JP2000149987A - Nonaqueous electrolyte solution and lithium secondary battery using it - Google Patents
Nonaqueous electrolyte solution and lithium secondary battery using itInfo
- Publication number
- JP2000149987A JP2000149987A JP11091497A JP9149799A JP2000149987A JP 2000149987 A JP2000149987 A JP 2000149987A JP 11091497 A JP11091497 A JP 11091497A JP 9149799 A JP9149799 A JP 9149799A JP 2000149987 A JP2000149987 A JP 2000149987A
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- Japan
- Prior art keywords
- battery
- solvent
- aqueous electrolyte
- negative electrode
- lithium secondary
- Prior art date
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Carbon And Carbon Compounds (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、電池のサイクル特
性や電気容量、保存特性などの電池特性にも優れたリチ
ウム二次電池を提供することができる非水電解液、およ
びそれを用いたリチウム二次電池に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-aqueous electrolyte capable of providing a lithium secondary battery having excellent battery characteristics such as cycle characteristics, electric capacity and storage characteristics of a battery, and lithium using the same. Related to secondary batteries.
【０００２】[0002]
【従来の技術】近年、リチウム二次電池は小型電子機器
などの駆動用電源として広く使用されている。リチウム
二次電池は、主に正極、非水電解液及び負極から構成さ
れており、特に、ＬｉＣｏＯ2などのリチウム複合酸化
物を正極とし、炭素材料又はリチウム金属を負極とした
リチウム二次電池が好適に使用されている。そして、そ
のリチウム二次電池用の非水電解液としては、エチレン
カーボネート（ＥＣ）、プロピレンカーボネート（Ｐ
Ｃ）などのカーボネート類が好適に使用されている。2. Description of the Related Art In recent years, lithium secondary batteries have been widely used as power sources for driving small electronic devices and the like. Lithium secondary batteries are mainly composed of a positive electrode, a non-aqueous electrolyte, and a negative electrode. In particular, lithium secondary batteries using a lithium composite oxide such as LiCoO 2 as a positive electrode and a carbon material or lithium metal as a negative electrode are known. It is preferably used. As the non-aqueous electrolyte for the lithium secondary battery, ethylene carbonate (EC), propylene carbonate (P
Carbonates such as C) are preferably used.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、電池の
サイクル特性および電気容量などの電池特性について、
さらに優れた特性を有する二次電池が求められている。
正極として、例えばＬｉＣｏＯ2、ＬｉＭｎ2Ｏ4、Ｌｉ
ＮｉＯ2などを用いたリチウム二次電池は、非水電解液
中の溶媒が充電時に局部的に一部酸化分解することによ
り、該分解物が電池の望ましい電気化学的反応を阻害す
るために電池性能の低下を生じる。これは正極材料と非
水電解液との界面における溶媒の電気化学的酸化に起因
するものと思われる。また、負極として例えば天然黒鉛
や人造黒鉛などの高結晶化した炭素材料を用いたリチウ
ム二次電池は、非水電解液中の溶媒が充電時に負極表面
で還元分解し、非水電解液溶媒として一般に広く使用さ
れているＥＣにおいても充放電を繰り返す間に一部還元
分解が起こり、電池性能の低下が起こる。このため、電
池のサイクル特性および電気容量などの電池特性は必ず
しも満足なものではないのが現状である。However, regarding the battery characteristics such as the cycle characteristics and the electric capacity of the battery,
There is a demand for a secondary battery having more excellent characteristics.
As the positive electrode, for example, LiCoO 2 , LiMn 2 O 4 , Li
Lithium secondary batteries using NiO 2 or the like have a problem in that the solvent in the non-aqueous electrolyte partially oxidizes and decomposes at the time of charging, and the decomposition products hinder a desirable electrochemical reaction of the battery. This results in reduced performance. This is thought to be due to electrochemical oxidation of the solvent at the interface between the positive electrode material and the non-aqueous electrolyte. In addition, in a lithium secondary battery using a highly crystallized carbon material such as natural graphite or artificial graphite as the negative electrode, the solvent in the nonaqueous electrolyte is reductively decomposed on the surface of the negative electrode during charging, and as a nonaqueous electrolyte solvent Even in ECs that are generally widely used, reductive decomposition occurs partially during repetition of charge / discharge, and battery performance deteriorates. Therefore, at present, the battery characteristics such as the cycle characteristics and the electric capacity of the battery are not always satisfactory.
