JPH05234583A - Negative electrode for lithium secondary battery and lithium secondary battery using it - Google Patents
Negative electrode for lithium secondary battery and lithium secondary battery using itInfo
- Publication number
- JPH05234583A JPH05234583A JP4037542A JP3754292A JPH05234583A JP H05234583 A JPH05234583 A JP H05234583A JP 4037542 A JP4037542 A JP 4037542A JP 3754292 A JP3754292 A JP 3754292A JP H05234583 A JPH05234583 A JP H05234583A
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- lithium
- secondary battery
- lithium secondary
- thin film
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Cell Electrode Carriers And Collectors (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、リチウム二次電池用負
極およびそれを構成要素とするリチウム二次電池、さら
に詳しくは、エネルギー密度・放電特性・サイクル特性
に優れたリチウム二次電池用の負極およびそれを構成要
素とするリチウム二次電池に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a negative electrode for a lithium secondary battery and a lithium secondary battery having the negative electrode for the lithium secondary battery, and more specifically, a lithium secondary battery having excellent energy density, discharge characteristics and cycle characteristics. The present invention relates to a negative electrode and a lithium secondary battery including the negative electrode.
【０００２】[0002]
【従来の技術】負極活物質としてリチウム、正極活物質
として金属カルコゲン化物、金属酸化物を用い、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も
のを用いた、いわゆるリチウム二次電池は高エネルギー
密度型二次電池の一種として注目され、盛んに研究が行
われている。2. Description of the Related Art A so-called lithium secondary battery using lithium as a negative electrode active material, a metal chalcogenide or a metal oxide as a positive electrode active material, and an electrolyte prepared by dissolving various salts in an aprotic organic solvent. Batteries have attracted attention as a type of high energy density secondary battery and are being actively researched.
【０００３】しかしながら、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如き単体で用いら
れることが多く、充放電を繰り返すうちに、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。However, in the conventional lithium battery,
Lithium as a negative electrode active material is often used as a simple substance such as a foil, and has a drawback that the cycle life of charge / discharge is short because dendritic lithium is deposited and both electrodes are short-circuited during repeated charge / discharge.
【０００４】そこで、アルミニウムや、鉛、カドミウム
及びインジウムを含む可融性合金を用い、充電時にリチ
ウムを合金として析出させ、放電時には合金からリチウ
ムを溶解させる方法が提案されている[米国特許第４０
０２４９号(１９７７)参照]。しかし、このような方法
では、樹枝状リチウムの折出は抑止できるが、エネルギ
ー密度は低下する。Therefore, a method has been proposed in which a fusible alloy containing aluminum, lead, cadmium and indium is used to deposit lithium as an alloy during charging and to dissolve lithium from the alloy during discharging [US Pat. No. 40.
0249 (1977)]. However, such a method can suppress the protrusion of dendritic lithium, but lowers the energy density.
【０００５】さらに、放電容量を向上させることを目的
に、リチウムをカーボン材に担持させようという試みも
種々行われている。例えば、種々の繊維状、あるいは粉
末状のカーボン材を用いる試みがなされている[東芝電
池および三菱油化共願の特開昭６３−１１４０５６号
(１９８８)、三菱瓦斯化学出願の特開昭６２−２６８０
５６号(１９８７)参照]。Further, various attempts have been made to support lithium on a carbon material for the purpose of improving discharge capacity. For example, attempts have been made to use various fibrous or powdery carbon materials [Toshiba Battery and Mitsubishi Petrochemical Co-Application No. 63-114056.
(1988), Japanese Patent Application Laid-Open No. 62-2680 filed by Mitsubishi Gas Chemical Co., Ltd.
56 (1987)].
【０００６】[0006]
【発明が解決しようとする課題】しかしながら、カーボ
ン材をリチウムの担持体とした負極を用いた従来のリチ
ウム二次電池では、溶媒和力の大きな有機溶媒を電解液
に使用した場合に、リチウムイオンが溶媒和された状態
でいわゆるカーボン層間にインターカレーション(コイ
ンターカレーション)し、その結果、カーボン層が損傷
を受けたり破壊するなどして、サイクル特性の急速な劣
化を引き起こすという問題生じていた。従って、この点
の改良が要望されていた。However, in a conventional lithium secondary battery using a negative electrode in which a carbon material is a lithium carrier, a lithium ion is used when an organic solvent having a large solvation power is used as an electrolytic solution. Has been solvated, so-called intercalation between carbon layers (co-intercalation), resulting in damage or destruction of the carbon layer, causing rapid deterioration of cycle characteristics. .. Therefore, improvement of this point has been demanded.
