JP3071856B2 - Method for producing negative electrode material for lithium battery - Google Patents
Method for producing negative electrode material for lithium batteryInfo
- Publication number
- JP3071856B2 JP3071856B2 JP3089327A JP8932791A JP3071856B2 JP 3071856 B2 JP3071856 B2 JP 3071856B2 JP 3089327 A JP3089327 A JP 3089327A JP 8932791 A JP8932791 A JP 8932791A JP 3071856 B2 JP3071856 B2 JP 3071856B2
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- lithium
- carbon
- electrode material
- lithium battery
- 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.)
- Expired - Fee Related
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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- 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
- H01M4/04—Processes of manufacture in general
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/043—Processes of manufacture in general involving compressing or compaction
-
- 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
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、リチウム電池に用いら
れる負極材料の製造方法に関する。The present invention relates to a method for producing a negative electrode material used for a lithium battery.
【０００２】[0002]
【従来の技術】従来、リチウム電池に用いられる負極材
料としては、リチウム、リチウム−アルミニウム合金、
グラファイトなどの炭素があり、また炭素繊維にリチウ
ムを、電気的方法により、あるいはリチウム塩溶液に含
浸させたものも知られている。2. Description of the Related Art Conventionally, lithium, lithium-aluminum alloy,
There is carbon such as graphite, and carbon fibers in which lithium is impregnated with an electric method or in a lithium salt solution are also known.
【０００３】[0003]
【発明が解決しようとする課題】上記のようなリチウ
ム、リチウム−アルミニウム、炭素などの負極では、充
分なサイクル寿命が得られなかったり、充分な電池電圧
が得られないという問題がある。また、電気化学的方法
やリチウム塩含浸法により炭素にリチウムを吸蔵させた
負極もあるが、ＬｉＣ6 という結晶構造を作り出すこと
が困難で、従って容量が充分に出せない。本発明は、こ
のような従来技術の課題を背景になされたもので、電気
化学的方法やリチウム塩溶液に炭素を含浸するといった
方法をとらずに、炭素をリチウム化することができ、従
って高容量で安定性に優れている負極材料を得ることが
できるリチウム電池用負極材料の製造方法を提供するこ
とを目的とする。The above-mentioned negative electrodes of lithium, lithium-aluminum, carbon and the like have a problem that a sufficient cycle life cannot be obtained or a sufficient battery voltage cannot be obtained. In addition, there are negative electrodes in which lithium is occluded in carbon by an electrochemical method or a lithium salt impregnation method, but it is difficult to create a crystal structure of LiC 6 , so that sufficient capacity cannot be obtained. The present invention has been made in view of such problems of the prior art, and can lithiate carbon without using an electrochemical method or a method of impregnating the lithium salt solution with carbon. An object of the present invention is to provide a method for producing a negative electrode material for a lithium battery, which can obtain a negative electrode material having excellent capacity and stability.
【０００４】[0004]
【課題を解決するための手段】本発明は、１９０〜５０
０℃の溶融リチウム中に、炭素材料を１０〜１２０分間
浸漬し、リチウム化炭素となすことを特徴とするリチウ
ム電池用負極材料の製造方法を提供するものである。Means for Solving the Problems The present invention is, from 190 to 50
A method for producing a negative electrode material for a lithium battery, characterized in that a carbon material is immersed in molten lithium at 0 ° C for 10 to 120 minutes to form lithiated carbon .
【０００５】本発明の製造方法に用いられる炭素材料
は、繊維、板状、棒状、スポンジなどのどのような形状
であってもよい。本発明では、このような炭素材料を、
好ましくはアセトンなどの有機溶媒で洗浄したのち、所
定時間、アルゴンガス、ヘリウムガスなどの不活性雰囲
気中で、１９０〜５００℃の溶融リチウムに浸漬する。
溶融リチウムの温度は、好ましくは２５０〜４５０℃で
ある。また、浸漬時間は、１０〜１２０分、好ましくは
１０〜６０分である。これらの条件の最適値は、炭素材
料やその形状、大きさによって異なり、スポンジ状炭素
材料（ポーラスカーボン；厚さ２mm）の場合、温度３０
０℃程度で３０〜６０分が最適である。浸漬終了後、冷
却し、表面に付着したリチウムを除去する。[0005] The carbon material used in the production method of the present invention may be in any shape such as fiber, plate, rod, sponge and the like. In the present invention, such a carbon material is
Preferably, after washing with an organic solvent such as acetone, it is immersed in molten lithium at 190 to 500 ° C. for a predetermined time in an inert atmosphere such as an argon gas or a helium gas.
