JPH11185806A - Lithium ion battery - Google Patents
Lithium ion batteryInfo
- Publication number
- JPH11185806A JPH11185806A JP9347778A JP34777897A JPH11185806A JP H11185806 A JPH11185806 A JP H11185806A JP 9347778 A JP9347778 A JP 9347778A JP 34777897 A JP34777897 A JP 34777897A JP H11185806 A JPH11185806 A JP H11185806A
- Authority
- JP
- Japan
- Prior art keywords
- carbonate
- battery
- double bond
- lithium ion
- organic electrolyte
- 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
Classifications
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- 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
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- Carbon And Carbon Compounds (AREA)
- 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、リチウムイオン電池に
係わり、詳しくは保存特性及びサイクル特性の改善を目
的とした、有機電解液の改良に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithium ion battery, and more particularly to an improvement in an organic electrolyte for the purpose of improving storage characteristics and cycle characteristics.
【0002】[0002]
【従来の技術及び発明が解決しようとする課題】近年、
コークス、黒鉛等の炭素材料が、可撓性に優れること、
樹枝状の電析リチウムの成長に因る内部短絡の虞れが無
いことなどの理由から、従前の金属リチウムに代わるリ
チウムイオン電池の新しい負極材料として提案されてい
る。2. Description of the Related Art In recent years,
Coke, carbon material such as graphite, excellent in flexibility,
It has been proposed as a new negative electrode material for lithium ion batteries in place of conventional metal lithium because there is no risk of internal short circuit due to the growth of dendritic lithium.
【0003】このように、負極材料として炭素材料を用
いた電池では、有機電解液の種類により電池特性が大き
く変化することが知られている。この場合、有機電解液
にメチルエチルカーボネート等の非対称鎖状カーボネー
トを用いると、初期特性を向上させることができる。As described above, it is known that battery characteristics using a carbon material as a negative electrode material greatly change depending on the type of organic electrolyte. In this case, when an asymmetric chain carbonate such as methyl ethyl carbonate is used as the organic electrolyte, the initial characteristics can be improved.
【0004】しかしながら、炭素材料〔特に、格子面
(002)面におけるd値(d002 )が3.40Å未満
の黒鉛系炭素材料〕を負極材料として用い、且つ、メチ
ルエチルカーボネートを有機電解液の溶媒として用いた
場合には、長期保存或いは充放電サイクルを繰り返した
際、メチルエチルカーボネートが炭素材料から成る負極
表面上でエステル交換反応を起こすため、負極表面上に
不導体皮膜が形成される。このため、保存特性やサイク
ル特性が低下するという課題を有していた。However, a carbon material (particularly, a graphite-based carbon material having a d value (d 002 ) of less than 3.40 ° on a lattice plane (002) plane) is used as a negative electrode material, and methyl ethyl carbonate is used as an organic electrolyte solution. When used as a solvent, methyl ethyl carbonate causes a transesterification reaction on the surface of the negative electrode made of a carbon material when a long-term storage or charge / discharge cycle is repeated, so that a nonconductive film is formed on the surface of the negative electrode. For this reason, there was a problem that storage characteristics and cycle characteristics were deteriorated.
【0005】本発明は、以上の事情に鑑みなされたもの
であって、初期特性を低下させることなく、保存特性と
サイクル特性とを向上させることができるリチウムイオ
ン電池を提供することを目的としている。The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a lithium ion battery capable of improving storage characteristics and cycle characteristics without deteriorating initial characteristics. .
【0006】[0006]
【課題を解決するための手段】上記目的を達成するため
の本発明に係るリチウムイオン電池は、正極と、炭素材
料を負極材料とする負極と、有機電解液とを備えるリチ
ウムイオン電池において、前記有機電解液の溶媒とし
て、下記化3に示す非対称鎖状カーボネートと、下記化
4に示す二重結合を有する環状カーボネートとが含まれ
ていることを特徴とする。According to the present invention, there is provided a lithium ion battery including a positive electrode, a negative electrode using a carbon material as a negative electrode material, and an organic electrolyte. As a solvent of the organic electrolytic solution, an asymmetric chain carbonate represented by the following formula (3) and a cyclic carbonate having a double bond represented by the following formula (4) are contained.
【0007】[0007]
【化3】 〔但し、R1 及びR2 はアルキル基を表し、且つR1 ≠
R2 である。〕Embedded image Wherein R 1 and R 2 represent an alkyl group, and R 1 ≠
R 2 . ]
【0008】[0008]
【化4】 Embedded image
【0009】上記構成の如く、非対称鎖状カーボネート
の他に二重結合を有する環状カーボネートが有機電解液
に含まれていれば、二重結合を有する環状カーボネート
と炭素材料から成る負極とが優先的に反応して、負極表
面に良質の皮膜(Li2 CO 3 )が生成される。したが
って、非対称鎖状カーボネートの存在に起因する負極表
面上の不導体皮膜の形成が抑制されるので、保存特性や
サイクル特性を向上させることができる。また、非対称
鎖状カーボネートを含有しているので、初期特性が低下
するようなことはない。As described above, an asymmetric chain carbonate
In addition to the cyclic carbonate having a double bond is an organic electrolyte
A cyclic carbonate having a double bond if contained in
And the negative electrode made of carbon material react preferentially,
A good quality film (LiTwoCO Three) Is generated. But
Thus, the negative electrode table caused by the presence of the asymmetric chain carbonate
The formation of nonconductive film on the surface is suppressed,
Cycle characteristics can be improved. Also asymmetric
Lower initial properties due to containing chain carbonate
There is nothing to do.
【0010】更に、炭素材料のd002 が3.40Å未満
の結晶性の高い高容量の炭素材料を用いた場合には、エ
ステル交換反応が特に生じ易くなるので、本発明の効果
が十分に発揮される。かかる結晶性の高い炭素材料とし
ては、天然黒鉛及び人造黒鉛等が例示される。Further, when a high-capacity carbon material having a d 002 of less than 3.40 ° and high crystallinity is used, a transesterification reaction is particularly likely to occur, so that the effect of the present invention is sufficiently exhibited. Is done. Examples of such a highly crystalline carbon material include natural graphite and artificial graphite.
