JP2548460B2 - Negative electrode for non-aqueous electrolyte secondary battery - Google Patents
Negative electrode for non-aqueous electrolyte secondary batteryInfo
- Publication number
- JP2548460B2 JP2548460B2 JP3009641A JP964191A JP2548460B2 JP 2548460 B2 JP2548460 B2 JP 2548460B2 JP 3009641 A JP3009641 A JP 3009641A JP 964191 A JP964191 A JP 964191A JP 2548460 B2 JP2548460 B2 JP 2548460B2
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- binder
- electrolyte secondary
- aqueous electrolyte
- butadiene rubber
- 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 - Lifetime
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明はリチウムを吸蔵、放出す
る金属粉末、炭素材料、硫化物、酸化物を活物質とする
非水電解質二次電池用負極に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a negative electrode for a non-aqueous electrolyte secondary battery containing a metal powder, a carbon material, a sulfide and an oxide as an active material, which absorbs and releases lithium.
【０００２】[0002]
【従来の技術】リチウムまたはリチウム化合物を負極と
する非水電解質二次電池は、高電圧で高エネルギー密度
が期待され、多くの研究が行われている。2. Description of the Related Art Non-aqueous electrolyte secondary batteries using lithium or a lithium compound as a negative electrode are expected to have high energy density at high voltage, and many studies have been conducted.
【０００３】従来、この種の非水電解質二次電池の正極
活物質には、ＬｉＣｏＯ2、Ｖ2Ｏ5、Ｃｒ2Ｏ5、Ｍｎ
Ｏ2、ＴｉＳ2、ＭｏＳ2などの遷移金属の酸化物および
カルコゲン化合物が知られおり、これらは層状構造もし
くはトンネル構造を有し、リチウムイオンが出入りでき
る結晶構造を持っている。一方、負極活物質としては金
属リチウムが多く検討されてきた。Conventionally, LiCoO 2 , V 2 O 5 , Cr 2 O 5 , and Mn have been used as positive electrode active materials for this type of non-aqueous electrolyte secondary battery.
O 2, TiS 2, MoS 2 oxides and chalcogen compounds of transition metals are known, such as, it has a layered structure or a tunnel structure, has a crystal structure in which lithium ions can enter and exit. On the other hand, as a negative electrode active material, many metallic lithiums have been studied.
【０００４】しかし、このような従来の構成では、充電
時にリチウム表面に樹枝状にリチウムが析出し、充放電
サイクルを繰り返すと充放電効率を低下させたり、正極
と接して内部短絡を生じるという問題点を有していた。
このような問題を解決するために、リチウムの樹枝状成
長を抑制し、リチウムを吸蔵、放出することのできるリ
チウム−アルミニウムなどのリチウム合金板もしくはリ
チウムを吸蔵、放出することのできる金属粉末、炭素材
料、酸化物または硫化物を負極活物質に用いる検討がな
されている。しかし、リチウム合金板を用いた場合は、
深い充放電を繰り返すと電極が崩壊して微細化が生じ、
充放電サイクル特性が低下するという問題があった。ま
た金属粉末や炭素材料あるいは酸化物や硫化物を用いた
場合は、通常これら粉末単独では電極が形成できないた
め、金属粉末、酸化物、硫化物に関しては黒鉛などの導
電剤とポリエチレンなどの結着剤を加えて形成してい
た。また、炭素材料を用いる場合は結着剤と一緒に電極
を作製していた。例えば、特開平１−２７６５６３号公
報記載には、合金粉末とカーボンブラックとエチレン−
プロピレンゴムとの組み合わせで電極を形成する方法が
示されている。また、負極結着剤に、正極で一般に使用
されているフッ素樹脂を用いると、充電時に電解液の分
解を促進するためなどの理由からも、これまではポリエ
チレンなどのポリオレフィン系高分子が用いられてい
た。 [0004] However, in such a conventional structure, the lithium is precipitated in the dendritic lithium surface during charging, the repeated charging and discharging cycles or decrease the charge-discharge efficiency, resulting in internal short circuit in contact with the cathode I had a problem.
