JP2001023689A - Nonaqueous electrolyte and lithium secondary battery using the same - Google Patents
Nonaqueous electrolyte and lithium secondary battery using the sameInfo
- Publication number
- JP2001023689A JP2001023689A JP11198352A JP19835299A JP2001023689A JP 2001023689 A JP2001023689 A JP 2001023689A JP 11198352 A JP11198352 A JP 11198352A JP 19835299 A JP19835299 A JP 19835299A JP 2001023689 A JP2001023689 A JP 2001023689A
- Authority
- JP
- Japan
- Prior art keywords
- carbonate
- butyl methyl
- methyl carbonate
- cyclic
- battery
- 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、正極材料、負極材
料、セパレータに対する非水電解液の浸透性に優れ、高
温環境下での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。The present invention relates to a battery having excellent permeability of a non-aqueous electrolyte into a positive electrode material, a negative electrode material, and a separator, and to a battery characteristic such as a cycle characteristic, an electric capacity and a storage characteristic under a high temperature environment. The present invention relates to a non-aqueous electrolyte capable of providing an excellent lithium secondary battery, and a lithium secondary battery using the same.
【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、ＬｉＭｎ2Ｏ4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（ＰＣ）などの環状カーボネート類や、γ−ブ
チロラクトン（ＧＢＬ）、γ−バレロラクトン（ＧＶ
Ｌ）などの環状エステル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, a lithium composite oxide such as LiCoO 2 or LiMn 2 O 4 as a positive electrode, and a carbon material or lithium metal as a negative electrode. Lithium secondary batteries are preferably used. As the non-aqueous electrolyte for the lithium secondary battery, cyclic carbonates such as ethylene carbonate (EC) and propylene carbonate (PC), γ-butyrolactone (GBL), γ-valerolactone (GV
Cyclic esters such as L) 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、負極として、例えば黒鉛、コークスなど
の炭素材料、セパレータとしてポリエチレン、ポリプロ
ピレンなどのポリオレフィンを用いたリチウム二次電池
において、ＥＣ、ＰＣ、ＧＢＬを主溶媒とした非水電解
液は、引火点が高いため、電池の安全上からも望ましい
が、該非水電解液はセパレータに対する濡れ性の欠点が
顕著に現れるため、リチウム電池製造時の注液工程に課
題を有するとともに、電池のサイクル特性および電池特
性においても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
In a lithium secondary battery using a carbon material such as graphite and coke as a negative electrode such as NiO 2 and a polyolefin such as polyethylene and polypropylene as a separator, a non-aqueous electrolyte containing EC, PC, and GBL as a main solvent is ignited. However, the non-aqueous electrolyte has a problem in the liquid injection step at the time of manufacturing a lithium battery because the non-aqueous electrolyte has a remarkable defect of wettability to the separator. At present, battery characteristics are not always satisfactory.
【０００４】本発明は、前記のようなリチウム二次電池
用電解液の正極、負極、セパレータに対する濡れ性に関
する課題を解決し、高温環境下での電池のサイクル特性
や電気容量などの電池特性に優れ、さらに引火点が高く
て、しかもセパレータに対する濡れ性に優れたリチウム
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 wettability of the electrolyte solution for a lithium secondary battery with respect to the positive electrode, the negative electrode, and the separator, and improves the battery characteristics such as cycle characteristics and electric capacity under a high temperature environment. Provided are a non-aqueous electrolyte for a lithium secondary battery, which is capable of forming a lithium secondary battery that is excellent, has a high flash point, and has excellent wettability to a separator, and a lithium secondary battery using the same. The purpose is to:
【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、該非水溶媒
が環状カーボネートおよび／または環状エステルと、分
枝したＣ4Ｈ9基を有するブチルメチルカーボネートとか
らなることを特徴とする非水電解液に関する。また、本
発明は、リチウム複合酸化物を含む材料からなる正極、
炭素を含む材料からなる負極、セパレータ、および非水
溶媒に電解質が溶解されている非水電解液を備えたリチ
ウム二次電池において、該非水溶媒が環状カーボネート
および／または環状エステルと、分枝したＣ4Ｈ9基を有
するブチルメチルカーボネートとからなることを特徴と
するリチウム二次電池に関する。According to the present invention, there is provided a non-aqueous electrolytic solution in which an electrolyte is dissolved in a non-aqueous solvent, wherein the non-aqueous solvent contains a cyclic carbonate and / or a cyclic ester and a branched C 4 H 9 group. And butyl methyl carbonate having the formula: Further, the present invention provides a positive electrode made of a material containing a lithium composite oxide,
In a lithium secondary battery including a negative electrode made of a material containing carbon, a separator, and a nonaqueous electrolyte in which an electrolyte is dissolved in a nonaqueous solvent, the nonaqueous solvent is branched with a cyclic carbonate and / or a cyclic ester. And a butyl methyl carbonate having a C 4 H 9 group.
