JP2679447B2 - Negative electrode for non-aqueous electrolyte secondary battery - Google Patents
Negative electrode for non-aqueous electrolyte secondary batteryInfo
- Publication number
- JP2679447B2 JP2679447B2 JP3137414A JP13741491A JP2679447B2 JP 2679447 B2 JP2679447 B2 JP 2679447B2 JP 3137414 A JP3137414 A JP 3137414A JP 13741491 A JP13741491 A JP 13741491A JP 2679447 B2 JP2679447 B2 JP 2679447B2
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- resin
- vinyl chloride
- binder
- 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.)
- 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
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、最近開発が盛んに行わ
れてい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, which has been actively developed recently.
【０００２】[0002]
【従来の技術】リチウム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 as a negative electrode are expected to have high energy density at high voltage, and many studies have been conducted.
【０００３】非水電解質二次電池の正極活物質として
は、ＬｉＣｏＯ2，Ｖ2Ｏ5，Ｃｒ2Ｏ5，ＭｎＯ2，ＴｉＳ
2，ＭｏＳ2などの遷移金属の酸化物およびカルコゲン化
合物が知られている。これらは層状もしくはトンネル構
造の結晶で、充電および放電によりリチウムイオンがこ
れら結晶に出入りできる構造である。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。しかしな
がら充電時にリチウム表面に樹枝状結晶のリチウムが析
出し易く、充放電効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
題を解決する手段として、リチウムの樹枝状結晶の生成
を抑制するため、リチウムを吸蔵，放出することができ
るアルミニウムやアルミニウム合金などの単体金属およ
びその合金の板もしくは粉末を負極活物質保持体に用い
る検討がなされてきた。As positive electrode active materials for non-aqueous electrolyte secondary batteries, LiCoO 2 , V 2 O 5 , Cr 2 O 5 , MnO 2 and TiS are used.
Oxides of transition metals such as 2 , MoS 2 and chalcogen compounds are known. These are layered or tunnel-structured crystals in which lithium ions can enter and leave these crystals by charging and discharging. On the other hand, lithium metal has been widely studied as a negative electrode active material. However, there is a problem that dendrite lithium is likely to be deposited on the lithium surface during charging, resulting in a decrease in charge / discharge efficiency or an internal short circuit in contact with the positive electrode. As a means for solving such a problem, in order to suppress the formation of dendrites of lithium, a single metal such as aluminum or an aluminum alloy capable of inserting and extracting lithium and a plate or a powder of the alloy are used as the negative electrode active material. Studies have been made for use as a holder.
【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単体金属およびその合金の板を負
極活物質保持体として用いた場合、深い充放電を繰り返
すと活物質保持体の微細化が起こって負極が崩れてしま
い充分な充放電サイクル特性が得られなかった。また、
前記単体金属およびその合金の粉末を負極活物質保持体
として用いるに当たり、結着剤を添加し負極を形成する
方法も検討されている。当初正極で頻繁に使用されてい
るフッ素樹脂が検討されたが、電解液の分解を促進した
りリチウムと反応してしまう問題があった。このため負
極用結着剤としてはポリエチレンなどのポリオレフィン
系の合成樹脂が用いられていた。しかしながらこの場合
においてもリチウムの吸蔵、放出に伴う負極の膨張、収
縮により、活物質の保持性や導電性の不良が生じ充分な
充放電サイクル特性が得られないという欠点を有してい
た。そこで、より結着力の強い塩化ビニル樹脂を用いる
ことが検討されたが、塩化ビニル樹脂だけでは、金属製
の芯材等からなる集電体に対する接着力がまだ不十分な
ため、集電体上に結着剤として塩化ビニル樹脂を含むペ
ースト状の負極合剤を塗布してシート状の電極を形成さ
せた場合、負極合剤層が集電体から剥離して導電性不良
を起こし易い。本発明はこのような問題を解決し、充放
電サイクル特性が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, it absorbs lithium such as aluminum or aluminum alloy,
When a plate of a single metal or its alloy that can be released is used as the negative electrode active material holder, repeated deep charge and discharge causes the active material holder to become finer and the negative electrode collapses, resulting in sufficient charge / discharge cycle characteristics. Was not obtained. Also,
