囲の
所定量のリチウムを担持させる。その後、正極には負極
ＰＡＳにリチウムを供給した後、リチウムとの電気化学
的接触によりリチウムを担持させる。この時の、リチウ
ム量は、正極単独の充放電効率等を考慮して決定される
が、負極由来のリチウム量相当、あるいは負極由来のリ
チウム量より少なくすることが、好ましい。この負極由
来のリチウムを担持させる一連の操作は、一回で行って
もよいが、数回の繰り返しの操作により行ってもよい。
本発明において、正極リチウム含有酸化物にリチウムと
の電気化学的接触によりリチウムを担持させる事が終了
したとき、電池完成とする。負極リチウムの担持方法と
しては、電池組立前に担持させる、すなわち、あらかじ
め負極ＰＡＳに所定のリチウムを担持させた後、電池を
組み立てる方法もあるが、電池生産において、その工程
が煩雑になる事から、好ましくない。The battery of the present invention can greatly improve the capacity as compared with a conventional battery by using the above PAS as the negative electrode and appropriately controlling the amount of lithium contained in the battery. In the present invention, the total amount of lithium in the battery is the total of lithium derived from the positive electrode, lithium derived from the electrolyte, and lithium derived from the negative electrode. The lithium derived from the positive electrode is (lithium contained in the positive electrode during battery assembly) + (lithium supplied to the positive electrode from the lithium source) − (lithium supplied to the negative electrode). Further, the lithium derived from the electrolyte is lithium in the electrolyte contained in the separator, the positive electrode, the negative electrode, and the like. Further, the lithium derived from the negative electrode refers to the negative electrode P of the present invention.
Prior to completion of the battery, the AS is lithium supported by supply from the positive electrode (lithium other than lithium derived from the positive electrode and lithium derived from the electrolyte). In the present invention, the lithium derived from the negative electrode is supported on the negative electrode PAS from the positive electrode lithium-containing metal oxide after the battery is assembled. Specifically, for example, when assembling a cylindrical battery, after winding the positive electrode and the negative electrode via a separator, electrochemically from the positive electrode lithium-containing oxide to the negative electrode PAS of a predetermined amount in the range described below from the positive electrode lithium-containing oxide Lithium is supported. Then, after supplying lithium to the negative electrode PAS, lithium is supported on the positive electrode by electrochemical contact with lithium. At this time, the amount of lithium is determined in consideration of the charge / discharge efficiency of the positive electrode alone, and it is preferable that the amount of lithium is equivalent to the amount of lithium derived from the negative electrode or smaller than the amount of lithium derived from the negative electrode. The series of operations for supporting the lithium derived from the negative electrode may be performed once, or may be performed several times.
In the present invention, when the lithium is supported on the positive electrode lithium-containing oxide by electrochemical contact with lithium, the battery is completed. As a method for supporting the negative electrode lithium, there is a method of supporting the battery before assembling the battery, that is, a method of supporting the predetermined lithium on the negative electrode PAS in advance and then assembling the battery. Is not preferred.

【００１４】本発明において電池内の総リチウム量は、
負極ＰＡＳに対し５００ｍＡｈ／ｇ以上，好ましくは６
００ｍＡｈ／ｇ以上であり、５００ｍＡｈ／ｇ未満の場
合、容量が充分に得られない。また、本発明における負
極由来のリチウムは負極ＰＡＳに対し１００ｍＡｈ／ｇ
以上、好ましくは１５０ｍＡｈ／ｇ以上であり、１００
ｍＡｈ／ｇ未満の場合、たとえ総リチウム量が負極ＰＡ
Ｓに対し５００ｍＡｈ／ｇ以上であったとしても充分な
容量が得られない。また、正極にリチウム含有酸化物を
用いる場合においては、負極由来のリチウムは負極ＰＡ
Ｓに対し６００ｍＡｈ／ｇ以下にすることが、実用的で
ある。本発明における正極由来のリチウム、電解液由来
のリチウムは上記条件を満たしていればよいが、正極由
来のリチウムが負極ＰＡＳに対し３００ｍＡｈ／ｇ以上
であることが好ましい。In the present invention, the total amount of lithium in the battery is:
500 mAh / g or more, preferably 6
When the value is not less than 00 mAh / g and less than 500 mAh / g, sufficient capacity cannot be obtained. Further, the lithium derived from the negative electrode in the present invention is 100 mAh / g with respect to the negative electrode PAS.
Or more, preferably 150 mAh / g or more, and 100
If it is less than mAh / g, even if the total amount of lithium is negative electrode PA
Even if it is 500 mAh / g or more with respect to S, a sufficient capacity cannot be obtained. In the case where a lithium-containing oxide is used for the positive electrode, lithium derived from the negative electrode is used for the negative electrode PA.
It is practical to set S to 600 mAh / g or less. The lithium derived from the positive electrode and the lithium derived from the electrolyte in the present invention may satisfy the above conditions, but the lithium derived from the positive electrode is preferably at least 300 mAh / g with respect to the negative electrode PAS.

