JP2002352852A - Nonaqueous electrolyte secondary cell - Google Patents

Nonaqueous electrolyte secondary cell

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Publication number
JP2002352852A
JP2002352852A JP2001153396A JP2001153396A JP2002352852A JP 2002352852 A JP2002352852 A JP 2002352852A JP 2001153396 A JP2001153396 A JP 2001153396A JP 2001153396 A JP2001153396 A JP 2001153396A JP 2002352852 A JP2002352852 A JP 2002352852A
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JP
Japan
Prior art keywords
carbonate
lithium
general formula
compound represented
carbon atoms
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
Application number
JP2001153396A
Other languages
Japanese (ja)
Other versions
JP5239106B2 (en
Inventor
Minoru Kotado
稔 古田土
Takashi Fujii
隆 藤井
Shinichi Kinoshita
信一 木下
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Chemical Corp
Original Assignee
Mitsubishi Chemical Corp
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Filing date
Publication date
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Priority to JP2001153396A priority Critical patent/JP5239106B2/en
Publication of JP2002352852A publication Critical patent/JP2002352852A/en
Application granted granted Critical
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Expired - Lifetime legal-status Critical Current

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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

Abstract

PROBLEM TO BE SOLVED: To provide a lithium secondary cell which has superior preservation and cycle performances under high temperatures. SOLUTION: A nonaqueous electrolyte secondary cell comprises a negative electrode capable of occluding and releasing lithium, a positive electrode, and an electrolyte dissolving lithium salts in a nonaqueous solvent, wherein the nonaqueous solvent includes a vinylene carbonate compound represented by the general formula I (wherein, each of R<1> and R<2> is H atom or a 1-4C alkyl) and/or a vinylethylene carbonate compound represented by the general formula II (wherein, each of R<3> to R<5> is H atom or a 1-4C alkyl; and each of R<6> to R<8> is H atom, a 1-4C alkyl or a 2-7C alkenyl), and further an acid anhydride.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明は、非水系電解液二次
電池に関する。詳しくは特定の非水系電解液を使用する
ことにより、高容量で保存特性、サイクル特性に優れた
非水液系電解液二次電池を提供するものである。[0001] The present invention relates to a non-aqueous electrolyte secondary battery. More specifically, the present invention provides a non-aqueous liquid electrolyte secondary battery having a high capacity and excellent storage characteristics and cycle characteristics by using a specific non-aqueous electrolyte.

【０００２】[0002]

【従来の技術】近年の電気製品の軽量化、小型化にとも
ない、高いエネルギー密度を持つリチウム二次電池の開
発が進められている。また、リチウム二次電池の適用分
野の拡大に伴い電池特性の改善も要望されている。金属
リチウムを負極とする二次電池は高容量化を達成できる
電池として古くから盛んに研究が行われている。しか
し、金属リチウムは充放電の繰り返しによりデンドライ
ト状に成長し、最終的には正極に達して電池内部におい
て短絡が生じてしまうという問題がある。この問題は金
属リチウム二次電池を実用化する際の最大の技術的な課
題となっている。2. Description of the Related Art With the recent reduction in the weight and size of electric products, development of lithium secondary batteries having a high energy density has been promoted. In addition, with the expansion of the application field of the lithium secondary battery, improvement in battery characteristics is also demanded. Secondary batteries using metal lithium as a negative electrode have been actively studied for a long time as batteries capable of achieving high capacity. However, there is a problem in that metallic lithium grows in a dendrite shape by repeated charge and discharge, and eventually reaches the positive electrode to cause a short circuit inside the battery. This problem is the biggest technical problem when putting a lithium metal secondary battery into practical use.

【０００３】これに対しては負極に、例えばコークス、
人造黒鉛、天然黒鉛等のリチウムを吸蔵・放出すること
が可能な炭素質材料を用いた非水系電解液二次電池が提
案されている。このような非水系電解液二次電池では、
リチウムが金属状態で存在しないためデンドライトの形
成が抑制され、電池寿命と安全性を向上することができ
る。特に人造黒鉛、天然黒鉛等の黒鉛系炭素質材料を用
いた非水系電解液二次電池は、高容量化の要求に応える
ものとして注目されている。[0003] On the other hand, for example, coke,
A non-aqueous electrolyte secondary battery using a carbonaceous material capable of inserting and extracting lithium such as artificial graphite and natural graphite has been proposed. In such a non-aqueous electrolyte secondary battery,
Since lithium does not exist in a metallic state, formation of dendrites is suppressed, and battery life and safety can be improved. In particular, non-aqueous electrolyte secondary batteries using graphite-based carbonaceous materials such as artificial graphite and natural graphite have been receiving attention as meeting the demand for higher capacity.

【０００４】上記炭素質材料を使用するリチウム二次電
池においては、非水系電解液の高誘電率溶媒として通
常、プロピレンカーボネートやエチレンカーボネート等
の環状カーボネートが広く用いられ、コークスなどの非
黒鉛系炭素質材料を用いた非水系電解液二次電池では、
プロピレンカーボネートを含む溶媒が好適に用いられて
いる。In a lithium secondary battery using the above carbonaceous material, a cyclic carbonate such as propylene carbonate or ethylene carbonate is generally widely used as a high dielectric constant solvent for a non-aqueous electrolyte, and a non-graphite carbon such as coke is generally used. Non-aqueous electrolyte secondary batteries using porous materials
Solvents containing propylene carbonate are preferably used.

【０００５】一方、黒鉛系炭素質材料を単独で、或い
は、これとリチウムを吸蔵・放出可能な他の負極材と混
合して負極とした非水系電解液二次電池では、プロピレ
ンカーボネートを含む溶媒を用いると、充電時に電極表
面でプロピレンカーボネートの分解反応が激しく進行し
て、黒鉛系炭素質負極への円滑なリチウムの吸蔵・放出
が不可能になる。On the other hand, in a non-aqueous electrolyte secondary battery in which a graphite-based carbonaceous material is used alone or in combination with another anode material capable of inserting and extracting lithium, a non-aqueous electrolyte solution containing propylene carbonate is used. When, the decomposition reaction of propylene carbonate progresses violently on the electrode surface during charging, and it becomes impossible to smoothly insert and release lithium into the graphite-based carbonaceous negative electrode.

【０００６】一方、エチレンカーボネートはこのような
分解が少ないことから、黒鉛系炭素質負極を用いた非水
系電解液二次電池では、エチレンカーボネートが電解液
用の高誘電率溶媒として多用されている。しかしなが
ら、エチレンカーボネートを主溶媒としても、充放電過
程において電極表面で電解液が分解するために充放電効
率の低下、サイクル特性の低下、ガス発生による電池内
圧の上昇等の問題があった。On the other hand, since ethylene carbonate is less decomposed, ethylene carbonate is frequently used as a high-dielectric solvent for an electrolyte in a non-aqueous electrolyte secondary battery using a graphite-based carbonaceous negative electrode. . However, even when ethylene carbonate is used as the main solvent, there are problems such as a decrease in charge / discharge efficiency, a decrease in cycle characteristics, an increase in battery internal pressure due to gas generation, and the like, because the electrolyte is decomposed on the electrode surface in the charge / discharge process.

【０００７】そこで、非水系電解液二次電池の特性向上
のために種々の添加剤を含有させた電解液が提案されて
いる。黒鉛系負極を用いた非水系電解液電池の電解液の
分解を抑制するために、ビニレンカーボネート及びその
誘導体を含有する電解液（特開平８−４５５４５号公
報）や側鎖に非共役不飽和結合を有するエチレンカーボ
ネート誘導体を含む電解液（特開２０００‐４０５２６
号公報）が提案されている。これらの化合物を含む電解
液は、前記化合物が、負極表面で還元分解されて皮膜を
形成し、この皮膜により電解液の過度の分解が抑制され
る。[0007] To improve the characteristics of non-aqueous electrolyte secondary batteries, electrolytes containing various additives have been proposed. In order to suppress the decomposition of the electrolyte of a non-aqueous electrolyte battery using a graphite-based negative electrode, a non-conjugated unsaturated bond is added to an electrolyte containing vinylene carbonate or a derivative thereof (JP-A-8-45545) or a side chain. Electrolyte solution containing ethylene carbonate derivative having nitrogen (Japanese Patent Laid-Open No. 2000-40526)
Publication). In the electrolytic solution containing these compounds, the compounds are reduced and decomposed on the surface of the negative electrode to form a film, and the film suppresses excessive decomposition of the electrolytic solution.

