JPH11121007A - Manufacture of carbonaceous powder for lithium ion secondary battery negative electrode active material - Google Patents

Manufacture of carbonaceous powder for lithium ion secondary battery negative electrode active material

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Publication number
JPH11121007A
JPH11121007A JP10225371A JP22537198A JPH11121007A JP H11121007 A JPH11121007 A JP H11121007A JP 10225371 A JP10225371 A JP 10225371A JP 22537198 A JP22537198 A JP 22537198A JP H11121007 A JPH11121007 A JP H11121007A
Authority
JP
Japan
Prior art keywords
carbonaceous powder
organic amine
solution
pitch
amine solvent
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
JP10225371A
Other languages
Japanese (ja)
Other versions
JP3000272B2 (en
Inventor
Toretsu Jo
東 烈 徐
Soeki Ri
相 益 李
Heikun Bin
丙 勳 閔
Eikei Kin
榮 奎 金
Seiko In
聖 昊 尹
Dae H Lee
大 浩 李
Ko Rin
弘 林
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.)
DB HiTek Co Ltd
Original Assignee
Dongbu Hannong Chemical 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 Dongbu Hannong Chemical Co Ltd filed Critical Dongbu Hannong Chemical Co Ltd
Publication of JPH11121007A publication Critical patent/JPH11121007A/en
Application granted granted Critical
Publication of JP3000272B2 publication Critical patent/JP3000272B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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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
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/96—Carbon-based electrodes
    • 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of carbonaceous powder for lithium ion secondary battery negative electrode active material by dissolving pitch as a carbon source using an organic amine solvent, and softening the organic amine solvent. SOLUTION: This manufacturing method comprises a dissolving step dissolving pitch in organic amine solvent, a salt forming step adding acid aqueous solution to the solution obtained in the dissolving step so as to let the organic amine solvent form a salt, a filtering step filtering carbonaceous powder deposited by the salt formation of the organic amine solvent from the acid aqueous solution, an aftertreatment step washing and drying the filtered carbonaceous powder, and a carbonizing step carbonizing or graphitizing the carbonaceous powder in an non-oxidizing atmosphere after causing the dried carbonaceous powder to be nonfusible in an oxidizing atmosphere. Thereby, the carbonaceous powder having a proper particle size and chemical characteristics for using as lithium ion secondary battery negative electrode active material can be manufactured very easily without such process as pulverization and classification.

Description

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

【０００１】[0001]

【発明の属する技術分野】本発明はリチウムイオン２次
電池負極活物質用炭素質粉末の製造方法に関するもので
ある。より詳しくは、有機アミン溶剤を使用して炭素源
としてのピッチを溶解させて、有機アミン溶剤を塩化さ
せる方法で炭素質粉末を得るリチウムイオン２次電池負
極活物質用炭素質粉末の製造方法に関するものである。The present invention relates to a method for producing a carbonaceous powder for a negative electrode active material of a lithium ion secondary battery. More specifically, the present invention relates to a method for producing carbonaceous powder for a negative electrode active material of a lithium ion secondary battery, in which a pitch as a carbon source is dissolved using an organic amine solvent to obtain a carbonaceous powder by a method of salifying the organic amine solvent. Things.

【０００２】[0002]

【従来の技術】最近、携帯用電話機、ビデオカメラ、ノ
ートブックコンピュータなどポータブル電子機器、電子
製品の電源として２次電池の需要が急激に増大された
し、ポータブル製品の特性上小型、軽量であってもエネ
ルギーの密度が高く、安定的な出力を提供することがで
き、また反復的な充電、放電が可能で、さらに放電の後
の再充電時非可逆容量による充、放電容量の制限のよう
な現像を示さない２電池の開発のための努力が競争され
ているし、これのための２次電池の構成要素に対する研
究が並行されてきた。2. Description of the Related Art In recent years, demand for secondary batteries as a power source for portable electronic devices such as portable telephones, video cameras, and notebook computers, and electronic products has been rapidly increased. Even with a high energy density, it can provide a stable output, and can be repeatedly charged and discharged.Furthermore, the charge and discharge capacity is limited by irreversible capacity when recharging after discharging. Efforts have been made to develop a secondary battery that does not show any serious development, and research on the components of the secondary battery has been conducted in parallel.

【０００３】負極活物質で炭素を使用するリチウムイオ
ン２次電池の充電、放電過程においてのリチウムイオン
の負極活物質としての炭素への吸蔵、脱蔵挙動は大きく
ドーピング（Ｄｏｐｉｎｇ）及びディドーピング（Ｄｅ
ｄｏｐｉｎｇ）のメカニズムと、インターカレーション
（Ｉｎｔｅｒｃａｌａｔｉｏｎ）及びディインターカレ
ーション（Ｄｅｉｎｔｅｒｃａｌａｔｉｏｎ）のメカニ
ズムでできていることと推定されているし、前者は、難
黒鉛化性炭素（Ｎｏｎ−ｇｒａｐｈｉｔｉｚａｂｌｅ
ｃａｒｂｏｎ）及び易黒鉛化性炭素（Ｇｒａｐｈｉｔｉ
ｚａｂｌｅ ｃａｒｂｏｎ ｏｒ Ｓｏｆｔ ｃａｒｂ
ｏｎ）の低温焼成炭（Ｌｏｗ ｔｅｍｐｅｒａｔｕｒｅ
ｃａｌｃｉｎｅｄ ｃａｒｂｏｎ）に、後者は易黒鉛
化性炭素の黒鉛化処理品（Ａｒｔｉｆｉｃｉａｌ ｇｒ
ａｐｈｉｔｅ，Ｇｒａｐｈｉｔｉｚｅｄ ｃａｒｂｏ
ｎ）または天然黒鉛（Ｎａｔｕｒａｌ ｇｒａｐｈｉｔ
ｅ）に該当するものと知られているが、まだ明確なメカ
ニズムは明らかになっていない。既存の黒鉛層間化合物
との類似性から、結晶構造と密接な関連性があるし、電
解塩と溶媒などの２次電池の構成要素によって最適の結
晶構造が決定されるものと知られている。また、２次電
池の充電、放電反応時に発生する非可逆容量は明白では
ないが、主に電極活物質と電解質との副反応によって生
成されるものと知られている。A lithium ion secondary battery using carbon as a negative electrode active material has a large absorption and desorption behavior of lithium ions into carbon as a negative electrode active material during charging and discharging processes. Doping and dedoping (De)
Doping and intercalation and deintercalation mechanisms are presumed. The former is non-graphitizable carbon (Non-graphitizable).
carbon and graphitizable carbon (Graphiti)
double carbon or soft carb
on) low temperature coal (Low temperature)
calcined carbon, and the latter is a graphitized carbonized product (Artificial gr) of graphitizable carbon.
aphite, Graphitized carbo
n) or natural graphite (Natural graphite)
Although it is known to correspond to e), a clear mechanism has not been clarified yet. It is known that the similarity with the existing graphite intercalation compound closely relates to the crystal structure, and that the optimum crystal structure is determined by the components of the secondary battery such as the electrolytic salt and the solvent. Although the irreversible capacity generated during the charging and discharging reactions of the secondary battery is not clear, it is known that the irreversible capacity is mainly generated by a side reaction between the electrode active material and the electrolyte.

【０００４】一般的に、易黒鉛化性炭素と難黒鉛化性炭
素は炭素材を高温熱処理する場合、面間隙（ｄ002 ）と
ｃ軸方向の結晶子の大きさ（ＬC ）及びａ軸方向の結晶
子の大きさ（Ｌa ）などがどの程度発達したかの程度に
よって決定されるし、易黒鉛化性炭素の場合、２，４０
０℃以上の熱処理時、ｄ002 は３．４Å以下、ＬC （０
０２）は５０Å以上の数値を示すものと知られている。
これに反して、難黒鉛化性炭素は２，４００℃以上の温
度で熱処理してもＬC （００２）が５０Å以上大きくな
らないという特性を有している。[0004] Generally, graphitizable carbon and non-graphitizable carbon are produced by heat-treating a carbon material at a high temperature, where the plane gap (d 002 ), the crystallite size in the c-axis direction (L C ), and the a-axis The size (L a ) of the crystallite in the direction is determined by the degree of development, and in the case of graphitizable carbon, it is determined by 2,40.
At the time of heat treatment at 0 ° C. or more, d 002 is 3.4 ° or less and L C (0
02) is known to indicate a numerical value of 50 ° or more.
On the other hand, non-graphitizable carbon has a property that L C (002) does not increase by 50 ° or more even when heat-treated at a temperature of 2,400 ° C. or more.

【０００５】前記易黒鉛化性炭素及び難黒鉛化性炭素の
特徴としてリチウムイオン２次電池の負極活物質用炭素
材としては、このような結晶子の大きさを制御して製造
した例が多数報告されている。難黒鉛化性炭素材料とし
ては日本国特開昭６３−１６４１７７号公報でｄ002 が
３．７Åより大きい難黒鉛化性炭素を電池用炭素として
優秀な特性を有するものと記述している。As a feature of the graphitizable carbon and the non-graphitizable carbon, there are many examples of the carbon material for a negative electrode active material of a lithium ion secondary battery manufactured by controlling the size of such crystallites. It has been reported. As a non-graphitizable carbon material, Japanese Unexamined Patent Publication (Kokai) No. 63-164177 describes that non-graphitizable carbon having d 002 of more than 3.7% has excellent properties as carbon for batteries.

【０００６】易黒鉛化成炭素の例としてはコークス、異
方性微小球体（ＭＣＭＢ；Ｍｅｓｏ−ｃａｒｂｏｎ Ｍ
ｉｃｒｏｂｅａｄ）及び高性能ピッチ系炭素繊維（Ｍｅ
ｓｏｐｈａｓｅ ｐｉｔｃｈ ｂａｓｅｄ ｃａｒｂｏ
ｎ ｆｉｂｅｒ；ＭＣＦ）などが挙げられる。このよう
な人造黒鉛質の炭素材料の製造方法に関して多数の特許
が報告されている。例えば、日本国特開平４−１９０５
５６号公報では広角Ｘ線の回折によって測定されたｃ軸
方向の結晶子の厚さＬC が２００Å以上であるもので、
またＬC とａ軸の方向の結晶子の厚さ（Ｌa ）との比Ｌ
C ／Ｌa が１．３以上である易黒鉛化性黒鉛質炭素材料
が負極活物質として良い性能を提供するものと記述され
ており、日本国特開平４−１９０５５７号公報ではＬa
が１５０Å以上で、ＬC ／Ｌa が１．６７以下である易
黒鉛化性黒鉛質炭素材料が負極活物質として良い性能を
提供するものと記述されている。また、日本国特開平４
−１８８５５９号公報では格子間隙であるｄ002 が３．
４５Å以下であるし、ＬC及びＬa が２００Å以上で、
真密度２．００ｇ／ｃｍ3 乃至２．２５ｇ／ｃｍ3であ
る材料がリチウムイオン２次電池用負極活物質として適
合なものと記述されている。Examples of easily graphitized carbon include coke and anisotropic microspheres (MCMB; Meso-carbon M).
microbeads) and high-performance pitch-based carbon fibers (Me
sophase pitch based carbo
n fiber; MCF). Numerous patents have been reported on such a method for producing an artificial graphite carbon material. For example, Japanese Unexamined Patent Publication No. Hei.
No. 56, the thickness of the crystallite in the c-axis direction L C measured by wide-angle X-ray diffraction is 200 ° or more,
Also, the ratio L of L C to the thickness (L a ) of the crystallite in the direction of the a-axis is
C / L a have been described as those graphitizable graphitic carbon material is 1.3 or higher provides a good performance as a negative electrode active material, in Japanese Patent Laid-Open 4-190557 discloses L a
It is described that an easily graphitizable graphitic carbon material having a temperature of 150 ° or more and an LC / La of 1.67 or less provides good performance as a negative electrode active material. Also, Japanese Patent Application Laid-Open
In JP-A-188559, d 002 which is a lattice gap is 3.
It is 45Å or less, with L C and L a is 200Å or more,
It is described that a material having a true density of 2.00 g / cm 3 to 2.25 g / cm 3 is suitable as a negative electrode active material for a lithium ion secondary battery.

