JPH08138653A - Non-aqueous electrolyte secondary battery - Google Patents
Non-aqueous electrolyte secondary batteryInfo
- Publication number
- JPH08138653A JPH08138653A JP6279119A JP27911994A JPH08138653A JP H08138653 A JPH08138653 A JP H08138653A JP 6279119 A JP6279119 A JP 6279119A JP 27911994 A JP27911994 A JP 27911994A JP H08138653 A JPH08138653 A JP H08138653A
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- battery
- negative electrode
- tin oxide
- stainless steel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、非水電解液二次電池
の、特にその負極に用いる物質に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a substance used for a non-aqueous electrolyte secondary battery, especially for its negative electrode.
【０００２】[0002]
【従来の技術】非水電解液二次電池は、小型、軽量で、
かつ高エネルギー密度を有するため、機器のポータブル
化、コードレス化が進む現在、その期待は高まってい
る。2. Description of the Related Art Non-aqueous electrolyte secondary batteries are small and lightweight,
In addition, since it has a high energy density, the expectation is increasing at present with the progress of portable and cordless devices.
【０００３】従来、非水電解液二次電池用の正極活物質
としてＬｉＣｏＯ2、ＬｉＮｉＯ2等のリチウム含有金属
酸化物が提案されている。一方、負極としては金属リチ
ウムやリチウム合金、またはリチウムを吸蔵・放出する
ことができる黒鉛材料などが提案されている。Conventionally, lithium-containing metal oxides such as LiCoO 2 and LiNiO 2 have been proposed as positive electrode active materials for non-aqueous electrolyte secondary batteries. On the other hand, as the negative electrode, metallic lithium, a lithium alloy, or a graphite material capable of inserting and extracting lithium has been proposed.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、金属リ
チウムを負極に用いた電池では、充電時に負極板表面に
金属リチウムが針状結晶となって析出し、この針状結晶
がセパレーターを突き破って、正極と接触して内部短絡
を起こすことがあった。また、負極に黒鉛材料を用いた
場合には、極板表面で電解液の分解によるガス発生が起
こり、電池内部の圧力が増加し、その結果、電解液の漏
液の原因となることがあった。本発明は、このような課
題を解決するもので、負極表面で金属リチウムが針状に
析出することを防止するとともに、電解液の分解による
ガス発生を防止することができる負極を用いた非水電解
液二次電池を提供するものである。However, in a battery using metallic lithium in the negative electrode, metallic lithium is deposited as needle-like crystals on the surface of the negative electrode plate during charging, and the needle-like crystals pierce the separator to cause a positive electrode. May come into contact with and cause an internal short circuit. In addition, when a graphite material is used for the negative electrode, gas is generated due to decomposition of the electrolytic solution on the surface of the electrode plate, and the pressure inside the battery increases, which may result in leakage of the electrolytic solution. It was The present invention is to solve such a problem, non-aqueous using a negative electrode that can prevent the metal lithium is deposited in a needle shape on the negative electrode surface, and can also prevent gas generation due to decomposition of the electrolytic solution. An electrolyte secondary battery is provided.
【０００５】[0005]
【課題を解決するための手段】これらの課題を解決する
ために本発明の非水電解液二次電池は、負極に一般式Ｌ
ｉxＳｎＯy（２≦ｘ≦８，３≦ｙ≦６）で表されるリチ
ウム含有スズ酸化物を用いるものである。In order to solve these problems, the non-aqueous electrolyte secondary battery of the present invention has a negative electrode of the general formula L
The lithium-containing tin oxide represented by i x SnO y (2 ≦ x ≦ 8, 3 ≦ y ≦ 6) is used.
【０００６】[0006]
【作用】本構成では負極にＬｉxＳｎＯy（２≦ｘ≦８，
３≦ｙ≦６）を用いているので、負極と電解液との反応
を防止して電解液の分解によるガスの発生を防止できる
とともに、スズ酸化物はリチウムイオンを取り込みやす
いことにより負極板上に針状リチウムが析出することを
防止することができる。In this structure, Li x SnO y (2 ≦ x ≦ 8,
Since 3 ≦ y ≦ 6) is used, the reaction between the negative electrode and the electrolytic solution can be prevented, and the generation of gas due to the decomposition of the electrolytic solution can be prevented, and the tin oxide can easily take in lithium ions, so that the negative electrode plate It is possible to prevent acicular lithium from precipitating.
【０００７】[0007]
【実施例】以下、図面とともに本発明の実施例を説明す
る。Embodiments of the present invention will be described below with reference to the drawings.
