JPH05275076A - Negative electrode for lithium secondary battery - Google Patents
Negative electrode for lithium secondary batteryInfo
- Publication number
- JPH05275076A JPH05275076A JP4066404A JP6640492A JPH05275076A JP H05275076 A JPH05275076 A JP H05275076A JP 4066404 A JP4066404 A JP 4066404A JP 6640492 A JP6640492 A JP 6640492A JP H05275076 A JPH05275076 A JP H05275076A
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- secondary battery
- electrode body
- lithium secondary
- carbon
- 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
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 42
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000010409 thin film Substances 0.000 claims abstract description 21
- 229910003481 amorphous carbon Inorganic materials 0.000 claims abstract description 16
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 12
- 239000011248 coating agent Substances 0.000 claims abstract description 4
- 238000000576 coating method Methods 0.000 claims abstract description 4
- 239000000470 constituent Substances 0.000 claims description 7
- 238000005229 chemical vapour deposition Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052799 carbon Inorganic materials 0.000 abstract description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 4
- 239000011357 graphitized carbon fiber Substances 0.000 abstract description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract description 4
- 239000007791 liquid phase Substances 0.000 abstract description 3
- 238000012856 packing Methods 0.000 abstract description 3
- -1 polypropylene Polymers 0.000 abstract description 3
- 238000007789 sealing Methods 0.000 abstract description 3
- 239000004743 Polypropylene Substances 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract description 2
- 229910052759 nickel Inorganic materials 0.000 abstract description 2
- 229920001155 polypropylene Polymers 0.000 abstract description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 abstract description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 abstract description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000013543 active substance Substances 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 abstract 1
- 239000004744 fabric Substances 0.000 abstract 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 abstract 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 abstract 1
- 238000001291 vacuum drying Methods 0.000 abstract 1
- 239000007773 negative electrode material Substances 0.000 description 10
- 238000009830 intercalation Methods 0.000 description 5
- 238000007599 discharging Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000004770 chalcogenides Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 229910000743 fusible alloy Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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
- Chemical Vapour Deposition (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、エネルギー密度、放電
特性、サイクル特性などに優れたリチウム二次電池およ
びそれに用いる負極用材料に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithium secondary battery excellent in energy density, discharge characteristics, cycle characteristics and the like, and a negative electrode material used therein.
【０００２】[0002]
【従来技術】負極活物質としてリチウムを使用し、正極
活物質として金属カルコゲン化物或いは金属酸化物を使
用し、電解液として非プロトン性有機溶媒に種々の塩を
溶解させた溶液を使用する、いわゆるリチウム二次電池
は、高エネルギー密度型二次電池として注目され、盛ん
に研究されている。2. Description of the Related Art Lithium is used as a negative electrode active material, metal chalcogenide or metal oxide is used as a positive electrode active material, and a solution prepared by dissolving various salts in an aprotic organic solvent is used as an electrolytic solution. BACKGROUND ART A lithium secondary battery has attracted attention as a high energy density secondary battery and has been actively studied.
【０００３】従来のリチウム電池では、負極活物質とし
てのリチウムは、箔状の単体で用いられることが多く、
充放電を繰り返すと、樹枝状リチウムが析出して両極が
短絡するため、充放電のサイクル寿命が短いという欠点
を有する。In a conventional lithium battery, lithium as a negative electrode active material is often used as a foil-shaped simple substance,
When charging and discharging are repeated, dendritic lithium is deposited and both electrodes are short-circuited, which has a drawback that the cycle life of charging and discharging is short.
【０００４】樹枝状リチウムの析出を防止するために、
負極活物質としてアルミニウム或いは鉛、カドミウムお
よびインジウムを含む可融性合金を使用して、充電時に
リチウムを合金として析出させ、放電時にこの合金から
リチウムを溶解させる方法が提案されている（米国特許
４００２４９２号参照）。しかしながら、このような方
法によれば、樹枝状リチウムの析出は抑止できるもの
の、電池のエネルギー密度が低下する。In order to prevent the deposition of dendritic lithium,
A method has been proposed in which a fusible alloy containing aluminum or lead, cadmium, and indium is used as a negative electrode active material, lithium is deposited as an alloy during charging, and lithium is dissolved from this alloy during discharging (US Pat. No. 4,002492). No.). However, according to such a method, although the deposition of dendritic lithium can be suppressed, the energy density of the battery is lowered.