【０００６】[0006]
【発明の実施の形態】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。DESCRIPTION OF THE PREFERRED EMBODIMENTS 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】本発明で使用される非水溶媒としては、環
状カーボネートおよび／または環状エステルと、分枝し
たＣ4Ｈ9基を含有するメチルブチルカーボネートとから
なるものが使用される。環状カーボネートとしては、エ
チレンカーボネート（ＥＣ）、プロピレンカーボネート
（ＰＣ）、ブチレンカーボネート（ＢＣ）、ビニレンカ
ーボネート（ＶＣ）が好適に挙げられる。これらの環状
カーボネートは、１種類で使用してもよく、また２種類
以上組み合わせて使用してもよい。As the non-aqueous solvent used in the present invention, those comprising a cyclic carbonate and / or a cyclic ester and methyl butyl carbonate containing a branched C 4 H 9 group are used. Preferable examples of the cyclic carbonate include ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), and vinylene carbonate (VC). One of these cyclic carbonates may be used, or two or more thereof may be used in combination.
【０００８】環状エステルとしては、γ−ブチロラクト
ン（ＧＢＬ）、γ−バレロラクトン（ＧＶＬ）が好適に
挙げられる。これらの環状エステルは、１種類で使用し
てもよく、また２種類を組み合わせて使用してもよい。Preferred examples of the cyclic ester include γ-butyrolactone (GBL) and γ-valerolactone (GVL). One of these cyclic esters may be used, or two or more thereof may be used in combination.
【０００９】分枝したＣ4Ｈ9基を有するブチルメチルカ
ーボネートとしては、下記構造式で表されるｓｅｃ−ブ
チルメチルカーボネート（Ｉ）、イソブチルメチルカー
ボネート（ＩＩ）およびｔｅｒｔ−ブチルメチルカーボ
ネート（ＩＩＩ）が挙げられる。これらの分枝したＣ4
Ｈ9基を有するブチルメチルカーボネートは１種類で使
用してもよく、また２種類以上を組み合わせて使用して
もよい。The butyl methyl carbonate having a branched C 4 H 9 group includes sec-butyl methyl carbonate (I), isobutyl methyl carbonate (II) and tert-butyl methyl carbonate (III) represented by the following structural formulas. Is mentioned. These branched C 4
One type of butyl methyl carbonate having an H 9 group may be used, or two or more types may be used in combination.
【化７】 Embedded image
【化８】 Embedded image
【化９】 環状カーボネートおよび／または環状エステルと、分枝
したＣ4Ｈ9基を有するブチルメチルカーボネートとは、
それぞれ任意に選択され組み合わせて使用される。前記
環状カーボネートおよび／または環状エステルは３０〜
９０体積％、前記の分枝したＣ4Ｈ9基を含有するブチル
メチルカーボネートは１０〜７０体積％で使用される。Embedded image Cyclic carbonates and / or cyclic esters and butylmethyl carbonate having a branched C 4 H 9 group are:
Each is arbitrarily selected and used in combination. The cyclic carbonate and / or cyclic ester is 30 to
90 vol%, butyl methyl carbonate containing C 4 H 9 groups branched in the are used by 10 to 70% by volume.