【００１５】本発明に用いる電解液を構成する溶媒とし
ては非プロトン性有機溶媒が用いられる。非プロトン性
有機溶媒としては、例えば、エチレンカーボネイト、プ
ロピレンカーボネイト、ジメチルカーボネート、ジエチ
ルカーボネート、γ−ブチロラクトン、アセトニトリ
ル、ジメトキシエタン、テトラヒドロフラン、ジオキソ
ラン、塩化メチレン、スルホラン等が挙げられ、更に、
これら非プロトン性有機溶媒の二種以上の混合液も用い
ることができる。An aprotic organic solvent is used as a solvent constituting the electrolytic solution used in the present invention. Examples of the aprotic organic solvent include, for example, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, γ-butyrolactone, acetonitrile, dimethoxyethane, tetrahydrofuran, dioxolan, methylene chloride, sulfolane, and the like.
A mixture of two or more of these aprotic organic solvents can also be used.

【００１６】また、上記の混合又は単一の溶媒に溶解さ
せる電解質は、リチウムイオンを生成しうる電解質のい
ずれでも良い。このような電解質としては、例えばＬｉ
Ｉ、ＬｉＣｌＯ4 、ＬｉＡｓＦ6 、ＬｉＢＦ4 、ＬｉＰ
Ｆ6 、又はＬｉＨＦ2 等が挙げられる。上記の電解質及
び溶媒は充分に脱水された状態で混合され、電解液とす
るのであるが、電解液中の電解質の濃度は電解液による
内部抵抗を小さくするため少なくとも０．１モル／ｌ以
上とするのが好ましく、通常０．２〜１．５モル／ｌと
するのが更に好ましい。The electrolyte mixed or dissolved in a single solvent may be any electrolyte that can generate lithium ions. As such an electrolyte, for example, Li
I, LiClO 4 , LiAsF 6 , LiBF 4 , LiP
F 6 , LiHF 2 and the like. The electrolyte and the solvent are mixed in a sufficiently dehydrated state to form an electrolyte. The concentration of the electrolyte in the electrolyte is at least 0.1 mol / l or more in order to reduce the internal resistance due to the electrolyte. It is preferable that the amount is usually 0.2 to 1.5 mol / l.

【００１７】電池外部に電流を取り出すための集電体、
あるいはリード端子としては、例えば、炭素、白金、ニ
ッケル、ステンレス、アルミニウム、銅等を用いること
が出来、箔状、ネット状の集電体を用いる場合、電極を
集電体上に成形することにより集電体一体型電極として
用いることもできる。A current collector for extracting a current outside the battery;
Alternatively, as the lead terminal, for example, carbon, platinum, nickel, stainless steel, aluminum, copper, or the like can be used.When a foil-shaped or net-shaped current collector is used, an electrode is formed on the current collector. It can also be used as a current collector integrated electrode.

【００１８】次に図面により本発明の実施態様の一例を
説明する。図１は本発明に係る電池の基本構成説明図で
ある。図１において、（１）は正極であり、（２）は負
極である。（３），（３′）は集電体であり、各電極及
び外部端子（７），（７′）に電圧降下を生じないよう
に接続されている。（４）は電解液であり、ドーピング
されうるイオンを生成し得る前述の化合物が非プロトン
性有機溶媒に溶解されている。電解液は通常液状である
が漏液を防止するためゲル状又は固体状にして用いるこ
ともできる。（５）は正負両極の接触を阻止する事及び
電解液を保持する事を目的として配置されたセパレータ
ーである。Next, an embodiment of the present invention will be described with reference to the drawings. FIG. 1 is a diagram illustrating the basic configuration of a battery according to the present invention. In FIG. 1, (1) is a positive electrode, and (2) is a negative electrode. (3) and (3 ') are current collectors, which are connected to each electrode and the external terminals (7) and (7') so as not to cause a voltage drop. (4) is an electrolytic solution in which the above-mentioned compound capable of generating ions that can be doped is dissolved in an aprotic organic solvent. The electrolyte is usually liquid, but may be used in a gel or solid state to prevent liquid leakage. (5) is a separator arranged for the purpose of preventing contact between the positive and negative electrodes and holding the electrolytic solution.

