JP2001126761A - Nonaqueous electrolyte secondary battery - Google Patents
Nonaqueous electrolyte secondary batteryInfo
- Publication number
- JP2001126761A JP2001126761A JP30484799A JP30484799A JP2001126761A JP 2001126761 A JP2001126761 A JP 2001126761A JP 30484799 A JP30484799 A JP 30484799A JP 30484799 A JP30484799 A JP 30484799A JP 2001126761 A JP2001126761 A JP 2001126761A
- Authority
- JP
- Japan
- Prior art keywords
- secondary battery
- aqueous electrolyte
- solvent
- electrolyte secondary
- aqueous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、非水系電解液二次
電池及びそれに使用する非水系電解液に関する。詳しく
は、特定の非水溶媒に特定の構造のビニルエチレンカー
ボネートを添加した電解液を使用する非水系電解液二次
電池の改良に関する。本発明によれば、高比誘電率の非
水溶媒を使用した二次電池において、充放電効率が高く
かつサイクル特性に優れ、安全性の高い二次電池が提供
可能となる。The present invention relates to a non-aqueous electrolyte secondary battery and a non-aqueous electrolyte used therefor. More specifically, the present invention relates to an improvement of a non-aqueous electrolyte secondary battery using an electrolyte obtained by adding a vinyl ethylene carbonate having a specific structure to a specific non-aqueous solvent. ADVANTAGE OF THE INVENTION According to this invention, in a secondary battery using a nonaqueous solvent having a high relative dielectric constant, a secondary battery having high charge / discharge efficiency, excellent cycle characteristics, and high safety can be provided.
【０００２】[0002]
【従来の技術】近年の電気製品の軽量化、小型化に伴
い、高いエネルギー密度を持つリチウム二次電池の需要
が高まってきている。さらに、リチウム二次電池の適用
分野の拡大に伴い、電池特性の一層の向上も要望されて
いる。従来、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
われているが、金属リチウムが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ことが実用化を阻む
最大の技術的な課題となっていた。2. Description of the Related Art With the recent reduction in the weight and size of electric products, demand for lithium secondary batteries having a high energy density has been increasing. Further, with the expansion of application fields of lithium secondary batteries, further improvement in battery characteristics has been demanded. Conventionally, secondary batteries using lithium metal as a negative electrode have been actively studied for a long time as batteries capable of achieving high capacity.However, metal lithium grows in a dendrite shape by repeated charge and discharge, and eventually becomes Has reached the positive electrode, and the occurrence of a short circuit inside the battery has been the biggest technical problem preventing 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ている。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る
ことができる。一方、黒鉛系炭素質材料を単独で、或い
は、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
鉛電極への円滑なリチウムの吸蔵・放出が不可能にな
る。In a lithium secondary battery using the above carbonaceous material, a high dielectric constant solvent for a non-aqueous electrolyte is usually used.
Cyclic carbonates such as propylene carbonate and ethylene carbonate are widely used. In a non-aqueous electrolyte secondary battery using a non-graphite carbonaceous material such as coke, a solvent containing propylene carbonate can be suitably used. On the other hand, in a non-aqueous electrolyte secondary battery in which a graphite-based carbonaceous material is used alone or mixed with another anode material capable of inserting and extracting lithium, a non-aqueous electrolyte secondary battery is charged when a solvent containing propylene carbonate is used. Occasionally, the decomposition reaction of propylene carbonate progresses violently on the electrode surface, making it impossible to smoothly insert and extract lithium into and from the graphite electrode.
【０００５】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、黒鉛系負極を用いた非水系電解
液二次電池の電解液ではエチレンカーボネートが高誘電
率溶媒として多用されているが、電解液の分解によるサ
イクル特性の低下等の問題については十分であるとは言
えない。更に、エチレンカーボネートはプロピレンカー
ボネートに比べ、凝固点が３６．４℃と高いため単独で
用いられることはなく、一般に低粘度溶媒と混合して用
いられる。このような理由により、黒鉛系負極を用いる
リチウム二次電池用電解液には、エチレンカーボネート
とジエチルカーボネートの混合溶媒などが通常用いられ
ているが、低粘度溶媒は一般的に沸点も低い場合が多い
ため、大量に添加すると電解液の性能面では良好である
が溶媒の引火点が低下する問題があり、逆に少量しか添
加しないと低温での電気伝導率及び粘度の面で問題があ
る。On the other hand, since ethylene carbonate is less decomposed, ethylene carbonate is frequently used as a high dielectric constant solvent in a non-aqueous electrolyte secondary battery using a graphite-based negative electrode. However, it cannot be said that problems such as deterioration of cycle characteristics due to decomposition of the catalyst are sufficient. Further, ethylene carbonate has a higher freezing point of 36.4 ° C. than propylene carbonate, and therefore is not used alone, and is generally used in a mixture with a low-viscosity solvent. For such a reason, a mixed solvent of ethylene carbonate and diethyl carbonate is usually used as an electrolyte for a lithium secondary battery using a graphite-based negative electrode, but a low-viscosity solvent generally has a low boiling point. When added in large amounts, the performance of the electrolytic solution is good when added in large amounts, but there is a problem in that the flash point of the solvent is lowered. Conversely, when added in small amounts, there are problems in terms of electrical conductivity and viscosity at low temperatures.
