JPH08106909A - Nonaqueous electrolytic battery - Google Patents
Nonaqueous electrolytic batteryInfo
- Publication number
- JPH08106909A JPH08106909A JP6266165A JP26616594A JPH08106909A JP H08106909 A JPH08106909 A JP H08106909A JP 6266165 A JP6266165 A JP 6266165A JP 26616594 A JP26616594 A JP 26616594A JP H08106909 A JPH08106909 A JP H08106909A
- Authority
- JP
- Japan
- Prior art keywords
- carbonate
- battery
- aqueous electrolyte
- solvent
- negative electrode
- 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.)
- Pending
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
Landscapes
- Carbon And Carbon Compounds (AREA)
- Primary Cells (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、非水電解液電池に係わ
り、詳しくは、その負荷特性を改善することを目的とし
た非水電解液の溶媒の改良に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-aqueous electrolyte battery, and more particularly to improvement of a solvent of a non-aqueous electrolyte solution for the purpose of improving its load characteristics.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】近年、
負極材料として、格子面（００２）面に於けるｄ値（ｄ
002 ）が小さく、且つｃ軸方向の結晶子の大きさ
（ＬC ）が大きい黒鉛又は黒鉛化度の大きい炭素材料を
使用した非水電解液電池が、電池容量が大きい、電
位平坦性に優れる、サイクル特性に優れる等の利点を
有していることから注目されている。2. Description of the Related Art In recent years,
As a negative electrode material, the d value (d
002 ), and a non-aqueous electrolyte battery using graphite having a large crystallite size (L C ) in the c-axis direction or a carbon material having a high degree of graphitization has a large battery capacity and excellent potential flatness. It has attracted attention because it has advantages such as excellent cycle characteristics.
【０００３】この種の炭素材料を使用した非水電解液電
池では、プロピレンカーボネートは溶媒として使用でき
ない。プロピレンカーボネートは充電時にガスを発生し
て分解してしまうからである。このため、従来、黒鉛又
は黒鉛化度の大きい炭素材料を使用した非水電解液電池
には、エチレンカーボネート（ＥＣ）等の環状炭酸エス
テルと、ジメチルカーボネート（ＤＭＣ）等の非環状炭
酸エステルとからなる混合溶媒が使用されていた。Propylene carbonate cannot be used as a solvent in a non-aqueous electrolyte battery using this type of carbon material. This is because propylene carbonate generates gas during charging and decomposes. Therefore, conventionally, a non-aqueous electrolyte battery using graphite or a carbon material having a high degree of graphitization comprises a cyclic carbonate such as ethylene carbonate (EC) and a non-cyclic carbonate such as dimethyl carbonate (DMC). The following mixed solvents were used.
【０００４】しかしながら、非水電解液の溶媒としてこ
の種の混合溶媒を使用し、且つ負極材料として黒鉛又は
黒鉛化度の大きい炭素材料を使用した非水電解液電池に
は、負荷特性が良くないという問題があった。However, the non-aqueous electrolyte battery using this kind of mixed solvent as the solvent of the non-aqueous electrolyte and graphite or a carbon material having a high degree of graphitization as the negative electrode material does not have good load characteristics. There was a problem.
【０００５】本発明は、この問題を解決するべくなされ
たものであって、その目的とするところは、非水電解液
の溶媒を改良することにより、負荷特性に優れた非水電
解液電池を提供するにある。The present invention has been made to solve this problem, and an object of the present invention is to improve the solvent of the non-aqueous electrolyte to provide a non-aqueous electrolyte battery having excellent load characteristics. To provide.
【０００６】[0006]
【課題を解決するための手段】上記目的を達成するため
の本発明に係る非水電解液電池（以下、「本発明電池
Ａ」と称する）は、正極と、格子面（００２）面に於け
るｄ値（ｄ002 ）が３．３５〜３．３９Åであり、且つ
ｃ軸方向の結晶子の大きさ（ＬC ）が１５０Å以上であ
る炭素材料を負極材料とする負極と、溶媒及び溶質から
なる非水電解液と、セパレータとを備えてなる非水電解
液電池において、前記溶媒が、ジフェニルカーボネー
ト、メチルフェニルカーボネート及びエチルフェニルカ
ーボネートよりなる群から選ばれた少なくとも一種のフ
ェニル基を少なくとも１個含有する非環状炭酸エステル
（Ａ）１０〜５０体積％と、ジエチルカーボネート、ジ
メチルカーボネート及びメチルエチルカーボネートより
なる群から選ばれた少なくとも一種の非環状炭酸エステ
ル（Ｂ）９０〜５０体積％とからなる。A non-aqueous electrolyte battery according to the present invention (hereinafter referred to as "invention battery A") for achieving the above object has a positive electrode and a lattice plane (002) plane. kicking d value (d 002) is 3.35～3.39A, and a negative electrode size in the c-axis direction of the crystallite (L C) to the negative electrode material a carbon material is more than 150 Å, the solvent and solute In a non-aqueous electrolyte battery comprising a non-aqueous electrolyte consisting of, and a separator, the solvent contains at least one phenyl group selected from the group consisting of diphenyl carbonate, methylphenyl carbonate and ethylphenyl carbonate. 10 to 50% by volume of the non-cyclic carbonic acid ester (A) contained therein, and a small amount selected from the group consisting of diethyl carbonate, dimethyl carbonate and methyl ethyl carbonate. Comprising a non-cyclic carbonate (B) 90-50% by volume of Kutomo kind.
