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JPH10294111A - Graphite carbon material coated with graphite for lithium secondary battery negative electrode material and its manufacture - Google Patents

Graphite carbon material coated with graphite for lithium secondary battery negative electrode material and its manufacture

Info

Publication number
JPH10294111A
JPH10294111A JP9115020A JP11502097A JPH10294111A JP H10294111 A JPH10294111 A JP H10294111A JP 9115020 A JP9115020 A JP 9115020A JP 11502097 A JP11502097 A JP 11502097A JP H10294111 A JPH10294111 A JP H10294111A
Authority
JP
Japan
Prior art keywords
graphite
pitch
coated
carbon
capacity
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.)
Granted
Application number
JP9115020A
Other languages
Japanese (ja)
Other versions
JP3054379B2 (en
Inventor
Akira Yokoyama
昭 横山
Takanobu Kawai
河井隆伸
Takashi Wakizaka
敬 脇阪
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Carbon Co Ltd
Original Assignee
Nippon Carbon Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nippon Carbon Co Ltd filed Critical Nippon Carbon Co Ltd
Priority to JP9115020A priority Critical patent/JP3054379B2/en
Publication of JPH10294111A publication Critical patent/JPH10294111A/en
Application granted granted Critical
Publication of JP3054379B2 publication Critical patent/JP3054379B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Landscapes

  • Carbon And Carbon Compounds (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

PROBLEM TO BE SOLVED: To provide a graphite carbon material coated with graphite having a large charge and discharge capacity and high cycle characteristics, and its manufacturing method. SOLUTION: Carbon or graphite powder particles of ratio a/b of a longer particle diameter (a) to a shorter diameter (b) being 1<=a/b<=3 and of an average particle diameter being 1-30 μm, are coated with coal or petroleum pitch on their surface; the pitch on the surfaces is made infusible, slightly crushed, carbonized and transformed into graphite. Since the entire powder particles are of graphite, they can maintain high potential in discharging; the graphite on the surfaces is of a pitch base having low capacity loss; the pore diameters and pore surface areas to attach and remove lithium ions are so controlled as to increase the capacity; micro pores are suppressed and their specific surface areas are decreased so that the decomposing reaction of the electrolyte can be suppressed.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【0001】[0001]

【産業上の利用分野】本発明は、リチウム二次電池に係
わり、詳しくは、負極材料として黒鉛を使用したリチウ
ム二次電池の高容量で容量ロスの少ない黒鉛質炭素材を
提供する。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithium secondary battery, and more particularly, to a graphitic carbon material having a high capacity and a small capacity loss for a lithium secondary battery using graphite as a negative electrode material.

【0002】[0002]

【従来の技術及び発明が解決しようとする課題】リチウ
ムイオン二次電池用負極材には、大きく分けて結晶化の
進んだ黒鉛質系と結晶化度の低い炭素質系又は難黒鉛化
性炭素とがあり、これらを用いたものが、既に上市され
て久しい。
2. Description of the Related Art A negative electrode material for a lithium ion secondary battery is roughly classified into a graphitic type having a high degree of crystallization and a carbon type or a non-graphitizable carbon having a low crystallinity. There is a thing that used these, and it has already been on the market for a long time.

【0003】これらは充放電曲線にそれぞれ特徴があ
り、例えば実際の搭載機器を駆動させるときの放電曲線
で比較してみると、黒鉛質系は3.6V程度の高電位を
保って放電し続け、放電末期に急激に電位が降下する。
[0003] Each of these has a characteristic in a charge / discharge curve. For example, when comparing the discharge curves when an actual mounted device is driven, the graphite-based material keeps discharging at a high potential of about 3.6 V. , The potential drops sharply at the end of discharge.

【0004】一方炭素質系又は難黒鉛化性炭素は4Vを
越える高電位から放電が始まり、放電時間と共に電位が
降下する。これから搭載される機器の要求諸元又は制御
回路等の設計思想の差などにより使い分けられている。
On the other hand, the discharge of carbonaceous or non-graphitizable carbon starts from a high potential exceeding 4 V, and the potential drops with the discharge time. They are properly used depending on the required specifications of the devices to be mounted or differences in the design concept of the control circuit and the like.