【０００６】このような状況において、特開平４−８７
１５６号公報には、負極にリチウム金属を用いた非水系
電解液電池において、溶媒としてリチウムと反応しにく
い不飽和の炭素−炭素結合を鎖式に有する化合物、例え
ばビニルエチレンカーボネートを用いる電解液が提案さ
れている。しかしながら、ビニルエチレンカーボネート
は、等体積の低沸点溶媒である１，２−ジメトキシエタ
ンと混合使用されているので、上述の課題を解消するも
のではない。In such a situation, Japanese Unexamined Patent Publication No. 4-87
No. 156 discloses a non-aqueous electrolyte battery using lithium metal for the negative electrode, and an electrolyte using a compound having an unsaturated carbon-carbon bond in a chain formula that does not easily react with lithium as a solvent, for example, vinylethylene carbonate. Proposed. However, vinylethylene carbonate does not solve the above-mentioned problem because it is mixed with 1,2-dimethoxyethane, which is an equal volume of a low boiling point solvent.
【０００７】一方、環状エステルであるγ−ブチロラク
トン等は、高い比誘電率を有すると共に、凝固点も低
く、低粘度溶媒を混合することなく用いることが可能で
あるが、γ−ブチロラクトン系の電解液も、充電時に黒
鉛電極表面でγ−ブチロラクトンの分解反応が進行し、
電池としての特性の悪化が問題である。特開平１１−３
１５２５号公報には、負極に黒鉛系炭素材料を用いた非
水系電解液二次電池におけるγ−ブチロラクトンの分解
を抑えるために、γ−ブチロラクトンを主成分とし、副
成分として１５〜３５容量％程度のエチレンカーボネー
トを含み、さらに実用的にはジエチルカーボネートを１
６容量％以上含む組成である電解液の溶媒が提案されて
いる。On the other hand, γ-butyrolactone, which is a cyclic ester, has a high relative dielectric constant, a low freezing point, and can be used without mixing a low-viscosity solvent. Also, the decomposition reaction of γ-butyrolactone proceeds on the graphite electrode surface during charging,
Deterioration of characteristics as a battery is a problem. JP-A-11-3
No. 1525 discloses that in order to suppress the decomposition of γ-butyrolactone in a non-aqueous electrolyte secondary battery using a graphite-based carbon material for the negative electrode, γ-butyrolactone is used as a main component, and about 15 to 35% by volume as an auxiliary component. Of ethylene carbonate, and more practically, 1 part of diethyl carbonate.
A solvent for an electrolytic solution having a composition containing at least 6% by volume has been proposed.
【０００８】[0008]
【発明が解決しようとする課題】しかしながら、公知技
術として提案されている電解液は、それなりの効果は見
られるものの更なる改良が望まれている。本発明は、引
火点の比較的高い、比誘電率が２５以上の非水系溶媒を
主たる溶媒として使用した場合においても、良好な電池
特性を発揮できる非水系電解液二次電池の提供を課題と
するものである。However, although the electrolyte proposed as a known technique has a certain effect, further improvement is desired. An object of the present invention is to provide a nonaqueous electrolyte secondary battery that can exhibit good battery characteristics even when a nonaqueous solvent having a relatively high flash point and a relative dielectric constant of 25 or more is used as a main solvent. Is what you do.
【０００９】[0009]
【課題を解決するための手段】本発明者等は、かかる事
情に鑑み鋭意検討した結果、非水系電解液二次電池の電
解液の溶媒として、比誘電率が２５以上の溶媒から選ば
れる１種又は２種以上の溶媒を９０重量％以上含有し、
且つ引火点が７０℃以上である非水溶媒に、更に、特定
の構造を有するビニルエチレンカーボネート化合物を少
なくとも１種添加して使用することにより、充放電効率
が高くかつサイクル特性に優れ安全性も向上させること
ができることを見いだし、本発明を完成させるに至っ
た。Means for Solving the Problems The present inventors have made intensive studies in view of such circumstances, and as a result, as a solvent for an electrolyte of a non-aqueous electrolyte secondary battery, a solvent having a relative dielectric constant of at least 25 is selected. Containing 90% by weight or more of one or more solvents,
In addition, a non-aqueous solvent having a flash point of 70 ° C. or higher, and further adding at least one vinylethylene carbonate compound having a specific structure, has high charge / discharge efficiency and excellent cycle characteristics, and also has excellent safety. They have found that they can be improved, and have completed the present invention.
【００１０】即ち、本発明は、負極と、正極と、溶質及
び非水溶媒とからなる非水系電解液とを少なくとも備え
た非水系電解液二次電池において、非水溶媒が比誘導率
２５以上の溶媒から選ばれる１種又は２種以上の溶媒を
９０重量％以上含有し、かつ該非水溶媒の引火点が７０
℃以上であり、更に該非水溶媒に下記一般式（Ｉ）で表
わされるビニルエチレンカーボネートを少なくとも１種
が添加されていることを特徴とする非水系電解液二次電
池、及びそれを使用する非水系電解液、にある。That is, the present invention provides a non-aqueous electrolyte secondary battery comprising at least a non-aqueous electrolyte comprising a negative electrode, a positive electrode, and a solute and a non-aqueous solvent. Contains 90% by weight or more of one or more solvents selected from the solvents described above, and the non-aqueous solvent has a flash point of 70
C. or higher, and at least one vinylethylene carbonate represented by the following general formula (I) is added to the non-aqueous solvent. Aqueous electrolyte.
【００１１】[0011]
【化３】 Embedded image
【００１２】（式中Ｒ1 、Ｒ2 、Ｒ3 、Ｒ4 、Ｒ5 及び
Ｒ6 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。） 尚、本発明の二次電池に用いられる非水溶媒は、比誘電
率２５以上の溶媒から選ばれる１種又は２種以上の溶媒
に前記一般式（Ｉ）で表わされるビニルエチレンカーボ
−ネートの少なくとも１種が添加されていることが好ま
しい。(Wherein R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently a hydrogen atom or a C 1 -C 4)
Represents an alkyl group. The non-aqueous solvent used in the secondary battery of the present invention may be one or two or more solvents selected from solvents having a relative dielectric constant of 25 or more in the form of vinylethylene carbonate represented by the general formula (I). Is preferably added.
