JPH077680B2 - Non-aqueous solvent secondary battery - Google Patents

Non-aqueous solvent secondary battery

Info

Publication number
JPH077680B2
JPH077680B2 JP61188570A JP18857086A JPH077680B2 JP H077680 B2 JPH077680 B2 JP H077680B2 JP 61188570 A JP61188570 A JP 61188570A JP 18857086 A JP18857086 A JP 18857086A JP H077680 B2 JPH077680 B2 JP H077680B2
Authority
JP
Japan
Prior art keywords
lithium
negative electrode
secondary battery
fired body
aqueous solvent
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
JP61188570A
Other languages
Japanese (ja)
Other versions
JPS6345748A (en
Inventor
圀昭 稲田
克治 池田
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.)
FDK Twicell Co Ltd
Original Assignee
Toshiba Battery Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toshiba Battery Co Ltd filed Critical Toshiba Battery Co Ltd
Priority to JP61188570A priority Critical patent/JPH077680B2/en
Publication of JPS6345748A publication Critical patent/JPS6345748A/en
Publication of JPH077680B2 publication Critical patent/JPH077680B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/043—Processes of manufacture in general involving compressing or compaction
    • H01M4/0433—Molding
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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

Description

【発明の詳細な説明】 〔産業上の利用分野〕 本発明は小型で充放電サイクル寿命の長く安定な電池、
詳しくはリチウムもしくはリチウムを主体とするアルカ
リ金属よりなる負極活物質を担持してなる有機物焼成体
と、同アルカリ金属を担持していない有機物焼成体より
なる負極とを、負極端子を兼ねる負極缶内に着設したこ
とを特徴とするものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention relates to a small and stable battery having a long charge / discharge cycle life,
Specifically, in a negative electrode can that also serves as a negative electrode terminal, an organic material fired body carrying a negative electrode active material made of lithium or an alkali metal mainly containing lithium and a negative electrode made of an organic matter fired body not carrying the same alkali metal. It is characterized by being installed in.

〔従来の技術〕[Conventional technology]

従来から正極には遷移金属のカルコゲン化合物を用い、
リチウムもしくはリチウムを主体とするアルカリ金属を
負極として用いる高エネルギー密度を有する非水溶媒二
次電池が商品化されてきた。Conventionally, a transition metal chalcogen compound is used for the positive electrode,
Non-aqueous solvent secondary batteries having a high energy density using lithium or an alkali metal mainly containing lithium as a negative electrode have been commercialized.

〔発明が解決しようとする問題点〕[Problems to be solved by the invention]

しかしながら、これら従来の電池は、負極にリチウム金
属を用いているため、放電時にはイオンとして溶出した
リチウムが充電時にリチウムとして電析する際、デンド
ライトが形成され、その強活性により非水溶媒の分解を
引きおこし、充放電サイクル特性の低下をもたらす欠点
があつた。更に加えて、リチウムデンドライトが成長し
てセパレーターを通過し、正負極を短絡せしめ短寿命を
もたらす欠点もあつた。However, since these conventional batteries use lithium metal for the negative electrode, dendrites are formed when lithium, which is eluted as ions during discharge, is deposited as lithium during charge, and decomposition of the non-aqueous solvent due to its strong activity. However, there is a drawback that it causes deterioration of charge and discharge cycle characteristics. In addition, there is a drawback that lithium dendrite grows and passes through the separator, short-circuiting the positive and negative electrodes and shortening the life.

本発明は前述した現状を改善するため提案されたもの
で、負極には、リチウムもしくはリチウムを主体とする
アルカリ金属を担持してなる有機物焼成体と、同アルカ
リ金属を担持していない有機物焼成体とを、混合し、成
形もしくはシート状とした負極を、負極端子を兼ねる負
極缶内に着設一体化させることを特徴とし、その目的
は、小型にして優れた充放電特性を有し、特にサイクル
寿命特性の非常に長い信頼性のある非水溶媒二次電池を
提供することにある。The present invention has been proposed in order to improve the above-mentioned current situation, in the negative electrode, an organic material fired body which carries lithium or an alkali metal mainly composed of lithium, and an organic matter fired body which does not carry the same alkali metal. And a molded or sheet-shaped negative electrode is mixed and attached to a negative electrode can that also serves as a negative electrode terminal, and is integrated. The purpose is to have a small size and excellent charge / discharge characteristics, and It is intended to provide a reliable non-aqueous solvent secondary battery having a very long cycle life characteristic.

〔問題点を解決するための手段〕[Means for solving problems]

本発明を説明すると、本発明による非水溶媒二次電池に
用いる負極は、リチウムもしくはリチウムを主体とする
アルカリ金属を含有してなる有機物焼成体と、リチウム
もしくはリチウムを主体とするアルカリ金属を担持して
いない有機物焼成体とを混合成形もしくはシート化し
て、負極端子を兼ねる負極缶内に着設一体化したもので
ある。To explain the present invention, the negative electrode used in the non-aqueous solvent secondary battery according to the present invention carries an organic fired body containing lithium or an alkali metal mainly containing lithium and lithium or an alkali metal mainly containing lithium. It is formed by mixing with an organic material fired body that is not formed into a sheet or by forming it into a sheet, which is attached and integrated in a negative electrode can that also serves as a negative electrode terminal.

