JPH06239607A - Production of highly graphitized carbonaceous material and secondary battery - Google Patents
Production of highly graphitized carbonaceous material and secondary batteryInfo
- Publication number
- JPH06239607A JPH06239607A JP5047314A JP4731493A JPH06239607A JP H06239607 A JPH06239607 A JP H06239607A JP 5047314 A JP5047314 A JP 5047314A JP 4731493 A JP4731493 A JP 4731493A JP H06239607 A JPH06239607 A JP H06239607A
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- carbon material
- present
- secondary battery
- organic compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/96—Carbon-based electrodes
-
- 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
-
- 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)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、高黒鉛化炭素材料の製
造方法及びその製造方法に係わる二次電池に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a highly graphitized carbon material and a secondary battery relating to the method.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】近年、
リチウム二次電池などの負極材料として、炭素材料が、
デンドライトの生成がなくサイクル特性に優れるなどの
理由から、従前のリチウム金属などに代わる材料として
脚光を浴びつつある。2. Description of the Related Art In recent years,
As a negative electrode material for lithium secondary batteries, carbon materials are
Due to the fact that it does not generate dendrites and has excellent cycle characteristics, it is in the spotlight as a material replacing conventional lithium metal and the like.
【０００３】この種の二次電池においては、充放電時に
炭素材料の層間にリチウムイオンが吸蔵又は放出される
が、このときのリチウムイオンの吸蔵放出量すなわち負
極容量は、結晶性の高い黒鉛化の進んだ炭素材料ほど大
きいことが知られている。In this type of secondary battery, lithium ions are occluded or desorbed between the layers of the carbon material during charging / discharging. At this time, the amount of occluding / releasing lithium ions, that is, the negative electrode capacity, is highly crystalline graphitization. It is known that the more advanced carbon materials are, the larger.
【０００４】このような黒鉛化の程度（黒鉛化度）の高
い炭素材料を人工的に得るためには、炭素原料たる有機
化合物を高温、高圧下で焼成する必要がある。しかし、
高温、高圧雰囲気を作り出すことは至難である。このた
め、従来、次善策として、大気圧下で高温焼成すること
が行われている。この方法では、焼成温度を高くするこ
とによりある程度黒鉛化度の高い炭素材料が得られる。In order to artificially obtain a carbon material having such a high degree of graphitization (graphitization degree), it is necessary to calcine an organic compound as a carbon raw material under high temperature and high pressure. But,
Creating a high temperature, high pressure atmosphere is extremely difficult. For this reason, conventionally, as a second best measure, high temperature firing under atmospheric pressure has been performed. In this method, a carbon material having a high degree of graphitization can be obtained by increasing the firing temperature.
【０００５】しかしながら、焼成温度を高くするにも限
度があるので、上記の方法では、黒鉛化度の極めて高
い、すなわち二次電池の負極材料として好適な炭素材料
を製造することは困難である。このため、従来、黒鉛化
度の高い炭素材料（人造黒鉛）を簡便に得る方法の出現
が嘱望されていた。However, since there is a limit to raising the firing temperature, it is difficult to produce a carbon material having an extremely high degree of graphitization, that is, a carbon material suitable as a negative electrode material of a secondary battery, by the above method. For this reason, conventionally, there has been a strong demand for the appearance of a method for easily obtaining a carbon material having a high degree of graphitization (artificial graphite).
【０００６】本発明は、この要望に応えるべくなされた
ものであって、その目的とするところは、黒鉛化度の高
い炭素材料を簡便に得ることができる製造方法及びその
方法により得た炭素材料を負極に使用してなる大容量の
二次電池を提供するにある。The present invention has been made to meet this demand, and an object of the present invention is to provide a production method by which a carbon material having a high degree of graphitization can be easily obtained and a carbon material obtained by the method. In order to provide a large-capacity secondary battery in which is used as a negative electrode.
【０００７】[0007]
【課題を解決するための手段】上記目的を達成するため
の請求項１記載の発明に係る高黒鉛化炭素材料の製造方
法（以下、「本発明方法」と称する。）は、出発原料た
る液状有機化合物を層状構造を有する粘土鉱物の層間に
挿入した後、前記液状有機化合物を不活性ガス雰囲気下
において２０００°Ｃ以上の温度で焼成し、次いで前記
粘土鉱物を溶剤に溶かして除去する方法である。A method for producing a highly graphitized carbon material according to the invention of claim 1 (hereinafter, referred to as "the method of the present invention") for achieving the above-mentioned object is a liquid as a starting material. After inserting the organic compound between the layers of the clay mineral having a layered structure, the liquid organic compound is baked at a temperature of 2000 ° C. or higher in an inert gas atmosphere, and then the clay mineral is dissolved in a solvent to be removed. is there.
【０００８】また、請求項３記載の発明に係る二次電池
（以下、「本発明電池」と称する。）は、請求項１記載
の製造方法により製造された高黒鉛化炭素材料が、負極
に使用されてなる。In the secondary battery according to the invention of claim 3 (hereinafter referred to as "the battery of the invention"), the highly graphitized carbon material manufactured by the manufacturing method of claim 1 is used as a negative electrode. Be used.
