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.)
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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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- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (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)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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)
| Publication Number | Publication Date |
|---|---|
| JPH11185806A true JPH11185806A (en) | 1999-07-09 |
| JP3332834B2 JP3332834B2 (en) | 2002-10-07 |
Family
ID=18392519
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP34777897A Expired - Lifetime JP3332834B2 (en) | 1997-12-17 | 1997-12-17 | Lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3332834B2 (en) |
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