JPH08250117A - Carbon material for lithium secondary battery negative electrode, and manufacture thereof - Google Patents
Carbon material for lithium secondary battery negative electrode, and manufacture thereofInfo
- Publication number
- JPH08250117A JPH08250117A JP7049766A JP4976695A JPH08250117A JP H08250117 A JPH08250117 A JP H08250117A JP 7049766 A JP7049766 A JP 7049766A JP 4976695 A JP4976695 A JP 4976695A JP H08250117 A JPH08250117 A JP H08250117A
- Authority
- JP
- Japan
- Prior art keywords
- carbon material
- fluorine
- negative electrode
- secondary battery
- lithium secondary
- 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
- 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、リチウム二次電池負極
用炭素材料及びその製造方法に関するものである。TECHNICAL FIELD The present invention relates to a carbon material for a negative electrode of a lithium secondary battery and a method for producing the same.
【０００２】[0002]
【従来の技術】負極活物質としてリチウムを用いるリチ
ウム二次電池は、充放電を繰り返すと充電時に、樹枝状
のリチウムが負極活物質上に析出するいわゆるデンドラ
イトが発生する。デンドライトが大きくなり、正極活物
質と接触すると電池が内部短絡し、電池のサイクル寿命
が短かくなる上、電池が発熱、発火する危険がある。そ
こで、リチウムと他の金属との合金（リチウム合金）を
負極活物質として用いることが提案された。しかしなが
ら、リチウム合金を負極活物質として用いるとエネルギ
ー密度の低下が大きくなる。そこで、リチウムイオンの
吸蔵、放出が可能な炭素材料を負極材として用いること
が提案された。この種の電池では、リチウムイオンが炭
素材料内に吸蔵、放出されて電池の充放電が行われるた
め、リチウムが負極上に析出することがなく、デンドラ
イトの発生を抑制できる。そして炭素材料はリチウムに
近い卑な電位で作動するので、リチウム合金を負極活物
質として用いる場合に比べて、エネルギー密度の低下を
低く抑えることができる。2. Description of the Related Art In a lithium secondary battery using lithium as a negative electrode active material, when charging and discharging are repeated, so-called dendrites in which dendritic lithium is deposited on the negative electrode active material are generated during charging. When the dendrite becomes large and comes into contact with the positive electrode active material, the battery is internally short-circuited, the cycle life of the battery is shortened, and there is a risk of heat generation and ignition of the battery. Therefore, it has been proposed to use an alloy of lithium and another metal (lithium alloy) as the negative electrode active material. However, when a lithium alloy is used as the negative electrode active material, the energy density is greatly reduced. Therefore, it has been proposed to use a carbon material capable of inserting and extracting lithium ions as the negative electrode material. In this type of battery, since lithium ions are inserted into and discharged from the carbon material to charge and discharge the battery, lithium is not deposited on the negative electrode and dendrite generation can be suppressed. Since the carbon material operates at a base potential close to that of lithium, the decrease in energy density can be suppressed to a low level as compared with the case where a lithium alloy is used as the negative electrode active material.
【０００３】しかしながら、炭素材料の表面には、水酸
基（−ＣＯ）、カルボニル基（−ＣＯＯＨ）等の酸素官
能基があるため、この種の電池を充電すると、炭素材料
の表面に酸素官能基によって不可逆な反応が起こり、初
回の充電量が増加し、しかも充電量のばらつきが大きく
なる。炭素材料を負極材として用いる電池では、初回充
電を行ってリチウムイオンを炭素材料内に吸蔵しなけれ
ばならないので、初回充電量のばらつきが大きいと電池
性能に大きなばらつきが生じることになる。そこで、特
開平４−１１２４５５号公報、特開平５−２８９９６号
公報、特開平５−１４４４４０号公報に示されるように
炭素材料を加熱して炭素材料の表面から酸素官能基を低
減することが提案された。However, since the surface of the carbon material has oxygen functional groups such as a hydroxyl group (-CO) and a carbonyl group (-COOH), when a battery of this kind is charged, the surface of the carbon material is affected by the oxygen functional group. An irreversible reaction occurs, the amount of charge for the first time increases, and moreover, the variation in the amount of charge increases. In a battery using a carbon material as a negative electrode material, lithium ions must be occluded in the carbon material by carrying out initial charging, so that large variations in the initial charge amount cause large variations in battery performance. Therefore, as disclosed in JP-A-4-112455, JP-A-5-28996, and JP-A-5-144440, it is proposed to heat the carbon material to reduce oxygen functional groups from the surface of the carbon material. Was done.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、炭素材
料を加熱して酸素官能基を低減しても初回充電量のばら
つきを少なくするのは、限界があった。また炭素材料を
加熱する法では、酸素官能基を効率良く除去するのが困
難であった。However, even if the carbon material is heated to reduce the oxygen functional groups, there is a limit in reducing the variation in the initial charge amount. Further, it is difficult to efficiently remove the oxygen functional group by the method of heating the carbon material.