【０００８】図１に本発明の試験用コイン形非水電解液
二次電池の縦断面図を示す。図において１は耐有機電解
液性のステンレス鋼板を加工した電池ケース、２は同材
料の封口板、３は同材料の集電体で、ケース１の内面に
スポット溶接されている。４は金属リチウムで、封口板
２の内部に圧着されている。５は、ＬｉＯＨとＳｎＯ 2
を重量比８：１で混合し、窒素または空気雰囲気下にお
いて１０００℃で合成したＬｉxＳｎＯy（２≦ｘ≦８，
３≦ｙ≦６）８８重量部に、カーボンブラック６重量部
および結着材であるポリ４フッ化エチレン樹脂粉末６重
量部を混合した合剤を所定量、集電体３上に成型したも
のである。６は微孔性のポリプロピレン製セパレータ、
７はポリプロピレン製絶縁ガスケットである。FIG. 1 shows a coin-type non-aqueous electrolytic solution for a test according to the present invention.
The longitudinal cross-sectional view of a secondary battery is shown. In the figure, 1 is organic electrolysis resistant
Battery case made of liquid stainless steel plate, 2 is the same material
Sealing plate 3 is a collector made of the same material, and is attached to the inner surface of case 1.
It is spot welded. 4 is metallic lithium, sealing plate
It is crimped inside 2. 5 is LiOH and SnO 2
At a weight ratio of 8: 1 and mixed under a nitrogen or air atmosphere.
Li synthesized at 1000 ° CxSnOy(2 ≦ x ≦ 8,
3 ≦ y ≦ 6) 88 parts by weight, carbon black 6 parts by weight
And 6 layers of polytetrafluoroethylene resin powder as a binder
A predetermined amount of the mixture mixed with the parts was molded on the current collector 3.
Of. 6 is a microporous polypropylene separator,
7 is a polypropylene insulating gasket.
【０００９】電解液には、炭酸エチレンと１、３−ジメ
トキシエタンの等体積混合溶媒に溶質として過塩素酸リ
チウムを１ｍｏｌ／ｌ溶解したものを用いた。この電池
の寸法は直径２０、電池総高１．６ｍｍとした。The electrolyte used was a solvent in which 1 mol / l of lithium perchlorate was dissolved as a solute in a mixed solvent of ethylene carbonate and 1,3-dimethoxyethane in an equal volume. The battery had a diameter of 20 and a total battery height of 1.6 mm.
【００１０】この電池を用いて、２０℃において電流密
度を１．０ｍＡ／ｃｍ2とし、電圧２．０Ｖから０Ｖの
範囲で充放電試験を行った。その結果を図２に示す。Using this battery, a charge / discharge test was carried out at a voltage of 2.0 V to 0 V at a current density of 1.0 mA / cm 2 at 20 ° C. The result is shown in FIG.
【００１１】図２に示したように、ＬｉxＳｎＯyの放電
容量は約３２０ｍＡｈ／ｇであった。As shown in FIG. 2, the discharge capacity of Li x SnO y was about 320 mAh / g.
【００１２】次に、ガス発生の定量には、図３に示すよ
うな電池を構成して評価を行った。図３において、８は
前記合剤をステンレス鋼製のネットに成型した作用極で
あり、９は金属リチウムをステンレス鋼製のネットに圧
着した対極であり、１０は発生したガス量を定量するた
めのガラス管であり、微量の電解液で管をふさいであ
る。また、作用極８と対極９を前記電解液中に入れてい
る。Next, for quantitative determination of gas generation, a battery as shown in FIG. 3 was constructed and evaluated. In FIG. 3, 8 is a working electrode formed by molding the mixture into a stainless steel net, 9 is a counter electrode in which metallic lithium is pressure-bonded to a stainless steel net, and 10 is for quantifying the amount of generated gas. This is a glass tube, and the tube is covered with a small amount of electrolyte. Further, the working electrode 8 and the counter electrode 9 are put in the electrolytic solution.
【００１３】また、ＬｉxＳｎＯyの代わりに黒鉛を用い
た以外は本発明と同様の電池を構成した。A battery similar to that of the present invention was constructed except that graphite was used instead of Li x SnO y .
【００１４】これらの電池を用いて、電流密度０．５ｍ
Ａ／ｃｍ2で充電した際に発生するガスの量を測定し
た。この結果を（表１）に示す。Using these batteries, a current density of 0.5 m
The amount of gas generated when charged at A / cm 2 was measured. The results are shown in (Table 1).
【００１５】[0015]
【表１】 [Table 1]
【００１６】（表１）に示したように、黒鉛を用いた場
合には１２０分後１ｇあたり０．６ｃｃのガスが発生し
たのに対し、ＬｉxＳｎＯyを用いた場合では、ガスの発
生量は１ｇあたり０．１ｃｃであり、さらにＬｉxＳｎ
Ｏyを用いたものでは充電経過後、電極表面状に針状結
晶は確認されなかった。As shown in (Table 1), when graphite was used, 0.6 cc of gas was generated per 1 g after 120 minutes, whereas when Li x SnO y was used, gas was generated. The amount is 0.1 cc per 1 g, and Li x Sn
In the case of using O y , needle-like crystals were not confirmed on the surface of the electrode after charging was completed.