【００１３】又、添加されている前記一般式（Ｉ）で表
わされるビニルエチレンカーボネートの量は、該非水溶
媒と該一般式（Ｉ）で表わされるビニルエチレンカーボ
ネートの合計量に基づいて、０．０１〜１０重量％であ
るのが好ましい。更に、本発明の二次電池に用いられる
負極は、リチウムを吸蔵・放出することが可能な炭素質
物を含有するものが好ましい。The amount of the vinyl ethylene carbonate represented by the general formula (I) added is set to 0.1 based on the total amount of the nonaqueous solvent and the vinyl ethylene carbonate represented by the general formula (I). It is preferably from 0.01 to 10% by weight. Further, the negative electrode used in the secondary battery of the present invention preferably contains a carbonaceous substance capable of inserting and extracting lithium.
【００１４】[0014]
【発明の実施の形態】本発明の非水系電解液二次電池
は、負極と、正極と、溶質及び非水溶媒とからなる非水
系電解液とを備えた非水系電解液二次電池において、非
水溶媒が、比誘電率が２５以上の溶媒から選ばれる１種
又は２種以上の溶媒を９０重量％以上含有し、且つ該非
水溶媒の引火点が７０℃以上であり、更に前記一般式
（Ｉ）で表されるビニルエチレンカーボネートが少なく
とも１種添加されていることを特徴とする。DESCRIPTION OF THE PREFERRED EMBODIMENTS A non-aqueous electrolyte secondary battery according to the present invention is a non-aqueous electrolyte secondary battery comprising a negative electrode, a positive electrode, and a non-aqueous electrolyte comprising a solute and a non-aqueous solvent. The non-aqueous solvent contains at least 90% by weight of one or more solvents selected from solvents having a relative dielectric constant of 25 or more, and the non-aqueous solvent has a flash point of 70 ° C. or more; It is characterized in that at least one kind of vinylethylene carbonate represented by (I) is added.
【００１５】本発明に使用される比誘電率が２５以上の
非水溶媒としては、特に限定されないがエチレンカーボ
ネート、プロピレンカーボネート、ブチレンカーボネー
ト、γ−ブチロラクトン、γ−バレロラクトン、スルホ
ラン、３−メチルスルホラン、ジメチルスルホキシド等
が挙げられ、中でも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
ンが好ましい。これらの溶媒は二種以上混合して用いて
も良く、組み合わせは特に制限されない。本発明で使用
する非水溶媒には、下記一般式（Ｉ）で表わされるビニ
ルエチレンカーボネートが添加される。The non-aqueous solvent having a relative dielectric constant of 25 or more used in the present invention is not particularly limited, but ethylene carbonate, propylene carbonate, butylene carbonate, γ-butyrolactone, γ-valerolactone, sulfolane, 3-methylsulfolane And dimethyl sulfoxide, among which ethylene carbonate, propylene carbonate, γ-butyrolactone and γ-valerolactone are preferred. These solvents may be used as a mixture of two or more kinds, and the combination is not particularly limited. A vinyl ethylene carbonate represented by the following general formula (I) is added to the non-aqueous solvent used in the present invention.
【００１６】[0016]
【化４】 Embedded image
【００１７】式（Ｉ）において、Ｒ1 、Ｒ2 、Ｒ3 、Ｒ
4 、Ｒ5 及びＲ6 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。Ｒ1 、Ｒ2 、Ｒ3 、
Ｒ4、Ｒ5 及びＲ6 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 formula (I), R 1 , R 2 , R 3 , R
4 , R 5 and R 6 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R 1 , R 2 , R 3 ,
When R 4 , R 5 and R 6 are an alkyl group having 1 to 4 carbon atoms, specific examples thereof include a methyl group, an ethyl group and an n-
Propyl group, i-propyl group, n-butyl group, sec-
Butyl group and tert-butyl group. Of these, a methyl group and an ethyl group are preferred.
【００１８】そして、このような一般式（Ｉ）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−エテニル−１，３−ジオキソラン−２−オン
（ビニルエチレンカーボネート）、４−エテニル−４−
メチル−１，３−ジオキソラン−２−オン、４−エテニ
ル−４−エチル−１，３−ジオキソラン−２−オン、４
−エテニル−４−ｎ−プロピル−１，３−ジオキソラン
−２−オン、４−エテニル−５−メチル−１，３−ジオ
キソラン−２−オン、４−エテニル−５−エチル−１，
３−ジオキソラン−２−オン、４−エテニル−５−ｎ−
プロピル−１，３−ジオキソラン−２−オン等を挙げる
ことができる。Specific examples of the vinylethylene carbonate compound represented by the general formula (I) include 4-ethenyl-1,3-dioxolan-2-one (vinylethylene carbonate) and 4-ethenyl- 4-
Methyl-1,3-dioxolan-2-one, 4-ethenyl-4-ethyl-1,3-dioxolan-2-one,
-Ethenyl-4-n-propyl-1,3-dioxolan-2-one, 4-ethenyl-5-methyl-1,3-dioxolan-2-one, 4-ethenyl-5-ethyl-1,
3-dioxolan-2-one, 4-ethenyl-5-n-
Propyl-1,3-dioxolan-2-one and the like can be mentioned.