The temperature of the molten lithium is preferably from 250 to 450C. The immersion time is 10 to 120 minutes, preferably 10 to 60 minutes. The optimum values of these conditions differ depending on the carbon material and its shape and size.
Optimally at about 0 ° C. for 30 to 60 minutes. After the immersion, cooling is performed to remove lithium adhering to the surface.
【０００６】本発明の製造方法により、すなわち溶融し
たリチウムへの炭素材料の浸漬によるリチウムの炭素中
への熱拡散作用により、得られたリチウム化炭素は、理
論値であるＬｉＣ6 の結晶構造を持ったものと、ＬｉＣ
7-12の混合物であり、これを用いることにより、容量が
大きく、かつ安定性に優れた負極材料を得ることができ
る。このようなリチウム化炭素を得ることは、従来より
行われている、電気化学的方法、あるいはリチウム塩溶
液に含浸させる方法では非常に難しかったものである。The lithiated carbon obtained by the production method of the present invention, that is, by the thermal diffusion effect of lithium into carbon by immersing the carbon material in molten lithium, has a theoretical LiC 6 crystal structure. What you have, LiC
7-12 , and by using this, a negative electrode material having a large capacity and excellent stability can be obtained. Obtaining such lithiated carbon has been very difficult with the conventional electrochemical method or the method of impregnating with a lithium salt solution.
【０００７】このようにして得られたリチウム化炭素を
負極に用いる場合、そのまま負極として用いることもで
きるし、これを粉砕して粉状とし結合剤を加えて製品化
することもでき、どのような形状の負極も非常に容易に
作製することができる。例えば、本発明のリチウム化炭
素を負極に用いる場合、該リチウム化炭素粉末に導電性
バインダーを加え、ＳＵＳ板などの集電体に膜状に塗布
し、負極とすることができる。When the lithiated carbon thus obtained is used for a negative electrode, it can be used as it is as a negative electrode, or it can be pulverized into a powder form and added with a binder to produce a product. A negative electrode having an arbitrary shape can be produced very easily. For example, when the lithiated carbon of the present invention is used for a negative electrode , a conductive binder is added to the lithiated carbon powder, and the resultant is applied in a film form to a current collector such as a SUS plate to form a negative electrode.
【０００８】本発明の負極材料は、リチウム電池の負極
として広範囲に使用でき、各種の正極、例えば二酸化マ
ンガン、五酸化バナジウムなどの酸化物やポリピロール
などの有機高分子を用いた正極などと組み合わせて使用
することができる。電解質溶液としては、ＬｉＣｌ
Ｏ4 、ＬｉＡｓＦ6 、ＬｉＢＦ4 などのＬｉ塩などの電
解質を溶媒により溶解された状態で使用され、この溶媒
としては、プロピレンカーボネート、エチレンカーボネ
ート、テトラヒドロフラン、ジメトキシエタンなどの１
種または２種以上の混合物を用いることができる。電池
システムとしては、多種の正極、電解質溶液との組み合
わせが可能である。また、電解質溶液の代わりにゲル状
電解質を用いることもできる。The negative electrode material of the present invention can be widely used as a negative electrode of a lithium battery, and can be used in combination with various positive electrodes, for example, a positive electrode using an oxide such as manganese dioxide or vanadium pentoxide or an organic polymer such as polypyrrole. Can be used. As the electrolyte solution, LiCl
An electrolyte such as an O 4 , LiAsF 6 or LiBF 4 salt such as LiBF 4 is used in a state of being dissolved by a solvent. Examples of the solvent include propylene carbonate, ethylene carbonate, tetrahydrofuran and dimethoxyethane.
Species or a mixture of two or more can be used. The battery system can be combined with various kinds of positive electrodes and electrolyte solutions. Also, a gel electrolyte can be used instead of the electrolyte solution.
【０００９】以下、本発明の負極材料を使用したリチウ
ム電池を図面を参照してさらに詳細に説明する。すなわ
ち、本発明の負極材料を使用したリチウム電池は、図１
に示すように一対の正極板１０と負極板２０とを側面封
止材３０を介して離反状態に配置し、前記正極板１０の
裏面に正極材料４０を圧着して正極５０を形成し、一方
負極板２０の裏面側にリチウム化炭素からなる負極材料
６０を圧着して負極７０を形成し、しかもこれらの正極
材料４０と負極材料６０との間にセパレータ８０を介在
させたものである。Hereinafter, a lithium battery using the negative electrode material of the present invention will be described in more detail with reference to the drawings. That is, the lithium battery using the negative electrode material of the present invention has a structure shown in FIG.
