JPH11339850A - Lithium-ion secondary battery - Google Patents
Lithium-ion secondary batteryInfo
- Publication number
- JPH11339850A JPH11339850A JP10148790A JP14879098A JPH11339850A JP H11339850 A JPH11339850 A JP H11339850A JP 10148790 A JP10148790 A JP 10148790A JP 14879098 A JP14879098 A JP 14879098A JP H11339850 A JPH11339850 A JP H11339850A
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- ion secondary
- secondary battery
- battery
- electrolyte
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
-
- 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、リチウムイオンを
ドープおよび脱ドープする負極を有するリチウムイオン
二次電池に関するものであり、とくにサイクル寿命が良
好なリチウムイオン電池に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithium ion secondary battery having a negative electrode for doping and undoping lithium ions, and more particularly to a lithium ion battery having a good cycle life.
【０００２】[0002]
【従来の技術】携帯電話、カムコーダ、ノート型パソコ
ン等の小型の電子機器の普及に伴って、エネルギー密度
の高い再充電可能な電池が求められている。とくに、リ
チウムイオンのドープおよび脱ドープを利用したリチウ
ムイオン電池は動作電圧が高く、エネルギー密度が高く
安定した特性が得られるので、小型でエネルギー密度が
大きな電池として広く用いられるようになっている。2. Description of the Related Art With the spread of small electronic devices such as mobile phones, camcorders, and notebook computers, rechargeable batteries having a high energy density have been demanded. In particular, lithium ion batteries using lithium ion doping and undoping have a high operating voltage, high energy density, and stable characteristics. Therefore, lithium ion batteries are widely used as small and high energy density batteries.
【０００３】リチウムイオン二次電池は、コバルト酸リ
チウム（ＬｉＣｏＯ2） 、マンガン酸リチウム（ＬｉＭ
ｎ2Ｏ4）、ニッケル酸リチウム（ＬｉＮｉＯ2 ）等のリ
チウム遷移金属酸化物を含有する合剤をアルミニウム箔
に塗布した正極箔と、黒鉛をはじめとする炭素質化合
物、金属複合酸化物等を含有する合剤を銅箔等に塗布し
た負極箔とを、微多孔性合成樹脂製セパレータを介在さ
せて対向させて渦巻状に巻回した発電要素を電池缶に収
容してエチレンカーボネート、ジエチルカーボネートに
六フッ化リン酸リチウム等を溶解した電解液を注入して
封口することによって製造されている。[0003] Lithium ion secondary batteries include lithium cobaltate (LiCoO 2 ) and lithium manganate (LiM
n 2 O 4 ), a positive electrode foil obtained by applying a mixture containing a lithium transition metal oxide such as lithium nickel oxide (LiNiO 2 ) to an aluminum foil, a carbonaceous compound such as graphite, a metal composite oxide, etc. A negative electrode foil in which the mixture contained is coated on a copper foil or the like, and a power generation element spirally wound oppositely with a microporous synthetic resin separator interposed therebetween is accommodated in a battery can, and ethylene carbonate and diethyl carbonate are contained therein. It is manufactured by injecting an electrolyte solution in which lithium hexafluorophosphate or the like is dissolved and sealing it.
【０００４】リチウムイオン二次電池では、負極にリチ
ウムあるいはリチウム合金を用いた電池のように充放電
の繰り返しによってデンドライト状リチウムが、正極と
負極を隔離するセパレータを貫通し正極と接触して内部
短絡を引き起こすという問題もなく、長期にわたり繰り
返し使用可能であるという特徴を有している。In a lithium ion secondary battery, as in a battery using lithium or a lithium alloy for the negative electrode, repetition of charging and discharging causes the dendritic lithium to penetrate the separator that separates the positive electrode and the negative electrode, come into contact with the positive electrode, and cause an internal short circuit. It has the feature that it can be used repeatedly for a long time without the problem of causing
【０００５】しかしながら、リチウムイオン電池の使用
形態によっては、負極の炭素質材料と電解液が反応した
り、あるいは正極合剤中の遷移金属酸化物が電解液中に
溶解する等の現象が起こり、サイクル寿命が低下すると
いう問題があった。例えば、正極活物質としてマンガン
酸リチウムを使用したリチウムイオン二次電池の場合に
は、４５℃程度の高温下で使用すると、電解液中に溶解
しサイクル寿命が低下するという現象があった。However, depending on the type of use of the lithium ion battery, phenomena such as a reaction between the carbonaceous material of the negative electrode and the electrolytic solution or a dissolution of the transition metal oxide in the positive electrode mixture into the electrolytic solution occur. There was a problem that the cycle life was shortened. For example, in the case of a lithium ion secondary battery using lithium manganate as a positive electrode active material, when used at a high temperature of about 45 ° C., there is a phenomenon that the lithium ion secondary battery is dissolved in an electrolytic solution and the cycle life is reduced.
