JPH10106542A - Lithium secondary battery - Google Patents
Lithium secondary batteryInfo
- Publication number
- JPH10106542A JPH10106542A JP8274181A JP27418196A JPH10106542A JP H10106542 A JPH10106542 A JP H10106542A JP 8274181 A JP8274181 A JP 8274181A JP 27418196 A JP27418196 A JP 27418196A JP H10106542 A JPH10106542 A JP H10106542A
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- weight
- montmorillonite
- secondary battery
- battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Description
【０００１】[0001]
【発明が属する技術分野】本発明は、リチウムイオンを
電気化学的に吸蔵及び放出することが可能な炭素粉末を
負極材料とするリチウム二次電池に係わり、詳しくは充
放電サイクル特性を改善することを目的とした、負極に
使用する結着剤の改良に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithium secondary battery using a carbon powder capable of electrochemically absorbing and releasing lithium ions as a negative electrode material, and more particularly, to improving charge / discharge cycle characteristics. The present invention relates to improvement of a binder used for a negative electrode for the purpose of.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】近年、
リチウム二次電池の負極材料として、リチウムイオンを
電気化学的に吸蔵及び放出することが可能な黒鉛、コー
クス等の炭素材料が、（１）放電電位が平坦である、
（２）高容量である、（３）樹枝状の電析リチウムの成
長に因る内部短絡の虞れが無い、等の理由から注目され
ている。2. Description of the Related Art In recent years,
As a negative electrode material of a lithium secondary battery, a carbon material such as graphite and coke capable of electrochemically absorbing and releasing lithium ions is used. (1) The discharge potential is flat.
Attention has been paid to such reasons as (2) high capacity, and (3) there is no fear of internal short circuit due to the growth of dendritic lithium.
【０００３】炭素材料を用いる負極（炭素負極）は、炭
素粉末と、結着剤と、増粘剤の水溶液とを混合して得た
スラリーを、集電体に塗布し、乾燥することにより作製
される。A negative electrode using a carbon material (carbon negative electrode) is prepared by applying a slurry obtained by mixing a carbon powder, a binder, and an aqueous solution of a thickener to a current collector and drying the slurry. Is done.
【０００４】而して、従来は、結着剤として、スチレン
−ブタジエンゴム（ＳＢＲ）、ブタジエン−アクリロニ
リルゴム（ＮＢＲ）等のゴム系重合体、ポリフッ化ビニ
リデン等のフッ素系重合体などが用いられていた（特開
平６−２１５７６１号公報参照）。[0004] Conventionally, as a binder, rubber polymers such as styrene-butadiene rubber (SBR) and butadiene-acrylonilyl rubber (NBR) and fluorine polymers such as polyvinylidene fluoride have been used. (See Japanese Patent Application Laid-Open No. 6-215761).
【０００５】しかしながら、従来の炭素負極を備えるリ
チウム二次電池には、充放電サイクルを繰り返すと、形
成した炭素層（負極合剤層）が集電体から剥離するた
め、電池容量が短サイクル裡に減少してしまうという課
題があった。However, in a conventional lithium secondary battery having a carbon negative electrode, when the charge / discharge cycle is repeated, the formed carbon layer (negative electrode mixture layer) is separated from the current collector, so that the battery capacity is short. There was a problem that it would decrease.
【０００６】本発明は、この課題を解決するべくなされ
たものであって、充放電サイクルを重ねても炭素層が集
電体から剥離しにくい、充放電サイクル特性に優れたリ
チウム二次電池を提供することを目的とする。SUMMARY OF THE INVENTION The present invention has been made to solve this problem, and an object of the present invention is to provide a lithium secondary battery excellent in charge / discharge cycle characteristics in which a carbon layer is hardly peeled off from a current collector even after repeated charge / discharge cycles. The purpose is to provide.
【０００７】[0007]
【課題を解決するための手段】本発明に係るリチウム二
次電池（本発明電池）は、リチウムイオンを電気化学的
に吸蔵及び放出することが可能な炭素粉末と、モンモリ
ロナイトと、増粘剤の水溶液とを混合して得たスラリー
を、集電体に塗布し、乾燥して成る負極を備える。The lithium secondary battery (battery of the present invention) according to the present invention comprises a carbon powder capable of electrochemically absorbing and releasing lithium ions, montmorillonite, and a thickener. A negative electrode formed by applying a slurry obtained by mixing with an aqueous solution to a current collector and drying the slurry is provided.
【０００８】リチウムイオンを電気化学的に吸蔵及び放
出することが可能な炭素粉末としては、黒鉛、コーク
ス、有機物焼成体が例示される。Examples of the carbon powder capable of electrochemically storing and releasing lithium ions include graphite, coke, and a fired organic material.