When using the powder of the elemental metal or its alloy as a negative electrode active material holder, a method of adding a binder to form a negative electrode has also been studied. Initially, a fluororesin frequently used for the positive electrode was studied, but there was a problem that it accelerates decomposition of the electrolytic solution or reacts with lithium. Therefore, a polyolefin-based synthetic resin such as polyethylene has been used as the binder for the negative electrode. However, even in this case, the negative electrode expands and contracts due to the occlusion and release of lithium, which results in poor retention of the active material and poor conductivity, resulting in insufficient charge / discharge cycle characteristics. Therefore, the use of vinyl chloride resin, which has a stronger binding force, was examined, but vinyl chloride resin alone was
The adhesive force is still insufficient for the current collector made from the core material or the like of
Therefore, by applying a paste-like negative electrode mixture containing a vinyl chloride resin as a binder on a current collector if to form a sheet-like electrode, the conductive negative electrode mixture layer is peeled off from the current collector Easy to cause defects. An object of the present invention is to solve such problems and provide a negative electrode for a non-aqueous electrolyte secondary battery having excellent charge / discharge cycle characteristics.
【０００５】[0005]
【課題を解決するための手段】本発明は、上記目的を達
成するために、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、金属硫化物または金属酸化物から
なる活物質保持体、および結着剤を含有する負極合剤
と、前記負極合剤を保持する集電体を具備する非水電解
質二次電池の負極において、前記結着剤として、塩化ビ
ニル−酢酸ビニル共重合樹脂、酢酸ビニル樹脂およびブ
チラール樹脂からなる群より選ばれた少なくとも一種と
塩化ビニル樹脂との混合物を用いるものである。In order to achieve the above-mentioned object, the present invention uses a metal powder, a carbon material , a metal sulfide or a metal oxide capable of inserting and extracting lithium.
Negative electrode mixture containing active material holder and binder
And a non-aqueous electrolyte comprising a current collector holding the negative electrode mixture
In the negative electrode of a high quality secondary battery, the binder is vinyl chloride.
Nyl-vinyl acetate copolymer resin, vinyl acetate resin and vinyl
At least one selected from the group consisting of chiral resin
A shall with a mixture of vinyl chloride resin.
【０００６】[0006]
【作用】リチウムを吸蔵、放出することのできる単体の
金属およびその合金粉末、炭素材料、金属酸化物または
金属硫化物からなる活物質保持体、および結着剤を含有
する負極合剤において、前記結着剤に結着力の強い合成
樹脂を用いると、充放電を繰り返しても負極合剤中の導
電性が充分保持され、従来のような比較的少ない充放電
サイクル数で放電容量が低下することがなくなる。その
結果、この負極合剤を具備する非水電解質二次電池用負
極は、安定した電池特性を有することが可能となる。と
ころが、結着力の強い樹脂として塩化ビニル樹脂のみを
用いた場合、頑丈な負極合剤構造を形成することはでき
るが、この負極合剤は、集電体との接着性が不十分であ
り、集電体上にこの負極合剤ペーストを塗布しシート状
電極を形成した場合、集電体と負極合剤層間で剥離が生
じ、導電性が不十分となる。そこで、負極合剤に、塩化
ビニル樹脂とともに、金属板などに対して優れた接着性
を有する塩化ビニル−酢酸ビニル共重合樹脂、酢酸ビニ
ル樹脂またはブチラール樹脂を添加することにより、負
極合剤層と集電体との接着性を向上させると、充分な導
電性を得ることが可能となり、従来みられたような比較
的少ない充放電サイクル数で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
池用負極を提供することができる。[Function] A simple substance metal capable of inserting and extracting lithium and its alloy powder , carbon material , metal oxide or
Contains active material holder made of metal sulfide and binder
In the negative electrode mixture, when a synthetic resin having a strong binding force is used as the binder, the conductivity in the negative electrode mixture is sufficiently retained even if charging and discharging are repeated, and the number of charge and discharge cycles is relatively small as in the conventional case. in discharge capacity may turn without decrease. That
As a result, a negative electrode for a non-aqueous electrolyte secondary battery equipped with this negative electrode mixture was prepared.