【０００６】また、有機電解液として知られているプロ
ピレンカーボネートは、支持塩の溶解度が大きく、使用
可能な温度範囲が広く、電位窓が大きく優れた電解液で
あるとともに、融点が低く沸点が高いために、電解液注
入時の電解液の取り扱いが容易であるという特徴を有し
ているが、黒鉛系の炭素質材料を負極に用いたリチウム
イオン二次電池にあっては、プロピレンカーボネートが
充電時に黒鉛上で電気分解され、電池として機能しなく
なるという現象が生じていた。[0006] Propylene carbonate, which is known as an organic electrolyte, has a high solubility of a supporting salt, a wide usable temperature range, a large potential window and an excellent electrolyte, and has a low melting point and a high boiling point. Therefore, it is easy to handle the electrolyte when injecting the electrolyte.However, in a lithium ion secondary battery using a graphite-based carbonaceous material for the negative electrode, propylene carbonate is charged. Occasionally, electrolysis occurs on graphite, causing the battery to no longer function.
【０００７】活物質の好ましくない溶解や電解液の分解
等を防ぐ試みとしては、負極にリチウム金属あるいはリ
チウム合金を用いた電池においては、電解液あるいは電
解液の一部に溶解や分解を防止する物質を添加すること
が提案されている。例えば、特開昭６３−１０２１７３
号公報には、電解液中に１，３−プロパンスルトンを添
加することによって、充電時の電池リチウムと電解液と
の反応により充放電サイクルの特性が低下したり、電着
リチウムのデンドライトの析出による短絡を防止する方
法が提案されているが、リチウムイオン電池における前
記した問題点を特定の物質を電解液としたり、あるいは
電解液中に特定の物質を添加して解決することを提案し
たものはなかった。As an attempt to prevent undesired dissolution of the active material or decomposition of the electrolytic solution, in a battery using lithium metal or a lithium alloy for the negative electrode, dissolution or decomposition of the electrolytic solution or a part of the electrolytic solution is prevented. It has been proposed to add substances. For example, JP-A-63-102173
Japanese Patent Application Laid-Open Publication No. H11-157,199 discloses that by adding 1,3-propane sultone to an electrolytic solution, the characteristics of a charge / discharge cycle are degraded due to a reaction between the battery lithium and the electrolytic solution during charging, or the deposition of electrodeposited lithium dendrite. Although a method of preventing short-circuiting due to has been proposed, it has been proposed to solve the above-mentioned problems in lithium ion batteries by using a specific substance as an electrolyte or adding a specific substance to the electrolyte. There was no.
【０００８】[0008]
【発明が解決しようとする課題】本発明は、リチウムイ
オン二次電池において、サイクル寿命を長期化すること
を課題とするものであり、とくにマンガン酸リチウムを
正極に用いた場合の高温度でのサイクル寿命の低下を防
止するとともに、プロピレンカーボネートを電解液とし
た場合の黒鉛表面での電気分解を防止し特性の優れた電
池を提供することを課題とするものである。SUMMARY OF THE INVENTION It is an object of the present invention to provide a lithium ion secondary battery having a prolonged cycle life, particularly at a high temperature when lithium manganate is used for a positive electrode. It is an object of the present invention to provide a battery having excellent characteristics by preventing a decrease in cycle life and preventing electrolysis on a graphite surface when propylene carbonate is used as an electrolyte.