【００１９】該セパレーターは、電解液或は電極活物質
等に対し、耐久性のある連通気孔を有する電子伝導性の
ない多孔体であり、通常ガラス繊維、ポリエチレン或は
ポリプロピレン等からなる布、不織布或は多孔体が用い
られる。好ましくは、３次元的な孔を有するセパレ−タ
であり、リチウム担持時間が短くなる効果が得られる。
セパレータの厚さは電池の内部抵抗を小さくするため薄
い方が好ましいが、電解液の保持量、流通性、強度等を
勘案して決定される。正負極及びセパレータは電池ケー
ス（６）内に実用上問題が生じないように固定される。
電極の形状、大きさ等は目的とする電池の形状、性能に
より適宜決められる。本発明の電池形状は上記基本構成
を満足する、コイン型、円筒型、角形、箱型等が挙げら
れ、その形状は特に限定されない。The separator is a porous material having continuous holes for the electrolyte or the electrode active material and having no electron conductivity, and is usually made of glass fiber, polyethylene or polypropylene, or a non-woven fabric. Alternatively, a porous body is used. Preferably, the separator is a separator having three-dimensional holes, and the effect of shortening the lithium carrying time can be obtained.
The thickness of the separator is preferably thin in order to reduce the internal resistance of the battery, but is determined in consideration of the amount of retained electrolyte, flowability, strength, and the like. The positive and negative electrodes and the separator are fixed in the battery case (6) so that there is no practical problem.
The shape, size, and the like of the electrode are appropriately determined depending on the shape and performance of the intended battery. The shape of the battery of the present invention includes a coin shape, a cylindrical shape, a square shape, a box shape, and the like satisfying the above basic configuration, and the shape is not particularly limited.

【００２０】[0020]

【発明の効果】本発明の有機電解質電池は、負極にＰＡ
Ｓ、正極に金属酸化物を用い、かつ電池内のリチウム
量、負極ＰＡＳ由来のリチウム量の両者を適切に制御
し、かつ、負極ＰＡＳ由来のリチウムの担持方法を適切
に選択することにより、高容量、高電圧かつ低内部抵抗
の電池であり、また、製造も容易な電池である。以下、
実施例を挙げて本発明を具体的に説明する。The organic electrolyte battery of the present invention has a negative electrode
S, by using a metal oxide for the positive electrode, properly controlling both the amount of lithium in the battery and the amount of lithium derived from the negative electrode PAS, and appropriately selecting a method of supporting lithium derived from the negative electrode PAS, The battery has high capacity, high voltage and low internal resistance, and is easy to manufacture. Less than,
The present invention will be described specifically with reference to examples.

【００２１】[0021]