Pole, becomes possible and Turkey for having a stable battery characteristics. However, when only vinyl chloride resin is used as the resin with strong binding force, it is not possible to form a sturdy negative electrode mixture structure.
That is, the negative electrode mixture, adhesion between the current collector is inadequate
Therefore , when this negative electrode material mixture paste is applied onto the current collector to form a sheet-like electrode, peeling occurs between the current collector and the negative electrode material mixture layer, resulting in insufficient conductivity. Therefore, in the negative electrode mixture, chloride
Excellent adhesion to metal plates with vinyl resin
Vinyl chloride-vinyl acetate copolymer resin having vinyl acetate
By adding Le resin or butyral resin and improve adhesion between the negative electrode mixture layer and the current collector, it is possible to obtain a sufficient conductivity and Do Ri, relatively small as Observed conventional prevents the discharge capacity in the charge-discharge cycles is lowered, it is possible to provide a stable negative electrode for nonaqueous electrolyte secondary batteries have a battery characteristics.
【０００７】[0007]
【実施例】以下、本発明について実施例により詳細に説
明するがこれら実施例に限定されるものではない。EXAMPLES The present invention will now be described in detail with reference to examples, but the invention is not limited to these examples.
【０００８】（実施例１）本実施例においては、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
極活物質保持体に、結着剤として塩化ビニル樹脂単独お
よび塩化ビニル樹脂に、それぞれ塩化ビニルの含有率が
６０モル％の塩化ビニル−酢酸ビニル共重合樹脂（以
下、塩ビ−酢ビと略記）を５０％添加したもの、および
酢酸ビニル樹脂２０％を添加したもの、またブチラール
樹脂を２０％添加したものを用いた負極で構成され電池
について説明する。また従来例として結着剤にポリエチ
レンを用いたものも比較して示す。Example 1 In this example, aluminum powder capable of occluding and releasing lithium was used as a negative electrode active material holder, and as a binder, vinyl chloride resin alone and vinyl chloride resin, respectively. Of vinyl chloride-vinyl acetate copolymer resin (hereinafter abbreviated as vinyl chloride-vinyl acetate) having a content of 60 mol% of 50%, vinyl acetate resin of 20%, butyral resin of 20% A battery composed of a negative electrode using the added one will be described. In addition, as a conventional example, a comparative example using polyethylene as a binder is also shown.
【０００９】負極は、３００メッシュ通過した活物質保
持体のアルミニウム粉末と導電剤としてのアセチレンブ
ラックと予め溶剤で溶解した前記結着剤とを重量比で７
０：２０：１０ならびに７０：２５：５の割合で練合し
て得られた負極合剤ペーストを、厚さ０．０２mmの銅基
板上に塗布した。乾燥後、２トン／cm2でプレスし厚さ
０．０８mmとし、これを直径１７．５mmの円盤状に打ち
抜き負極とした。正極は活物質の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０．１ｇを、直径１７．５mmに２トン／
cm2でプレス成型して作製した。試作した電池の断面図
を図１を示す。図１において、成型した正極１をケース
２におき、正極１の上にさらにセパレータの微孔性ポリ
プロピレンフィルム３を置いた。負極４を、ポリプロピ
レン製ガスケット５を外周に嵌着した封口板６の内面中
央部に圧着した。非水電解質として、１モル／１の過塩
素酸リチウムのプロピレンカーボネート溶液を用い、こ
れをセパレータ上および負極上に滴加した。その後封口
して電池を完成させた。The negative electrode has a weight ratio of the aluminum powder of the active material-holding material which has passed through 300 mesh, acetylene black as a conductive agent, and the binder previously dissolved in a solvent in a weight ratio of 7%.