【０００９】[0009]
【課題を解決するための手段】本発明は、リチウムイオ
ンをドープおよび脱ドープする正極および負極を有する
リチウムイオン二次電池において、スルトンを電解液と
するか、もしくは電解液の一部に添加したリチウムイオ
ン二次電池である。スルトン化合物が１，３−プロパン
スルトンまたは１，４−ブタンスルトンであるリチウム
イオン二次電池である。また、正極活物質として、リチ
ウムコバルト酸、リチウムマンガン酸、リチウムニッケ
ル酸から選ばれる少なくとも１種を用いたリチウムイオ
ン二次電池である。電解液としてプロピレンカーボネー
トを用いたリチウムイオン二次電池である。 負極とし
て黒鉛質の炭素材料を用いたリチウムイオン二次電池で
ある。本発明のように、スルトンをリチウムイオン二次
電池の電解液中に添加することによってサイクル寿命等
が増加する理由は定かではないが、正極活物質および負
極活物質の表面に、イオン導電性の保護皮膜を形成する
ことによって、正極活物質中からのマンガンの溶解を抑
制し、また黒鉛表面での電解液の分解を抑制するものと
推察される。SUMMARY OF THE INVENTION The present invention provides a lithium ion secondary battery having a positive electrode and a negative electrode for doping and undoping lithium ions, wherein sultone is used as an electrolyte or is added to a part of the electrolyte. It is a lithium ion secondary battery. A lithium ion secondary battery in which the sultone compound is 1,3-propane sultone or 1,4-butane sultone. Further, the present invention is a lithium ion secondary battery using at least one selected from lithium cobalt acid, lithium manganate, and lithium nickel acid as a positive electrode active material. This is a lithium ion secondary battery using propylene carbonate as an electrolyte. This is a lithium ion secondary battery using a graphite carbon material as a negative electrode. As in the present invention, the reason why the cycle life and the like are increased by adding sultone to the electrolyte solution of the lithium ion secondary battery is not clear, but the surface of the positive electrode active material and the negative electrode active material has an ionic conductivity. It is presumed that by forming the protective film, dissolution of manganese from the positive electrode active material is suppressed, and decomposition of the electrolytic solution on the graphite surface is suppressed.
【００１０】[0010]
【発明の実施の形態】本発明のリチウム二次電池の正極
としては、リチウムをドープおよび脱ドープすることが
でき、リチウムを含む遷移金属複合酸化物を用いること
が好ましい。具体的には、コバルト酸リチウム（ＬｉＣ
ｏＯ2） 、マンガン酸リチウム（ＬｉＭｎ2Ｏ4）、ニッ
ケル酸リチウム（ＬｉＮｉＯ2 ）等のリチウム遷移金属
酸化物を挙げることができ、なかでもリチウムマンガン
酸を用いる場合には、リチウムマンガン酸からのマンガ
ンの溶解を抑制することができるのでとくに大きな効果
が期待できる。また、負極には、天然黒鉛、人造黒鉛、
黒鉛化メソカーボンマイクロビーズ、黒鉛化炭素繊維等
のような黒鉛質炭素材料、黒鉛前駆体炭素等の各種の炭
素質物質、遷移金属複合酸化物等を挙げることができ
る。スルトン化合物としては、以下に示す１，３−プロ
パンスルトン、１，４−ブタンスルトンを挙げることが
できる。BEST MODE FOR CARRYING OUT THE INVENTION As the positive electrode of the lithium secondary battery of the present invention, it is preferable to use a transition metal composite oxide containing lithium, which can be doped and dedoped with lithium. Specifically, lithium cobaltate (LiC
oO 2 ), lithium transition metal oxides such as lithium manganate (LiMn 2 O 4 ) and lithium nickelate (LiNiO 2 ). Among them, when lithium manganate is used, A particularly great effect can be expected because the dissolution of manganese can be suppressed. For the negative electrode, natural graphite, artificial graphite,
Examples include graphitic carbon materials such as graphitized mesocarbon microbeads and graphitized carbon fibers, various carbonaceous materials such as graphite precursor carbon, and transition metal composite oxides. Examples of the sultone compound include 1,3-propane sultone and 1,4-butane sultone shown below.