As shown in FIG. 2, a pair of the positive electrode plate 10 and the negative electrode plate 20 are arranged in a separated state via the side surface sealing material 30, and the positive electrode material 40 is pressed on the back surface of the positive electrode plate 10 to form the positive electrode 50. The negative electrode material 60 made of lithiated carbon is pressure-bonded to the back side of the negative electrode plate 20 to form a negative electrode 70, and a separator 80 is interposed between the positive electrode material 40 and the negative electrode material 60.
【００１０】前記正極板１０および負極板２０は、例え
ばＳＵＳ３０４などの導電性素材からなる基板である。
前記側面封止材３０は、正極板１０と負極板２０とを離
反状態に支持して電池の側面を封止するエポキシ樹脂な
どからなる絶縁部材である。前記正極５０に用いられる
正極材料４０としは、リチウム含有五酸化バナジウム、
リチウム含有二酸化マンガンなどの焼成体粒子を使用す
ることができる。前記セパレータ８０としては、多孔質
で電解液（前記電解質＋溶媒）を通したり含んだりする
ことできる、例えばポリテトラフルオロエチレン、ポリ
プロピレン、ポリエチレンなどの合成樹脂製の不織布、
織布、編布などが使用でる。なお、このセパレータ８０
および電解液の代わりに、シート状の高分子架橋体に電
解質を含浸させたゲル状電解質を用いることもできる。The positive electrode plate 10 and the negative electrode plate 20 are substrates made of a conductive material such as SUS304.
The side surface sealing material 30 is an insulating member made of an epoxy resin or the like that supports the positive electrode plate 10 and the negative electrode plate 20 in a separated state and seals the side surface of the battery. As the positive electrode material 40 used for the positive electrode 50, lithium-containing vanadium pentoxide,
Fired particles such as lithium-containing manganese dioxide can be used. As the separator 80, a nonwoven fabric made of a synthetic resin such as polytetrafluoroethylene, polypropylene, or polyethylene, which is porous and can pass or contain an electrolyte solution (the electrolyte and the solvent),
Woven cloth, knitted cloth, etc. can be used. This separator 80
Instead of the electrolyte, a gel electrolyte in which a sheet-like crosslinked polymer is impregnated with an electrolyte can also be used.
【００１１】[0011]
【実施例】以下、本発明の実施例を説明するが、本発明
は必ずしもこの実施例に限定されない。 実施例１ 炭素材料として、ポーラスカーボンＳＧ−２００〔昭和
電工（株）製〕を用い、これをアセトンで洗浄したの
ち、アルゴンガス雰囲気下において、４００℃の溶融リ
チウム中へ浸漬した。３０分後、これを引上げ、材料表
面の余分なリチウムを落とし、室温で冷却した。炭素材
料の表面で生成したリチウム化炭素を削りとり、これの
Ｘ線回折を行った。結果を図２〜３に示す。図２がリチ
ウム化前のもの、図３がリチウム化したものであり、Ｌ
ｉＣ6 が生成していることが分かる。DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described below, but the present invention is not necessarily limited to these embodiments. Example 1 Porous carbon SG-200 (manufactured by Showa Denko KK) was used as a carbon material, washed with acetone, and then immersed in molten lithium at 400 ° C. in an argon gas atmosphere. After 30 minutes, this was pulled up, the excess lithium on the material surface was dropped and cooled at room temperature. The lithiated carbon generated on the surface of the carbon material was scraped off and subjected to X-ray diffraction. The results are shown in FIGS. FIG. 2 shows a state before lithiation, and FIG. 3 shows a state after lithiation.
It can be seen that iC 6 is generated.
【００１２】次いで、得られたリチウム化炭素を用い、
電池を作製した。すなわち、前記のようにして得られた
リチウム化炭素を乳鉢で粉砕し、これにアセチレンブラ
ック、フッ素樹脂（テフロン）を、各々１０重量％加え
混合した。これを、圧粉成形し、ＳＵＳ３０４に圧着し
て負極とした。また、五酸化バナジウムの粉末とバイン
ダーとを混合してペースト状になしたものを、ＳＵＳ３
０４に塗布し、乾燥したものを正極とし、プロピレンカ
ーボネートとジメトキシエタンとの溶媒にＬｉＣｌＯ4
を１モル／ｌ溶解したものを電解液として使用し、図１
のような電池を組み立てた。この負極の容量は、１４２
Ａｈ／ｋｇを示した。さらに、１．５ｍＡ／cm以上の電
流密度をもって放電することが確認された。Next, using the obtained lithiated carbon,
A battery was manufactured. That is, the lithiated carbon obtained as described above was pulverized in a mortar, and acetylene black and a fluororesin (Teflon) were added and mixed with 10% by weight of each. This was compacted and pressed to SUS304 to form a negative electrode. Further, a mixture of a powder of vanadium pentoxide and a binder to form a paste is used as SUS3.