【０００５】さらに、放電容量を向上させるために、カ
ーボン材にリチウムを担持させることが試みられてい
る。例えば、繊維状乃至粉末状のカーボン材にリチウム
を担持させることが提案されている（特開昭６３−１１
４０５６号公報、特開昭６２−２６８０５６号公報参
照）。しかしながら、カーボン材をリチウムの担持体と
して使用するリチウム二次電池においても、有機溶媒と
して溶媒和する力の大きなものを使用する場合には、溶
媒和された状態でリチウムイオンがカーボン層間にイン
ターカレートする（コインターカレーション）という問
題が生ずる。その結果、カーボン層が損傷を受けたり、
破壊されたりして、電池のサイクル特性の急速な劣化を
引き起こす。Further, in order to improve the discharge capacity, it has been attempted to support lithium on a carbon material. For example, it has been proposed to support lithium on a fibrous or powdery carbon material (Japanese Patent Laid-Open No. 63-11).
No. 4056, JP-A No. 62-268056). However, even in a lithium secondary battery that uses a carbon material as a carrier for lithium, when an organic solvent having a large solvating power is used, lithium ions are intercalated between the carbon layers in a solvated state. The problem of co-intercalation occurs. As a result, the carbon layer is damaged,
If it is destroyed, it causes rapid deterioration of the cycle characteristics of the battery.
【０００６】[0006]
【発明が解決しようとする課題】従って、本発明は、リ
チウム二次電池の特性を大幅に改善し得る新しい負極活
物質を提供することを主な目的とする。SUMMARY OF THE INVENTION Therefore, the main object of the present invention is to provide a new negative electrode active material capable of significantly improving the characteristics of a lithium secondary battery.
【０００７】[0007]
【課題を解決するための手段】本発明者は、上記のよう
な技術の現状に鑑みて鋭意研究を重ねた結果、リチウム
二次電池において負極の構成要素として使用されるカー
ボン材の表面をアモルファス炭素の薄膜でコーティング
することにより、カーボン層間へのインターカレーショ
ンが防止され、その目的を達成し得ることを見出した。The present inventor has conducted extensive studies in view of the above-mentioned state of the art, and as a result, the surface of a carbon material used as a constituent element of a negative electrode in a lithium secondary battery is amorphous. It has been found that by coating with a thin film of carbon, intercalation between carbon layers can be prevented and the purpose can be achieved.
【０００８】即ち、本発明は、下記のリチウム二次電池
およびその負極材料を提供するものである： １．負極の構成要素として用いられるカーボン材の表面
をアモルファス炭素の薄膜でコーティングしたリチウム
二次電池用の負極。That is, the present invention provides the following lithium secondary battery and its negative electrode material: A negative electrode for a lithium secondary battery in which the surface of a carbon material used as a constituent element of the negative electrode is coated with a thin film of amorphous carbon.
【０００９】２．アモルファス炭素の薄膜をＣＶＤ法に
より形成してなる上記項１に記載のリチウム二次電池用
の負極。2. 2. The negative electrode for a lithium secondary battery according to item 1, wherein a thin film of amorphous carbon is formed by a CVD method.
【００１０】３．カーボン材の表面をアモルファス炭素
の薄膜でコーティングした材料を負極の構成要素とする
リチウム二次電池。3. A lithium secondary battery in which a material obtained by coating the surface of a carbon material with a thin film of amorphous carbon is used as a constituent element of a negative electrode.
【００１１】４．アモルファス炭素の薄膜をＣＶＤ法に
より形成してなる上記項３に記載のリチウム二次電池。4. Item 4. The lithium secondary battery according to Item 3, wherein a thin film of amorphous carbon is formed by a CVD method.
【００１２】本発明において、負極の基本構成要素とし
て用いられるカーボン材の由来（ピッチ系、石油系、Ｐ
ＡＮ系など）、種類（炭素繊維、黒鉛化炭素繊維な
ど）、形態（粉末、繊維状、ペレット、電極などの成形
体など）などは、特に制限されない。In the present invention, the origin of the carbon material used as the basic constituent element of the negative electrode (pitch-based, petroleum-based, P-based
There is no particular limitation on the AN type, etc.), the type (carbon fiber, graphitized carbon fiber, etc.), the form (powder, fibrous form, pellet, molded body such as electrode).