【００１１】[0011]
【化１】 Embedded image
【００１２】スルトン化合物の利用形態としては、スル
トン化合物を電解液として用いる場合、およびスルトン
化合物を電解液に混合する方法が挙げられる。スルトン
化合物を電解液として使用する場合には、スルトン化合
物に支持電解質として、ＬｉＣｌＯ4、ＬｉＰＦ6、Ｌｉ
ＡｓＦ6、ＬｉＳｂＦ6、ＬｉＢＦ4、ＬｉＢ（Ｃ
6Ｈ5）4、ＬｉＳＯ3ＣＦ3、ＬｉＮ（ＳＯ2ＣＦ3）2、Ｌ
ｉＮ（ＳＯ2ＣＦ2ＣＦ3）2からなる群から選ばれる少な
くとも１種を電解液に溶解することによって調製する。The sultone compound can be used in a case where the sultone compound is used as an electrolyte and a method in which the sultone compound is mixed with the electrolyte. When a sultone compound is used as an electrolyte, LiClO 4 , LiPF 6 , Li
AsF 6 , LiSbF 6 , LiBF 4 , LiB (C
6 H 5) 4, LiSO 3 CF 3, LiN (SO 2 CF 3) 2, L
It is prepared by dissolving at least one selected from the group consisting of iN (SO 2 CF 2 CF 3 ) 2 in an electrolytic solution.
【００１３】また、他の電解液に混合する場合には、ス
ルトン化合物と１，２−ジメトキシエタン、１，２−ジ
エトキシエタン、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、テトラヒドロフラ
ン、１，３−ジオキソラン、４−メチル−１，３−ジオ
キソラン、スルホランなどの有機溶媒の少なくとも１種
を混合した混合溶媒に、スルトン化合物を電解液として
単独で用いる場合と同様に、支持電解質として、ＬｉＣ
ｌＯ4、ＬｉＰＦ6、ＬｉＡｓＦ6、ＬｉＳｂＦ6、ＬｉＢ
Ｆ4、ＬｉＢ（Ｃ6Ｈ5）4、ＬｉＳＯ3ＣＦ3、ＬｉＮ（Ｓ
Ｏ2ＣＦ3）2、ＬｉＮ（ＳＯ2ＣＦ2ＣＦ3）2などの電解
質の少なくとも１種以上溶解することによって調製す
る。When mixed with another electrolytic solution, a sultone compound and 1,2-dimethoxyethane, 1,2-diethoxyethane, ethylene carbonate, propylene carbonate, γ-butyrolactone, tetrahydrofuran, As in the case of using a sultone compound alone as an electrolyte in a mixed solvent obtained by mixing at least one of organic solvents such as dioxolan, 4-methyl-1,3-dioxolan, and sulfolane, LiC is used as a supporting electrolyte.
lO 4, LiPF 6, LiAsF 6 , LiSbF 6, LiB
F 4 , LiB (C 6 H 5 ) 4 , LiSO 3 CF 3 , LiN (S
It is prepared by dissolving at least one or more kinds of electrolytes such as O 2 CF 3 ) 2 and LiN (SO 2 CF 2 CF 3 ) 2 .
【００１４】スルトン化合物を有機溶媒の混合物として
プロピレンカーボネートに混合して用いる場合には、プ
ロピレンカーボネートの黒鉛表面での分解を防止するこ
とができるのでとくに好ましい。It is particularly preferable to use the sultone compound as a mixture of an organic solvent in a mixture with propylene carbonate, since the decomposition of propylene carbonate on the graphite surface can be prevented.
【００１５】本発明において、スルトン化合物を他の電
解液と混合して用いる場合には、１，３−プロパンスル
トン、１．４−ブタンスルトンの少なくともいずれか一
種が電解液の全重量中に０．１〜９重量％とすることが
好ましく、０．１〜５重量％とすることが好ましく、
０．１重量％より少なくなると、充放電サイクル特性を
向上させる効果が充分に発揮されなくなる。In the present invention, when the sultone compound is used in a mixture with another electrolyte, at least one of 1,3-propane sultone and 1.4-butane sultone is contained in an amount of 0.1% in the total weight of the electrolyte. 1 to 9% by weight, preferably 0.1 to 5% by weight,
If the content is less than 0.1% by weight, the effect of improving the charge / discharge cycle characteristics cannot be sufficiently exhibited.