【０００９】本発明においては結着剤として使用される
モンモリロナイトは、含水アルミニウムケイ酸塩の一種
であり、その理論組成はＡｌ2 Ｏ3 ・４ＳｉＯ2 ・ｎＨ
2 Ｏで示される。In the present invention, montmorillonite used as a binder is a kind of hydrous aluminum silicate, and its theoretical composition is Al 2 O 3 .4SiO 2 .nH.
Indicated by 2 O.
【００１０】本発明における増粘剤とは、塗布したスラ
リーが集電体から流れ落ちるのを防止するための剤であ
る。増粘剤としては、水溶性であって、増粘効果を有す
るものであれば特に制限されない。具体例としては、カ
ルボキシメチルセルロース（ＣＭＣ）、メチルセルロー
ス（ＭＣ）、ヒドロキシプロピルセルロース（ＨＰ
Ｃ）、ポリビニルアルコール（ＰＶＡ）、ポリビニルピ
ロリドン（ＰＶＰ）が挙げられる。The thickener in the present invention is an agent for preventing the applied slurry from flowing down from the current collector. The thickener is not particularly limited as long as it is water-soluble and has a thickening effect. Specific examples include carboxymethyl cellulose (CMC), methyl cellulose (MC), and hydroxypropyl cellulose (HP
C), polyvinyl alcohol (PVA) and polyvinyl pyrrolidone (PVP).
【００１１】炭素粉末、モンモリロナイト及び増粘剤の
総量に対するモンモリロナイト及び増粘剤の総量の好適
な比率は、０．５〜５重量％であり、またモンモリロナ
イトと増粘剤（固形分）との好適な重量比は、１：１〜
１：４である。これらの比率又は重量比が上記各範囲を
外れると充放電サイクル特性が低下する傾向がある。The preferred ratio of the total amount of montmorillonite and thickener to the total amount of carbon powder, montmorillonite and thickener is 0.5 to 5% by weight, and the preferred ratio of montmorillonite and thickener (solid content) is Weight ratio is 1: 1
1: 4. If these ratios or weight ratios are out of the above ranges, the charge / discharge cycle characteristics tend to decrease.
【００１２】本発明の最大の特徴は、炭素負極を備える
リチウム二次電池の負極集電体（銅箔など）と炭素層と
の良好な付着性を、特定の結着剤、すなわちモンモリロ
ナイトを用いることにより達成した点にある。それゆ
え、正極活物質、電解液など、電池を構成する他の部材
・要素については従来リチウム二次電池用として提案さ
れ、或いは実用されている種々のものを特に制限なく用
いることが可能である。The most important feature of the present invention is that a good adhesion between a negative electrode current collector (such as a copper foil) of a lithium secondary battery having a carbon negative electrode and a carbon layer is achieved by using a specific binder, namely, montmorillonite. The point achieved by this. Therefore, as for other members and elements constituting the battery, such as the positive electrode active material and the electrolytic solution, it is possible to use various materials which have been conventionally proposed or practically used for lithium secondary batteries without particular limitation. .
【００１３】正極活物質の具体例としては、ＬｉＣｏＯ
2 、ＬｉＮｉＯ2 、ＬｉＭｎＯ2 、ＬｉＭｎ2 Ｏ4 、Ｌ
ｉＶＯ2 及びＬｉＮｂＯ2 が挙げられる。As a specific example of the positive electrode active material, LiCoO
2 , LiNiO 2 , LiMnO 2 , LiMn 2 O 4 , L
iVO 2 and LiNbO 2 .
【００１４】また、電解液の具体例としては、エチレン
カーボネート、ビニレンカーボネート、プロピレンカー
ボネートなどの有機溶媒、又は、これらとジメチルカー
ボネート、ジエチルカーボネート、１，２−ジメトキシ
エタン、１，２−ジエトキシエタン、エトキシメトキシ
エタン等の低沸点溶媒との混合溶媒に、ＬｉＰＦ6 、Ｌ
ｉＣｌＯ4 、ＬｉＣＦ3 ＳＯ3 などの溶質を０．７〜
１．５Ｍ（モル／リットル）溶かした溶液が挙げられ
る。固体電解質を用いることも可能である。Specific examples of the electrolytic solution include organic solvents such as ethylene carbonate, vinylene carbonate and propylene carbonate, or a mixture thereof with dimethyl carbonate, diethyl carbonate, 1,2-dimethoxyethane, 1,2-diethoxyethane. LiPF 6 , L in a mixed solvent with a low boiling point solvent such as
Solutes such as iClO 4 and LiCF 3 SO 3
A solution in which 1.5 M (mol / liter) is dissolved is exemplified. It is also possible to use a solid electrolyte.