【０００８】しかしこれらの化合物は、８０℃以上の高
温環境下での保存特性については、必ずしも満足できる
ものではない。また、ビニレンカーボネート化合物は充
電状態の正極材とも反応しやすく、添加量が多くなると
保存特性が更に低下する傾向にある。However, these compounds are not always satisfactory in storage characteristics under a high temperature environment of 80 ° C. or higher. Further, the vinylene carbonate compound tends to react with the positive electrode material in a charged state, and the storage characteristics tend to be further deteriorated as the amount added increases.

【０００９】[0009]

【発明が解決しようとする課題】本発明は前記問題点を
鑑みてなされたものであり、非水系電解液二次電池の電
解液の分解を最小限に抑えて、充放電効率が高く、高温
下でも保存特性、サイクル特性の優れた高エネルギー密
度の非水系電解液二次電池を提供するものである。SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and minimizes the decomposition of an electrolytic solution of a non-aqueous electrolyte secondary battery to achieve high charge / discharge efficiency and high temperature. An object of the present invention is to provide a high energy density non-aqueous electrolyte secondary battery having excellent storage characteristics and cycle characteristics even under a battery.

【００１０】[0010]

【課題を解決するための手段】本発明者等は、上記目的
を達成するために種々の検討を重ねた結果、特定の電解
液を用いることで、電解液の分解を最小限に抑えて充放
電効率を向上させ、保存特性、サイクル特性を向上させ
ることができることを見いだし、この発明を完成させる
に至った。Means for Solving the Problems The present inventors have conducted various studies to achieve the above object, and as a result, by using a specific electrolytic solution, the decomposition of the electrolytic solution was minimized. It has been found that the discharge efficiency can be improved and the storage characteristics and cycle characteristics can be improved, and the present invention has been completed.

【００１１】即ち本発明は、リチウムを吸蔵・放出する
ことが可能な負極と、正極と、非水溶媒にリチウム塩を
溶解してなる電解液とから少なくとも構成される非水系
電解液二次電池において、非水溶媒中に一般式（Ｉ）で
表されるビニレンカーボネート化合物及び／又は一般式
（II）で表されるビニルエチレンカーボネート化合物を
含有し、更に酸無水物を含有することを特徴とするもの
である。That is, the present invention provides a non-aqueous electrolyte secondary battery comprising at least a negative electrode capable of inserting and extracting lithium, a positive electrode, and an electrolyte obtained by dissolving a lithium salt in a non-aqueous solvent. Wherein the non-aqueous solvent contains a vinylene carbonate compound represented by the general formula (I) and / or a vinylethylene carbonate compound represented by the general formula (II), and further contains an acid anhydride. Is what you do.

【００１２】また、本発明は、リチウムを吸蔵・放出す
ることが可能な負極と、正極を少なくとも備えた非水系
電解液二次電池用の非水系電解液であって、該非水系電
解液が非水溶媒とリチウム塩から少なくとも構成され、
前記非水溶媒中に一般式（Ｉ）で表されるビニレンカー
ボネート化合物及び／又は一般式（II）で表されるビニ
ルエチレンカーボネート化合物を含有し、更に酸無水物
を含有することを特徴とする前記非水系電解液、にあ
る。The present invention also provides a non-aqueous electrolyte for a non-aqueous electrolyte secondary battery comprising at least a negative electrode capable of inserting and extracting lithium and a positive electrode, wherein the non-aqueous electrolyte is non-aqueous. At least composed of a water solvent and a lithium salt,
The non-aqueous solvent contains a vinylene carbonate compound represented by the general formula (I) and / or a vinylethylene carbonate compound represented by the general formula (II), and further contains an acid anhydride. The non-aqueous electrolyte.

【００１３】上記電解液を使用することにより、初期の
充電時から、負極表面の電解液分解活性の高い部位に、
ビニレンカーボネート化合物及び／又はビニルエチレン
カーボネート化合物由来の還元反応生成物の被膜と、酸
無水物の還元反応生成物の皮膜が効率よく生成し、理由
は明確ではないが、この複合被膜が高温環境下やサイク
ル中において安定であり、過度の電解液の分解を抑制す
ると思われ、充放電効率や保存特性、サイクル特性を向
上させると推定される。By using the above-mentioned electrolytic solution, from the time of initial charging, a portion having a high electrolytic solution decomposing activity on the surface of the negative electrode can be used.
A film of a reduction reaction product derived from a vinylene carbonate compound and / or a vinylethylene carbonate compound and a film of a reduction reaction product of an acid anhydride are efficiently formed, and the reason is not clear. It is considered that the electrolyte is stable during the heat treatment and in the cycle and suppresses excessive decomposition of the electrolytic solution, and improves the charge / discharge efficiency, storage characteristics, and cycle characteristics.

【００１４】[0014]

【発明の実施の形態】本発明は、このような知見に基づ
いて完成されたものであり、リチウムを吸蔵・放出する
ことが可能な負極と、正極と、非水溶媒にリチウム塩を
溶解してなる電解液とから少なくとも構成される非水系
電解液二次電池において、非水溶媒中に一般式（Ｉ）で
表されるビニレンカーボネート化合物及び／又は一般式
（II）で表されるビニルエチレンカーボネート化合物を
含有し、更に酸無水物を含有することを特徴とするもの
である。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention has been completed on the basis of such findings, and comprises a negative electrode capable of inserting and extracting lithium, a positive electrode, and a lithium salt dissolved in a non-aqueous solvent. A non-aqueous electrolyte secondary battery comprising at least a vinylene carbonate compound represented by the general formula (I) and / or vinyl ethylene represented by the general formula (II) in a non-aqueous solvent. It contains a carbonate compound and further contains an acid anhydride.

【００１５】本発明に使用される非水溶媒は、下記一般
式（Ｉ）で表されるビニレンカーボネート化合物及び下
記一般式（II）で表されるビニルエチレンカーボネート
化合物を単独で又は混合して含有し、更に酸無水物を含
有することを特徴とする。The non-aqueous solvent used in the present invention contains a vinylene carbonate compound represented by the following general formula (I) and a vinylethylene carbonate compound represented by the following general formula (II) singly or as a mixture. And an acid anhydride.

【００１６】[0016]

【化５】 一般式（Ｉ）において、Ｒ1 、Ｒ2 は、それぞれ独立し
て、水素原子又は炭素数１〜４のアルキル基を表す。Ｒ
1 、Ｒ2が炭素数１〜４のアルキル基である場合、その
具体例としては、メチル基、エチル基、ｎ−プロピル
基、ｉ−プロピル基、ｎ−ブチル基、ｓｅｃ−ブチル
基、ｔｅｒｔ−ブチル基が挙げられる。これらの中、メ
チル基、エチル基が好ましい。Embedded image In the general formula (I), R 1 and R 2 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R
When 1 and R 2 are an alkyl group having 1 to 4 carbon atoms, specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group and a tert. -Butyl group. Of these, a methyl group and an ethyl group are preferred.

【００１７】そして、このような一般式（Ｉ）で表され
るビニレンカーボネート化合物の具体例としては、ビニ
レンカーボネート、メチルビニレンカーボネート、エチ
ルビニレンカーボネート、４，５−ジメチルビニレンカ
ーボネート、４，５−ジエチルビニレンカーボネート等
を挙げることができる。中でもビニレンカーボネート、
４，５−ジメチルビニレンカーボネートが好ましく、ビ
ニレンカーボネートが特に好ましい。これらは２種以上
混合して用いてもよい。Specific examples of the vinylene carbonate compound represented by the general formula (I) include vinylene carbonate, methyl vinylene carbonate, ethyl vinylene carbonate, 4,5-dimethylvinylene carbonate, and 4,5-diethylene. Vinylene carbonate and the like can be mentioned. Among them, vinylene carbonate,
4,5-Dimethylvinylene carbonate is preferred, and vinylene carbonate is particularly preferred. These may be used as a mixture of two or more.