【００１６】本発明の電池の一例を図１に示す。図１
は、厚みの薄い角柱状の角型電池１の一部を切り欠いた
斜視図である。角型電池は、円筒型電池と同様にセパレ
ータ２を介在させて正極側集電体３に正極活物質を塗布
し、負極側集電体４に負極活物質を塗布して巻回して発
電要素からなるジェリーロール５を作製して電池缶６内
に収容し、電解液を注液し、上部の電極ヘッダ７を電池
缶６に溶接することによって電池を密閉し、充電した後
に電池として使用される。FIG. 1 shows an example of the battery of the present invention. FIG.
FIG. 1 is a perspective view of a prismatic battery 1 having a thin prism and a part of which is cut away. The prismatic battery is, similarly to the cylindrical battery, coated with a positive electrode active material on a positive electrode current collector 3 with a separator 2 interposed therebetween, and coated with a negative electrode active material on a negative electrode current collector 4 and wound. A jelly roll 5 made of is made and housed in a battery can 6, an electrolytic solution is injected, the upper electrode header 7 is welded to the battery can 6 to seal the battery, and the battery is used after being charged. You.
【００１７】[0017]
【実施例】以下に本発明の実施例を示し、本発明を説明
する。 実施例１ 幅が５．５ｃｍ、長さ６６ｃｍの厚さ２０μｍのアルミ
ニウム箔の両面にスピネル構造を有するマンガン酸リチ
ウム（Ｌｉ1+XＭｎ2+XＯ4 ）粉末９２重量部、カーボン
ブラック５重量部、ポリフッ化ビニリデン３重量部から
なる混合物を、アルミニウム箔を含む乾燥後の厚みが１
７８μｍとなるように塗布して正極とした。負極は、幅
が５．７５ｃｍ、長さ７３．５ｃｍの厚さ１０μｍの銅
箔に、黒鉛化メソカーボンマイクロビーズ（大阪ガス
製）９４重量部、ポリフッ化ビニリデン６重量部からな
る混合物を銅箔を含む乾燥後の厚みが１２４μｍとなる
ように塗布して乾燥して作製した。正極および負極を微
孔性ポリプロピレン膜を介して積層して、渦巻状に巻回
して発電要素を作製して電池缶に収容して図１と同様の
電池を作製した。電解液として、プロピレンカーボネー
ト５容量部、エチレンカーボネート３０容量部、ジエチ
ルカーボネート６５容量部からなる混合溶媒に、濃度
１．０ｍｏｌ／ｌとなるようにＬｉＰＦ6 を溶解して作
製した電解液中に１，３−プロパンスルトンの含有量が
３重量％となるように添加して電解液を作製して使用し
た。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below by showing embodiments of the present invention. Example 1 92 parts by weight of lithium manganate (Li 1 + X Mn 2 + X O 4 ) powder having a spinel structure on both sides of an aluminum foil having a width of 5.5 cm and a length of 66 cm and a thickness of 20 μm, and 5 parts by weight of carbon black Parts, a mixture consisting of 3 parts by weight of polyvinylidene fluoride, having a thickness of 1 after drying containing aluminum foil.
It was applied to a thickness of 78 μm to form a positive electrode. The negative electrode is a copper foil having a mixture of 94 parts by weight of graphitized mesocarbon microbeads (manufactured by Osaka Gas) and 6 parts by weight of polyvinylidene fluoride on a copper foil having a width of 5.75 cm and a length of 73.5 cm and a thickness of 10 μm. And dried so as to have a dry thickness of 124 μm. The positive electrode and the negative electrode were laminated with a microporous polypropylene film interposed therebetween, spirally wound to produce a power generating element, and housed in a battery can to produce a battery similar to that of FIG. As an electrolytic solution, 1 part of an electrolytic solution prepared by dissolving LiPF 6 at a concentration of 1.0 mol / l in a mixed solvent composed of 5 parts by volume of propylene carbonate, 30 parts by volume of ethylene carbonate, and 65 parts by volume of diethyl carbonate was used. , 3-propane sultone was added so as to have a content of 3% by weight to prepare and use an electrolytic solution.