【０００７】以下において、ｄ002 が３．３５〜３．３
９Åであり、且つＬC が１５０Å以上の炭素材料を黒鉛
と称することがある。In the following, d 002 is 3.35-3.3.
A carbon material having a length of 9Å and an L C of 150Å or more may be referred to as graphite.
【０００８】本発明電池の負極材料としては、ｄ002 及
びＬC の値が上記した範囲にある天然黒鉛又は人造黒鉛
を粉砕したものをそのまま使用してもよく、また必要に
応じて精製処理、加熱処理（５００〜３０００°Ｃ）、
酸処理、アルカリ処理、膨張化処理等の前処理を施した
ものを使用してもよい。As the negative electrode material of the battery of the present invention, natural graphite or artificial graphite having a value of d 002 and L C within the above-mentioned ranges may be used as it is, and if necessary, purification treatment, Heat treatment (500-3000 ° C),
You may use what performed pre-treatment, such as acid treatment, alkali treatment, and expansion treatment.
【０００９】高容量の電池を組み立てるためには、負極
材料として、ｄ002 が３．３５〜３．３７Åであり、且
つＬC が４００Å以上の炭素材料を使用することが好ま
しい。In order to assemble a high capacity battery, it is preferable to use a carbon material having d 002 of 3.35 to 3.37Å and L C of 400 Å or more as a negative electrode material.
【００１０】本発明におけるフェニル基を少なくとも１
個含有する非環状炭酸エステル（Ａ）は、ジフェニルカ
ーボネート、メチルフェニルカーボネート又はエチルフ
ェニルカーボネートである。これらのフェニル基を少な
くとも１個含有する非環状炭酸エステル（Ａ）は、それ
ぞれを一種単独使用してもよく、必要に応じて二種以上
併用してもよい。At least one phenyl group in the present invention is used.
The acyclic carbonic acid ester (A) contained individually is diphenyl carbonate, methylphenyl carbonate or ethylphenyl carbonate. The acyclic carbonic acid ester (A) containing at least one of these phenyl groups may be used alone or in combination of two or more, if necessary.
【００１１】本発明における非環状炭酸エステル（Ｂ）
は、ジエチルカーボネート、ジメチルカーボネート又は
メチルエチルカーボネートである。これらの非環状炭酸
エステル（Ｂ）も、それぞれを一種単独使用してもよ
く、必要に応じて二種以上併用してもよい。The acyclic carbonic acid ester (B) in the present invention
Is diethyl carbonate, dimethyl carbonate or methyl ethyl carbonate. These non-cyclic carbonic acid esters (B) may be used alone or in combination of two or more as required.
【００１２】本発明電池に使用される非水電解液の溶媒
は、非環状炭酸エステル（Ａ）１０〜５０体積％と、非
環状炭酸エステル（Ｂ）９０〜５０体積％とからなる。
非環状炭酸エステル（Ａ）の配合量が１０〜５０体積％
に限定されるのは、後述する実施例に示すように、体積
比がこの範囲内にあるものを使用した場合に極めて優れ
た負荷特性が発現されるからである。フェニル基を少な
くとも１個含有する非環状炭酸エステル（Ａ）の好適な
配合量は、溶媒の２０〜４５体積％である。The solvent of the non-aqueous electrolytic solution used in the battery of the present invention comprises 10 to 50% by volume of non-cyclic carbonic acid ester (A) and 90 to 50% by volume of non-cyclic carbonic acid ester (B).
Amount of non-cyclic carbonic acid ester (A) is 10 to 50% by volume
The reason for this is that, as shown in the examples described later, when a material having a volume ratio within this range is used, extremely excellent load characteristics are exhibited. A suitable amount of the acyclic carbonic acid ester (A) containing at least one phenyl group is 20 to 45% by volume of the solvent.
【００１３】本発明電池は、フェニル基を少なくとも１
個含有する１種又は２種以上の特定の非環状炭酸エステ
ル（Ａ）と、１種又は２種以上の特定の非環状炭酸エス
テル（Ｂ）とを所定の割合で混合してなる混合溶媒を使
用した点に特徴を有する。それ故、正極活物質、電解
液、セパレータなどについては特に制限はなく、従来非
水電解液電池用として実用され、あるいは提案されてい
る種々の材料を使用することが可能である。The battery of the present invention has at least one phenyl group.
A mixed solvent obtained by mixing one or two or more specific acyclic carbonic acid esters (A) contained individually and one or more specific acyclic carbonic acid esters (B) at a predetermined ratio. It is characterized by the points used. Therefore, the positive electrode active material, the electrolytic solution, the separator and the like are not particularly limited, and various materials that have been practically used or proposed for conventional non-aqueous electrolytic solution batteries can be used.