【０００５】本発明の目的は、リチウム二次電池の初回
充電量のばらつきを少なくできるリチウム二次電池負極
用炭素材料及びリチウム二次電池負極を提供することに
ある。An object of the present invention is to provide a carbon material for a lithium secondary battery negative electrode and a lithium secondary battery negative electrode which can reduce variations in the amount of initial charge of the lithium secondary battery.
【０００６】本発明の他の目的は、初回充電量のばらつ
きを少ないリチウム二次電池を提供することにある。Another object of the present invention is to provide a lithium secondary battery with less variation in the initial charge amount.
【０００７】本発明の他の目的は、表面にある酸素官能
基を効率良く除去して、リチウム二次電池の初回充電量
のばらつきを少なくできるリチウム二次電池負極用炭素
材料の製造方法を提供することにある。Another object of the present invention is to provide a method for producing a carbon material for a lithium secondary battery negative electrode, by which oxygen functional groups on the surface can be efficiently removed to reduce variations in the initial charge amount of the lithium secondary battery. To do.
【０００８】[0008]
【課題を解決するための手段】本発明は、リチウム二次
電池負極用炭素材料を改良の対象にして、表面の酸素官
能基の一部または全部をフッ素で置換する。The present invention aims to improve a carbon material for a negative electrode of a lithium secondary battery, and substitutes part or all of oxygen functional groups on the surface with fluorine.
【０００９】このリチウム二次電池負極用炭素材料を主
成分としてリチウム二次電池負極を構成することができ
る。また、このリチウム二次電池負極を用い、電解質と
して固体電解質または非水電解液を用いてリチウム二次
電池を構成することができる。A lithium secondary battery negative electrode can be constituted by using this carbon material for a lithium secondary battery negative electrode as a main component. Further, a lithium secondary battery can be constructed by using this lithium secondary battery negative electrode and using a solid electrolyte or a non-aqueous electrolyte as an electrolyte.
【００１０】炭素材料の酸素官能基の一部または全部を
フッ素で置換した後には、炭素材料からフッ素の一部ま
たは全部を除去してリチウム二次電池負極用炭素材料を
製造することもできる。フッ素を置換させる反応及びフ
ッ素を除去する反応は、従来の炭素材料を加熱して酸素
官能基を除去する反応よりバラツキが少ない状態で酸素
官能基を除去できる。After substituting part or all of the oxygen functional groups of the carbon material with fluorine, part or all of the fluorine can be removed from the carbon material to produce a carbon material for a lithium secondary battery negative electrode. The reaction for substituting fluorine and the reaction for removing fluorine can remove the oxygen functional group with less variation than the conventional reaction for heating the carbon material to remove the oxygen functional group.
【００１１】[0011]
【作用】本発明のように、表面の酸素官能基の一部また
は全部をフッ素で置換すると、電池の初回充電量を小さ
くできる上、初回充電量のばらつきを少なくして、電池
性能のばらつきを減少させることができる。この理由は
定かではないが、酸素官能基は−ＣＯＯＨ、−ＯＨ等の
種々の構造を有するものがあり、電池を初回充電した際
に不可逆な種々の形式の反応が生じるのに対して、酸素
官能基をフッ素と置換した炭素材料では、炭素材料の表
面にフッ素だけが存在しているので、不可逆な反応形式
は一種類になるためであると考えられる。By replacing part or all of the oxygen functional groups on the surface with fluorine as in the present invention, the initial charge of the battery can be reduced, and the fluctuation of the initial charge can be reduced to reduce the fluctuation of the battery performance. Can be reduced. The reason for this is not clear, but oxygen functional groups have various structures such as -COOH and -OH, and various types of irreversible reactions occur when the battery is first charged, whereas oxygen functional groups have different structures. It is considered that in the carbon material in which the functional group is replaced with fluorine, only the fluorine is present on the surface of the carbon material, so that the irreversible reaction mode becomes one kind.