【００１８】（充電方法）作製したリチウムイオン二次
電池を、４．２Ｖまで定電流で充電し、４．２Ｖから定
電圧充電に切り替えて定電流充電開始からの総充電時間
が２．５時間で充電を終了した。 （保存容量試験）充電直後、および２０℃で４週間保存
後の電池容量を放電終止電圧を３Ｖとして０．２Ｃの放
電率で放電して電池容量を測定した。(Charging Method) The produced lithium ion secondary battery was charged with a constant current up to 4.2 V, and switched from 4.2 V to a constant voltage charge, and the total charging time from the start of the constant current charging was 2.5 hours. To finish charging. (Storage capacity test) Immediately after charging and after storage at 20 ° C for 4 weeks, the battery capacity was measured by discharging at a discharge rate of 0.2 C with a discharge end voltage of 3 V.
【００１９】（サイクル試験）充電後、２０℃で１週間
保存した電池を、２０℃および４５℃において１Ｃ
（１．６Ａ）の放電率で放電した後に、充電し１Ｃの放
電率で放電を繰り返すサイクル試験を行い、１０サイク
ル目の放電容量に対する１００サイクル目の放電容量
を、表１において１００分率で示した。また、放電容量
の変化を図２に示した。図２（Ａ）は、２０℃での放電
容量の変化を示す図であり、図２（Ｂ）は、４５℃での
放電容量の変化を示す。(Cycle test) After charging, the battery stored at 20 ° C. for 1 week was subjected to 1C at 20 ° C. and 45 ° C.
After discharging at a discharge rate of (1.6A), a cycle test was repeated in which the battery was charged and discharged at a discharge rate of 1C, and the discharge capacity at the 100th cycle with respect to the discharge capacity at the 10th cycle was 100% in Table 1. Indicated. FIG. 2 shows the change in the discharge capacity. FIG. 2A shows a change in discharge capacity at 20 ° C., and FIG. 2B shows a change in discharge capacity at 45 ° C.
【００２０】実施例２ 電解液をプロピレンカーボネート１０容量部、エチレン
カーボネート３０容量部、ジエチルカーボネート６０容
量部からなる混合溶媒に、濃度が１．０ｍｏｌ／ｌとな
るようにＬｉＰＦ6 を溶解し、さらに１，３−プロパン
スルトンを電解液中の含有量が３重量％となるように添
加した電解液を使用した点を除き実施例１と同様に電池
を作製して同様に特性を評価した。Example 2 LiPF 6 was dissolved in a mixed solvent consisting of 10 parts by volume of propylene carbonate, 30 parts by volume of ethylene carbonate, and 60 parts by volume of diethyl carbonate so as to have a concentration of 1.0 mol / l. A battery was prepared in the same manner as in Example 1, except that 1,3-propane sultone was used so that the content in the electrolyte was 3% by weight, and the characteristics were evaluated in the same manner.
【００２１】比較例１ 電解液をエチレンカーボネート３０容量部、ジエチルカ
ーボネート７０容量部からなる混合溶媒に、支持電解質
として濃度が１．０ｍｏｌ／ｌとなるようにＬｉＰＦ6
を溶解して作製した電解液を使用した点を除き実施例１
と同様に電池を作製して同様に特性を評価した。COMPARATIVE EXAMPLE 1 LiPF 6 was added to a mixed solvent of 30 parts by volume of ethylene carbonate and 70 parts by volume of diethyl carbonate so that the concentration of the electrolyte was 1.0 mol / l as a supporting electrolyte.
Example 1 except that an electrolytic solution prepared by dissolving
A battery was prepared in the same manner as in the above, and the characteristics were similarly evaluated.