【００１３】本発明においては、上記のカーボン材の表
面にアモルファス炭素の薄膜を形成する。アモルファス
炭素薄膜は、リチウムのインターカレーション反応を起
こさないでリチウムを吸着するか、或いはインターカレ
ーションしてもコインターカレーションしないという性
質を具備している。その結果、このアモルファス炭素薄
膜を通り抜ける際にリチウムイオンに溶媒和していた溶
媒が脱離するので、溶媒和された状態でリチウムイオン
がカーボン層にインターカレーション（コインターカレ
ーション）しなくなり、その結果、カーボン層が損傷さ
れたり、破壊されたりして、電池のサイクル特性が急速
に劣化することが回避される。また、形成された炭素隔
膜自体も、リチウムを吸蔵することができるので、単位
当たりの放電容量は、炭素以外の薄膜を使用する場合に
比して、増加する。In the present invention, a thin film of amorphous carbon is formed on the surface of the above carbon material. The amorphous carbon thin film has the property of adsorbing lithium without causing an intercalation reaction of lithium, or not co-intercalating even if intercalated. As a result, when passing through this amorphous carbon thin film, the solvent that had been solvated with lithium ions is desorbed, so that lithium ions do not intercalate (co-intercalate) with the carbon layer in the solvated state. As a result, it is avoided that the carbon layer is damaged or destroyed and the cycle characteristics of the battery are rapidly deteriorated. In addition, since the formed carbon membrane itself can also occlude lithium, the discharge capacity per unit is increased as compared with the case where a thin film other than carbon is used.
【００１４】薄膜を形成する手法は、この様なアモルフ
ァス炭素が形成される限り、限定されるものではない
が、ＣＶＤ法、液相反応法などが例示される。The method for forming the thin film is not limited as long as such amorphous carbon is formed, but a CVD method, a liquid phase reaction method and the like are exemplified.
【００１５】薄膜の厚さは、特に限定されるものではな
いが、通常０．０１〜１０μｍ程度である。The thickness of the thin film is not particularly limited, but is usually about 0.01 to 10 μm.
【００１６】本発明によるアモルファス炭素薄膜を形成
されたカーボン材は、常法に従ってリチウムを付与さ
れ、リチウム二次電池の負極活物質として使用される。The carbon material on which the amorphous carbon thin film according to the present invention is formed is provided with lithium according to a conventional method and used as a negative electrode active material of a lithium secondary battery.
【００１７】[0017]
【発明の効果】本発明によれば、負極活物質のカーボン
層の損傷、破壊などによりリチウム二次電池のサイクル
特性が急速に劣化することが抑制される。また、エネル
ギー密度を高めることができるので、負極活物質の単位
当たりの放電容量は、アモルファス炭素以外の薄膜を使
用する場合に比して、増加する。According to the present invention, rapid deterioration of the cycle characteristics of a lithium secondary battery due to damage or destruction of the carbon layer of the negative electrode active material can be suppressed. Further, since the energy density can be increased, the discharge capacity per unit of the negative electrode active material is increased as compared with the case where a thin film other than amorphous carbon is used.
【００１８】[0018]
【実施例】以下に実施例を示し、本発明の特徴とすると
ころをより一層明確にする。EXAMPLES Examples will be shown below to further clarify the features of the present invention.
【００１９】実施例１負極の作製 黒鉛化炭素繊維（ＳＧ−２４１、（株）ドナック製）の
ミルド（０．１mm）９９重量部とＰＴＦＥのディスパー
ジョン（Ｄ−１、ダイキン工業（株）製）１重量部（固
形分として）とを液相で均一に混合攪拌した後、乾燥さ
せ、ペースト状とした。この様にして得られた負極物質
３mgをニッケルメッシュに圧着して、負極体を作製し、
２００℃で６時間真空乾燥した。Example 1 Preparation of Negative Electrode Milled (0.1 mm) 99 parts by weight of graphitized carbon fiber (SG-241, manufactured by Donac Co., Ltd.) and PTFE dispersion (D-1, manufactured by Daikin Industries, Ltd.) ) 1 part by weight (as solid content) was uniformly mixed and stirred in a liquid phase, and then dried to obtain a paste. 3 mg of the negative electrode material thus obtained was pressure bonded to a nickel mesh to prepare a negative electrode body,
It was vacuum dried at 200 ° C. for 6 hours.