【００１５】本発明電池では、炭素負極の結着剤とし
て、従来のゴム系重合体やフッ素系重合体に代えて、モ
ンモリロナイトが用いられているので、炭素層が負極集
電体から剥離しにくい。このため、充放電サイクルを繰
り返した際の電池容量の減少が小さい。In the battery of the present invention, montmorillonite is used as a binder for the carbon negative electrode instead of the conventional rubber-based polymer or fluorine-based polymer, so that the carbon layer is hardly peeled off from the negative electrode current collector. . Therefore, a decrease in the battery capacity when the charge / discharge cycle is repeated is small.
【００１６】[0016]
【実施例】以下、本発明を実施例に基づいてさらに詳細
に説明するが、本発明は下記実施例に何ら限定されるも
のではなく、その要旨を変更しない範囲において適宜変
更して実施することが可能なものである。EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples, and the present invention may be practiced by appropriately changing the gist of the invention. Is possible.
【００１７】（実施例１） 〔正極の作製〕正極活物質としてのコバルト酸リチウム
（ＬｉＣｏＯ2 ）と導電剤としての人造黒鉛とを重量比
９：１で混合し、この混合物９５重量部と、結着剤とし
てのポリフッ化ビニリデン５重量部のＮ−メチル−２−
ピロリドン（ＮＭＰ）溶液とを混合して、スラリーを調
製した。次いで、このスラリーを正極集電体としてのア
ルミニウム箔の両面にドクターブレード法により塗布
し、１５０°Ｃで２時間真空乾燥して、正極を作製し
た。Example 1 [Preparation of Positive Electrode] Lithium cobaltate (LiCoO 2 ) as a positive electrode active material and artificial graphite as a conductive agent were mixed at a weight ratio of 9: 1, and 95 parts by weight of this mixture was mixed with: 5 parts by weight of polyvinylidene fluoride as a binder N-methyl-2-
A slurry was prepared by mixing with a pyrrolidone (NMP) solution. Next, this slurry was applied to both sides of an aluminum foil as a positive electrode current collector by a doctor blade method, and vacuum dried at 150 ° C. for 2 hours to produce a positive electrode.
【００１８】〔負極の作製〕天然黒鉛塊（ｄ002 ＝３．
３５６Å；Ｌｃ＞１０００Å）に空気流を噴射して粉砕
（ジェット粉砕）し、黒鉛粉末を得た。この黒鉛粉末９
５重量部と、モンモリロナイト（クニミネ工業社製、商
品コード「ＫＵＮＩＰＩＡ−Ｆ」）１重量部及びカルボ
キシメチルセルロース４重量部を含有する４重量％水懸
濁液とを混合して、スラリーを調製した。次いで、この
スラリーを負極集電体としての銅箔の両面にドクターブ
レード法により塗布し、４００°Ｃで２時間真空乾燥し
て、負極を作製した。[Preparation of Negative Electrode] Lump of natural graphite (d 002 = 3.
356 °; Lc> 1000 °) and pulverized by jetting (jet pulverization) to obtain a graphite powder. This graphite powder 9
A slurry was prepared by mixing 5 parts by weight with a 4% by weight aqueous suspension containing 1 part by weight of montmorillonite (manufactured by Kunimine Industries, product code "KUNIPIA-F") and 4 parts by weight of carboxymethylcellulose. Next, this slurry was applied to both surfaces of a copper foil as a negative electrode current collector by a doctor blade method, and vacuum dried at 400 ° C. for 2 hours to produce a negative electrode.
【００１９】〔電解液の調製〕エチレンカーボネートと
ジエチルカーボネートとの体積比１：１の混合溶媒に、
ＬｉＰＦ6 を１Ｍ（モル／リットル）の割合で溶かして
電解液を調製した。[Preparation of electrolyte solution] In a mixed solvent of ethylene carbonate and diethyl carbonate at a volume ratio of 1: 1,
LiPF 6 was dissolved at a rate of 1 M (mol / liter) to prepare an electrolytic solution.
【００２０】〔リチウム二次電池の組立〕上記の正極、
負極及び電解液を用いてＡＡサイズ（円筒型）の本発明
電池Ａを組み立てた。なお、セパレータとしては、リチ
ウムイオン透過性を有するポリプロピレン製の微多孔膜
を使用した。[Assembly of Lithium Secondary Battery]
An AA-size (cylindrical) battery A of the present invention was assembled using the negative electrode and the electrolytic solution. As the separator, a microporous film made of polypropylene having lithium ion permeability was used.
【００２１】（実施例２）負極の作製において、結着剤
分散液として、重量比１：２のモンモリロナイトとカル
ボキシメチルセルロースとを総量で５重量部含有する４
重量％水懸濁液を用いたこと以外は実施例１と同様にし
て、本発明電池Ｂを組み立てた。Example 2 In the preparation of a negative electrode, a binder dispersion liquid containing 5 parts by weight of montmorillonite and carboxymethyl cellulose in a weight ratio of 1: 2 in a total amount of 4 parts was prepared.