【００１８】一般式（II）において、Ｒ3、Ｒ4及びＲ5
は、それぞれ独立して、水素原子又は炭素数１〜４のア
ルキル基を表し、Ｒ6、Ｒ7及びＲ8は、それぞれ独立し
て、水素原子又は炭素数１〜４のアルキル基または炭素
数２〜７のアルケニル基を表す。Ｒ 3、Ｒ4、Ｒ5、Ｒ6、
Ｒ7及びＲ8が炭素数１〜４のアルキル基である場合、そ
の具体例としては、メチル基、エチル基、n−プロピル
基、ｉ−プロピル基、ｎ−ブチル基、ｓｅｃ−ブチル
基、ｔｅｒｔ−ブチル基が挙げられる。これらの中、メ
チル基、エチル基が好ましい。In the general formula (II), RThree, RFourAnd RFive
Are each independently a hydrogen atom or an atom having 1 to 4 carbon atoms.
Represents a alkyl group;6, R7And R8Are independent
A hydrogen atom or an alkyl group having 1 to 4 carbon atoms or carbon
Represents an alkenyl group of the formulas 2 to 7; R Three, RFour, RFive, R6,
R7And R8Is an alkyl group having 1 to 4 carbon atoms,
Specific examples of a methyl group, an ethyl group, n-propyl
Group, i-propyl group, n-butyl group, sec-butyl
And a tert-butyl group. Of these,
A tyl group and an ethyl group are preferred.

【００１９】また、Ｒ6、Ｒ7及びＲ8が炭素数２〜７の
アルケニル基である場合、その具体例としては、ビニル
基、１−メチルビニル基、２−メチルビニル基、プロペ
ニル基、１−メチルプロペニル基、２−メチルプロペニ
ル基、３−メチルプロペニル基、ブテニル基等が挙げら
れる。そしてこのような一般式（II）で表されるビニル
エチレンカーボネート化合物の具体例としては、４−ビ
ニルエチレンカーボネート、４−メチル−４−ビニルエ
チレンカーボネート、４−エチル−４−ビニルエチレン
カーボネート、４−ｎ−プロピル−４−ビニルエチレン
カーボネート、５−メチル−４−ビニルエチレンカーボ
ネート、４，４−ジビニルエチレンカーボネート、４，
５−ジビニルエチレンカーボネート等を挙げることがで
きる。When R 6 , R 7 and R 8 are alkenyl groups having 2 to 7 carbon atoms, specific examples thereof include vinyl, 1-methylvinyl, 2-methylvinyl, propenyl, Examples thereof include a 1-methylpropenyl group, a 2-methylpropenyl group, a 3-methylpropenyl group, and a butenyl group. Specific examples of such a vinylethylene carbonate compound represented by the general formula (II) include 4-vinylethylene carbonate, 4-methyl-4-vinylethylene carbonate, 4-ethyl-4-vinylethylene carbonate, -N-propyl-4-vinylethylene carbonate, 5-methyl-4-vinylethylene carbonate, 4,4-divinylethylene carbonate, 4,
5-divinylethylene carbonate and the like can be mentioned.

【００２０】中でも４−ビニルエチレンカーボネート、
４−メチル−４−ビニルエチレンカーボネート、４，５
−ジビニルエチレンカーボネートが好ましく、４−ビニ
ルエチレンカーボネートが特に好ましい。これらは一般
式（Ｉ）の化合物として２種以上、又は一般式（II）の
化合物として２種以上、又は一般式（Ｉ）の化合物と一
般式（II）の化合物をそれぞれ１種つづ以上混合して用
いてもよい。Among them, 4-vinylethylene carbonate,
4-methyl-4-vinylethylene carbonate, 4,5
-Divinylethylene carbonate is preferred, and 4-vinylethylene carbonate is particularly preferred. These may be two or more compounds of the general formula (I), two or more compounds of the general formula (II), or a mixture of one or more compounds of the general formula (I) and one compound of the general formula (II). You may use it.

【００２１】本発明に使用される酸無水物は、その種類
は限定されない。また、酸無水物の構造を１分子中に複
数個有する化合物であってもよい。本発明に使用される
酸無水物の具体例として、無水酢酸、無水プロピオン
酸、無水酪酸、無水コハク酸、無水グルタル酸、無水マ
レイン酸、無水シトラコン酸、無水グルタコン酸、無水
イタコン酸、無水ジグリコール酸、シクロヘキサンジカ
ルボン酸無水物、シクロペンタンテトラカルボン酸二無
水物、４−シクロヘキセン−１，２−ジカルボン酸無水
物、３，４，５，６−テトラヒドロフタル酸無水物、５
−ノルボルネン−２，３−ジカルボン酸無水物、フェニ
ルコハク酸無水物、２−フェニルグルタル酸無水物、無
水フタル酸、無水ピロメリット酸等が挙げることができ
る。中でも好ましいのは、無水コハク酸、無水グルタル
酸、無水マレイン酸である。これらの酸無水物は２種以
上混合して用いてもよい。The type of the acid anhydride used in the present invention is not limited. Further, it may be a compound having a plurality of acid anhydride structures in one molecule. Specific examples of the acid anhydride used in the present invention include acetic anhydride, propionic anhydride, butyric anhydride, succinic anhydride, glutaric anhydride, maleic anhydride, citraconic anhydride, glutaconic anhydride, itaconic anhydride, and diaconic anhydride. Glycolic acid, cyclohexanedicarboxylic anhydride, cyclopentanetetracarboxylic dianhydride, 4-cyclohexene-1,2-dicarboxylic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 5
-Norbornene-2,3-dicarboxylic anhydride, phenylsuccinic anhydride, 2-phenylglutaric anhydride, phthalic anhydride, pyromellitic anhydride and the like. Among them, succinic anhydride, glutaric anhydride and maleic anhydride are preferred. These acid anhydrides may be used as a mixture of two or more kinds.

【００２２】本発明において、非水溶媒中の一般式
（Ｉ）で表されるビニレンカーボネート化合物及び／又
は一般式（II）で表されるビニルエチレンカーボネート
化合物の含有量は特に限定されないが、溶媒総重量に基
づいて好ましくは０．０１〜５重量％である。尚、溶媒
総重量とは、電解液を非水溶媒とリチウム塩の溶質に分
けて考えた場合の、非水溶媒部の総重量とする。In the present invention, the content of the vinylene carbonate compound represented by the general formula (I) and / or the vinylethylene carbonate compound represented by the general formula (II) in the nonaqueous solvent is not particularly limited. It is preferably 0.01 to 5% by weight based on the total weight. Note that the total weight of the solvent is the total weight of the non-aqueous solvent portion when the electrolyte is considered as being divided into a non-aqueous solvent and a solute of a lithium salt.

【００２３】本発明において、非水溶媒中の酸無水物の
含有量は特に限定されないが、溶媒総重量に基づいて好
ましくは０．０１〜５重量％である。本発明に使用され
る非水溶媒としては、特に限定されず、例えば、エチレ
ンカーボネート、プロピレンカーボネート、ブチレンカ
ーボネート等の環状カーボネート、ジメチルカーボネー
ト、ジエチルカーボネート、ジ−ｎ−プロピルカーボネ
ート、エチルメチルカーボネート等のジアルキル（炭素
数１〜４のものが好ましい）カーボネート、テトラヒド
ロフラン、２−メチルテトラヒドロフラン等の環状エー
テル、ジメトキシエタン、ジメトキシメタン等の鎖状エ
ーテル、γ−ブチロラクトン、γ−バレロラクトン等の
環状エステル、酢酸メチル、プロピオン酸メチル、プロ
ピオン酸エチル等の鎖状エステル、スルフォラン、ジエ
チルスルホン等の含硫黄有機溶媒、リン酸トリメチル、
リン酸トリエチル等の含燐有機溶媒等が挙げられる。こ
れらの溶媒は二種類以上混合して用いても良い。In the present invention, the content of the acid anhydride in the non-aqueous solvent is not particularly limited, but is preferably 0.01 to 5% by weight based on the total weight of the solvent. The non-aqueous solvent used in the present invention is not particularly limited, and includes, for example, ethylene carbonate, propylene carbonate, cyclic carbonate such as butylene carbonate, dimethyl carbonate, diethyl carbonate, di-n-propyl carbonate, ethyl methyl carbonate and the like. Dialkyl (preferably having 1 to 4 carbon atoms); cyclic ethers such as carbonate, tetrahydrofuran and 2-methyltetrahydrofuran; chain ethers such as dimethoxyethane and dimethoxymethane; cyclic esters such as γ-butyrolactone and γ-valerolactone; Methyl, methyl propionate, chain esters such as ethyl propionate, sulfolane, sulfur-containing organic solvents such as diethyl sulfone, trimethyl phosphate,
Examples include a phosphorus-containing organic solvent such as triethyl phosphate. These solvents may be used as a mixture of two or more kinds.