【００１２】[0012]
（実施例１）図１は本実施例のリチウム二次電池の破断
断面図である。本実施例のリチウム二次電池は、正極集
電体１の片面に形成された正極材２と負極集電体３の片
面に形成された負極材４とが電解質層５を介して積層さ
れた構造を有している。正極集電体１は厚み０．２mmの
ステンレス板により形成されており、正極端子を兼ねて
いる。正極材２は、ＬｉＣｌＯ4 からなる活物質材料８
５重量％と、アセチレンブラックからなる導電材１０重
量％と、ポリテトラフルオロエチレン微粉末からなる結
着剤５重量％とを混合した混合物を乾燥した後、圧縮成
形して形成した厚み２mmのペレットにより構成されてい
る。負極集電体３は厚み０．２mmのステンレス板により
形成されており、負極端子を兼ねている。負極材４はグ
ラファイトからなる炭素材料を主成分としており、次の
ようにして形成した。まず、日本黒鉛株式会社からＪＳ
Ｐの製品名で販売されている平均粒子径５μｍの人造の
黒鉛粉末（グラファイト粉末）３重量％と硝酸ナトリウ
ム２重量％と濃硫酸８４重量％と過マンガン酸カリウム
１１重量％とを１００℃中で混合して酸化グラファイト
を作ってから、１４０℃で熱分解してグラファイト粉末
に酸素官能基を付加して炭素素材を作った。これによ
り、後述する試験に用いる比較例の電池に用いるグラフ
ァイト粉末と素材としての条件を同じにした。なおグラ
ファイト粉末の平均粒径は５〜５０μｍが好ましい。次
にグラファイト粉末を温度７５℃のフッ素ガス雰囲気中
に５時間放置して、酸素官能基をフッ素と置換させた。
これにより酸素官能基の約９０％をフッ素と置換した炭
素材料を作成した。酸素官能基の９０％以上をフッ素と
置換するのが好ましい。なおフッ素と置換するには、温
度５０〜１００℃のフッ素ガス雰囲気中に２〜５時間炭
素材料を放置するのが好ましい。(Embodiment 1) FIG. 1 is a cutaway sectional view of a lithium secondary battery of this embodiment. In the lithium secondary battery of this example, the positive electrode material 2 formed on one surface of the positive electrode current collector 1 and the negative electrode material 4 formed on one surface of the negative electrode current collector 3 were laminated with the electrolyte layer 5 interposed therebetween. It has a structure. The positive electrode current collector 1 is formed of a stainless plate having a thickness of 0.2 mm and also serves as a positive electrode terminal. The positive electrode material 2 is an active material 8 made of LiClO 4.
Pellets having a thickness of 2 mm formed by drying a mixture obtained by mixing 5% by weight, 10% by weight of a conductive material made of acetylene black, and 5% by weight of a binder made of fine powder of polytetrafluoroethylene and then compression-molding the mixture. It is composed by. The negative electrode current collector 3 is formed of a stainless plate having a thickness of 0.2 mm and also serves as a negative electrode terminal. The negative electrode material 4 contains a carbon material made of graphite as a main component, and was formed as follows. First, JS from Nippon Graphite Co., Ltd.
3% by weight of artificial graphite powder (graphite powder) having an average particle size of 5 μm sold under the product name of P (graphite powder), 2% by weight of sodium nitrate, 84% by weight of concentrated sulfuric acid and 11% by weight of potassium permanganate in 100 ° C. Was mixed to prepare graphite oxide and then pyrolyzed at 140 ° C. to add oxygen functional groups to the graphite powder to prepare a carbon material. As a result, the conditions of the graphite powder used in the battery of the comparative example used in the test described later were the same as those of the raw material. The average particle size of the graphite powder is preferably 5 to 50 μm. Next, the graphite powder was left in a fluorine gas atmosphere at a temperature of 75 ° C. for 5 hours to replace the oxygen functional group with fluorine.