【０００７】このような炭素結晶子の大きさ及び粒度な
どは主に原料及び原料に内包されているフリーカーボン
（Ｆｒｅｅ ｃａｒｂｏｎ）の含量に関連があるし、こ
のフリーカーボンの含量を制御して結晶子の大きさを制
御した例もある。しかし、まだ熱処理温度及び原料前駆
体であるピッチの含有物などに対する一貫で普遍的な基
準は十分明らかになっていない状態である。The size and particle size of the carbon crystallites are mainly related to the raw material and the content of free carbon contained in the raw material, and the crystal content is controlled by controlling the content of the free carbon. In some cases, the size of the child is controlled. However, a consistent and universal standard for the heat treatment temperature and the content of the pitch, which is a raw material precursor, has not yet been sufficiently clarified.

【０００８】このように、リチウムイオン２次電池の負
極活物質用炭素材料は、リチウムイオン２次電池に対応
して、他の結晶構造が要求されており、それぞれの電池
に適切な粒度、粒子の形態及び結晶構造を有する炭素材
料が要求されている。それで、好ましい粒度、粒子の形
態及び結晶構造を有する負極活物質用炭素材料を工業的
に適切に生産することができる技術を開発することが重
要な課題になっている。[0008] As described above, the carbon material for the negative electrode active material of the lithium ion secondary battery is required to have another crystal structure corresponding to the lithium ion secondary battery. Are required. Therefore, it has become an important issue to develop a technology capable of industrially appropriately producing a carbon material for a negative electrode active material having a preferable particle size, particle shape, and crystal structure.

【０００９】現在まで、炭素材料の製造などに対する多
くの提案があったし、その中で日本国特開平４−１１５
４５８号、４−１８４８６２号、４−１８８５５９号、
４−１９０５５６号、４−１９０５５７号及び４−３３
２４８４号公報にはピッチ類を熱処理して生成される異
方性微小球体（ＭＣＭＢ）を高温熱処理して得られる炭
素材料がリチウムイオン２次電池用負極活物質で適切で
あるとしているし、このような異方性微小球体は一般的
に石油系ピッチ、コールタールピッチ、エチレンボタム
オイル（Ｅｔｈｙｌｅｎｅ Ｂｏｔｔｏｍ Ｏｉｌ）な
どを加圧または減圧下で４００℃前後の温度に熱処理す
ることによって発生する光学的異方性微小球体を、溶剤
としてマトリックス（ｍａｔｒｉｘ）成分と呼ばれる小
球体以外の成分と分離することで得られる異方性微小球
体を非活性または還元性雰囲気下で、焼成処理すること
でリチウムイオン２次電池用炭素材料を製造する例を記
述している。ここでの異方性微小球体は直径が数十μｍ
乃至数μｍ程度の微小球体で、リチウムイオンの挿入、
離脱のサイトが多く、電極製造時において、充填率が大
きい炭素材料であることに加えてこのような異方性微小
球体が、１０００℃以上の熱処理によって適切な結晶構
造を有するので、リチウムイオン２次電池負極活物質用
炭素材料に多く使用されてきている。To date, there have been many proposals for the production of carbon materials and the like.
No. 458, No. 4-184862, No. 4-188559,
4-190556, 4-190557 and 4-33
No. 2484 states that a carbon material obtained by heat-treating anisotropic microspheres (MCMB) formed by heat-treating pitches at a high temperature is suitable as a negative electrode active material for a lithium ion secondary battery. Such anisotropic microspheres are generally generated by heat-treating petroleum pitch, coal tar pitch, ethylene bottom oil, etc. to a temperature of about 400 ° C. under pressure or reduced pressure. The anisotropic microspheres obtained by separating the anisotropic microspheres from a component other than the small spheres called a matrix component as a solvent are subjected to a baking treatment in an inert or reducing atmosphere to obtain lithium ion. An example of manufacturing a carbon material for a secondary battery is described. The anisotropic microsphere here has a diameter of several tens of μm.
Insertion of lithium ions in microspheres of
In the production of the electrode, in addition to being a carbon material having a large filling factor, such an anisotropic microsphere has an appropriate crystal structure by heat treatment at 1000 ° C. or more, so that lithium ions 2 It has been widely used as a carbon material for a secondary battery negative electrode active material.

【００１０】このようなリチムウイオン２次電池負極活
物質用炭素材料の生産は多様な方法によって行われる
し、また生産方法によって多様な物性が発現されるもの
と知られている。前記の炭素材料の製造は、一般的に反
応時の状によって気状、液状、固状の全状態で反応が進
行され得るが、現在リチウムイオン２次電池負極活物質
用炭素材料は、主に液状の炭化工程によって前駆体また
はコークスを製造した後、これを一定の形態に粉砕また
は加工した後、一定の温度まで熱処理して生産されてい
る。特定の粒度を有する粒子を製造する過程は繊維状及
び異方性状微小球体を除外しては、バルク状の炭素材を
粉砕して粒子化した後、熱処理することを含むと知られ
ている。一般的に炭素質粉末に使用される炭素材の粒度
は５μｍ乃至１００μｍの大きさの粒子が主に使用され
るし、非粉砕法よって生産される異方性微小球体は６μ
ｍ乃至４０μｍ、高性能炭素繊維の微粒粉は繊維径が６
μｍ乃至１５μｍ、繊維長が約３００μｍ以下であるも
のが主に使用されている。It is known that the production of such a carbon material for a negative electrode active material of a lithium secondary battery is carried out by various methods, and that various physical properties are exhibited by the production method. In the production of the carbon material, generally, the reaction can proceed in a gaseous state, a liquid state, or a solid state depending on the state of the reaction. Currently, carbon materials for a negative electrode active material of a lithium ion secondary battery mainly include: A precursor or coke is produced by a liquid carbonization process, then crushed or processed into a certain form, and then heat-treated to a certain temperature. It is known that the process of producing particles having a specific particle size includes, after excluding fibrous and anisotropic microspheres, pulverizing and granulating a bulk carbon material, followed by heat treatment. Generally, the particle size of the carbon material used for the carbonaceous powder is mainly 5 μm to 100 μm, and the anisotropic microspheres produced by the non-pulverization method are 6 μm.
m to 40 μm, high-performance carbon fiber fine powder has a fiber diameter of 6
Those having a size of from 15 μm to 15 μm and a fiber length of about 300 μm or less are mainly used.

【００１１】バルク状の炭素材を粉砕して５μｍ乃至１
００μｍの大きさを有する２次電池用炭素質粉末を製造
するためには、長時間の粉砕と粉砕のための大規模の設
備が要求されるし、粉砕後一定の粒度の大きさに分級
（Ｃｌａｓｓｉｆｉｃａｔｉｏｎ）する工程が要求され
る。特に、負極活物質用炭素材料でより適合な６乃至２
０μｍ程度に粉砕及び分級するためには長時間の粉砕と
共に、高性能の粒度分級機を連続的に数回使用して分級
しなければならないので、大量生産時、生産単価の上昇
の主な原因となる問題点があった。また、粉砕時に粉砕
機としてのボール−ミールでのボールなどの衝突、破壊
による不純物の添加及び分級による収率の低下などが伴
い、副反応の原因提供及び生産収率の減少などを誘発さ
せるし、粉砕による結晶子の破壊、表面酸化官能基の生
成、炭素先端面の突出及び超微粒子の表面の汚染などを
伴うようになって、リチウム２次電池負極活物質用炭素
材料に使用するためには別途の後処理が要求される問題
点があった。The bulk carbon material is pulverized to 5 μm to 1 μm.
In order to produce a carbonaceous powder for a secondary battery having a size of 00 μm, a large-scale facility for long-time pulverization and pulverization is required. Classification) is required. In particular, 6 to 2 which is more suitable for a carbon material for a negative electrode active material.
In order to pulverize and classify to about 0 μm, it is necessary to classify using a high-performance particle sizer several times continuously with long-time pulverization. There was a problem. Further, at the time of pulverization, collision of balls and the like with a ball-meal as a pulverizer, addition of impurities due to destruction and a decrease in yield due to classification, etc. are accompanied, thereby causing a side reaction and reducing the production yield. In order to use as a carbon material for negative electrode active material of lithium secondary battery, it is accompanied by destruction of crystallites by grinding, generation of surface oxidation functional groups, protrusion of carbon tip surface and contamination of ultrafine particle surface. However, there is a problem that separate post-processing is required.

【００１２】非粉砕法で製造される異方性微小球体の場
合、原料であるピッチを３００乃至５００℃の温度の範
囲内で一定時間熱処理して異方性微小球体を等方性ピッ
チマトリックスに発生させた後、これを有機溶剤などを
使用して抽出し、適切に分級した後、炭化して製造す
る。この過程で実質的にはキノリン不溶分として原料ピ
ッチに内包されたフリーカーボン（Ｆｒｅｅ ｃａｒｂ
ｏｎ）などを調整して粒度及び結晶化度を調節する技術
が日本国特開平４−１９０５５７号に記述されている。
このようなピッチの熱処理及び有機溶剤抽出による異方
性微小球体の生産は生成される異方性微小球体の粒度を
小さく均一にすることはできるが、粒子の生成収率が一
般的に３０重量％を超えないという問題点があるし、最
終のリチウムイオン２次電池用黒鉛化異方性微小球体に
生産される収率は原料の１０重量％内外であるものと知
られているし、抽出時、有機溶剤の使用による汚染及び
生産単価の上昇などの問題点があった。In the case of anisotropic microspheres produced by a non-pulverization method, the pitch, which is a raw material, is heat-treated for a certain time within a temperature range of 300 to 500 ° C. to convert the anisotropic microspheres into an isotropic pitch matrix. After generation, this is extracted using an organic solvent or the like, appropriately classified, and carbonized to produce. In this process, free carbon (Free carb) substantially contained in the raw material pitch as a quinoline insoluble matter is contained.
on) and the like to adjust the particle size and crystallinity are described in JP-A-4-190557.
The production of anisotropic microspheres by heat treatment of the pitch and extraction with an organic solvent can make the size of the anisotropic microspheres produced small and uniform, but the production yield of the particles is generally 30% by weight. %, And the yield of final graphitized anisotropic microspheres for lithium ion secondary batteries is known to be around 10% by weight of the raw material. There have been problems such as contamination due to the use of an organic solvent and an increase in the production unit price.