【0005】リチウムイオン二次電池の普及に伴い近年
携帯電話、ノート型パソコン等長時間使用が可能になる
よう電池容量の増大が求められている。従来の黒鉛質系
材料は理論容量372mAh/gに対し容量ロスがあり
上市されているものは270〜310mAh/gであ
る。
[0005] With the spread of lithium-ion secondary batteries, in recent years, there has been a demand for an increase in battery capacity so that mobile phones, notebook computers and the like can be used for a long time. Conventional graphite-based materials have a capacity loss of 372 mAh / g of theoretical capacity, and 270 to 310 mAh / g are commercially available.

【0006】一方炭素質系材料では黒鉛質系の容量を大
巾に上回る400〜850mAh/gの容量のものが報
告されているが、初回充放電での容量ロスが140〜2
50mAh/gを越えること、容量のうち電池電位の低
い部分が主で駆動上高電位を必要とする機器には不向き
である。
On the other hand, a carbonaceous material having a capacity of 400 to 850 mAh / g, which is much larger than the capacity of graphite, has been reported.
If it exceeds 50 mAh / g, it is unsuitable for a device which requires a high potential for driving mainly due to a low battery potential portion of the capacity.

【0007】更に充放電を繰返すサイクル特性で容量保
持率が低下していくなどの欠点がある。黒鉛粉末の表面
に炭素材を被覆する従来特許には下記がある。特開平5
−121066では面間隔d002 が0.337nm未満
の黒鉛の表面に面間隔d002 が0.337nm以上の炭
素質炭素を被覆したもの。
Further, there is a drawback that the capacity retention rate decreases due to the cycle characteristics of repeating charge and discharge. Conventional patents covering the surface of graphite powder with a carbon material include the following. JP 5
In the case of -12166, graphite having a plane spacing d 002 of less than 0.337 nm is coated with carbonaceous carbon having a plane spacing d 002 of 0.337 nm or more.

【0008】特開平6−84516では負極材料にX線
回折による面間隔のd002 が3.354Å以上でC軸方
向の結晶子の大きさが200Å以上の黒鉛表面をアモル
ファスカーボン層又はX線回折による面間隔d002
3.43Å以上でC軸方向の結晶子の大きさが200Å
以下のコークス層で被覆したものがある。
Japanese Patent Application Laid-Open No. 6-84516 discloses that a negative electrode material has a graphite surface having an interplanar spacing d 002 of 3.354 ° or more and a crystallite size of 200 ° or more in the C-axis direction of amorphous carbon layer or X-ray diffraction. 200Å is the magnitude of the C-axis direction of crystallites in terms spacing d 002 is more than 3.43Å by
Some are coated with the following coke layer.

【0009】この2方法では充放電容量は幾分高くなる
が、放電末期に端子(電池)電圧が低下するため一定電
圧で使用可能な電池容量は充放電容量の80%以下に止
まる。 また特開平8−180903では黒鉛粉末の表
面を無定形炭素で被覆したものがある。
In these two methods, the charge / discharge capacity is somewhat higher, but the terminal (battery) voltage drops at the end of discharge, so that the battery capacity usable at a constant voltage is less than 80% of the charge / discharge capacity. In Japanese Patent Application Laid-Open No. 8-180903, there is a graphite powder whose surface is coated with amorphous carbon.

【0010】この方法では単に放電末期に負極電位が上
昇して電池電圧が急激に低下するのを緩やかにし、再充
電のタイミングを適正にし充放電のサイクル特性を維持
するもので、本質的に充放電容量をアップするものでは
ない。
In this method, the negative electrode potential simply rises at the end of discharge and the battery voltage suddenly decreases, and the recharge timing is adjusted appropriately to maintain the charge / discharge cycle characteristics. It does not increase the discharge capacity.

【0011】以上3方法は放電末期の電池電圧の低下を
緩やかにする目的であって、本発明の充放電容量を増大
させる目的とは異なり、利用可能な充放電容量は逆に低
下し80%以下になってしまう欠点があり、市場要求の
一定電圧で大容量のリチウムイオン二次電池には不向き
である。
The above three methods are intended to moderate the decrease in the battery voltage at the end of discharge, and unlike the purpose of increasing the charge / discharge capacity of the present invention, the available charge / discharge capacity is reduced to 80%. It has the following disadvantages, and is not suitable for a large-capacity lithium-ion secondary battery at a constant voltage required by the market.