【0011】また、請求項2記載の発明は、請求項1記
載の発明において、前記化1におけるR1 及びR2 は、
炭素数1〜3のアルキル基であることを特徴とする。こ
のように、化1におけるR1 及びR2 が炭素数1〜3の
アルキル基であれば、上記効果が一層発揮される。Further, the invention according to claim 2 is the invention according to claim 1, wherein R 1 and R 2 in the chemical formula 1 are:
It is an alkyl group having 1 to 3 carbon atoms. As described above, when R 1 and R 2 in Chemical Formula 1 are alkyl groups having 1 to 3 carbon atoms, the above-described effect is further exhibited.
【0012】また、請求項3記載の発明は、請求項1又
は2記載の発明において、前記非対称鎖状カーボネート
の前記有機電解液中に占める割合が10〜80体積%で
あることを特徴とする。このように規制するのは、非対
称鎖状カーボネートの有機電解液中に占める割合が10
体積%未満では、添加効果が不十分であるため初期容量
の低下を招来する一方、80体積%を超えた場合にも、
やはり初期容量の低下を招来するからである。According to a third aspect of the present invention, in the first or second aspect, the ratio of the asymmetric chain carbonate in the organic electrolyte is 10 to 80% by volume. . The reason for this restriction is that the ratio of the asymmetric chain carbonate in the organic electrolyte is 10%.
If the amount is less than volume%, the effect of the addition is insufficient, leading to a decrease in the initial capacity.
This is also because the initial capacity is reduced.
【0013】また、請求項4記載の発明は、請求項1又
は2記載の発明において、前記二重結合を有する環状カ
ーボネートを除く前記有機電解液に対する前記二重結合
を有する環状カーボネートの割合が0.1〜5重量%で
あることを特徴とする。このように規制するのは、二重
結合を有する環状カーボネートを除く有機電解液に対す
る二重結合を有する環状カーボネートの割合が0.1重
量%未満では、添加効果が不十分であるため保存特性や
サイクル特性の低下を招来する一方、5重量%を超え
る、初期容量の低下を招来するからである。According to a fourth aspect of the present invention, in the first or second aspect, the ratio of the cyclic carbonate having a double bond to the organic electrolyte except for the cyclic carbonate having the double bond is 0. 0.1 to 5% by weight. The reason for this restriction is that if the proportion of the cyclic carbonate having a double bond to the organic electrolyte solution is less than 0.1% by weight, excluding the cyclic carbonate having a double bond, the effect of addition is insufficient and the storage characteristics and This is because while the cycle characteristics are lowered, the initial capacity is reduced by more than 5% by weight.
【0014】また、請求項5記載の発明は、請求項1又
は2記載の発明において、前記非対称鎖状カーボネート
の前記有機電解液中に占める割合が10〜80体積%で
あり、前記二重結合を有する環状カーボネートを除く前
記有機電解液に対する前記二重結合を有する環状カーボ
ネートの割合が0.1〜5重量%であることを特徴とす
る。上記請求項4及び5で示す理由と同様のことによ
り、このように規制するのが望ましい。According to a fifth aspect of the present invention, in the first or second aspect, the proportion of the asymmetric chain carbonate in the organic electrolyte is 10 to 80% by volume, and the double bond Wherein the ratio of the cyclic carbonate having a double bond to the organic electrolytic solution excluding the cyclic carbonate having a content of 0.1 to 5% by weight. It is desirable to regulate in this way for the same reason as set forth in claims 4 and 5 above.
【0015】また、請求項6記載の発明は、請求項1、
2、3、4又は5記載の発明において、前記非対称鎖状
カーボネートがメチルエチルカーボネートであり、前記
二重結合を有する環状カーボネートがビニレンカーボネ
ートであることを特徴とする。但し、これらに限定する
ものではなく、その他、非対称鎖状カーボネートとして
はメチルプロピルカーボネート、エチルプロピルカーボ
ネート等が例示され、二重結合を有する環状カーボネー
トとしてはプロペンカーボネート等が例示される。[0015] The invention according to claim 6 is based on claim 1,
The invention according to 2, 3, 4 or 5, wherein the asymmetric chain carbonate is methyl ethyl carbonate, and the cyclic carbonate having a double bond is vinylene carbonate. However, the present invention is not limited thereto. In addition, examples of the asymmetric chain carbonate include methyl propyl carbonate and ethyl propyl carbonate, and examples of the cyclic carbonate having a double bond include propene carbonate.
【0016】また、請求項7記載の発明は、請求項1、
2、3、4、5又は6記載の発明において、前記有機電
解液に、さらにエチレンカーボネートが含まれているこ
とを特徴とする。[0016] The invention according to claim 7 is based on claim 1,
The invention according to 2, 3, 4, 5, or 6, wherein the organic electrolyte further contains ethylene carbonate.
【0017】[0017]
【発明の実施の形態】本発明の実施の形態を、図1に基
づいて、以下に説明する。 〔正極〕正極活物質としてのLiCoO2 と導電剤とし
ての炭素とを重量比9:1で混合して得た混合物を、ポ
リフッ化ビニリデンの5重量%N−メチルピロリドン
(NMP)溶液に分散させてスラリーを調製し、このス
ラリーをドクターブレード法にて正極集電体としてのア
ルミニウム箔の両面に塗布した後、150°Cで2時間
真空乾燥して正極を作製した。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of the present invention will be described below with reference to FIG. [Positive electrode] A mixture obtained by mixing LiCoO 2 as a positive electrode active material and carbon as a conductive agent at a weight ratio of 9: 1 was dispersed in a 5% by weight N-methylpyrrolidone (NMP) solution of polyvinylidene fluoride. A slurry was prepared by applying the slurry to both surfaces of an aluminum foil as a positive electrode current collector by a doctor blade method, and then vacuum-dried at 150 ° C. for 2 hours to produce a positive electrode.
【0018】〔負極〕黒鉛粉末(d002 =3.37Å)
を結着剤としてのポリフッ化ビニリデンの5重量%NM
P溶液に分散させてスラリーを調製し、このスラリーを
ドクターブレード法にて負極集電体としての銅箔の両面
に塗布した後、150°Cで2時間真空乾燥して負極を
作製した。[Anode] Graphite powder (d 002 = 3.37 °)
5% by weight of polyvinylidene fluoride as binder
A slurry was prepared by dispersing the slurry in a P solution, and this slurry was applied to both surfaces of a copper foil as a negative electrode current collector by a doctor blade method, and then dried under vacuum at 150 ° C. for 2 hours to prepare a negative electrode.