A battery B of the present invention was assembled in the same manner as in Example 1 except that a weight-% water suspension was used.
【００２２】（実施例３）負極の作製において、結着剤
分散液として、重量比１：１のモンモリロナイトとカル
ボキシメチルセルロースとを総量で５重量部含有する４
重量％水懸濁液を用いたこと以外は実施例１と同様にし
て、本発明電池Ｃを組み立てた。Example 3 In the preparation of a negative electrode, a binder dispersion liquid containing 5 parts by weight of montmorillonite and carboxymethyl cellulose in a weight ratio of 1: 1 was used.
A battery C of the present invention was assembled in the same manner as in Example 1 except that a weight-% water suspension was used.
【００２３】（実施例４）負極の作製において、結着剤
分散液として、重量比１：８のモンモリロナイトとカル
ボキシメチルセルロースとを総量で５重量部含有する４
重量％水懸濁液を用いたこと以外は実施例１と同様にし
て、本発明電池Ｄを組み立てた。Example 4 In the preparation of the negative electrode, a binder dispersion liquid containing 5 parts by weight of montmorillonite and carboxymethyl cellulose in a weight ratio of 1: 8 was used.
A battery D of the present invention was assembled in the same manner as in Example 1 except that a weight-% water suspension was used.
【００２４】（実施例５）負極の作製において、結着剤
分散液として、重量比９：８のモンモリロナイトとカル
ボキシメチルセルロースとを総量で５重量部含有する４
重量％水懸濁液を用いたこと以外は実施例１と同様にし
て、本発明電池Ｅを組み立てた。Example 5 In the preparation of a negative electrode, a binder dispersion liquid containing 5 parts by weight of montmorillonite and carboxymethyl cellulose in a weight ratio of 9: 8 was used.
A battery E of the present invention was assembled in the same manner as in Example 1 except that a weight-% water suspension was used.
【００２５】（実施例６）負極の作製において、黒鉛粉
末９９．９重量部と、重量比１：４のモンモリロナイト
とカルボキシメチルセルロースとを総量で０．１重量部
含有する４重量％水懸濁液とを混合したこと以外は実施
例１と同様にして、本発明電池Ｆを組み立てた。Example 6 A 4% by weight aqueous suspension containing 99.9 parts by weight of graphite powder and 0.1 part by weight of montmorillonite and carboxymethylcellulose in a weight ratio of 1: 4 in the preparation of a negative electrode. Was prepared in the same manner as in Example 1 except that was mixed.
【００２６】（実施例７）負極の作製において、黒鉛粉
末９９．５重量部と、重量比１：４のモンモリロナイト
とカルボキシメチルセルロースとを総量で０．５重量部
含有する４重量％水懸濁液とを混合したこと以外は実施
例１と同様にして、本発明電池Ｇを組み立てた。Example 7 A 4% by weight aqueous suspension containing 99.5 parts by weight of graphite powder and 0.5 parts by weight of montmorillonite and carboxymethylcellulose in a weight ratio of 1: 4 in the preparation of a negative electrode. Was prepared in the same manner as in Example 1 except that was mixed.
【００２７】（実施例８）負極の作製において、黒鉛粉
末９７重量部と、重量比１：４のモンモリロナイトとカ
ルボキシメチルセルロースとを総量で３重量部含有する
４重量％水懸濁液とを混合したこと以外は実施例１と同
様にして、本発明電池Ｈを組み立てた。Example 8 In the preparation of a negative electrode, 97 parts by weight of graphite powder and a 4% by weight aqueous suspension containing 3 parts by weight of montmorillonite and carboxymethyl cellulose in a weight ratio of 1: 4 were mixed. A battery H of the present invention was assembled in the same manner as in Example 1 except for the above.
【００２８】（実施例９）負極の作製において、黒鉛粉
末９３重量部と、重量比１：４のモンモリロナイトとカ
ルボキシメチルセルロースとを総量で７重量部含有する
４重量％水懸濁液とを混合したこと以外は実施例１と同
様にして、本発明電池Ｉを組み立てた。Example 9 In the preparation of the negative electrode, 93 parts by weight of graphite powder and a 4% by weight aqueous suspension containing 7 parts by weight of montmorillonite and carboxymethyl cellulose in a weight ratio of 1: 4 were mixed. A battery I of the present invention was assembled in the same manner as in Example 1 except for the above.