【0012】[0012]

【課題を解決するための手段】上記課題を達成するため
本発明の負極材用炭素材料は、炭素質又は黒鉛質炭素粉
末を基材として表面に石炭系又は石油系ピッチをコーテ
ィングし、軽度の酸化熱処理をし、解砕し、炭化焼成、
黒鉛化し、粉体全体を黒鉛質とする。
Means for Solving the Problems To achieve the above object, a carbon material for a negative electrode material of the present invention comprises a carbonaceous or graphitic carbon powder as a base material and a surface coated with coal or petroleum pitch. Oxidation heat treatment, crushing, carbonization firing,
It is graphitized and the whole powder is made of graphite.

【0013】このため、粉体表面が二重構造となり界面
部分にリチウムイオンをドープするポア部分が生成し充
放電容量を増せる。表層部分を容量ロスの少ないピッチ
ベースの黒鉛材とするため、放電時高い端子(電池)電
圧を放電終了まで続ける。
For this reason, the powder surface has a double structure, and a pore portion for doping lithium ions is formed at the interface portion, thereby increasing the charge / discharge capacity. In order to make the surface layer a pitch-based graphite material with a small capacity loss, a high terminal (battery) voltage at the time of discharge is continued until the end of discharge.

【0014】ピッチベースの黒鉛材で基材の黒鉛粉末を
被覆するため比表面積が小さくマイクロポアーを抑えら
れることから電解液との反応が低くなり、電解液の分解
を抑えることが出来る。
Since the graphite powder of the base material is coated with the pitch-based graphite material, the specific surface area is small and the micropores can be suppressed, so that the reaction with the electrolytic solution is reduced and the decomposition of the electrolytic solution can be suppressed.

【0015】容量増加の理論は判然としないが、表層の
ピッチベース黒鉛材の形態がリチウムイオンの直径より
も大きいポア径を多数包含するものとなるため、リチウ
ムイオンの脱着が容易となり、炭素材表面の反応容量が
増大するものと推定している。
Although the theory of the capacity increase is not clear, the shape of the surface pitch-based graphite material includes a large number of pore diameters larger than the diameter of lithium ions, so that lithium ions can be easily desorbed and carbon material can be easily removed. It is estimated that the surface reaction capacity increases.

【0016】これは表面積の大きい活性炭を用いても大
容量ものが得られていないことから活性炭の極微細なマ
イクロポアはリチウムイオンの脱着には不適当で、むし
ろイオンの脱着は炭素材内部のポアでなく炭素材外表面
の脱着が主体と考えられる。
This is because, even if activated carbon having a large surface area is used, a large-capacity one cannot be obtained, so that ultrafine micropores of activated carbon are unsuitable for desorption of lithium ions. It is thought that the desorption of the outer surface of the carbon material, not the pores, is mainly involved.

【0017】同種の電荷を持つリチウムイオンは互いに
反発しながら炭素材外表面に存在するため炭素材内部の
マイクロポアには出入りできないと推定される。本発明
により、リチウムイオンの脱着に実際に寄与する炭素材
外表面積を増加させることにより電池容量を増大させ、
電解液の分解を促進させるマイクロポアや内部クラック
を減少させることが出来る。
It is presumed that lithium ions having the same kind of charge are present on the outer surface of the carbon material while repelling each other, and cannot enter or leave the micropores inside the carbon material. According to the present invention, the battery capacity is increased by increasing the outer surface area of the carbon material that actually contributes to the desorption of lithium ions,
Micropores and internal cracks that promote decomposition of the electrolytic solution can be reduced.

【0018】[0018]

【実施例】以下、本発明を実施例により詳細に説明す
る。
DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to embodiments.

【0019】[0019]

【実施例1】石油系コークスを粉砕し、整粒し、平均粒
子径13μm、6〜32μmが全体の70vol%とな
るような粉末を得た。粒子の長径aと短径の比がa/b
=3である。
Example 1 Petroleum coke was pulverized and sized to obtain a powder having an average particle diameter of 13 μm and 6 to 32 μm of 70 vol% of the whole. The ratio of the major axis a to the minor axis is a / b
= 3.