【０００４】本発明は、前記のようなリチウム二次電池
用非水電解液に関する課題を解決し、電池のサイクル特
性に優れ、さらに電気容量や充電状態での保存特性など
の電池特性にも優れたリチウム二次電池を構成すること
ができるリチウム二次電池用の非水電解液、およびそれ
を用いたリチウム二次電池を提供することを目的とす
る。The present invention solves the above-mentioned problems relating to the non-aqueous electrolyte for a lithium secondary battery, and is excellent in battery cycle characteristics, and is also excellent in battery characteristics such as electric capacity and storage characteristics in a charged state. It is an object of the present invention to provide a non-aqueous electrolyte for a lithium secondary battery that can constitute a lithium secondary battery, and a lithium secondary battery using the same.
【０００５】[0005]
【課題を解決するための手段】本発明は、非水溶媒に電
解質が溶解されている非水電解液において、該非水電解
液中に下記式（Ｉ） Ｃ6Ｈ5−Ｓ−Ｓ−Ｃ6Ｈ5 （Ｉ） で表されるジフェニルジスルフィドが０．０１〜０．５
重量％含有されていることを特徴とする非水電解液に関
する。また、正極、負極および非水溶媒に電解質が溶解
されている非水電解液からなるリチウム二次電池におい
て、該非水電解液中に下記式（Ｉ） Ｃ6Ｈ5−Ｓ−Ｓ−Ｃ6Ｈ5 （Ｉ） で表されるジフェニルジスルフィドが０．０１〜０．５
重量％含有されていることを特徴とするリチウム二次電
池に関する。The present invention relates to a non-aqueous electrolyte in which an electrolyte is dissolved in a non-aqueous solvent, wherein the non-aqueous electrolyte contains the following formula (I): C 6 H 5 -S-S-C-C 6 H 5 diphenyl disulfide 0.01 to 0.5 of the formula (I)
The present invention relates to a non-aqueous electrolyte solution characterized by containing by weight. Further, in a lithium secondary battery comprising a positive electrode, a negative electrode and a non-aqueous electrolyte in which an electrolyte is dissolved in a non-aqueous solvent, the following formula (I) C 6 H 5 -S-S-C 6 H 5 diphenyl disulfide is 0.01 to 0.5 of the formula (I)
The present invention relates to a lithium secondary battery characterized in that the lithium secondary battery is contained by weight%.
【０００６】本発明の非水電解液は、リチウム二次電池
の構成部材として使用される。二次電池を構成する非水
電解液以外の構成部材については特に限定されず、従来
使用されている種々の構成部材を使用できる。The non-aqueous electrolyte of the present invention is used as a component of a lithium secondary battery. The constituent members other than the non-aqueous electrolyte constituting the secondary battery are not particularly limited, and various constituent members conventionally used can be used.
【０００７】[0007]
【発明の実施の形態】非水電解液中に含有される前記式
（Ｉ）で表されるジフェニルジスルフィドの含有量は、
過度に多いと電池性能が低下することがあり、また、過
度に少ないと期待した十分な電池性能が得られない。し
たがって、その含有量は非水電解液の重量に対して０．
０１〜０．５重量％の範囲がサイクル特性が向上するの
でよい。BEST MODE FOR CARRYING OUT THE INVENTION The content of diphenyl disulfide represented by the above formula (I) contained in a non-aqueous electrolyte is as follows:
If the amount is excessively large, the battery performance may be reduced, and if the amount is excessively small, sufficient expected battery performance cannot be obtained. Therefore, the content is 0.1% based on the weight of the non-aqueous electrolyte.
The range of 01 to 0.5% by weight is preferable because cycle characteristics are improved.