【００２９】（比較例１）負極の作製において、結着剤
分散液として、重量比１：４のスチレン−ブタジエンゴ
ムとカルボキシメチルセルロースとを総量で５重量部含
有する４重量％水懸濁液を用いたこと、及び、真空乾燥
温度を１５０°Ｃに変えたこと以外は実施例１と同様に
して、比較電池Ｊを組み立てた。Comparative Example 1 In the preparation of the negative electrode, a 4% by weight aqueous suspension containing 5 parts by weight of styrene-butadiene rubber and carboxymethyl cellulose in a weight ratio of 1: 4 was used as a binder dispersion. A comparative battery J was assembled in the same manner as in Example 1 except that the battery was used and the vacuum drying temperature was changed to 150 ° C.
【００３０】（比較例２）負極の作製において、結着剤
分散液として、重量比１：２のスチレン−ブタジエンゴ
ムとカルボキシメチルセルロースとを総量で５重量部含
有する４重量％水懸濁液を用いたこと、及び、真空乾燥
温度を１５０°Ｃに変えたこと以外は実施例１と同様に
して、比較電池Ｋを組み立てた。Comparative Example 2 In the preparation of the negative electrode, a 4% by weight aqueous suspension containing a total of 5 parts by weight of styrene-butadiene rubber and carboxymethylcellulose in a weight ratio of 1: 2 was used as a binder dispersion. A comparative battery K was assembled in the same manner as in Example 1 except that the battery was used and the vacuum drying temperature was changed to 150 ° C.
【００３１】（比較例３）負極の作製において、結着剤
分散液として、重量比１：１のスチレン−ブタジエンゴ
ムとカルボキシメチルセルロースとを総量で５重量部含
有する４重量％水懸濁液を用いたこと、及び、真空乾燥
温度を１５０°Ｃに変えたこと以外は実施例１と同様に
して、比較電池Ｌを組み立てた。Comparative Example 3 In the preparation of the negative electrode, a 4% by weight aqueous suspension containing 5 parts by weight of styrene-butadiene rubber and carboxymethyl cellulose in a weight ratio of 1: 1 was used as a binder dispersion. A comparative battery L was assembled in the same manner as in Example 1 except that the battery was used and the vacuum drying temperature was changed to 150 ° C.
【００３２】（比較例４）負極の作製において、結着剤
分散液として、重量比１：８のスチレン−ブタジエンゴ
ムとカルボキシメチルセルロースとを総量で５重量部含
有する４重量％水懸濁液を用いたこと、及び、真空乾燥
温度を１５０°Ｃに変えたこと以外は実施例１と同様に
して、比較電池Ｍを組み立てた。Comparative Example 4 In the preparation of the negative electrode, a 4% by weight aqueous suspension containing 5 parts by weight of styrene-butadiene rubber and carboxymethyl cellulose in a weight ratio of 1: 8 was used as a binder dispersion. A comparative battery M was assembled in the same manner as in Example 1 except that the battery was used and the vacuum drying temperature was changed to 150 ° C.
【００３３】（比較例５）負極の作製において、結着剤
分散液として、重量比９：８のスチレン−ブタジエンゴ
ムとカルボキシメチルセルロースとを総量で５重量部含
有する４重量％水懸濁液を用いたこと、及び、真空乾燥
温度を１５０°Ｃに変えたこと以外は実施例１と同様に
して、比較電池Ｎを組み立てた。Comparative Example 5 In the preparation of the negative electrode, a 4% by weight aqueous suspension containing 5 parts by weight of a total of 9: 8 styrene-butadiene rubber and carboxymethylcellulose was used as a binder dispersion. A comparative battery N was assembled in the same manner as in Example 1 except that the battery was used and the vacuum drying temperature was changed to 150 ° C.
【００３４】（比較例６）負極の作製において、黒鉛粉
末９９．９重量部と、重量比１：４のスチレン−ブタジ
エンゴムとカルボキシメチルセルロースとを総量で０．
１重量部含有する４重量％水懸濁液とを混合したこと以
外は比較例１と同様にして、比較電池Ｏを組み立てた。Comparative Example 6 In the preparation of a negative electrode, 99.9 parts by weight of graphite powder, a styrene-butadiene rubber having a weight ratio of 1: 4 and carboxymethylcellulose were added in a total amount of 0.1%.
A comparative battery O was assembled in the same manner as in Comparative Example 1 except that a 4% by weight aqueous suspension containing 1 part by weight was mixed.
【００３５】（比較例７）負極の作製において、黒鉛粉
末９９．５重量部と、重量比１：４のスチレン−ブタジ
エンゴムとカルボキシメチルセルロースとを総量で０．
５重量部含有する４重量％水懸濁液とを混合したこと以
外は比較例１と同様にして、比較電池Ｐを組み立てた。(Comparative Example 7) In the preparation of a negative electrode, 99.5 parts by weight of graphite powder, a styrene-butadiene rubber having a weight ratio of 1: 4 and carboxymethyl cellulose in a total amount of 0.1% were used.
