JP2701586B2 - Negative electrode for non-aqueous electrolyte secondary battery - Google Patents
Negative electrode for non-aqueous electrolyte secondary batteryInfo
- Publication number
- JP2701586B2 JP2701586B2 JP3127321A JP12732191A JP2701586B2 JP 2701586 B2 JP2701586 B2 JP 2701586B2 JP 3127321 A JP3127321 A JP 3127321A JP 12732191 A JP12732191 A JP 12732191A JP 2701586 B2 JP2701586 B2 JP 2701586B2
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- binder
- aqueous electrolyte
- electrolyte secondary
- conductive agent
- 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
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、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.
【０００２】[0002]
【従来の技術】リチウム，リチウム合金またはリチウム
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 A non-aqueous electrolyte secondary battery using lithium, a lithium alloy or a lithium compound as a negative electrode is expected to have a high voltage and a high energy density, and much research has been conducted.
【０００３】これまで非水電解質二次電池の正極活物質
には、ＬｉＣｏＯ2，Ｖ2Ｏ5，Ｃｒ2Ｏ5，ＭｎＯ2，Ｔｉ
Ｓ2，ＭｏＳ2などの遷移金属の酸化物およびカルコゲン
化合物が知られており、これらは層状もしくはトンネル
構造を有し、リチウムイオンが出入りできる結晶構造を
持つ。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。しかしながら充電時にリチウム表面に樹
枝状にリチウムを析出し、充放電率の低下もしくは正極
と接して内部短絡を生じるという問題点を有していた。
このような問題点を解決する手段として、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
きるアルミニウムやアルミニウム合金などのリチウムを
吸蔵，放出することのできる金属または合金の板もしく
は粉末を負極活物質に用いる検討がなされている。Hitherto, the positive electrode active materials of non-aqueous electrolyte secondary batteries include LiCoO 2 , V 2 O 5 , Cr 2 O 5 , MnO 2 , and Ti.
Oxides of transition metals such as S 2 and MoS 2 and chalcogen compounds are known, which have a layered or tunnel structure and a crystal structure through which lithium ions can enter and exit. On the other hand, lithium metal has been widely studied as a negative electrode active material. However, there has been a problem that lithium is deposited in a dendritic manner on the surface of lithium during charging, and the charge / discharge rate is reduced or an internal short circuit occurs due to contact with the positive electrode.
As a means for solving such problems, a metal or alloy plate or a metal or alloy capable of absorbing and releasing lithium, such as aluminum or an aluminum alloy, capable of suppressing lithium dendritic growth and absorbing and releasing lithium can be used. Studies have been made to use powder as a negative electrode active material.
【０００４】[0004]
【発明が解決しようとする課題】しかしながらアルミニ
ウムもしくはアルミニウム合金などのリチウムを吸蔵，
放出することのできる金属または合金の板を負極活物質
として用いた場合、深い充放電を繰り返すと活物質の微
細化が起こって電極が崩れてしまい充分な充放電サイク
ル特性が得られない。また、前記金属または合金の粉末
を負極活物質として用いる場合は結着剤を添加し負極を
形成する方法も検討されている。正極で頻繁に使用され
ているフッ素樹脂も検討されたが、充電時に電解液の分
解を促進してしまった。このため負極用結着剤としてポ
リエチレンなどのポリオレフィン系の結着剤が用いられ
ている。しかしながらこの場合においてもリチウムの吸
蔵，放出に伴う電極の膨張，収縮の結果、活物質保持の
不良や集電不良が生じ充分なサイクル特性が得られない
という欠点を有している。本発明はこのような問題を解
決するもので、充放電サイクル特性に優れた非水電解質
二次電池用負極を提供することを目的とする。However, lithium, such as aluminum or aluminum alloy, is absorbed,
When a metal or alloy plate that can be released is used as a negative electrode active material, if the charge and discharge are repeated deeply, the active material becomes finer and the electrode collapses, and sufficient charge / discharge cycle characteristics cannot be obtained. In the case where the metal or alloy powder is used as a negative electrode active material, a method of forming a negative electrode by adding a binder has been studied. Fluorine resins frequently used in the positive electrode were also studied, but they accelerated the decomposition of the electrolyte during charging. Therefore, a polyolefin-based binder such as polyethylene is used as the binder for the negative electrode. However, even in this case, as a result of the expansion and contraction of the electrode caused by the occlusion and release of lithium, there is a defect that a poor active material retention or a poor current collection occurs and sufficient cycle characteristics cannot be obtained. The present invention solves such a problem, and an object of the present invention is to provide a negative electrode for a nonaqueous electrolyte secondary battery having excellent charge / discharge cycle characteristics.
