JPH04355052A - Negative electrode for nonaqueous electrolyte secondary battery - Google Patents
Negative electrode for nonaqueous electrolyte secondary batteryInfo
- Publication number
- JPH04355052A JPH04355052A JP3127321A JP12732191A JPH04355052A JP H04355052 A JPH04355052 A JP H04355052A JP 3127321 A JP3127321 A JP 3127321A JP 12732191 A JP12732191 A JP 12732191A JP H04355052 A JPH04355052 A JP H04355052A
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- electrolyte secondary
- vinyl chloride
- secondary battery
- charge
- 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.)
- Granted
Links
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 28
- 239000010439 graphite Substances 0.000 claims abstract description 28
- 229920005989 resin Polymers 0.000 claims abstract description 22
- 239000011347 resin Substances 0.000 claims abstract description 22
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 18
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 claims abstract description 17
- 239000006258 conductive agent Substances 0.000 claims description 29
- 239000011230 binding agent Substances 0.000 claims description 23
- 239000000843 powder Substances 0.000 claims description 16
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 12
- 229910045601 alloy Inorganic materials 0.000 claims description 12
- 239000000956 alloy Substances 0.000 claims description 12
- 239000011149 active material Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 238000009830 intercalation Methods 0.000 claims description 3
- 238000009831 deintercalation Methods 0.000 claims description 2
- 239000011883 electrode binding agent Substances 0.000 abstract description 8
- 239000003795 chemical substances by application Substances 0.000 abstract 2
- 230000014759 maintenance of location Effects 0.000 description 15
- 239000007773 negative electrode material Substances 0.000 description 9
- 229910000838 Al alloy Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- -1 Cr2O5 Chemical compound 0.000 description 7
- 239000006230 acetylene black Substances 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 238000007600 charging Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 229920006026 co-polymeric resin Polymers 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910032387 LiCoO2 Inorganic materials 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229910003092 TiS2 Inorganic materials 0.000 description 2
- 150000001786 chalcogen compounds Chemical class 0.000 description 2
- 238000010277 constant-current charging Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052961 molybdenite Inorganic materials 0.000 description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 2
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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)
Abstract
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 non-aqueous electrolyte secondary batteries.
【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
。BACKGROUND OF THE INVENTION Nonaqueous electrolyte secondary batteries using lithium, lithium alloys, or lithium compounds as negative electrodes are expected to have high voltage and high energy density, and much research has been conducted on them.
【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
，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。[0003] Until now, positive electrode active materials for non-aqueous electrolyte secondary batteries include LiCoO2, V2O5, Cr2O5, MnO2
, TiS2, MoS2, and other transition metal oxides and chalcogen compounds are known, and these have a layered or tunnel structure, and have a crystal structure in which lithium ions can enter and exit. On the other hand, metallic lithium has been widely studied as a negative electrode active material. However, during charging, lithium precipitates on the lithium surface in a dendritic form, resulting in a reduction in the charge/discharge rate or in contact with the positive electrode, resulting in an internal short circuit. As a means to solve these problems, metal or alloy plates or alloys that can store and release lithium, such as aluminum and aluminum alloys that can store and release lithium, suppress the dendritic growth of lithium. Studies are underway 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。[Problem to be solved by the invention] However, it is difficult to occlude lithium such as aluminum or aluminum alloy.