【００１７】また、ＬｉxＳｎＯy（２≦ｘ≦８，３≦ｙ
≦６）はＬｉ2ＳｎＯ3の組成が高温でも安定しているも
のであるが、ＬｉＯＨとＳｎＯ2を重量比８：１にして
合成したＬｉ8ＳｎＯ6の組成まで結晶が形成され、上記
のような効果を得ることができる。Further, Li x SnO y (2≤x≤8, 3≤y
In the case of ≦ 6), the composition of Li 2 SnO 3 is stable even at high temperature, but crystals are formed up to the composition of Li 8 SnO 6 synthesized with LiOH and SnO 2 at a weight ratio of 8: 1, and Such an effect can be obtained.
【００１８】なお、ＬｉxＳｎＯyの合成に関しては、Ｌ
ｉＯＨの代わりにＬｉ2ＣＯ3，ＬｉＮＯ3等のリチウム
塩を用いても良く、またＳｎＯ2の代わりにＳｎＯ等の
スズ塩を用いても良い。また、ＬｉxＳｎＯyを用いた負
極は、ＬｉＣｏＯ2，ＬｉＮｉＯ2，ＬｉＭｎ2Ｏ4などの
正極活物質や本実施例以外の有機電解液と組み合わせて
も、負極表面に針状結晶が発生することを防止できると
ともに電解液の分解によるガスの発生を防止できる。Regarding the synthesis of Li x SnO y , L
A lithium salt such as Li 2 CO 3 or LiNO 3 may be used in place of iOH, and a tin salt such as SnO may be used in place of SnO 2 . Further, when the negative electrode using Li x SnO y is combined with a positive electrode active material such as LiCoO 2 , LiNiO 2 , LiMn 2 O 4 or an organic electrolytic solution other than this example, needle-like crystals are generated on the negative electrode surface. It is possible to prevent this and also to prevent the generation of gas due to the decomposition of the electrolytic solution.
【００１９】[0019]
【発明の効果】本発明によれば、一般式ＬｉxＳｎＯ
y（２≦ｘ≦８，３≦ｙ≦６）で表わされるリチウム含
有スズ酸化物を負極に用いているので、電解液と負極と
の反応に起因したガスの発生や負極表面での針状リチウ
ムの析出を防止することができ、高容量で充放電特性に
優れた非水電解液二次電池を提供できる。According to the present invention, the general formula Li x SnO
Since the lithium-containing tin oxide represented by y (2 ≦ x ≦ 8, 3 ≦ y ≦ 6) is used for the negative electrode, gas is generated due to the reaction between the electrolytic solution and the negative electrode and needle-shaped on the negative electrode surface. It is possible to provide a non-aqueous electrolyte secondary battery which can prevent lithium from being deposited, have a high capacity, and have excellent charge / discharge characteristics.
【図１】本発明のコイン形電池の縦断面図FIG. 1 is a vertical sectional view of a coin-type battery of the present invention.
【図２】同電池の充放電電気量を示す図FIG. 2 is a diagram showing charge and discharge electricity of the battery.
【図３】負極のガス発生量を測定する電池を示す図FIG. 3 is a diagram showing a battery for measuring a gas generation amount of a negative electrode.
１ 電池ケース ２ 封口板 ３ 集電体 ４ 金属リチウム ５ 合剤 ６ セパレータ ７ ガスケット ８ 作用極 ９ 対極 １０ ガラス管 1 Battery Case 2 Sealing Plate 3 Current Collector 4 Metal Lithium 5 Mixture 6 Separator 7 Gasket 8 Working Electrode 9 Counter Electrode 10 Glass Tube
Claims (1)
Ｏy（２≦ｘ≦８，３≦ｙ≦６）で表されるリチウム含
有スズ酸化物を用いた負極とからなる非水電解液二次電
池。1. A nonaqueous electrolytic solution, a positive electrode, and a general formula Li x Sn.
A non-aqueous electrolyte secondary battery comprising a negative electrode using a lithium-containing tin oxide represented by O y (2 ≦ x ≦ 8, 3 ≦ y ≦ 6).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6279119A JPH08138653A (en) | 1994-11-14 | 1994-11-14 | Non-aqueous electrolyte secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6279119A JPH08138653A (en) | 1994-11-14 | 1994-11-14 | Non-aqueous electrolyte secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08138653A true JPH08138653A (en) | 1996-05-31 |
Family
ID=17606699
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6279119A Pending JPH08138653A (en) | 1994-11-14 | 1994-11-14 | Non-aqueous electrolyte secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08138653A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000033399A1 (en) * | 1998-11-30 | 2000-06-08 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous electrolyte secondary cell |
| KR100439739B1 (en) * | 2002-03-18 | 2004-07-12 | 한국과학기술연구원 | Coin type lithium polymer battery |
-
1994
- 1994-11-14 JP JP6279119A patent/JPH08138653A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000033399A1 (en) * | 1998-11-30 | 2000-06-08 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous electrolyte secondary cell |
| US6410188B1 (en) | 1998-11-30 | 2002-06-25 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous electrolyte secondary cell |
| KR100439739B1 (en) * | 2002-03-18 | 2004-07-12 | 한국과학기술연구원 | Coin type lithium polymer battery |
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