【実施例】 実施例１ 厚さ０．５ｍｍのフェノール樹脂成形板をシリコニット
電気炉中に入れ窒素雰囲気下で１０℃／時間の速度で昇
温し、６５０℃まで熱処理し、不溶不融性基体（ＰＡＳ
と記す）を合成した。かくして得られたＰＡＳ板をディ
スクミルで粉砕することにより平均粒径約１５μｍのＰ
ＡＳ粉体を得た。Ｈ／Ｃ比は０．２２であった。次に上
記ＰＡＳ粉末１００重量部と、ポリフッ化ビニリデン粉
末１０重量部をＮ，Ｎ−ジメチルホルムアミド９０重量
部に溶解した溶液１００重量部とを充分に混合する事に
よりスラリーを得た。該スラリーをアプリケーターを用
い厚さ１０μｍの銅箔（負極集電体）上の片面に塗布
し、乾燥、プレスし、厚さ１００μｍのＰＡＳ負極を得
た。ＬｉＣｏＯ2 １００部、グラファイト５部対し、ポ
リフッ化ビニリデン粉末１０重量部、、Ｎ，Ｎ−ジメチ
ルホルムアミド９０重量部に溶解した溶液５０重量部を
充分に混合する事によりスラリーを得た。該スラリーを
アプリケーターを用い厚さ２０μｍのアルミ箔（正極集
電体）上の片面に塗布し、乾燥、プレスし、厚さ１１５
μｍの正極１を得た。Example 1 A phenolic resin molded plate having a thickness of 0.5 mm was placed in a siliconite electric furnace, heated at a rate of 10 ° C./hour under a nitrogen atmosphere, and heat-treated to 650 ° C. to obtain an insoluble infusible substrate. (PAS
Described below) were synthesized. The PAS plate thus obtained is pulverized with a disk mill to obtain a PS having an average particle size of about 15 μm.
AS powder was obtained. The H / C ratio was 0.22. Next, 100 parts by weight of the PAS powder and 100 parts by weight of a solution obtained by dissolving 10 parts by weight of polyvinylidene fluoride powder in 90 parts by weight of N, N-dimethylformamide were sufficiently mixed to obtain a slurry. The slurry was applied to one side of a 10 μm thick copper foil (negative electrode current collector) using an applicator, dried and pressed to obtain a 100 μm thick PAS negative electrode. A slurry was obtained by sufficiently mixing 100 parts of LiCoO 2 , 5 parts of graphite, 10 parts by weight of polyvinylidene fluoride powder, and 50 parts by weight of a solution dissolved in 90 parts by weight of N, N-dimethylformamide. The slurry was applied to one side of a 20 μm-thick aluminum foil (positive electrode current collector) using an applicator, dried, pressed, and dried to a thickness of 115 μm.
A positive electrode 1 of μm was obtained.

【００２２】上記負極と正極１をセパレータを介して対
向させ図１のような電池を組んだ。正極及び負極のサイ
ズはいずれも５×３ｃｍ2とした。セパレーターとして
は、厚さ２５μｍのポリプロピレン製を用いた。また電
解液としてはプロピレンカーボネートとジエチルカーボ
ネ−トの１：１（重量比）混合液に、１モル／ｌの濃度
にＬｉＰＦ6を溶解した溶液を用いた。上記電池に０．
２５ｍＡ／ｃｍ2 の定電流にて、負極ＰＡＳに対して３
３０ｍＡｈ／ｇに相当する電気量を通じ、負極ＰＡＳに
３３０ｍＡｈ／ｇのリチウムを正極よりドーピングし
た。続いて、電池系外のリチウム金属と正極の間に０．
０２ｍＡ／ｃｍ2 の定電流により負極ＰＡＳに対して３
１５ｍＡｈ／ｇに相当する電気量を通じ、正極にリチウ
ムを担持させた。電池内の負極ＰＡＳに対する総リチウ
ム量は、１１３０ｍＡｈ／ｇであった。電池完成に要し
た時間は１０日であった。上記電池に０．２５ｍＡ／ｃ
ｍ2 の定電流で電池電圧が４．３Ｖになるまで充電し、
続いて０．２５ｍＡ／ｃｍ2 の定電流で電池電圧が２．
５Ｖになるまで放電した。この４．３Ｖ−２．５Ｖのサ
イクルを繰り返し、３回目の放電において、体積容量
（ｍＡｈ／ｃｃ）にて評価した。体積基準としては、電
極体積、セパレータ体積、集電体体積の総計を用いた。
結果を表１に示す。The above-described negative electrode and positive electrode 1 were opposed to each other with a separator interposed therebetween, and a battery as shown in FIG. 1 was assembled. The size of each of the positive electrode and the negative electrode was 5 × 3 cm 2 . As the separator, a 25-μm-thick polypropylene product was used. As the electrolytic solution, a solution obtained by dissolving LiPF 6 at a concentration of 1 mol / l in a 1: 1 (weight ratio) mixture of propylene carbonate and diethyl carbonate was used. 0.
At a constant current of 25 mA / cm 2 , 3
The anode PAS was doped with 330 mAh / g of lithium from the cathode through an amount of electricity corresponding to 30 mAh / g. Subsequently, 0.1 mm is applied between the lithium metal outside the battery system and the positive electrode.
With a constant current of 02 mA / cm 2 , 3
Lithium was supported on the positive electrode by passing an amount of electricity corresponding to 15 mAh / g. The total amount of lithium with respect to the negative electrode PAS in the battery was 1130 mAh / g. The time required to complete the battery was 10 days. 0.25 mA / c for the above battery
The battery is charged with a constant current of m 2 until the battery voltage reaches 4.3 V,
Subsequently, at a constant current of 0.25 mA / cm 2 , the battery voltage was 2.
It discharged until it became 5V. This cycle of 4.3 V-2.5 V was repeated, and the third discharge was evaluated by volume capacity (mAh / cc). As a volume standard, the total of the electrode volume, the separator volume, and the current collector volume was used.
Table 1 shows the results.