【０００５】[0005]
【課題を解決するための手段】この課題を解決するため
本発明の非水電解質二次電池用負極は、リチウムを吸
蔵，放出することのできる金属粉末もしくは合金粉末を
活物質とし、結着剤として塩化ビニル−酢酸ビニル共重
合樹脂を用いるもので、前記負極中に導電剤として繊維
状黒鉛を用いる。In order to solve this problem, a negative electrode for a non-aqueous electrolyte secondary battery according to the present invention uses a metal powder or an alloy powder capable of inserting and extracting lithium as an active material and a binder. And a fibrous graphite as a conductive agent in the negative electrode.
【０００６】結着剤である塩化ビニル−酢酸ビニル共重
合樹脂としては、塩化ビニル含有量が９５％から６０％
であることが好ましい。The vinyl chloride-vinyl acetate copolymer resin as a binder has a vinyl chloride content of 95% to 60%.
It is preferred that
【０００７】[0007]
【作用】この構成により本発明の非水電解質二次電池用
負極は、アルミニウムもしくはアルミニウム合金などの
リチウムを吸蔵，放出することのできる金属または合金
の粉末を活物質の結着剤として、結着性に富む塩化ビニ
ル−酢酸ビニル共重合樹脂を用いることで、充放電を繰
り返しても電極中の活物質が保持され、さらに、導電剤
として繊維状黒鉛を添加することにより、電極の膨張時
においても充分な集電が得られることとなる。その結
果、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。According to this structure, the negative electrode for a non-aqueous electrolyte secondary battery of the present invention uses a powder of a metal or alloy capable of occluding and releasing lithium such as aluminum or an aluminum alloy as a binder for an active material. By using a vinyl chloride-vinyl acetate copolymer resin rich in properties, the active material in the electrode is retained even after repeated charging and discharging, and furthermore, by adding fibrous graphite as a conductive agent, the electrode expands when expanded. Thus, sufficient current collection can be obtained. As a result, the charge / discharge capacity does not decrease with a relatively small number of charge / discharge cycles, and a negative electrode for a non-aqueous electrolyte secondary battery having stable battery characteristics can be configured.
【０００８】[0008]
【実施例】以下、本発明の実施例の非水電解質二次電池
用負極を図面を基にして詳細に説明するが、これら実施
例に限定されるものではない。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the present invention is not limited to these embodiments.
【０００９】（実施例１）本実施例においては、アルミ
ニウム粉末を負極活物質に、結着剤に塩化ビニル樹脂を
用いたものならびに塩化ビニルの含有量が８５モル％，
６５モル％の塩化ビニルと酢酸ビニルの共重合樹脂を用
い、さらに導電剤として繊維径が０．１μｍから０．３
μｍ、繊維径と繊維長さの比率が１：７５（アスペクト
比７５）の繊維状黒鉛を用いて構成した負極について説
明する。(Example 1) In this example, aluminum powder was used as a negative electrode active material, a vinyl chloride resin was used as a binder, and the content of vinyl chloride was 85 mol%,
65 mol% of a copolymer resin of vinyl chloride and vinyl acetate was used, and the fiber diameter was 0.1 to 0.3 μm as a conductive agent.
A negative electrode made of fibrous graphite having a ratio of μm and a fiber diameter to a fiber length of 1:75 (aspect ratio 75) will be described.
【００１０】負極は、３００メッシュパスのアルミニウ
ム粉末と導電剤としての繊維状黒鉛と結着剤を重量比で
４５：４５：１０ならびに４７．５：４７．５：５の割
合で混合し負極合剤を得た。この負極合剤０．１ｇを直
径１７．５mmに２トン／cm2でプレス成型し負極とし
た。正極活物質にはＬｉＣｏＯ2を用い、正極はＬｉＣ
ｏＯ2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１７．５
mmに２トン／cm2でプレス成型することで作製した。図
１において、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
５を付けた封口板６に圧着した。非水電解質として、１
モル／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。その後ケース２の上縁部をかしめて電池
を封口した。なお従来例として、導電剤として繊維状黒
鉛ではなくアセチレンブラックを添加し形成した負極を
用いた電池も上記と同様の方法で作製した。The negative electrode was prepared by mixing aluminum powder of 300 mesh pass, fibrous graphite as a conductive agent and a binder in a weight ratio of 45:45:10 and 47.5: 47.5: 5. Agent was obtained. 0.1 g of this negative electrode mixture was press-formed at a diameter of 17.5 mm at 2 ton / cm 2 to obtain a negative electrode. LiCoO 2 is used for the positive electrode active material, and LiC
oO 2 , acetylene black as a conductive agent and polytetrafluoroethylene resin as a binder were mixed at a weight ratio of 7: 2: 1, and 0.2 g of the obtained positive electrode mixture was mixed with 17.5 mm in diameter.