【０００７】[0007]
【課題を解決するための手段】かかる事情に鑑み、本発
明者らは、鋭意研究を重ねた結果、負極活物質担持体と
してのカーボン材の表面を特定の金属を含む金属薄膜で
コーティングすることにより、意外にも前記コインター
カレーションを防止できることを見出し、本発明を完成
するに至った。In view of the above circumstances, the inventors of the present invention have conducted extensive studies, and as a result, coated the surface of a carbon material as a negative electrode active material carrier with a metal thin film containing a specific metal. As a result, it was surprisingly found that the co-intercalation can be prevented, and the present invention has been completed.
【０００８】即ち、本発明は、リチウムと合金化可能な
金属を含む金属薄膜でコーティングしたカーボン材を負
極活物質の担持体として用いたことを特徴とするリチウ
ム二次電池用負極を提供するものである。That is, the present invention provides a negative electrode for a lithium secondary battery, characterized in that a carbon material coated with a metal thin film containing a metal capable of alloying with lithium is used as a carrier for a negative electrode active material. Is.
【０００９】まず、本発明のリチウム二次電池用負極で
使用するカーボン材は特に限定されるものではなく、従
来より負極活物質たるリチウムの担持体として用いられ
てきたいずれの種類のものも使用できる。また、その形
態としては、例えば、粉末、繊維状、フィルム状等、お
よびこれらを単一であるいは複合物として成形したもの
などが挙げられる。First, the carbon material used in the negative electrode for a lithium secondary battery of the present invention is not particularly limited, and any kind of carbon material conventionally used as a carrier for lithium as a negative electrode active material may be used. it can. Examples of the form include powder, fiber, film, and the like, and those formed by molding these alone or as a composite.
【００１０】本発明では、かかるカーボン材の表面を金
属薄膜でコーティングする。この金属薄膜はリチウムと
可融性の、換言すれば、リチウムと合金化可能な金属を
含むものであり、そのような合金化可能な金属の単体ま
たはそれらのみを成分とする合金あるいはそれらを主成
分とする合金が該当する。ことに、結晶格子中における
リチウムの易動度の観点より、アルミニウムを含む金属
薄膜が好ましい。In the present invention, the surface of the carbon material is coated with a metal thin film. This metal thin film contains a metal that is fusible with lithium, in other words, a metal that can be alloyed with lithium, and a simple substance of such an alloyable metal, an alloy containing only these metals, or a main component thereof. The alloy used as a component is applicable. In particular, a metal thin film containing aluminum is preferable from the viewpoint of the mobility of lithium in the crystal lattice.
【００１１】コーティングを行なう段階としては、粉体
や繊維状等の原料段階のカーボン材に施してもよく、あ
るいは賦形された状態やさらに電極にまで加工された状
態で行ってもよい。作業性等の観点からは、賦形後ある
いは加工後に行なうのが便利である。The step of coating may be performed on a carbon material in a raw material stage such as powder or fibrous material, or may be performed in a shaped state or further processed into an electrode. From the viewpoint of workability, it is convenient to carry out after shaping or processing.
【００１２】コーティングの方法としては、例えば、化
学メッキ法、電気化学メッキ法等の湿式法や、真空蒸着
法、陰極スパッタリング法、イオンプレーティング法等
の乾式法などが適用できる。例えば、賦形後カーボン材
あるいは加工後のカーボン材の場合には、電気化学メッ
キ法の一つである溶融塩電解法が適用できる。なお、金
属薄膜の厚さは、カーボン材の種類やコーティング法等
にもよるが、通常、０.０１〜１μｍの範囲の厚さが好
ましい。As a coating method, for example, a wet method such as a chemical plating method or an electrochemical plating method, or a dry method such as a vacuum deposition method, a cathode sputtering method or an ion plating method can be applied. For example, in the case of a carbon material after shaping or a carbon material after processing, a molten salt electrolysis method which is one of electrochemical plating methods can be applied. The thickness of the metal thin film is preferably in the range of 0.01 to 1 μm, although it depends on the type of carbon material and the coating method.