【００１０】本発明で使用される電解質としては、例え
ば、ＬｉＰＦ6、ＬｉＢＦ4、ＬｉＣｌＯ4、ＬｉＮ（Ｓ
Ｏ2ＣＦ3）2、ＬｉＮ（ＳＯ2Ｃ2Ｆ5）2、ＬｉＣ（ＳＯ2
ＣＦ3）3などが挙げられる。これらの電解質は、１種類
で使用してもよく、２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 (S
O 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 usually 0.1 to
It is used after being dissolved at a concentration of 3M, preferably 0.5 to 1.5M.
【００１１】本発明の非水電解液は、例えば、前記の環
状カーボネートおよび／または環状エステルと、前記の
分枝したＣ4Ｈ9基を含有するブチルメチルカーボネート
とを混合し、これに前記の電解質を溶解することにより
得られる。The non-aqueous electrolyte solution of the present invention is obtained, for example, by mixing the above-mentioned cyclic carbonate and / or cyclic ester with the above-mentioned butyl methyl carbonate containing a branched C 4 H 9 group, Obtained by dissolving the electrolyte.
【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１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, as the positive electrode active material, 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. 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, pressed and then heat-treated at a temperature of about 50 to 250 ° C. for about 2 hours under vacuum. It is produced by this.
【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０．３３５〜０．３４０ｎｍ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（ＰＶＤ
Ｆ）などの結着剤と混練して負極合剤として使用され
る。Examples of the negative electrode active material include lithium metals, lithium alloys, and carbon materials 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 0.335 to 0.340 nm. In addition, powder materials such as carbon materials are ethylene propylene diene terpolymer (EPDM), polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVD).
It is used as a negative electrode mixture by kneading with a binder such as F).
【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]
ＥＣ：ＧＢＬ：ＩＢＭＣ（容量比）＝３０：５０：２０
の非水溶媒を調製し、これにＬｉＢＦ4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。ただし、Ｉ
ＢＭＣはイソブチルメチルカーボネートである。EC: GBL: IBMC (capacity ratio) = 30: 50: 20
Was prepared, and LiBF 4 was dissolved therein to a concentration of 1M to prepare a non-aqueous electrolyte. Where I
BMC is isobutyl methyl carbonate.
【００１７】〔リチウム二次電池の作製および電池特性
の測定〕ＬｉＭｎ2Ｏ4（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。人造黒鉛（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−ＧＢＬ（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８０．５％であった。セパレータに対する濡れ性
を観測したところ、接触角は５０．４度であり、濡れ性
は比較例１に比べ良好であった。本発明のセパレータに
対する電解液の濡れ性は、以下の装置を用いて測定し
た。測定条件は、温度２３℃、湿度５０％の雰囲気で、
該非水電解液を、セパレータの上に滴下したものについ
て、液滴形成直後の接触角を測定した。測定装置は、協
和界面科学（株）製、画像処理式接触角計 ＣＡ−Ｘ
型。測定された接触角が小さいほど、セパレータの非水
電解液に対する濡れ性および浸透性に優れることをあら
わす。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] LiMn 2 O 4 (cathode active material) was 80% by weight, acetylene black (conductive agent) was 10% by weight, and polyvinylidene fluoride (binder) was used. The mixture was mixed at a ratio of 10% by weight, and a mixture obtained by adding a 1-methyl-2-pyrrolidone solvent to the mixture was applied onto an aluminum foil, followed by drying, pressure molding and heat treatment to prepare a positive electrode. 90% by weight of artificial graphite (negative electrode active material) and 10% by weight of polyvinylidene fluoride (binder) were mixed, 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). This coin battery was charged at room temperature (20 ° C.) at a constant current and a constant voltage of 0.8 mA to a final voltage of 4.2 V for 5 hours, and then charged at a current of 0.8 m
Under the constant current of A, the battery was discharged to a final voltage of 2.7 V, and this charge / discharge was repeated. The initial charge / discharge capacity is EC-GBL (1
/ 2) as the non-aqueous electrolyte (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 80%. 0.5%. When the wettability to the separator was observed, the contact angle was 50.4 degrees, and the wettability was better than that of Comparative Example 1. The wettability of the electrolytic solution to the separator of the present invention was measured using the following device. The measurement conditions were as follows: 23 ° C., 50% humidity
The contact angle of the non-aqueous electrolyte dropped on the separator was measured immediately after the formation of the droplet. The measuring device was manufactured by Kyowa Interface Science Co., Ltd., image processing type contact angle meter CA-X.