【００１３】また、非粉砕法による２次電池負極活物質
用炭素材料を生産する方法としては液晶ピッチを放射し
て短繊維を収得した後、これを安定化及び炭化、黒鉛化
する方法があった。このような方法は一定の繊維状の炭
素材を提供する長所があるが、使用する放射用液晶ピッ
チ原料が高価で、繊維を提供する放射工程が複雑で生産
単価を上昇させる原因になるし、長繊維及び単繊維に製
造された繊維状を再び適切な粒度を有する微粒粉（Ｍｉ
ｌｌｅｄ ｆｉｂｅｒｓ）で作らなければならないので
製造時間が増大され、やはり複雑な設備が要求されるな
どの問題点があった。As a method of producing a carbon material for a secondary battery negative electrode active material by a non-pulverization method, there is a method of radiating a liquid crystal pitch to obtain short fibers, and then stabilizing, carbonizing, and graphitizing the short fibers. Was. Such a method has the advantage of providing a certain fibrous carbon material, but the radiation liquid crystal pitch raw material to be used is expensive, and the radiation process of providing the fibers is complicated, causing an increase in the production unit price, The fibrous materials produced into long fibers and single fibers are again converted into fine powder (Mi
Since it must be made with lled fibers, manufacturing time is increased, and complicated facilities are required.

【００１４】一方、リチウムイオン２次電池の単位セル
を基準に考慮する時、最大の電池容量を実現するために
は、負極活物質用炭素材料の集電板上での充填率を最大
にする必要があるし、従って、球形を有する異方性微小
球体が最適であるものと考慮されている。このような充
填率と共に粒子がもつ構造の発達もとても重要な因子と
考慮され、非可逆容量を増加させないし、リチウムイオ
ンの吸蔵、脱蔵に寄与することができる発達された構造
を有する微細構造の実現もとても重要な因子と考慮され
なければならない。On the other hand, when considering the unit cell of the lithium ion secondary battery as a reference, in order to realize the maximum battery capacity, the filling rate of the carbon material for the negative electrode active material on the current collector plate is maximized. It is necessary and therefore considered that anisotropic microspheres having a spherical shape are optimal. The development of the structure of the particles together with such a filling factor is also considered to be a very important factor, and the microstructure having an advanced structure that does not increase the irreversible capacity and can contribute to occlusion and desorption of lithium ions. Implementation must also be considered a very important factor.

【００１５】従って、リチウムイオン２次電池負極活物
質用炭素材料は結晶構造、粒子形態及び粒子の微細構造
を最適化することが要求されるし、このような因子に満
足しながらも工業的に大量生産することができる新しい
炭素材料の製造方法の開発が未だに要求されている。Therefore, the carbon material for the negative electrode active material of the lithium ion secondary battery is required to optimize the crystal structure, the particle morphology and the fine structure of the particles. There is still a need to develop new methods for producing carbon materials that can be mass-produced.

【００１６】[0016]

【発明が解決しようとする課題】本発明の目的は、有機
アミン溶剤を使用して炭素源としてのピッチを微分して
リチウム２次電池の負極活物質用炭素質粉末を製造する
方法を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a carbonaceous powder for a negative electrode active material of a lithium secondary battery by differentiating a pitch as a carbon source using an organic amine solvent. It is in.

【００１７】[0017]

【課題を解決するための手段】前記目的を達成するため
の本発明によるリチウムイオン２次電池負極活物質用炭
素質粉末の製造方法は、ピッチを有機アミン溶剤に溶解
させる溶解段階；前記溶解段階で得られた溶液と酸水溶
液を混合して有機アミン溶剤を塩化させる塩化段階；有
機アミン溶剤の塩化によって析出される炭素質粉末を塩
水溶液から濾過する濾過段階；濾過された炭素質粉末を
水洗及び乾燥する後処理段階；及び乾燥された炭素質粉
末を、非酸化性雰囲気中で加熱して炭化させる炭化段
階：を含む。In order to achieve the above object, a method for producing carbonaceous powder for a negative electrode active material of a lithium ion secondary battery according to the present invention comprises a dissolving step of dissolving pitch in an organic amine solvent; A salting step of mixing the solution obtained in the above with an acid aqueous solution to salinate the organic amine solvent; a filtering step of filtering the carbonaceous powder precipitated by the salting of the organic amine solvent from the salt aqueous solution; washing the filtered carbonaceous powder with water And a post-treatment step of drying; and a carbonization step of heating and carbonizing the dried carbonaceous powder in a non-oxidizing atmosphere.

【００１８】前記で炭素源に使用されるピッチがコール
タール、コールタールピッチ、石油系中質油、高分子の
熱分解ピッチ、芳香族炭化水素のピッチ誘導体などとそ
れらから製造される全ての種類の軟化点１３０℃以上の
光学的等方性及び異方性ピッチが使用され得る。The pitch used as the carbon source is coal tar, coal tar pitch, petroleum medium oil, pyrolysis pitch of a polymer, pitch derivative of an aromatic hydrocarbon, etc., and all kinds produced from them. An optical isotropic and anisotropic pitch having a softening point of 130 ° C. or higher can be used.

【００１９】前記有機アミン溶剤が液状の脂肪族アミ
ン、芳香族アミンからなるグループの中で選択されたも
の、或いは前記有機アミン溶剤が炭素数１乃至４の液状
の脂肪族アミンでできているグループの中で選択された
もの、或いは前記有機アミン溶剤がピリジン、ピリミジ
ン、ピロール、ピロリン、ピロリジン、キノリン、アイ
ソキノリン、キノキサリン、またはこれらの２つ以上の
混合物からなるグループの中で選択されたものが使用さ
れ得る。The organic amine solvent is selected from the group consisting of a liquid aliphatic amine and an aromatic amine, or the organic amine solvent is a liquid aliphatic amine having 1 to 4 carbon atoms. Or the organic amine solvent is selected from the group consisting of pyridine, pyrimidine, pyrrole, pyrroline, pyrrolidine, quinoline, isoquinoline, quinoxaline, or a mixture of two or more thereof. Can be used.

【００２０】前記溶解段階で、炭素源としてのピッチが
前記有機アミン溶剤に０．１乃至５０重量％の量で溶解
され得るし、望ましくは３乃至２０重量％の量で溶解さ
れ得る。In the dissolving step, the pitch as a carbon source may be dissolved in the organic amine solvent in an amount of 0.1 to 50% by weight, preferably in an amount of 3 to 20% by weight.

【００２１】前記塩化段階で前記酸水溶液は前記有機ア
ミン溶剤のアミンと塩を形成することができる塩酸、窒
酸、硫酸、燐酸、過塩素酸、弗酸、酢酸、パラトルエン
スルホン酸、シュウ酸、またはこれらの２つ以上の混合
物からなるグループの中で選択されたものが使用され得
る。In the salification step, the aqueous acid solution is capable of forming a salt with the amine of the organic amine solvent. Hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, perchloric acid, hydrofluoric acid, acetic acid, paratoluenesulfonic acid, oxalic acid Or a member selected from the group consisting of a mixture of two or more thereof.

【００２２】前記塩化段階で、前記有機アミン溶剤に前
記ピッチが溶解された溶液が前記酸水溶液の０．５乃至
９０重量％の量で混合されることができるし、望ましく
は５乃至５０重量％の量で混合されることができる。In the salification step, a solution in which the pitch is dissolved in the organic amine solvent may be mixed in an amount of 0.5 to 90% by weight of the aqueous acid solution, preferably 5 to 50% by weight. Can be mixed.

【００２３】前記炭化段階の前に、前記水洗及び乾燥さ
れた前記炭素質粉末を不融化溶液の中で酸化させて不融
化する不融化段階が遂行される。Before the carbonizing step, an infusibilizing step of oxidizing the washed and dried carbonaceous powder in an infusibilizing solution to infusibilize is performed.

【００２４】前記不融化段階で、不融化溶液は窒酸水溶
液または過酸化水素水が使用されることができる。In the infusibilizing step, the infusibilizing solution may be an aqueous solution of nitric acid or an aqueous solution of hydrogen peroxide.

【００２５】前記で不融化溶液として窒酸水溶液が使用
される場合では、窒酸水溶液の５乃至９８重量％の量の
炭素質粉末が、そして過酸化水素水が使用される場合で
は過酸化水素水の５乃至９０重量％の量の炭素質粉末が
使用され、安定化時間が０．１乃至１０時間、不融化温
度が１０乃至８０℃の温度範囲以内である。In the case where an aqueous solution of nitric acid is used as the infusibilizing solution, carbonaceous powder in an amount of 5 to 98% by weight of the aqueous solution of nitric acid is used, and in the case where aqueous hydrogen peroxide is used, hydrogen peroxide is used. Carbonaceous powder is used in an amount of 5 to 90% by weight of water, with a stabilization time of 0.1 to 10 hours and an infusibilization temperature within the temperature range of 10 to 80 ° C.

【００２６】また、前記不融化段階は、酸化性雰囲気の
中で２００乃至３５０℃の温度の範囲以内で１乃至２４
時間の間熱処理することからなることができる。The infusibilizing step may be performed in an oxidizing atmosphere at a temperature of 200 to 350 ° C. for 1 to 24 hours.
It can consist of heat treating for a time.

【００２７】前記炭化段階では、前記炭素質粉末が７０
０乃至３，０００℃の温度範囲以内で２分乃至１０時間
の間熱処理することからなる。In the carbonization step, the carbonaceous powder is
The heat treatment is performed within a temperature range of 0 to 3,000 ° C. for 2 minutes to 10 hours.

【００２８】前記炭化段階で炭素源が低温焼成炭由来で
ある炭素質粉末の場合、７００乃至１，２００℃の温度
範囲以内で１０分乃至１０時間の間熱処理ことからな
る。When the carbon source is carbonaceous powder derived from low-temperature calcined carbon in the carbonization step, the carbon source is heat-treated at a temperature within a range of 700 to 1,200 ° C. for 10 minutes to 10 hours.