【００２０】次いで、上記で得られた負極体を赤外線加
熱方式のイメージ炉に収容し、１０００℃でアルゴンを
ベースとするベンゼン蒸気を送給して、負極体表面に熱
分解炭素のアモルファス薄膜を生成させた。Next, the negative electrode body obtained above was placed in an infrared heating type image furnace, and benzene vapor based on argon was fed at 1000 ° C. to form an amorphous thin film of pyrolytic carbon on the surface of the negative electrode body. Was generated.
【００２１】得られた負極体を作用極とし、対極および
参照極にリチウム金属を用いて、電位が０Ｖとなるまで
負極体にリチウムを吸蔵させた。この操作における条件
（電解液、電流密度など）は、以後行なう電池特性の測
定条件と同様にした。The obtained negative electrode body was used as a working electrode, and lithium metal was used for the counter electrode and the reference electrode, and lithium was occluded in the negative electrode body until the potential became 0V. The conditions (electrolyte solution, current density, etc.) in this operation were the same as the measurement conditions of the battery characteristics performed later.
【００２２】電池の作製 次いで、下記の構成材料を使用して、図１に断面図とし
て示すリチウム二次電池を作製した。Preparation of Battery Next, the following constituent materials were used to prepare a lithium secondary battery shown in a sectional view in FIG.
【００２３】正極体１…電解二酸化マンガン セパレータ２…ポリプロピレン不織布 負極体３…上記で得られたもの 電解液…ＬｉＣｌＯ4 を１モル／ｌの濃度で溶解させた
プロピレンカーボネート 図１において、リチウム二次電池は、上記以外の構成部
品として、電池は、ケース４、封口板５、絶縁パッキン
グ６を備えている。Cathode body 1 ... Electrolytic manganese dioxide separator 2 ... Polypropylene nonwoven fabric Negative body 3 ... What was obtained above Electrolyte solution ... Propylene carbonate in which LiClO 4 was dissolved at a concentration of 1 mol / l In FIG. The battery is provided with a case 4, a sealing plate 5, and an insulating packing 6 as components other than the above.
【００２４】電池特性の測定 上記で得られたリチウム二次電池の放電特性を調べるた
めに５０ｍＡ／ｇ（負極カーボン基準）の定電流条件下
で充放電を行なった。放電容量は、電池電圧が２．０Ｖ
に低下するまでの容量とした。 Measurement of Battery Characteristics In order to investigate the discharge characteristics of the lithium secondary battery obtained above, charging / discharging was performed under a constant current condition of 50 mA / g (negative electrode carbon standard). Battery capacity is 2.0V
It was set as the capacity until it decreased.
【００２５】なお、対照として、アモルファス炭素薄膜
を形成しない黒鉛化炭素繊維（上記と同様のもの）を使
用する負極体を用いた従来型のリチウム二次電池のつい
ても、同一条件下に電池特性の測定を行なった。As a control, a conventional lithium secondary battery using a negative electrode body using a graphitized carbon fiber (similar to the above) that does not form an amorphous carbon thin film has the same battery characteristics under the same conditions. Was measured.
【００２６】結果は、表１に示す通りである。The results are shown in Table 1.
【００２７】 表 １ 放 電 容 量（Ａｈ／ｋｇ） １サイクル １０サイクル 実施例１ ２２０ ２１５ 対照 ２１０ １５５ 表１に示す結果から明らかな様に、本発明によるリチウ
ム二次電池は、従来のリチウム二次電池に比して、コイ
ンターカレーションによるものと推測されるサイクル劣
化が殆ど認められない。Table 1 Discharge capacity (Ah / kg) 1 cycle 10 cycles Example 1 220 215 Control 210 155 As is apparent from the results shown in Table 1, the lithium secondary battery according to the present invention is a conventional lithium secondary battery. Compared to the secondary battery, the cycle deterioration presumed to be caused by co-intercalation is hardly observed.
【図１】図１は、実施例１で得られた本発明のリチウム
二次電池の断面図である。FIG. 1 is a cross-sectional view of the lithium secondary battery of the present invention obtained in Example 1.