Type. The smaller the measured contact angle, the better the wettability and permeability of the separator with respect to the non-aqueous electrolyte. Table 1 shows the manufacturing conditions and battery characteristics of the coin battery.
【００１８】実施例２ ＥＣ：ＧＢＬ：ＳＢＭＣ（容量比）＝３０：５０：２０
の非水溶媒を調製し、これにＬｉＢＦ4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。ただし、Ｓ
ＢＭＣはｓｅｃ−ブチルメチルカーボネートである。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、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８０．２％であった。セパレータに対
する濡れ性を観測したところ、５３．３度であり、濡れ
性は良好であった。コイン電池の作製条件および電池特
性を表１に示す。Example 2 EC: GBL: SBMC (capacity ratio) = 30: 50: 20
Was prepared, and LiBF 4 was dissolved therein to a concentration of 1M to prepare a non-aqueous electrolyte. Where S
BMC is sec-butyl methyl carbonate. Using this non-aqueous electrolyte, a coin battery was produced in the same manner as in Example 1, and the battery characteristics after 50 cycles were measured.
The discharge capacity retention was 80.2%. When the wettability with respect to the separator was observed, it was 53.3 degrees, and the wettability was good. Table 1 shows the manufacturing conditions and battery characteristics of the coin battery.
【００１９】実施例３ ＥＣ：ＧＢＬ：ＴＢＭＣ（容量比）＝３０：５０：２０
の非水溶媒を調製し、これにＬｉＢＦ4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。ただし、Ｔ
ＢＭＣはｔｅｒｔ−ブチルメチルカーボネートである。
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、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８０．３％であった。セパレータ
に対する濡れ性を観測したところ、５３．１度であり、
濡れ性は良好であった。コイン電池の作製条件および電
池特性を表１に示す。Example 3 EC: GBL: TBMC (capacity ratio) = 30: 50: 20
Was prepared, and LiBF 4 was dissolved therein to a concentration of 1M to prepare a non-aqueous electrolyte. Where T
BMC is tert-butyl methyl carbonate.
Using this non-aqueous electrolyte, a coin battery was manufactured in the same manner as in Example 1, and the battery characteristics after 50 cycles were measured. As a result, the discharge capacity retention ratio was 80.3%. When the wettability to the separator was observed, it was 53.1 degrees,
The wettability was good. Table 1 shows the manufacturing conditions and battery characteristics of the coin battery.
【００２０】比較例１ ＥＣ：ＧＢＬ（容量比）＝１：２の非水溶媒を調製し、
これにＬｉＢＦ4を１Ｍの濃度になるように溶解した。
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６５．６％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。セパレータに対する濡れ性を観測したところ、接触
角は７７．２度であり、濡れ性の面で劣っていた。Comparative Example 1 A non-aqueous solvent of EC: GBL (volume ratio) = 1: 2 was prepared.
LiBF 4 was dissolved therein to a concentration of 1M.
Using this non-aqueous electrolyte, a coin battery was produced in the same manner as in Example 1, and the battery characteristics were measured. For the initial discharge capacity,
The discharge capacity retention rate after 50 cycles was 65.6%. Table 1 shows the manufacturing conditions and battery characteristics of the coin battery. When the wettability with respect to the separator was observed, the contact angle was 77.2 degrees, and the wettability was poor.
【００２１】比較例２ ＥＣ：ＧＢＬ：ＤＢＣ（容量比）＝３０：５０：２０の
非水溶媒を調製し、これにＬｉＢＦ4を１Ｍの濃度にな
るように溶解した。ただし、ＤＢＣはジｎ−ブチルカー
ボネートである。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６
９．４％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 2 A non-aqueous solvent of EC: GBL: DBC (volume ratio) = 30: 50: 20 was prepared, and LiBF 4 was dissolved therein to a concentration of 1M. However, DBC is di-n-butyl carbonate. 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 is 6 relative to the initial discharge capacity.