【００２２】[0022]
【表１】 電池容量（ｍＡｈ） 100サイクル/10サイクル電池容量変化（％） 充電直後 ４週間保存後 ２０℃ ４５℃ 実施例１ １７６１ １６８５ ９５．３ ８０．１ 実施例２ １７５４ １６６３ ９５．０ ８０．０ 比較例１ １７０２ １６３４ ９５．２ ７４．５Table 1 Battery capacity (mAh) 100 cycle / 10 cycle battery capacity change (%) Immediately after charging After storage for 4 weeks 20 ° C 45 ° C Example 1 1761 1685 95.3 80.1 Example 2 1754 1663 95.0 80 0.0 Comparative Example 1 1702 1634 95.2 74.5
【００２３】実施例３ 電解液として、エチレンカーボネートとジエチルカーボ
ネートを体積比３：７の比率で混合した混合溶媒に、濃
度１．０ｍｏｌ／ｌとなるようにＬｉＰＦ6 を添加し、
さらに、１，３−プロパンスルトンをその含有量が１重
量％となるように添加した電解液を使用した点を除き、
実施例１と同様にして作製したリチウムイオン二次電池
を、実施例１と同様の条件で６０℃で１００回の充放電
を繰り返した後に、電池から電解液を取り出して電解液
中のマンガンの濃度をＩＣＰ発光分光分析装置で測定し
たところ、マンガン濃度は８ｐｐｍであった。Example 3 As an electrolytic solution, LiPF 6 was added to a mixed solvent obtained by mixing ethylene carbonate and diethyl carbonate at a volume ratio of 3: 7 so as to have a concentration of 1.0 mol / l.
Further, except that an electrolytic solution to which 1,3-propane sultone was added so as to have a content of 1% by weight was used.
A lithium ion secondary battery manufactured in the same manner as in Example 1 was repeatedly charged and discharged 100 times at 60 ° C. under the same conditions as in Example 1, and then the electrolytic solution was taken out of the battery to remove manganese in the electrolytic solution. When the concentration was measured with an ICP emission spectrometer, the manganese concentration was 8 ppm.
【００２４】比較例２ １，３−プロパンスルトンを用いなかった点を除き、実
施例２と同様にして電池を作製して充放電試験を行い、
電解液中のマンガン濃度を測定したところ、２３ｐｐｍ
であった。Comparative Example 2 A battery was prepared and subjected to a charge / discharge test in the same manner as in Example 2, except that 1,3-propane sultone was not used.
When the manganese concentration in the electrolyte was measured, it was 23 ppm
Met.
【００２５】[0025]
【発明の効果】本発明のリチウムイオン二次電池は、電
解液中にスルトン化合物を添加したことによって、高温
度で保存した後の電池容量の減少率が小さく、また黒鉛
を負極とした場合には、プロピレンカーボネートの分解
を減少することができ、また正極活物質としてマンガン
酸リチウムを用いた場合には、高温での電解液への溶出
量が少なくすることができるので、電池容量の低下が小
さく、サイクル寿命の長い電池を得ることができる。According to the lithium ion secondary battery of the present invention, by adding a sultone compound to the electrolyte, the reduction rate of the battery capacity after storage at a high temperature is small, and when the graphite is used as the negative electrode, Can reduce the decomposition of propylene carbonate, and when lithium manganate is used as the positive electrode active material, the amount of elution into the electrolytic solution at high temperatures can be reduced, so that the battery capacity decreases. A small battery having a long cycle life can be obtained.
【図１】リチウムイオン電池の一例を説明する一部を切
り欠いた斜視図である。FIG. 1 is a partially cutaway perspective view illustrating an example of a lithium ion battery.
【図２】本発明の実施例および比較例の電池容量の変化
を説明する図である。FIG. 2 is a diagram illustrating a change in battery capacity according to an example of the present invention and a comparative example.