【０００８】本発明で使用される非水溶媒としては、高
誘電率溶媒と低粘度溶媒とからなるものが好ましい。高
誘電率溶媒としては、例えば、エチレンカーボネート
（ＥＣ）、プロピレンカーボネート（ＰＣ）、ブチレン
カーボネート（ＢＣ）などの環状カーボネート類が好適
に挙げられる。これらの高誘電率溶媒は、一種類で使用
してもよく、また二種類以上組み合わせて使用してもよ
い。The non-aqueous solvent used in the present invention is preferably a solvent comprising a high dielectric constant solvent and a low viscosity solvent. Preferred examples of the high dielectric constant solvent include cyclic carbonates such as ethylene carbonate (EC), propylene carbonate (PC), and butylene carbonate (BC). These high dielectric constant solvents may be used alone or in combination of two or more.
【０００９】低粘度溶媒としては、例えば、ジメチルカ
ーボネート（ＤＭＣ）、メチルエチルカーボネート（Ｍ
ＥＣ）、ジエチルカーボネート（ＤＥＣ）などの鎖状カ
ーボネート類、テトラヒドロフラン、２−メチルテトラ
ヒドロフラン、１，４−ジオキサン、１，２−ジメトキ
シエタン、１，２−ジエトキシエタン、１，２−ジブト
キシエタンなどのエーテル類、γ−ブチロラクトンなど
のラクトン類、アセトニトリルなどのニトリル類、プロ
ピオン酸メチルなどのエステル類、ジメチルホルムアミ
ドなどのアミド類が挙げられる。これらの低粘度溶媒は
一種類で使用してもよく、また二種類以上組み合わせて
使用してもよい。高誘電率溶媒と低粘度溶媒とはそれぞ
れ任意に選択され組み合わせて使用される。なお、前記
の高誘電率溶媒および低粘度溶媒は、容量比（高誘電率
溶媒：低粘度溶媒）で通常１：９〜４：１、好ましくは
１：４〜７：３の割合で使用される。Examples of the low-viscosity solvent include dimethyl carbonate (DMC) and methyl ethyl carbonate (M
EC), chain carbonates such as diethyl carbonate (DEC), tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-dibutoxyethane And lactones such as γ-butyrolactone, nitriles such as acetonitrile, esters such as methyl propionate, and amides such as dimethylformamide. These low-viscosity solvents may be used alone or in combination of two or more. The high dielectric constant solvent and the low viscosity solvent are arbitrarily selected and used in combination. The high dielectric constant solvent and the low viscosity solvent are used in a volume ratio (high dielectric constant solvent: low viscosity solvent) of usually 1: 9 to 4: 1, preferably 1: 4 to 7: 3. You.
【００１０】本発明で使用される電解質としては、例え
ば、ＬｉＰＦ6 、ＬｉＢＦ4 、ＬｉＣｌＯ4、ＬｉＮ
（ＳＯ2ＣＦ3）2、ＬｉＮ（ＳＯ2Ｃ2Ｆ5）2、ＬｉＣ
（ＳＯ2ＣＦ3）3などが挙げられる。これらの電解質
は、一種類で使用してもよく、二種類以上組み合わせて
使用してもよい。これら電解質は、前記の非水溶媒に通
常０．１〜３Ｍ、好ましくは０．５〜１．５Ｍの濃度で
溶解されて使用される。The electrolyte used in the present invention includes, for example, LiPF 6 , LiBF 4 , LiClO 4 , LiN
(SO 2 CF 3 ) 2 , LiN (SO 2 C 2 F 5 ) 2 , LiC
(SO 2 CF 3 ) 3 and the like. These electrolytes may be used alone or in combination of two or more. These electrolytes are used after being dissolved in the above non-aqueous solvent at a concentration of usually 0.1 to 3M, preferably 0.5 to 1.5M.
【００１１】本発明の非水電解液は、例えば、前記の高
誘電率溶媒や低粘度溶媒を混合し、これに前記の電解質
を溶解し、前記式（Ｉ）で表されるジフェニルジスルフ
ィドを溶解することにより得られる。The non-aqueous electrolyte of the present invention is prepared by, for example, mixing the above-mentioned high-dielectric solvent or low-viscosity solvent, dissolving the above-mentioned electrolyte, and dissolving the diphenyl disulfide represented by the above formula (I). It is obtained by doing.