It was 9.4%. Table 1 shows the manufacturing conditions and battery characteristics of the coin battery.
【００２２】比較例３ ＥＣ：ＧＢＬ：ＢＭＣ（容量比）＝３０：５０：２０の
非水溶媒を調製し、これにＬｉＢＦ4を１Ｍの濃度にな
るように溶解した。ただし、ＢＭＣはｎ−ブチルメチル
カーボネートである。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７０．２％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。Comparative Example 3 A non-aqueous solvent of EC: GBL: BMC (volume ratio) = 30: 50: 20 was prepared, and LiBF 4 was dissolved therein to a concentration of 1M. However, BMC is n-butyl methyl carbonate. 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 70.2%. Table 1 shows the manufacturing conditions and battery characteristics of the coin battery.
【００２３】比較例４ ＥＣ：ＧＢＬ：ＭＥＣ（容量比）＝３０：５０：２０の
非水溶媒を調製し、これにＬｉＢＦ4を１Ｍの濃度にな
るように溶解した。ただし、ＭＥＣはメチルエチルカー
ボネートである。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７
６．８％であった。しかしながら、非水電解液の引火点
が低くなるという問題が生じた。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 4 A non-aqueous solvent of EC: GBL: MEC (volume ratio) = 30: 50: 20 was prepared, and LiBF 4 was dissolved therein to a concentration of 1M. However, MEC is methyl ethyl carbonate. 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 is 7 with respect to the initial discharge capacity.
It was 6.8%. However, there has been a problem that the flash point of the non-aqueous electrolyte is low. Table 1 shows the manufacturing conditions and battery characteristics of the coin battery.
【００２４】実施例４ 正極活物質として、ＬｉＭｎ2Ｏ4に代えてＬｉＣｏＯ2
を使用した以外は実施例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、５０サイクル後の放電
容量維持率は８２．２％であった。また、実施例１と同
様にセパレータに対する濡れ性も良好であった。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 As a positive electrode active material, LiCoO 2 was used instead of LiMn 2 O 4
A coin battery was prepared in the same manner as in Example 1 except that was used, and the battery characteristics were measured. As a result, the discharge capacity retention ratio after 50 cycles was 82.2%. Further, similarly to Example 1, the wettability to the separator was also good. Table 1 shows the manufacturing conditions and battery characteristics of the coin battery.
【００２５】実施例５ 電解質として、１Ｍ ＬｉＢＦ4に代えて０．５Ｍ Ｌ
ｉＢＦ4＋０．５Ｍ ＬｉＰＦ6を使用した以外は実施例
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、５０サイクル後の放電容量維持率は８０．３％で
あった。また、実施例１と同様にセパレータに対する濡
れ性も良好であった。コイン電池の作製条件および電池
特性を表１に示す。Example 5 0.5 M L instead of 1 M LiBF 4 was used as the electrolyte.
A coin battery was prepared in the same manner as in Example 1 except that iBF 4 +0.5 M LiPF 6 was used, and the battery characteristics were measured. As a result, the discharge capacity retention ratio after 50 cycles was 80.3%. Further, similarly to Example 1, the wettability to the separator was also good. Table 1 shows the manufacturing conditions and battery characteristics of the coin battery.
【００２６】実施例６ 負極活物質として、人造黒鉛に代えて天然黒鉛を使用し
た以外は実施例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、５０サイクル後の放電容量維持率
は８１．２％であった。また、実施例１と同様にセパレ
ータに対する濡れ性も良好であった。コイン電池の作製
条件および電池特性を表１に示す。Example 6 A coin battery was manufactured in the same manner as in Example 1 except that natural graphite was used instead of artificial graphite as the negative electrode active material, and the battery characteristics were measured. Was 81.2%. Further, similarly to Example 1, the wettability to the separator was also good. Table 1 shows the manufacturing conditions and battery characteristics of the coin battery.