【0019】〔有機電解液〕体積混合比率が30:70
の割合で混合したエチレンカーボネート(EC)とメチ
ルエチルカーボネート(MEC)に、エチレンカーボネ
ートとメチルエチルカーボネートとの総重量に対してビ
ニレンカーボネート(VC)を1重量%の割合で添加し
て混合溶媒を作製し、更に、LiPF6 を1M(モル/
リットル)の割合で溶かして有機電解液を調製した。[Organic electrolyte solution] The volume mixing ratio is 30:70.
To ethylene carbonate (EC) and methyl ethyl carbonate (MEC) mixed at a ratio of 1% by weight of vinylene carbonate (VC) with respect to the total weight of ethylene carbonate and methyl ethyl carbonate, and the mixed solvent was added. Then, LiPF 6 was added at 1 M (mol / mol).
Liter) to prepare an organic electrolyte solution.
【0020】〔電池の作製〕以上の正負両極及び有機電
解液を用いて本発明電池(円筒形で、直径:18mm、
高さ:65mm)を作製した。なお、セパレータとして
は、ポリプロピレン製の微多孔膜を使用し、これに先の
有機電解液を含浸させた。[Preparation of Battery] The battery of the present invention (cylindrical, diameter: 18 mm,
(Height: 65 mm). In addition, as a separator, a microporous film made of polypropylene was used, and this was impregnated with the organic electrolytic solution.
【0021】図1は作製した本発明電池を模式的に示す
断面図であり、図示の本発明電池は、正極1、負極2、
これら両電極を離間するセパレータ3、正極リード4、
負極リード5、正極外部端子6、負極缶7などからな
る。正極1及び負極2は、非水系電解液を注入されたセ
パレータ3を介して渦巻き状に巻き取られた状態で負極
缶7内に収容されており、正極1は正極リード4を介し
て正極外部端子6に、また負極2は負極リード5を介し
て負極缶7に接続され、電池内部で生じた化学エネルギ
ーを電気エネルギーとして外部へ取り出し得るようにな
っている。FIG. 1 is a cross-sectional view schematically showing a manufactured battery of the present invention.
Separator 3, positive electrode lead 4, separating these two electrodes,
It comprises a negative electrode lead 5, a positive electrode external terminal 6, a negative electrode can 7, and the like. The positive electrode 1 and the negative electrode 2 are housed in a negative electrode can 7 in a state of being spirally wound through a separator 3 into which a non-aqueous electrolyte is injected. The terminal 6 and the negative electrode 2 are connected to a negative electrode can 7 via a negative electrode lead 5, so that chemical energy generated inside the battery can be taken out as electric energy.
【0022】尚、本発明は、炭素材料を負極材料として
用いた場合に問題となっていた負極表面上でのエステル
交換反応を、当該有機電解液に二重結合を有する環状カ
ーボネートを含有せしめることによって抑制し、もって
保存特性及びサイクル特性の改善を実現したものであ
る。それゆえ、正極材料、有機電解液の溶質などについ
ては従来リチウムイオン電池用として提案され、或いは
実用されている種々の材料を特に制限なく用いることが
可能である。In the present invention, the transesterification reaction on the surface of the negative electrode, which has been a problem when a carbon material is used as the negative electrode material, comprises causing the organic electrolytic solution to contain a cyclic carbonate having a double bond. Thus, the storage characteristics and the cycle characteristics are improved. Therefore, as for the positive electrode material, the solute of the organic electrolyte, and the like, it is possible to use various materials that have been conventionally proposed or practically used for lithium ion batteries without any particular limitation.
【0023】正極材料(活物質)としては、上記LiC
oO2 の他に、LiNiO2 、LiMnO2 、LiFe
O2 が例示され、また非水系電解液の溶質としては、上
記LiPF6 の他に、LiClO4 、LiCF3 SO3
が例示される。As the positive electrode material (active material), the above LiC
In addition to oO 2 , LiNiO 2 , LiMnO 2 , LiFe
O 2 is exemplified. In addition to the above-mentioned LiPF 6 , LiClO 4 , LiCF 3 SO 3
Is exemplified.
【0024】[0024]
【実施例】〔第1実施例〕 (実施例1)実施例1としては、上記発明の実施の形態
に示す電池を用いた。このようにして作製した電池を、
以下、本発明電池A1と称する。EXAMPLES [First Example] (Example 1) As Example 1, the battery described in the embodiment of the present invention was used. The battery fabricated in this way is
Hereinafter, the battery is referred to as Battery A1 of the invention.
【0025】(実施例2〜5)ビニレンカーボネートの
添加割合を、各々0.05重量%、0.1重量%、5重
量%及び10重量%とする他は、上記実施例1と同様に
して電池を作製した。このようにして作製した電池を、
以下、それぞれ本発明電池A2〜A5と称する。(Examples 2 to 5) Except that the addition ratio of vinylene carbonate was 0.05% by weight, 0.1% by weight, 5% by weight and 10% by weight, respectively, in the same manner as in Example 1 above. A battery was manufactured. The battery fabricated in this way is
Hereinafter, these batteries are referred to as present invention batteries A2 to A5, respectively.
【0026】(比較例1)ビニレンカーボネートを添加
しない他は、上記実施例1と同様にして電池を作製し
た。このようにして作製した電池を、以下、比較電池X
1と称する。Comparative Example 1 A battery was manufactured in the same manner as in Example 1 except that vinylene carbonate was not added. The battery fabricated in this manner is hereinafter referred to as Comparative Battery X
No. 1.
【0027】(実験1)本発明電池A1〜A5及び比較
電池X1について、初期の電池容量、高温保存後(60
℃で20日間)の電池容量、及び500サイクル充放電
した後の電池容量を調べたので、それらの結果を表1に
示す。尚、充放電条件を下記に示す。 充電条件:所定の電流で充電終止電圧4.1Vまで充電
した後、電圧を4.1Vに維持しつつ電流値を徐々に低
下させ、電流値が27mAになった時点で充電を終了し
た。但し、3時間経過しても電流値が27mAを超えて
いる場合には3時間で充電を終了した。 放電条件:所定の電流で放電終止電圧2.75Vまで放
電した。(Experiment 1) For the batteries A1 to A5 of the present invention and the comparative battery X1, the initial battery capacity and after storage at high temperatures (60
(For 20 days at 20 ° C.) and the battery capacity after 500 cycles of charging and discharging. The results are shown in Table 1. The charge and discharge conditions are shown below. Charging conditions: After charging to a charge end voltage of 4.1 V with a predetermined current, the current value was gradually reduced while maintaining the voltage at 4.1 V, and charging was terminated when the current value reached 27 mA. However, if the current value exceeded 27 mA even after 3 hours, charging was completed in 3 hours. Discharge conditions: Discharge was performed at a predetermined current to a discharge end voltage of 2.75V.