【００２４】ここで非水溶媒が、アルキレン基の炭素数
が２〜４のアルキレンカーボネートからなる群から選ば
れた環状カーボネートと、アルキル基の炭素数が１〜４
であるジアルキルカーボネートよりなる群から選ばれた
鎖状カーボネートとをそれぞれ２０容量％以上含有し、
且つこれらのカーボネートが全体の７０容量％以上を占
める混合溶媒であるものが好ましい。Here, the nonaqueous solvent is a cyclic carbonate selected from the group consisting of alkylene carbonates having 2 to 4 carbon atoms in an alkylene group, and a cyclic carbonate having 1 to 4 carbon atoms in the alkyl group.
A linear carbonate selected from the group consisting of dialkyl carbonates, each containing 20% by volume or more,
Further, it is preferable that these carbonates are a mixed solvent occupying 70% by volume or more of the whole.

【００２５】アルキレン基の炭素数が２〜４のアルキレ
ンカーボネートの具体例としては、例えばエチレンカー
ボネート、プロピレンカーボネート、ブチレンカーボネ
ート等を挙げることができ、これらの中、エチレンカー
ボネート、プロピレンカーボネートが好ましい。アルキ
ル基の炭素数が１〜４であるジアルキルカーボネートの
具体例としては、ジメチルカーボネート、ジエチルカー
ボネート、ジ−ｎ−プロピルカーボネート、エチルメチ
ルカーボネート、メチル−ｎ−プロピルカーボネート、
エチル−ｎ−プロピルカーボネート等を挙げることがで
きる。これらの中、ジメチルカーボネート、ジエチルカ
ーボネート、エチルメチルカーボネートが好ましい。な
お混合非水溶媒中には、カーボネート以外の溶媒を含有
してもよい。Specific examples of the alkylene carbonate having 2 to 4 carbon atoms of the alkylene group include, for example, ethylene carbonate, propylene carbonate, butylene carbonate and the like. Of these, ethylene carbonate and propylene carbonate are preferable. Specific examples of the dialkyl carbonate having 1 to 4 carbon atoms of the alkyl group include dimethyl carbonate, diethyl carbonate, di-n-propyl carbonate, ethyl methyl carbonate, methyl-n-propyl carbonate,
Ethyl-n-propyl carbonate and the like can be mentioned. Among them, dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate are preferred. The mixed non-aqueous solvent may contain a solvent other than carbonate.

【００２６】他の好ましい電解液の非水溶媒の態様とし
て、比誘電率２５以上の１種または２種以上の溶媒を９
０容量％以上含有する組み合わせが高温安定性の面から
好ましい。また、比誘電率２５以上の非水溶媒としてエ
チレンカーボネート、プロピレンカーボネート、γ−ブ
チロラクトン、γ−バレロラクトンの内、１種または２
種以上を９０容量％以上含むものが好ましい。さらに前
記非水系電解液には、他の有用な化合物、例えば従来公
知の添加剤、過充電防止剤、脱水剤、脱酸剤と混合して
用いても良い。As another preferred embodiment of the non-aqueous solvent of the electrolytic solution, one or two or more solvents having a relative dielectric constant of 25 or more are used.
A combination containing 0% by volume or more is preferable from the viewpoint of high-temperature stability. As a non-aqueous solvent having a relative dielectric constant of 25 or more, one or two of ethylene carbonate, propylene carbonate, γ-butyrolactone, and γ-valerolactone are used.
Those containing 90% by volume or more of the seed or more are preferable. Further, the non-aqueous electrolyte may be used by mixing with other useful compounds, for example, a conventionally known additive, an overcharge inhibitor, a dehydrating agent, and a deoxidizing agent.

【００２７】例えば、従来公知の添加剤であるエチレン
サルファイト等のサルファイト、フェニルエチレンカー
ボネート、フルオロエチレンカーボネートのエチレンカ
ーボネート誘導体、プロパンスルトン等のスルホン酸エ
ステル、１‐メチル‐２‐ピロリジノン、１‐メチル‐
２‐ピペリドン、３‐メチル‐２‐オキサゾリジノン、
１，３‐ジメチル‐２‐イミダゾリジノン、Ｎ‐メチル
スクシイミド等の含窒素化合物群から選ばれる一種以上
の化合物を、０.１〜５重量％含有していると、含まな
い場合と比較して、より容量維持特性、サイクル特性が
良好である。For example, conventionally known additives such as sulfites such as ethylene sulfite, phenylethylene carbonate, ethylene carbonate derivatives of fluoroethylene carbonate, sulfonic acid esters such as propane sultone, 1-methyl-2-pyrrolidinone, Methyl-
2-piperidone, 3-methyl-2-oxazolidinone,
When one or more compounds selected from the group of nitrogen-containing compounds such as 1,3-dimethyl-2-imidazolidinone and N-methylsuccinimide are contained in an amount of 0.1 to 5% by weight, In comparison, the capacity retention characteristics and the cycle characteristics are better.

【００２８】前述の過充電防止剤としては、特開平８−
２０３５６０号、同７−３０２６１４号、同９−５０８
２２号、同８−２７３７００号、同９−１７４４７号各
公報等に記載されるベンゼン誘導体、特開平９−１０６
８３５号、同９−１７１８４０号、同１０−３２１２５
８号、同７−３０２６１４号、同７−３０２６１４号、
同１１−１６２５１２号、特許２９３９４６９号、特許
２９６３８９８号各公報等に記載されるビフェニル及び
その誘導体、特開平９−４５３６９号、同１０−３２１
２５８号各公報等に記載されるピロール誘導体、特開平
７−３２０７７８号、同７−３０２６１４号各公報等に
記載されるアニリン誘導体等の芳香族化合物や特許２９
８３２０５号公報等に記載のエーテル系化合物、その他
特開２００１‐１５１５８号公報に記載の化合物群等を
挙げることができる。The above-mentioned overcharge preventing agent is disclosed in
203560, 7-302614, 9-508
22, benzene derivatives described in JP-A Nos. 8-273700, 9-17447 and the like;
No. 835, No. 9-171840, No. 10-32125
No. 8, No. 7-302614, No. 7-302614,
Biphenyls and derivatives thereof described in JP-A-11-162512, JP-A-2939469 and JP-A-2963898, JP-A-9-45369, JP-A-10-321
Patent No. 258, pyrrole derivatives, and aromatic compounds such as aniline derivatives described in JP-A-7-320778 and JP-A-7-302614, and Patent No. 29
Examples thereof include ether compounds described in JP-A-83205 and other compound groups described in JP-A-2001-15158.