【0020】この粉末100重量部に対して平均粒子径
10μmに粉砕した軟化点300℃のメソフェーズピッ
チ粉末25重量部をブレンダーに仕込み均一に混合させ
た。次いでこの混合物を擂潰機に移し5時間メカノケミ
カル反応を行い、コークス粉末の周囲にメソフェーズピ
ッチをコーティングした。
To 100 parts by weight of this powder, 25 parts by weight of a mesophase pitch powder having a softening point of 300 ° C. pulverized to an average particle diameter of 10 μm was charged into a blender and mixed uniformly. Next, the mixture was transferred to a crusher and subjected to a mechanochemical reaction for 5 hours to coat a mesophase pitch around the coke powder.

【0021】これを空気中で徐々に昇温し、最終的に2
80℃で処理し、コーティングされたメソフェーズピッ
チ部分を熱不溶融化した。
The temperature is gradually raised in the air, and finally
The coated mesophase pitch portion was treated at 80 ° C. to be thermally infused.

【0022】全体を軽くほぐして解砕処理した後、窒素
雰囲気下1000℃で焼成後、更に黒鉛化炉に移し、ア
ルゴン雰囲気下3000℃で処理して全体が黒鉛構造を
有する二層状黒鉛粉末を得た。
After the whole is lightly crushed and crushed, it is baked at 1000 ° C. in a nitrogen atmosphere, further transferred to a graphitization furnace, and treated at 3000 ° C. in an argon atmosphere to obtain a two-layered graphite powder having a graphite structure as a whole. Obtained.

【0023】[0023]

【実施例2】人造黒鉛ブロックを粉砕及び整粒して粒子
の長径aと短径bの比がa/b=1.6、平均粒子径1
2μm、6〜32μmが全体の60vol%となるよう
な粉末を得た。この粉末100重量部に対して実施例1
で用いたメソフェーズピッチを15重量部を使い、実施
例1と同様の処理を行った。
Example 2 An artificial graphite block was pulverized and sized to obtain a particle having a ratio of a / b = 1.6 of a major axis to a minor axis b of 1.6 and an average particle diameter of 1.
A powder was obtained in which 2 μm and 6 to 32 μm accounted for 60 vol% of the whole. Example 1 based on 100 parts by weight of this powder
The same processing as in Example 1 was performed using 15 parts by weight of the mesophase pitch used in the above.

【0024】[0024]

【実施例3】実施例2で用いた人造黒鉛粉末100重量
部に対して、軟化点260℃の光学的等方性ピッチの平
均粒径11μmとしたもの15重量部を用いた他は実施
例1と同様に行った。
Example 3 The procedure of Example 2 was repeated except that 100 parts by weight of the artificial graphite powder used in Example 2 and 15 parts by weight of an optically isotropic pitch having a softening point of 260 ° C. and an average particle size of 11 μm were used. Performed similarly to 1.

【0025】[0025]

【実施例4】実施例2で用いた人造黒鉛粉末100重量
部を、これの20重量部に相当する石炭系バインダーピ
ッチのキシレン可溶分をキシレンに溶解した溶液中に投
入撹拌した。次いでこれをスプレードライヤーにかけ基
材の周囲にバインダーピッチをコーティングした。
Example 4 100 parts by weight of the artificial graphite powder used in Example 2 were charged and stirred in a solution in which xylene-soluble components of coal-based binder pitch equivalent to 20 parts by weight were dissolved in xylene. This was then placed in a spray drier to coat a binder pitch around the substrate.

【0026】ガラス製容器に移し変え50℃の加温下で
三塩化ヨウ素をガス化させたものを吹き込むことによっ
てコーティング層を不溶融化させた。あとは、実施例1
の方法に従って最終的に3000℃で処理して黒鉛粉末
を得た。
The coating layer was transferred to a glass container and blown with gasified iodine trichloride at a temperature of 50 ° C. to make the coating layer infusible. After that, Example 1
Finally, the powder was treated at 3000 ° C. to obtain a graphite powder.

【0027】[0027]

【比較例1】実施例1で行った方法と同様に処理を行っ
たが、コークス粉末100重量部に対して用いたメソフ
ェーズピッチが5重量部とした。
Comparative Example 1 The same treatment as in Example 1 was performed, except that the mesophase pitch used was 5 parts by weight per 100 parts by weight of the coke powder.