【００２９】また、本発明によるリチウムイオン２次電
池負極活物質用炭素質粉末の製造方法は、ピッチを有機
アミン溶剤に溶解させる溶解段階；前記溶解段階で得ら
れた溶液と酸水溶液を混合して有機アミン溶剤を塩化さ
せる塩化段階；有機アミン溶剤の塩化によって析出され
る炭素質粉末を塩水溶液から濾過する濾過段階；濾過さ
れた炭素質粉末を水洗及び乾燥する後処理段階；前記濾
過段階で濾過の後、余液としての塩水溶液に塩基水溶液
を加える塩基水溶液付加段階；前記塩基水溶液の添加に
よって中和された中和液を放置して水性層と有機アミン
溶剤層に分離された中和液から有機アミン溶剤を回収す
る回収段階；及び乾燥された炭素質粉末を非酸化性雰囲
気の中で加熱して炭化させる炭化段階；を含む。The method for producing carbonaceous powder for a negative electrode active material of a lithium ion secondary battery according to the present invention comprises a dissolving step of dissolving pitch in an organic amine solvent; mixing the solution obtained in the dissolving step with an aqueous acid solution. A step of filtering the carbonaceous powder deposited by the salting of the organic amine solvent from the salt solution; a post-treatment step of washing and drying the filtered carbonaceous powder; After the filtration, an aqueous base solution is added to the remaining salt aqueous solution as a base aqueous solution; the neutralized solution neutralized by the addition of the aqueous base solution is allowed to stand, and the neutralized solution is separated into an aqueous layer and an organic amine solvent layer A recovery step of recovering the organic amine solvent from the liquid; and a carbonization step of heating and carbonizing the dried carbonaceous powder in a non-oxidizing atmosphere.

【００３０】[0030]

【発明の実施の形態】以下、本発明を具体的な実施例を
参照に詳しく説明する。本発明の一実施例によるリチウ
ムイオン２次電池負極活物質用炭素質粉末の製造方法
は、ピッチを有機アミン溶剤に溶解させる溶解段階；前
記溶解段階で得られた溶液と酸水溶液を混合して有機ア
ミン溶剤を塩化させる塩化段階；有機アミン溶剤の塩化
によって析出される炭素質粉末を塩水溶液から濾過する
濾過段階；濾過された炭素質粉末を水洗及び乾燥する後
処理段階；及び乾燥された炭素質粉末を非酸化性雰囲気
中で加熱して炭化或いは黒鉛化させる炭化段階を含むこ
とを特徴とする。DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to specific embodiments. A method of manufacturing a carbonaceous powder for a negative electrode active material of a lithium ion secondary battery according to an embodiment of the present invention includes a dissolving step of dissolving pitch in an organic amine solvent; mixing the solution obtained in the dissolving step with an aqueous acid solution. A salting step of salinizing the organic amine solvent; a filtering step of filtering carbonaceous powder precipitated by salinization of the organic amine solvent from a salt solution; a post-treatment step of washing and drying the filtered carbonaceous powder; and dried carbon. And carbonizing or graphitizing by heating the porous powder in a non-oxidizing atmosphere.

【００３１】前記で炭素源として使用されるピッチは、
ピッチの軟化点が１３０℃以上のものでコールタール、
コールタールピッチ、石油系中質油、高分子の熱分解ピ
ッチ、芳香族炭化水素のピッチ誘導体などとこれらから
製造される全ての種類の軟化点１３０℃以上の光学的等
方性及び異方性ピッチが使用可能である。前記の高軟化
点ピッチはリチウムイオン２次電池に適用される時、電
解質との副反応の発生率を減らし、黒鉛化度を高くする
ために原料に内包されたフリーカーボンを除去した後、
適切な処理によって高軟化点化させたもので、最終的に
２次キノリン不溶分（Ｓｅｃｏｎｄａｒｙ Ｑｕｉｎｏ
ｌｉｎｅ Ｉｎｓｏｌｕｂｌｅｓ）の含量が０．１乃至
５０重量％、望ましくは０．５乃至３０重量％が含まれ
ているものが適合であると分かった。特に、軟化点が１
３０℃以下であるピッチは粒子生成後、酸化工程での不
融化時、不融化されないか、不融化に長時間が所要され
る問題点があり得るし、不完全な不融化によって以後の
高温熱処理過程で粒子の融着などを起こし、粒度を不均
一にして、さらに電池容量を低下させる原因になるので
炭素質粉末の炭素源として望ましくないものと確認され
た。The pitch used as a carbon source in the above is:
Coal tar with a softening point of 130 ° C or higher
Optical isotropy and anisotropy of coal tar pitch, petroleum medium oil, pyrolysis pitch of polymer, pitch derivative of aromatic hydrocarbon, etc. and all kinds produced from them with softening point of 130 ° C or more Pitch is available. When the high softening point pitch is applied to a lithium ion secondary battery, after removing the free carbon included in the raw material to reduce the incidence of side reactions with the electrolyte and increase the degree of graphitization,
It has a high softening point by an appropriate treatment, and finally has a secondary quinoline-insoluble matter (Secondary Quino).
Line Insolubles having a content of 0.1 to 50% by weight, preferably 0.5 to 30% by weight, were found to be suitable. In particular, the softening point is 1
A pitch having a temperature of 30 ° C. or less may not be infused during the infusibilization in the oxidation process after the particles are formed, or may require a long time for infusibilization. It was confirmed that it was not desirable as a carbon source of the carbonaceous powder because the particles caused fusion and the like in the process, causing the particle size to become non-uniform and further reducing the battery capacity.

【００３２】前記有機アミン溶剤は液状の脂肪族アミン
や芳香族アミンでなるグループの中で選択されるもの
で、前記炭素源としてのピッチを溶解させる溶剤として
機能する。ここで、有機アミン溶剤というのは液状の有
機アミンの通称で前記炭素源としてのピッチを溶解させ
るのに適切な溶剤を意味する。The organic amine solvent is selected from the group consisting of liquid aliphatic amines and aromatic amines, and functions as a solvent for dissolving the pitch as the carbon source. Here, the organic amine solvent is a so-called liquid organic amine and means a solvent suitable for dissolving the pitch as the carbon source.

【００３３】前記有機アミン溶剤は、望ましくは炭素水
１乃至４の液状の脂肪族アミンでなるグループの中で選
択されたものが使用され得る。炭素水５以上の脂肪族ア
ミンは常温または一般的な作業条件で液状で存在し難い
固体状で存在するので本発明で溶剤として使用するには
適切ではない。As the organic amine solvent, one selected from the group consisting of liquid aliphatic amines of 1 to 4 carbon waters may be used. Aliphatic amines having carbon water of 5 or more are not suitable for use as a solvent in the present invention because they are present in a liquid state at room temperature or under general operating conditions and are hardly present.

【００３４】また、前記有機アミン溶剤はピリジン、ピ
リミジン、ピロール、ピロリン、ピロリジン、キノリ
ン、アイソキノリン、キノキサリンまたはこれらの２以
上の混合物からなるグループの中で選択されたものが使
用され得るし、これら芳香族アミンもやはり常温または
一般的な作業条件で液状で存在することができて本発明
で溶剤に使用するのに適切であるという長所を有してい
る。The organic amine solvent may be selected from the group consisting of pyridine, pyrimidine, pyrrole, pyrroline, pyrrolidine, quinoline, isoquinoline, quinoxaline or a mixture of two or more of these. Aromatic amines also have the advantage that they can be present in liquid form at room temperature or under general operating conditions and are suitable for use as solvents in the present invention.

【００３５】前記溶解段階で、炭素源としてのピッチが
前記有機アミン溶剤に０．１乃至５０重量％の量で溶解
され得るし、前記ピッチの量が前記有機アミン溶剤に対
して０．１重量％未満である場合、工業的に大量生産す
ることにおいて得られる炭素質粉末に対して有機アミン
溶剤の損失がとても大きくなる問題点があり得るし、ま
た、５０重量％を超過する場合、溶液内の不溶分である
キノリン不溶分が増加して得られる炭素質粉末の粒径が
均一にならないし、粒径が大きい粉末が得られるなどの
問題点が起り得る。前記溶解段階で炭素源としてのピッ
チが前記有機アミン溶剤に３乃至２０重量％の量に溶解
されることが望ましい。In the dissolving step, pitch as a carbon source may be dissolved in the organic amine solvent in an amount of 0.1 to 50% by weight, and the amount of the pitch may be 0.1% by weight based on the organic amine solvent. %, There is a problem that the loss of the organic amine solvent is very large with respect to the carbonaceous powder obtained in industrial mass production. The quinoline insolubles, which are the insolubles of the above, may increase the insoluble content of the resulting carbonaceous powder so that the particle size may not be uniform, and a powder having a large particle size may be obtained. Preferably, in the dissolving step, the pitch as a carbon source is dissolved in the organic amine solvent in an amount of 3 to 20% by weight.

【００３６】前記酸水溶液は前記有機アミン溶剤のアミ
ンと塩を形成することができる酸の水溶液になり得る。
このような酸水溶液は前記炭素源としてのピッチが溶解
された有機アミン溶剤に混合されて前記有機アミン溶剤
を塩化させるので、ピッチに対する前記有機アミン溶剤
の溶解度を低下させて有機アミン溶剤の中に溶解されて
いたピッチを強制的に析出させる機能をする。従って、
前記有機アミン溶剤は塩化されて酸水溶液の媒質として
の水中に溶解された状態に存在し塩水溶液になり、一般
的に水に対して溶解度が低いピッチは強制的に析出され
るし、この際、析出されるピッチは微粒化になることが
できる。The aqueous acid solution may be an aqueous solution of an acid capable of forming a salt with the amine of the organic amine solvent.
Since such an acid aqueous solution is mixed with the organic amine solvent in which pitch as the carbon source is dissolved and chlorinates the organic amine solvent, it lowers the solubility of the organic amine solvent in pitch and reduces the solubility in the organic amine solvent. It functions to forcibly precipitate the dissolved pitch. Therefore,
The organic amine solvent is salified to be dissolved in water as a medium of the aqueous acid solution and becomes a salt aqueous solution.In general, pitch having low solubility in water is forcibly precipitated. The deposited pitch can be atomized.

【００３７】前記酸水溶液は塩酸、窒酸、硫酸、燐酸、
過塩素酸、弗酸、酢酸、パラトルエンスルホン酸、シュ
ウ酸、またはこれらの２以上の混合物からなるグループ
の中で選択されたものが使用され得るし、これらは常用
的に購入して使用するのに容易で、有機アミン溶剤に使
用された弱塩基であるアミンを効果的に塩化させられる
ということが実験的に確認された。The aqueous acid solution may be hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid,
Perchloric acid, hydrofluoric acid, acetic acid, paratoluenesulfonic acid, oxalic acid, or a mixture selected from the group consisting of two or more thereof may be used, and these are purchased and used regularly. It has been experimentally confirmed that it is easy to effectively salify amines, which are weak bases used in organic amine solvents.