This produced a carbon material in which about 90% of the oxygen functional groups were replaced with fluorine. It is preferred to replace 90% or more of the oxygen functional groups with fluorine. In order to replace with fluorine, it is preferable to leave the carbon material in a fluorine gas atmosphere at a temperature of 50 to 100 ° C. for 2 to 5 hours.
【００１３】次に、フッ素置換した炭素粉末とポリフッ
化ビニリデンからなる結着剤とを９０：１０の重量比で
適量のＮ−メチルピロリドン液を溶媒として混合した混
合物を作った。次にこの混合物をステンレス網に塗布し
てから加熱真空乾燥してＮ−メチルピロリドン液を揮発
させて厚み０．１mmのシート状の負極材４を完成した。Next, a mixture was prepared by mixing fluorine-substituted carbon powder and a binder made of polyvinylidene fluoride in a weight ratio of 90:10 with an appropriate amount of N-methylpyrrolidone solution as a solvent. Next, this mixture was applied to a stainless steel net, and then heated and vacuum dried to volatilize the N-methylpyrrolidone solution to complete a sheet-shaped negative electrode material 4 having a thickness of 0.1 mm.
【００１４】電解質層５は、ポリプロピレン不織布から
なるセパレータに電解液が含浸されて構成されている。
電解液は、エチレンカーボネートとジエチルカーボネー
トを７５：２５の体積比で混合した混合液にＬｉＣｌＯ
4 １Ｍを溶かして作った。The electrolyte layer 5 is formed by impregnating a separator made of polypropylene nonwoven fabric with an electrolytic solution.
The electrolytic solution was a mixture of ethylene carbonate and diethyl carbonate in a volume ratio of 75:25, and LiClO.
4 Made by melting 1M.
【００１５】（実施例２）本実施例の電池では、実施例
１において酸素官能基をフッ素に置換した炭素材料を１
０-6Torrの高真空下において１０００℃の温度で４時間
加熱してフッ素を９５％除去したものを炭素材料として
用いた。フッ素は９０％以上除去するのが好ましい。そ
の他は実施例１の電池と同じ構成を有している。なおフ
ッ素を除去するには、１０-2Torr以下の真空中で６００
℃以上に加熱するのが好ましい。(Example 2) In the battery of this example, the carbon material obtained by substituting fluorine for the oxygen functional group in Example 1 was used.
A material obtained by heating at a temperature of 1000 ° C. for 4 hours under a high vacuum of 0 −6 Torr and removing 95% of fluorine was used as a carbon material. It is preferable to remove 90% or more of fluorine. Others have the same configuration as the battery of the first embodiment. In order to remove fluorine, 600 in a vacuum of 10 -2 Torr or less.
It is preferable to heat to ℃ or more.
【００１６】（比較例１）本比較例の電池では、実施例
１において酸素官能基を付加した炭素材料をアルゴン雰
囲気中において、１３００℃で４時間加熱して、酸素官
能基を減少させ、残った酸素官能基をフッ素と置換させ
ない炭素材料を用いた。その他は実施例１の電池と同じ
構成を有している。Comparative Example 1 In the battery of this comparative example, the carbon material to which the oxygen functional group was added in Example 1 was heated at 1300 ° C. for 4 hours in an argon atmosphere to reduce the oxygen functional group and leave it. A carbon material in which the oxygen functional group was not replaced with fluorine was used. Others have the same configuration as the battery of the first embodiment.