To solve such a problem, to suppress dendritic growth of lithium, absorbs lithium, lithium capable of releasing - lithium alloy plate or occlude lithium such as aluminum, metal powder capable of releasing carbon The use of materials, oxides or sulfides for the negative electrode active material has been studied. However, when using a lithium alloy plate,
When deep charge and discharge are repeated, the electrodes collapse and miniaturization occurs,
There is a problem that the charge / discharge cycle characteristics deteriorate. When metal powders, carbon materials, oxides, or sulfides are used, it is usually impossible to form electrodes with these powders alone. For metal powders, oxides, sulfides, binders such as graphite and conductive agents such as graphite are used. It was formed by adding the agent. Further, when a carbon material is used, an electrode was produced together with a binder. For example, Japanese Patent Laid-Open No. 1-276563
In the report, alloy powder, carbon black and ethylene-
The method of forming an electrode in combination with propylene rubber is
It is shown. Also commonly used in the positive electrode as a negative electrode binder.
If a fluororesin is used, the amount of electrolyte solution
For some reasons, such as to promote solutions,
Polyolefin polymers such as ethylene are used.
It was
【発明が解決しようとする課題】 しかし、いずれの構成
においても深い充放電を繰り返すと、リチウムの吸蔵、
放出に伴い電極の膨張、収縮が生じるため集電不良が生
じ、充放電サイクル特性が良くないという欠点を有して
おり、未だ充分な特性が得られていない。 [0006] However, repeated deep discharge In either configuration, the lithium occlusion,
Expansion of with the emission electrode, shrinkage occurs collector failure to produce is, has the disadvantage of poor charge-discharge cycle characteristics, not yet satisfactory characteristics are obtained.
【０００５】本発明はこのような課題を解決するもの
で、電池容量が大きく、優れた充放電サイクル特性を有
する非水電解質二次電池用負極を提供することを目的と
するものである。The present invention is intended to solve such problems, and an object thereof is to provide a negative electrode for a non-aqueous electrolyte secondary battery having a large battery capacity and excellent charge / discharge cycle characteristics.
【０００６】[0006]
【課題を解決するための手段】この課題を解決するため
に本発明は、リチウムを吸蔵、放出することのできる金
属粉末、炭素材料あるいは硫化物、酸化物を活物質とす
る非水電解質二次電池の負極において、前記負極材料の
結着剤としてスチレン・エチレン・ブチレン・スチレン
共重合体、スチレン・ブタジエンゴム、メタクリル酸メ
チル・ブタジエンゴム、アクリロニトリル・ブタジエン
ゴム、およびブタジエンゴムのうちから選ばれる少なく
とも１種を用いたものである。In order to solve this problem, the present invention provides a non-aqueous electrolyte secondary containing a metal powder capable of inserting and extracting lithium, a carbon material or a sulfide, or an oxide as an active material. In the negative electrode of a battery, styrene, ethylene, butylene, styrene is used as a binder for the negative electrode material.
Copolymer, styrene-butadiene rubber, methacrylate
Chill-butadiene rubber, acrylonitrile-butadiene
Less selected from rubber and butadiene rubber
Both use one kind .
【０００７】[0007]
【作用】リチウムを吸蔵、放出することのできる金属粉
末や炭素材料あるいは酸化物や硫化物を活物質とする非
水電解質二次電池用負極の結着剤として、弾性に富む上
記の高分子を用いることにより、充放電を繰り返しても
電極が微細化せず、負極中の導電性が充分保持される。
そのため、比較的少ない充放電サイクル数で充放電容量
が低下することがなくなり、安定した電池特性を有する
非水電解質二次電池用負極を構成することが可能とな
る。[Action] The lithium occlusion, as a binder for metallic powder or carbon material or an oxide or sulfide of a negative electrode for a nonaqueous electrolyte secondary battery according to an active material capable of releasing, on highly elastic
By using the above-mentioned polymer, the electrode does not become finer even if charging and discharging are repeated, and the conductivity in the negative electrode is sufficiently maintained.
Therefore, the charge / discharge capacity does not decrease with a relatively small number of charge / discharge cycles, and it is possible to configure a negative electrode for a non-aqueous electrolyte secondary battery having stable battery characteristics.