【００２９】更に、前記非水系電解液には、セパレータ
や電極材との塗れ性を良くするために、公知の界面活性
剤を溶媒総重量に基づいて０．０１〜２重量％の範囲で
添加しても良い。本発明で使用される電解液の溶質とし
ては、リチウム塩が用いられる。リチウム塩について
は、溶質として使用し得るものであれば特に限定はされ
ないが、その具体例として例えば、 １）無機リチウム塩：ＬｉＰＦ6、ＬｉＡｓＦ6、ＬｉＢ
Ｆ4、ＬｉＴａＦ6、ＬｉＡｌＦ4、ＬｉＡｌＦ6、ＬｉＳ
ｉＦ6等の無機フッ化物塩、ＬｉＣｌＯ4等の過ハロゲン
酸塩、 ２）有機リチウム塩：ＬｉＣＦ3ＳＯ3等の有機スルホン
酸塩、ＬｉＮ（ＣＦ3ＳＯ2）2 、ＬｉＮ（Ｃ2Ｆ5Ｓ
Ｏ2）2、ＬｉＮ（ＣＦ3ＳＯ2）（Ｃ4Ｆ9ＳＯ2）等のパ
ーフルオロアルキルスルホン酸イミド塩、ＬｉＣ（ＣＦ
3ＳＯ2）3等のパーフルオロアルキルスルホン酸メチド
塩、ＬｉＰＦ3（Ｃ2Ｆ5）3、ＬｉＢＦ2（ＣＦ3）2、Ｌ
ｉＢＦ3（ＣＦ3）等の無機フッ化物塩の一部のフッ素を
パーフルオロアルキル基で置換した塩、ＬｉＢ（ＣＦ3
ＣＯＯ）4、ＬｉＢ（ＯＣＯＣＦ2ＣＯＯ）2、ＬｉＢ
（ＯＣＯＣ2Ｆ4ＣＯＯ）2、等のリチウムテトラキス
（パーフルオロカルボキシレート）ボレート塩が挙げら
れる。これらの溶質は２種類以上混合して用いても良
い。これらの中で、溶解度、イオン解離度、電気伝導率
特性の面から、ＬｉＰＦ6、ＬｉＢＦ4、ＬｉＮ（ＣＦ3
ＳＯ2）2 、ＬｉＮ（Ｃ2Ｆ5ＳＯ2）2、ＬｉＮ（ＣＦ 3
ＳＯ2）（Ｃ4Ｆ9ＳＯ2）、ＬｉＰＦ3（ＣＦ3）3、Ｌｉ
ＰＦ3（Ｃ2Ｆ5）3、ＬｉＢＦ2（Ｃ2Ｆ5）2、ＬｉＢ（Ｏ
ＣＯＣＦ2ＣＯＯ）2がより好ましく、ＬｉＰＦ6、Ｌｉ
ＢＦ4がさらに好ましい。特に、誘電率２５以上の非水
溶媒としてγ−ブチロラクトンを６０重量％以上含む非
水溶媒を選択した場合には、ＬｉＢＦ4がリチウム塩全
体の５０重量％以上であることが好ましい。Further, the non-aqueous electrolytic solution contains a separator.
Known surface activity to improve paintability with
Agent in the range of 0.01 to 2% by weight based on the total weight of the solvent
It may be added. As a solute of the electrolytic solution used in the present invention
In this case, a lithium salt is used. About lithium salt
Is not particularly limited as long as it can be used as a solute.
There are no specific examples, for example: 1) Inorganic lithium salt: LiPF6, LiAsF6, LiB
FFour, LiTaF6, LiAlFFour, LiAlF6, LiS
iF6Inorganic fluoride salts such as LiClOFourSuch as perhalogen
Acid salt, 2) organic lithium salt: LiCFThreeSOThreeAnd other organic sulfones
Acid salt, LiN (CFThreeSOTwo)Two , LiN (CTwoFFiveS
OTwo)Two, LiN (CFThreeSOTwo) (CFourF9SOTwo) Etc.
-Fluoroalkylsulfonic acid imide salt, LiC (CF
ThreeSOTwo)ThreeAnd other perfluoroalkylsulfonic acid methides
Salt, LiPFThree(CTwoFFive)Three, LiBFTwo(CFThree)Two, L
iBFThree(CFThree)) And some fluorine of inorganic fluoride salts
A salt substituted with a perfluoroalkyl group, LiB (CFThree
COO)Four, LiB (OCOCFTwoCOO)Two, LiB
(OCOCTwoFFourCOO)Two, Such as lithium tetrakis
(Perfluorocarboxylate) borate salts
It is. These solutes may be used as a mixture of two or more.
No. Among these, solubility, ionic dissociation, electrical conductivity
In terms of characteristics, LiPF6, LiBFFour, LiN (CFThree
SOTwo)Two , LiN (CTwoFFiveSOTwo)Two, LiN (CF Three
SOTwo) (CFourF9SOTwo), LiPFThree(CFThree)Three, Li
PFThree(CTwoFFive)Three, LiBFTwo(CTwoFFive)Two, LiB (O
COCFTwoCOO)TwoIs more preferable, and LiPF6, Li
BFFourIs more preferred. In particular, non-water with a dielectric constant of 25 or more
Non-solvent containing at least 60% by weight of γ-butyrolactone as a solvent
If an aqueous solvent is selected, LiBFFourIs all lithium salt
It is preferably at least 50% by weight of the body.

【００３０】電解液中の溶質のリチウム塩モル濃度は、
０．５〜３モル／リットルであることが望ましい。０．
５モル／リットル以下もしくは３モル／リットル以上で
は、電解液の電気伝導率が低く、電池の性能が低下する
ため好ましくない。本発明の電池を構成する負極の材料
としては、様々な熱分解条件での有機物の熱分解物や人
造黒鉛、天然黒鉛等のリチウムを吸蔵・放出可能な炭素
質材料、酸化錫、酸化珪素等のリチウムを吸蔵・放出可
能な金属酸化物材料、リチウム金属、種々のリチウム合
金を用いることができる。これらの負極材料は二種類以
上混合して用いても良い。The molar concentration of the lithium salt of the solute in the electrolyte is
Desirably, it is 0.5 to 3 mol / liter. 0.
If it is 5 mol / l or less or 3 mol / l or more, the electric conductivity of the electrolytic solution is low, and the performance of the battery is undesirably reduced. Examples of the material of the negative electrode constituting the battery of the present invention include pyrolysates of organic substances under various pyrolysis conditions, artificial graphite, carbonaceous materials capable of occluding and releasing lithium such as natural graphite, tin oxide, silicon oxide and the like. Metal oxide materials capable of occluding and releasing lithium, lithium metal, and various lithium alloys can be used. These negative electrode materials may be used as a mixture of two or more.

【００３１】上記の中でも好ましいものであるリチウム
を吸蔵・放出可能な炭素質材料の具体例としては、例え
ば様々な熱分解条件での有機物の熱分解物や、人造黒
鉛、天然黒鉛等が挙げられる。好適には種々の原料から
得た易黒鉛性ピッチの高温熱処理によって製造された人
造黒鉛及び精製天然黒鉛或いはこれらの黒鉛にピッチを
含む種々の表面処理を施した材料が主として使用される
が、これらの黒鉛材料は学振法によるＸ線回折で求めた
格子面（００２面）のｄ値（層間距離）は０．３３５〜
０．３３８ｎｍであり、０．３３５〜０．３３７ｎｍで
あるものが好ましい。灰分は１重量％以下であるのが好
ましく、０．５重量％以下であるのがより好ましく、
０．１重量％以下であるのが特に好ましい。また、学振
法によるＸ線回折で求めた結晶子サイズ（Ｌｃ）は３０
ｎｍ以上であるのが好ましく、５０ｎｍ以上であるのが
より好ましく、１００ｎｍ以上であるのが特に好まし
い。Specific examples of the preferable carbonaceous materials capable of occluding and releasing lithium include thermal decomposition products of organic substances under various thermal decomposition conditions, artificial graphite, and natural graphite. . Preferably, artificial graphite and refined natural graphite produced by high-temperature heat treatment of easily-graphitizable pitch obtained from various raw materials, or materials obtained by subjecting these graphites to various surface treatments including pitch are mainly used. The d value (interlayer distance) of the lattice plane (002 plane) obtained by X-ray diffraction according to the Gakushin method is 0.335 to
0.338 nm, and preferably 0.335 to 0.337 nm. The ash content is preferably 1% by weight or less, more preferably 0.5% by weight or less,
It is particularly preferred that the content is 0.1% by weight or less. The crystallite size (Lc) determined by X-ray diffraction according to the Gakushin method is 30.
It is preferably at least nm, more preferably at least 50 nm, particularly preferably at least 100 nm.