【００１７】次に上記各電池をそれぞれ１０個作り、各
電池を０．５ mA/cm2 の定電流密度で４．２Ｖの定電圧
充電を行った後に０．５ mA/cm2 の定電流密度で終止電
圧：２．８Ｖまで放電を行い、各電池の電圧による放電
容量の変化を調べた。図２（Ａ），（Ｂ）はその測定結
果を示している。本図において斜線に示す範囲は、試験
に用いた１０個の電池のばらつきの範囲である。本図よ
り実施例１及び２の電池は比較例１の電池に比べてばら
つきが少ないのが分る。[0017] Then each cell 10 or making each constant current of 0.5 mA / cm 2 after the constant-voltage charging at 4.2V at a constant current density of 0.5 mA / cm 2 each battery Discharge was carried out to a final voltage of 2.8 V in terms of density, and the change in discharge capacity depending on the voltage of each battery was examined. 2A and 2B show the measurement results. The hatched range in this figure is the range of variation of the 10 batteries used in the test. From this figure, it can be seen that the batteries of Examples 1 and 2 have less variation than the battery of Comparative Example 1.
【００１８】次に酸素官能基をフッ素に置換した場合、
電池の初回充電量にどのようなばらつきの変化が生じる
かを調べた。最初に次のようにして酸素官能基の量が異
なる炭素材料と、フッ素の量が異なる炭素材料とを作っ
た。まず実施例１において酸素官能基を付加した炭素材
料をアルゴン雰囲気中において、６００℃〜１３００℃
の温度範囲で４時間加熱して、酸素官能基の量が異なる
各種の炭素材料を作った。なお酸素官能基の量は、光電
子分光法によりＣ1SとＯ1S原子数比により、Ｃ1SとＯ1S
とを合わせたものに対してＯ1Sが０〜２０％の範囲で異
なるものとした。次に前述と同様に酸素官能基の量が異
なる各種の炭素材料を作ってから、これらの炭素材料を
温度５０〜１００℃のフッ素ガス雰囲気中に５時間放置
して、酸素官能基をフッ素と置換させた。これによりフ
ッ素の量が異なる各種の炭素材料を作った。なおフッ素
の量は、光電子分光法によりＣ1SとＦ1S原子数比によ
り、Ｃ1SとＦ1Sとを合わせたものに対してＦ1Sが０〜２
０％の範囲で異なるものとした。次に酸素官能基及びフ
ッ素の量がそれぞれ異なる各炭素粉末炭素とポリフッ化
ビニリデンからなる結着剤とを９０：１０の重量比で適
量のＮ−メチルピロリドン液を溶媒として混合した混合
物を作った。次にこの混合物をステンレス網に塗布して
から加熱真空乾燥してＮ−メチルピロリドン液を揮発さ
せて酸素官能基及びフッ素の量が異なる炭素電極を作っ
た。Next, when the oxygen functional group is replaced with fluorine,
The variation of the initial charge of the battery was investigated. First, carbon materials having different amounts of oxygen functional groups and carbon materials having different amounts of fluorine were prepared as follows. First, the carbon material having an oxygen functional group added in Example 1 was heated to 600 ° C. to 1300 ° C. in an argon atmosphere.
In the temperature range of 4 hours, various carbon materials having different amounts of oxygen functional groups were prepared. The amount of oxygen functional groups was determined by photoelectron spectroscopy based on the C1S and O1S atomic ratio.
O1S was different in the range of 0 to 20% with respect to the combination of the above. Next, similar to the above, various carbon materials having different amounts of oxygen functional groups were produced, and then these carbon materials were left in a fluorine gas atmosphere at a temperature of 50 to 100 ° C. for 5 hours to convert the oxygen functional groups to fluorine. Replaced. This produced various carbon materials with different amounts of fluorine. The amount of fluorine depends on the atomic ratio of C1S and F1S by photoelectron spectroscopy, and F1S is 0 to 2 with respect to the total of C1S and F1S.
Different in the range of 0%. Next, a mixture was prepared by mixing carbon powder carbons having different amounts of oxygen functional groups and fluorine and a binder made of polyvinylidene fluoride at a weight ratio of 90:10 with an appropriate amount of N-methylpyrrolidone solution as a solvent. . Next, this mixture was applied to a stainless steel mesh and dried under heating and vacuum to volatilize the N-methylpyrrolidone liquid to prepare carbon electrodes having different amounts of oxygen functional groups and fluorine.