【０００８】リチウムを吸蔵、放出することのできる金
属粉末としては、リチウムを比較的簡単に吸蔵、放出す
ることができるアルミニウム、錫、鉛、インジウム、ビ
スマスが望ましく、また導電剤には、黒鉛もしくはカー
ボンブラックが望ましい。[0008] occluding lithium and a metal powder capable of releasing, relatively easy to absorb lithium, aluminum can be released, tin, lead, indium, bismuth is desirable, also the conductive agent, graphite Alternatively, carbon black is desirable.
【０００９】[0009]
【実施例】（実施例１） 以下に本発明の一実施例を図面を参照しながら説明す
る。図１に示すように、ケー２中に正極１を置き、その
上にセパレータ３、負極４を置き、電解液を注入してガ
スケット６を介してケース２を封口板５にかしめて構成
される。負極４はリチウムを吸蔵、放出することのでき
るアルミニウム粉末を負極活物質に、結着剤としてスチ
レン・エチレン・ブチレン・スチレン共重合体、スチレ
ン・ブタジエンゴム、メタクリル酸メチル・ブタジエン
ゴム、アクリロニトリル・ブタジエンゴムまたはブタジ
エンゴムのいずれかを用いて構成される。(Embodiment 1) An embodiment of the present invention will be described below with reference to the drawings. As shown in FIG. 1, a positive electrode 1 is placed in a case 2, a separator 3 and a negative electrode 4 are placed thereon, an electrolytic solution is injected, and a case 2 is caulked through a gasket 6 onto a sealing plate 5 to form a structure. . Negative electrode 4 occludes lithium, aluminum powder that can be released into the negative electrode active material, steel as a binder
Styrene / ethylene / butylene / styrene copolymer, styrene
Butadiene rubber, methyl methacrylate butadiene
It is composed of either rubber, acrylonitrile-butadiene rubber or butadiene rubber .
【００１０】負極４は、３００メッシュパスのアルミニ
ウム粉末と導電剤としてのアセチレンブラックと結着剤
としてゴム系高分子を重量比で４５：４５：１０ならび
に４７．５：４７．５：５の割合で混合し、得られた負
極合剤０．１ｇを直径１７．５mmに２ton／cm2の圧力で
プレス成型して１０重量％と５重量％の結着剤を含む負
極を作製した。正極活物質にはＬｉＣｏＯ2を用い、正
極はＬｉＣｏＯ2と導電剤であるアセチレンブラックと
結着剤であるポリ４フッ化エチレン樹脂を重量比で７：
２：１の割合で混合し、得られた正極合剤０．２gを直
径１７．５mmに２ton／cm2でプレス成型して作製した。
製造した電池の構成を図１に示す。成型した正極１をケ
ース２に置く。正極１の上にセパレータ３としての多孔
性ポリプロピレンフィルムを置いた。負極４を、ポリプ
ロピレン製ガスケット６を付けた封口板５に圧着した。
非水電解質として、１mol／lの過塩素酸リチウムを溶解
したプロピレンカーボネート溶媒を用い、これをセパレ
ータ３上および負極４上に加えた。その後電池を封口し
た。負極４の結着剤には、ゴム系高分子であるスチレン
・エチレン・ブチレン・スチレン共重合体（ＳＥＢ
Ｓ）、ブタジエンゴム（ＢＲ）、スチレン・ブタジエン
ゴム（ＳＢＲ）、メタクリル酸メチル・ブタジエンゴム
（ＭＢＲ）またはアクリロニトリル・ブタジエンゴム
（ＮＢＲ）のいずれかを用いた。なお、従来例として、
負極の結着剤にポリエチレン（ＰＥ）を用いた電池も実
施例１と同様の方法で作製した。The negative electrode 4 comprises aluminum powder of 300 mesh pass, acetylene black as a conductive agent, and a rubber polymer as a binder in a weight ratio of 45:45:10 and 47.5: 47.5: 5. Then, 0.1 g of the obtained negative electrode mixture was press-molded to a diameter of 17.5 mm at a pressure of 2 ton / cm 2 to prepare a negative electrode containing 10% by weight and 5% by weight of a binder. LiCoO 2 was used as the positive electrode active material, and LiCoO 2 and acetylene black as the conductive agent and polytetrafluoroethylene resin as the binder were used in the positive electrode in a weight ratio of 7:
The mixture was mixed in a ratio of 2: 1 and 0.2 g of the obtained positive electrode mixture was press-molded to a diameter of 17.5 mm at 2 ton / cm 2 .