【００１４】例えば、正極活物質としては、ＬｉＣｏＯ
2 、ＬｉＮｉＯ2 、ＬｉＭｎＯ2 、ＬｉＭｎ2 Ｏ4 が挙
げられる。For example, as the positive electrode active material, LiCoO 2
2 , LiNiO 2 , LiMnO 2 and LiMn 2 O 4 can be mentioned.
【００１５】[0015]
【作用】本発明電池においては、フェニル基を少なくと
も１個含有する特定の非環状炭酸エステル（Ａ）と、特
定の非環状炭酸エステル（Ｂ）とを所定の割合で混合し
てなる混合溶媒が非水電解液の溶媒として使用されてい
るので、大電流で放電（高率放電）した場合の放電容量
が、エチレンカーボネート（ＥＣ）等の環状炭酸エステ
ルと、ジメチルカーボネート（ＤＭＣ）等の非環状炭酸
エステルとからなる混合溶媒を非水電解液の溶媒として
使用した従来の非水電解液電池に比べて、大きくなる。
すなわち、非水電解液の溶媒の改良により負荷特性（高
率放電特性）が改善される。In the battery of the present invention, a mixed solvent prepared by mixing a specific acyclic carbonic acid ester (A) containing at least one phenyl group and a specific acyclic carbonic acid ester (B) at a predetermined ratio is used. Since it is used as a solvent for non-aqueous electrolytes, the discharge capacity when discharged with a large current (high-rate discharge) is a cyclic carbonate such as ethylene carbonate (EC) and a non-cyclic carbonate such as dimethyl carbonate (DMC). This is larger than that of a conventional non-aqueous electrolyte battery in which a mixed solvent composed of carbonic acid ester is used as a solvent for the non-aqueous electrolyte.
That is, the load characteristics (high rate discharge characteristics) are improved by improving the solvent of the non-aqueous electrolyte.
【００１６】[0016]
【実施例】以下、本発明を実施例に基づいてさらに詳細
に説明するが、本発明は下記実施例により何ら限定され
るものではなく、その要旨を変更しない範囲において適
宜変更して実施することが可能なものである。The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited by the following examples, and various modifications can be made without departing from the scope of the invention. Is possible.
【００１７】（製造例１） 〔正極の作製〕正極活物質としてのＬｉＣｏＯ2 粉末
と、導電剤としての人造黒鉛とを、重量比９：１で混合
し、これに結着剤としてのポリフッ化ビニリデンの５重
量％Ｎ−メチルピロリドン溶液を、ＬｉＣｏＯ2 及び黒
鉛の混合物とポリフッ化ビニリデンとの重量比が９５：
５となるように混合してスラリーを調製した。このスラ
リーを正極集電体としてのアルミニウム箔の両面にドク
ターブレード法により塗布し、１５０°Ｃで２時間真空
乾燥して正極を作製した。(Production Example 1) [Production of Positive Electrode] LiCoO 2 powder as a positive electrode active material and artificial graphite as a conductive agent were mixed at a weight ratio of 9: 1, and polyfluoride as a binder was added thereto. A 5 wt% solution of vinylidene in N-methylpyrrolidone was added to a mixture of LiCoO 2 and graphite and polyvinylidene fluoride in a weight ratio of 95:
5 was mixed to prepare a slurry. This slurry was applied on both sides of an aluminum foil as a positive electrode current collector by the doctor blade method and vacuum dried at 150 ° C. for 2 hours to produce a positive electrode.
【００１８】〔負極の作製〕黒鉛塊（ｄ002 ＝３．３５
Å、Ｌc ＞１０００Å）に空気流を噴射して、粉砕（ジ
ェット粉砕）し、得られた黒鉛粉末に、結着剤としての
ポリフッ化ビニリデンの５重量％Ｎ−メチルピロリドン
溶液を、黒鉛粉末とポリフッ化ビニリデンの重量比が９
５：５となるように混練してスラリーを調製した。この
スラリーを負極集電体としての銅箔の両面にドクターブ
レード法により塗布し、１５０°Ｃで２時間真空乾燥し
て負極を作製した。[Production of Negative Electrode] Graphite lump (d 002 = 3.35)
Å, L c > 1000 Å), an air stream is sprayed and crushed (jet crushed), and a 5 wt% N-methylpyrrolidone solution of polyvinylidene fluoride as a binder is added to the obtained graphite powder. And the weight ratio of polyvinylidene fluoride is 9
A slurry was prepared by kneading so as to be 5: 5. This slurry was applied on both surfaces of a copper foil as a negative electrode current collector by the doctor blade method and vacuum dried at 150 ° C. for 2 hours to produce a negative electrode.
【００１９】〔非水電解液の調製〕ジフェニルカーボネ
ートに、ＬｉＰＦ6 を１モル／リットル溶かして非水電
解液を調製した。[Preparation of Non-Aqueous Electrolyte] LiPF 6 was dissolved in diphenyl carbonate at 1 mol / liter to prepare a non-aqueous electrolyte.
【００２０】〔電池の組立〕上記の正負両極及び非水電
解液を使用して、ＡＡサイズの電池Ａ１を組み立てた。
なお、セパレータとしては、ポリプロピレン製の微多孔
膜を使用し、これに上記した非水電解液を含浸させた。[Assembly of Battery] An AA-sized battery A1 was assembled by using the above-mentioned positive and negative electrodes and the non-aqueous electrolyte.