【００１９】中でもビニルエチレンカーボネート、４−
エテニル−４−メチル−１，３−ジオキソラン−２−オ
ンが好ましく、ビニルエチ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。本発明
で使用する一般式（Ｉ）で表されるビニルエチレンカー
ボネートの添加量は、好ましくは、上記非水溶媒と一般
式（Ｉ）で表されるビニルエチレンカーボネートの合計
量に基づいて、０．０１〜１０重量％であり、更に好ま
しくは、０．１〜１０重量％であり、特に０．５〜７重
量％が好ましい。Among them, vinyl ethylene carbonate, 4-
Ethenyl-4-methyl-1,3-dioxolan-2-one is preferred, and vinylethylene carbonate is particularly preferred. These may be used as a mixture of two or more. The amount of the vinylethylene carbonate represented by the general formula (I) used in the present invention is preferably 0 based on the total amount of the non-aqueous solvent and the vinylethylene carbonate represented by the general formula (I). 0.01 to 10% by weight, more preferably 0.1 to 10% by weight, and particularly preferably 0.5 to 7% by weight.
【００２０】本発明で使用する非水溶媒には、上記比誘
電率が２５以上の溶媒が９０重量％以上含有される。本
発明においては、非水溶媒が上記比誘電率が２５以上の
溶媒に上記一般式（Ｉ）で表わされるビニルエチレンカ
ーボネートが添加されているものが好ましい。又、本発
明においては、非水溶媒が上記比誘電率が２５以上の溶
媒に上記以外の非水溶媒、例えば、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、酢酸メチル、プロピオン酸エチル等の鎖状エス
テル等、を１種以上添加することができる。この場合、
追加された溶媒を含む非水溶媒の引火点が７０℃以上と
なる範囲及び溶媒の組合せで添加できる。The non-aqueous solvent used in the present invention contains 90% by weight or more of the solvent having the relative dielectric constant of 25 or more. In the present invention, the non-aqueous solvent is preferably a solvent in which vinylethylene carbonate represented by the above general formula (I) is added to a solvent having a relative dielectric constant of 25 or more. In the present invention, the non-aqueous solvent may be a solvent having the relative dielectric constant of 25 or more and a non-aqueous solvent other than the above, for example, dialkyl (e.g., dimethyl carbonate, diethyl carbonate, di-n-propyl carbonate, ethyl methyl carbonate). One having a carbon number of 1 to 4 is preferable. One kind of cyclic ethers such as carbonate, tetrahydrofuran and 2-methyltetrahydrofuran, chain ethers such as dimethoxyethane and dimethoxymethane, chain esters such as methyl acetate and ethyl propionate, etc. The above can be added. in this case,
The non-aqueous solvent containing the added solvent can be added in a range where the flash point is 70 ° C. or higher and a combination of solvents.
【００２１】本発明で使用する電解液には、溶質として
リチウム塩を用いる。使用し得るリチウム塩は、電解液
の溶質として使用し得るものであればその種類は特に制
限されない。例えばＬｉＣｌＯ4 、ＬｉＰＦ6 、ＬｉＢ
Ｆ4 から選ばれる無機リチウム塩やＬｉＣＦ3 ＳＯ3 、
ＬｉＮ（ＣＦ3 ＳＯ2 ）2 、ＬｉＮ（ＣＦ3 ＣＦ2 ＳＯ
2 ）2 、ＬｉＮ（ＣＦ3 ＳＯ2 ）（Ｃ4 Ｆ9 ＳＯ2 ）、
ＬｉＣ（ＣＦ3 ＳＯ2）3 等の含フッ素有機リチウム塩
を用いることができる。中でもＬｉＰＦ6 、ＬｉＢＦ4
を用いることが好ましい。これらのリチウム塩は２種類
以上混合して用いても良い。In the electrolytic solution used in the present invention, a lithium salt is used as a solute. The type of the lithium salt that can be used is not particularly limited as long as it can be used as a solute of the electrolytic solution. For example, LiClO 4 , LiPF 6 , LiB
An inorganic lithium salt selected from F 4 , LiCF 3 SO 3 ,
LiN (CF 3 SO 2 ) 2 , LiN (CF 3 CF 2 SO
2 ) 2 , LiN (CF 3 SO 2 ) (C 4 F 9 SO 2 ),
Fluorine-containing organic lithium salts such as LiC (CF 3 SO 2 ) 3 can be used. Among them, LiPF 6 , LiBF 4
It is preferable to use These lithium salts may be used as a mixture of two or more kinds.
【００２２】電解液中の溶質のリチウム塩モル濃度は、
０．５〜２．０モル／リットルであることが望ましい。
０．５モル／リットル未満もしくは２．０モル／リット
ルを超えると、電解液の電気伝導率が低くなって、電池
の性能が低下する傾向にある。本発明の電池を構成する
負極の材料としては、リチウムを吸蔵及び放出し得る炭
素質物を含有するものが好ましい。該炭素質物の具体例
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並びに黒鉛化メソフェーズ小球体、
黒鉛化メソフェーズピッチ系炭素繊維等の他の人造黒鉛
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使用される。The solute lithium salt molarity in the electrolyte is
Desirably, it is 0.5 to 2.0 mol / liter.
If it is less than 0.5 mol / liter or more than 2.0 mol / liter, the electric conductivity of the electrolytic solution tends to decrease, and the performance of the battery tends to decrease. As the material of the negative electrode constituting the battery of the present invention, a material containing a carbonaceous substance capable of inserting and extracting lithium is preferable. Specific examples of the carbonaceous material include, for example, thermal decomposition products of organic substances under various thermal decomposition conditions, artificial graphite, natural graphite, and the like. Preferably artificial graphite and graphitized mesophase spheres produced by high-temperature heat treatment of easily graphitic pitch obtained from various raw materials,
Other artificial graphite and refined natural graphite, such as graphitized mesophase pitch-based carbon fiber, or materials obtained by performing various surface treatments including pitch on these graphites are used.