The negative electrode mixture paste obtained by kneading at a ratio of 0:20:10 and 70: 25: 5 was applied on a copper substrate having a thickness of 0.02 mm. After drying, it was pressed at 2 ton / cm 2 to a thickness of 0.08 mm, which was punched out into a disk shape having a diameter of 17.5 mm to obtain a negative electrode. The positive electrode was prepared by mixing LiCoO 2 as an active material, acetylene black as a conductive agent, and polytetrafluoroethylene resin as a binder in a weight ratio of 7: 2: 1 to obtain 0.1 g of a positive electrode mixture obtained. 2 tons / diameter of 17.5 mm
It was produced by press molding at cm 2 . A cross-sectional view of the prototype battery is shown in FIG. In FIG. 1, the molded positive electrode 1 was placed in the case 2, and the microporous polypropylene film 3 of the separator was further placed on the positive electrode 1. The negative electrode 4 was pressure-bonded to the center of the inner surface of the sealing plate 6 having the polypropylene gasket 5 fitted on the outer periphery. As a non-aqueous electrolyte, a 1 mol / 1 solution of lithium perchlorate in propylene carbonate was used, and this was added dropwise to the separator and the negative electrode. After that, the battery was sealed to complete the battery.
【００１０】なお従来例の負極結着剤にポリエチレンを
用いた電池も本実施例と同様の方法で作製した。A battery using polyethylene as the negative electrode binder in the conventional example was also manufactured by the same method as in this example.
【００１１】ただし、塩化ビニル樹脂単独を結着剤とし
て用いた場合には、負極合剤が銅基板から剥離してしま
い電池を作製することができなかった。However, when the vinyl chloride resin alone was used as the binder, the negative electrode mixture was peeled off from the copper substrate, and the battery could not be manufactured.
【００１２】以上、塩化ビニル樹脂単独を結着剤として
用いた場合を除く、８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、負極の完全充放電
によるサイクル試験を行うため、充放電サイクルによる
電池容量が正極で劣化しないように充分大きい正極容量
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、２０℃で充放電とも０．５ｍＡ定電流で４．０Ｖま
で充電したのち３．０Ｖまで放電することを繰り返し
た。The charge / discharge cycle characteristics of eight types of batteries were compared with each other except for the case where the vinyl chloride resin alone was used as the binder. In this example, since the cycle test is performed by completely charging and discharging the negative electrode, the battery is constructed under the condition that the positive electrode has a sufficiently large positive electrode capacity so that the battery capacity due to the charge and discharge cycle does not deteriorate. In the charge / discharge cycle test, charging and discharging were repeated at 20 ° C. at a constant current of 0.5 mA to 4.0 V and then to 3.0 V.
【００１３】（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。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.
【００１４】[0014]
【表１】 [Table 1]
【００１５】（表１）に示されるように、結着剤にポリ
エチレン５重量％および１０重量％を含む負極を用いた
従来例の電池は、初期それぞれ３．７ｍＡｈおよび３．
６ｍＡｈの放電容量を示すが、充放電サイクルとともに
容量が低下し５０サイクル目の放電容量維持率が４０％
程度まで低下する。一方負極結着剤に塩化ビニル樹脂と
塩化ビニル−酢酸ビニル共重合樹脂、酢酸ビニル樹脂ま
たはブチラール樹脂との混合物を用いた本実施例の電池
はいずれも初期放電容量が従来例の電池と同等もしくは
それ以上を示し、また５０サイクル目の放電容量維持率
も７０％以上と充放電サイクル特性が向上している。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
い電池が望まれることから、本発明の結着剤は負極合剤
に適用して優れた特性を発揮できるといえる。[0015] (Table 1) as shown in the battery of the conventional example using a negative electrode containing polyethylene 5 wt% and 10 wt% as a binder, the initial respectively 3.7mAh and 3.
It shows a discharge capacity of 6 mAh, but the capacity decreases with charge and discharge cycles, and the discharge capacity retention rate at the 50th cycle is 40%.
To a degree. On the other hand, vinyl chloride resin is used as the negative electrode binder.