The structure of the manufactured battery is shown in FIG. The molded positive electrode 1 is placed in the case 2. A porous polypropylene film as the separator 3 was placed on the positive electrode 1. The negative electrode 4 was pressure-bonded to the sealing plate 5 provided with the polypropylene gasket 6.
As the non-aqueous electrolyte, a propylene carbonate solvent in which 1 mol / l lithium perchlorate was dissolved was used and added to the separator 3 and the negative electrode 4. Thereafter, the battery was sealed. The binder of the negative electrode 4 is a rubber-based polymer such as styrene / ethylene / butylene / styrene copolymer (SEB
S), butadiene rubber (BR), styrene-butadiene rubber (SBR), methyl methacrylate-butadiene rubber (MBR) or acrylonitrile-butadiene rubber (NBR). As a conventional example,
A battery using polyethylene (PE) as the binder for the negative electrode was also manufactured by the same method as in Example 1.
【００１１】以上、負極結着剤ならびに結着剤量の異な
る１２種類の電池の充放電サイクル特性の比較を行っ
た。なお本実施例では、負極の充放電サイクル寿命を評
価するために、正極に基因するサイクル劣化を防ぐた
め、負極より十分に大きい正極容量をもつように電池を
構成した。充放電サイクル試験は、充放電電流０．５m
A、電圧範囲４．０Vから３．０Vの間で定電流充放電を
行った。（表１）に初期放電容量ならびに初期放電容量
に対する５０サイクル目の放電容量の比で放電容量維持
率を示す。As described above, the charge / discharge cycle characteristics of 12 kinds of batteries having different amounts of the negative electrode binder and the binder were compared. In this example, in order to evaluate the charge / discharge cycle life of the negative electrode, the battery was constructed to have a positive electrode capacity sufficiently larger than that of the negative electrode in order to prevent cycle deterioration due to the positive electrode. Charge / discharge cycle test is 0.5m charge / discharge current
A, constant-current charging / discharging was performed in the voltage range of 4.0V to 3.0V. The discharge capacity retention ratio is shown in (Table 1) as the initial discharge capacity and the ratio of the discharge capacity at the 50th cycle to the initial discharge capacity.
【００１２】[0012]
【表１】 [Table 1]
【００１３】（表１）に示すように、結着剤としてポリ
エチレン５重量％または１０重量％を含む負極を用いた
従来例の電池は、初期６．９ｍＡｈ、６．５ｍＡｈの放
電容量を示すが、充放電サイクルが進むとともに容量が
低下し、５０サイクル後の放電容量維持率が４０％程度
まで低下する。一方、本実施例の負極を用いた電池は、
いずれも初期には従来の電池と同等もしくはそれ以上の
放電容量を示し、また５０サイクル後の放電容量維持率
も６０％と充放電サイクル特性が向上している。スチレ
ン・ブタジエンゴムを負極の結着剤に用いた電池を除い
て、初期放電容量ならびに容量維持率とも大きく向上し
た。中でもスチレン・エチレン・ブチレン・スチレン共
重合体とブタジエンゴムを負極の結着剤に用いた電池が
初期放電容量も大きく、優れたサイクル寿命特性を示し
た。スチレン・ブタジエンゴムを負極の結着剤に用いた
電池は容量維持率が向上するものの、初期放電容量がポ
リエチレンと同じく小さいのは、負極活物質を覆うよう
な形で結着し、電極反応を阻害したためであると考えら
れる。As shown in Table 1, the battery of the conventional example using the negative electrode containing 5% by weight or 10% by weight of polyethylene as the binder shows the discharge capacity of 6.9 mAh and 6.5 mAh in the initial stage. The capacity decreases as the charging / discharging cycle progresses, and the discharge capacity retention ratio after 50 cycles decreases to about 40%. On the other hand, the battery using the negative electrode of this example ,
In each case, the discharge capacity was equal to or higher than that of the conventional battery in the initial stage, and the discharge capacity retention ratio after 50 cycles was 60 %, which is an improvement in charge / discharge cycle characteristics. Except for batteries using styrene-butadiene rubber as the binder for the negative electrode, both initial discharge capacity and capacity retention rate were greatly improved. Among them, a battery using a styrene / ethylene / butylene / styrene copolymer and butadiene rubber as a binder for the negative electrode had a large initial discharge capacity and exhibited excellent cycle life characteristics. Batteries that use styrene-butadiene rubber as the binder for the negative electrode have an improved capacity retention rate, but the initial discharge capacity is as small as that of polyethylene. It is thought that this is because of the inhibition.