【００１９】そして、各炭素電極を図３に示す試験用セ
ル内に配置した。図３において、１１は炭素電極、１２
はリチウム電極、１３はセパレータ、１４はリチウム基
準の参照極、１５はエチレンカーボネートとジエチルカ
ーボネートを７５：２５の体積比で混合した混合液にＬ
ｉＣｌＯ4 １Ｍを溶かして作った電解液、１６は正負極
の切替えが可能な充放電用電源、１７は電圧計である。
そして、炭素電極１１に負極端子を接続し、リチウム電
極１２に正極端子を接続するように充放電用電源１６の
正負極を設定し、炭素電極１１とリチウム電極１２との
間に０．５ mA/cm2 の電流密度で電流を流した。これに
より、リチウム電極１２から炭素電極１１にリチウムイ
オンが流れる。そして、参照極１４により測定した炭素
電極１１の電位が０Ｖになるまでの充電して初回充電容
量を測定した。図４はフッ素の量が異なる炭素電極にお
けるフッ素の量と初回充電容量との関係を示している。
本図において斜線に示す範囲は、フッ素の量が異なるそ
れぞれ１０個の炭素電極のばらつきの範囲である。図５
は酸素官能基の量が異なる炭素電極における酸素官能基
の量と初回充電容量との関係を示している。本図におい
て斜線に示す範囲は、酸素官能素基の量が異なるそれぞ
れ１０個の炭素電極のばらつきの範囲である。両図より
酸素官能素基をフッ素に置換した炭素電極は、フッ素に
置換しない炭素電極に比べて初回充電量のばらつきが少
ないのが分る。Then, each carbon electrode was placed in the test cell shown in FIG. In FIG. 3, 11 is a carbon electrode, 12
Is a lithium electrode, 13 is a separator, 14 is a reference electrode based on lithium, and 15 is L in a mixed solution in which ethylene carbonate and diethyl carbonate are mixed in a volume ratio of 75:25.
An electrolytic solution prepared by dissolving 1M of iClO 4 ; 16 is a charging / discharging power source capable of switching between positive and negative electrodes; and 17 is a voltmeter.
Then, the positive and negative electrodes of the charging / discharging power supply 16 are set so that the negative electrode terminal is connected to the carbon electrode 11 and the positive electrode terminal is connected to the lithium electrode 12, and 0.5 mA is set between the carbon electrode 11 and the lithium electrode 12. A current was applied at a current density of / cm 2 . As a result, lithium ions flow from the lithium electrode 12 to the carbon electrode 11. Then, charging was performed until the potential of the carbon electrode 11 measured by the reference electrode 14 became 0 V, and the initial charge capacity was measured. FIG. 4 shows the relationship between the amount of fluorine and the initial charge capacity in carbon electrodes having different amounts of fluorine.
In the figure, the hatched range is the range of variation of 10 carbon electrodes having different amounts of fluorine. Figure 5
Shows the relationship between the amount of oxygen functional groups and the initial charge capacity in carbon electrodes having different amounts of oxygen functional groups. In the figure, the hatched range is the range of variation of 10 carbon electrodes having different amounts of oxygen functional groups. From both figures, it can be seen that the carbon electrode in which the oxygen functional group is replaced with fluorine has less variation in the initial charge amount than the carbon electrode in which the oxygen functional group is not replaced with fluorine.
【００２０】なお、上記実施例では、フッ素置換した炭
素材料を加熱処理してフッ素を除去したが、フッ素置換
した炭素材料を電解液中で還元反応させてもフッ素を除
去することができる。In the above embodiment, the fluorine-substituted carbon material was heat-treated to remove fluorine, but fluorine can be removed by reducing the fluorine-substituted carbon material in the electrolytic solution.
【００２１】以下、明細書に記載した複数の発明の中で
いくつかの発明についてその構成を示す。The constitution of some of the inventions described in the specification will be shown below.
【００２２】（１）リチウムイオンの吸蔵と放出とが可
能で表面に酸素官能基を有する炭素材料をフッ素ガスと
反応させて前記酸素官能基の９０％以上をフッ素で置換
することによりリチウム二次電池負極用炭素材料を製造
することを特徴とするリチウム二次電池負極用炭素材料
の製造方法。(1) Lithium secondary by reacting a carbon material capable of inserting and extracting lithium ions and having an oxygen functional group on the surface with fluorine gas to replace 90% or more of the oxygen functional group with fluorine. A method for producing a carbon material for a lithium secondary battery negative electrode, which comprises producing a carbon material for a battery negative electrode.