【００１３】コーティングを施した原料カーボン材また
は賦形後カーボン材を使用し、常法に従って電極に形成
・加工し、あるいは加工後電極にコーティングを施した
後、カーボン材にリチウムを担持させることによって本
発明のリチウム二次電池用負極を得ることができる。カ
ーボン材にリチウムを担持させる方法としては、例え
ば、カーボン電極と金属リチウムを電解液中で短絡させ
るという方法がある。By using a coated carbon material or a shaped carbon material, an electrode is formed and processed according to a conventional method, or after the processed electrode is coated, the carbon material is loaded with lithium. The negative electrode for lithium secondary batteries of the present invention can be obtained. As a method of supporting lithium on the carbon material, for example, there is a method of short-circuiting the carbon electrode and metallic lithium in the electrolytic solution.
【００１４】かくして得られる本発明のリチウム二次電
池用負極は、リチウム二次電池の構成要素として好適に
用いられ、プロピレンカーボネート、エチレンカーボネ
ート、γ−ブチロラクトン、テトラヒドロフラン、２−
メチルテトラヒドロフラン、ジオキソラン、４−メチル
ジオキサラン、スルホラン、アセトニトリル等の電解
液、ＭｎＯ2、Ｖ2Ｏ5等の正極と組み合わせて、常法に
より、二次電池を作成することができる。かかるリチウ
ム二次電池も本発明の範囲内のものであり、ポータブル
電子機器等の電源、その他各種メモリーやソーラーのバ
ックアップ等に好適に使用することができる。The thus obtained negative electrode for a lithium secondary battery of the present invention is suitably used as a constituent element of a lithium secondary battery, and includes propylene carbonate, ethylene carbonate, γ-butyrolactone, tetrahydrofuran and 2-
A secondary battery can be prepared by a conventional method in combination with an electrolytic solution such as methyltetrahydrofuran, dioxolane, 4-methyldioxalane, sulfolane or acetonitrile, and a positive electrode such as MnO 2 or V 2 O 5 . Such a lithium secondary battery is also within the scope of the present invention, and can be suitably used as a power source for portable electronic devices and the like, backup of various memories and solars, and the like.
【００１５】本発明においては、前記したごとく、カー
ボン材の表面にリチウムと合金化可能な金属を含む金属
薄膜をコーティングすることにより、充電時に電極表面
のリチウムイオンがまず金属薄膜と反応して合金化し、
その際にリチウムイオンに溶媒和していた有機溶媒が脱
離し、その後金属薄膜内を拡散したリチウムイオンのみ
がカーボン材に吸蔵される。その結果、インターカレー
ションが防がれ、インターカレーションに基づくカーボ
ン層の損傷・破損あるいはサイクル特性の急激な劣化と
いった性能劣化が回避される。In the present invention, as described above, by coating the surface of the carbon material with a metal thin film containing a metal capable of alloying with lithium, lithium ions on the electrode surface first react with the metal thin film during charging, and the alloy is formed. Turned into
At that time, the organic solvent solvated with lithium ions is desorbed, and only the lithium ions diffused in the metal thin film are occluded in the carbon material. As a result, intercalation is prevented, and performance deterioration such as damage / damage to the carbon layer or rapid deterioration of cycle characteristics due to intercalation is avoided.
【００１６】[0016]
【実施例】以下に実施例を挙げて本発明をさらに詳しく
説明する。負極体の作成 黒鉛化炭素繊維(ドナック（株）製、ＳＧ−２４１)のミ
ルド(０.１mm長)９９重量部、ディスパージョンタイプ
のポリテトラフルオロエチレン(ダイキン工業（株）
製、Ｄ−１)１重量部を混合し、液相で均一に撹拌した
後、乾燥し、ペースト状とした。この負極物質２〜３mg
をニッケルメッシュに圧着させ、さらに、２００℃で６
時間の真空乾燥を行った。得られた電極をカソード、炭
素電極をアノードとし、６５０℃の恒温槽で浴電圧１.