【００１２】例えば、正極活物質としてはコバルト、マ
ンガン、ニッケル、クロム、鉄およびバナジウムからな
る群より選ばれる少なくとも一種類の金属とリチウムと
の複合金属酸化物が使用される。このような複合金属酸
化物としては、例えば、ＬｉＣｏＯ2、ＬｉＭｎ2Ｏ4、
ＬｉＮｉＯ2などが挙げられる。For example, a composite metal oxide of lithium and at least one metal selected from the group consisting of cobalt, manganese, nickel, chromium, iron and vanadium is used as the positive electrode active material. Examples of such a composite metal oxide include LiCoO 2 , LiMn 2 O 4 ,
LiNiO 2 and the like.
【００１３】正極は、前記の正極活物質をアセチレンブ
ラック、カーボンブラックなどの導電剤、ポリテトラフ
ルオロエチレン（ＰＴＦＥ）、ポリフッ化ビニリデン
（ＰＶＤＦ）などの結着剤および溶剤と混練して正極合
剤とした後、この正極材料を集電体としてのアルミニウ
ム箔やステンレス製のラス板に塗布して、乾燥、加圧成
型後、５０℃〜２５０℃程度の温度で２時間程度真空下
で加熱処理することにより作製される。The positive electrode is prepared by kneading the positive electrode active material with a conductive agent such as acetylene black and carbon black, a binder such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF) and a solvent, and mixing the positive electrode active material with a solvent. After that, this positive electrode material is applied to an aluminum foil or a stainless steel lath plate as a current collector, dried and pressed, and then heat-treated under a vacuum at a temperature of about 50 ° C. to 250 ° C. for about 2 hours. It is produced by doing.
【００１４】負極活物質としては、リチウム金属やリチ
ウム合金、およびリチウムを吸蔵・放出可能な黒鉛型結
晶構造を有する炭素材料〔熱分解炭素類、コークス類、
グラファイト類（人造黒鉛、天然黒鉛など）、有機高分
子化合物燃焼体、炭素繊維〕や複合スズ酸化物などの物
質が使用される。特に、格子面（００２）の面間隔（ｄ
002）が３．３５〜３．４０Å（オングストローム）で
ある黒鉛型結晶構造を有する炭素材料を使用することが
好ましい。なお、炭素材料のような粉末材料はエチレン
プロピレンジエンターポリマー（ＥＰＤＭ）、ポリテト
ラフルオロエチレン（ＰＴＦＥ）、ポリフッ化ビニリデ
ン（ＰＶＤＦ）などの結着剤と混練して負極合剤として
使用される。As the negative electrode active material, lithium metal, lithium alloy, and a carbon material having a graphite type crystal structure capable of inserting and extracting lithium [pyrolytic carbons, cokes,
Materials such as graphites (artificial graphite, natural graphite, etc.), organic polymer compound burners, carbon fibers] and composite tin oxide are used. In particular, the spacing (d) of the lattice plane (002)
It is preferable to use a carbon material having a graphite type crystal structure in which ( 002 ) is 3.35 to 3.40 ° (angstrom). A powder material such as a carbon material is kneaded with a binder such as ethylene propylene diene terpolymer (EPDM), polytetrafluoroethylene (PTFE), or polyvinylidene fluoride (PVDF) and used as a negative electrode mixture.
【００１５】リチウム二次電池の構造は特に限定される
ものではなく、正極、負極および単層又は複層のセパレ
ータを有するコイン型電池、さらに、正極、負極および
ロール状のセパレータを有する円筒型電池や角型電池な
どが一例として挙げられる。なお、セパレータとしては
公知のポリオレフィンの微多孔膜、織布、不織布などが
使用される。The structure of the lithium secondary battery is not particularly limited. A coin-type battery having a positive electrode, a negative electrode, and a single-layer or multiple-layer separator, and a cylindrical battery having a positive electrode, a negative electrode, and a roll-shaped separator And a prismatic battery. As the separator, a known microporous polyolefin membrane, woven fabric, nonwoven fabric, or the like is used.
【００１６】[0016]
【実施例】次に、実施例および比較例を挙げて、本発明
を具体的に説明する。 実施例１ 〔非水電解液の調製〕ＥＣ：ＤＭＣ（容量比）＝１：２
の非水溶媒を調製し、これにＬｉＰＦ6を１Ｍの濃度に
なるように溶解して非水電解液を調製した後、さらにジ
フェニルジスルフィドを非水電解液に対して０．０５重
量％となるように加えた。Next, the present invention will be specifically described with reference to examples and comparative examples. Example 1 [Preparation of non-aqueous electrolyte] EC: DMC (volume ratio) = 1: 2
After preparing a non-aqueous solvent by dissolving LiPF 6 to a concentration of 1 M to prepare a non-aqueous electrolyte, diphenyl disulfide is further added to 0.05% by weight based on the non-aqueous electrolyte. So added.