【００２３】これらの炭素質物は、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
０．３３５〜０．３４ｎｍであるものが好ましく、０．
３３５〜０．３３７ｎｍであるものがより好ましい。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３０ｎｍ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。For these carbonaceous materials, the d value (interlayer distance) of the lattice plane (002 plane) determined by X-ray diffraction according to the Gakushin method is preferably from 0.335 to 0.34 nm.
Those having a thickness of 335 to 0.337 nm are more preferred. The ash content is preferably 1% by weight or less, more preferably 0.5% by weight or less, and particularly preferably 0.1% by weight or less. The crystallite size (Lc) determined by X-ray diffraction according to the Gakushin method is preferably 30 nm or more, more preferably 50 nm or more, and 100 nm or more.
The above is particularly preferred.
【００２４】また、レーザー回折・散乱法による炭素質
物のメジアン径は、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、５〜４
０μｍ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、０．３〜２５．
０ｍ2 ／ｇであるのが好ましく、０．５〜２０．０ｍ2
／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、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、１５８０
〜１６２０ｃｍ-1の範囲のピークＰA （ピーク強度
ＩA ）及び１３５０〜１３７０ｃｍ-1の範囲のピークＰ
B （ピーク強度ＩB ）の強度比Ｒ＝ＩB ／ＩA は０〜
１．２が好ましく、１５８０〜１６２０ｃｍ-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。The median diameter of the carbonaceous material measured by a laser diffraction / scattering method is preferably 1 to 100 μm, more preferably 3 to 50 μm or less, and 5 to 4 μm.
The thickness is more preferably 0 μm, and particularly preferably 7 to 30 μm. The BET specific surface area is 0.3 to 25.
Is preferably from 0m 2 / g, 0.5~20.0m 2
/ G, more preferably 0.7 to 15.0 m 2 / g.
g, more preferably 0.8 to 10.0 m 2 / g.
Is particularly preferred. In Raman spectrum analysis using argon ion laser light, 1580
Range ～1620Cm -1 peak P A (peak intensity I A) and the peak P in the range of 1350 -1
B is the intensity ratio R = I B / I A of (peak intensity I B) 0 to
1.2 Preferably, the half-value width of the peak in the range of 1580~1620cm -1 26cm -1 or less, and particularly preferably between 25 cm -1 or less.
【００２５】これらの炭素質物にリチウムを吸蔵・放出
可能な負極材を更に混合して用いることもできる。炭素
質物以外のリチウムを吸蔵・放出可能な負極材として
は、酸化錫、酸化珪素等の金属酸化物材料、更にはリチ
ウム金属並びに種々のリチウム合金を例示することがで
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。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。A negative electrode material capable of inserting and extracting lithium can be further mixed with these carbonaceous materials and used. Examples of the negative electrode material capable of occluding and releasing lithium other than the carbonaceous material include metal oxide materials such as tin oxide and silicon oxide, as well as lithium metal and various lithium alloys. These negative electrode materials may be used as a mixture of two or more. 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 can be roll-formed as it is to form a sheet electrode, or can be formed into a pellet electrode by compression molding.
【００２６】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、カゼ
イン等が挙げられる。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。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 include carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, ethyl cellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, casein and the like. Examples of the conductive material include metal materials such as copper and nickel, and carbon materials such as graphite and carbon black. The material of the negative electrode current collector is copper,
Metals such as nickel and stainless steel are used, and among these, copper foil is preferred from the viewpoint of easy processing into a thin film and cost.
【００２７】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。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
又はその合金が用いられる。これらの中で、特にアルミ
ニウム又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。As the material of the positive electrode constituting the battery of the present invention, a material capable of occluding and releasing lithium, such as a lithium transition metal composite oxide material such as lithium cobalt oxide, lithium nickel oxide, and lithium manganese oxide. Can be used. 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 a material of the current collector for the positive electrode, a metal such as aluminum, titanium, and tantalum or an alloy thereof is used. Among these, aluminum or its alloy is desirable in terms of energy density because it is lightweight.
【００２８】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又は不織布等を用いる
のが好ましい。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 with respect to the electrolyte 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.
【００２９】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。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 method for producing the battery of the present invention having at least the negative electrode, the positive electrode, and the non-aqueous electrolyte is not particularly limited, and can be appropriately selected from commonly employed methods. The shape of the battery is not particularly limited, a cylinder type in which the sheet electrode and the separator are spiral, a cylinder type having an inside-out structure in which the pellet electrode and the separator are combined,
A coin type in which a pellet electrode and a separator are laminated can be used.
【００３０】[0030]
【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）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。EXAMPLES The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples unless it exceeds the gist. Example 1 85 parts by weight of LiCoO 2 as a positive electrode active material, 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.