【００１４】以上のように、アルミニウム粉末を負極活
物質に用いる電池に、本発明を適用することで、充放電
サイクル特性に優れた非水電解質二次電池を作製できる
ことを確認した。As described above, it was confirmed that by applying the present invention to a battery using aluminum powder as a negative electrode active material, a non-aqueous electrolyte secondary battery having excellent charge / discharge cycle characteristics can be produced.
【００１５】なお、実施例１では、金属粉末としてアル
ミニウム、導電剤としてアセチレンブラックの組合せで
説明したが、リチウムを吸蔵、放出しリチウムと合金と
形成することのできるスズ、鉛、インジウム、ビスマス
粉末と導電剤として黒鉛、カーボンブラックのいずれの
組合せにおいても、ほぼ同様の効果が得られることを確
認した。In Example 1, the combination of aluminum as the metal powder and acetylene black as the conductive agent was explained, but tin, lead, indium and bismuth powders capable of absorbing and releasing lithium and forming an alloy with lithium can be obtained. It was confirmed that almost the same effect can be obtained with any combination of graphite and carbon black as the conductive agent.
【００１６】（実施例２） 実施例２においては、リチウムを吸蔵、放出することの
できる炭素材料を負極活物質に、結着剤にスチレン・エ
チレン・ブチレン・スチレン共重合体、スチレン・ブタ
ジエンゴム、メタクリル酸メチル・ブタジエンゴム、ア
クリロニトリル・ブタジエンゴムまたはブタジエンゴム
を用いて実施例１と同様に構成した負極について説明す
る。[0016] In (Example 2) Example 2, occlude lithium, a carbon material capable of releasing a negative electrode active material, scan the binder styrene-ethylene-butylene-styrene copolymer, a styrene-butadiene rubber, methyl methacrylate-butadiene rubber, acrylonitrile-butadiene rubber or Butajiengo arm
The negative electrode configured in the same manner as in Example 1 will be described.
【００１７】負極は、炭素材料と結着剤を重量比で９：
１ならびに９５：５の割合で混合し、得られた負極合剤
０．１ｇを直径１７．５ｍｍに２ton／ｃｍ2の圧力でプ
レス成型して結着剤を１０重量％と５重量％含む負極を
作製した。正極活物質はＬｉＣｏＯ2を用い、実施例１
と同様の条件で正極を作製した。電池の製造も、実施例
１と同様の条件で行った。負極の結着剤には、スチレン
・エチレン・ブチレン・スチレン共重合体（ＳＥＢ
Ｓ）、ブタジエンゴム（ＢＲ）、スチレン・ブタジエン
ゴム（ＳＢＲ）、メタクリル酸メチル・ブタジエンゴム
（ＭＢＲ）、またはアクリロニトリル・ブタジエンゴム
（ＮＢＲ）を用いた。なお従来例として、負極の結着剤
にポリエチレン（ＰＥ）を用いた電池も実施例２と同様
の方法で作製した。The negative electrode comprises a carbon material and a binder in a weight ratio of 9:
1 and 95: 5 were mixed, and 0.1 g of the obtained negative electrode mixture was press-molded into a diameter of 17.5 mm at a pressure of 2 ton / cm 2 to obtain a negative electrode containing 10% by weight and 5% by weight of a binder. Was produced. Example 1 using LiCoO 2 as the positive electrode active material
A positive electrode was produced under the same conditions as in. The battery was also manufactured under the same conditions as in Example 1. Styrene is used as the binder for the negative electrode.