【0028】[0028]
【表1】 [Table 1]
【0029】表1から明らかなように、本発明電池A1
〜A5は比較電池X1に比べて、初期容量は略同等であ
るが、高温保存後の電池容量、及び500サイクル充放
電した後の電池容量は格段に大きくなっていることが認
められる。したがって、有機電解液の溶媒にビニレンカ
ーボネートを含有させることが望ましいことを確認でき
る。As is clear from Table 1, the battery A1 of the present invention
A5 has substantially the same initial capacity as the comparative battery X1, but it is recognized that the battery capacity after high-temperature storage and the battery capacity after charging and discharging for 500 cycles are significantly larger. Therefore, it can be confirmed that it is desirable that vinylene carbonate be contained in the solvent of the organic electrolyte.
【0030】ただし、ビニレンカーボネートを除く有機
電解液に対するビニレンカーボネートの割合(以下、単
にビニレンカーボネートの割合と略する)が0.1重量
%未満の本発明電池A2及びビニレンカーボネートの割
合が5重量%を超える本発明電池A5は、ビニレンカー
ボネートの割合が0.1〜5重量%の本発明電池A1、
A3、A4に比べて高温保存後の電池容量、及び500
サイクル充放電した後の電池容量が若干小さくなること
が認められる。したがって、ビニレンカーボネートの割
合は、0.1〜5重量%であることが望ましい。However, the battery A2 of the present invention in which the ratio of vinylene carbonate to the organic electrolytic solution excluding vinylene carbonate (hereinafter, simply referred to as the ratio of vinylene carbonate) is less than 0.1% by weight, and the ratio of vinylene carbonate is 5% by weight. The battery A5 of the present invention has a vinylene carbonate content of 0.1 to 5% by weight.
Battery capacity after high-temperature storage compared to A3 and A4, and 500
It is recognized that the battery capacity after cycle charge / discharge is slightly reduced. Therefore, the ratio of vinylene carbonate is desirably 0.1 to 5% by weight.
【0031】(比較例2)メチルエチルカーボネートの
代わりにジメチルカーボネート(DMC)を用いる他
は、上記実施例1と同様にして電池を作製した。このよ
うにして作製した電池を、以下、比較電池X2と称す
る。Comparative Example 2 A battery was manufactured in the same manner as in Example 1 except that dimethyl carbonate (DMC) was used instead of methyl ethyl carbonate. The battery fabricated in this manner is hereinafter referred to as Comparative Battery X2.
【0032】(比較例3)ビニレンカーボネートを添加
しない他は、上記比較例2と同様にして電池を作製し
た。このようにして作製した電池を、以下、比較電池X
3と称する。Comparative Example 3 A battery was prepared in the same manner as in Comparative Example 2 except that vinylene carbonate was not added. The battery fabricated in this manner is hereinafter referred to as Comparative Battery X
No. 3.
【0033】(比較例4)メチルエチルカーボネートの
代わりにジエチルカーボネート(DEC)を用いる他
は、上記実施例1と同様にして電池を作製した。このよ
うにして作製した電池を、以下、比較電池X4と称す
る。Comparative Example 4 A battery was produced in the same manner as in Example 1 except that diethyl carbonate (DEC) was used instead of methyl ethyl carbonate. The battery fabricated in this manner is hereinafter referred to as Comparative Battery X4.
【0034】(比較例5)ビニレンカーボネートを添加
しない他は、上記比較例4と同様にして電池を作製し
た。このようにして作製した電池を、以下、比較電池X
5と称する。Comparative Example 5 A battery was prepared in the same manner as in Comparative Example 4 except that vinylene carbonate was not added. The battery fabricated in this manner is hereinafter referred to as Comparative Battery X
No. 5.
【0035】(実験2)上記比較電池X2〜X5につい
て、初期の電池容量、高温保存後の電池容量、及び50
0サイクル充放電した後の電池容量を調べたので、それ
らの結果を表2に示す。尚、充放電条件は前記実験1と
同様の条件である。また、比較の容易のために、本発明
電池A1の結果についても表2に併せて示す。(Experiment 2) For the comparative batteries X2 to X5, the initial battery capacity, the battery capacity after high-temperature storage, and 50
Table 2 shows the results of examining the battery capacity after 0 cycles of charging and discharging. The charge and discharge conditions were the same as those in Experiment 1. Table 2 also shows the results of the battery A1 of the present invention for easy comparison.
【0036】[0036]
【表2】 [Table 2]
【0037】表2から明らかなように、比較電池X2、
X4は、比較電池X3、X5に比べれば、高温保存後の
電池容量、及び500サイクル充放電した後の電池容量
が大きくなっているが、本発明電池A1に比べると両電
池容量とも小さいことが認められる。したがって、メチ
ルエチルカーボネート等の非対称鎖状カーボネートの代
わりにジメチルカーボネート、ジエチルカーボネート等
の対称鎖状カーボネートを用いた場合には、本発明の効
果は十分に発揮されないことが確認できる。As is clear from Table 2, the comparative battery X2,
X4 has a larger battery capacity after high-temperature storage and a larger battery capacity after 500 cycles of charging and discharging than the comparative batteries X3 and X5, but both battery capacities are smaller than the battery A1 of the present invention. Is recognized. Therefore, it can be confirmed that the effect of the present invention is not sufficiently exhibited when a symmetric chain carbonate such as dimethyl carbonate or diethyl carbonate is used in place of an asymmetric chain carbonate such as methyl ethyl carbonate.
【0038】(実施例6)有機電解液として、体積混合
比率が30:40:30の割合で混合したエチレンカー
ボネートとメチルエチルカーボネートとジメチルカーボ
ネートに、これらの総重量に対してビニレンカーボネー
トを1重量%の割合で添加したものを用いる他は、前記
実施例1と同様にして電池を作製した。このようにして
作製した電池を、以下、本発明電池A6と称する。Example 6 As an organic electrolytic solution, ethylene carbonate, methyl ethyl carbonate and dimethyl carbonate mixed at a volume mixing ratio of 30:40:30, and vinylene carbonate in an amount of 1 wt. A battery was fabricated in the same manner as in Example 1, except that the battery was added at a ratio of 0.1%. The battery fabricated in this manner is hereinafter referred to as Battery A6 of the invention.