A comparative battery P was assembled in the same manner as in Comparative Example 1 except that a 4% by weight aqueous suspension containing 5 parts by weight was mixed.
【００３６】（比較例８）負極の作製において、黒鉛粉
末９７重量部と、重量比１：４のスチレン−ブタジエン
ゴムとカルボキシメチルセルロースとを総量で３重量部
含有する４重量％水懸濁液とを混合したこと以外は比較
例１と同様にして、比較電池Ｑを組み立てた。Comparative Example 8 In the preparation of the negative electrode, 97 parts by weight of graphite powder and a 4% by weight aqueous suspension containing 3 parts by weight of styrene-butadiene rubber and carboxymethyl cellulose in a weight ratio of 1: 4 were prepared. Was assembled in the same manner as Comparative Example 1 except that was mixed.
【００３７】（比較例９）負極の作製において、黒鉛粉
末９３重量部と、重量比１：４のスチレン−ブタジエン
ゴムとカルボキシメチルセルロースとを総量で７重量部
含有する４重量％水懸濁液とを混合したこと以外は比較
例１と同様にして、比較電池Ｒを組み立てた。Comparative Example 9 In the preparation of a negative electrode, 93 parts by weight of graphite powder and a 4% by weight aqueous suspension containing 7 parts by weight of styrene-butadiene rubber and carboxymethyl cellulose in a weight ratio of 1: 4 were used. Was assembled in the same manner as Comparative Example 1 except that was mixed.
【００３８】本発明電池Ａ〜Ｉ及び比較電池Ｊ〜Ｒの結
着剤とカルボキシメチルセルロース（増粘剤）の重量
比、並びに、炭素粉末、結着剤及び増粘剤の総量に対す
るモンモリロナイト及び増粘剤の総量の比率（重量％）
を、表１及び表２に示す。The weight ratio of the binder to carboxymethylcellulose (thickening agent) of the batteries A to I of the present invention and the comparative batteries JR, and montmorillonite and thickening with respect to the total amount of the carbon powder, the binding agent and the thickener. Ratio of total amount of agent (% by weight)
Are shown in Tables 1 and 2.
【００３９】[0039]
【表１】 [Table 1]
【００４０】[0040]
【表２】 [Table 2]
【００４１】〈充放電サイクル特性〉本発明電池Ａ〜Ｉ
及び比較電池Ｊ〜Ｒについて、２００ｍＡで４．１Ｖま
で充電した後、２００ｍＡで２．７５Ｖまで放電する工
程を１サイクルとする充放電サイクル試験を行い、各電
池の充放電サイクル特性を調べた。充放電サイクル特性
は、５００サイクルまでの１サイクル当たりの容量劣化
率（％／サイクル）〔容量劣化率＝｛（１サイクル目の
電池容量−５００サイクル目の電池容量）／１サイクル
目の電池容量｝×１００÷５００〕で評価した。結果を
先の表１及び表２に示す。<Charge / discharge cycle characteristics> Batteries A to I of the present invention
For the comparative batteries J to R, a charge / discharge cycle test was performed in which the process of charging the battery to 200 V to 4.1 V and then discharging the battery to 200 V to 2.75 V was one cycle, and the charge / discharge cycle characteristics of each battery were examined. The charge / discharge cycle characteristics are as follows: capacity deterioration rate per cycle up to 500 cycles (% / cycle) [capacity deterioration rate = ｛(battery capacity at first cycle−battery capacity at 500th cycle) / battery capacity at first cycle ｝ × 100 ÷ 500]. The results are shown in Tables 1 and 2 above.
【００４２】〈剥離強度〉本発明電池Ａ〜Ｉ及び比較電
池Ｊ〜Ｒに使用した負極について、炭素層の剥離強度を
測定した。負極の炭素層の表面に０．５ｃｍ角の紐付き
両面接着テープを貼着し、バネ秤のフックに両面接着テ
ープの紐を結び付けた後、バネ秤を引っ張り、炭素層が
両面接着テープとともに銅箔から剥離し始めたときの引
張荷重（ｋｇ／ｃｍ2 ）を求め、剥離強度とした。結果
を先の表１及び表２に示す。<Peel Strength> The peel strength of the carbon layer was measured for the negative electrodes used in the batteries A to I of the present invention and the comparative batteries J to R. Affix a 0.5cm square double-sided adhesive tape with a string on the surface of the carbon layer of the negative electrode, tie the double-sided adhesive tape string to the hook of the spring scale, pull the spring scale, and the carbon layer is copper foil with the double-sided adhesive tape The tensile load (kg / cm 2 ) when peeling was started was determined, and the result was defined as the peel strength. The results are shown in Tables 1 and 2 above.