【００３８】前記塩化段階で、前記有機アミン溶剤に前
記ピッチが溶解された溶液が前記酸水溶液の０．５乃至
９０重量％の量で混合され得るし、前記ピッチが溶解さ
れた溶液が前記酸水溶液の０．５重量％未満で使用され
る場合、収得される炭素質粉末の量に比べ相対的に酸水
溶液が浪費される問題点があり得るし、前記ピッチが溶
解された溶液が前記酸水溶液の９０重量％を超える場
合、ピッチが溶解された有機アミン溶剤を十分に塩化さ
せないようになり、ピッチが完全に粉末に析出されない
という問題点があり得る。In the salification step, a solution in which the pitch is dissolved in the organic amine solvent may be mixed in an amount of 0.5 to 90% by weight of the aqueous acid solution, and the solution in which the pitch is dissolved may be mixed with the acid. If the aqueous solution is used at less than 0.5% by weight of the aqueous solution, there may be a problem that the aqueous acid solution is wasted relatively to the amount of the obtained carbonaceous powder. If it exceeds 90% by weight of the aqueous solution, the organic amine solvent in which the pitch is dissolved is not sufficiently salified, and there may be a problem that the pitch is not completely deposited on the powder.

【００３９】特に、前記溶解段階で有機アミン溶剤を混
合することができるし、有機アミン溶剤の撹拌によって
有機化合物の溶解度を高め、溶解時間を短縮させること
ができる。In particular, an organic amine solvent can be mixed in the dissolving step, and the solubility of the organic compound can be increased by stirring the organic amine solvent to shorten the dissolving time.

【００４０】前記塩化段階で、酸水溶液を撹拌すること
ができるし、この時の撹拌速度によって微粒化しようと
するピッチの粒径を調節することができ、撹拌速度が速
いほど微細な炭素質粉末を得られることが実験的に確認
された。In the chlorination step, the aqueous acid solution can be stirred, and the particle size of the pitch to be atomized can be adjusted by the stirring speed at this time. The higher the stirring speed, the finer the carbonaceous powder. Was confirmed experimentally.

【００４１】また、前記炭化段階の前に、前記水洗及び
乾燥された前記炭素質粉末を不融化溶液の中で酸化させ
て不融化する不融化段階が遂行されることができるし、
これを湿式不溶化とするし、この時、不融化は前記炭素
質粉末を安定化させて後続される炭化段階で炭素質粉末
が溶融されて凝集されることを防止する機能をする。Before the carbonization step, an infusibilizing step of oxidizing the washed and dried carbonaceous powder in an infusibilizing solution to infusibilize the carbonaceous powder may be performed;
This is referred to as wet insolubilization. At this time, the infusibilization functions to stabilize the carbonaceous powder and prevent the carbonaceous powder from being melted and aggregated in a subsequent carbonization step.

【００４２】前記不融化段階で、不融化に使用される不
融化溶液は窒酸水溶液または過酸化水素水が使用され得
るし、窒酸水溶液が使用される場合には窒酸水溶液の５
乃至９８重量％の量の炭素質粉末が不融化処理され得る
し、過酸化水素水の場合、過酸化水素水の５乃至９０重
量％の炭素質粉末が不融化処理され得るし、この際の安
定化時間は、１０乃至８０℃の温度で０．１乃至１０時
間、望ましくは０．５乃至８時間の間処理されるという
ことが実験的に明らかになった。In the infusibilizing step, the infusibilizing solution used for infusibilizing may be an aqueous solution of nitric acid or an aqueous solution of hydrogen peroxide.
To 98% by weight of carbonaceous powder, and in the case of hydrogen peroxide solution, 5 to 90% by weight of carbonaceous powder of hydrogen peroxide solution can be infusibilized. It has been experimentally found that the stabilization time is between 0.1 and 10 hours at a temperature between 10 and 80 ° C., preferably between 0.5 and 8 hours.

【００４３】また、前記不融化段階は、酸化性雰囲気中
で２００乃至３５０℃の温度範囲以内で１乃至２４時間
の間熱処理することからなり得るし、これを乾式不融化
とする。前記乾式不融化もやはり前記湿式不融化と同じ
く前記炭素質粉末を安定化させて後続される炭化段階で
炭素質粉末が溶融されて凝集することを防止する機能を
する。In addition, the infusibilizing step may include performing a heat treatment in an oxidizing atmosphere at a temperature in the range of 200 to 350 ° C. for 1 to 24 hours, which is referred to as dry infusibilizing. Like the wet infusibilization, the dry infusibilization also functions to stabilize the carbonaceous powder and prevent the carbonaceous powder from melting and agglomerating in a subsequent carbonization step.

【００４４】前記のようにして得られた炭素質粉末は炭
化段階で炭化或いは黒鉛化されリチウムイオン２次電池
負極活物質用炭素質粉末になり得るし、この炭化段階で
は炭素質粉末に形成される炭素源の種類によって７００
乃至３，０００℃の温度範囲以内で２分乃至１０時間の
間熱処理するものからなる。前記炭素質粉末で形成され
る炭素源が低温焼成炭由来の炭素質粉末の場合、７００
乃至１，２００℃の温度範囲以内で１０分乃至１０時間
の間熱処理して炭化され得るし、前記炭素質粉末で形成
される炭素源が黒鉛質由来の炭素質粉末の場合、２，３
００乃至３，０００℃の温度範囲以内で２分乃至２時間
の間熱処理して炭化され得る。The carbonaceous powder obtained as described above can be carbonized or graphitized in a carbonization stage to become a carbonaceous powder for a negative electrode active material of a lithium ion secondary battery. In this carbonization stage, the carbonaceous powder is formed into a carbonaceous powder. 700 depending on the type of carbon source
The heat treatment is performed within a temperature range of 3,000 ° C. to 3,000 ° C. for 2 minutes to 10 hours. When the carbon source formed from the carbonaceous powder is a carbonaceous powder derived from low-temperature calcined coal, 700
And carbonized by heat treatment for 10 minutes to 10 hours within a temperature range of 1 to 1,200 ° C., and when the carbon source formed from the carbonaceous powder is graphite-derived carbonaceous powder,
It can be carbonized by heat treatment within a temperature range of 00 to 3000 ° C. for 2 minutes to 2 hours.

【００４５】本発明の他の一実施例による炭素材料の製
造方法は、ピッチを有機アミン溶剤に溶解させる溶解段
階；前記溶解段階で得られた溶液を酸水溶液と混合し
て、有機アミン溶剤を塩化させる塩化段階；有機アミン
溶剤の塩化によって析出される炭素質粉末を塩水溶液か
ら濾過する濾過段階；濾過された炭素質粉末を水洗及び
乾燥する後処理段階；前記濾過段階で濾過後の濾液とし
ての塩水溶液に塩基水溶液を加える塩基水溶液付加段
階；前記塩基水溶液の添加によって中和された中和液を
放置して水性層と有機アミン溶剤層に分離された中和液
から有機アミン溶剤を回収する回収段階；及び乾燥され
た炭素質粉末を非酸化性雰囲気中で加熱して炭化させる
炭化段階；を含むことを特徴とする。According to another embodiment of the present invention, there is provided a method for producing a carbon material, comprising: dissolving pitch in an organic amine solvent; mixing the solution obtained in the dissolving step with an aqueous acid solution to remove the organic amine solvent. A filtration step of filtering a carbonaceous powder precipitated by the salting of an organic amine solvent from an aqueous salt solution; a post-treatment step of washing and drying the filtered carbonaceous powder; as a filtrate after filtration in the filtration step. A step of adding a base aqueous solution to an aqueous salt solution of the above; leaving the neutralized solution neutralized by the addition of the base aqueous solution to recover an organic amine solvent from the neutralized solution separated into an aqueous layer and an organic amine solvent layer And carbonizing the dried carbonaceous powder by heating in a non-oxidizing atmosphere.

【００４６】前記塩基水溶液付加段階では塩水溶液中に
塩の形態に存在する有機アミン溶剤を塩基水溶液と反応
させて単離された状態の有機アミン溶剤に回収すること
ができるようにする機能をする。In the step of adding the aqueous base solution, the organic amine solvent present in the form of salt in the aqueous salt solution is reacted with the aqueous base solution to recover the isolated organic amine solvent. .

【００４７】前記塩水溶液は水酸化ナトリウムや水酸化
カリウムなどのような強塩基の水溶液になり得るし、こ
れは前記有機アミン溶剤を塩化させてピッチに対する溶
解度を調節するのに使用された酸水溶液の中の酸を中和
させて、塩水溶液中に塩の形態に存在する有機アミン溶
剤を単離させる機能をする。The aqueous salt solution may be an aqueous solution of a strong base such as sodium hydroxide or potassium hydroxide, and may be an aqueous acid solution used to adjust the solubility in pitch by salinating the organic amine solvent. And a function of isolating the organic amine solvent present in the form of a salt in the aqueous salt solution by neutralizing the acid therein.

【００４８】以下で、本発明の望ましい実施例及び比較
例が記述される。以下の実施例は本発明を例証するため
のもので本発明の範囲を局限させることに理解されては
ならない。Hereinafter, preferred examples and comparative examples of the present invention will be described. The following examples are intended to illustrate the invention and should not be construed as limiting the scope of the invention.

【００４９】実施例１ 軟化点２４０℃の光学的な等方性ピッチ（２次キノリン
不融分含有量１５重量％）を有機アミン溶剤としてのキ
ノリンに５重量％の濃度で９０℃で１，０００ｒｐｍに
撹拌しながら溶解させて溶液１００ｍｌを得た。得られ
た溶液をバフル（ｂａｆｆｌｅ）が装着された撹拌用反
応槽に２５℃の窒酸２０％の水溶液４００ｍｌ中にやは
り１，０００ｒｐｍに撹拌しながら一回に全部添加し、
５分間反応させてピッチの粒子を分散させた。分散され
たピッチ粒子を濾過して６０℃、１０-2ｔｏｒｒの真空
下で８時間の間乾燥させて乾燥されたピッチ粒子４．９
５ｇを得た。得られたピッチ粒子は空気を注入しながら
常温で２８０℃まで昇温速度２℃／ｍｉｎの速度に昇温
した後、２８０℃で１時間の間維持させて不融化処理し
た。不融化処理された前記ピッチ粒子は非酸化性雰囲気
の中で炭化温度１，０００℃の温度で処理して炭素質粉
末４ｇを得た。得られた炭素質粉末は面間隙（ｄ002 ）
が３．４３０Å、ｃ軸方向の決定子の大きさ（Ｌc (00
2) ）が２０Åであったし、平均粒径は１２μｍ、標準
偏差は７．４であった。Example 1 An optically isotropic pitch having a softening point of 240 ° C. (secondary quinoline insoluble content: 15% by weight) was added to quinoline as an organic amine solvent at a concentration of 5% by weight at 90 ° C. The solution was dissolved with stirring at 000 rpm to obtain 100 ml of the solution. The resulting solution was added all at once to 400 ml of a 20% aqueous solution of nitric acid at 25 ° C. while also stirring at 1,000 rpm into a stirring reaction vessel equipped with a baffle,
The reaction was carried out for 5 minutes to disperse the particles of the pitch. The dispersed pitch particles were filtered and dried at 60 ° C. under a vacuum of 10 −2 torr for 8 hours, and the dried pitch particles were 4.9.
5 g were obtained. The obtained pitch particles were heated to 280 ° C. at room temperature at a rate of 2 ° C./min while injecting air, and then maintained at 280 ° C. for 1 hour for infusibility treatment. The infusibilized pitch particles were treated at a carbonization temperature of 1,000 ° C. in a non-oxidizing atmosphere to obtain 4 g of carbonaceous powder. The obtained carbonaceous powder has a surface gap (d 002 )
Is 3.430 °, and the size of the determinant in the c-axis direction (L c (00
2)) was 20 °, the average particle size was 12 μm, and the standard deviation was 7.4.