【0039】(比較例6)ビニレンカーボネートを添加
しない他は、上記実施例6と同様にして電池を作製し
た。このようにして作製した電池を、以下、比較電池X
6と称する。Comparative Example 6 A battery was manufactured in the same manner as in Example 6 except that vinylene carbonate was not added. The battery fabricated in this manner is hereinafter referred to as Comparative Battery X
No. 6.
【0040】(実験3)上記本発明電池A6及び比較電
池X6について、初期の電池容量、高温保存後の電池容
量、及び500サイクル充放電した後の電池容量を調べ
たので、それらの結果を表3に示す。尚、充放電条件は
前記実験1と同様の条件である。また、比較の容易のた
めに、本発明電池A1の結果についても表3に併せて示
す。(Experiment 3) For the battery A6 of the present invention and the comparative battery X6, the initial battery capacity, the battery capacity after high-temperature storage, and the battery capacity after charging and discharging for 500 cycles were examined. 3 is shown. The charge and discharge conditions were the same as those in Experiment 1. Table 3 also shows the results of the battery A1 of the present invention for easy comparison.
【0041】[0041]
【表3】 [Table 3]
【0042】表3から明らかなように、本発明電池A6
は、比較電池X6に比べて、高温保存後の電池容量、及
び500サイクル充放電した後の電池容量が大きくなっ
ており、本発明電池A1と略同等の性能を有することが
認められる。したがって、有機電解液にジメチルカーボ
ネート等の対称鎖状カーボネートを含んでいても、メチ
ルエチルカーボネート等の非対称鎖状カーボネートを含
んでいれば、本発明の効果は十分に発揮されることが確
認できる。As is clear from Table 3, the battery A6 of the present invention
Indicates that the battery capacity after high-temperature storage and the battery capacity after 500 cycles of charge / discharge are larger than the comparative battery X6, and it is recognized that the battery has substantially the same performance as the battery A1 of the present invention. Therefore, it can be confirmed that the effects of the present invention can be sufficiently exerted when the organic electrolyte solution contains a symmetric chain carbonate such as dimethyl carbonate, but also contains an asymmetric chain carbonate such as methyl ethyl carbonate.
【0043】(実施例7〜13)エチレンカーボネート
とメチルエチルカーボネートとの体積比率を、それぞれ
10:90、20:80、50:50、70:30、8
0:20、90:10、95:5とする他は、上記実施
例1と同様にして電池を作製した。このようにして作製
した電池を、以下、それぞれ本発明電池A7〜A13と
称する。Examples 7 to 13 The volume ratios of ethylene carbonate and methyl ethyl carbonate were 10:90, 20:80, 50:50, 70:30 and 8 respectively.
A battery was fabricated in the same manner as in Example 1 except that 0:20, 90:10, and 95: 5 were set. The batteries fabricated in this manner are hereinafter referred to as Batteries A7 to A13 of the invention, respectively.
【0044】(実験4)上記本発明電池A7〜A13に
ついて、初期の電池容量、高温保存後の電池容量、及び
500サイクル充放電した後の電池容量を調べたので、
それらの結果を表4に示す。尚、充放電条件は前記実験
1と同様の条件である。また、本発明電池A1の結果に
ついても表4に併せて示す。(Experiment 4) For the batteries A7 to A13 of the present invention, the initial battery capacity, the battery capacity after high-temperature storage, and the battery capacity after 500 charge / discharge cycles were examined.
Table 4 shows the results. The charge and discharge conditions were the same as those in Experiment 1. Table 4 also shows the results of the battery A1 of the present invention.
【0045】[0045]
【表4】 [Table 4]
【0046】表4から明らかなように、本発明電池A
1、A8〜A12は、本発明電池A7、A13に比べ
て、高温保存後の電池容量、及び500サイクル充放電
した後の電池容量が大きくなっていることが認められ
る。したがって、エチレンカーボネートとメチルエチル
カーボネートとの体積比率は、20:80〜90:10
であることが望ましいことを確認できる。As is clear from Table 4, the battery A of the present invention
1 and A8 to A12 show that the battery capacity after high-temperature storage and the battery capacity after 500 cycles of charge / discharge were larger than those of the batteries A7 and A13 of the present invention. Therefore, the volume ratio between ethylene carbonate and methyl ethyl carbonate is from 20:80 to 90:10.
Can be confirmed to be desirable.
【0047】(実施例14)負極材料として、格子面
(002)面におけるd値(d002 )が3.35Åの黒
鉛系炭素材料を用いた他は、上記実施例1と同様にして
電池を作製した。このようにして作製した電池を、以
下、本発明電池A14と称する。Example 14 A battery was fabricated in the same manner as in Example 1 except that a graphite-based carbon material having a d value (d 002 ) of 3.35 ° in the lattice plane (002) was used as a negative electrode material. Produced. The battery fabricated in this manner is hereinafter referred to as Battery A14 of the invention.
【0048】(比較例7、8)負極材料として、格子面
(002)面におけるd値(d002 )がそれぞれ3.4
0Å、3.45Åの黒鉛系炭素材料を用いた他は、上記
実施例1と同様にして電池を作製した。このようにして
作製した電池を、以下、それぞれ比較電池X7、X8と
称する。(Comparative Examples 7 and 8) As the negative electrode material, the d value (d 002 ) on the lattice plane (002) plane was 3.4, respectively.
A battery was manufactured in the same manner as in Example 1 except that a graphite-based carbon material of 0 ° and 3.45 ° was used. The batteries fabricated in this manner are hereinafter referred to as comparative batteries X7 and X8, respectively.
【0049】(実験5)上記本発明電池A14及び比較
電池X7、X8について、初期の電池容量、高温保存後
の電池容量、及び500サイクル充放電した後の電池容
量を調べたので、それらの結果を表5に示す。尚、充放
電条件は前記実験1と同様の条件である。また、本発明
電池A1の結果についても表5に併せて示す。(Experiment 5) The initial battery capacity, the battery capacity after high-temperature storage, and the battery capacity after 500 cycles of charging and discharging were examined for the battery A14 of the present invention and the comparative batteries X7 and X8. Are shown in Table 5. The charge and discharge conditions were the same as those in Experiment 1. Table 5 also shows the results of the battery A1 of the present invention.