【００１７】〔リチウム二次電池の作製および電池特性
の測定〕ＬｉＣｏＯ2（正極活物質）を８０重量％、ア
セチレンブラック（導電剤）を１０重量％、ポリフッ化
ビニリデン（結着剤）を１０重量％の割合で混合し、こ
れに１−メチル−２−ピロリドン溶剤を加えて混合した
ものをアルミニウム箔上に塗布し、乾燥、加圧成型、加
熱処理して正極を調製した。天然黒鉛（負極活物質）を
９０重量％、ポリフッ化ビニリデン（結着剤）を１０重
量％の割合で混合し、これに１−メチル−２−ピロリド
ン溶剤を加え、混合したものを銅箔上に塗布し、乾燥、
加圧成型、加熱処理して負極を調製した。そして、ポリ
プロピレン微多孔性フィルムのセパレータを用い、上記
の非水電解液を注入させてコイン電池（直径２０ｍｍ、
厚さ３．２ｍｍ）を作製した。このコイン電池を用い
て、室温（２０℃）下、０．８ｍＡの定電流及び定電圧
で、終止電圧４．２Ｖまで５時間充電し、次に０．８ｍ
Ａの定電流下、終止電圧２．７Ｖまで放電し、この充放
電を繰り返した。初期充放電容量は、ＥＣ−ＤＭＣ（１
／２）を非水電解液として用いた場合（比較例１）とほ
ぼ同等であり、５０サイクル後の電池特性を測定したと
ころ、初期放電容量を１００％としたときの放電容量維
持率は９２．７％であった。また、低温特性も良好であ
った。コイン電池の作製条件および電池特性を表１に示
す。[Preparation of Lithium Secondary Battery and Measurement of Battery Characteristics] LiCoO 2 (cathode active material) was 80% by weight, acetylene black (conductive agent) was 10% by weight, and polyvinylidene fluoride (binder) was 10% by weight. % Of the mixture, a 1-methyl-2-pyrrolidone solvent was added to the mixture, and the mixture was applied onto an aluminum foil, dried, press-molded, and heat-treated to prepare a positive electrode. 90% by weight of natural graphite (negative electrode active material) and 10% by weight of polyvinylidene fluoride (binder) were added, and a 1-methyl-2-pyrrolidone solvent was added thereto. Applied, dried,
A negative electrode was prepared by pressure molding and heat treatment. Then, using a separator made of a polypropylene microporous film, the above non-aqueous electrolyte was injected, and a coin battery (20 mm in diameter,
(Thickness: 3.2 mm). Using this coin battery, the battery was charged to a final voltage of 4.2 V for 5 hours at a constant current and a constant voltage of 0.8 mA at room temperature (20 ° C.).
Under the constant current of A, the battery was discharged to a final voltage of 2.7 V, and the charging and discharging were repeated. The initial charge / discharge capacity is EC-DMC (1
/ 2) as the non-aqueous electrolyte solution (Comparative Example 1), and the battery characteristics after 50 cycles were measured. The discharge capacity retention ratio when the initial discharge capacity was 100% was 92%. 0.7%. Also, the low-temperature characteristics were good. Table 1 shows the manufacturing conditions and battery characteristics of the coin battery.
【００１８】実施例２ 添加剤として、ジフェニルジスルフィドを非水電解液に
対して０．２重量％使用したほかは実施例１と同様に非
水電解液を調製してコイン電池を作製し、５０サイクル
後の電池特性を測定したところ、放電容量維持率は９
０．５％であった。コイン電池の作製条件および電池特
性を表１に示す。Example 2 A coin battery was prepared by preparing a non-aqueous electrolyte in the same manner as in Example 1 except that diphenyl disulfide was used as an additive in an amount of 0.2% by weight based on the non-aqueous electrolyte. When the battery characteristics after cycling were measured, the discharge capacity retention ratio was 9
0.5%. Table 1 shows the manufacturing conditions and battery characteristics of the coin battery.