A polypropylene microporous film was used as the separator, and the above nonaqueous electrolytic solution was impregnated into the microporous film.
【００２１】図１は、作製した電池Ａ１の断面図であ
り、同図に示す電池Ａ１は、正極１、負極２、これら両
電極１、２を互いに離間するセパレータ３、正極リード
４、負極リード５、正極外部端子６、負極缶７などから
なる。FIG. 1 is a cross-sectional view of the produced battery A1. The battery A1 shown in FIG. 1 has a positive electrode 1, a negative electrode 2, a separator 3 for separating these electrodes 1, 2 from each other, a positive electrode lead 4, and a negative electrode lead. 5, a positive electrode external terminal 6, a negative electrode can 7 and the like.
【００２２】正極１及び負極２は、非水電解液を含浸し
たセパレータ３を介して渦巻き状に巻き取られた状態で
負極缶７内に収容されており、正極１は正極リード４を
介して正極外部端子６に、また負極２は負極リード５を
介して負極缶７に、それぞれ接続され、電池内部に生じ
た化学エネルギーを正極外部端子６及び負極缶７から電
気エネルギーとして外部へ取り出し得るようになってい
る。The positive electrode 1 and the negative electrode 2 are housed in the negative electrode can 7 in a state of being spirally wound via the separator 3 impregnated with the nonaqueous electrolytic solution, and the positive electrode 1 is connected via the positive electrode lead 4. The positive electrode external terminal 6 and the negative electrode 2 are connected to the negative electrode can 7 via the negative electrode lead 5, respectively, so that the chemical energy generated in the battery can be extracted to the outside from the positive electrode external terminal 6 and the negative electrode can 7 as electric energy. It has become.
【００２３】（製造例２〜１１）ジフェニルカーボネー
トとジエチルカーボネートとの体積比を、９０：１０、
８０：２０、７０：３０、６０：４０、５０：５０、４
０：６０、３０：７０、２０：８０、１０：９０、０：
１００（単一溶媒）として非水電解液の溶媒を調製し、
これらの各溶媒を使用したこと以外は製造例１と同様に
して、順に電池Ａ２〜Ａ１１を組み立てた。(Production Examples 2 to 11) The volume ratio of diphenyl carbonate and diethyl carbonate was 90:10,
80:20, 70:30, 60:40, 50:50, 4
0:60, 30:70, 20:80, 10:90, 0:
Prepare the solvent of the non-aqueous electrolyte as 100 (single solvent),
Batteries A2 to A11 were sequentially assembled in the same manner as in Production Example 1 except that these solvents were used.
【００２４】（製造例１２〜１４）ジフェニルカーボネ
ートと、ジメチルカーボネート、メチルエチルカーボネ
ート、又は、ジエチルカーボネート及びジメチルカーボ
ネートの等体積混合溶媒とを、体積比４０：６０で混合
して非水電解液の溶媒を調製し、これらの各溶媒を使用
したこと以外は製造例１と同様にして、順に電池Ａ１２
〜Ａ１４を組み立てた。(Production Examples 12 to 14) Diphenyl carbonate and dimethyl carbonate, methyl ethyl carbonate, or an equal volume mixed solvent of diethyl carbonate and dimethyl carbonate were mixed at a volume ratio of 40:60 to prepare a non-aqueous electrolyte solution. A battery A12 was sequentially prepared in the same manner as in Production Example 1 except that solvents were prepared and these solvents were used.
Assembled A14.
【００２５】（製造例１５〜１８）メチルフェニルカー
ボネートと、ジエチルカーボネート、ジメチルカーボネ
ート、メチルエチルカーボネート、又は、ジエチルカー
ボネート及びジメチルカーボネートの等体積混合溶媒と
を、体積比４０：６０で混合して非水電解液の溶媒を調
製し、これらの各溶媒を使用したこと以外は製造例１と
同様にして、順に電池Ｂ１〜Ｂ４を組み立てた。(Production Examples 15 to 18) Methyl phenyl carbonate and diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate, or an equal volume mixed solvent of diethyl carbonate and dimethyl carbonate were mixed at a volume ratio of 40:60 to prepare a mixture. Batteries B1 to B4 were sequentially assembled in the same manner as in Production Example 1 except that the solvents for the water electrolyte were prepared and these solvents were used.
【００２６】（製造例１９〜２２）エチルフェニルカー
ボネートと、ジエチルカーボネート、ジメチルカーボネ
ート、メチルエチルカーボネート、又は、ジエチルカー
ボネート及びジメチルカーボネートの等体積混合溶媒と
を、体積比４０：６０で混合して非水電解液の溶媒を調
製し、これらの各溶媒を使用したこと以外は製造例１と
同様にして、順に電池Ｃ１〜Ｃ４を組み立てた。(Production Examples 19 to 22) Ethyl phenyl carbonate and diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate, or an equal volume mixed solvent of diethyl carbonate and dimethyl carbonate were mixed at a volume ratio of 40:60 to prepare a non-mixed solution. Batteries C1 to C4 were sequentially assembled in the same manner as in Production Example 1 except that solvents for the water electrolyte were prepared and these solvents were used.