【００２３】（２）リチウムイオンの吸蔵と放出とが可
能で表面に酸素官能基を有する炭素材料を５０〜１００
℃の雰囲気中でフッ素ガスと反応させて前記酸素官能基
の９０％以上をフッ素で置換した後、前記炭素材料から
前記フッ素の９０％以上を除去してリチウム二次電池負
極用炭素材料を製造することを特徴とするリチウム二次
電池負極用炭素材料の製造方法。(2) 50 to 100 carbon materials capable of absorbing and desorbing lithium ions and having oxygen functional groups on the surface are used.
90% or more of the oxygen functional groups are replaced with fluorine by reacting with fluorine gas in an atmosphere of ° C, and 90% or more of the fluorine is removed from the carbon material to produce a carbon material for a lithium secondary battery negative electrode. A method for producing a carbon material for a lithium secondary battery negative electrode, comprising:
【００２４】（３）前記表面に酸素官能基を有する炭素
材料は平均粒径５〜５０μｍのグラファイト粉末である
上記（１）または（２）に記載のリチウム二次電池負極
用炭素材料の製造方法。(3) The method for producing a carbon material for a lithium secondary battery negative electrode according to the above (1) or (2), wherein the carbon material having an oxygen functional group on the surface is graphite powder having an average particle size of 5 to 50 μm. .
【００２５】（４）前記炭素材料を真空中で加熱処理し
て前記フッ素を除去することを特徴とする上記（２）に
記載のリチウム二次電池負極用炭素材料の製造方法。(4) The method for producing a carbon material for a lithium secondary battery negative electrode according to (2), wherein the carbon material is heat-treated in vacuum to remove the fluorine.
【００２６】（５）前記加熱処理は前記炭素材料を１０
-2Toor以下の真空中で６００℃以上に加熱することを特
徴とする上記（４）に記載のリチウム二次電池負極用炭
素材料の製造方法。(5) In the heat treatment, the carbon material is added to 10
The method for producing a carbon material for a negative electrode of a lithium secondary battery according to (4) above, wherein the carbon material is heated to 600 ° C. or higher in a vacuum of −2 Toor or lower.
【００２７】（６）前記炭素材料を電解液中で還元反応
させて前記フッ素を除去することを特徴とする上記
（２）に記載のリチウム二次電池負極用炭素材料の製造
方法。(6) The method for producing a carbon material for a negative electrode of a lithium secondary battery according to (2), wherein the carbon material is subjected to a reduction reaction in an electrolytic solution to remove the fluorine.
【００２８】（７）表面の酸素官能基の９０％以上がフ
ッ素で置換されてなるグラファイト粉末を主成分として
作られた負極と、ＬｉＣｌＯ4 を主成分として作られた
正極と、エチレンカーボネート及びジエチルカーボネー
トを混合してなる電解液とを用いて構成されるリチウム
二次電池。(7) Negative electrode made mainly of graphite powder in which 90% or more of oxygen functional groups on the surface are substituted with fluorine, positive electrode made mainly of LiClO4, ethylene carbonate and diethyl carbonate A lithium secondary battery configured by using an electrolytic solution obtained by mixing
【００２９】[0029]
【発明の効果】本発明によれば、炭素材料の表面の酸素
官能基の一部または全部をフッ素で置換するので、初回
充電量を小さくできる上、電池の初回充電量のばらつき
を少なくして、電池性能のばらつきを減少させることが
できる。According to the present invention, part or all of the oxygen functional groups on the surface of the carbon material are replaced with fluorine, so that the initial charge amount can be reduced and the variation in the initial charge amount of the battery can be reduced. It is possible to reduce variations in battery performance.
【図１】 本実施例のリチウム二次電池の破断断面図で
ある。FIG. 1 is a cutaway sectional view of a lithium secondary battery according to an embodiment.