電解液は、溶媒にはプロピレンカーボネイト、1,2ジメ
トキシエタン、γ−ブチルラクトン等の非プロトン性有
機溶媒を、溶質には過塩素酸リチウムのようなリチウム
塩を用い、一般にリチウムを負極活物質として用いた電
池で使用される電解液を用いることができる。The electrolytic solution uses an aprotic organic solvent such as propylene carbonate, 1,2 dimethoxyethane and γ-butyl lactone as a solvent and a lithium salt such as lithium perchlorate as a solute, and generally uses lithium as a negative electrode active material. The electrolytic solution used in the battery used as can be used.

セパレーターとしては多孔質ポリプロピレン等よりなる
薄膜もしくは不織布が用いることができる。As the separator, a thin film made of porous polypropylene or the like or a non-woven fabric can be used.

〔作用〕[Action]

本発明電池の負極は、リチウムもしくはリチウムを主体
とするアルカリ金属を担持した有機物焼成体（イ）と、
同アルカリ金属を担持していない有機物焼成体（ロ）と
を、混合し、成形もしくはシート化して、負極端子を兼
ねる負極缶内に着設させることで、両者間の結着能が有
機物焼成体（イ）のみに比較して増加することに着目
し、充放電サイクルの進行と共に生じる有機物焼成体内
へのリチウムの電析による有機物焼成体の破損、脱落を
防止し、充放電効率の低下と電池内部抵抗の上昇を防止
し、充放電サイクル寿命を向上させたものである。The negative electrode of the battery of the present invention comprises an organic fired body (a) carrying lithium or an alkali metal mainly containing lithium,
The organic substance fired body (b) that does not carry the same alkali metal is mixed, molded or formed into a sheet, and the resultant is attached to the inside of the negative electrode can that also serves as the negative electrode terminal. Focusing on the increase compared to (a) only, it is possible to prevent damage and drop-off of the organic material fired body due to electrodeposition of lithium into the organic material fired body that occurs with the progress of the charge / discharge cycle, and to reduce the charge / discharge efficiency and the battery. The internal resistance is prevented from increasing and the charge / discharge cycle life is improved.

このため、有機物焼成体（イ）と（ロ）の配合比につい
ては、有機物焼成体（ロ）の量が増加しすぎた場合は、
結着能は増加するが容量絶対値の低下が生じ、又有機物
焼成体（イ）が減少しすぎた場合は、結着能が発揮でき
ずサイクル寿命の長期化への効果はなく、有機物焼成体
（イ）と（ロ）の配合比は、重量比で、1:0.01〜1:1の
範囲であることが好ましい。Therefore, regarding the compounding ratio of the organic material fired bodies (a) and (b), when the amount of the organic material fired bodies (b) is excessively increased,
If the binding capacity increases but the absolute value of the capacity decreases, and if the amount of the organic material fired product (a) decreases too much, the binding ability cannot be exhibited and there is no effect on the extension of cycle life. The mixing ratio of the bodies (a) and (b) is preferably in the range of 1: 0.01 to 1: 1 by weight.

〔実施例〕〔Example〕

第１図は、本発明による電池の一実施例であるボタン型
非水溶媒二次電池の断面図である。FIG. 1 is a cross-sectional view of a button type non-aqueous solvent secondary battery which is an embodiment of the battery according to the present invention.

（１）は端子を兼ねた正極缶である。（２）は遷移金属
カルコゲン化合物とカーボン粉、ニッケル粉よりなる混
合物を成形して得た正極で、正極缶（１）内に充填して
着設一体化されている。(1) is a positive electrode can that also serves as a terminal. (2) is a positive electrode obtained by molding a mixture of a transition metal chalcogen compound, carbon powder, and nickel powder, and is filled and integrated in the positive electrode can (1).

（３）は電解液を保持してなる電解液保持材で、耐酸化
耐還元性のあるポリオレフイン系樹脂の不織布であり、
正負極と対峙している。(3) is an electrolyte solution holding material holding an electrolyte solution, which is a non-woven fabric of polyolefin resin having oxidation resistance and reduction resistance,
It faces the positive and negative electrodes.

（４）はその内部にリチウムを担持してなる有機物焼成
体粉10重量部と、リチウムを担持していない有機物焼成
体粉１重量部とを混合、成形してなる本発明電池の負極
で、負極端子を兼ねる負極缶（５）内に導電膜（７）を
介して着設されている。(4) is a negative electrode of a battery of the present invention, which is obtained by mixing and molding 10 parts by weight of an organic fired body powder having lithium supported therein and 1 part by weight of an organic fired body powder not supporting lithium, It is attached via a conductive film (7) in a negative electrode can (5) which also functions as a negative electrode terminal.

（６）は正負極を分ける絶縁パツキングで、電池は正極
缶の開口部を内方向へ曲折させて密閉されている。(6) is an insulating packing that separates the positive and negative electrodes, and the battery is sealed by bending the opening of the positive electrode can inward.