【００２３】実施例２ 実施例１と同様に電池を組み、正極１から負極ＰＡＳへ
３３０ｍＡｈ／ｇのリチウムを同様にドーピングした。
続いて、実施例１と同様に電池系外のリチウム金属と正
極の間に２Ｖの電圧を印加し、負極ＰＡＳに対して３１
５ｍＡｈ／ｇに相当する電気量を通じ、正極にリチウム
を担持させ実施例１と同様に体積容量を評価した。電池
完成後の電池内の負極ＰＡＳに対する総リチウム量は、
１１３０ｍＡｈ／ｇであった。電池完成に要した時間は
１５日であった。結果を表１に示す。 実施例３ 実施例１において、正極１のサイズを５×４３ｃｍ2 、
負極のサイズを５×４８ｃｍ2とした。正極端子として
は厚さ１５０μｍ、幅５ｍｍのアルミニウム端子、負極
端子としては正極と同サイズのニッケルを用い、それぞ
れ、電極の端（幅５ｃｍの側）にとりつけた。正極１と
負極をセパレータを介して渦巻き状に巻き取り、円筒状
の電池を組んだ。実施例１と同様にして正極から負極Ｐ
ＡＳへ３３０ｍＡｈ／ｇのリチウムをドーピングした。
続いて、実施例１と同様に電池系外のリチウム金属と正
極の間に０．０２ｍＡ／ｃｍ2 の定電流により負極ＰＡ
Ｓに対して３１５ｍＡｈ／ｇに相当する電気量を通じ、
正極にリチウムを担持させた。電池内の負極ＰＡＳに対
する総リチウム量は、１１３０ｍＡｈ／ｇであった。電
池完成に要した時間は１１日であった。結果を表１に示
す。Example 2 A battery was assembled in the same manner as in Example 1, and 330 mAh / g of lithium was similarly doped from the positive electrode 1 to the negative electrode PAS.
Subsequently, as in Example 1, a voltage of 2 V was applied between the lithium metal outside the battery system and the positive electrode, and 31 V was applied to the negative electrode PAS.
Lithium was supported on the positive electrode by passing an amount of electricity corresponding to 5 mAh / g, and the volume capacity was evaluated as in Example 1. The total amount of lithium with respect to the negative electrode PAS in the battery after completion of the battery is:
It was 1130 mAh / g. The time required to complete the battery was 15 days. Table 1 shows the results. Example 3 In Example 1, the size of the positive electrode 1 was 5 × 43 cm 2 ,
The size of the negative electrode was 5 × 48 cm 2 . An aluminum terminal having a thickness of 150 μm and a width of 5 mm was used as a positive electrode terminal, and nickel having the same size as the positive electrode was used as a negative electrode terminal. The positive electrode 1 and the negative electrode were spirally wound via a separator to form a cylindrical battery. From the positive electrode to the negative electrode P in the same manner as in Example 1,
AS was doped with 330 mAh / g of lithium.
Subsequently, the negative electrode PA was applied between the lithium metal outside the battery system and the positive electrode by a constant current of 0.02 mA / cm 2 as in Example 1.
Through an amount of electricity equivalent to 315 mAh / g with respect to S,
Lithium was supported on the positive electrode. The total amount of lithium with respect to the negative electrode PAS in the battery was 1130 mAh / g. The time required to complete the battery was 11 days. Table 1 shows the results.