【比較例2】実施例2で使った人造黒鉛粉末をそのまま
擂潰機に投入して5時間磨砕処理した。
Comparative Example 2 The artificial graphite powder used in Example 2 was directly charged into a grinder and ground for 5 hours.

【0028】[0028]

【比較例3】実施例2で使った人造黒鉛粉末100重量
部と平均粒径10μmのメソフェーズピッチ粉末を熱不
溶融化後最終的に3000℃で処理した粉末20重量部
をブレンダーに投入して混合した。
Comparative Example 3 100 parts by weight of the artificial graphite powder used in Example 2 and 20 parts by weight of a mesophase pitch powder having an average particle diameter of 10 μm which were heat-infused and finally treated at 3000 ° C. were put into a blender. Mixed.

【0029】[0029]

【比較例4】実施例2で行ったものを最終的処理を30
00℃とせず1000℃に留めて得た。
[Comparative Example 4] The final processing performed in Example 2 was 30
The temperature was kept at 1000 ° C instead of 00 ° C.

【0030】[0030]

【比較例5】粒子長径aと短径bとの比がa/b>10
であるような天然黒鉛粉末(平均粒径18μm)を基材
とし、この基材100重量部に対して軟化点260℃の
光学的等方性ピッチ15重量部を用いて擂潰機で5時間
メカノケミカル反応を行った。a/bが大きすぎうまく
コーティングできなかった。
Comparative Example 5 The ratio of the major axis a to the minor axis b is a / b> 10.
A natural graphite powder (average particle size: 18 μm) is used as a base material, and 15 parts by weight of an optically isotropic pitch having a softening point of 260 ° C. is used for 5 hours with respect to 100 parts by weight of the base material using a crusher. A mechanochemical reaction was performed. a / b was too large to coat successfully.

【0031】[0031]

【比較例6】実施例1と同じ材料を用いて石油系コーク
ス粉末100重量部に対して、メソフェーズピッチ粉を
40重量部加えて調製した他は実施例1と同様の処理を
行った。
Comparative Example 6 The same treatment as in Example 1 was carried out except that the same material as in Example 1 was used, except that 40 parts by weight of mesophase pitch powder was added to 100 parts by weight of petroleum-based coke powder.

【0032】[0032]

【比較例7】実施例1で用いたメソフェーズピッチ粉だ
けを空気酸化した後Ar中で3000℃で処理し、黒鉛
粉末を得た。
Comparative Example 7 Only the mesophase pitch powder used in Example 1 was oxidized by air and then treated in Ar at 3000 ° C. to obtain a graphite powder.

【比較例8】実施例1で用いたコークス粉だけをAr中
で3000℃で処理し黒鉛粉末を得た。
Comparative Example 8 Only the coke powder used in Example 1 was treated at 3000 ° C. in Ar to obtain a graphite powder.

【0033】各実施例及び比較例のサンプルについて次
の様にしてテストセルを作って充放電特性を評価した。
炭素粉末90重量部とポリフッ化ビニリデン10重量部
にN−メチル−2−ピロリドンを併せて三本ロールで練
り、ペースト化し、これをコーターを用いて銅箔上に塗
布し、乾燥させた後、銅箔より剥離させ3c〓の面積に
なるように円形に打ち抜き、ニッケル網と共に加圧成形
して作った。
With respect to the samples of the respective examples and comparative examples, test cells were prepared in the following manner, and charge / discharge characteristics were evaluated.
N-methyl-2-pyrrolidone was combined with 90 parts by weight of carbon powder and 10 parts by weight of polyvinylidene fluoride, kneaded with a three-roll mill, pasted, applied on a copper foil using a coater, and dried. It was peeled off from the copper foil, punched out in a circular shape so as to have an area of 3 cm, and formed by pressing together with a nickel net.

【0034】対極としてLi金属を用い、電解液として
1MLiClO4 −EC/DEC(体積比1:1)を用
いて二極式試験セルを構成し、定電流で充放電サイクル
試験を行った。測定範囲は0〜1.5V、電流密度0.
1mA/c〓、温度30℃である。結果を表1に示し
た。
A bipolar test cell was constructed using Li metal as a counter electrode and 1M LiClO 4 -EC / DEC (volume ratio 1: 1) as an electrolytic solution, and a charge / discharge cycle test was performed at a constant current. The measurement range is 0 to 1.5 V, and the current density is 0.
1 mA / c〓, temperature 30 ° C. The results are shown in Table 1.