このようにして作成した本発明の非水溶媒二次電池
（Ａ）を、30KΩの定抵抗負荷で2Vまで放電を行なつ
た。この時の各サイクルにおける容量維持率（初期容量
＝100）は、第２図（Ａ）のような値になつた。The non-aqueous solvent secondary battery (A) of the present invention thus produced was discharged to 2 V under a constant resistance load of 30 KΩ. At this time, the capacity retention ratio (initial capacity = 100) in each cycle reached a value as shown in FIG. 2 (A).

又、金属リチウムを担持した有機物焼成体粉のみよりな
り、他は実施例と同一条件で作成した負極よりなる同型
従来電池（Ｂ）の各サイクルにおける容量維持率は、第
２図（Ｂ）のようになつた。In addition, the capacity retention rate in each cycle of the same type conventional battery (B), which is made of only the organic material calcined powder supporting metallic lithium and is made under the same conditions as in Example, is shown in FIG. 2 (B). It became like this.

なお、同様に0.9Vまでの充放電サイクルの結果は、第３
図のようになつた。In addition, similarly, the result of the charge and discharge cycle up to 0.9V is the third
It became like the figure.

なお実施例はボタン型電池で示しているが、本発明はこ
の電池形状に加えて、薄型の偏平角型電池、筒型電池に
もその応用は可能である。Although the embodiment shows a button type battery, the present invention can be applied to a thin flat rectangular battery and a cylindrical battery in addition to this battery shape.

〔発明の効果〕〔The invention's effect〕

以上の結果より明らかなように、本発明は充放電サイク
ル寿命の長い小型高エネルギー密度の非水溶媒二次電池
を提供するものである。As is clear from the above results, the present invention provides a small-sized and high-energy-density non-aqueous solvent secondary battery having a long charge / discharge cycle life.

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

第１図は本発明の一実施例であるボタン型非水溶媒二次
電池の断面図、第２図、第３図は本発明の実施例、比較
例における電池の放電容量維持率とサイクル数との関係
図である。 １…正極缶、２…正極 ３…電解液保持材、４…負極 ５…負極缶、６…パツキングFIG. 1 is a cross-sectional view of a button type non-aqueous solvent secondary battery which is one embodiment of the present invention, and FIGS. 2 and 3 are discharge capacity maintenance ratios and cycle numbers of the batteries of Examples and Comparative Examples of the present invention. FIG. DESCRIPTION OF SYMBOLS 1 ... Positive electrode can, 2 ... Positive electrode 3 ... Electrolyte holding material, 4 ... Negative electrode 5 ... Negative electrode can, 6 ... Packing

Claims (2)

【特許請求の範囲】[Claims] 【請求項１】リチウムもしくリチウムを主体とするアル
カリ金属を担持してなる有機物焼成体と、リチウムもし
くリチウムを主体とするアルカリ金属を担持していない
有機物焼成体とを混合し、成形もしくはシート状とした
負極を、端子を兼ねる負極缶に着設したことを特徴とす
る非水溶媒二次電池。1. A mixture of an organic fired body containing lithium or an alkali metal mainly containing lithium and an organic fired body not containing an alkali metal mainly containing lithium or lithium, and molded or A non-aqueous solvent secondary battery in which a sheet-shaped negative electrode is attached to a negative electrode can that also serves as a terminal. 【請求項２】該リチウムもしくリチウムを主体とするア
ルカリ金属を担持してなる有機物焼成体と、リチウムも
しくリチウムを主体とするアルカリ金属を担持していな
い有機物焼成体との混合重量比が、1:0.01〜1:1の範囲
であることを特徴とする特許請求の範囲第１項記載の非
水溶媒二次電池。2. A mixture weight ratio of the organic material fired body carrying an alkali metal mainly containing lithium or lithium and the organic matter fired body not carrying an alkali metal mainly containing lithium or lithium. The non-aqueous solvent secondary battery according to claim 1, wherein the secondary battery is in the range of 1: 0.01 to 1: 1.
JP61188570A 1986-08-13 1986-08-13 Non-aqueous solvent secondary battery Expired - Fee Related JPH077680B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP61188570A JPH077680B2 (en) 1986-08-13 1986-08-13 Non-aqueous solvent secondary battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP61188570A JPH077680B2 (en) 1986-08-13 1986-08-13 Non-aqueous solvent secondary battery

Publications (2)

Publication Number Publication Date
JPS6345748A JPS6345748A (en) 1988-02-26
JPH077680B2 true JPH077680B2 (en) 1995-01-30

Family

ID=16225999

Family Applications (1)

Application Number Title Priority Date Filing Date
JP61188570A Expired - Fee Related JPH077680B2 (en) 1986-08-13 1986-08-13 Non-aqueous solvent secondary battery

Country Status (1)

Country Link
JP (1) JPH077680B2 (en)

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60112264A (en) * 1983-11-18 1985-06-18 Sanyo Chem Ind Ltd Negative pole material and battery
JPH0789483B2 (en) * 1984-05-07 1995-09-27 三洋化成工業株式会社 Secondary battery

Also Published As

Publication number Publication date
JPS6345748A (en) 1988-02-26

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