It was produced by press molding at 2 ton / cm 2 to mm. In FIG. 1, a molded positive electrode 1 is placed in a case 2. Positive electrode 1
A porous polypropylene film as a separator 3 was placed on the substrate. The negative electrode 4 was pressure-bonded to a sealing plate 6 to which a polypropylene gasket 5 was attached. As a non-aqueous electrolyte, 1
A propylene carbonate solvent in which mol / l of lithium perchlorate was dissolved was used, and was added onto the separator 3 and the negative electrode 4. Thereafter, the upper edge of the case 2 was swaged to seal the battery. As a conventional example, a battery using a negative electrode formed by adding acetylene black instead of fibrous graphite as a conductive agent was also manufactured by the same method as described above.
【００１１】以上、負極結着剤、および導電剤の異なる
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試験を行うた
め、正極によるサイクル劣化を除外できるだけの充分な
正極容量をもつ条件で電池を構成している。充放電サイ
クル試験は、充放電電流０．５mA，電圧範囲４．０Ｖか
ら３．０Ｖの間で定電流充放電することで行った。The charge / discharge cycle characteristics of 12 types of batteries having different negative electrode binders and conductive agents were compared.
In the present embodiment, the battery is configured under conditions that have a sufficient positive electrode capacity to exclude cycle deterioration due to the positive electrode in order to perform a charge / discharge cycle test on the negative electrode. The charge / discharge cycle test was performed by charging / discharging a constant current at a charge / discharge current of 0.5 mA and a voltage range of 4.0 V to 3.0 V.
【００１２】（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容量維持率を
示す。サンプル数ｎはそれぞれ５０個とした。Table 1 shows the initial discharge capacity and the capacity retention ratio of the discharge capacity at the 50th cycle with respect to the initial discharge capacity. The number n of samples was 50 each.
【００１３】[0013]
【表１】 [Table 1]
【００１４】（表１）に示すように、導電剤としてアセ
チレンブラックを添加した負極を用いた従来例の電池
は、５０サイクル後の放電容量維持率が７５％から８０
％程度まで低下する。一方、導電剤として繊維状黒鉛を
含む負極を用いた本実施例の電池は、塩化ビニル−酢酸
ビニル共重合樹脂を結着剤に用いた場合には、いずれも
従来例の電池と比較し放電容量が大きく向上し、また５
０サイクル後の放電容量維持率が８５％以上とサイクル
特性も向上している。結着剤量が５重量％ならびに１０
重量％の塩化ビニル樹脂単独を負極結着剤に用いた電池
の初期放電容量は、塩化ビニル−酢酸ビニル共重樹脂を
用いた電池に比べ若干大きいものの、５０サイクル目の
放電容量維持率は５重量％のものが６６％、１０重量％
のものが６９％まで低下する。二次電池においては、放
電容量ならびに容量維持率が大きい電極が望まれること
から、塩化ビニル−酢酸ビニル共重合樹脂を結着剤と
し、導電剤として繊維状黒鉛を用いた負極が優れた特性
を有している。これら実施例の負極を用いた電池の放電
容量の向上は、導電剤としてアセチレンブラックを添加
した場合には集電がまだ不十分であったものが、導電剤
としての繊維状黒鉛を添加することによって充分な集電
が得られるようになったためと考えられる。As shown in Table 1, in the conventional battery using the negative electrode to which acetylene black was added as a conductive agent, the discharge capacity retention rate after 50 cycles was from 75% to 80%.