１…正極 ２…セパレータ ３…負極 ４…ケース ５…封口板 ６…絶縁パッキング 1 ... Positive electrode 2 ... Separator 3 ... Negative electrode 4 ... Case 5 ... Sealing plate 6 ... Insulating packing
フロントページの続き (72)発明者 樋口 俊一 大阪府箕面市牧落５丁目８番２−212 (72)発明者 馬淵 昭弘 大阪府大阪市中央区平野町四丁目１番２号 大阪瓦斯株式会社内 (72)発明者 中川 喜照 大阪府大阪市中央区平野町四丁目１番２号 大阪瓦斯株式会社内Front page continuation (72) Inventor Shunichi Higuchi 5-8-2, Makihama, Minoh-shi, Osaka 2-212 (72) Inventor Akihiro Mabuchi 4-1-2, Hiranocho, Chuo-ku, Osaka-shi, Osaka 72) Inventor, Yoshiteru Nakagawa, Osaka Gas Co., Ltd. 4-1-2 Hirano-cho, Chuo-ku, Osaka
Claims (4)
材の表面をアモルファス炭素の薄膜でコーティングした
リチウム二次電池用の負極。1. A negative electrode for a lithium secondary battery in which the surface of a carbon material used as a constituent element of the negative electrode is coated with a thin film of amorphous carbon.
形成してなる請求項１に記載のリチウム二次電池用の負
極。2. The negative electrode for a lithium secondary battery according to claim 1, wherein a thin film of amorphous carbon is formed by a CVD method.
膜でコーティングした材料を負極の構成要素とするリチ
ウム二次電池。3. A lithium secondary battery comprising a material obtained by coating the surface of a carbon material with a thin film of amorphous carbon as a constituent element of a negative electrode.
形成してなる請求項３に記載のリチウム二次電池。4. The lithium secondary battery according to claim 3, wherein a thin film of amorphous carbon is formed by a CVD method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4066404A JPH05275076A (en) | 1992-03-24 | 1992-03-24 | Negative electrode for lithium secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4066404A JPH05275076A (en) | 1992-03-24 | 1992-03-24 | Negative electrode for lithium secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05275076A true JPH05275076A (en) | 1993-10-22 |
Family
ID=13314837
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4066404A Pending JPH05275076A (en) | 1992-03-24 | 1992-03-24 | Negative electrode for lithium secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05275076A (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996032751A1 (en) * | 1995-04-10 | 1996-10-17 | Daikin Industries, Ltd. | Water-repellency agent for cells and cells |
| EP0752729A3 (en) * | 1995-06-27 | 1997-07-02 | Hitachi Ltd | Secondary lithium battery |
| JPH1040914A (en) * | 1996-05-23 | 1998-02-13 | Sharp Corp | Manufacture of nonaqueous secondary battery and negative pole active substance |
| US6040092A (en) * | 1995-12-25 | 2000-03-21 | Sharp Kabushiki Kaisha | Nonaqueous secondary battery |
| US6432583B1 (en) | 1998-07-31 | 2002-08-13 | Mitsui Mining Co., Ltd. | Anode material for lithium secondary battery, process for production thereof, and lithium secondary battery |
| JP2002241117A (en) * | 2001-02-13 | 2002-08-28 | Osaka Gas Co Ltd | Graphite based carbon material, manufacturing method therefor, negative electrode material for lithium secondary battery, and lithium secondary battery |
| WO2003012898A1 (en) * | 2001-07-31 | 2003-02-13 | Nec Corporation | Negative pole for secondary cell, secondary cell using the negative pole, and negative pole manufacturing method |
| US6764791B2 (en) | 2000-07-19 | 2004-07-20 | Sanyo Electric Co., Ltd. | Rechargeable lithium battery |
| KR100511232B1 (en) * | 2001-09-03 | 2005-08-31 | 닛본 덴끼 가부시끼가이샤 | Anode for a secondary battery |
| JP2009193924A (en) * | 2008-02-18 | 2009-08-27 | Nec Tokin Corp | Negative electrode for lithium ion secondary battery and lithium ion secondary battery using the same |
| JP2010153346A (en) * | 2008-05-27 | 2010-07-08 | Kobe Steel Ltd | Negative electrode material for lithium ion secondary battery, its manufacturing method, and lithium-ion secondary battery |
| US7781103B2 (en) * | 2004-04-12 | 2010-08-24 | Samsung Sdi Co., Ltd. | Negative active material for lithium secondary battery and negative electrode and lithium secondary battery comprising same |