Vinyl chloride-vinyl acetate copolymer resin, vinyl acetate resin
In each of the batteries of this example using a mixture with a butyral resin, the initial discharge capacity was equal to or higher than that of the battery of the conventional example, and the discharge capacity retention ratio at the 50th cycle was 70% or more, that is, charge / discharge. Cycle characteristics are improved. Since the secondary battery is desired to have a large discharge capacity and a high capacity retention rate, it can be said that the binder of the present invention can be applied to a negative electrode mixture to exhibit excellent characteristics.
【００１６】以上のように、アルミニウム粉末を負極活
物質保持体に用いる非水電解質二次電池において、負極
結着剤に塩化ビニル樹脂と塩化ビニル−酢酸ビニル共重
合樹脂、酢酸ビニル樹脂またはブチラール樹脂との混合
物を用いることにより、充放電サイクル特性に優れた非
水電解質二次電池が作製できることを確認した。As described above, in the non-aqueous electrolyte secondary battery using aluminum powder as the negative electrode active material holder, the negative electrode binder is vinyl chloride resin and vinyl chloride-vinyl acetate copolymer.
By using a mixture with synthetic resin, vinyl acetate resin or butyral resin, it is possible to obtain a non- stable resin with excellent charge / discharge cycle characteristics.
It was confirmed that a water electrolyte secondary battery could be produced.
【００１７】なお実施例では、活物質保持体用金属粉末
としてアルミニウム，導電剤としてアセチレンブラック
の組み合わせで説明したが、同様にリチウムを吸蔵，放
出しリチウムと合金を形成することのできるスズ，鉛，
インジウム，ビスマス、及びこれらを主成分とする合金
やアルミニウム合金粉末と、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付記する。 （実施例２）本実施例においては、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保持体に、結
着剤に塩化ビニル樹脂単独および塩化ビニル樹脂にそれ
ぞれ塩化ビニルの含有率が６０モル％の塩化ビニル−酢
酸ビニル共重合樹脂（塩ビ−酢ビ）を５０％添加したも
の、酢酸ビニル樹脂２０％を添加したもの、およびブチ
ラール樹脂を２０％添加したものを用いた負極で構成し
た電池について説明する。また従来例として結着剤にポ
リエチレンを用いたものも示す。In the examples, the combination of aluminum as the metal powder for the active material holder and acetylene black as the conductive agent has been explained, but tin and lead capable of absorbing and releasing lithium and forming an alloy with lithium can be similarly used. ，
It is additionally noted that almost the same effect can be obtained with any combination of indium, bismuth, and an alloy or aluminum alloy powder containing these as a main component and graphite or carbon black as the conductive agent. (Example 2) In this example, a carbon material capable of occluding and releasing lithium is used as a negative electrode active material holder, a vinyl chloride resin alone as a binder, and a vinyl chloride resin content as a vinyl chloride resin. Consists of a negative electrode using one containing 50% of 60 mol% vinyl chloride-vinyl acetate copolymer resin (vinyl chloride-vinyl acetate), one containing 20% of vinyl acetate resin, and one containing 20% of butyral resin. The prepared battery will be described. Further, as a conventional example, the one using polyethylene as a binder is also shown.
【００１８】負極は、炭素材料と予め溶剤で溶解した前
記結着剤を重量比で９０：１０ならびに９５：５の割合
で混合し、得られた負極合剤ペーストを、厚さ０．０２
mmの銅基板上に塗布した。乾燥後、２トン／cm2でプレ
スし厚さ０．１７mmとし、これを直径１７．５mmの円盤
状に打ち抜き負極とした。正極は活物質にＬｉＣｏＯ 2
を用い、実施例１と同様の条件で作製した。電池の試作
も、実施例１と同様の条件で行った。The negative electrode is prepared by dissolving the carbon material and the solvent in advance.
90:10 and 95: 5 weight ratio of binder
And mix the resulting negative electrode mixture paste to a thickness of 0.02
It was applied on a copper substrate of mm. After drying, 2 ton / cmTwoPre
And a thickness of 0.17 mm, which is a disk with a diameter of 17.5 mm.
It was stamped out into a negative electrode. The active material of the positive electrode is LiCoO 2. Two
Was manufactured under the same conditions as in Example 1. Battery prototype
Also, the same conditions as in Example 1 were used.