【0050】[0050]
【表5】 [Table 5]
【0051】表5から明らかなように、本発明電池A
1、A13は、比較電池X7、X8に比べて、高温保存
後の電池容量、及び500サイクル充放電した後の電池
容量が大きくなっていることが認められる。したがっ
て、格子面(002)面におけるd値(d002 )は、
3.40Å未満であることが望ましいことを確認でき
る。As is clear from Table 5, the battery A of the present invention
1 and A13, the battery capacity after high-temperature storage and the battery capacity after 500 cycles of charging and discharging are larger than those of the comparative batteries X7 and X8. Therefore, the d value (d 002 ) on the lattice plane (002) plane is
It can be confirmed that it is desirable that the angle is less than 3.40 °.
【0052】〔第2実施例〕 (実施例1)メチルエチルカーボネートの代わりに、メ
チルプロピルカーボネート(MPC)を用いる他は、前
記第1実施例の実施例1と同様にして電池を作製した。
このようにして作製した電池を、以下、本発明電池B1
と称する。[Second Embodiment] (Example 1) A battery was manufactured in the same manner as in Example 1 of the first embodiment except that methylpropyl carbonate (MPC) was used instead of methyl ethyl carbonate.
The battery fabricated in this manner is hereinafter referred to as Battery B1 of the invention.
Called.
【0053】(実施例2〜5)ビニレンカーボネートの
添加割合を、各々0.05重量%、0.1重量%、5重
量%及び10重量%とする他は、上記実施例1と同様に
して電池を作製した。このようにして作製した電池を、
以下、それぞれ本発明電池B2〜B5と称する。(Examples 2 to 5) Except that the addition ratio of vinylene carbonate was 0.05% by weight, 0.1% by weight, 5% by weight and 10% by weight, respectively, in the same manner as in Example 1 above. A battery was manufactured. The battery fabricated in this way is
Hereinafter, these batteries are referred to as present invention batteries B2 to B5, respectively.
【0054】(比較例1)ビニレンカーボネートを添加
しない他は、上記実施例1と同様にして電池を作製し
た。このようにして作製した電池を、以下、比較電池Y
1と称する。Comparative Example 1 A battery was manufactured in the same manner as in Example 1 except that vinylene carbonate was not added. The battery fabricated in this manner is hereinafter referred to as Comparative Battery Y.
No. 1.
【0055】(実験1)本発明電池B1〜B5及び比較
電池Y1について、初期の電池容量、高温保存後の電池
容量、及び500サイクル充放電した後の電池容量を調
べたので、それらの結果を表6に示す。尚、充放電条件
は前記第1実施例の実験1と同様の条件である。(Experiment 1) For the batteries B1 to B5 of the present invention and the comparative battery Y1, the initial battery capacity, the battery capacity after high-temperature storage, and the battery capacity after 500 charge / discharge cycles were examined. It is shown in Table 6. The charging and discharging conditions are the same as those in Experiment 1 of the first embodiment.
【0056】[0056]
【表6】 [Table 6]
【0057】表6から明らかなように、本発明電池B1
〜B5は比較電池Y1に比べて、初期容量は略同等であ
るが、高温保存後の電池容量、及び500サイクル充放
電した後の電池容量は格段に大きくなっていることが認
められる。したがって、有機電解液の溶媒にビニレンカ
ーボネートを含有させることが望ましいことが確認でき
る。As is clear from Table 6, the battery B1 of the present invention
B5 has substantially the same initial capacity as the comparative battery Y1, but it is recognized that the battery capacity after high-temperature storage and the battery capacity after 500 cycles of charge / discharge are significantly larger. Therefore, it can be confirmed that it is desirable to include vinylene carbonate in the solvent of the organic electrolyte.
【0058】ただし、ビニレンカーボネートを除く有機
電解液に対するビニレンカーボネートの割合(以下、単
にビニレンカーボネートの割合と略する)が0.1重量
%未満の本発明電池B2及びビニレンカーボネートの割
合が5重量%を超える本発明電池B5は、ビニレンカー
ボネートの割合が0.1〜5重量%の本発明電池B1、
B3、B4に比べて高温保存後の電池容量、及び500
サイクル充放電した後の電池容量が若干小さくなること
が認められる。したがって、ビニレンカーボネートの割
合は、0.1〜5重量%であることが望ましい。However, when the ratio of vinylene carbonate to the organic electrolyte solution excluding vinylene carbonate (hereinafter, simply referred to as the ratio of vinylene carbonate) is less than 0.1% by weight, the battery B2 of the present invention and the ratio of vinylene carbonate are 5% by weight. Inventive battery B5 having a vinylene carbonate ratio of 0.1 to 5% by weight,
Battery capacity after high temperature storage compared to B3 and B4, and 500
It is recognized that the battery capacity after cycle charge / discharge is slightly reduced. Therefore, the ratio of vinylene carbonate is desirably 0.1 to 5% by weight.
【0059】(実施例6)有機電解液として、体積混合
比率が30:40:30の割合で混合したエチレンカー
ボネートとメチルプロピルカーボネートとジメチルカー
ボネートに、これらの総重量に対してビニレンカーボネ
ートを1重量%の割合で添加したものを用いる他は、前
記実施例1と同様にして電池を作製した。このようにし
て作製した電池を、以下、本発明電池B6と称する。Example 6 As an organic electrolytic solution, ethylene carbonate, methyl propyl carbonate and dimethyl carbonate mixed at a volume mixing ratio of 30:40:30, and vinylene carbonate in an amount of 1 wt. A battery was fabricated in the same manner as in Example 1, except that the battery was added at a ratio of 0.1%. The battery fabricated in this manner is hereinafter referred to as Battery B6 of the invention.
【0060】(比較例2)ビニレンカーボネートを添加
しない他は、上記実施例6と同様にして電池を作製し
た。このようにして作製した電池を、以下、比較電池Y
2と称する。Comparative Example 2 A battery was fabricated in the same manner as in Example 6 except that vinylene carbonate was not added. The battery fabricated in this manner is hereinafter referred to as Comparative Battery Y.
No. 2.