・ Ethylene / butylene / styrene copolymer (SEB
S), butadiene rubber (BR), styrene-butadiene
Rubber (SBR), methyl methacrylate-butadiene rubber (MBR), or acrylonitrile-butadiene rubber
(NBR) was used. As a conventional example, a battery using polyethylene (PE) as a binder for the negative electrode was also manufactured by the same method as in Example 2.
【００１８】以上、負極結着剤ならびに結着剤量の異な
る１２種類の電池の充放電サイクル特性の比較を行っ
た。なお本実施例では、実施例１同様、負極の充放電サ
イクル特性を評価するため、正極に基因するサイクル劣
化を防ぐのに充分に大きい正極容量をもつよう電池を構
成している。充放電サイクル試験は、充放電電流０．５
mA、電圧範囲４．１Vから３．０Vの間で定電流充放電し
て行った。（表２）に初期放電容量ならびに初期放電容
量に対する５０サイクル目の放電容量の比で容量維持率
を示す。The charge / discharge cycle characteristics of 12 types of batteries having different amounts of the negative electrode binder and the binder were compared with each other. In this example, as in Example 1, in order to evaluate the charge / discharge cycle characteristics of the negative electrode, the battery is constructed to have a positive electrode capacity large enough to prevent cycle deterioration due to the positive electrode. Charge / discharge cycle test is 0.5
Constant current charging / discharging was performed in the range of mA and voltage range 4.1V to 3.0V. Table 2 shows the capacity retention rate by the initial discharge capacity and the ratio of the discharge capacity at the 50th cycle to the initial discharge capacity.
【００１９】[0019]
【表２】 [Table 2]
【００２０】（表２）に示すように、結着剤としてポリ
エチレン５重量％または１０重量％を含む負極を用いた
従来例の電池は、初期には６．４ｍＡｈ、６．２ｍＡｈ
の放電容量を示すが、充放電サイクルが進むとともに放
電容量が低下し、５０サイクル後の放電容量維持率は４
０％前後まで低下する。一方、本実施例２の電池は、い
ずれも初期には従来例の電池と同等もしくはそれ以上の
放電容量を示し、また５０サイクル後の放電容量維持率
も６０％以上とサイクル特性が向上している。スチレン
・ブタジエンゴムを負極の結着剤に用いた電池を除い
て、初期放電容量ならびに容量維持率とも大きく向上し
た。中でもスチレン・エチレン・ブチレン・スチレン共
重合体とブタジエンゴムを負極の結着剤に用いた電池が
初期放電容量も大きく、優れたサイクル特性を示した。
スチレン・ブタジエンゴムを負極の結着剤に用いた電池
は、容量維持率が向上するものの、初期放電容量がポリ
エチレンと同じく小さいのは、実施例１と同様に、負極
活物質を覆うような形で結着し、電極反応を阻害したた
めであると考えられる。As shown in (Table 2), the battery of the conventional example using the negative electrode containing 5% by weight or 10% by weight of polyethylene as the binder was initially 6.4 mAh and 6.2 mAh.
The discharge capacity decreases as the charge / discharge cycle progresses, and the discharge capacity retention ratio after 50 cycles is 4
It decreases to around 0%. On the other hand, the battery of this embodiment 2 are both initially a battery equal to or higher discharge capacity of the conventional example, also improved the discharge capacity retention rate after 50 cycles 60% and cycle characteristics There is. styrene
-Except for batteries using butadiene rubber as the binder for the negative electrode, the initial discharge capacity and capacity retention rate were greatly improved. Above all, styrene, ethylene, butylene, styrene
The battery using the polymer and butadiene rubber as the binder for the negative electrode had a large initial discharge capacity and showed excellent cycle characteristics.
Cells used in the styrene-butadiene and the anode of the binder, although the improved capacity retention rate, the initial discharge capacity is also small as poly <br/> ethylene emissions, as in Example 1, the negative electrode active It is considered that this is because the substance was bound to cover the substance and inhibited the electrode reaction.
【００２１】以上のように、炭素材料を負極活物質に用
いる電池に本発明を適用することにより、充放電サイク
ル特性に優れた非水電解質二次電池を作製できる。As described above, by applying the present invention to a battery using a carbon material as a negative electrode active material, a non-aqueous electrolyte secondary battery having excellent charge / discharge cycle characteristics can be produced.