【００１９】なお従来例である負極結着剤にポリエチレ
ンを用いた電池も本実施例と同様の方法で作製した。A battery using polyethylene as a negative electrode binder, which is a conventional example, was also manufactured by the same method as in this example.
【００２０】ただし、塩化ビニル樹脂単独を結着剤とい
て用いた場合には、負極合剤が銅基板から剥離してしま
い電池を作製することができなかった。However, when the vinyl chloride resin alone was used as the binder, the negative electrode mixture was peeled off from the copper substrate, and the battery could not be manufactured.
【００２１】以上、塩化ビニル樹脂単独を結着剤として
用いた場合を除く、８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
極の完全充放電によるサイクル試験を行うため、充放電
サイクルにより電池容量が正極で劣化しないように、充
分大きい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、２０℃で充放電とも０．５ｍＡ定
電流で、４．１Ｖまで充電し、３．０Ｖまで放電するこ
とを繰り返した。The charge / discharge cycle characteristics of eight kinds of batteries were compared with each other except for the case where the vinyl chloride resin alone was used as the binder. In this example, as in Example 1, a cycle test was performed by completely charging and discharging the negative electrode, and thus the battery was constructed under conditions having a sufficiently large positive electrode capacity so that the battery capacity would not deteriorate in the positive electrode due to the charge / discharge cycle. There is. In the charge / discharge cycle test, charging and discharging were repeated at 20 ° C. at a constant current of 0.5 mA to 4.1 V and then discharged to 3.0 V.
【００２２】（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.
【００２３】[0023]
【表２】 [Table 2]
【００２４】（表２）に示されるように、結着剤にポリ
エチレン５重量％および１０重量％を含む負極を用いた
従来例の電池は、初期それぞれ３．２ｍＡｈおよび３．
１ｍＡｈの放電容量を示すが、充放電サイクルとともに
容量が低下し５０サイクル目の放電容量維持率が４０％
前後まで低下する。一方負極結着剤に塩化ビニル樹脂と
塩化ビニル−酢酸ビニル共重合樹脂、酢酸ビニル樹脂ま
たはブチラール樹脂との混合物を用いた本実施例の電池
はいずれも初期放電容量が従来例の電池と同等もしくは
それ以上を示し、また５０サイクル目の放電容量維持率
も７０％以上と充放電サイクル特性が向上している。本
発明の結着剤は負極合剤に適用して優れた特性を発揮す
るものといえる。[0024] (Table 2) as shown in the battery of the conventional example of using a negative electrode containing polyethylene 5 wt% and 10 wt% binder, initial respectively 3.2mAh and 3.
It shows a discharge capacity of 1 mAh, but the capacity decreases with charge and discharge cycles, and the discharge capacity retention rate at the 50th cycle is 40%.
It decreases to the front and back. On the other hand, vinyl chloride resin is used as the negative electrode binder.
Vinyl chloride-vinyl acetate copolymer resin, vinyl acetate resin
In each of the batteries of this example using a mixture with a butyral resin, the initial discharge capacity was equal to or higher than that of the battery of the conventional example, and the discharge capacity retention ratio at the 50th cycle was 70% or more, that is, charge / discharge. Cycle characteristics are improved. Binder of the present invention can be said to exhibit excellent properties by applying the negative electrode mixture.
【００２５】以上のように、炭素材料を負極活物質保持
体に用いる非水電解質二次電池において、負極結着剤に
塩化ビニル樹脂と塩化ビニル−酢酸ビニル共重合樹脂、
酢酸ビニル樹脂またはブチラール樹脂との混合物を用い
ることにより、充放電サイクル特性に優れた非水電解質
二次電池が作製できることを確認した。As described above, in the non-aqueous electrolyte secondary battery using the carbon material as the negative electrode active material holder, the negative electrode binder is vinyl chloride resin and vinyl chloride-vinyl acetate copolymer resin,
By using a mixture with vinyl acetate resin or butyral resin, a non-aqueous electrolyte with excellent charge-discharge cycle characteristics
It was confirmed that the secondary battery can be produced.