【００５０】また、収得された炭素質粉末の電気化学的
特性を調査するために得られた炭素質粉末を真空中、１
５０℃で乾燥させた後、１０重量％のポリビニリデンフ
ルオライドをバインダーにして混合した後、重量３７ｇ
で直径１５．５ｍｍの円形ペレット成形し、製造された
ペレットは約４００ｋｇ／ｃｍ2 の圧力でニッケル金属
網に圧着、固定させてコイン型のセルを製造したし、セ
ルの製造条件及び充電、放電試験条件を各表１及び表２
に示したし、充電、放電テスターは日本国いわき市に所
在のトーヨー社のサイクラー（Ｔｏｙｏ Ｃｙｃｌｅ
ｒ）を使用して、その結果の炭素質粉末の一般物性及び
電気化学的物性を下の表３に整理して示した。Further, the obtained carbonaceous powder was examined under vacuum in order to investigate the electrochemical characteristics of the obtained carbonaceous powder.
After drying at 50 ° C. and mixing with 10% by weight of polyvinylidene fluoride as a binder, the weight was 37 g.
The resulting pellets were pressed into a nickel metal mesh at a pressure of about 400 kg / cm 2 and fixed to form a coin-shaped cell, and the cell manufacturing conditions, charging and discharging were performed. Table 1 and Table 2
The charge and discharge tester is a Toyo Cycler (Toyo Cycle) located in Iwaki, Japan.
Table 3 below summarizes the general and electrochemical properties of the resulting carbonaceous powder using r).

【００５１】[0051]

【表１】 [Table 1]

【００５２】[0052]

【表２】 [Table 2]

【００５３】実施例２ 軟化点２４０℃のコールタールピッチに製造した光学的
等方性ピッチ（２次キノリン不溶分含有量１５重量％）
を有機アミン溶剤としてのキノリンに５重量％の濃度で
９０℃で１，０００ｒｐｍに撹拌しながら溶解させて溶
液１００ｍｌを得た。得られた溶液をバフルが装着され
た撹拌用反応槽に２５℃の燐酸２０％の水溶液４００ｍ
ｌ中にやはり１，０００ｒｐｍで撹拌しながら一回に全
部添加し、５分間反応させてピッチの粒子を分散させ
た。分散されたピッチ粒子を濾過して８０℃、常圧下で
４時間の間乾燥させて乾燥されたピッチ粒子４．９８ｇ
を得た。得られたピッチ粒子は空気を注入しながら常温
で２８０℃まで昇温速度２℃／ｍｉｎに昇温した後、２
８０℃で１時間維持させて不融化処理した。不融化処理
された前記ピッチ粒子は非酸化性雰囲気の中で炭化温度
１，０００℃の温度で処理して炭素質粉末４ｇを得た。
得られた炭素質粉末はｄ002 が３．４３０Å、Ｌc (00
2) が２０Åであったし、平均粒径は１５μｍ、標準偏
差は５．５であった。また、得られた炭素質粉末の電気
化学性特性を前記実施例１と同一に遂行したし、その結
果をやはり表３に示した。Example 2 Optically isotropic pitch produced on a coal tar pitch having a softening point of 240 ° C. (secondary quinoline insoluble content: 15% by weight)
Was dissolved in quinoline as an organic amine solvent at a concentration of 5% by weight at 90 ° C. with stirring at 1,000 rpm to obtain 100 ml of a solution. The obtained solution is placed in a stirring reaction vessel equipped with a baffle and placed in a 400 m aqueous solution of 20% phosphoric acid at 25 ° C.
The mixture was added all at once while also stirring at 1,000 rpm in the mixture, and reacted for 5 minutes to disperse the particles of the pitch. The dispersed pitch particles were filtered, dried at 80 ° C. under normal pressure for 4 hours, and 4.98 g of the dried pitch particles were dried.
I got The obtained pitch particles were heated to 280 ° C. at room temperature at a rate of 2 ° C./min while injecting air.
The mixture was maintained at 80 ° C. for 1 hour for infusibility treatment. The infusibilized pitch particles were treated at a carbonization temperature of 1,000 ° C. in a non-oxidizing atmosphere to obtain 4 g of carbonaceous powder.
The resulting carbonaceous powder had d 002 of 3.430 ° and L c (00
2) was 20 °, the average particle size was 15 μm, and the standard deviation was 5.5. Also, the electrochemical properties of the obtained carbonaceous powder were the same as in Example 1, and the results are also shown in Table 3.

【００５４】実施例３ 軟化点２４０℃のナフタレンで製造した光学的な異方性
ピッチ（２次キノリン不溶分含有量３２重量％）を有機
アミン溶剤としてのキノリンに５重量％の濃度に９０℃
で、１，０００ｒｐｍで撹拌しながら溶解させて溶液１
００ｍｌを得た。得られた溶液をバフルが装着された撹
拌用反応槽に２５℃の窒酸２０％の水溶液４００ｍｌの
中にやはり１，０００ｒｐｍで撹拌しながら一回に全部
添加し、５分間反応させてピッチ粒子を分散させた。分
散されたピッチ粒子を濾過して６０℃、１０-2ｔｏｒｒ
の真空下で８時間の間乾燥させて乾燥されたピッチ粒子
４．９５ｇを得た。得られたピッチ粒子は空気を注入し
ながら常温で２７０℃まで昇温速度５℃／ｍｉｎに昇温
した後、２７０℃で１時間維持させて不融化処理した。
不融化処理された前記ピッチ粒子は非酸化性雰囲気の中
で炭化温度７００℃の温度で処理して炭素質粉末４．２
２ｇを得た後、３，０００℃の温度で２分間不活性雰囲
気で熱処理して黒鉛質炭素質粉末４．１０ｇを得た。得
られた炭素質粉末はｄ002 が３．３９０Å、Ｌc (002)
が４５０Åであったし、平均粒径９．１μｍ、標準偏差
は３．９であった。また、得られた炭素質粉末の電気化
学的特性を前記実施例１と同一に遂行したし、その結果
をやはり表３に示した。Example 3 An optically anisotropic pitch (with a secondary quinoline insoluble content of 32% by weight) made of naphthalene having a softening point of 240 ° C. was added to quinoline as an organic amine solvent at a concentration of 5% by weight at 90 ° C.
And dissolve with stirring at 1,000 rpm to obtain solution 1
00 ml were obtained. The obtained solution was added all at once to a stirring reaction vessel equipped with a baffle in 400 ml of a 20% aqueous solution of nitric acid at 25 ° C. while also stirring at 1,000 rpm, and reacted for 5 minutes to prepare pitch particles. Was dispersed. The dispersed pitch particles are filtered at 60 ° C. and 10 −2 torr.
For 8 hours to obtain 4.95 g of dried pitch particles. The obtained pitch particles were heated at room temperature to 270 ° C. at a heating rate of 5 ° C./min while injecting air, and then maintained at 270 ° C. for 1 hour for infusibility treatment.
The infusibilized pitch particles are treated at a carbonization temperature of 700 ° C. in a non-oxidizing atmosphere to obtain a carbonaceous powder 4.2.
After obtaining 2 g, the mixture was heat-treated at 3,000 ° C. for 2 minutes in an inert atmosphere to obtain 4.10 g of a graphitic carbonaceous powder. The resulting carbonaceous powder had d 002 of 3.390 ° and L c (002)
Was 450 °, the average particle size was 9.1 μm, and the standard deviation was 3.9. Also, the electrochemical properties of the obtained carbonaceous powder were the same as in Example 1, and the results are also shown in Table 3.

【００５５】実施例４ 軟化点２３０℃のメチルナフタレンで製造した光学的異
方性ピッチ（２次キノリン不溶分含有量３０重量％）を
有機アミン溶剤としてのキノリンに５重量％の濃度に９
０℃で１，０００ｒｐｍで撹拌しながら溶解させて溶液
１００ｍｌを得た。得られた溶液をバフルが装着された
撹拌用反応槽に２５℃の窒酸２０％の水溶液４００ｍｌ
の中にやはり１，０００ｒｐｍで撹拌しながら一回に全
部添加して、５分間反応させてピッチ粒子を分散させ
た。分散されたピッチ粒子を濾過して６０℃、１０-2ｔ
ｏｒｒの真空下で８時間の間乾燥させて乾燥されたピッ
チ粒子４．９６ｇを得た。得られたピッチ粒子は空気を
注入しながら常温で２７０℃まで昇温速度５℃／ｍｉｎ
で昇温した後、２７０℃で１時間維持させて不融化処理
した。不融化処理された前記ピッチ粒子は非酸化性雰囲
気中で炭化温度７００℃の温度で処理して炭素質粉末
４．２ｇを得た後、３，０００℃の温度で２分間不活性
雰囲気で熱処理して黒鉛質炭素質粉末４．０５ｇを得
た。得られた炭素質粉末はｄ002 が３．３６０Å、Ｌc
(002) が５５０Åであったし、平均粒径１２μｍ、標準
偏差は３．４であった。また、得られた炭素質粉末の電
気化学的特性を前記実施例１と同一に遂行し、その結果
をやはり表３に示した。Example 4 An optically anisotropic pitch (30% by weight of secondary quinoline insolubles) prepared from methylnaphthalene having a softening point of 230 ° C. was added to quinoline as an organic amine solvent at a concentration of 5% by weight.
The mixture was dissolved at 0 ° C. with stirring at 1,000 rpm to obtain 100 ml of the solution. 400 ml of a 20% aqueous solution of nitric acid at 25 ° C. was placed in a stirring reaction vessel equipped with a baffle.
Was added all at once while stirring at 1,000 rpm, and reacted for 5 minutes to disperse the pitch particles. The dispersed pitch particles are filtered at 60 ° C. and 10 −2 t.
Drying under orr vacuum for 8 hours gave 4.96 g of dried pitch particles. The obtained pitch particles are heated up to 270 ° C. at room temperature while injecting air at a rate of 5 ° C./min.
, And maintained at 270 ° C. for 1 hour for infusibility treatment. The infusibilized pitch particles are treated in a non-oxidizing atmosphere at a carbonization temperature of 700 ° C. to obtain 4.2 g of carbonaceous powder, and then heat-treated at 3,000 ° C. for 2 minutes in an inert atmosphere. As a result, 4.05 g of a graphitic carbonaceous powder was obtained. The resulting carbonaceous powder had d 002 of 3.360 ° and L c
(002) was 550 °, the average particle size was 12 μm, and the standard deviation was 3.4. The electrochemical properties of the obtained carbonaceous powder were the same as in Example 1, and the results are also shown in Table 3.