【００２７】（製造例２３〜２６）ジフェニルカーボネ
ート及びメチルフェニルカーボネートの等体積混合溶媒
と、ジエチルカーボネート、ジメチルカーボネート、メ
チルエチルカーボネート、又は、ジエチルカーボネート
及びジメチルカーボネートの等体積混合溶媒とを、体積
比４０：６０で混合して非水電解液の溶媒を調製し、こ
れらの各溶媒を使用したこと以外は製造例１と同様にし
て、順に電池Ｄ１〜Ｄ４を組み立てた。(Production Examples 23 to 26) A volume ratio of an equal volume mixed solvent of diphenyl carbonate and methylphenyl carbonate to diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate or an equal volume mixed solvent of diethyl carbonate and dimethyl carbonate was used. Batteries D1 to D4 were assembled in order in the same manner as in Production Example 1 except that the solvents of the non-aqueous electrolytic solution were prepared by mixing at 40:60 and these solvents were used.
【００２８】（製造例２７〜３６）エチレンカーボネー
トとジエチルカーボネートとの体積比を、１００：０
（単一溶媒）、９０：１０、８０：２０、７０：３０、
６０：４０、５０：５０、４０：６０、３０：７０、２
０：８０、１０：９０として非水電解液の溶媒を調製
し、これらの各溶媒を使用したこと以外は製造例１と同
様にして、順に電池Ｅ１〜Ｅ１０を組み立てた。(Production Examples 27 to 36) The volume ratio of ethylene carbonate to diethyl carbonate was 100: 0.
(Single solvent), 90:10, 80:20, 70:30,
60:40, 50:50, 40:60, 30:70, 2
Batteries E1 to E10 were assembled in order in the same manner as in Production Example 1 except that the solvents of the non-aqueous electrolytic solution were prepared as 0:80 and 10:90 and these solvents were used.
【００２９】（製造例３７〜３９）エチレンカーボネー
トと、ジメチルカーボネート、メチルエチルカーボネー
ト又はジメチルカーボネート及びメチルエチルカーボネ
ートの等体積混合溶媒とを、体積比４０：６０で混合し
て非水電解液の溶媒を調製し、これらの各溶媒を使用し
たこと以外は製造例１と同様にして、順に電池Ｅ１１〜
Ｅ１３を組み立てた。(Production Examples 37 to 39) Ethylene carbonate and a mixed solvent of dimethyl carbonate, methyl ethyl carbonate or an equal volume of dimethyl carbonate and methyl ethyl carbonate were mixed at a volume ratio of 40:60 to prepare a solvent for the non-aqueous electrolyte. Was prepared in the same manner as in Production Example 1 except that each of these solvents was used.
E13 was assembled.
【００３０】〔充放電特性〕電池Ａ１〜Ａ１３、Ｂ１〜
Ｂ４、Ｃ１〜Ｃ４、Ｄ１〜Ｄ４、Ｅ１〜Ｅ１３を、０．
２Ａで終止電圧５Ｖまで充電した後、０．２Ａで終止電
圧２Ｖまで放電して、各電池の充放電特性を調べた。ま
た、２Ａで同様にして充放電を行い、各電池の充放電特
性を調べた。[Charge / Discharge Characteristics] Batteries A1 to A13 and B1
B4, C1 to C4, D1 to D4, E1 to E13 are set to 0.
After charging to a final voltage of 5 V at 2 A, the battery was discharged to a final voltage of 2 V at 0.2 A to examine the charge / discharge characteristics of each battery. Also, charging and discharging were performed in the same manner at 2A, and the charging and discharging characteristics of each battery were examined.
【００３１】放電電流を０．２Ａ及び２Ａとした場合の
電池Ａ１〜Ａ１１、Ｅ１〜Ｅ１０の電池容量と、使用し
た溶媒の組成との関係を図２に示す。FIG. 2 shows the relationship between the battery capacities of the batteries A1 to A11 and E1 to E10 and the composition of the solvent used when the discharge currents were 0.2 A and 2 A, respectively.
【００３２】図２は、縦軸に各電池容量（ｍＡｈ）、横
軸に溶媒の混合比（体積比）をとって示したグラフであ
る。同図より、ジフェニルカーボネートとジエチルカー
ボネートとを、体積比１０：９０〜５０：５０で混合し
た溶媒を使用した本発明電池Ａ６〜Ａ１０において、負
荷特性が大幅に向上していることが分かる。FIG. 2 is a graph showing the battery capacity (mAh) on the vertical axis and the solvent mixture ratio (volume ratio) on the horizontal axis. From the figure, it can be seen that the load characteristics are significantly improved in the batteries A6 to A10 of the present invention using a solvent in which diphenyl carbonate and diethyl carbonate are mixed at a volume ratio of 10:90 to 50:50.
【００３３】表１に、放電電流を０．２Ａ及び２Ａとし
た場合の電池Ａ７、Ａ１２〜Ａ１４、Ｂ１〜Ｂ４、Ｃ１
〜Ｃ４、Ｄ１〜Ｄ４、Ｅ７、Ｅ１１〜１３の各放電容量
（ｍＡｈ）を示す。Table 1 shows batteries A7, A12 to A14, B1 to B4 and C1 when the discharge currents are 0.2 A and 2 A, respectively.