【００２６】なお本実施例では、負極活物質保持体とし
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、負極活物質保持体として期待されるＦ
ｅ2Ｏ3や、ＷＯ2やＴｉＳ2などの金属の酸化物や硫化物
についても、ほぼ同様の効果が得られることはいうまで
もない。In this example, the carbon material capable of inserting and extracting lithium was described as the negative electrode active material holder, but F expected as the negative electrode active material holder was described.
It goes without saying that substantially the same effects can be obtained with e 2 O 3 and oxides and sulfides of metals such as WO 2 and TiS 2 .
【００２７】[0027]
【発明の効果】以上のように、本発明によると、負極合
剤中の結着剤として、結着力の優れた塩化ビニル樹脂
と、金属板などに対して優れた接着性を有する塩化ビニ
ル−酢酸ビニル共重合樹脂、酢酸ビニル樹脂またはブチ
ラール樹脂の混合物を用いるので、負極合剤層と集電体
との接着性を向上させることができ、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シート状負極を
容易に得ることができる。As described above, according to the present invention , the negative electrode mixture is
Vinyl chloride resin with excellent binding strength as a binder in the agent
And vinyl chloride that has excellent adhesion to metal plates, etc.
-Vinyl acetate copolymer resin, vinyl acetate resin or buty
Since a mixture of RAL resin is used, the negative electrode mixture layer and the current collector
A sheet-shaped negative electrode for a non-aqueous electrolyte secondary battery having excellent charge-discharge cycle characteristics can be easily obtained.
【図１】本発明の実施例の電池の縦断面図FIG. 1 is a vertical sectional view of a 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 ７ 銅基板 1 Positive Electrode 2 Case 3 Separator 4 Negative Electrode 5 Gasket 6 Sealing Plate 7 Copper Substrate
───────────────────────────────────────────────────── フロントページの続き (72)発明者 美藤 靖彦 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 豊口 ▲よし▼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 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yasuhiko Mito 1006 Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. (72) Inventor Toyoguchi ▲ Yoshi ▼ Taku Instrument industry Co., Ltd.
Claims (1)
金属粉末、炭素材料、金属硫化物または金属酸化物から
なる活物質保持体、および結着剤を含有する負極合剤
と、前記負極合剤を保持する集電体を具備し、前記結着
剤が、塩化ビニル−酢酸ビニル共重合樹脂、酢酸ビニル
樹脂およびブチラール樹脂からなる群より選ばれた少な
くとも一種と塩化ビニル樹脂との混合物であることを特
徴とする非水電解質二次電池用負極。1. From a metal powder, a carbon material , a metal sulfide or a metal oxide capable of inserting and extracting lithium.
Negative electrode mixture containing active material holder and binder
And a current collector that holds the negative electrode mixture,
Agent is vinyl chloride-vinyl acetate copolymer resin, vinyl acetate
Resin selected from the group consisting of resins and butyral resins
Kutomo one a mixture der Rukoto nonaqueous electrolyte secondary battery negative electrode, wherein the vinyl chloride resin.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3137414A JP2679447B2 (en) | 1991-06-10 | 1991-06-10 | 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 |
|---|---|---|---|
| JP3137414A JP2679447B2 (en) | 1991-06-10 | 1991-06-10 | Negative electrode for non-aqueous electrolyte secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04363864A JPH04363864A (en) | 1992-12-16 |
| JP2679447B2 true JP2679447B2 (en) | 1997-11-19 |
Family
ID=15198080
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3137414A Expired - Fee Related JP2679447B2 (en) | 1991-01-30 | 1991-06-10 | Negative electrode for non-aqueous electrolyte secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2679447B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU6237794A (en) * | 1993-02-12 | 1994-08-29 | Valence Technology, Inc. | Electrodes for rechargeable lithium batteries |
| WO2014010570A1 (en) * | 2012-07-11 | 2014-01-16 | 日本電気株式会社 | Secondary cell |
-
1991
- 1991-06-10 JP JP3137414A patent/JP2679447B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04363864A (en) | 1992-12-16 |
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