【００１９】実施例３ 添加剤として、ジフェニルジスルフィドを非水電解液に
対して０．０２重量％使用したほかは実施例１と同様に
非水電解液を調製してコイン電池を作製し、５０サイク
ル後の電池特性を測定したところ、放電容量維持率は９
１．２％であった。コイン電池の作製条件および電池特
性を表１に示す。Example 3 A coin battery was prepared by preparing a non-aqueous electrolyte in the same manner as in Example 1 except that diphenyl disulfide was used as an additive in an amount of 0.02% by weight based on the non-aqueous electrolyte. When the battery characteristics after cycling were measured, the discharge capacity retention ratio was 9
1.2%. Table 1 shows the manufacturing conditions and battery characteristics of the coin battery.
【００２０】実施例４ ＥＣ：ＰＣ：ＤＭＣ（容量比）＝１：１：２の非水溶媒
を調製し、これにＬｉＰＦ6を１Ｍの濃度になるように
溶解して非水電解液を調整した後、さらにジフェニルジ
スルフィドを非水電解液に対して０．１重量％となるよ
うに加えた。この非水電解液を使用して実施例１と同様
にコイン電池を作製し、電池特性を測定したところ、初
期放電容量はＥＣ−ＤＭＣ（容量比１／２）のみを非水
電解液として用いた場合（比較例１）とほぼ同等であ
り、５０サイクル後の電池特性を測定したところ、初期
放電容量を１００％としたときの放電容量維持率は９
２．３％であった。また、低温特性も良好であった。コ
イン電池の作製条件および電池特性を表１に示す。Example 4 A non-aqueous solvent of EC: PC: DMC (volume ratio) = 1: 1: 2 was prepared, and LiPF 6 was dissolved therein to a concentration of 1M to prepare a non-aqueous electrolyte. After that, diphenyl disulfide was further added so as to be 0.1% by weight based on the non-aqueous electrolyte. Using this non-aqueous electrolyte, a coin battery was prepared in the same manner as in Example 1, and the battery characteristics were measured. The initial discharge capacity was only EC-DMC (capacity ratio 1/2) as the non-aqueous electrolyte. When the battery characteristics after 50 cycles were measured, the discharge capacity retention ratio was 9 when the initial discharge capacity was 100%.
2.3%. Also, the low-temperature characteristics were good. Table 1 shows the manufacturing conditions and battery characteristics of the coin battery.
【００２１】実施例５ 負極活物質として、天然黒鉛に代えて人造黒鉛を使用し
たほかは実施例１と同様に非水電解液を調製してコイン
電池を作製し、５０サイクル後の電池特性を測定したと
ころ、放電容量維持率は８８．５％であった。コイン電
池の作製条件および電池特性を表１に示す。Example 5 A non-aqueous electrolyte was prepared in the same manner as in Example 1 except that artificial graphite was used in place of natural graphite as the negative electrode active material, and a coin battery was manufactured. As a result of the measurement, the discharge capacity retention ratio was 88.5%. Table 1 shows the manufacturing conditions and battery characteristics of the coin battery.
【００２２】実施例６ 正極活物質として、ＬｉＣｏＯ2に代えてＬｉＭｎ2Ｏ4
を使用したほかは実施例１と同様に非水電解液を調製し
てコイン電池を作製し、５０サイクル後の電池特性を測
定したところ、放電容量維持率は９３．８％であった。
コイン電池の作製条件および電池特性を表１に示す。Example 6 As a positive electrode active material, LiMn 2 O 4 was used instead of LiCoO 2.
A non-aqueous electrolyte solution was prepared in the same manner as in Example 1 to prepare a coin battery, and the battery characteristics after 50 cycles were measured. As a result, the discharge capacity retention ratio was 93.8%.
Table 1 shows the manufacturing conditions and battery characteristics of the coin battery.
【００２３】比較例１ ＥＣ：ＤＭＣ（容量比）＝１：２の非水溶媒を調製し、
これにＬｉＰＦ6を１Ｍの濃度になるように溶解した。
このときジフェニルジスルフィドは全く添加しなかっ
た。この非水電解液を使用して実施例１と同様にコイン
電池を作製し、電池特性を測定した。初期放電容量に対
し、５０サイクル後の放電容量維持率は８３．８％であ
った。コイン電池の作製条件および電池特性を表１に示
す。Comparative Example 1 A non-aqueous solvent of EC: DMC (volume ratio) = 1: 2 was prepared.