When a plate of metal or alloy that can emit gas is used as a negative electrode active material, repeated deep charging and discharging causes the active material to become finer and the electrode collapses, making it impossible to obtain sufficient charge-discharge cycle characteristics. Further, when using the metal or alloy powder as a negative electrode active material, a method of adding a binder to form a negative electrode is also being considered. Fluororesin, which is frequently used in positive electrodes, was also considered, but it accelerated the decomposition of the electrolyte during charging. For this reason, polyolefin binders such as polyethylene are used as binders for negative electrodes. However, even in this case, as a result of the expansion and contraction of the electrode due to intercalation and desorption of lithium, there is a drawback that insufficient active material retention and current collection occur, making it impossible to obtain sufficient cycle characteristics. The present invention solves these problems and aims to provide a negative electrode for a non-aqueous electrolyte secondary battery with 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。[Means for Solving the Problem] In order to solve this problem, the negative electrode for a nonaqueous electrolyte secondary battery of the present invention uses a metal powder or alloy powder that can absorb and release lithium as an active material, and a binder. A vinyl chloride-vinyl acetate copolymer resin is used as the negative electrode, and fibrous graphite is used 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 used as a binder has a vinyl chloride content of 95% to 60%.
It is preferable 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。[Operation] With this configuration, the negative electrode for non-aqueous electrolyte secondary batteries of the present invention uses powder of a metal or alloy, such as aluminum or aluminum alloy, that can occlude and release lithium as a binder for the active material. By using a vinyl chloride-vinyl acetate copolymer resin with high properties, the active material in the electrode is retained even after repeated charging and discharging.Furthermore, by adding fibrous graphite as a conductive agent, the active material in the electrode is retained even when the electrode expands. Also, 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, making it possible to construct a negative electrode for a non-aqueous electrolyte secondary battery having stable battery characteristics.
【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。EXAMPLES Hereinafter, negative electrodes for non-aqueous electrolyte secondary batteries according to examples of the present invention will be explained in detail with reference to the drawings, but the present invention is not limited to these examples.
【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 the negative electrode active material, vinyl chloride resin was used as the binder, and the content of vinyl chloride was 85 mol%.
A copolymer resin of 65 mol% vinyl chloride and vinyl acetate is used, and a fiber diameter of 0.1 μm to 0.3 μm is used as a conductive agent.
A negative electrode constructed using fibrous graphite with a ratio of fiber diameter to 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Ｌｉ
ＣｏＯ２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 is made by mixing 300 mesh pass aluminum powder, fibrous graphite as a conductive agent, and a binder in a weight ratio of 45:45:10 and 47.5:47.5:5. obtained the drug. 0.1 g of this negative electrode mixture was press-molded to a diameter of 17.5 mm at 2 tons/cm 2 to obtain a negative electrode. LiCoO2 is used as the positive electrode active material, and Li is used as the positive electrode.
CoO2, acetylene black as a conductive agent, and polytetrafluoroethylene resin as a binder are mixed in a weight ratio of 7:2:1, and 0.2 g of the resulting positive electrode mixture is heated to a diameter of 17 mm.
It was produced by press molding to 5 mm at 2 tons/cm2. In FIG. 1, a molded positive electrode 1 is placed in a case 2. A porous polypropylene film as a separator 3 was placed on the positive electrode 1 . The negative electrode 4 was crimped onto a sealing plate 6 equipped with a polypropylene gasket 5. A propylene carbonate solvent in which 1 mol/l of lithium perchlorate was dissolved was used as a non-aqueous electrolyte, and this was added onto the separator 3 and the negative electrode 4. Thereafter, the upper edge of the case 2 was caulked 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 produced in the same manner as 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 using different negative electrode binders and conductive agents were compared. In this example, in order to perform a charge/discharge cycle test on the negative electrode, the battery was constructed under conditions that the battery had a sufficient positive electrode capacity to exclude cycle deterioration due to the positive electrode. Charge/discharge cycle test: Charge/discharge current 0.5mA, voltage range 4.0V
This was carried out by constant current charging and discharging between 3.0V and 3.0V.