【0061】(実験3)上記本発明電池B6及び比較電
池Y2について、初期の電池容量、高温保存後の電池容
量、及び500サイクル充放電した後の電池容量を調べ
たので、それらの結果を表7に示す。尚、充放電条件は
前記実験1と同様の条件である。また、比較の容易のた
めに、本発明電池B1の結果についても表3に併せて示
す。(Experiment 3) With respect to the battery B6 of the present invention and the comparative battery Y2, the initial battery capacity, the battery capacity after high-temperature storage, and the battery capacity after 500 charge / discharge cycles were examined. FIG. The charge and discharge conditions were the same as those in Experiment 1. Table 3 also shows the results of the battery B1 of the present invention for easy comparison.
【0062】[0062]
【表7】 [Table 7]
【0063】表7から明らかなように、本発明電池B6
は、比較電池Y6に比べて、高温保存後の電池容量、及
び500サイクル充放電した後の電池容量が大きくなっ
ており、本発明電池B1と略同等の性能を有することが
認められる。したがって、有機電解液にジメチルカーボ
ネート等の対称鎖状カーボネートを含んでいても、メチ
ルプロピルカーボネート等の非対称鎖状カーボネートを
含んでいれば、本発明の効果は十分に発揮されることが
確認できる。As is clear from Table 7, the battery B6 of the present invention
Indicates that the battery capacity after high-temperature storage and the battery capacity after 500 cycles of charging and discharging are larger than those of the comparative battery Y6, and it is recognized that the battery has substantially the same performance as the battery B1 of the present invention. Therefore, it can be confirmed that the effects of the present invention can be sufficiently exerted even if the organic electrolyte solution contains a symmetric chain carbonate such as dimethyl carbonate, but also contains an asymmetric chain carbonate such as methyl propyl carbonate.
【0064】(実施例7〜13)エチレンカーボネート
とメチルプロピルカーボネートとの体積比率を、それぞ
れ10:90、20:80、50:50、70:30、
80:20、90:10、95:5とする他は、上記実
施例1と同様にして電池を作製した。このようにして作
製した電池を、以下、それぞれ本発明電池B7〜B13
と称する。Examples 7 to 13 The volume ratios of ethylene carbonate and methyl propyl carbonate were 10:90, 20:80, 50:50, 70:30,
A battery was fabricated in the same manner as in Example 1 except that the batteries were 80:20, 90:10, and 95: 5. The batteries fabricated in this manner are hereinafter referred to as Batteries B7 to B13 of the invention, respectively.
Called.
【0065】(実験4)上記本発明電池B7〜B13に
ついて、初期の電池容量、高温保存後の電池容量、及び
500サイクル充放電した後の電池容量を調べたので、
それらの結果を表8に示す。尚、充放電条件は前記実験
1と同様の条件である。また、本発明電池B1の結果に
ついても表8に併せて示す。(Experiment 4) For the batteries B7 to B13 of the present invention, the initial battery capacity, the battery capacity after high-temperature storage, and the battery capacity after 500 charge / discharge cycles were examined.
Table 8 shows the results. The charge and discharge conditions were the same as those in Experiment 1. Table 8 also shows the results of the battery B1 of the present invention.
【0066】[0066]
【表8】 [Table 8]
【0067】表8から明らかなように、本発明電池B
1、B8〜B12は、本発明電池B7、B13に比べ
て、高温保存後の電池容量、及び500サイクル充放電
した後の電池容量が大きくなっていることが認められ
る。したがって、エチレンカーボネートとメチルプロピ
ルカーボネートとの体積比率は、20:80〜90:1
0であることが望ましいことを確認できる。As is clear from Table 8, the battery B of the present invention
1 and B8 to B12 show that the battery capacity after high-temperature storage and the battery capacity after 500 cycles of charging and discharging are larger than those of the batteries B7 and B13 of the present invention. Therefore, the volume ratio of ethylene carbonate to methyl propyl carbonate is from 20:80 to 90: 1.
It can be confirmed that 0 is desirable.
【0068】(実施例14)負極材料として、格子面
(002)面におけるd値(d002 )が3.35Åの黒
鉛系炭素材料を用いた他は、上記実施例1と同様にして
電池を作製した。このようにして作製した電池を、以
下、本発明電池B14と称する。Example 14 A battery was fabricated in the same manner as in Example 1 except that a graphite-based carbon material having a d-value (d 002 ) of 3.35 ° in the lattice plane (002) was used as a negative electrode material. Produced. The battery fabricated in this manner is hereinafter referred to as Battery B14 of the invention.
【0069】(比較例3、4)負極材料として、格子面
(002)面におけるd値(d002 )がそれぞれ3.4
0Å、3.45Åの黒鉛系炭素材料を用いた他は、上記
実施例1と同様にして電池を作製した。このようにして
作製した電池を、以下、それぞれ比較電池Y3、Y4と
称する。(Comparative Examples 3 and 4) As the negative electrode material, the d value (d 002 ) on the lattice plane (002) plane was 3.4, respectively.
A battery was manufactured in the same manner as in Example 1 except that a graphite-based carbon material of 0 ° and 3.45 ° was used. The batteries fabricated in this manner are hereinafter referred to as comparative batteries Y3 and Y4, respectively.
【0070】(実験5)上記本発明電池B14及び比較
電池Y3、Y4について、初期の電池容量、高温保存後
の電池容量、及び500サイクル充放電した後の電池容
量を調べたので、それらの結果を表9に示す。尚、充放
電条件は前記実験1と同様の条件である。また、本発明
電池B1の結果についても表9に併せて示す。(Experiment 5) With respect to the battery B14 of the present invention and the comparative batteries Y3 and Y4, the initial battery capacity, the battery capacity after high-temperature storage, and the battery capacity after 500 cycles of charging and discharging were examined. Are shown in Table 9. The charge and discharge conditions were the same as those in Experiment 1. Table 9 also shows the results of the battery B1 of the present invention.
【0071】[0071]
【表9】 [Table 9]
【0072】表9から明らかなように、本発明電池B
1、B13は、比較電池Y7、Y8に比べて、高温保存
後の電池容量、及び500サイクル充放電した後の電池
容量が大きくなっていることが認められる。したがっ
て、格子面(002)面におけるd値(d002 )は、
3.40Å未満であることが望ましいことを確認でき
る。As is clear from Table 9, the battery B of the present invention
1 and B13, it is recognized that the battery capacity after high-temperature storage and the battery capacity after 500 cycles of charging and discharging are larger than those of the comparative batteries Y7 and Y8. Therefore, the d value (d 002 ) on the lattice plane (002) plane is
It can be confirmed that it is desirable that the angle is less than 3.40 °.