【００３２】また、レーザー回折・散乱法による炭素質
材料粉体のメジアン径は、１〜１００μｍであるのが好
ましく、３〜５０μｍ以下であるのがより好ましく、５
〜４０μｍであるのが更に好ましく、７〜３０μｍであ
るのが特に好ましい。ＢＥＴ法比表面積は、０．３〜２
５．０ｍ2／ｇであるのが好ましく、０．５〜２０．０
ｍ2／ｇであるのがより好ましく、０．７〜１５．０ｍ2
／ｇであるのが更に好ましく、０．８〜１０．０ｍ2／
ｇであるのが特に好ましい。また、前記径に調整された
粉体をアルゴンイオンレーザー光を用いたラマンスペク
トル分析した場合、１５７０〜１６２０ｃｍ-1の範囲の
ピークＰA （ピーク強度ＩA ）及び１３００〜１４００
ｃｍ-1の範囲のピークＰB （ピーク強度ＩB ）の強度比
Ｒ＝ＩB／ＩA は０．０１〜０．５が好ましく、１５７
０〜１６２０ｃｍ-1の範囲のピークの半値幅は２６ｃｍ
-1以下、特に２５ｃｍ-1以下であるのが好ましい。Further, the median diameter of the carbonaceous material powder by the laser diffraction / scattering method is preferably 1 to 100 μm, more preferably 3 to 50 μm or less, and
The thickness is more preferably from 40 to 40 μm, and particularly preferably from 7 to 30 μm. BET specific surface area is 0.3 to 2
It is preferably 5.0 m 2 / g, and 0.5 to 20.0 g.
m 2 / g, more preferably 0.7 to 15.0 m 2
/ G, more preferably 0.8 to 10.0 m 2 / g.
g is particularly preferred. When the powder adjusted to the above-mentioned diameter is subjected to Raman spectrum analysis using argon ion laser light, the peak PA (peak intensity IA) in the range of 1570 to 1620 cm -1 and 1300 to 1400
The intensity ratio R = IB / IA of the peak PB (peak intensity IB) in the range of cm -1 is preferably 0.01 to 0.5, and
The half width of the peak in the range of 0 to 1620 cm -1 is 26 cm.
-1 or less, particularly preferably 25 cm -1 or less.

【００３３】これらの負極材料を用いて負極を製造する
方法については、特に限定されない。例えば、負極材料
に、必要に応じて結着剤、増粘剤、導電材、溶媒等を加
えてスラリー状とし、集電体の基板に塗布し、乾燥する
ことにより負極を製造することができるし、また、該負
極材料をそのままロール成形してシート電極としたり、
圧縮成形によりペレット電極とすることもできる。The method for producing a negative electrode using these negative electrode materials is not particularly limited. For example, a negative electrode can be manufactured by adding a binder, a thickener, a conductive material, a solvent, and the like to a negative electrode material as needed to form a slurry, applying the slurry to a current collector substrate, and drying. Alternatively, the negative electrode material may be directly roll-formed into a sheet electrode,
A pellet electrode can be obtained by compression molding.

【００３４】電極の製造に用いられる結着剤について
は、電極製造時に使用する溶媒や電解液に対して安定な
材料であれば、特に限定されない。その具体例として
は、ポリフッ化ビニリデン、ポリテトラフルオロエチレ
ン、スチレン・ブタジエンゴム、イソプレンゴム、ブタ
ジエンゴム等を挙げることができる。増粘剤としては、
カルボキシルメチルセルロース、メチルセルロース、ヒ
ドロキシメチルセルロース、エチルセルロース、ポリビ
ニルアルコール、酸化スターチ、リン酸化スターチ、ガ
ゼイン等が挙げられる。The binder used in the production of the electrode is not particularly limited as long as it is a material that is stable with respect to the solvent and the electrolyte used in the production of the electrode. Specific examples thereof include polyvinylidene fluoride, polytetrafluoroethylene, styrene / butadiene rubber, isoprene rubber, and butadiene rubber. As a thickener,
Examples thereof include carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, ethyl cellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, and casein.

【００３５】導電材としては、銅やニッケル等の金属材
料、グラファイト、カーボンブラック等のような炭素材
料が挙げられる。負極用集電体の材質は、銅、ニッケ
ル、ステンレス等の金属が使用され、これらの中で薄膜
に加工しやすいという点とコストの点から銅箔が好まし
い。本発明の電池を構成する正極の材料としては、リチ
ウムコバルト酸化物、リチウムニッケル酸化物、リチウ
ムマンガン酸化物等のリチウム遷移金属複合酸化物材料
等のリチウムを吸蔵及び放出可能な材料を使用すること
ができる。Examples of the conductive material include metal materials such as copper and nickel, and carbon materials such as graphite and carbon black. As the material of the current collector for the negative electrode, metals such as copper, nickel, and stainless steel are used, and among these, copper foil is preferable from the viewpoint of easy processing into a thin film and cost. As the material of the positive electrode constituting the battery of the present invention, a material capable of inserting and extracting lithium, such as a lithium transition metal composite oxide material such as lithium cobalt oxide, lithium nickel oxide, and lithium manganese oxide, is used. Can be.

【００３６】正極の製造方法については、特に限定され
ず、上記の負極の製造方法に準じて製造することができ
る。また、その形状については、正極材料に必要に応じ
て結着剤、導電材、溶媒等を加えて混合後、集電体の基
板に塗布してシート電極としたり、プレス成形を施して
ペレット電極とすることができる。正極用集電体の材質
は、アルミニウム、チタン、タンタル等の金属またはそ
の合金が用いられる。これらの中で、特にアルミニウム
またはその合金が軽量であるためエネルギー密度の点で
望ましい。The method for manufacturing the positive electrode is not particularly limited, and the positive electrode can be manufactured according to the above-described method for manufacturing the negative electrode. As for the shape, a binder, a conductive material, a solvent, and the like are added to the positive electrode material as necessary and mixed, and then applied to a current collector substrate to form a sheet electrode, or a pellet electrode formed by press molding. It can be. As the material of the positive electrode current collector, a metal such as aluminum, titanium, and tantalum or an alloy thereof is used. Among them, aluminum or its alloy is particularly preferable in terms of energy density because of its light weight.

【００３７】本発明の電池に使用するセパレーターの材
質や形状については、特に限定されない。但し、電解液
に対して安定で、保液性の優れた材料の中から選ぶのが
好ましく、ポリエチレン、ポリプロピレン等のポリオレ
フィンを原料とする多孔性シートまたは不織布等を用い
るのが好ましい。負極、正極及び非水系電解液を少なく
とも有する本発明の電池を製造する方法については、特
に限定されず、通常採用されている方法の中から適宜選
択することができる。The material and shape of the separator used in the battery of the present invention are not particularly limited. However, it is preferable to select from materials that are stable to the electrolytic solution and have excellent liquid retention properties, and it is preferable to use a porous sheet or nonwoven fabric made of a polyolefin such as polyethylene or polypropylene as a raw material. The method for producing the battery of the present invention having at least the negative electrode, the positive electrode, and the nonaqueous electrolyte is not particularly limited, and can be appropriately selected from commonly employed methods.

【００３８】また、電池の形状については特に限定され
ず、シート電極及びセパレータをスパイラル状にしたシ
リンダータイプ、ペレット電極及びセパレータを組み合
わせたインサイドアウト構造のシリンダータイプ、ペレ
ット電極及びセパレータを積層したコインタイプ等が使
用可能である。The shape of the battery is not particularly limited, and is a cylinder type in which a sheet electrode and a separator are formed in a spiral shape, a cylinder type having an inside-out structure in which a pellet electrode and a separator are combined, and a coin type in which a pellet electrode and a separator are laminated. Etc. can be used.