【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 of samples n was 50 for 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５０
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, conventional batteries using negative electrodes containing acetylene black as a conductive agent have a discharge capacity retention rate of 75% to 80% after 50 cycles.
decrease to a certain extent. On the other hand, the battery of this example using a negative electrode containing fibrous graphite as a conductive agent has a lower discharge than the conventional battery when vinyl chloride-vinyl acetate copolymer resin is used as a binder. Capacity has greatly improved, and 50
The cycle characteristics are also improved, with a discharge capacity retention rate of 85% or more after cycling. Although the initial discharge capacity of batteries using vinyl chloride resin alone as the negative electrode binder with a binder amount of 5% or 10% by weight is slightly larger than that of batteries using vinyl chloride-vinyl acetate copolymer resin, The discharge capacity retention rate at the 50th cycle decreases to 66% for 5% by weight and 69% for 10% by weight. In secondary batteries, since electrodes with high discharge capacity and capacity retention are desired, vinyl chloride-vinyl acetate copolymer resin is used as a binder.
A negative electrode using fibrous graphite as a conductive agent has excellent characteristics. The discharge capacity of batteries using the negative electrodes of these examples was improved by adding fibrous graphite as a conductive agent, although current collection was still insufficient when acetylene black was added as a conductive agent. This is thought to be due to the fact that sufficient current collection could be 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。Furthermore, an attempt was made to add fibrous graphite having different aspect ratios as a conductive agent. Using fibrous graphite with an aspect ratio of 20 as a conductive agent and a vinyl chloride-vinyl acetate copolymer resin with a vinyl chloride content of 85% as a binder, the active material, conductive agent, and binder were prepared in the same manner as above. When a battery was fabricated using a negative electrode with a weight ratio of 45:45:10, the capacity retention rate at the 50th cycle was 84%.
A slight effect was seen. Further, when fibrous graphite with an aspect ratio of 150 was used, the capacity retention rate at the 50th cycle was 89%, which was almost the same effect as in the case of an aspect ratio of 75 (Table 1). From the above, it is considered preferable to use fibrous graphite with 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 that uses aluminum powder as the negative electrode active material and vinyl chloride-vinyl acetate copolymer resin as the negative electrode binder, the use of fibrous graphite as the conductive agent improves the charge-discharge cycle characteristics. It was confirmed that an excellent non-aqueous electrolyte secondary battery could be produced.
【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。[0017] In the example, the case where aluminum was used as the metal powder was explained, but it is also possible to use tin, lead, indium, or bismuth powder, which can absorb and release lithium and form an alloy with lithium. It was confirmed that almost the same effect could be obtained.
【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。(Example 2) In this example, 96%
One in which aluminum alloy powder with a composition expressed by Al-6%Ni is used as a negative electrode active material and vinyl chloride resin is used as a binder, and vinyl chloride and vinyl acetate with a vinyl chloride content of 85 mol% and 65 mol%. Using a copolymer resin of
A negative electrode constructed using fibrous graphite will be explained.
【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Ｌ
ｉＣｏＯ２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 made of 96% Al with a 300 mesh pass.
-6% Ni aluminum alloy powder, fibrous graphite as a conductive agent, and binder in a weight ratio of 45:45:10 and 4
A negative electrode mixture was obtained by mixing at a ratio of 7.5:47.5:5:5. 0.1 g of this negative electrode mixture was press-molded to a diameter of 17.5 mm at 2 tons/cm 2 to obtain a negative electrode. L in the positive electrode active material
A positive electrode was produced using iCoO2 under the same conditions as in Example 1. The battery was also 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 produced in the same manner as 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 using different negative electrode binders were compared. In this example, as in Example 1, in order to conduct a charge/discharge cycle test on the negative electrode, the battery was constructed under conditions that the positive electrode capacity was sufficient to exclude charge/discharge cycle deterioration due to the positive electrode. The charge/discharge cycle test was conducted using a charge/discharge current of 0.5 mA and a voltage range of 4.
．． This was carried out by constant current charging and discharging between 0V and 3.0V.