The discharge capacities (mAh) of C4, D1 to D4, E7, and E11 to 13 are shown.
【００３４】[0034]
【表１】 [Table 1]
【００３５】表１において、ＤＰｈＣはジフェニルカー
ボネート、ＭＰｈＣはメチルフェニルカーボネート、Ｅ
ＰｈＣはエチルフェニルカーボネート、ＥＣはエチレン
カーボネート、ＤＥＣはジエチルカーボネート、ＤＭＣ
はジメチルカーボネート、ＭＥＣはメチルエチルカーボ
ネートを表す。In Table 1, DPhC is diphenyl carbonate, MPhC is methylphenyl carbonate, E
PhC is ethyl phenyl carbonate, EC is ethylene carbonate, DEC is diethyl carbonate, DMC
Represents dimethyl carbonate, and MEC represents methyl ethyl carbonate.
【００３６】表１より、０．２Ａで充放電したときの放
電容量については、本発明電池Ａ７、Ａ１２〜Ａ１４、
Ｂ１〜Ｂ４、Ｃ１〜Ｃ４、Ｄ１〜Ｄ４と、比較電池Ｅ
７、Ｅ１１〜１３との間に殆ど差は認められないが、２
Ａで充放電（急速充電及び高率放電）したときの放電容
量については、本発明電池の方が比較電池に比べて格段
大きい。このことから、本発明電池は、比較電池に比べ
て負荷特性に優れていることが分かる。From Table 1, the discharge capacities at the time of charging / discharging at 0.2 A are shown in Tables A7, A12 to A14 of the present invention,
B1-B4, C1-C4, D1-D4 and comparative battery E
7 and E11 to 13 have almost no difference, but 2
Regarding the discharge capacity at the time of charge / discharge (rapid charge and high rate discharge) in A, the battery of the present invention is significantly larger than the comparative battery. From this, it is understood that the battery of the present invention is superior in load characteristics to the comparative battery.
【００３７】叙上の実施例では、本発明を円筒型の非水
電解液電池に適用する場合の具体例について説明した
が、電池の形状に特に制限はなく、本発明は、扁平型、
角型、フィルム型など、種々の形状の非水電解液電池に
適用し得るものである。In the above embodiment, a specific example in which the present invention is applied to a cylindrical non-aqueous electrolyte battery has been described, but the shape of the battery is not particularly limited, and the present invention is a flat type,
It is applicable to non-aqueous electrolyte batteries of various shapes such as prismatic type and film type.
【００３８】[0038]
【発明の効果】本発明電池は負荷特性に優れる。The battery of the present invention has excellent load characteristics.
【図１】実施例で組み立てた円筒型の非水電解液電池
（本発明電池）の断面図である。FIG. 1 is a cross-sectional view of a cylindrical non-aqueous electrolyte battery (the battery of the present invention) assembled in an example.
【図２】放電容量（高率放電容量及び低率放電容量）と
電解液の溶媒組成の関係を示すグラフである。FIG. 2 is a graph showing the relationship between the discharge capacity (high rate discharge capacity and low rate discharge capacity) and the solvent composition of the electrolytic solution.
Ａ１ 非水電解液電池 １ 正極 ２ 負極 ３ セパレータ A1 non-aqueous electrolyte battery 1 positive electrode 2 negative electrode 3 separator
【表２】 [Table 2]
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成６年１０月６日[Submission date] October 6, 1994
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００３３[Correction target item name] 0033
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００３３】表１及び表２に、放電電流を０．２Ａ及び
２Ａとした場合の電池Ａ７、Ａ１２〜Ａ１４、Ｂ１〜Ｂ
４、Ｃ１〜Ｃ４、Ｄ１〜Ｄ４、Ｅ７、Ｅ１１〜Ｅ１３の
各放電容量（ｍＡｈ）を示す。Tables 1 and 2 show batteries A7, A12 to A14, B1 to B when the discharge currents are 0.2 A and 2 A, respectively.
4, each discharge capacity (mAh) of C1-C4, D1-D4, E7, E11-E13 is shown.
【手続補正２】[Procedure Amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００３４[Correction target item name] 0034
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００３４】[0034]
【表１】 [Table 1]
【表２】 [Table 2]
【手続補正３】[Procedure 3]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００３５[Correction target item name] 0035
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００３５】表１及び表２において、ＤＰｈＣはジフェ
ニルカーボネート、ＭＰｈＣはメチルフェニルカーボネ
ート、ＥＰｈＣはエチルフェニルカーボネート、ＥＣは
エチレンカーボネート、ＤＥＣはジエチルカーボネー
ト、ＤＭＣはジメチルカーボネート、ＭＥＣはメチルエ
チルカーボネートを表す。In Tables 1 and 2 , DPhC is diphenyl carbonate, MPhC is methylphenyl carbonate, EPhC is ethylphenyl carbonate, EC is ethylene carbonate, DEC is diethyl carbonate, DMC is dimethyl carbonate, and MEC is methyl ethyl carbonate.