【００３１】負極活物質として、Ｘ線回折における格子
面（００２面）のｄ値が０．３３６ｎｍ、晶子サイズ
（Ｌｃ）が、１００ｎｍ以上（２６４ｎｍ）、灰分が
０．０４重量％、レーザー回折・散乱法によるメジアン
径が１７μｍ、ＢＥＴ法比表面積が８．９ｍ2 ／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１５８０〜１６２０ｃｍ-1の範囲のピークＰA
（ピーク強度ＩA ）および１３５０〜１３７０ｃｍ-1の
範囲のピークＰB （ピーク強度ＩB ）の強度比Ｒ＝ＩB
／ＩA が０．１５、１５８０〜１６２０ｃｍ-1の範囲の
ピークの半値幅が２２．２ｃｍ-1である人造黒鉛粉末Ｋ
Ｓ−４４（ティムカル社製、商品名）９５重量部にポリ
フッ化ビニリデン５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。As the negative electrode active material, the d value of the lattice plane (002 plane) in X-ray diffraction is 0.336 nm, the crystallite size (Lc) is 100 nm or more (264 nm), the ash content is 0.04% by weight, A peak P A in the range of 1580 to 1620 cm −1 in Raman spectrum analysis using an argon ion laser beam with a median diameter of 17 μm, a BET specific surface area of 8.9 m 2 / g by a scattering method, and
Intensity ratio (peak intensity I A) and 1350 -1 ranging peak P B (peak intensity I B) R = I B
/ I A is artificial graphite powder K half-width of a peak in the range of 0.15,1580～1620Cm -1 is 22.2Cm -1
95 parts by weight of S-44 (manufactured by Timcal Co., Ltd.) and 5 parts by weight of polyvinylidene fluoride were mixed, and N-methyl-2-
A slurry obtained by dispersing with 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.
【００３２】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六フッ化リン酸リチウム（Ｌｉ
ＰＦ6 ）を溶質として用い、プロピレンカーボネートと
エチレンカーボネートの混合物（１：１容積比）９７重
量％にビニルエチレンカーボネートを３重量％の割合で
溶解し、更にＬｉＰＦ6 を１モル／リットルの割合で溶
解して調製した。これらの正極、負極、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ポリエチレン製の
セパレーターを介して負極を載置した。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。As for the electrolytic solution, lithium hexafluorophosphate (Li) was sufficiently dried in a dry argon atmosphere.
Using PF 6 ) as a solute, vinylethylene carbonate was dissolved at a rate of 3% by weight in 97% by weight of a mixture of propylene carbonate and ethylene carbonate (1: 1 by volume), and LiPF 6 was further dissolved at a rate of 1 mol / L. Prepared by dissolution. Using these positive electrode, negative electrode, and electrolytic solution, the positive electrode was housed in a stainless steel can that also serves as a positive electrode conductor, and the negative electrode was placed thereon via a polyethylene 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.
【００３３】（比較例１）プロピレンカーボネートとエ
チレンカーボネートの混合物（１：１容量比）に、Ｌｉ
ＰＦ6 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。Comparative Example 1 A mixture of propylene carbonate and ethylene carbonate (1: 1 by volume) was mixed with Li
A coin-type battery was produced in the same manner as in Example 1, except that an electrolyte prepared by dissolving PF 6 at a rate of 1 mol / liter was used.
【００３４】（実施例２）エチレンカーボネートとγ−
ブチロラクトンの混合物（１：１容量比）９７重量％に
ビニルエチレンカーボネートを３重量％の割合で溶解
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 Ethylene carbonate and γ-
Except that an electrolyte prepared by dissolving vinyl ethylene carbonate at a ratio of 3% by weight in 97% by weight of a butyrolactone mixture (1: 1 by volume) and further dissolving LiPF 6 at a ratio of 1 mol / L was used. In the same manner as in Example 1, a coin-type battery was produced.
【００３５】（比較例２）エチレンカーボネートとγ−
ブチロラクトンの混合物（１：１容量比）に、ＬｉＰＦ
6 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。Comparative Example 2 Ethylene carbonate and γ-
LiPF was added to a mixture of butyrolactone (1: 1 by volume).
A coin-type battery was produced in the same manner as in Example 1, except that an electrolytic solution prepared by dissolving 6 at a ratio of 1 mol / liter was used.
【００３６】（実施例３）プロピレンカーボネートとγ
−ブチロラクトンの混合物（１：１容量比）９７重量％
にビニルエチレンカーボネートを３重量％の割合で溶解
し、更にＬｉＰＦ 6 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 3) Propylene carbonate and γ
97% by weight of a mixture of butyrolactone (1: 1 by volume)
3% by weight of vinyl ethylene carbonate
And then LiPF 6Dissolved at a rate of 1 mol / liter
As in Example 1 except that the electrolyte solution prepared in
Thus, a coin-type battery was produced.
【００３７】（比較例３）プロピレンカーボネートとγ
−ブチロラクトンの混合物（１：１容量比）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。Comparative Example 3 Propylene carbonate and γ
-Butyrolactone mixture (1: 1 by volume) with LiP
Except for using the F 6 1 mol / liter electrolyte solution prepared by dissolving at a rate of in the same manner as in Example 1 to prepare a coin battery.
【００３８】（実施例４）プロピレンカーボネート９７
重量％にビニルエチレンカーボネートを３重量％の割合
で溶解し、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 4) Propylene carbonate 97
A coin-type battery was prepared in the same manner as in Example 1 except that an electrolyte prepared by dissolving 3% by weight of vinylethylene carbonate in 1% by weight and further dissolving LiPF 6 at a rate of 1 mol / L was used. Was prepared.
【００３９】（比較例４）プロピレンカーボネートにＬ
ｉＰＦ6 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。(Comparative Example 4) L was added to propylene carbonate.
A coin-type battery was produced in the same manner as in Example 1, except that an electrolytic solution prepared by dissolving iPF 6 at a rate of 1 mol / liter was used.