%. On the other hand, in the battery of this example using the negative electrode containing fibrous graphite as the conductive agent, when the vinyl chloride-vinyl acetate copolymer resin was used as the binder, the discharge of the battery was lower than that of the conventional battery. Capacity is greatly improved
When the discharge capacity retention rate after 0 cycles is 85% or more, the cycle characteristics are also improved. 5% by weight or 10% by weight of binder
Although the initial discharge capacity of the battery using the vinyl chloride resin alone in the negative electrode binder by weight% is slightly larger than the battery using the vinyl chloride-vinyl acetate copolymer resin, the discharge capacity retention ratio at the 50th cycle is 5%. 66% by weight, 10% by weight
Are reduced to 69%. In a secondary battery, since an electrode having a large discharge capacity and a large capacity retention ratio is desired, a negative electrode using a vinyl chloride-vinyl acetate copolymer resin as a binder and fibrous graphite as a conductive agent has excellent characteristics. Have. The improvement of the discharge capacity of the battery using the negative electrode of these examples is due to the fact that the current collection was still insufficient when acetylene black was added as a conductive agent, but the addition of fibrous graphite as a conductive agent It is considered that sufficient current collection has been obtained.
【００１５】さらに、アスペクト比の異なる繊維状黒鉛
を導電剤として添加することを試みた。導電剤としてア
スペクト比２０の繊維状黒鉛を、結着剤として塩化ビニ
ル含有量が８５％の塩化ビニル−酢酸ビニル共重合樹脂
を用い、前記と同様の方法で活物質，導電剤，結着剤の
重量比が４５：４５：１０である負極を用いた電池を作
製したところ、５０サイクル目での容量維持率は８４％
と若干の効果がみられた。また、アスペクト比１５０の
繊維状黒鉛を用いた場合には、５０サイクル目での容量
維持率は８９％と（表１）のアスペクト比７５の場合と
ほぼ同様の効果が得られた。以上のことより、アスペク
ト比２０以上の繊維状黒鉛を用いることが好ましいと考
えられる。Further, an attempt was made to add fibrous graphite having a different aspect ratio as a conductive agent. Using a fibrous graphite having an aspect ratio of 20 as a conductive agent and a vinyl chloride-vinyl acetate copolymer resin having a vinyl chloride content of 85% as a binder, an active material, a conductive agent, and a binder in the same manner as described above. When a battery using a negative electrode having a weight ratio of 45:45:10 was produced, the capacity retention at the 50th cycle was 84%.
And some effects were seen. When fibrous graphite having an aspect ratio of 150 was used, the capacity retention ratio at the 50th cycle was 89%, and almost the same effect as in the case of the aspect ratio of 75 in Table 1 was obtained. From the above, it is considered preferable to use fibrous graphite having an aspect ratio of 20 or more.
【００１６】以上のように、アルミニウム粉末を負極活
物質として、塩化ビニル−酢酸ビニル共重合樹脂を負極
結着剤として用いる電池において、導電剤として繊維状
黒鉛を用いることにより、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ことを確認した。As described above, in a battery using aluminum powder as a negative electrode active material and a vinyl chloride-vinyl acetate copolymer resin as a negative electrode binder, by using fibrous graphite as a conductive agent, charge-discharge cycle characteristics are improved. It was confirmed that an excellent non-aqueous electrolyte secondary battery could be manufactured.
【００１７】なお、実施例では、金属粉末としてアルミ
ニウムを用いた場合について説明したが、同様にリチウ
ムを吸蔵，放出しリチウムと合金形成することのできる
スズ，鉛，インジウム，ビスマス粉末を用いた場合にお
いても、ほぼ同様の効果が得られることを確認した。Although the embodiment has been described in connection with the case where aluminum is used as the metal powder, the case where tin, lead, indium, and bismuth powder which can occlude and release lithium to form an alloy with lithium is used. It was confirmed that almost the same effect was obtained also in the above.
【００１８】（実施例２）本実施例においては、９６％
Ａｌ−６％Ｎｉで表わされる組成のアルミニウム合金粉
末を負極活物質に、結着剤に塩化ビニル樹脂を用いたも
のならびに塩化ビニルの含有量が８５モル％，６５モル
％の塩化ビニルと酢酸ビニルの共重合樹脂を用い、さら
に導電剤として繊維径が０．１μｍから０．３μｍ、繊
維径と繊維長さの比率が１：７５（アスペクト比７５）
の繊維状黒鉛を用いて構成した負極について説明する。(Embodiment 2) In this embodiment, 96%
An aluminum alloy powder having a composition represented by Al-6% Ni as a negative electrode active material, using a vinyl chloride resin as a binder, and vinyl chloride and vinyl acetate having a vinyl chloride content of 85 mol% and 65 mol%. And a conductive agent having a fiber diameter of 0.1 μm to 0.3 μm and a ratio of fiber diameter to fiber length of 1:75 (aspect ratio 75)
The negative electrode constituted by using the fibrous graphite will be described.