【００４３】表１に示すように、本発明電池Ａ，Ｂ，
Ｃ，Ｄ，Ｅは、それぞれ比較電池Ｊ，Ｋ，Ｌ，Ｍ，Ｎに
比べて、剥離強度が大きく、容量劣化率が小さい。ま
た、本発明電池Ａ〜Ｅの中でも、本発明電池Ａ，Ｂ，Ｃ
の容量劣化率が特に小さい。この事実から、モンモリロ
ナイトとカルボキシメチルセルロースの重量比は１：１
〜１：４とすることが好ましいことが分かる。As shown in Table 1, the batteries A, B,
C, D, and E have higher peel strengths and lower capacity deterioration rates than the comparative batteries J, K, L, M, and N, respectively. Also, among the batteries A to E of the present invention, the batteries A, B, and C of the present invention
Has a particularly small capacity deterioration rate. From this fact, the weight ratio of montmorillonite to carboxymethyl cellulose is 1: 1.
It is understood that the ratio is preferably set to １ ： 1: 4.
【００４４】表２に示すように、本発明電池Ｆ〜Ｉ及び
Ａの中でも、本発明電池Ｇ，Ｈ，Ａの容量劣化率が特に
小さい。この事実から、黒鉛粉末、モンモリロナイト及
びカルボキシメチルセルロースの総量に対するモンモリ
ロナイト及びカルボキシメチルセルロースの総量の比率
は、０．５〜５重量％とすることが好ましいことが分か
る。As shown in Table 2, among the batteries B to I and A of the present invention, the batteries G, H and A of the present invention have particularly small capacity deterioration rates. From this fact, it can be seen that the ratio of the total amount of montmorillonite and carboxymethyl cellulose to the total amount of graphite powder, montmorillonite and carboxymethyl cellulose is preferably 0.5 to 5% by weight.
【００４５】上記の実施例では、本発明を円筒型電池に
適用する場合を例に挙げて説明したが、本発明は電池形
状に特に制限はなく、扁平型、角型など、他の種々の形
状の非水系一次電池又は非水系二次電池に適用し得るも
のである。In the above embodiment, the case where the present invention is applied to a cylindrical battery has been described as an example. However, the present invention is not particularly limited in the shape of the battery, and various other types such as a flat type and a square type are available. The present invention can be applied to a non-aqueous primary battery or a non-aqueous secondary battery having a shape.
【００４６】また、上記の実施例では、増粘剤としてカ
ルボキシメチルセルロースを用いたが、先に挙げた他の
増粘剤を使用した場合にも、上記と同様の結果が得られ
ることを確認した。In the above examples, carboxymethylcellulose was used as a thickener, but it was confirmed that the same results as described above were obtained when the other thickeners mentioned above were used. .
【００４７】[0047]
【発明の効果】本発明電池は、炭素負極の結着剤として
モンモリロナイトが用いられているので、充放電サイク
ルを重ねても炭素層が集電体から剥離しにくく、充放電
サイクル特性に優れる。According to the battery of the present invention, montmorillonite is used as a binder for the carbon negative electrode, so that the carbon layer hardly peels off from the current collector even after repeated charge / discharge cycles, and is excellent in charge / discharge cycle characteristics.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 山崎 幹也 大阪府守口市京阪本通２丁目５番５号 三 洋電機株式会社内 (72)発明者 能間 俊之 大阪府守口市京阪本通２丁目５番５号 三 洋電機株式会社内 (72)発明者 西尾 晃治 大阪府守口市京阪本通２丁目５番５号 三 洋電機株式会社内 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Mikiya Yamazaki 2-5-5 Keihanhondori, Moriguchi-shi, Osaka Sanyo Electric Co., Ltd. (72) Toshiyuki Noma 2-chome Keihanhondori, Moriguchi-shi, Osaka No.5-5 Sanyo Electric Co., Ltd. (72) Inventor Koji Nishio 2-5-5 Keihanhondori, Moriguchi-shi, Osaka Sanyo Electric Co., Ltd.
Claims (4)
出することが可能な炭素粉末と、モンモリロナイトと、
増粘剤の水溶液とを混合して得たスラリーを、集電体に
塗布し、乾燥して成る負極を備えるリチウム二次電池。1. A carbon powder capable of electrochemically storing and releasing lithium ions, montmorillonite,
A lithium secondary battery including a negative electrode obtained by applying a slurry obtained by mixing an aqueous solution of a thickener to a current collector and drying the slurry.
チルセルロース、ヒドロキシプロピルセルロース、ポリ
ビニルアルコール又はポリビニルピロリドンである請求
項１記載のリチウム二次電池。2. The lithium secondary battery according to claim 1, wherein the thickener is carboxymethylcellulose, methylcellulose, hydroxypropylcellulose, polyvinyl alcohol or polyvinylpyrrolidone.