【0073】[0073]
【発明の効果】以上説明したように本発明によれば、負
極表面上に不導体皮膜が形成されるのを抑制することが
できるので、初期特性を低下させることなく、保存特性
とサイクル特性とを飛躍的に向上させることができると
いった優れた効果を奏する。As described above, according to the present invention, the formation of a nonconductive film on the surface of the negative electrode can be suppressed, so that the storage characteristics and the cycle characteristics can be improved without lowering the initial characteristics. It has an excellent effect that it can be dramatically improved.
【図1】本発明電池の断面図である。FIG. 1 is a sectional view of a battery of the present invention.
1 正極 2 負極 3 セパレータ 1 positive electrode 2 negative electrode 3 separator
─────────────────────────────────────────────────────
────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成10年1月30日[Submission date] January 30, 1998
【手続補正1】[Procedure amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】請求項1[Correction target item name] Claim 1
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【化1】 〔但し、R1 及びR2 はアルキル基を表し、且つR1 ≠
R2 である。〕Embedded image Wherein R 1 and R 2 represent an alkyl group, and R 1 ≠
R 2 . ]
【化2】 Embedded image
【手続補正2】[Procedure amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】請求項6[Correction target item name] Claim 6
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【手続補正3】[Procedure amendment 3]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】0008[Correction target item name] 0008
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【0008】[0008]
【化4】 Embedded image
【手続補正4】[Procedure amendment 4]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】0015[Correction target item name] 0015
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【0015】また、請求項6記載の発明は、請求項1、
2、3、4又は5記載の発明において、前記非対称鎖状
カーボネートがメチルエチルカーボネート又はメチルプ
ロピルカーボネートであり、前記二重結合を有する環状
カーボネートがビニレンカーボネートであることを特徴
とする。但し、これらに限定するものではなく、その
他、非対称鎖状カーボネートとしてはエチルプロピルカ
ーボネート等が例示され、二重結合を有する環状カーボ
ネートとしてはプロペンカーボネート等が例示される。[0015] The invention according to claim 6 is based on claim 1,
In the invention according to 2, 3, 4 or 5, the asymmetric chain carbonate is methyl ethyl carbonate or methyl ethyl carbonate .
It is ropyl carbonate , and the cyclic carbonate having a double bond is vinylene carbonate. However, not limited thereto, other, ethylpropyl mosquitoes as asymmetric chain carbonate
And a cyclic carbonate having a double bond, such as propene carbonate.
Claims (7)
値(d002 )が3.40Å未満の黒鉛系炭素材料を負極
材料とする負極と、有機電解液とを備えるリチウムイオ
ン電池において、 前記有機電解液の溶媒として、下記化1に示す非対称鎖
状カーボネートと、下記化2に示す二重結合を有する環
状カーボネートとが含まれていることを特徴とするリチ
ウムイオン電池。 【化1】 〔但し、R1 及びR2 はアルキル基を表し、且つR1 ≠
R2 である。〕 【化2】 1. A positive electrode and d in a lattice plane (002) plane
In a lithium ion battery including a negative electrode using a graphite-based carbon material having a value (d 002 ) of less than 3.40 ° as a negative electrode material and an organic electrolyte, an asymmetric chain represented by the following chemical formula 1 is used as a solvent for the organic electrolyte: A lithium ion battery comprising a carbonate and a cyclic carbonate having a double bond represented by the following chemical formula 2. Embedded image Wherein R 1 and R 2 represent an alkyl group, and R 1 ≠
R 2 . [Chemical formula 2]
数1〜3のアルキル基である、請求項1記載のリチウム
イオン電池。2. The lithium ion battery according to claim 1, wherein R 1 and R 2 in Chemical Formula 1 are alkyl groups having 1 to 3 carbon atoms.
電解液中に占める割合が10〜80体積%である、請求
項1又は2記載のリチウムイオン電池。3. The lithium ion battery according to claim 1, wherein the proportion of the asymmetric chain carbonate in the organic electrolyte is 10 to 80% by volume.
を除く前記有機電解液に対する前記二重結合を有する環
状カーボネートの割合が0.1〜5重量%である、請求
項1又は2記載のリチウムイオン電池。4. The lithium ion according to claim 1, wherein a ratio of the cyclic carbonate having a double bond to the organic electrolyte except for the cyclic carbonate having a double bond is 0.1 to 5% by weight. battery.
電解液中に占める割合が10〜80体積%であり、前記
二重結合を有する環状カーボネートを除く前記有機電解
液に対する前記二重結合を有する環状カーボネートの割
合が0.1〜5重量%である、請求項1又は2記載のリ
チウムイオン電池。5. A cyclic structure having the double bond with respect to the organic electrolytic solution excluding the cyclic carbonate having a double bond, wherein the proportion of the asymmetric chain carbonate in the organic electrolytic solution is 10 to 80% by volume. 3. The lithium ion battery according to claim 1, wherein the proportion of carbonate is 0.1 to 5% by weight.
チルカーボネートであり、前記二重結合を有する環状カ
ーボネートがビニレンカーボネートである、請求項1、
2、3、4又は5記載のリチウムイオン電池。6. The method according to claim 1, wherein the asymmetric chain carbonate is methyl ethyl carbonate, and the cyclic carbonate having a double bond is vinylene carbonate.
The lithium ion battery according to 2, 3, 4 or 5.
ボネートが含まれている、請求項1、2、3、4、5又
は6記載のリチウムイオン電池。7. The lithium ion battery according to claim 1, wherein the organic electrolyte further contains ethylene carbonate.
Priority Applications (1)
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JP34777897A JP3332834B2 (en) | 1997-12-17 | 1997-12-17 | Lithium ion battery |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP34777897A JP3332834B2 (en) | 1997-12-17 | 1997-12-17 | Lithium ion battery |
Publications (2)
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---|---|
JPH11185806A true JPH11185806A (en) | 1999-07-09 |
JP3332834B2 JP3332834B2 (en) | 2002-10-07 |
Family
ID=18392519
Family Applications (1)
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JP34777897A Expired - Lifetime JP3332834B2 (en) | 1997-12-17 | 1997-12-17 | Lithium ion battery |
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JP (1) | JP3332834B2 (en) |
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