【００１９】負極は、３００メッシュパスの９６％Ａｌ
−６％Ｎｉアルミニウム合金粉末と導電剤としての繊維
状黒鉛と結着剤を重量比で４５：４５：１０ならびに４
７．５：４７．５：５：５の割合で混合し負極合剤を得
た。この負極合剤０．１ｇを直径１７．５mmに２トン／
cm2でプレス成型し負極とした。正極活物質にはＬｉＣ
ｏＯ2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。な
お従来例として、導電剤として繊維状黒鉛ではなくアセ
チレンブラックを添加し形成した負極を用いた電池も上
記と同様の方法で作製した。The negative electrode is a 300 mesh pass 96% Al
-6% Ni aluminum alloy powder, fibrous graphite as a conductive agent and a binder in a weight ratio of 45:45:10 and 4
The mixture was mixed at a ratio of 7.5: 47.5: 5: 5 to obtain a negative electrode mixture. 0.1 g of this negative electrode mixture was added to 2 ton /
A negative electrode was formed by press molding with cm 2 . LiC for the positive electrode active material
A positive electrode was produced using oO 2 under the same conditions as in Example 1. The battery was manufactured under the same conditions as in Example 1. As a conventional example, a battery using a negative electrode formed by adding acetylene black instead of fibrous graphite as a conductive agent was also manufactured by the same method as described above.
【００２０】以上、負極結着剤の異なる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
も実施例１と同様、負極の充放電サイクル試験を行うた
め、正極による充放電サイクル劣化を除外できるだけの
充分な正極容量をもつ条件で電池を構成している。充放
電サイクル試験は、充放電電流０．５mA，電圧範囲４．
０Ｖから３．０Ｖの間で定電流充放電することで行っ
た。As described above, the charge / discharge cycle characteristics of 12 types of batteries having different negative electrode binders were compared. In this example, as in Example 1, the battery was constructed under conditions that have a sufficient positive electrode capacity to exclude charge / discharge cycle deterioration due to the positive electrode in order to perform a charge / discharge cycle test on the negative electrode. In the charge / discharge cycle test, the charge / discharge current was 0.5 mA and the voltage range was 4.
This was performed by charging and discharging at a constant current between 0 V and 3.0 V.
【００２１】（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容量維持率を
示す。Table 2 shows the initial discharge capacity and the capacity retention ratio of the discharge capacity at the 50th cycle with respect to the initial discharge capacity.
【００２２】[0022]
【表２】 [Table 2]
【００２３】（表２）に示すように、導電剤としてアセ
チレンブラックを添加した負極を用いた従来例の電池
は、５０サイクル後の放電容量維持率が６０％程度まで
低下する。一方、導電剤として繊維状黒鉛を含む負極を
用いた本実施例の電池は、塩化ビニル−酢酸ビニル共重
合樹脂を用いた場合は、いずれも従来例の電池と比較し
放電容量が大きく向上し、また５０サイクル後の放電容
量維持率が８５％以上と充放電サイクル特性も向上して
いる。結着剤量が５重量％ならびに１０重量％のポリ塩
化ビニル樹脂単独を負極結着剤に用いた電池の初期放電
容量は塩化ビニル−酢酸ビニル共重合樹脂を用いた電池
に比べて若干大きいものの、５０サイクル目の放電容量
維持率は５重量％のものが６７％、１０重量％のものが
７１％まで低下する。二次電池においては、放電容量な
らびに容量維持率が大きい電極が望まれることから、塩
化ビニルと酢酸ビニルの共重合樹脂を結着剤とし、導電
剤として繊維状黒鉛を用いた負極が優れた特性を有して
いる。実施例の負極を用いた電池の大幅な放電容量の向
上は、導電剤としてアセチレンブラックを添加した場合
には集電がまだ不十分であったものが、導電剤としての
繊維状黒鉛を添加することによって充分な集電が得られ
るようになったためと考えられる。As shown in Table 2, in the conventional battery using the negative electrode to which acetylene black is added as a conductive agent, the discharge capacity retention rate after 50 cycles is reduced to about 60%. On the other hand, the battery of the present example using the negative electrode containing fibrous graphite as the conductive agent, when using a vinyl chloride-vinyl acetate copolymer resin, the discharge capacity was greatly improved as compared with the conventional battery. In addition, the discharge capacity retention rate after 50 cycles is 85% or more, and the charge / discharge cycle characteristics are also improved. Although the initial discharge capacity of a battery using a polyvinyl chloride resin alone having a binder amount of 5% by weight or 10% by weight as a negative electrode binder is slightly larger than that of a battery using a vinyl chloride-vinyl acetate copolymer resin, In the 50th cycle, the discharge capacity retention rate of 5% by weight is reduced to 67% and that of 10% by weight is reduced to 71%. In secondary batteries, an electrode with a large discharge capacity and a large capacity retention ratio is desired, so a negative electrode using a vinyl chloride-vinyl acetate copolymer resin as a binder and fibrous graphite as a conductive agent has excellent characteristics. have. Significant improvement in the discharge capacity of the battery using the negative electrode of the example, when acetylene black was added as a conductive agent, the current collection was still insufficient, but fibrous graphite as a conductive agent was added. It is considered that a sufficient current collection has been obtained.