総量に対するモンモリロナイト及び増粘剤の総量の比率
が、０．５〜５重量％である請求項１又は２記載のリチ
ウム二次電池。3. The lithium secondary battery according to claim 1, wherein the ratio of the total amount of montmorillonite and thickener to the total amount of carbon powder, montmorillonite and thickener is 0.5 to 5% by weight.
の重量比が１：１〜１：４である請求項１〜３のいずれ
かに記載のリチウム二次電池。4. The lithium secondary battery according to claim 1, wherein the weight ratio of montmorillonite to the thickener in the slurry is from 1: 1 to 1: 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8274181A JPH10106542A (en) | 1996-09-24 | 1996-09-24 | Lithium secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8274181A JPH10106542A (en) | 1996-09-24 | 1996-09-24 | Lithium secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10106542A true JPH10106542A (en) | 1998-04-24 |
Family
ID=17538177
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8274181A Pending JPH10106542A (en) | 1996-09-24 | 1996-09-24 | Lithium secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10106542A (en) |
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|---|---|---|---|---|
| KR100591615B1 (en) * | 2000-03-21 | 2006-06-20 | 에스케이씨 주식회사 | Lithium secondary battery |
| JP2008071757A (en) * | 2006-09-11 | 2008-03-27 | Lg Chem Ltd | Electrode binder containing clay mineral, and electrochemical cell using this |
| CN102290574A (en) * | 2010-06-18 | 2011-12-21 | 丰田自动车株式会社 | Negative electrode material and method of manufacture thereof |
| JP2012146477A (en) * | 2011-01-12 | 2012-08-02 | Hitachi Ltd | Nonaqueous electrolyte battery |
| JP2013020967A (en) * | 2011-07-07 | 2013-01-31 | Samsung Sdi Co Ltd | Electrode for lithium secondary battery, method of manufacturing the same, and lithium secondary battery including the same |
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| WO2022130749A1 (en) * | 2020-12-14 | 2022-06-23 | パナソニックＩｐマネジメント株式会社 | Method for producing positive electrode slurry and method for producing positive electrode |
| US11539048B2 (en) | 2018-10-01 | 2022-12-27 | Toyota Jidosha Kabushiki Kaisha | Negative electrode, battery, and method of producing negative electrode |
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-
1996
- 1996-09-24 JP JP8274181A patent/JPH10106542A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100591615B1 (en) * | 2000-03-21 | 2006-06-20 | 에스케이씨 주식회사 | Lithium secondary battery |
| JP2008071757A (en) * | 2006-09-11 | 2008-03-27 | Lg Chem Ltd | Electrode binder containing clay mineral, and electrochemical cell using this |
| KR100927246B1 (en) | 2006-09-11 | 2009-11-16 | 주식회사 엘지화학 | Electrode mixture containing clay mineral and electrochemical cell using the same |
| US8603674B2 (en) | 2009-12-24 | 2013-12-10 | Sanyo Electric Co., Ltd. | Composition for electrode of nonaqueous electrolyte secondary battery, electrode for nonaqueous electrolyte secondary battery using the same and nonaqueous electrolyte secondary battery |
| CN102290574A (en) * | 2010-06-18 | 2011-12-21 | 丰田自动车株式会社 | Negative electrode material and method of manufacture thereof |
| US8568612B2 (en) | 2010-06-18 | 2013-10-29 | Toyota Jidosha Kabushiki Kaisha | Negative electrode material and method of manufacture thereof |
| JP2012004021A (en) * | 2010-06-18 | 2012-01-05 | Toyota Motor Corp | Negative electrode material and method for producing the same |
| JP2012146477A (en) * | 2011-01-12 | 2012-08-02 | Hitachi Ltd | Nonaqueous electrolyte battery |
| JP2013020967A (en) * | 2011-07-07 | 2013-01-31 | Samsung Sdi Co Ltd | Electrode for lithium secondary battery, method of manufacturing the same, and lithium secondary battery including the same |
| JP2013134896A (en) * | 2011-12-26 | 2013-07-08 | Sumitomo Bakelite Co Ltd | Mixture for negative electrode, negative electrode for lithium ion secondary battery, and lithium ion secondary battery |
| US11735714B2 (en) | 2017-11-06 | 2023-08-22 | Lg Energy Solution, Ltd. | Negative electrode slurry composition for lithium secondary battery, and method for preparing the same |
| US11539048B2 (en) | 2018-10-01 | 2022-12-27 | Toyota Jidosha Kabushiki Kaisha | Negative electrode, battery, and method of producing negative electrode |
| WO2022130749A1 (en) * | 2020-12-14 | 2022-06-23 | パナソニックＩｐマネジメント株式会社 | Method for producing positive electrode slurry and method for producing positive electrode |
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