LiPF 6 was dissolved therein to a concentration of 1M.
At this time, no diphenyl disulfide was added. Using this non-aqueous electrolyte, a coin battery was produced in the same manner as in Example 1, and the battery characteristics were measured. The discharge capacity retention rate after 50 cycles with respect to the initial discharge capacity was 83.8%. Table 1 shows the manufacturing conditions and battery characteristics of the coin battery.
【００２４】[0024]
【表１】 [Table 1]
【００２５】なお、本発明は記載の実施例に限定され
ず、発明の趣旨から容易に類推可能な様々な組み合わせ
が可能である。特に、上記実施例の溶媒の組み合わせは
限定されるものではない。更には、上記実施例はコイン
電池に関するものであるが、本発明は円筒形、角柱形の
電池にも適用される。It should be noted that the present invention is not limited to the described embodiments, and various combinations that can be easily inferred from the gist of the invention are possible. In particular, the combinations of the solvents in the above examples are not limited. Further, while the above embodiments relate to coin batteries, the present invention is also applicable to cylindrical and prismatic batteries.
【００２６】[0026]
【発明の効果】本発明によれば、電池のサイクル特性、
電気容量、保存特性などの電池特性に優れたリチウム二
次電池を提供することができる。According to the present invention, the cycle characteristics of the battery,
A lithium secondary battery having excellent battery characteristics such as electric capacity and storage characteristics can be provided.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 松森 保男 山口県宇部市大字小串1978番地の５ 宇部 興産株式会社宇部研究所内 Ｆターム(参考） 5H003 AA02 AA03 AA04 BB01 BD04 5H014 AA02 AA06 EE08 HH01 5H029 AJ03 AJ04 AJ05 AK03 AL07 AM01 AM03 AM04 AM05 AM07 BJ02 BJ03 BJ14 HJ01 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Yasuo Matsumori 5F, 1978 Kogushi, Ube City, Ube City, Yamaguchi Prefecture F-term in the Ube Research Laboratory, Ube Industries, Ltd. 5H003 AA02 AA03 AA04 BB01 BD04 5H014 AA02 AA06 EE08 HH01 5H029 AJ03 AJ04 AJ05 AK03 AL07 AM01 AM03 AM04 AM05 AM07 BJ02 BJ03 BJ14 HJ01
Claims (3)
電解液において、該非水電解液中に下記式（Ｉ） Ｃ6Ｈ5−Ｓ−Ｓ−Ｃ6Ｈ5 （Ｉ） で表されるジフェニルジスルフィドが０．０１〜０．５
重量％含有されていることを特徴とする非水電解液。1. A non-aqueous electrolyte in which an electrolyte is dissolved in a non-aqueous solvent, wherein the non-aqueous electrolyte is represented by the following formula (I): C 6 H 5 -SS-C 6 H 5 (I) Diphenyl disulfide is 0.01 to 0.5
Non-aqueous electrolyte solution characterized by containing by weight.
解されている非水電解液からなるリチウム二次電池にお
いて、該非水電解液中に下記式（Ｉ） Ｃ6Ｈ5−Ｓ−Ｓ−Ｃ6Ｈ5 （Ｉ） で表されるジフェニルジスルフィドが０．０１〜０．５
重量％含有されていることを特徴とするリチウム二次電
池。2. A lithium secondary battery comprising a positive electrode, a negative electrode, and a non-aqueous electrolyte in which an electrolyte is dissolved in a non-aqueous solvent, wherein the non-aqueous electrolyte contains the following formula (I) C 6 H 5 -S-S The diphenyl disulfide represented by —C 6 H 5 (I) is 0.01 to 0.5;
A lithium secondary battery characterized in that the lithium secondary battery is contained by weight%.