【００２７】実施例７ ＥＣ：ＧＢＬ：ＩＢＭＣ（容量比）＝３０：３０：４０
の非水溶媒を調製し、これにＬｉＢＦ4を１Ｍの濃度に
なるように溶解した。この非水電解液を使用して実施例
６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、５０サイクル後の放電容量維持率は８０．７％で
あった。また、実施例６と同様にセパレータに対する濡
れ性も良好であった。コイン電池の作製条件および電池
特性を表１に示す。Example 7 EC: GBL: IBMC (capacity ratio) = 30: 30: 40
Was prepared, and LiBF 4 was dissolved therein to a concentration of 1M. Using this non-aqueous electrolyte, a coin battery was produced in the same manner as in Example 6, and the battery characteristics were measured. As a result, the discharge capacity retention rate after 50 cycles was 80.7%. Further, similarly to Example 6, the wettability to the separator was also good. Table 1 shows the manufacturing conditions and battery characteristics of the coin battery.
【００２８】実施例８ ＥＣ：ＧＢＬ：ＩＢＭＣ（容量比）＝３０：１０：６０
の非水溶媒を調製し、これにＬｉＢＦ4を１Ｍの濃度に
なるように溶解した。この非水電解液を使用して実施例
６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、５０サイクル後の放電容量維持率は８０．３％で
あった。また、実施例６と同様にセパレータに対する濡
れ性も良好であった。コイン電池の作製条件および電池
特性を表１に示す。Example 8 EC: GBL: IBMC (capacity ratio) = 30: 10: 60
Was prepared, and LiBF 4 was dissolved therein to a concentration of 1M. Using this non-aqueous electrolyte, a coin battery was fabricated in the same manner as in Example 6, and the battery characteristics were measured. As a result, the discharge capacity retention rate after 50 cycles was 80.3%. Further, similarly to Example 6, the wettability to the separator was also good. Table 1 shows the manufacturing conditions and battery characteristics of the coin battery.
【００２９】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.
【００３０】[0030]
【表１】 [Table 1]
【００３１】[0031]
【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、かつ濡れ性
が良好な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 and good wettability 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10 宇部 興産株式会社宇部ケミカル工場内 Ｆターム(参考） 5H029 AJ03 AJ04 AJ05 AK03 AL03 AL06 AL07 AL12 AM03 AM05 AM07 HJ02 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Yasuo Matsumori 10-figure, 1978 Kogushi, Obe-shi, Ube-shi, Yamaguchi F-term in the Ube Chemical Plant Ube Chemical Plant 5H029 AJ03 AJ04 AJ05 AK03 AL03 AL06 AL07 AL12 AM03 AM05 AM07 HJ02
Claims (8)
電解液において、該非水溶媒が環状カーボネートおよび
／または環状エステルと、分枝したＣ4Ｈ9基を有するブ
チルメチルカーボネートとからな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 solvent comprises cyclic carbonate and / or cyclic ester and butyl methyl carbonate having a branched C 4 H 9 group. Non-aqueous electrolyte solution characterized by the above-mentioned.
ト、プロピレンカーボネート、ブチレンカーボネートお
よびビニレンカーボネートから選ばれる少なくとも１種
以上である請求項１記載の非水電解液。2. The non-aqueous electrolyte according to claim 1, wherein the cyclic carbonate is at least one selected from ethylene carbonate, propylene carbonate, butylene carbonate, and vinylene carbonate.
び／またはγ−バレロラクトンである請求項１記載の非
水電解液。3. The non-aqueous electrolyte according to claim 1, wherein the cyclic ester is γ-butyrolactone and / or γ-valerolactone.
カーボネートが下記構造式で表されるｓｅｃ−ブチルメ
チルカーボネート（Ｉ）、イソブチルメチルカーボネー
ト（ＩＩ）およびｔｅｒｔ−ブチルメチルカーボネート
（ＩＩＩ）から選ばれる少なくとも１種以上である請求
項１記載の非水電解液。 【化１】 【化２】 【化３】 4. A butyl methyl carbonate having a branched C 4 H 9 group is represented by the following structural formula: sec-butyl methyl carbonate (I), isobutyl methyl carbonate (II) and tert-butyl methyl carbonate (III) 2. The non-aqueous electrolyte according to claim 1, which is at least one member selected from the group consisting of: Embedded image Embedded image Embedded image
正極、炭素を含む材料からなる負極、セパレータ、およ
び非水溶媒に電解質が溶解されている非水電解液を備え
たリチウム二次電池において、該非水溶媒が環状カーボ
ネートおよび／または環状エステルと、分枝したＣ4Ｈ9
基を有するブチルメチルカーボネートとからなることを
特徴とするリチウム二次電池。5. A lithium secondary battery comprising a positive electrode made of a material containing a lithium composite oxide, a negative electrode made of a material containing carbon, a separator, and a non-aqueous electrolyte in which an electrolyte is dissolved in a non-aqueous solvent. The non-aqueous solvent is a cyclic carbonate and / or a cyclic ester, and a branched C 4 H 9
And butyl methyl carbonate having a group.