８Ｖを印加するＡlＣl3の溶融塩電解によりカソード電
極表面にアルミニウム薄膜を生成させた。得られた負極
体を作用極として、対極及び参照極にリチウム金属を用
いて、電位が０Ｖになるまで負極体にリチウムを吸蔵さ
せた。この条件(電解液、電流密度等)は、後記電池特性
の測定の条件と同様にして行った。EXAMPLES The present invention will be described in more detail with reference to the following examples. Preparation of negative electrode body 99 parts by weight of graphitized carbon fiber (SG-241 manufactured by Donac Co., Ltd.) milled (0.1 mm length), dispersion type polytetrafluoroethylene (Daikin Industries, Ltd.)
Manufactured by D-1) was mixed with 1 part by weight, and the mixture was uniformly stirred in the liquid phase and then dried to obtain a paste. 2-3 mg of this negative electrode material
Is crimped onto a nickel mesh and further at 200 ° C for 6
Vacuum dried for an hour. The obtained electrode was used as the cathode and the carbon electrode was used as the anode, and the bath voltage was 1.50 in a constant temperature bath at 650 ° C.
An aluminum thin film was formed on the surface of the cathode electrode by molten salt electrolysis of AlCl 3 applying 8V. Using the obtained negative electrode body as a working electrode, lithium metal was used for the counter electrode and the reference electrode, and lithium was stored in the negative electrode body until the potential became 0V. The conditions (electrolyte, current density, etc.) were the same as the conditions for measuring battery characteristics described later.
【００１７】電池の作成 図１にその断面図を示すごとく、前記で得られた負極体
（１）の他、正極体（２）として電解二酸化マンガン、
電解液として１モル／リットルの濃度にＬiＣlＯ4を溶
解させたプロピレンカーボネート、セパレータ（３）と
してポリプロピレン不織布、さらにケース（４）、封口
板（５）および絶縁パッキング（６）を用いてリチウム
二次電池を作成した。Preparation of Battery As shown in the sectional view of FIG. 1, in addition to the negative electrode body (1) obtained above, electrolytic manganese dioxide as a positive electrode body (2),
Using a propylene carbonate in which LiClO 4 is dissolved at a concentration of 1 mol / liter as an electrolytic solution, a polypropylene nonwoven fabric as a separator (3), a case (4), a sealing plate (5) and an insulating packing (6), a lithium secondary I made a battery.
【００１８】電池特性の測定 本発明の負極を用いた前記リチウム二次電池の放電特性
を測定した。測定は、通常、５０mＡ／g(負極カーボン
基準)の定電流充放電下で行い、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。対照として、
未処理の上記黒鉛化炭素繊維を構成要素とする従来の負
極を用いたリチウム二次電池についても同条件下で測定
を行った。結果を表１に示す。 Measurement of Battery Characteristics The discharge characteristics of the lithium secondary battery using the negative electrode of the present invention were measured. The measurement was usually performed under a constant current charge / discharge of 50 mA / g (negative electrode carbon standard), and the discharge capacity was the capacity until the battery voltage dropped to 2.0V. As a control
A lithium secondary battery using a conventional negative electrode having the untreated graphitized carbon fiber as a constituent element was also measured under the same conditions. The results are shown in Table 1.
【表１】 表１から明らかなごとく、金属コーティングを施さない
従来の負極を用いたリチウム二次電池と比較して、本発
明の負極を用いたリチウム二次電池は、コインターカレ
ーションに基づくとみられるサイクル特性の劣化が見ら
れず、従来にない優れたサイクル特性を有することが判
明した。[Table 1] As is clear from Table 1, the lithium secondary battery using the negative electrode of the present invention has a cycle characteristic which is considered to be based on co-intercalation, as compared with the lithium secondary battery using the conventional negative electrode without metal coating. It was found that no deterioration was observed and that it had excellent cycle characteristics that were unprecedented.
【００１９】[0019]
【発明の効果】本発明により、脱溶媒和によりコインタ
ーカレーションが防止でき、サイクル特性に優れた高性
能なリチウム二次電池およびそのための負極が提供され
る。EFFECTS OF THE INVENTION The present invention provides a high-performance lithium secondary battery which can prevent co-intercalation by desolvation and has excellent cycle characteristics, and a negative electrode therefor.