04, dried and used as a positive electrode, and LiClO 4 in a solvent of propylene carbonate and dimethoxyethane.
1 mol / l was used as an electrolytic solution, and FIG.
A battery like that was assembled. The capacity of this negative electrode is 142
Ah / kg was indicated. Further, it was confirmed that the battery was discharged with a current density of 1.5 mA / cm or more.
【００１３】[0013]
【発明の効果】本発明の製造方法によれば、炭素材料の
リチウム化が電気化学的方法よりもはるかに容易になさ
れ、しかも得られたリチウム化炭素はＬｉＣ6 という構
造を持つため、高容量で安定性に優れたリチウム電池用
負極材料を得ることができる。According to the production method of the present invention, the lithiation of the carbon material is much easier than the electrochemical method, and the obtained lithiated carbon has a structure of LiC 6 , so that a high capacity is obtained. Thus, a negative electrode material for a lithium battery having excellent stability can be obtained.
【図１】本発明のリチウム電池用負極材料を使用したリ
チウム電池の断面図である。FIG. 1 is a cross-sectional view of a lithium battery using a negative electrode material for a lithium battery of the present invention.
【図２】実施例１で行ったＸ線回折のパターンであり、
リチウム溶融液に浸漬前の炭素のＸ線回折パターンであ
る。FIG. 2 is a pattern of X-ray diffraction performed in Example 1,
5 is an X-ray diffraction pattern of carbon before immersion in a lithium melt.
【図３】実施例１で行ったＸ線回折のパターンであり、
リチウム溶融液に浸漬後のリチウム化炭素のＸ線回折パ
ターンである。FIG. 3 is a pattern of X-ray diffraction performed in Example 1,
5 is an X-ray diffraction pattern of lithiated carbon after immersion in a lithium melt.
４０ 正極材料 ６０ 負極材料 ８０ セパレータ 40 positive electrode material 60 negative electrode material 80 separator
───────────────────────────────────────────────────── フロントページの続き (72)発明者 出町 敦 埼玉県和光市中央一丁目４番１号 株式 会社 本田技術研究所内 (72)発明者 野口 実 埼玉県和光市中央一丁目４番１号 株式 会社 本田技術研究所内 (56)参考文献 特開 平４−109554（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 4/02 - 4/04 H01M 4/58 H01M 10/40 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Atsushi Demachi 1-4-1 Chuo, Wako-shi, Saitama Stock Company Inside Honda R & D Co., Ltd. (72) Minoru Noguchi 1-4-1 Chuo, Wako-shi, Saitama Stock (56) References JP-A-4-109554 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) H01M 4/02-4/04 H01M 4/58 H01M 10/40
Claims (1)
炭素材料を１０〜１２０分間浸漬し、リチウム化炭素と
なすことを特徴とするリチウム電池用負極材料の製造方
法。1. In molten lithium at 190 to 500 ° C. ,
Immerse the carbon material for 10 to 120 minutes ,
A method for producing a negative electrode material for a lithium battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3089327A JP3071856B2 (en) | 1991-03-29 | 1991-03-29 | Method for producing negative electrode material for lithium battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3089327A JP3071856B2 (en) | 1991-03-29 | 1991-03-29 | Method for producing negative electrode material for lithium battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05151969A JPH05151969A (en) | 1993-06-18 |
| JP3071856B2 true JP3071856B2 (en) | 2000-07-31 |
Family
ID=13967581
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3089327A Expired - Fee Related JP3071856B2 (en) | 1991-03-29 | 1991-03-29 | Method for producing negative electrode material for lithium battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3071856B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102324509B (en) * | 2011-09-20 | 2013-07-24 | 北京工业大学 | Preparation method of metastable phase LiC6 alloy |
| CN109309197A (en) * | 2017-07-26 | 2019-02-05 | 中能中科（天津）新能源科技有限公司 | Improve the method and its equipment of the yield of lithium carbon composite mass production |
-
1991
- 1991-03-29 JP JP3089327A patent/JP3071856B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05151969A (en) | 1993-06-18 |
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