【００４０】（実施例５）プロピレンカーボネートとエ
チレンカーボネートの混合物（１：１容量比）９５重量
％にビニルエチレンカーボネートを５重量％の割合で溶
解し、更ＬｉＰＦ 6 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。上記実施例１〜５および
比較例１〜４で作製した電池を、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
２．５Ｖで充放電試験を行った。Example 5 Propylene carbonate and d
95 weight of a mixture of ethylene carbonate (1: 1 by volume)
% Of vinyl ethylene carbonate in 5% by weight
Release, further LiPF 6Dissolved at a rate of 1 mol / liter
As in Example 1 except that the electrolyte solution prepared in
Thus, a coin-type battery was produced. Examples 1 to 5 above and
The batteries prepared in Comparative Examples 1 to 4 were treated at 25 ° C. with 0.1%
End-of-charge voltage of 4.2 V and end-of-discharge voltage at a constant current of 5 mA
A charge / discharge test was performed at 2.5V.
【００４１】実施例１〜５に用いた電解液の２０℃と−
３０℃での電気伝導度を表１に示す。尚、電気伝導度の
測定は、電気伝導度計（東亜電波社製、ＣＭ−３０Ｓ）
を用いて測定した。引火点は、ＪＩＳ Ｋ−２２６５に
準拠して測定した。それぞれの電池における１サイクル
目の負極重量当たりの放電容量および充放電効率を表２
に示す。ここで、充放電効率は以下の式から求めたもの
である。At 20 ° C. of the electrolyte used in Examples 1 to 5,
Table 1 shows the electrical conductivity at 30 ° C. The electric conductivity was measured using an electric conductivity meter (Toa Denpasha Co., Ltd., CM-30S).
It measured using. The flash point was measured according to JIS K-2265. Table 2 shows the discharge capacity and charge / discharge efficiency per negative electrode weight in the first cycle in each battery.
Shown in Here, the charging / discharging efficiency is obtained from the following equation.
【００４２】[0042]
【数１】充放電効率（％）＝〔（放電容量）／（充電容
量）〕×１００## EQU1 ## Charge / discharge efficiency (%) = [(discharge capacity) / (charge capacity)] × 100
【００４３】表１、２に示す通り、比較例１、３、４は
電解液の分解が激しく電池として作動しなかった。一
方、本実施例の電解液は−３０℃においても凝固するこ
となく、比較的高い伝導度を有し、電池とした場合の、
容量、充放電効率も優れている。As shown in Tables 1 and 2, the electrolytes of Comparative Examples 1, 3, and 4 were so strongly decomposed that they did not operate as batteries. On the other hand, the electrolyte of the present example does not solidify even at −30 ° C., has a relatively high conductivity, and
Excellent capacity and charge / discharge efficiency.
【００４４】[0044]
【表１】 [Table 1]
【００４５】[0045]
【表２】 [Table 2]
【００４６】[0046]
【発明の効果】本発明の非水系電解液二次電池は、比誘
電率が２５以上の溶媒から選ばれる１種又は２種以上の
溶媒を９０重量％以上含有し、かつ引火点が７０℃以上
の非水溶媒を使用するので安全性が高く、かつ充放電効
率が高く、サイクル特性に優れたものである。更に、高
温下においてもサイクル特性、保存特性の良好な二次電
池を作製することを可能にすることができる。The nonaqueous electrolyte secondary battery of the present invention contains 90% by weight or more of one or more solvents selected from solvents having a relative dielectric constant of 25 or more, and has a flash point of 70 ° C. Since the above non-aqueous solvent is used, safety is high, charge / discharge efficiency is high, and cycle characteristics are excellent. Further, it is possible to manufacture a secondary battery having good cycle characteristics and storage characteristics even at a high temperature.
フロントページの続き (72)発明者 島 紀子 茨城県稲敷郡阿見町中央八丁目３番１号 三菱化学株式会社筑波研究所内 (72)発明者 鈴木 仁 茨城県稲敷郡阿見町中央八丁目３番１号 三菱化学株式会社筑波研究所内 Ｆターム(参考） 5H029 AJ05 AJ12 AK03 AL02 AL06 AL07 AL08 AL12 AL18 AM03 AM04 AM05 AM07 DJ08 HJ02 HJ04 HJ14 HJ16 Continuing from the front page (72) Noriko Shima, Innovator, Tsukuba Research Laboratory, Tsukuba Research Laboratory, Mitsubishi Chemical Corporation No. Mitsubishi Chemical Corporation Tsukuba Research Laboratory F-term (reference) 5H029 AJ05 AJ12 AK03 AL02 AL06 AL07 AL08 AL12 AL18 AM03 AM04 AM05 AM07 DJ08 HJ02 HJ04 HJ14 HJ16
Claims (8)
らなる非水系電解液とを少なくとも備えた非水系電解液
二次電池において、非水溶媒が比誘電率２５以上の溶媒
から選ばれる１種又は２種以上の溶媒を９０重量％以上
含有し、かつ該非水溶媒の引火点が７０℃以上であり、
更に該非水溶媒に下記一般式（Ｉ）で表わされるビニル
エチレンカーボネートを少なくとも１種が添加されてい
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 、Ｒ3 、Ｒ4 、Ｒ5 及びＲ6 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。）1. A non-aqueous electrolyte secondary battery comprising at least a non-aqueous electrolyte comprising a negative electrode, a positive electrode, and a solute and a non-aqueous solvent, wherein the non-aqueous solvent is selected from solvents having a relative dielectric constant of 25 or more. The non-aqueous solvent has a flash point of 70 ° C. or more
The non-aqueous electrolyte secondary battery further comprises at least one kind of vinylethylene carbonate represented by the following general formula (I) added to the non-aqueous solvent. Embedded image (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)
記一般式（Ｉ）で表わされるビニルエチレンカーボネー
トの少なくとも１種が添加されていることを特徴とする
請求項１記載の非水系電解液二次電池。2. The non-aqueous solvent according to claim 1, wherein the non-aqueous solvent has a relative dielectric constant of 25 or more, and at least one kind of vinylethylene carbonate represented by the general formula (I) is added. Electrolyte secondary battery.