【図面の簡単な説明】[Brief description of drawings]
【図１】 実施例で作成した本発明の負極を用いたリチ
ウム二次電池の断面図である。FIG. 1 is a cross-sectional view of a lithium secondary battery using the negative electrode of the present invention prepared in an example.
１：負極、２：正極、３：セパレータ、４：ケース、
５：封口板、６：絶縁パッキング1: negative electrode, 2: positive electrode, 3: separator, 4: case,
5: Sealing plate, 6: Insulation packing
Claims (3)
薄膜でコーティングしたカーボン材を負極活物質の担持
体として用いたことを特徴とするリチウム二次電池用負
極。1. A negative electrode for a lithium secondary battery, wherein a carbon material coated with a metal thin film containing a metal capable of alloying with lithium is used as a carrier for a negative electrode active material.
ニウムであることを特徴とする請求項１記載のリチウム
二次電池用負極。2. The negative electrode for a lithium secondary battery according to claim 1, wherein the metal capable of alloying with lithium is aluminum.
とを特徴とするリチウム二次電池。3. A lithium secondary battery comprising the negative electrode according to claim 1 as a constituent element.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4037542A JPH05234583A (en) | 1992-02-25 | 1992-02-25 | Negative electrode for lithium secondary battery and lithium secondary battery using it |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4037542A JPH05234583A (en) | 1992-02-25 | 1992-02-25 | Negative electrode for lithium secondary battery and lithium secondary battery using it |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05234583A true JPH05234583A (en) | 1993-09-10 |
Family
ID=12500413
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4037542A Pending JPH05234583A (en) | 1992-02-25 | 1992-02-25 | Negative electrode for lithium secondary battery and lithium secondary battery using it |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05234583A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002082567A1 (en) * | 2001-04-09 | 2002-10-17 | Sony Corporation | Negative electrode for non-aqueous electrolyte secondary cell and non-aqueous electrolyte secondary cell using the negative electrode |
| KR100378013B1 (en) * | 1999-09-28 | 2003-03-29 | 삼성에스디아이 주식회사 | A anode material for lithium secondary battery, an electrode for lithium secondary battery, a lithium secondary battery and the method of preparing anode material for lithium secondary battery |
| JP2004192829A (en) * | 2002-12-06 | 2004-07-08 | Nec Corp | Secondary battery |
| US6890685B2 (en) | 2001-03-27 | 2005-05-10 | Nec Corporation | Anode for secondary battery and secondary battery therewith |
| US7163768B2 (en) | 2002-08-29 | 2007-01-16 | Nec Corporation | Electrolyte solution for secondary battery and secondary battery using the same |
| EP2109177A1 (en) | 2008-04-07 | 2009-10-14 | NEC TOKIN Corporation | Non-aqueous electrolyte and non-aqueous electrolyte secondary battery using the same |
| US7662519B2 (en) | 2003-09-16 | 2010-02-16 | Nec Corporation | Non-aqueous electrolyte secondary battery |
| US8227116B2 (en) | 2003-12-15 | 2012-07-24 | Nec Corporation | Secondary battery |
| US8357471B2 (en) | 2003-12-15 | 2013-01-22 | Nec Corporation | Secondary battery using an electrolyte solution |
| CN112563604A (en) * | 2020-12-09 | 2021-03-26 | 中南大学 | Method for regenerating anode material of waste lithium ion battery |
-
1992
- 1992-02-25 JP JP4037542A patent/JPH05234583A/en active Pending
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100378013B1 (en) * | 1999-09-28 | 2003-03-29 | 삼성에스디아이 주식회사 | A anode material for lithium secondary battery, an electrode for lithium secondary battery, a lithium secondary battery and the method of preparing anode material for lithium secondary battery |
| US6890685B2 (en) | 2001-03-27 | 2005-05-10 | Nec Corporation | Anode for secondary battery and secondary battery therewith |
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| CN112563604A (en) * | 2020-12-09 | 2021-03-26 | 中南大学 | Method for regenerating anode material of waste lithium ion battery |
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