【００３９】[0039]

【実施例】以下に、実施例及び比較例を挙げて本発明を
更に具体的に説明するが、本発明は、その要旨を越えな
い限りこれらの実施例に限定されるものではない。 実施例１ Ｘ線回折における格子面（００２面）のｄ値が０．３３
６ｎｍ、晶子サイズ（Ｌｃ）が、１００ｎｍ以上（６５
２ｎｍ）、灰分が０．０７重量％、レーザー回折・散乱
法によるメジアン径が１２μｍ、ＢＥＴ法比表面積が
７．５ｍ2／ｇ、アルゴンイオンレーザー光を用いたラ
マンスペクトル分析において１５７０〜１６２０ｃｍ-1
の範囲のピークＰA（ピーク強度ＩA）および１３００〜
１４００ｃｍ-1の範囲のピークＰB（ピーク強度ＩB）の
強度比Ｒ＝ＩB／ＩAが０．１２、１５７０〜１６２０ｃ
ｍ-1の範囲のピークの半値幅が１９．９cm-1である天然
黒鉛粉末９４重量部にポリフッ化ビニリデン６重量部を
混合し、Ｎ−メチル−２−ピロリドンで分散させスラリ
ー状としたものを負極集電体である厚さ１８μｍの銅箔
上に均一に塗布し、乾燥後、直径１２．５ｍｍの円盤状
に打ち抜いて負極とした。EXAMPLES The present invention will be described more specifically below with reference to examples and comparative examples, but the present invention is not limited to these examples unless it exceeds the gist. Example 1 The d value of the lattice plane (002 plane) in X-ray diffraction was 0.33.
6 nm, crystallite size (Lc) is 100 nm or more (65
2 nm), an ash content of 0.07% by weight, a median diameter by laser diffraction / scattering method of 12 μm, a BET specific surface area of 7.5 m 2 / g, and 1570 to 1620 cm −1 in Raman spectrum analysis using argon ion laser light.
Range of the peak P A (peak intensity I A) and 1300 to
Intensity ratio R = I B / I A of 1400 cm -1 in the range of peak P B (peak intensity I B) is 0.12,1570~1620c
that the half-value width of the peak in the range m -1 were mixed polyvinylidene fluoride 6 parts by weight 94 parts by weight of natural graphite powder is 19.9cm -1, and a slurry dispersed in N- methyl-2-pyrrolidone Was uniformly coated on a copper foil having a thickness of 18 μm as a negative electrode current collector, dried, and then punched into a disk having a diameter of 12.5 mm to obtain a negative electrode.

【００４０】正極活物質としてＬｉＣｏＯ2 ８５重量部
にカーボンブラック６重量部、ポリフッ化ビニリデンＫ
Ｆ−１０００（呉羽化学社製、商品名）９重量部を加え
混合し、Ｎ−メチル−２−ピロリドンで分散し、スラリ
ー状としたものを正極集電体である厚さ２０μｍのアル
ミニウム箔上に均一に塗布し、乾燥後、直径１２．５ｍ
ｍの円盤状に打ち抜いて正極とした。電解液について
は、乾燥アルゴン雰囲気下で、十分に乾燥を行ったＬｉ
ＰＦ6を溶質として用い、エチレンカーボネートとエチ
ルメチルカーボネートの混合物（３：７容量比）にビニ
レンカーボネート１重量％と無水コハク酸０．２重量％
の割合（それぞれ溶媒総重量に基づいて配合割合を示し
た。以下の例においても同様である）で添加し、更にＬ
ｉＰＦ6 を１モル／リットルの割合で溶解して調製し
た。As a positive electrode active material, 85 parts by weight of LiCoO 2, 6 parts by weight of carbon black, and polyvinylidene fluoride K
9 parts by weight of F-1000 (manufactured by Kureha Chemical Co., Ltd.) were added and mixed, dispersed with N-methyl-2-pyrrolidone, and made into a slurry on a 20 μm-thick aluminum foil serving as a positive electrode current collector. 12.5m in diameter after applying uniformly and drying
m to form a positive electrode. As for the electrolyte, Li was sufficiently dried under a dry argon atmosphere.
Using PF 6 as a solute, 1% by weight of vinylene carbonate and 0.2% by weight of succinic anhydride were added to a mixture of ethylene carbonate and ethyl methyl carbonate (3: 7 by volume).
(The mixing ratio is shown based on the total weight of the solvent. The same applies to the following examples).
It was prepared by dissolving iPF 6 at a rate of 1 mol / liter.

【００４１】これらの負極、正極、電解液を用いて、正
極導電体を兼ねるステンレス鋼製の缶体に正極を収容
し、その上に電解液を含浸させたセパレーターを介して
負極を裁置した。この缶体と負極導電体を兼ねる封口板
とを、絶縁用のガスケットを介してかしめて密封し、コ
イン型電池を作製した。 比較例１ エチレンカーボネートとエチルメチルカーボネートの混
合物（３：７容量比）にビニレンカーボネートを１重量
％割合で添加し、更にＬｉＰＦ6を１モル／リットルの
割合で溶解して調製した電解液を用いた以外は実施例１
と同様にしてコイン型電池を作製した。Using the negative electrode, the positive electrode, and the electrolytic solution, the positive electrode was housed in a stainless steel can that also serves as the positive electrode conductor, and the negative electrode was placed thereon via a separator impregnated with the electrolytic solution. . The can body and the sealing plate also serving as the negative electrode conductor were caulked and sealed via an insulating gasket to produce a coin-type battery. Comparative Example 1 An electrolyte prepared by adding vinylene carbonate at a ratio of 1% by weight to a mixture of ethylene carbonate and ethyl methyl carbonate (3: 7 by volume) and further dissolving LiPF 6 at a ratio of 1 mol / liter was used. Example 1 except for
In the same manner as in the above, a coin-type battery was produced.

【００４２】実施例２ エチレンカーボネートとエチルメチルカーボネートの混
合物（３：７容量比）にビニルエチレンカーボネート１
重量％と無水コハク酸０．２重量％の割合で添加し、更
にＬｉＰＦ6を１モル／リットルの割合で溶解して調製
した電解液を用いたこと以外は実施例１と同様にしてコ
イン型電池を作製した。EXAMPLE 2 Vinyl ethylene carbonate 1 was added to a mixture of ethylene carbonate and ethyl methyl carbonate (3: 7 by volume).
% Of succinic anhydride and 0.2% by weight of succinic anhydride, and a coin-shaped electrolyte was prepared in the same manner as in Example 1 except that an electrolyte prepared by dissolving LiPF 6 at a rate of 1 mol / liter was used. A battery was manufactured.

【００４３】比較例２ エチレンカーボネートとエチルメチルカーボネートの混
合物（３：７容量比）にビニルエチレンカーボネートを
１重量％割合で添加し、更にＬｉＰＦ6を１モル／リッ
トルの割合で溶解して調製した電解液を用いた以外は実
施例１と同様にしてコイン型電池を作製した。Comparative Example 2 Vinyl ethylene carbonate was added to a mixture of ethylene carbonate and ethyl methyl carbonate (3: 7 by volume) at a ratio of 1% by weight, and LiPF 6 was further dissolved at a ratio of 1 mol / L. A coin-type battery was produced in the same manner as in Example 1 except that the electrolytic solution was used.

【００４４】実施例３ γ−ブチロラクトンにビニレンカーボネート１重量％と
無水コハク酸０．２重量％の割合で添加し、更にＬｉＢ
Ｆ4を１．５モル／リットルの割合で溶解して調製した
電解液を用いた以外は実施例１と同様にしてコイン型電
池を作製した。 比較例３ γ−ブチロラクトンにビニレンカーボネートを１重量％
の割合で添加し、更にＬｉＢＦ4を１．５モル／リット
ルの割合で溶解して調製した電解液を用いたこと以外は
実施例１と同様にしてコイン型電池を作製した。Example 3 1% by weight of vinylene carbonate and 0.2% by weight of succinic anhydride were added to γ-butyrolactone.
To prepare a coin-type battery except for using the F 4 an electrolyte solution prepared by dissolving at a rate of 1.5 mole / liter in the same manner as in Example 1. Comparative Example 3 1% by weight of vinylene carbonate to γ-butyrolactone
, And an electrolytic solution prepared by further dissolving LiBF 4 at a ratio of 1.5 mol / liter was used to produce a coin-type battery in the same manner as in Example 1.

【００４５】実施例４ γ−ブチロラクトンにビニレンカーボネート１重量％と
無水マレイン酸０．２重量％の割合で添加し、更にＬｉ
ＢＦ4を１．５モル／リットルの割合で溶解して調製し
た電解液を用いた以外は実施例１と同様にしてコイン型
電池を作製した。Example 4 To γ-butyrolactone was added 1% by weight of vinylene carbonate and 0.2% by weight of maleic anhydride.
A coin-type battery was produced in the same manner as in Example 1 except that an electrolyte prepared by dissolving BF 4 at a ratio of 1.5 mol / liter was used.