されるビニルエチレンカーボネートの量が、該非水溶媒
と該一般式（Ｉ）で表わされるビニルエチレンカーボネ
ートの合計量の０．０１〜１０重量％であることを特徴
とする請求項１又は２記載の非水系電解液二次電池。3. The amount of the vinyl ethylene carbonate represented by the general formula (I) added is 0.01 to 10 times the total amount of the nonaqueous solvent and the vinyl ethylene carbonate represented by the general formula (I). 3. The non-aqueous electrolyte secondary battery according to claim 1, wherein the content is% by weight. 4.
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、γ−ブチロラクトン及びγ−バレロラクトンで
あることを特徴とする請求項１〜３のいずれかに記載の
非水系電解液二次電池。4. The method according to claim 1, wherein the solvent having a non-dielectric constant of 25 or more is ethylene carbonate, propylene carbonate, butylene carbonate, γ-butyrolactone or γ-valerolactone. Aqueous electrolyte secondary battery.
が可能な炭素質物を含有することを特徴とする請求項１
〜４のいずれかに記載の非水系電解液二次電池。5. The negative electrode contains a carbonaceous material capable of inserting and extracting lithium.
5. The non-aqueous electrolyte secondary battery according to any one of items 1 to 4.
が可能な炭素質物、又は、該炭素質物とリチウム、リチ
ウム合金及びリチウムを吸蔵・放出することが可能な金
属酸化物からなる群から選ばれる１種以上との混合物で
あることを特徴とする請求項１〜５のいずれかに記載の
非水系電解液二次電池。6. The negative electrode is selected from the group consisting of a carbonaceous substance capable of occluding and releasing lithium, and a metal oxide capable of occluding and releasing lithium, a lithium alloy, and a metal oxide capable of occluding and releasing lithium. The non-aqueous electrolyte secondary battery according to claim 1, wherein the non-aqueous electrolyte secondary battery is a mixture with at least one of the following.
（００２面）のｄ値が０．３３５〜０．３４０ｎｍの黒
鉛であることを特徴とする請求項５又は６記載の非水系
電解液二次電池。7. The non-aqueous electrolyte according to claim 5, wherein the carbonaceous material is graphite having a lattice plane (002 plane) d value of 0.335 to 0.340 nm in X-ray diffraction. Rechargeable battery.
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、該非水系電解液が溶質と非水
溶媒とからなり、該非水溶媒が比誘電率２５以上の溶媒
から選ばれる１種又は２種以上の溶媒を９０重量％以上
含有し、かつ該非水溶媒の引火点が７０℃以上であり、
更に該非水溶媒に下記一般式（Ｉ）で表わされるビニル
エチレンカーボネートを少なくとも１種が添加されてい
ることを特徴とする前記非水系電解液。 【化２】 （式中Ｒ1 、Ｒ2 、Ｒ3 、Ｒ4 、Ｒ5 及びＲ6 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。）8. 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 solute and a non-aqueous solvent. The non-aqueous solvent contains 90% by weight or more of one or more solvents selected from solvents having a relative dielectric constant of 25 or more, and the non-aqueous solvent has a flash point of 70 ° C. or more,
The non-aqueous electrolyte solution further comprising at least one kind of vinylethylene carbonate represented by the following general formula (I) added to the non-aqueous solvent. Embedded image (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30484799A JP4211159B2 (en) | 1999-10-27 | 1999-10-27 | Non-aqueous electrolyte secondary battery |
| CNB008118043A CN1181592C (en) | 1999-06-18 | 2000-06-15 | Nonaqueous electrolytic solution type secondary battery |
| EP00937252.5A EP1205996B1 (en) | 1999-06-18 | 2000-06-15 | Nonaqueous electrolytic solution type secondary battery |
| US09/926,779 US6919145B1 (en) | 1999-06-18 | 2000-06-15 | Nonaqueous electrolytic solution type secondary battery |
| PCT/JP2000/003910 WO2000079632A1 (en) | 1999-06-18 | 2000-06-15 | Nonaqueous electrolytic solution type secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30484799A JP4211159B2 (en) | 1999-10-27 | 1999-10-27 | Non-aqueous electrolyte secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001126761A true JP2001126761A (en) | 2001-05-11 |
| JP4211159B2 JP4211159B2 (en) | 2009-01-21 |
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|---|---|---|---|
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|---|---|
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| WO2003036752A1 (en) * | 2001-10-26 | 2003-05-01 | Kabushiki Kaisha Toshiba | Non-aqueous electrolyte and non-aqueous electrolyte secondary cell |
| US6861175B2 (en) * | 2000-09-28 | 2005-03-01 | Kabushiki Kaisha Toshiba | Nonaqueous electrolyte and nonaqueous electrolyte secondary battery |
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| US6861175B2 (en) * | 2000-09-28 | 2005-03-01 | Kabushiki Kaisha Toshiba | Nonaqueous electrolyte and nonaqueous electrolyte secondary battery |
| WO2003036752A1 (en) * | 2001-10-26 | 2003-05-01 | Kabushiki Kaisha Toshiba | Non-aqueous electrolyte and non-aqueous electrolyte secondary cell |
| US6998194B2 (en) | 2001-10-26 | 2006-02-14 | Kabushiki Kaisha Toshiba | Nonaqueous electrolyte and nonaqueous electrolyte secondary battery |
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