【００２４】比較例１ 実施例１と同様の方法で厚さ３３０μｍの正極２を得
た。正極、負極のサイズはいずれも５×３ｃｍ2 とし
た。負極由来のリチウムを０ｍＡｈ／ｇとして、実施例
１と同様の方法で電池を組み、体積容量を評価した。電
池内の負極ＰＡＳに対する総リチウム量は、１２５０ｍ
Ａｈ／ｇであった。結果を表１に示す。 比較例２ 実施例１と同様に電池を組んだ。電極ユニットの断面方
向に３３０ｍＡｈ／ｇ相当のリチウム金属を配置し、負
極ＰＡＳと短絡させた。４０日室温にて放置後電池を分
解したところ、完全にリチウム金属は無くなっていた。
また実施例１と同様に体積容量を評価した。電池内の負
極ＰＡＳに対する総リチウム量は、１１３０ｍＡｈ／ｇ
であった。電池完成に要した時間は４０日であった。結
果を表１に示す。 比較例３ 実施例１と同様に電池を組んだ。電極ユニットの断面方
向に３３０ｍＡｈ／ｇ相当のリチウム金属を配置し、該
リチウム金属と負極の間に０Ｖの電圧を印加し、負極Ｐ
ＡＳに対して３３０ｍＡｈ／ｇのリチウムをドーピング
させた。また実施例１と同様に体積容量を評価した。電
池内の負極ＰＡＳに対する総リチウム量は、１１３０ｍ
Ａｈ／ｇであった。電池完成に要した時間は４０日であ
った。結果を表１に示す。Comparative Example 1 A positive electrode 2 having a thickness of 330 μm was obtained in the same manner as in Example 1. The size of each of the positive electrode and the negative electrode was 5 × 3 cm 2 . A battery was assembled in the same manner as in Example 1 except that lithium derived from the negative electrode was set to 0 mAh / g, and the volume capacity was evaluated. The total amount of lithium with respect to the negative electrode PAS in the battery is 1250 m
Ah / g. Table 1 shows the results. Comparative Example 2 A battery was assembled in the same manner as in Example 1. A lithium metal equivalent to 330 mAh / g was arranged in the cross-sectional direction of the electrode unit, and short-circuited with the negative electrode PAS. After leaving the battery at room temperature for 40 days, the battery was disassembled, and lithium metal was completely lost.
The volume capacity was evaluated in the same manner as in Example 1. The total amount of lithium with respect to the negative electrode PAS in the battery was 1130 mAh / g
Met. The time required to complete the battery was 40 days. Table 1 shows the results. Comparative Example 3 A battery was assembled in the same manner as in Example 1. A lithium metal equivalent to 330 mAh / g is arranged in the cross-sectional direction of the electrode unit, and a voltage of 0 V is applied between the lithium metal and the negative electrode to form a negative electrode P
The AS was doped with 330 mAh / g of lithium. The volume capacity was evaluated in the same manner as in Example 1. The total amount of lithium with respect to the negative electrode PAS in the battery is 1130 m
Ah / g. The time required to complete the battery was 40 days. Table 1 shows the results.

【００２５】負極由来のリチウムを電極ユニットの断面
方向に配置したリチウムから負極ＰＡＳへドーピングし
た場合、時間がかかり工業的には好ましくない。 比較例４ 実施例１と同様に電池を組んだ。電極ユニットの断面方
向に３３０ｍＡｈ／ｇ相当のリチウム金属を配置し、該
リチウム金属と負極の間に０．０２ｍＡ／ｃｍ2 の定電
流（実施例１と同等の速度）により負極ＰＡＳに対して
３３０ｍＡｈ／ｇに相当する電気量を通じたところ、電
極ユニットの断面部にリチウム金属が析出し正極と短絡
したため、体積容量の評価はできなかった。When lithium derived from the negative electrode is doped into the negative electrode PAS from lithium disposed in the cross-sectional direction of the electrode unit, it takes a long time and is not industrially preferable. Comparative Example 4 A battery was assembled in the same manner as in Example 1. A lithium metal equivalent to 330 mAh / g is arranged in the cross-sectional direction of the electrode unit, and a constant current of 0.02 mA / cm 2 (the same speed as in Example 1) is applied between the lithium metal and the negative electrode to 330 mAh with respect to the negative electrode PAS. When a quantity of electricity corresponding to / g was passed, lithium metal was deposited on the cross section of the electrode unit and short-circuited with the positive electrode, so that the volume capacity could not be evaluated.

【００２６】[0026]

【表１】 [Table 1]

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

【図１】本発明に係る電池の基本構成説明図。FIG. 1 is a diagram illustrating a basic configuration of a battery according to the present invention.