【表1】 [Table 1]

【0035】本発明の実施例ではいずれも、充電容量が
340mAh/g以上、放電容量が320mAh/g以
上で充放電の効率が94%以上と高く、サイクル特性も
良好なものが得られた。
In each of the examples of the present invention, a charge capacity of at least 340 mAh / g, a discharge capacity of at least 320 mAh / g, a charge / discharge efficiency of at least 94%, and good cycle characteristics were obtained.

【0036】即ち黒鉛粉末の表面に黒鉛で被覆すること
によって、リチウムイオンを脱着する実質的な表面積が
増大させ、高容量でサイクル特性も良好な負極材用炭素
材料が得られる。
That is, by coating the surface of the graphite powder with graphite, a substantial surface area for desorbing lithium ions is increased, and a carbon material for a negative electrode material having a high capacity and good cycle characteristics can be obtained.

─────────────────────────────────────────────────────
────────────────────────────────────────────────── ───

【手続補正書】[Procedure amendment]

【提出日】平成9年6月12日[Submission date] June 12, 1997

【手続補正1】[Procedure amendment 1]

【補正対象書類名】明細書[Document name to be amended] Statement

【補正対象項目名】発明の名称[Correction target item name] Name of invention

【補正方法】変更[Correction method] Change

【補正内容】[Correction contents]

【発明の名称】 リチウム二次電池負極材用黒
鉛を被覆した黒鉛質炭素材とその製法
Patent application title: Graphitic carbon material coated with graphite for negative electrode material of lithium secondary battery and method for producing the same

【手続補正2】[Procedure amendment 2]

【補正対象書類名】明細書[Document name to be amended] Statement

【補正対象項目名】請求項1[Correction target item name] Claim 1

【補正方法】変更[Correction method] Change

【補正内容】[Correction contents]

Claims (2)

【特許請求の範囲】[Claims] 【請求項1】粒子の長径aと短径bの比a/bが1≦a
/b≦3で、平均粒子径が1〜30μm、BET法によ
る比表面積が3〓/g以下でX線回折法による結晶子サ
イズd(002) が3.37Å以下のリチウムニ次電池負極
材に用いる黒鉛を被覆した黒鉛質炭素材。
1. The ratio a / b of the major axis a to the minor axis b of the particles is 1 ≦ a.
/ B ≦ 3, the average particle diameter is 1 to 30 μm, the specific surface area by the BET method is 3 ° / g or less, and the crystallite size d (002) by the X-ray diffraction method is 3.37 ° or less. Graphitic carbon material coated with graphite to be used.
【請求項2】粒子の長径aと短径bの比a/bが1≦a
/b≦3で平均粒子径が1〜30μmの炭素又は黒鉛粉
末100重量部と石炭系ピッチ又は石油系ピッチ10〜
25重量部とを加熱混合しピッチを炭素又は黒鉛粉末表
面にコートし、酸化性雰囲気中で軽度の熱処理により炭
素又は黒鉛粉末表面のピッチを不融化し、解砕(軽度の
粉砕)し、炭化焼成、必要に応じて解砕し黒鉛化する請
求項1の黒鉛を被覆した黒鉛質炭素材の製法。
2. The ratio a / b of the major axis a to the minor axis b of the particles is 1 ≦ a.
/ B ≦ 3 and 100 parts by weight of carbon or graphite powder having an average particle diameter of 1 to 30 μm and coal-based pitch or petroleum-based pitch 10
25 parts by weight are heated and mixed, and the pitch is coated on the surface of the carbon or graphite powder. The pitch on the surface of the carbon or graphite powder is made infusible by mild heat treatment in an oxidizing atmosphere, and crushed (lightly pulverized). 2. The method for producing a graphite-coated graphitic carbon material according to claim 1, wherein the material is calcined and, if necessary, crushed and graphitized.
JP9115020A 1997-04-18 1997-04-18 Graphite powder coated with graphite for negative electrode material of lithium secondary battery and its manufacturing method Expired - Fee Related JP3054379B2 (en)

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