【手続補正４】[Procedure amendment 4]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００３６[Correction target item name] 0036
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００３６】表１及び表２より、０．２Ａで充放電した
ときの放電容量については、本発明電池Ａ７、Ａ１２〜
Ａ１４、Ｂ１〜Ｂ４、Ｃ１〜Ｃ４、Ｄ１〜Ｄ４と、比較
電池Ｅ７、Ｅ１１〜１３との間に殆ど差は認められない
が、２Ａで充放電（急速充電及び高率放電）したときの
放電容量については、本発明電池の方が比較電池に比べ
て格段大きい。このことから、本発明電池は、比較電池
に比ベて負荷特性に優れていることが分かる。From Tables 1 and 2 , the discharge capacities at the time of charging / discharging at 0.2 A show the batteries A7 and A12 of the present invention.
There is almost no difference between A14, B1 to B4, C1 to C4, D1 to D4 and Comparative Batteries E7 and E11 to 13, but discharge when charging and discharging (quick charging and high rate discharging) at 2A. Regarding the capacity, the battery of the present invention is much larger than the comparative battery. From this, it can be seen that the battery of the present invention is superior to the comparative battery in load characteristics.
【手続補正５】[Procedure Amendment 5]
【補正対象書類名】図面[Document name to be corrected] Drawing
【補正対象項目名】全図[Correction target item name] All drawings
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【図１】 FIG.
【図２】 [Fig. 2]
───────────────────────────────────────────────────── フロントページの続き (72)発明者 斎藤 俊彦 大阪府守口市京阪本通２丁目５番５号 三 洋電機株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshihiko Saito 2-5-5 Keihan Hondori, Moriguchi City, Osaka Sanyo Electric Co., Ltd.
Claims (3)
（ｄ002 ）が３．３５〜３．３９Åであり、且つｃ軸方
向の結晶子の大きさ（ＬC ）が１５０Å以上である炭素
材料を負極材料とする負極と、溶媒及び溶質からなる非
水電解液と、セパレータとを備えてなる非水電解液電池
において、前記溶媒が、ジフェニルカーボネート、メチ
ルフェニルカーボネート及びエチルフェニルカーボネー
トよりなる群から選ばれた少なくとも一種のフェニル基
を少なくとも１個含有する非環状炭酸エステル（Ａ）１
０〜５０体積％と、ジエチルカーボネート、ジメチルカ
ーボネート及びメチルエチルカーボネートよりなる群か
ら選ばれた少なくとも一種の非環状炭酸エステル（Ｂ）
９０〜５０体積％とからなることを特徴とする非水電解
液電池。And 1. A positive electrode, in d values to the lattice plane (002) plane (d 002) is 3.35～3.39A, and the size of the c-axis direction of the crystallite (L C) is 150Å In a non-aqueous electrolyte battery comprising a negative electrode having a carbon material as a negative electrode material, a non-aqueous electrolytic solution consisting of a solvent and a solute, and a separator, the solvent is diphenyl carbonate, methylphenyl carbonate and ethylphenyl. Acyclic carbonic acid ester (A) 1 containing at least one phenyl group selected from the group consisting of carbonates
0-50% by volume and at least one acyclic carbonic acid ester (B) selected from the group consisting of diethyl carbonate, dimethyl carbonate and methyl ethyl carbonate
A non-aqueous electrolyte battery comprising 90 to 50% by volume.
１個含有する非環状炭酸エステル（Ａ）２０〜４５体積
％と、前記非環状炭酸エステル（Ｂ）８０〜５５体積％
とからなる請求項１記載の非水電解液電池。2. The solvent comprises 20 to 45% by volume of an acyclic carbonic acid ester (A) containing at least one phenyl group and 80 to 55% by volume of the acyclic carbonic acid ester (B).