１…角型電池、２…セパレータ、３…正極側集電体、４
…負極側集電体、５…ジェリーロール、６…電池缶、７
…電極ヘッダDESCRIPTION OF SYMBOLS 1 ... Square battery, 2 ... Separator, 3 ... Positive side collector, 4
... negative electrode side current collector, 5 ... jelly roll, 6 ... battery can, 7
… Electrode header
───────────────────────────────────────────────────── フロントページの続き (72)発明者 佐藤 一 神奈川県横浜市港北区新横浜２−５−５ 日本モリエナジー株式会社内 (72)発明者 太田 智行 東京都港区芝５−７−１ 日本電気株式会 社内 (72)発明者 粂内 友一 東京都港区芝５−７−１ 日本電気株式会 社内 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kazu Sato 2-5-5 Shin-Yokohama, Kohoku-ku, Yokohama, Kanagawa Prefecture Within Mori Energy Japan Co., Ltd. (72) Tomoyuki Ota 5-7-1 Shiba, Minato-ku, Tokyo Japan NEC Corporation In-house (72) Inventor Yuichi Kumeuchi 5-7-1 Shiba, Minato-ku, Tokyo NEC Corporation In-house
Claims (5)
する正極および負極を有するリチウムイオン二次電池に
おいて、スルトン化合物を電解液、もしくは電解液の一
部に添加したことを特徴とするリチウムイオン二次電
池。1. A lithium ion secondary battery having a positive electrode and a negative electrode for doping and undoping lithium ions, wherein a sultone compound is added to an electrolytic solution or a part of the electrolytic solution. .
トン、１，４−ブタンスルトンの少なくとも一種である
ことを特徴とする請求項１記載のリチウムイオン二次電
池。2. The lithium ion secondary battery according to claim 1, wherein the sultone compound is at least one of 1,3-propane sultone and 1,4-butane sultone.
ム、マンガン酸リチウム、ニッケル酸リチウムから選ば
れる少なくとも１種を用いたことを特徴とする請求項１
または２のいずれか１項に記載のリチウムイオン二次電
池。3. The method according to claim 1, wherein at least one selected from the group consisting of lithium cobaltate, lithium manganate and lithium nickelate is used as the positive electrode active material.
Or the lithium ion secondary battery according to any one of 2.
用いたことを特徴とする請求項１ないし３のいずれかに
１項に記載のリチウムイオン二次電池。4. The lithium ion secondary battery according to claim 1, wherein propylene carbonate is used as the electrolyte.
とを特徴とする請求項１ないし４のいずれか１項に記載
のリチウムイオン二次電池。5. The lithium ion secondary battery according to claim 1, wherein a graphite carbon material is used as the negative electrode.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10148790A JPH11339850A (en) | 1998-05-29 | 1998-05-29 | Lithium-ion secondary battery |
| KR1019990019488A KR19990088654A (en) | 1998-05-29 | 1999-05-28 | lithium ion secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10148790A JPH11339850A (en) | 1998-05-29 | 1998-05-29 | Lithium-ion secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11339850A true JPH11339850A (en) | 1999-12-10 |
Family
ID=15460760
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10148790A Pending JPH11339850A (en) | 1998-05-29 | 1998-05-29 | Lithium-ion secondary battery |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPH11339850A (en) |
| KR (1) | KR19990088654A (en) |
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| JP2001307773A (en) * | 2000-04-19 | 2001-11-02 | Gs-Melcotec Co Ltd | Nonaqueous electrolyte battery |
| JP2002170576A (en) * | 2000-11-30 | 2002-06-14 | Matsushita Electric Ind Co Ltd | Nonaqueous electrolyte cell |
| US6620553B2 (en) | 2000-07-10 | 2003-09-16 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Lithium secondary battery |
| EP1394888A1 (en) * | 2002-08-29 | 2004-03-03 | NEC Corporation | Electrolyte solution for secondary battery and secondary battery using the same |
| JP2004165151A (en) * | 2002-10-23 | 2004-06-10 | Matsushita Electric Ind Co Ltd | Nonaqueous electrolyte secondary battery and electrolyte used therein |
| JP2005149750A (en) * | 2003-11-11 | 2005-06-09 | Nec Corp | Nonaqueous electrolyte secondary battery |
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| WO2010016520A1 (en) | 2008-08-06 | 2010-02-11 | 三井化学株式会社 | Nonaqueous electrolyte solution and lithium secondary battery |
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| JP2001307773A (en) * | 2000-04-19 | 2001-11-02 | Gs-Melcotec Co Ltd | Nonaqueous electrolyte battery |
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Also Published As
| Publication number | Publication date |
|---|---|
| KR19990088654A (en) | 1999-12-27 |
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