| US7816037B2 (en) | 2002-01-25 | 2010-10-19 | Toyo Tanso Co., Ltd. | Anode material for lithium ion secondary battery |
| JP2019160730A (en) * | 2018-03-16 | 2019-09-19 | トヨタ自動車株式会社 | Lithium metal secondary battery |
| US11217783B2 (en) | 2017-12-22 | 2022-01-04 | Samsung Sdi Co., Ltd. | Negative electrode active material for lithium secondary battery, negative electrode including the same, and lithium secondary battery including the negative electrode |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61277157A (en) * | 1985-05-31 | 1986-12-08 | Sanyo Chem Ind Ltd | Secondary cell |
| JPS6313282A (en) * | 1986-07-02 | 1988-01-20 | Sharp Corp | Nonaqueous electrolyte secondary battery |
| JPS63244562A (en) * | 1987-03-30 | 1988-10-12 | Sharp Corp | Battery |
| JPH02174059A (en) * | 1988-12-26 | 1990-07-05 | Sumitomo Electric Ind Ltd | Positive electrode for lithium solid electrolyte battery and manufacture thereof |
| JPH03190053A (en) * | 1989-12-19 | 1991-08-20 | Sharp Corp | Manufacture of electrode |
| JPH04368778A (en) * | 1991-06-17 | 1992-12-21 | Sharp Corp | Carbon negative electrode for secondary battery |
-
1992
- 1992-03-24 JP JP4066404A patent/JPH05275076A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61277157A (en) * | 1985-05-31 | 1986-12-08 | Sanyo Chem Ind Ltd | Secondary cell |
| JPS6313282A (en) * | 1986-07-02 | 1988-01-20 | Sharp Corp | Nonaqueous electrolyte secondary battery |
| JPS63244562A (en) * | 1987-03-30 | 1988-10-12 | Sharp Corp | Battery |
| JPH02174059A (en) * | 1988-12-26 | 1990-07-05 | Sumitomo Electric Ind Ltd | Positive electrode for lithium solid electrolyte battery and manufacture thereof |
| JPH03190053A (en) * | 1989-12-19 | 1991-08-20 | Sharp Corp | Manufacture of electrode |
| JPH04368778A (en) * | 1991-06-17 | 1992-12-21 | Sharp Corp | Carbon negative electrode for secondary battery |
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996032751A1 (en) * | 1995-04-10 | 1996-10-17 | Daikin Industries, Ltd. | Water-repellency agent for cells and cells |
| US6156453A (en) * | 1995-04-10 | 2000-12-05 | Daikin Industries, Ltd. | Water-repelling agent for batteries and battery |
| CN1089955C (en) * | 1995-04-10 | 2002-08-28 | 大金工业株式会社 | Water-repellency agent for cells and cells |
| KR100337421B1 (en) * | 1995-04-10 | 2002-10-09 | 다이낑 고오교 가부시키가이샤 | Water repellent and battery |
| EP0752729A3 (en) * | 1995-06-27 | 1997-07-02 | Hitachi Ltd | Secondary lithium battery |
| US6040092A (en) * | 1995-12-25 | 2000-03-21 | Sharp Kabushiki Kaisha | Nonaqueous secondary battery |
| JPH1040914A (en) * | 1996-05-23 | 1998-02-13 | Sharp Corp | Manufacture of nonaqueous secondary battery and negative pole active substance |
| US6432583B1 (en) | 1998-07-31 | 2002-08-13 | Mitsui Mining Co., Ltd. | Anode material for lithium secondary battery, process for production thereof, and lithium secondary battery |
| US6764791B2 (en) | 2000-07-19 | 2004-07-20 | Sanyo Electric Co., Ltd. | Rechargeable lithium battery |
| JP2002241117A (en) * | 2001-02-13 | 2002-08-28 | Osaka Gas Co Ltd | Graphite based carbon material, manufacturing method therefor, negative electrode material for lithium secondary battery, and lithium secondary battery |
| JP2003115293A (en) * | 2001-07-31 | 2003-04-18 | Nec Corp | Negative electrode for secondary battery, secondary battery using it, and method of manufacturing negative electrode |
| WO2003012898A1 (en) * | 2001-07-31 | 2003-02-13 | Nec Corporation | Negative pole for secondary cell, secondary cell using the negative pole, and negative pole manufacturing method |
| US7202000B2 (en) | 2001-07-31 | 2007-04-10 | Nec Corporation | Anode for secondary battery, secondary battery using same and method for fabricating anode |