【００５６】実施例５ 軟化点２３０℃のコールタールで製造した光学的異方性
ピッチ（２次キノリン不溶分含有量４０重量％）を有機
アミン溶剤としてのキノリンに５重量％の濃度に９０℃
で、１，０００ｒｐｍで撹拌しながら溶解させて溶液１
００ｍｌを得た。得られた溶液をバフルが装着された撹
拌用反応槽に２５℃の窒酸２０％の水溶液４００ｍｌの
中にやはり１，０００ｒｐｍで撹拌しながら一回に全部
添加し、５分間反応させてピッチ粒子を分散させた。分
散されたピッチ粒子を濾過して６０℃、１０-2ｔｏｒｒ
の真空下で８時間の間乾燥させて乾燥されたピッチ粒子
４．９２ｇを得た。得られたピッチ粒子は空気を注入し
ながら常温で２７０℃まで昇温速度５℃／ｍｉｎで昇温
した後、２７０℃で１時間維持させて不融化処理した。
不融化処理された前記ピッチ粒子は非酸化性雰囲気中で
炭化温度７００℃の温度で処理して、炭素質粉末４．４
２ｇを得た後、３，０００℃の温度で２分間不活性雰囲
気で熱処理して黒鉛質炭素質粉末４．２５ｇを得た。得
られた炭素質粉末はｄ002 が３．３５９Å、Ｌc (002)
が７００Åであったし、平均粒径は１４μｍ、標準偏差
は３．５であった。また、得られた炭素質粉末の電気化
学的特性を前記実施例１と同一に行ったし、その結果を
やはり表３に示した。Example 5 An optically anisotropic pitch (40% by weight of secondary quinoline insolubles) prepared from coal tar having a softening point of 230 ° C. was added to quinoline as an organic amine solvent at a concentration of 5% by weight at 90 ° C.
And dissolve with stirring at 1,000 rpm to obtain solution 1
00 ml were obtained. The obtained solution was added all at once to a stirring reaction vessel equipped with a baffle in 400 ml of a 20% aqueous solution of nitric acid at 25 ° C. while also stirring at 1,000 rpm, and reacted for 5 minutes to prepare pitch particles. Was dispersed. The dispersed pitch particles are filtered at 60 ° C. and 10 −2 torr.
For 8 hours to obtain 4.92 g of dried pitch particles. The obtained pitch particles were heated to 270 ° C. at room temperature at a rate of 5 ° C./min while injecting air, and then maintained at 270 ° C. for 1 hour for infusibility treatment.
The infusibilized pitch particles are treated at a carbonization temperature of 700 ° C. in a non-oxidizing atmosphere to obtain a carbonaceous powder 4.4.
After obtaining 2 g, the mixture was heat-treated at 3,000 ° C. for 2 minutes in an inert atmosphere to obtain 4.25 g of a graphitic carbonaceous powder. The obtained carbonaceous powder had d 002 of 3.359 ° and L c (002)
Was 700 °, the average particle size was 14 μm, and the standard deviation was 3.5. In addition, the obtained carbonaceous powder was subjected to the same electrochemical properties as in Example 1, and the results are also shown in Table 3.

【００５７】比較例１ 軟化点２４０℃のコールタールピッチで製造した光学的
等方性ピッチ（２次キノリン不溶分含有量１５重量％）
５ｇを６００℃まで熱処理して、４．１ｇの返性コーク
スを製造した後、これを粗く粉砕し、ボールミールを使
用して３日間粉砕して３．３ｇの返性コークス粒子を製
造した。製造した粒子は平均粒径が１４μｍ、標準偏差
は１２．２であった。得られた返性コークス粒子を不活
性ガスとしてアルゴンガス雰囲気下で１，０００℃まで
熱処理して炭素質粉末を得た。得られた炭素質粉末はｄ
002 が３．４１０Å、Ｌc (002) が３０Åであったし、
平均粒径は１２μｍ、標準偏差は７．４であった。ま
た、得られた炭素質粉末の電気化学的特性を前記実施例
１と同一に行ったし、その結果をやはり表３に示した。Comparative Example 1 Optically isotropic pitch produced from coal tar pitch having a softening point of 240 ° C. (secondary quinoline insoluble content: 15% by weight)
5 g was heat-treated to 600 ° C. to produce 4.1 g of returnable coke, which was coarsely pulverized and pulverized for 3 days using a ball meal to produce 3.3 g of returnable coke particles. The manufactured particles had an average particle size of 14 μm and a standard deviation of 12.2. The resulting coke particles were heat-treated to 1,000 ° C. in an argon gas atmosphere as an inert gas to obtain a carbonaceous powder. The resulting carbonaceous powder is d
002 was 3.410Å, L c (002) was 30Å,
The average particle size was 12 μm, and the standard deviation was 7.4. In addition, the obtained carbonaceous powder was subjected to the same electrochemical properties as in Example 1, and the results are also shown in Table 3.

【００５８】比較例２ 前記比較例１で製造したコークスの粒子を不活性雰囲気
下、３，０００℃で２０分間処理して黒鉛化炭素質粉末
を得た。得られた炭素質粉末の平均粒径は１１．２μ
ｍ、標準偏差は６．５であった。また、得られた炭素質
粉末の電気化学的特性を前記実施例１と同一に遂行し、
その結果をやはり表３に示した。Comparative Example 2 The coke particles produced in Comparative Example 1 were treated in an inert atmosphere at 3,000 ° C. for 20 minutes to obtain a graphitized carbonaceous powder. The average particle size of the obtained carbonaceous powder is 11.2 μm.
m, standard deviation was 6.5. Further, the electrochemical properties of the obtained carbonaceous powder were performed in the same manner as in Example 1,
The results are also shown in Table 3.

【００５９】[0059]

【表３】 [Table 3]

【００６０】前記の実施例を綜合した結果、リチウムイ
オン２次電池負極活物質用に使用するのに適切な粒度及
び化学的特性を有する炭素質粉末を非常に容易に生産す
ることができることが確認された。As a result of integrating the above examples, it was confirmed that carbonaceous powder having appropriate particle size and chemical properties suitable for use as a negative electrode active material for a lithium ion secondary battery can be produced very easily. Was done.

【００６１】[0061]

【発明の効果】従って、本発明によると粉砕及び分級な
どの過程なしに、リチウムイオン２次電池負極活物質用
で使用するのに適切な粒度及び化学的特性を有する炭素
質粉末を非常に容易に生産することができる効果があ
る。以上で本発明は記載された具体例に対してのみ詳細
に説明されたが、本発明の技術思想範囲内で多様な変形
及び修正が可能であることは当業者にとって明白なこと
であり、このような変形及び修正が添付された特許請求
の範囲に属することは当然なことである。As described above, according to the present invention, it is very easy to prepare a carbonaceous powder having a suitable particle size and chemical properties for use as a negative electrode active material for a lithium ion secondary battery without a process such as pulverization and classification. There is an effect that can be produced. Although the present invention has been described in detail only with respect to the specific examples described above, it is apparent to those skilled in the art that various modifications and variations are possible within the technical idea of the present invention. Such variations and modifications are, of course, within the scope of the appended claims.

───────────────────────────────────────────────────── フロントページの続き (72)発明者 閔 丙 勳 大韓民国 大田廣域市 儒城区 田民洞 青丘ナレ アパート 103ー406号 (72)発明者 金 榮 奎 大韓民国 大田廣域市 儒城区 田民洞 462ー５番地 世宗アパート 109ー904号 (72)発明者 尹 聖 昊 大韓民国 大田廣域市 儒城区 田民洞 462ー５番地 世宗アパート 104ー304号 (72)発明者 李 大 浩 大韓民国 仁川廣域市 南洞区 萬壽６洞 金壷アパート 104ー1403号 (72)発明者 林 弘 大韓民国 ソウル 瑞草区 盤浦洞 盤浦 アパート 104ー203号 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Min Hee-hoon, Korea No.103-406, Aooka-nare Apartment, Tamin-dong, Yuseong-gu, Daejeon-gu, Republic of Korea (72) Inventor Kim Rong-euk-yu Tamin, Yuseong-gu, Daejeon, Korea 462-5, Dong Sejong Apartment No. 109-904 (72) Inventor Yoon Seung-ho, 462-5, Tanmin-dong, Yuseong-gu, Daejeon, South Korea 104-304 Sejong Apartment No. 104-304 (72) Inventor Lee Da-Hang, Incheon, Republic of Korea No. 104-1403, Kanbo Apartment, Manju 6-dong, Namdong-gu, Seoul (72) Inventor Hiroshi Hayashi

Claims (13)