【００２２】なお本実施例２では、負極活物質としてリ
チウムを吸蔵、放出することのできる炭素材料について
説明したが、負極活物質として期待されるＦｅ2Ｏ3や、
ＷＯ 2などの遷移金属酸化物についても、ほぼ同様の効
果が得られることを確認したIn Example 2, as the negative electrode active material,
About carbon materials that can store and release thium
As described above, Fe expected as a negative electrode active material2O3Or
WO 2For transition metal oxides such as
It was confirmed that fruit was obtained
【００２３】[0023]
【発明の効果】以上の実施例の説明からも明らかなよう
に本発明によれば、初期放電容量が大きく、優れた充放
電サイクル特性を有する非水電解質二次電池用負極を得
ることができる。 According to apparent the present invention from the above description of the embodiments according to the present invention, large initial discharge capacity, to obtain a negative electrode for a nonaqueous electrolyte secondary battery having excellent charge-discharge cycle characteristics it can.
【図１】本発明の一実施例の非水電解質二次電池の縦断
面図FIG. 1 is a vertical sectional view of a non-aqueous electrolyte secondary battery according to an embodiment of the present invention.
１ 正極 ２ ケース ３ セパレータ ４ 負極 ５ 封口板 ６ ガスケット 1 Positive electrode 2 Case 3 Separator 4 Negative electrode 5 Sealing plate 6 Gasket
フロントページの続き (72)発明者 豊口 吉徳 大阪府門真市大字門真1006番地 松下電 器産業株式会社内 (72)発明者 村井 祐之 大阪府門真市大字門真1006番地 松下電 器産業株式会社内 (56)参考文献 特開 平１−276563（ＪＰ，Ａ) 特開 昭54−103513（ＪＰ，Ａ)Front page continued (72) Inventor Toyoguchi Yoshinori 1006 Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. (72) Yuyuki Murai, 1006 Kadoma, Kadoma City, Osaka Matsushita Electric Industrial Co., Ltd. (56 ) Reference JP-A-1-276563 (JP, A) JP-A-54-103513 (JP, A)
Claims (1)
金属粉末、炭素材料、硫化物または酸化物を活物質とす
る非水電解質二次電池用負極において、結着剤としてス
チレン・エチレン・ブチレン・スチレン共重合体、スチ
レン・ブタジエンゴム、メタクリル酸メチル・ブタジエ
ンゴム、アクリロニトリル・ブタジエンゴムおよびブタ
ジエンゴムのうちから選ばれる少なくとも１種を用いた
ことを特徴とする非水電解質二次電池用負極。1. A negative electrode for a non-aqueous electrolyte secondary battery containing a metal powder capable of inserting and extracting lithium, a carbon material, a sulfide or an oxide as an active material, and a binder as a binder.
Ethylene / ethylene / butylene / styrene copolymer, styrene
Len / butadiene rubber, methyl methacrylate / butadien
Rubber, acrylonitrile-butadiene rubber and pig
At least one selected from diene rubber was used
A negative electrode for a non-aqueous electrolyte secondary battery, which is characterized in that :
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3009641A JP2548460B2 (en) | 1991-01-30 | 1991-01-30 | Negative electrode for non-aqueous electrolyte secondary battery |
| US07/826,993 US5262255A (en) | 1991-01-30 | 1992-01-28 | Negative electrode for non-aqueous electrolyte secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3009641A JP2548460B2 (en) | 1991-01-30 | 1991-01-30 | Negative electrode for non-aqueous electrolyte secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04255670A JPH04255670A (en) | 1992-09-10 |
| JP2548460B2 true JP2548460B2 (en) | 1996-10-30 |
Family
ID=11725850
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3009641A Expired - Lifetime JP2548460B2 (en) | 1991-01-30 | 1991-01-30 | Negative electrode for non-aqueous electrolyte secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2548460B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011096572A1 (en) | 2010-02-08 | 2011-08-11 | Ｎｅｃエナジーデバイス株式会社 | Nonaqueous electrolyte secondary battery |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4461498B2 (en) | 1997-12-16 | 2010-05-12 | パナソニック株式会社 | Nonaqueous electrolyte secondary battery and negative electrode thereof |