【００４６】実施例５ エチレンカーボネートとプロピレンカーボネートの混合
物（５：５容量比）にビニレンカーボネート１重量％と
無水コハク酸０．２重量％の割合で添加し、更にＬｉＰ
Ｆ6を１モル／リットルの割合で溶解して調製した電解
液を用いた以外は実施例１と同様にしてコイン型電池を
作製した。Example 5 1% by weight of vinylene carbonate and 0.2% by weight of succinic anhydride were added to a mixture of ethylene carbonate and propylene carbonate (5: 5 by volume).
To prepare a coin-type battery except for using an electrolytic solution prepared by dissolving F 6 at a rate of 1 mole / liter in the same manner as in Example 1.

【００４７】比較例４ エチレンカーボネートとプロピレンカーボネートの混合
物（５：５容量比）にビニレンカーボネートを１重量％
割合で添加し、更にＬｉＰＦ6を１モル／リットルの割
合で溶解して調製した電解液を用いた以外は実施例１と
同様にしてコイン型電池を作製した。Comparative Example 4 1% by weight of vinylene carbonate was added to a mixture of ethylene carbonate and propylene carbonate (5: 5 by volume).
A coin-type battery was produced in the same manner as in Example 1, except that an electrolyte solution prepared by dissolving LiPF 6 at a rate of 1 mol / liter was used.

【００４８】これらの実施例１〜５および比較例１〜４
の電池を２５℃において、０．５ｍＡの定電流で充電終
止電圧４．２Ｖ、放電終止電圧３Ｖで充放電を５サイク
ル行って安定させた後、充電状態で８５℃で３日間保存
した。保存後の電池を２５℃において０．５ｍＡの定電
流で放電終止電圧３Ｖまで放電させ、次に０．５ｍＡの
定電流で充電終止電圧４．２Ｖ、放電終止電圧３Ｖで充
放電を行って保存後の容量を測定した。保存前の放電容
量を１００とした場合の保存後の放電容量を表１に示
す。表１から明らかなように、本実施例の電池は、保存
前の放電容量に対する保存後の放電容量が向上してお
り、高温での保存特性の向上に効果がある。Examples 1 to 5 and Comparative Examples 1 to 4
The battery was stabilized at 25 ° C. by performing 5 cycles of charge and discharge at a constant current of 0.5 mA at a constant current of 0.5 mA and a discharge end voltage of 3 V for 5 cycles, and then stored in a charged state at 85 ° C. for 3 days. The battery after storage is discharged at 25 ° C. at a constant current of 0.5 mA to a discharge end voltage of 3 V, and then charged and discharged at a constant current of 0.5 mA at a charge end voltage of 4.2 V and a discharge end voltage of 3 V and stored. The subsequent capacity was measured. Table 1 shows the discharge capacity after storage when the discharge capacity before storage was 100. As is clear from Table 1, the battery of this example has an improved discharge capacity after storage with respect to a discharge capacity before storage, and is effective in improving storage characteristics at high temperatures.

【００４９】[0049]

【表１】 [Table 1]

【００５０】[0050]

【発明の効果】リチウムを吸蔵・放出することが可能な
負極と、正極と、非水溶媒にリチウム塩を溶解してなる
電解液とから少なくとも構成される非水系電解液二次電
池において、前記非水溶媒中に一般式（Ｉ）で表される
ビニレンカーボネート化合物及び／又は一般式（II）で
表されるビニルエチレンカーボネート化合物を含有し、
更に酸無水物を含有することにより、電解液の分解を最
小限に抑え、高い容量が得られると共に、高温下におい
ても、保存特性、サイクル特性の優れた電池を作製する
ことができ、非水系電解液二次電池の小型化、高性能化
に寄与することができる。According to a non-aqueous electrolyte secondary battery comprising at least a negative electrode capable of inserting and extracting lithium, a positive electrode, and an electrolyte obtained by dissolving a lithium salt in a non-aqueous solvent, A vinylene carbonate compound represented by the general formula (I) and / or a vinylethylene carbonate compound represented by the general formula (II) in a non-aqueous solvent,
Further, by containing an acid anhydride, decomposition of the electrolytic solution can be minimized, a high capacity can be obtained, and a battery having excellent storage characteristics and cycle characteristics can be produced even at a high temperature. This can contribute to miniaturization and high performance of the electrolyte secondary battery.

フロントページの続き (72)発明者 木下 信一 茨城県稲敷郡阿見町中央八丁目３番１号 三菱化学株式会社内 Ｆターム(参考） 5H029 AJ03 AJ04 AJ05 AK03 AL02 AL06 AL07 AL12 AL18 AM00 AM02 AM03 AM05 AM07 Continuing from the front page (72) Inventor Shinichi Kinoshita 3-3-1 Chuo, Ami-cho, Inashiki-gun, Ibaraki Prefecture Mitsubishi Chemical Corporation F-term (reference) 5H029 AJ03 AJ04 AJ05 AK03 AL02 AL06 AL07 AL12 AL18 AM00 AM02 AM03 AM05 AM07

Claims (2)

【特許請求の範囲】[Claims] 【請求項１】 リチウムを吸蔵・放出することが可能な
負極と、正極と、非水溶媒にリチウム塩を溶解してなる
電解液とから少なくとも構成される非水系電解液二次電
池において、前記非水溶媒中に下記一般式（Ｉ）で表さ
れるビニレンカーボネート化合物及び／又は下記一般式
（II）で表されるビニルエチレンカーボネート化合物を
含有し、更に酸無水物を含有することを特徴とする非水
系電解液二次電池。 【化１】 （式中Ｒ1、Ｒ2は、それぞれ独立して、水素原子又は炭
素数１〜４のアルキル基を表す。） 【化２】 （式中Ｒ3、Ｒ4及びＲ5は、それぞれ独立して、水素原
子又は炭素数１〜４のアルキル基を表し、Ｒ6、Ｒ7及び
Ｒ8は、それぞれ独立して、水素原子又は炭素数１〜４
のアルキル基または炭素数２〜７のアルケニル基を表
す。）1. A non-aqueous electrolyte secondary battery comprising at least a negative electrode capable of inserting and extracting lithium, a positive electrode, and an electrolyte obtained by dissolving a lithium salt in a non-aqueous solvent, The non-aqueous solvent contains a vinylene carbonate compound represented by the following general formula (I) and / or a vinylethylene carbonate compound represented by the following general formula (II), and further contains an acid anhydride. Non-aqueous electrolyte secondary battery. Embedded image (In the formula, R 1 and R 2 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) (Wherein R 3 , R 4 and R 5 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 6 , R 7 and R 8 each independently represent a hydrogen atom or C 1-4
Or an alkenyl group having 2 to 7 carbon atoms. ) 【請求項２】 リチウムを吸蔵・放出することが可能な
負極と、正極を少なくとも備えた非水系電解液二次電池
用の非水系電解液であって、該非水系電解液が非水溶媒
とリチウム塩から少なくとも構成され、前記非水溶媒中
に下記一般式（Ｉ）で表されるビニレンカーボネート化
合物及び／又は下記一般式（II）で表されるビニルエチ
レンカーボネート化合物を含有し、更に酸無水物を含有
することを特徴とする前記非水系電解液。 【化３】 （式中Ｒ1、Ｒ2は、それぞれ独立して、水素原子又は炭
素数１〜４のアルキル基を表す。） 【化４】 （式中Ｒ3、Ｒ4及びＲ5は、それぞれ独立して、水素原
子又は炭素数１〜４のアルキル基を表し、Ｒ6、Ｒ7及び
Ｒ8は、それぞれ独立して、水素原子又は炭素数１〜４
のアルキル基または炭素数２〜７のアルケニル基を表
す。）2. A non-aqueous electrolyte for a secondary battery comprising at least a negative electrode capable of inserting and extracting lithium and a positive electrode, wherein the non-aqueous electrolyte comprises a non-aqueous solvent and lithium. A vinylene carbonate compound represented by the following general formula (I) and / or a vinylethylene carbonate compound represented by the following general formula (II) in the non-aqueous solvent. The non-aqueous electrolyte solution comprising: Embedded image (In the formula, R 1 and R 2 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) (Wherein R 3 , R 4 and R 5 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 6 , R 7 and R 8 each independently represent a hydrogen atom or C 1-4
Or an alkenyl group having 2 to 7 carbon atoms. )
JP2001153396A 2001-05-23 2001-05-23 Non-aqueous electrolyte secondary battery Expired - Lifetime JP5239106B2 (en)

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