| KR100511232B1 (en) * | 2001-09-03 | 2005-08-31 | 닛본 덴끼 가부시끼가이샤 | Anode for a secondary battery |
| US7816037B2 (en) | 2002-01-25 | 2010-10-19 | Toyo Tanso Co., Ltd. | Anode material for lithium ion secondary battery |
| US7781103B2 (en) * | 2004-04-12 | 2010-08-24 | Samsung Sdi Co., Ltd. | Negative active material for lithium secondary battery and negative electrode and lithium secondary battery comprising same |
| US8110168B2 (en) | 2004-04-12 | 2012-02-07 | Samsung Sdi Co., Ltd. | Negative active material for lithium secondary battery and negative electrode and lithium secondary battery comprising same |
| US8440352B2 (en) | 2004-04-12 | 2013-05-14 | Samsung Sdi Co., Ltd. | Negative active material for lithium secondary battery and negative electrode and lithium secondary battery comprising same |
| JP2009193924A (en) * | 2008-02-18 | 2009-08-27 | Nec Tokin Corp | Negative electrode for lithium ion secondary battery and lithium ion secondary battery using the same |
| JP2010153346A (en) * | 2008-05-27 | 2010-07-08 | Kobe Steel Ltd | Negative electrode material for lithium ion secondary battery, its manufacturing method, and lithium-ion secondary battery |
| US11217783B2 (en) | 2017-12-22 | 2022-01-04 | Samsung Sdi Co., Ltd. | Negative electrode active material for lithium secondary battery, negative electrode including the same, and lithium secondary battery including the negative electrode |
| JP2019160730A (en) * | 2018-03-16 | 2019-09-19 | トヨタ自動車株式会社 | Lithium metal secondary battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2224514B1 (en) | Electric Storage Device, And Production Method Thereof | |
| Zhamu et al. | Reviving rechargeable lithium metal batteries: enabling next-generation high-energy and high-power cells | |
| KR20250078599A (en) | Negative electrode plate for sodium-ion battery, electrochemical apparatus, and electronic device | |
| JP6361599B2 (en) | Power storage device | |
| JPH05275077A (en) | Negative electrode for lithium secondary battery | |
| JPH05275076A (en) | Negative electrode for lithium secondary battery | |
| JP4426154B2 (en) | Method for producing electrode film and battery element including the electrode film | |
| FR2920255A1 (en) | LITHIUM ELECTROCHEMICAL GENERATOR OPERATING WITH AQUEOUS ELECTROLYTE. | |
| US20130280617A1 (en) | Gel electrode secondary cell | |
| Qin et al. | Solvent‐Engineered Scalable Production of Polysulfide‐Blocking Shields to Enhance Practical Lithium–Sulfur Batteries | |
| CN111785972A (en) | A kind of positive electrode material of zinc ion battery and its preparation method and application | |
| JPS61263069A (en) | Battery | |
| CN115548262A (en) | Negative pole piece, secondary battery and electric equipment | |
| CN114639797B (en) | Treatment method of negative electrode plate, sodium metal negative electrode plate and preparation device | |
| JP6832607B2 (en) | Power storage device and its charging method and manufacturing method | |
| JPH05234583A (en) | Negative electrode for lithium secondary battery and lithium secondary battery using it | |
| EP4481856A1 (en) | Lithium iron phosphate positive electrode active material, preparation method therefor, and lithium ion battery | |
| JPH1027601A (en) | Nonaqueous electrolyte secondary battery | |
| WO2023162942A1 (en) | Electrode forming composition | |
| WO2023282246A1 (en) | Composition for forming electrode | |
| JPH11185744A (en) | Nonaqueous electrolyte battery | |
| CN113964294A (en) | Lithium ion battery cathode and preparation method and application thereof | |
| JP6756258B2 (en) | Power storage device | |
| JPH04190557A (en) | Lithium secondary battery | |
| WO2020204728A1 (en) | Method for pre-lithiating a lithium-ion capacitor |