【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７
１％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 a negative electrode to which acetylene black was added as a conductive agent, the discharge capacity retention rate after 50 cycles decreased to about 60%. On the other hand, in the batteries of this example using a negative electrode containing fibrous graphite as a conductive agent, when vinyl chloride-vinyl acetate copolymer resin was used, the discharge capacity was greatly improved compared to conventional batteries. Moreover, 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 batteries using polyvinyl chloride resin alone as the negative electrode binder with a binder amount of 5% or 10% by weight is slightly larger than that of batteries using vinyl chloride-vinyl acetate copolymer resin, , the discharge capacity retention rate at the 50th cycle was 67% for the 5% by weight product and 7% for the 10% by weight product.
It drops to 1%. In secondary batteries, electrodes with high discharge capacity and capacity retention are desired, so a negative electrode that uses a copolymer resin of vinyl chloride and vinyl acetate as a binder and fibrous graphite as a conductive agent has excellent characteristics. have. The significant improvement in discharge capacity of the battery using the negative electrode of the example was due to the fact that current collection was still insufficient when acetylene black was added as a conductive agent, but when fibrous graphite was added as a conductive agent. This is thought to be due to the fact that sufficient current collection could be 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 different aspect ratios as a conductive agent. Using fibrous graphite with an aspect ratio of 20 as a conductive agent and a vinyl chloride-vinyl acetate copolymer resin with a vinyl chloride content of 85% as a binder, the active material, conductive agent, and binder were prepared in the same manner as above. When a battery was fabricated using a negative electrode with a weight ratio of 45:45:10, the capacity retention rate at the 50th cycle was 85%.
A slight effect was seen. Further, when fibrous graphite with an aspect ratio of 150 was used, the capacity retention rate at the 50th cycle was 90%, which was almost the same effect as in the case with an aspect ratio of 75 (Table 1). From the above, it is considered preferable to use fibrous graphite with 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 that uses aluminum alloy powder as the negative electrode active material and vinyl chloride-vinyl acetate copolymer resin as the negative electrode binder, the use of fibrous graphite as the conductive agent improves the charge-discharge cycle characteristics. It was confirmed that it was possible to create a non-aqueous electrolyte secondary battery with excellent performance.
【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 example, 94% of alloy powder was used.
Although we have explained the case where an aluminum alloy represented by Al-6%Ni is used, other aluminum alloys that can similarly absorb and release lithium, and alloys whose main component is a metal other than aluminum, such as wood alloy, may also be used. It was confirmed that almost the same effect can be obtained even when powder is 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，
Ｃｒ２Ｏ５，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 embodiments, Li was used as the positive electrode active material.
Although we have explained the case using CoO2, V2O5,
Almost the same effect can be obtained even when transition metal oxides such as Cr2O5, MnO2, TiS2, MoS2 and chalcogen compounds are used. However, in this case, it is necessary to bring the negative electrode active material into a charged state in which it has absorbed lithium 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。Effects of the Invention As is clear 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 alloy powder capable of intercalating and deintercalating 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] A vertical cross-sectional view of a battery using a negative electrode for a non-aqueous electrolyte secondary battery according to an example 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 1 Positive electrode 2 Case 3 Separator 4 Negative electrode 5 Gasket 6 Sealing plate
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 alloy powder capable of intercalating and deintercalating lithium as an active material and a vinyl chloride-vinyl acetate copolymer resin as a binder, the negative electrode comprising: A negative electrode for non-aqueous electrolyte secondary batteries that uses fibrous graphite 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 the binder is from 95 mol% 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 true JPH04355052A (en) | 1992-12-09 |
| JP2701586B2 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) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002507313A (en) * | 1997-06-27 | 2002-03-05 | エルジー・ケミカル・リミテッド | Lithium ion secondary battery and method of manufacturing the 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
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002507313A (en) * | 1997-06-27 | 2002-03-05 | エルジー・ケミカル・リミテッド | Lithium ion secondary battery and method of manufacturing the same |
| KR100615161B1 (en) * | 1999-11-11 | 2006-08-25 | 삼성에스디아이 주식회사 | Composition for surface-treating electrode current collector of lithium secondary battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2701586B2 (en) | 1998-01-21 |
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