The non-aqueous electrolyte battery according to claim 1, comprising:
るｄ値（ｄ002 ）が３．３５〜３．３７Åであり、且つ
ｃ軸方向の結晶子の大きさ（ＬC ）が４００Å以上であ
る請求項１又は２記載の非水電解液電池。3. The d value (d 002 ) on the lattice plane (002) plane of the carbon material is 3.35-3.37Å, and the crystallite size (L C ) in the c-axis direction is The non-aqueous electrolyte battery according to claim 1 or 2, which is 400 Å or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6266165A JPH08106909A (en) | 1994-10-04 | 1994-10-04 | Nonaqueous electrolytic battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6266165A JPH08106909A (en) | 1994-10-04 | 1994-10-04 | Nonaqueous electrolytic battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08106909A true JPH08106909A (en) | 1996-04-23 |
Family
ID=17427184
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6266165A Pending JPH08106909A (en) | 1994-10-04 | 1994-10-04 | Nonaqueous electrolytic battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08106909A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0803924A2 (en) * | 1996-04-25 | 1997-10-29 | Wilson Greatbatch Ltd. | Organic carbonate additives for nonaqueous electrolyte in alkali metal electrochemical cells |
| WO1999063612A1 (en) * | 1998-06-04 | 1999-12-09 | Mitsubishi Chemical Corporation | Secondary battery having nonaqueous electrolyte solution |
| US6759170B2 (en) | 1998-10-22 | 2004-07-06 | Wilson Greatbatch Technologies, Inc. | Organic carbonate additives for nonaqueous electrolyte rechargeable electrochemical cells |
| US6821677B2 (en) * | 2001-03-29 | 2004-11-23 | Kabushiki Kaisha Toshiba | Negative electrode active material and nonaqueous electrolyte battery |
| JP2006012696A (en) * | 2004-06-29 | 2006-01-12 | Matsushita Electric Ind Co Ltd | Nonaqueous electrolyte primary battery |
| JP2014017258A (en) * | 2008-02-29 | 2014-01-30 | Mitsubishi Chemicals Corp | Nonaqueous electrolyte and nonaqueous electrolyte battery |
| US8889302B2 (en) | 2008-02-29 | 2014-11-18 | Mitsubishi Chemical Corporation | Nonaqueous electrolytic solution and nonaqueous-electrolyte battery |
-
1994
- 1994-10-04 JP JP6266165A patent/JPH08106909A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0803924A2 (en) * | 1996-04-25 | 1997-10-29 | Wilson Greatbatch Ltd. | Organic carbonate additives for nonaqueous electrolyte in alkali metal electrochemical cells |
| EP0803924A3 (en) * | 1996-04-25 | 1998-12-09 | Wilson Greatbatch Ltd. | Organic carbonate additives for nonaqueous electrolyte in alkali metal electrochemical cells |
| WO1999063612A1 (en) * | 1998-06-04 | 1999-12-09 | Mitsubishi Chemical Corporation | Secondary battery having nonaqueous electrolyte solution |
| US6664008B1 (en) | 1998-06-04 | 2003-12-16 | Mitsubishi Chemical Corporation | Secondary battery having nonaqueous electrolyte solution |
| US6759170B2 (en) | 1998-10-22 | 2004-07-06 | Wilson Greatbatch Technologies, Inc. | Organic carbonate additives for nonaqueous electrolyte rechargeable electrochemical cells |
| US6821677B2 (en) * | 2001-03-29 | 2004-11-23 | Kabushiki Kaisha Toshiba | Negative electrode active material and nonaqueous electrolyte battery |
| JP2006012696A (en) * | 2004-06-29 | 2006-01-12 | Matsushita Electric Ind Co Ltd | Nonaqueous electrolyte primary battery |
| JP4687021B2 (en) * | 2004-06-29 | 2011-05-25 | パナソニック株式会社 | Non-aqueous electrolyte primary battery |
| JP2014017258A (en) * | 2008-02-29 | 2014-01-30 | Mitsubishi Chemicals Corp | Nonaqueous electrolyte and nonaqueous electrolyte battery |
| US8889302B2 (en) | 2008-02-29 | 2014-11-18 | Mitsubishi Chemical Corporation | Nonaqueous electrolytic solution and nonaqueous-electrolyte battery |
| US8916298B2 (en) | 2008-02-29 | 2014-12-23 | Mitsubishi Chemical Corporation | Nonaqueous electrolytic solution and nonaqueous-electrolyte battery |
| US9083058B2 (en) | 2008-02-29 | 2015-07-14 | Mitsubishi Chemical Corporation | Nonaqueous electrolytic solution and nonaqueous-electrolyte battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3213459B2 (en) | Non-aqueous electrolyte secondary battery | |
| JPH05290843A (en) | Lithium secondary battery | |
| JPH08236114A (en) | Lithium secondary battery | |
| JP2000003724A (en) | Nonaqueous electrolyte and lithium secondary battery using the same | |
| JPH08236155A (en) | Lithium secondary battery | |
| JP3444243B2 (en) | Nonaqueous electrolyte and lithium secondary battery using the same | |
| JP3244389B2 (en) | Lithium secondary battery | |
| JP3820748B2 (en) | Electrolyte for lithium secondary battery and lithium secondary battery using the same | |
| JPH11273725A (en) | Electrolytic solution for lithium secondary battery and lithium secondary battery using it | |
| JPH07114940A (en) | Non-aqueous electrolyte secondary battery | |
| JPH09147910A (en) | Lithium secondary battery | |
| US6482546B1 (en) | Rechargeable lithium battery | |
| JP5153134B2 (en) | Nonaqueous electrolyte secondary battery | |
| JPH08106909A (en) | Nonaqueous electrolytic battery | |
| JP2000260475A (en) | Lithium secondary battery | |
| JPH0745304A (en) | Organic electrolyte secondary battery | |
| JP2001307735A (en) | Lithium secondary battery | |
| JP3188032B2 (en) | Lithium secondary battery | |
| JP4042083B2 (en) | Nonaqueous electrolyte and lithium secondary battery using the same | |
| JPH08306386A (en) | Manaqueous electrolyte secondary battery | |
| JP3268924B2 (en) | Non-aqueous electrolyte battery | |
| JPH08171936A (en) | Lithium secondary battery | |
| JP3519766B2 (en) | Non-aqueous secondary battery | |
| JPH11273723A (en) | Electrolytic solution for lithium secondary battery and lithium secondary battery using same | |
| JPH08171934A (en) | Lithium secondary battery |