【符号の説明】[Explanation of symbols]

１ 正極 ２ 負極 ３、３’集電体 ４ 電解液 ５ セパレータ ６ 電池ケース ７、７’ 外部端子 DESCRIPTION OF SYMBOLS 1 Positive electrode 2 Negative electrode 3, 3 'current collector 4 Electrolyte 5 Separator 6 Battery case 7, 7' External terminal

───────────────────────────────────────────────────── フロントページの続き 審査官 種村 慈樹 (56)参考文献 特開 平４−167374（ＪＰ，Ａ) 特開 平４−206276（ＪＰ，Ａ) 特開 平４−345771（ＪＰ，Ａ) 特開 平３−182057（ＪＰ，Ａ) 特開 平４−34870（ＪＰ，Ａ) 特開 平３−233861（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) H01M 10/40 ──────────────────────────────────────────────────続 き Continued on the front page Examiner Yoshiki Tanemura (56) References JP-A-4-167374 (JP, A) JP-A-4-206276 (JP, A) JP-A-4-345771 (JP, A) JP-A-3-182057 (JP, A) JP-A-4-34870 (JP, A) JP-A-3-233861 (JP, A) (58) Fields investigated (Int. Cl. 6 , DB name) H01M 10/40

Claims (2)

(57)【特許請求の範囲】(57) [Claims] 【請求項１】 正極，負極並びに電解液としてリチウム
塩の非プロトン性有機溶媒溶液を備えた有機電解質電池
であって、（１）正極がリチウム含有金属酸化物を含み
（２）負極が芳香族系縮合ポリマーの熱処理物であって
水素原子／炭素原子の原子比が０．５〜０．０５である
ポリアセン系骨格構造を有する不溶不融性基体（ＰＡ
Ｓ）であり、（３）負極ＰＡＳに対し、電池内に含まれ
る総リチウム量が５００ｍＡｈ／ｇ以上であり、かつ負
極由来のリチウムが１００ｍＡｈ／ｇ以上であり、負極
由来のリチウムが、電池組立後に正極リチウム含有金属
酸化物より負極ＰＡＳに担持させたものであり、かつ正
極にはＰＡＳにリチウムを供給した後、リチウムとの電
気化学的接触によりリチウムを担持させる事を特徴とす
る有機電解質電池。An organic electrolyte battery comprising a positive electrode, a negative electrode, and a solution of a lithium salt in an aprotic organic solvent as an electrolytic solution, wherein (1) the positive electrode contains a lithium-containing metal oxide, and (2) the negative electrode is aromatic. Insoluble and infusible substrate (PA) having a polyacene skeleton structure in which a hydrogen atom / carbon atom atomic ratio is 0.5 to 0.05, which is a heat-treated product of a system condensation polymer.
S), and (3) relative to the negative electrode PAS, the total amount of lithium contained in the battery is 500 mAh / g or more, lithium from the negative electrode is 100 mAh / g or more, and lithium from the negative electrode is An organic electrolyte battery comprising a negative electrode PAS that is later supported by a positive electrode lithium-containing metal oxide, and lithium is supplied to the PAS on the positive electrode, and then lithium is supported by electrochemical contact with lithium. . 【請求項２】 正極、負極が３次元連通気孔を有するセ
パレータを介して対向させた事を特徴とする請求項１記
載の有機電解質電池。2. The organic electrolyte battery according to claim 1, wherein the positive electrode and the negative electrode are opposed to each other via a separator having three-dimensional communication holes.
JP6330721A 1994-12-06 1994-12-06 Organic electrolyte battery Expired - Fee Related JP2869355B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP6330721A JP2869355B2 (en) 1994-12-06 1994-12-06 Organic electrolyte battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP6330721A JP2869355B2 (en) 1994-12-06 1994-12-06 Organic electrolyte battery

Publications (2)

Publication Number Publication Date
JPH08162162A JPH08162162A (en) 1996-06-21
JP2869355B2 true JP2869355B2 (en) 1999-03-10

Family

ID=18235830

Family Applications (1)

Application Number Title Priority Date Filing Date
JP6330721A Expired - Fee Related JP2869355B2 (en) 1994-12-06 1994-12-06 Organic electrolyte battery

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Country Link
JP (1) JP2869355B2 (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1104941B1 (en) * 1998-07-27 2015-09-02 Fuji Jukogyo Kabushiki Kaisha Organic electrolytic cell

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