【００２４】さらに、アスペクト比の異なる繊維状黒鉛
を導電剤として添加することを試みた。導電剤としてア
スペクト比２０の繊維状黒鉛を、結着剤として塩化ビニ
ル含有量が８５％の塩化ビニル−酢酸ビニル共重合樹脂
を用い、前記と同様の方法で活物質，導電剤，結着剤が
重量比で４５：４５：１０である負極を用いて電池を作
製したところ、５０サイクル目での容量維持率は８５％
で若干の効果がみられた。また、アスペクト比１５０の
繊維状黒鉛を用いた場合には、５０サイクル目での容量
維持率は９０％と（表１）のアスペクト比７５の場合
と、ほぼ同様の効果が得られた。以上のことより、アス
ペクト比２０以上の繊維状黒鉛を用いることが好ましい
と考えられる。Furthermore, an attempt was made to add fibrous graphite having a different aspect ratio as a conductive agent. Using a fibrous graphite having an aspect ratio of 20 as a conductive agent and a vinyl chloride-vinyl acetate copolymer resin having a vinyl chloride content of 85% as a binder, an active material, a conductive agent, and a binder in the same manner as described above. When a battery was manufactured using a negative electrode having a weight ratio of 45:45:10, the capacity retention ratio at the 50th cycle was 85%.
Had some effect. When fibrous graphite having an aspect ratio of 150 was used, the capacity retention ratio at the 50th cycle was 90%, and almost the same effect as in the case of the aspect ratio of 75 in Table 1 was obtained. From the above, it is considered preferable to use fibrous graphite having an aspect ratio of 20 or more.
【００２５】以上のように、アルミニウム合金粉末を負
極活物質として、塩化ビニル−酢酸ビニル共重合樹脂を
負極結着剤として用いる電池において、導電剤として繊
維状黒鉛を用いることにより、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ことを確認した。As described above, in a battery using an aluminum alloy powder as a negative electrode active material and a vinyl chloride-vinyl acetate copolymer resin as a negative electrode binder, by using fibrous graphite as a conductive agent, the charge / discharge cycle characteristics can be improved. It was confirmed that a non-aqueous electrolyte secondary battery having excellent characteristics could be produced.
【００２６】なお本実施例では、合金粉末として９４％
Ａｌ−６％Ｎｉで表わされるアルミニウム合金を用いた
場合について説明したが、同様にリチウムを吸蔵，放出
することのできる他のアルミニウム合金や、ウッド合金
等のアルミニウム以外の金属を主成分とする合金粉末を
用いた場合においても、ほぼ同様の効果が得られること
を確認した。In this embodiment, the alloy powder is 94%
Although the case where the aluminum alloy represented by Al-6% Ni is used has been described, similarly, other aluminum alloys capable of inserting and extracting lithium, and alloys mainly composed of metals other than aluminum, such as wood alloys, etc. It was confirmed that substantially the same effect was obtained when powder was used.