からなることを特徴とする請求項２記載のリチウム二次
電池。3. The lithium secondary battery according to claim 2, wherein the negative electrode is made of a carbon material having a graphite type crystal structure.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09149799A JP4042083B2 (en) | 1998-09-03 | 1999-03-31 | Nonaqueous electrolyte and lithium secondary battery using the same |
| US10/383,790 US7691539B2 (en) | 1998-09-03 | 2003-03-06 | Non-aqueous secondary battery having increased discharge capacity retention |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10-248975 | 1998-09-03 | ||
| JP24897598 | 1998-09-03 | ||
| JP09149799A JP4042083B2 (en) | 1998-09-03 | 1999-03-31 | Nonaqueous electrolyte and lithium secondary battery using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000149987A true JP2000149987A (en) | 2000-05-30 |
| JP4042083B2 JP4042083B2 (en) | 2008-02-06 |
Family
ID=26432934
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP09149799A Expired - Lifetime JP4042083B2 (en) | 1998-09-03 | 1999-03-31 | Nonaqueous electrolyte and lithium secondary battery using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4042083B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002025614A (en) * | 2000-07-10 | 2002-01-25 | Hitachi Maxell Ltd | Nonaqueous secondary battery |
| KR100370383B1 (en) * | 2000-11-28 | 2003-01-30 | 제일모직주식회사 | Non-aqueous electrolyte solution for lithium battery |
| EP1304758A1 (en) * | 2000-06-26 | 2003-04-23 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous electrolyte and non-aqueous electrolyte secondary cell |
| KR100558842B1 (en) * | 2001-05-16 | 2006-03-10 | 에스케이씨 주식회사 | Organic electrolytic solution and lithium battery adopting the same |
| EP1176659A3 (en) * | 2000-07-25 | 2006-05-31 | Samsung SDI Co. Ltd. | Electrolyte for a lithium-sulfur battery and a lithium-sulfur battery using the same |
| KR100723264B1 (en) * | 2000-10-20 | 2007-05-30 | 우베 고산 가부시키가이샤 | Non-aqueous secondary battery having enhanced discharge capacity retention and non-aqueous electrolytic solution for manufacturing the battery |
| JP2010186751A (en) * | 2010-04-14 | 2010-08-26 | Hitachi Maxell Ltd | Nonaqueous secondary battery |
| CN116864654A (en) * | 2023-08-17 | 2023-10-10 | 广东工业大学 | Mesoporous carbon finite field ether organic positive electrode active material for water-based zinc battery, and preparation method and application thereof |
-
1999
- 1999-03-31 JP JP09149799A patent/JP4042083B2/en not_active Expired - Lifetime
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1304758A1 (en) * | 2000-06-26 | 2003-04-23 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous electrolyte and non-aqueous electrolyte secondary cell |
| EP1304758A4 (en) * | 2000-06-26 | 2006-03-29 | Matsushita Electric Ind Co Ltd | Non-aqueous electrolyte and non-aqueous electrolyte secondary cell |
| US7132199B2 (en) | 2000-06-26 | 2006-11-07 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous electrolyte and non-aqueous electrolyte secondary battery |
| JP2002025614A (en) * | 2000-07-10 | 2002-01-25 | Hitachi Maxell Ltd | Nonaqueous secondary battery |
| EP1176659A3 (en) * | 2000-07-25 | 2006-05-31 | Samsung SDI Co. Ltd. | Electrolyte for a lithium-sulfur battery and a lithium-sulfur battery using the same |
| KR100723264B1 (en) * | 2000-10-20 | 2007-05-30 | 우베 고산 가부시키가이샤 | Non-aqueous secondary battery having enhanced discharge capacity retention and non-aqueous electrolytic solution for manufacturing the battery |
| KR100370383B1 (en) * | 2000-11-28 | 2003-01-30 | 제일모직주식회사 | Non-aqueous electrolyte solution for lithium battery |
| KR100558842B1 (en) * | 2001-05-16 | 2006-03-10 | 에스케이씨 주식회사 | Organic electrolytic solution and lithium battery adopting the same |
| JP2010186751A (en) * | 2010-04-14 | 2010-08-26 | Hitachi Maxell Ltd | Nonaqueous secondary battery |
| CN116864654A (en) * | 2023-08-17 | 2023-10-10 | 广东工业大学 | Mesoporous carbon finite field ether organic positive electrode active material for water-based zinc battery, and preparation method and application thereof |
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