ト、プロピレンカーボネート、ブチレンカーボネートお
よびビニレンカーボネートから選ばれる少なくとも１種
以上である請求項５記載のリチウム二次電池。6. The lithium secondary battery according to claim 5, wherein the cyclic carbonate is at least one selected from ethylene carbonate, propylene carbonate, butylene carbonate, and vinylene carbonate.
び／またはγ−バレロラクトンである請求項５記載のリ
チウム二次電池。7. The lithium secondary battery according to claim 5, wherein the cyclic ester is γ-butyrolactone and / or γ-valerolactone.
カーボネートが下記構造式で表されるｓｅｃ−ブチルメ
チルカーボネート（Ｉ）、イソブチルメチルカーボネー
ト（ＩＩ）およびｔｅｒｔ−ブチルメチルカーボネート
（ＩＩＩ）から選ばれる少なくとも１種以上である請求
項５記載のリチウム二次電池。 【化４】 【化５】 【化６】 8. A butyl methyl carbonate having a branched C 4 H 9 group is represented by the following structural formula: sec-butyl methyl carbonate (I), isobutyl methyl carbonate (II) and tert-butyl methyl carbonate (III) The lithium secondary battery according to claim 5, which is at least one member selected from the group consisting of: Embedded image Embedded image Embedded image
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|---|---|---|---|
| JP19835299A JP4147691B2 (en) | 1999-07-13 | 1999-07-13 | Nonaqueous electrolyte and lithium secondary battery using the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19835299A JP4147691B2 (en) | 1999-07-13 | 1999-07-13 | Nonaqueous electrolyte and lithium secondary battery using the same |
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| Publication Number | Publication Date |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008507111A (en) * | 2004-07-23 | 2008-03-06 | ザ ジレット カンパニー | Non-aqueous electrochemical cell |
| EP1978588A1 (en) * | 2007-03-28 | 2008-10-08 | GM Global Technology Operations, Inc. | Lithium-ion battery electrolytes |
| WO2014156428A1 (en) * | 2013-03-25 | 2014-10-02 | 富士フイルム株式会社 | Electrolyte solution for nonaqueous secondary batteries, and nonaqueous secondary battery |
| CN104466247A (en) * | 2014-12-16 | 2015-03-25 | 东莞新能源科技有限公司 | Nonaqueous electrolyte and lithium ion battery utilizing same |
| CN109309256A (en) * | 2017-07-28 | 2019-02-05 | 宁德时代新能源科技股份有限公司 | Electrolyte and battery |
-
1999
- 1999-07-13 JP JP19835299A patent/JP4147691B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008507111A (en) * | 2004-07-23 | 2008-03-06 | ザ ジレット カンパニー | Non-aqueous electrochemical cell |
| EP1978588A1 (en) * | 2007-03-28 | 2008-10-08 | GM Global Technology Operations, Inc. | Lithium-ion battery electrolytes |
| WO2014156428A1 (en) * | 2013-03-25 | 2014-10-02 | 富士フイルム株式会社 | Electrolyte solution for nonaqueous secondary batteries, and nonaqueous secondary battery |
| CN104466247A (en) * | 2014-12-16 | 2015-03-25 | 东莞新能源科技有限公司 | Nonaqueous electrolyte and lithium ion battery utilizing same |
| CN109309256A (en) * | 2017-07-28 | 2019-02-05 | 宁德时代新能源科技股份有限公司 | Electrolyte and battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4147691B2 (en) | 2008-09-10 |
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