【００２７】以上の実施例では、正極活物質としてＬｉ
ＣｏＯ2を用いた場合について説明したが、Ｖ2Ｏ5，Ｃ
ｒ2Ｏ5，ＭｎＯ2，ＴｉＳ2，ＭｏＳ2などの遷移金属の
酸化物およびカルコゲン化合物を用いた場合において
も、ほぼ同様の効果が得られる。ただし、この場合には
負極活物質は予めリチウムを吸収した充電状態としてお
く必要がある。In the above embodiment, Li was used as the positive electrode active material.
Although the case where CoO 2 is used has been described, V 2 O 5 , C
Almost the same effects can be obtained even when an oxide of a transition metal such as r 2 O 5 , MnO 2 , TiS 2 or MoS 2 and a chalcogen compound are used. However, in this case, the negative electrode active material needs to be in a charged state in which lithium has been absorbed in advance.
【００２８】[0028]
【発明の効果】以上の実施例の説明で明らかなように本
発明の非水電解質二次電池用負極によれば、リチウムを
吸蔵，放出することのできる金属粉末もしくは合金粉末
を活物質とし、結着剤として塩化ビニル−酢酸ビニル共
重合樹脂を用いることにより、前記負極中に導電剤とし
て繊維状黒鉛を用いることで、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。As apparent from the above description of the embodiments, according to the negative electrode for a non-aqueous electrolyte secondary battery of the present invention, a metal powder or an alloy powder capable of occluding and releasing lithium is used as an active material, By using a vinyl chloride-vinyl acetate copolymer resin as a binder, and by using fibrous graphite as a conductive agent in the negative electrode, a negative electrode for a non-aqueous electrolyte secondary battery having excellent charge / discharge cycle characteristics is obtained. be able to.
【図１】本発明の実施例の非水電解質二次電池用負極を
用いた電池の縦断面図FIG. 1 is a longitudinal sectional view of a battery using a negative electrode for 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 ガスケット ６ 封口板 DESCRIPTION OF SYMBOLS 1 Positive electrode 2 Case 3 Separator 4 Negative electrode 5 Gasket 6 Sealing plate
───────────────────────────────────────────────────── 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４−294060（ＪＰ，Ａ) 特開 平４−286875（ＪＰ，Ａ) ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Toyoguchi ▲ Yoshitoku 1006 Kazuma Kadoma, Kadoma City, Osaka Prefecture Inside Matsushita Electric Industrial Co., Ltd. (56) References JP-A-4-294060 (JP, A) JP-A-4-286875 (JP, A)
Claims (2)
属粉末もしくは合金粉末を活物質とし、結着剤として塩
化ビニル−酢酸ビニル共重合樹脂を用いる非水電解質二
次電池の負極において、前記負極中に導電剤として繊維
状黒鉛を用いた非水電解質二次電池用負極。1. A negative electrode of a non-aqueous electrolyte secondary battery using a metal powder or an alloy powder capable of inserting and extracting lithium as an active material and using a vinyl chloride-vinyl acetate copolymer resin as a binder. A negative electrode for a non-aqueous electrolyte secondary battery in which fibrous graphite is used as a conductive agent.
合樹脂の塩化ビニルの含有量が９５モル％から６０モル
％である請求項１記載の非水電解質二次電池用負極。2. The negative electrode for a non-aqueous electrolyte secondary battery according to claim 1, wherein the vinyl chloride content of the vinyl chloride-vinyl acetate copolymer resin as a binder is 95 to 60 mol%.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3127321A JP2701586B2 (en) | 1991-05-30 | 1991-05-30 | 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 |
|---|---|---|---|
| JP3127321A JP2701586B2 (en) | 1991-05-30 | 1991-05-30 | Negative electrode for non-aqueous electrolyte secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04355052A JPH04355052A (en) | 1992-12-09 |
| JP2701586B2 true JP2701586B2 (en) | 1998-01-21 |
Family
ID=14957043
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3127321A Expired - Fee Related JP2701586B2 (en) | 1991-01-30 | 1991-05-30 | Negative electrode for non-aqueous electrolyte secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2701586B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1121731C (en) * | 1997-06-27 | 2003-09-17 | Lg化学株式会社 | Lithium ion secondary battery and mfg. method of same |
| KR100615161B1 (en) * | 1999-11-11 | 2006-08-25 | 삼성에스디아이 주식회사 | Composition for surface-treating electrode current collector of lithium secondary battery |
-
1991
- 1991-05-30 JP JP3127321A patent/JP2701586B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04355052A (en) | 1992-12-09 |
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