【図２】 （Ａ）及び（Ｂ）は試験に用いた電池の電圧
による放電容量の変化のばらつきを示す図である。FIG. 2A and FIG. 2B are diagrams showing variations in change in discharge capacity depending on the voltage of the battery used in the test.
【図３】 試験に用いた試験用セルの平面図である。FIG. 3 is a plan view of a test cell used in a test.
【図４】 炭素電極におけるフッ素の量による初回充電
容量の変化のばらつきを示す図である。FIG. 4 is a diagram showing variation in change in initial charge capacity depending on the amount of fluorine in a carbon electrode.
【図５】 炭素電極における酸素官能基の量による初回
充電容量の変化のばらつきを示す図である。FIG. 5 is a diagram showing variation in change in initial charge capacity depending on the amount of oxygen functional groups in a carbon electrode.
Claims (5)
素で置換されてなるリチウム二次電池負極用炭素材料。1. A carbon material for a lithium secondary battery negative electrode, wherein a part or all of oxygen functional groups on the surface are substituted with fluorine.
炭素材料を主成分とするリチウム二次電池負極。2. A lithium secondary battery negative electrode containing the carbon material for a lithium secondary battery negative electrode according to claim 1 as a main component.
用いられてなるリチウム二次電池。3. A lithium secondary battery using the negative electrode of the lithium secondary battery according to claim 2.
酸素官能基の一部または全部をフッ素で置換してリチウ
ム二次電池負極用炭素材料を製造することを特徴とする
リチウム二次電池負極用炭素材料の製造方法。4. A lithium secondary battery, wherein a carbon material for a lithium secondary battery negative electrode is produced by substituting a part or all of the oxygen functional groups of a carbon material having an oxygen functional group on the surface with fluorine. Manufacturing method of carbon material for negative electrode.
酸素官能基の一部または全部をフッ素で置換した後、前
記炭素材料から前記フッ素の一部または全部を除去して
リチウム二次電池負極用炭素材料を製造することを特徴
とするリチウム二次電池負極用炭素材料の製造方法。5. A lithium secondary battery in which a part or all of the oxygen functional groups of a carbon material having an oxygen functional group on the surface are replaced with fluorine and then part or all of the fluorine is removed from the carbon material. A method of manufacturing a carbon material for a negative electrode of a lithium secondary battery, which comprises manufacturing a carbon material for a negative electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7049766A JPH08250117A (en) | 1995-03-09 | 1995-03-09 | Carbon material for lithium secondary battery negative electrode, and manufacture thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7049766A JPH08250117A (en) | 1995-03-09 | 1995-03-09 | Carbon material for lithium secondary battery negative electrode, and manufacture thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08250117A true JPH08250117A (en) | 1996-09-27 |
Family
ID=12840304
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7049766A Pending JPH08250117A (en) | 1995-03-09 | 1995-03-09 | Carbon material for lithium secondary battery negative electrode, and manufacture thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08250117A (en) |
Cited By (16)
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|---|---|---|---|---|
| KR19980060803A (en) * | 1996-12-31 | 1998-10-07 | 손욱 | Method for producing a conductive agent and a secondary battery containing the conductive agent |
| JPH10284079A (en) * | 1997-02-06 | 1998-10-23 | Japan Storage Battery Co Ltd | Manufacture of host material and nonaqueous electrolyte secondary battery |
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| US6821675B1 (en) | 1998-06-03 | 2004-11-23 | Matsushita Electric Industrial Co., Ltd. | Non-Aqueous electrolyte secondary battery comprising composite particles |
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| JPH10284079A (en) * | 1997-02-06 | 1998-10-23 | Japan Storage Battery Co Ltd | Manufacture of host material and nonaqueous electrolyte secondary battery |
| US6824920B1 (en) | 1997-06-03 | 2004-11-30 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous electrolyte secondary battery comprising composite particles |
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| US6506520B1 (en) | 1998-12-02 | 2003-01-14 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous electrolyte secondary battery |
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| JP2014504000A (en) * | 2010-12-22 | 2014-02-13 | オーシャンズ キング ライティング サイエンスアンドテクノロジー カンパニー リミテッド | Electrode plate and method for preparing the same, super capacitor and lithium ion battery |
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