【特許請求の範囲】[Claims] 【請求項１】 ピッチを有機アミン溶剤に溶解させる溶
解段階；前記溶解段階で得られた溶液と酸水溶液を混合
して有機アミン溶剤を塩化させる塩化段階；有機アミン
溶剤の塩化によって析出される炭素質粉末を塩水溶液か
ら濾過する濾過段階；濾過された炭素質粉末を水洗及び
乾燥する後処理段階；及び乾燥された炭素質粉末を酸化
性雰囲気で不融化した後、非酸化性雰囲気中で加熱して
炭化させる炭化段階；を含むことを特徴とするリチウム
イオン２次電池負極活物質用炭素質粉末の製造方法。A dissolving step of dissolving the pitch in an organic amine solvent; a salting step of mixing the solution obtained in the dissolving step with an aqueous acid solution to salinate the organic amine solvent; carbon deposited by salification of the organic amine solvent. A filtration step of filtering the carbonaceous powder from the salt solution; a post-treatment step of washing and drying the filtered carbonaceous powder; and heating the dried carbonaceous powder in an oxidizing atmosphere and then in a non-oxidizing atmosphere. And carbonizing the carbonaceous material. The method for producing a carbonaceous powder for a negative electrode active material of a lithium ion secondary battery, comprising: 【請求項２】 前記炭素源に使用されるピッチがコール
タール、コールタールピッチ、石油系中質油、高分子の
熱分解ピッチ、芳香族炭化水素のピッチ誘導体などと、
それらから製造される全ての種類の軟化点１３０℃以上
の光学的等方性及び異方性ピッチであることを特徴とす
る請求項１に記載のリチウムイオン２次電池負極活物質
用炭素質粉末の製造方法。2. The pitch used for the carbon source is coal tar, coal tar pitch, petroleum-based medium oil, pyrolysis pitch of a polymer, pitch derivative of an aromatic hydrocarbon, or the like.
The carbonaceous powder for a negative electrode active material of a lithium ion secondary battery according to claim 1, wherein all kinds of the softening points have an optically isotropic and anisotropic pitch of 130 ° C or more. Manufacturing method. 【請求項３】 前記有機アミン溶剤が液状の脂肪族アミ
ンや芳香族アミンからなるグループの中で選択されたも
の、或いは前記有機アミン溶剤が炭素数１乃至４の液状
の脂肪族アミンでできているグループの中で選択された
もの、或いは前記有機アミン溶剤がピリジン、ピリミジ
ン、ピロール、ピロリン、ピロリジン、キノリン、アイ
ソキノリン、キノキサリン、またはこれらの２つ以上の
混合物からなるグループの中で選択されたものであるこ
とを特徴とする請求項１に記載のリチウムイオン２次電
池負極活物質用炭素質粉末の製造方法。3. The organic amine solvent is selected from the group consisting of a liquid aliphatic amine and an aromatic amine, or the organic amine solvent is a liquid aliphatic amine having 1 to 4 carbon atoms. Or the organic amine solvent is selected from the group consisting of pyridine, pyrimidine, pyrrole, pyrroline, pyrrolidine, quinoline, isoquinoline, quinoxaline, or a mixture of two or more thereof. The method for producing a carbonaceous powder for a negative electrode active material of a lithium ion secondary battery according to claim 1, wherein 【請求項４】 前記溶解段階で、炭素源としてのピッチ
が前記有機アミン溶剤に０．１乃至５０重量％の量で溶
解されることを特徴とする請求項１に記載のリチウムイ
オン２次電池負極活物質用炭素質粉末の製造方法。4. The lithium ion secondary battery as claimed in claim 1, wherein in the dissolving step, pitch as a carbon source is dissolved in the organic amine solvent in an amount of 0.1 to 50% by weight. A method for producing a carbonaceous powder for a negative electrode active material. 【請求項５】 前記塩化段階で前記酸水溶液が前記有機
アミン溶剤のアミンと塩を形成することができる塩酸、
窒酸、硫酸、燐酸、過塩素酸、弗酸、酢酸、パラトルエ
ンスルホン酸、シュウ酸、またはこれらの２つ以上の混
合物からなるグループの中で選択されたものであること
を特徴とする請求項１に記載のリチウムイオン２次電池
負極活物質用炭素質粉末の製造方法。5. The hydrochloric acid, wherein the aqueous acid solution can form a salt with the amine of the organic amine solvent in the salification step.
And at least one member selected from the group consisting of nitric acid, sulfuric acid, phosphoric acid, perchloric acid, hydrofluoric acid, acetic acid, paratoluenesulfonic acid, oxalic acid, and a mixture of two or more thereof. Item 4. The method for producing a carbonaceous powder for a negative electrode active material of a lithium ion secondary battery according to Item 1. 【請求項６】 前記塩化段階で、前記有機アミン溶剤に
前記ピッチが溶解された溶液が前記酸水溶液の０．５乃
至９０重量％の量で加えられることを特徴とする請求項
１に記載のリチウムイオン２次電池負極活物質用炭素質
粉末の製造方法。6. The method of claim 1, wherein in the salification step, a solution in which the pitch is dissolved in the organic amine solvent is added in an amount of 0.5 to 90% by weight of the aqueous acid solution. A method for producing a carbonaceous powder for a negative electrode active material of a lithium ion secondary battery. 【請求項７】 前記炭化段階の前に、前記水洗及び乾燥
された前記炭素質粉末を不融化溶液の中で酸化させて不
融化する不融化段階が遂行されることを特徴とする請求
項１に記載のリチウムイオン２次電池負極活物質用炭素
質粉末の製造方法。7. The infusibilizing step of oxidizing and infusing the washed and dried carbonaceous powder in an infusibilizing solution before the carbonizing step. 3. The method for producing a carbonaceous powder for a negative electrode active material of a lithium ion secondary battery according to item 1. 【請求項８】 前記不融化段階で、不融化溶液が窒酸水
溶液または過酸化水素水が使用されることを特徴とする
請求項１に記載のリチウムイオン２次電池負極活物質用
炭素質粉末の製造方法。8. The carbonaceous powder for a negative active material of a lithium ion secondary battery according to claim 1, wherein in the infusibilizing step, the infusibilizing solution is an aqueous solution of nitric acid or an aqueous solution of hydrogen peroxide. Manufacturing method. 【請求項９】 前記不融化段階で不融化溶液として窒酸
水溶液が使用される場合では、窒酸水溶液の５乃至９８
重量％の量の炭素質粉末が、そして過酸化水素水が使用
される場合では過酸化水素水の５乃至９０重量％の量の
炭素質粉末が使用され、安定化時間が０．１乃至１０時
間、不融化温度が１０乃至８０℃の温度範囲以内である
ことを特徴とする請求項８に記載のリチウムイオン２次
電池負極活物質用炭素質粉末の製造方法。9. In the case where an aqueous solution of nitric acid is used as the infusibilizing solution in the infusibilizing step, the aqueous solution of nitric acid may be 5 to 98%.
% Of carbonaceous powder, and if hydrogen peroxide is used, 5 to 90% by weight of hydrogen peroxide is used, and the stabilization time is 0.1 to 10%. The method for producing a carbonaceous powder for a negative electrode active material of a lithium ion secondary battery according to claim 8, wherein the time and the infusibilization temperature are within a temperature range of 10 to 80 ° C. 【請求項１０】 前記不融化段階は、酸化性雰囲気の中
で２００乃至３５０℃の温度の範囲以内で１乃至２４時
間の間熱処理することを特徴とする請求項１に記載のリ
チウムイオン２次電池負極活物質用炭素質粉末の製造方
法。10. The lithium ion secondary battery according to claim 1, wherein in the infusibilizing step, heat treatment is performed in an oxidizing atmosphere at a temperature of 200 to 350 ° C. for 1 to 24 hours. A method for producing a carbonaceous powder for a battery negative electrode active material. 【請求項１１】 前記炭化段階で、前記炭素質粉末が７
００乃至３，０００℃の温度範囲以内で２分乃至１０時
間の間熱処理することを特徴とする請求項１に記載のリ
チウムイオン２次電池負極活物質用炭素質粉末の製造方
法。11. The method according to claim 11, wherein in the carbonization step, the carbonaceous powder contains
The method of claim 1, wherein the heat treatment is performed at a temperature within a range of 00 to 3,000 ° C. for 2 minutes to 10 hours. 【請求項１２】 前記塩基水溶液付加段階で、塩基水溶
液が水酸化ナトリウムや水酸化カリウムなどのような強
塩基の水溶液であることを特徴とする請求項１に記載の
リチウムイオン２次電池負極活物質用炭素質粉末の製造
方法。12. The negative electrode active material for a lithium ion secondary battery according to claim 1, wherein in the step of adding the aqueous base solution, the aqueous base solution is an aqueous solution of a strong base such as sodium hydroxide or potassium hydroxide. A method for producing a carbonaceous powder for a substance. 【請求項１３】 ピッチを有機アミン溶剤に溶解させる
溶解段階；前記溶解段階で得られた溶液と酸水溶液を混
合して有機アミン溶剤を塩化させる塩化段階；有機アミ
ン溶剤の塩化によって析出される炭素質粉末を塩水溶液
から濾過する濾過段階；濾過された炭素質粉末を水洗及
び乾燥する後処理段階；前記濾過段階で濾過の後、濾液
としての塩水溶液に塩基水溶液を加える塩基水溶液付加
段階；中和された中和液を放置して水性層と有機アミン
溶剤層に分離された中和液から有機アミン溶剤を回収す
る回収段階；及び乾燥された炭素質粉末を酸化性雰囲気
で不融化した後、非酸化性雰囲気の中で加熱して炭化さ
せる炭化段階；を含むことを特徴とするリチウムイオン
２次電池負極活物質用炭素質粉末の製造方法。13. A dissolving step of dissolving the pitch in an organic amine solvent; a salting step of mixing the solution obtained in the dissolving step with an aqueous acid solution to salinate the organic amine solvent; carbon deposited by salification of the organic amine solvent. A filtration step of filtering the carbonaceous powder from the salt aqueous solution; a post-treatment step of washing and drying the filtered carbonaceous powder; a filtration step of adding a base aqueous solution to a salt solution as a filtrate after the filtration step; A recovery step of recovering the organic amine solvent from the neutralized liquid separated into an aqueous layer and an organic amine solvent layer by leaving the solubilized neutralized liquid; and after infusifying the dried carbonaceous powder in an oxidizing atmosphere. A carbonization step of heating and carbonizing in a non-oxidizing atmosphere; and a carbonaceous powder for a negative electrode active material of a lithium ion secondary battery.
JP10225371A 1997-07-30 1998-07-24 Method for producing carbonaceous powder for negative electrode active material of lithium ion secondary battery Expired - Fee Related JP3000272B2 (en)

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JP2018006271A (en) * 2016-07-07 2018-01-11 新日鉄住金化学株式会社 Carbon material for lithium ion secondary battery negative electrode, intermediate thereof, method for manufacturing the same, and negative electrode or battery arranged by use thereof
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KR100269923B1 (en) * 1998-03-10 2000-10-16 김순택 Method for manufacturing active material for negative electrode of lithium series secondary battery
KR100265203B1 (en) * 1998-03-10 2000-09-15 김순택 A method of preparing a negative active material for a lithium ion battery
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JPS6037046B2 (en) * 1978-02-06 1985-08-23 呉羽化学工業株式会社 Low-pulverization high-strength activated carbon and its manufacturing method
AU662644B2 (en) * 1992-06-04 1995-09-07 Conoco Inc. Process for producing solvated mesophase pitch and carbon artifacts therefrom

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JP2002110158A (en) * 2000-09-29 2002-04-12 Kawasaki Steel Corp Carbon material for lithium ion secondary battery negative pole and ite manufacturing method
JP4554795B2 (en) * 2000-09-29 2010-09-29 Ｊｆｅケミカル株式会社 Carbon material for negative electrode of lithium ion secondary battery and method for producing the same
JP2012022888A (en) * 2010-07-14 2012-02-02 Hitachi Ltd Nonaqueous electrolyte secondary battery and battery system including the same
JP2018006271A (en) * 2016-07-07 2018-01-11 新日鉄住金化学株式会社 Carbon material for lithium ion secondary battery negative electrode, intermediate thereof, method for manufacturing the same, and negative electrode or battery arranged by use thereof
CN117945391A (en) * 2024-03-27 2024-04-30 太原理工大学 Asphalt-based carbon material and preparation method and application thereof

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