| WO1999063612A1 (en) * | 1998-06-04 | 1999-12-09 | Mitsubishi Chemical Corporation | Secondary battery having nonaqueous electrolyte solution |
| EP1028478B1 (en) * | 1998-06-09 | 2010-03-24 | Panasonic Corporation | Negative electrode for secondary cell, negative plate for secondary cell, and secondary cell comprising the same |
| JP4280339B2 (en) * | 1998-10-16 | 2009-06-17 | パナソニック株式会社 | Solid electrolyte molded body, electrode molded body, and electrochemical element |
| FR2787243B1 (en) * | 1998-12-10 | 2003-10-03 | Cit Alcatel | LITHIUM RECHARGEABLE ELECTROCHEMICAL GENERATOR FOR USE AT LOW TEMPERATURE |
| US6756153B1 (en) | 1999-01-28 | 2004-06-29 | Zeon Corporation | Binder composition for electrode for lithium-ion secondary battery and utilization thereof |
| JP3627586B2 (en) * | 1999-09-03 | 2005-03-09 | 日本ゼオン株式会社 | Binder for lithium ion secondary battery electrode and use thereof |
| US7341804B2 (en) * | 2002-09-20 | 2008-03-11 | 3M Innovative Properties Company | Anode compositions having an elastomeric binder and an adhesion promoter |
| KR100537613B1 (en) | 2003-06-20 | 2005-12-19 | 삼성에스디아이 주식회사 | Anode composition of lithium battery, and anode and lithium battery employing the same |
| JP2010244936A (en) | 2009-04-08 | 2010-10-28 | Sony Corp | Negative electrode and non-aqueous electrolyte secondary battery |
| TW202203487A (en) * | 2020-05-13 | 2022-01-16 | 西班牙商狄諾索艾拉史托摩洛公司 | Electrode for a lithium-ion battery and process for its preparation |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54103513A (en) * | 1978-01-31 | 1979-08-15 | Matsushita Electric Industrial Co Ltd | Nonnelectrolyte cell |
| DE3200757C1 (en) * | 1982-01-13 | 1983-07-21 | Fa. Carl Freudenberg, 6940 Weinheim | Flexible electrolytic cell |
| JPS59228360A (en) * | 1983-06-08 | 1984-12-21 | Matsushita Electric Ind Co Ltd | Organic electrolyte battery |
| JPS6290863A (en) * | 1985-05-10 | 1987-04-25 | Asahi Chem Ind Co Ltd | Secondary cell |
| JPS631708A (en) * | 1986-06-23 | 1988-01-06 | Yutaka Giken:Kk | Sealed buffer for catalytic converter |
| JPH0782839B2 (en) * | 1986-11-08 | 1995-09-06 | 旭化成工業株式会社 | Secondary battery negative electrode |
| JPS63158745A (en) * | 1986-12-22 | 1988-07-01 | Hitachi Ltd | Non-aqueous secondary battery |
| JPS63266764A (en) * | 1987-04-23 | 1988-11-02 | Shin Kobe Electric Mach Co Ltd | Negative electrode for secondary battery |
| JPH07105237B2 (en) * | 1988-03-31 | 1995-11-13 | 松下電器産業株式会社 | Hydrogen storage alloy electrode |
| JP2923560B2 (en) * | 1988-04-28 | 1999-07-26 | 株式会社日立製作所 | Secondary battery and its negative electrode |
| JPH0353450A (en) * | 1989-07-21 | 1991-03-07 | Mitsubishi Petrochem Co Ltd | Electrodes for secondary batteries |
| JP2872354B2 (en) * | 1990-06-18 | 1999-03-17 | 旭化成工業株式会社 | Method for producing non-aqueous battery electrode |
| JPH0482156A (en) * | 1990-07-23 | 1992-03-16 | Yuasa Corp | Electrode for lithium secondary battery |
-
1991
- 1991-01-30 JP JP3009641A patent/JP2548460B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011096572A1 (en) | 2010-02-08 | 2011-08-11 | Ｎｅｃエナジーデバイス株式会社 | Nonaqueous electrolyte secondary battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04255670A (en) | 1992-09-10 |
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