【０００９】本発明方法では、高黒鉛化に必要な要件の
一つである高圧雰囲気が、出発原料たる液状有機化合物
を粘土鉱物の層間に挿入することにより創出される。In the method of the present invention, a high-pressure atmosphere, which is one of the requirements for high graphitization, is created by inserting a liquid organic compound as a starting material between the layers of clay minerals.
【００１０】粘土鉱物の層状構造は、主に分子間のファ
ンデルワールス力により維持されており、この層間はか
なりの高圧（５０ｋｇ／ｃｍ2 程度）下にあるので、液
状有機化合物を粘土鉱物の層間に挿入して焼成するとい
うことは、液状有機化合物を高圧反応容器内で焼成する
ことと同じことになる。本発明方法はこの原理を巧みに
利用したものである。The layered structure of clay minerals is mainly maintained by intermolecular Van der Waals forces, and since the layers are under a fairly high pressure (about 50 kg / cm 2 ), the liquid organic compound is added to the clay minerals. Inserting between layers and firing is the same as firing a liquid organic compound in a high-pressure reaction vessel. The method of the present invention skillfully utilizes this principle.
【００１１】本発明における粘土鉱物は、粘土の主成分
として天然に産出する含水ケイ酸塩の一種であり、層状
構造を有しその層間に液状有機化合物を挿入し得るもの
である。具体例としては、モンモリロナイト、バーミキ
ュライト、パイロフィライト、タルク、雲母などが挙げ
られるが、これらに限定されない。The clay mineral in the present invention is a kind of hydrous silicate that is naturally produced as a main component of clay, has a layered structure, and can insert a liquid organic compound between the layers. Specific examples include, but are not limited to, montmorillonite, vermiculite, pyrophyllite, talc, mica and the like.
【００１２】また、本発明における液状有機化合物につ
いても、粘土鉱物をこれに浸漬して、当該粘土鉱物の層
間に挿入し得るものであり、且つ、焼成により黒鉛化し
得る有機化合物であれば特に制限されない。具体例とし
ては、石油コークス、各種樹脂、コールタールピッチ、
メソフェーズピッチ、石油ピッチなどが挙げられる。な
お、常温では固形であっても加熱等の適宜の手段により
挿入時に液状となり流動性を有し得る有機化合物も本発
明における液状有機化合物に含まれる。Also, the liquid organic compound in the present invention is not particularly limited as long as it is an organic compound that can be immersed in a clay mineral to be inserted between layers of the clay mineral and can be graphitized by firing. Not done. Specific examples include petroleum coke, various resins, coal tar pitch,
Examples include mesophase pitch and petroleum pitch. The liquid organic compound in the present invention also includes an organic compound that is solid at room temperature and becomes liquid when inserted by an appropriate means such as heating to have fluidity.
【００１３】液状有機化合物は、たとえば液状有機化合
物に粘土鉱物を適宜の時間浸漬する方法などにより、容
易に粘土鉱物の層間に挿入することができる。The liquid organic compound can be easily inserted between the layers of the clay mineral by, for example, a method of immersing the clay mineral in the liquid organic compound for an appropriate time.
【００１４】本発明方法において、焼成温度が２０００
°Ｃ以上に規制されるのは、低温での焼成では、たとえ
高圧雰囲気下で行っても、黒鉛化度の高い炭素材料が得
られないからである。因みに、使用する粘土鉱物の層間
圧力によっても多少異なるが、本発明方法によれば、一
般に格子面（００２）面のｄ値（ｄ002 ）が３．３５〜
３．３６Å程度、ｃ軸方向の結晶子の大きさＬｃが１０
００Å以上の結晶性の極めて高い黒鉛化炭素材料が得ら
れる。In the method of the present invention, the firing temperature is 2000.
The reason why the temperature is regulated to not less than ° C is that a carbon material having a high degree of graphitization cannot be obtained by firing at a low temperature even if it is performed in a high pressure atmosphere. By the way, according to the method of the present invention, the d value (d 002 ) of the lattice plane (002) plane is generally 3.35 to 35 although it is slightly different depending on the interlayer pressure of the clay mineral used.
About 3.36Å, the crystallite size Lc in the c-axis direction is 10
A graphitized carbon material having an extremely high crystallinity of at least 00Å can be obtained.
【００１５】本発明電池は、上記した本発明方法により
製造した高黒鉛化炭素材料を負極に使用した二次電池で
ある。負極のリチウムイオン吸蔵放出量が多いため、容
量が大きい点が他の二次電池と異なるところである。そ
れゆえ、本発明電池を構成する正極、電解液等の他の部
材については特に制限されず、二次電池用として従来使
用され、或いは提案されている種々の材料を使用するこ
とが可能である。The battery of the present invention is a secondary battery in which the highly graphitized carbon material produced by the above-mentioned method of the present invention is used for the negative electrode. This is different from other secondary batteries in that it has a large capacity because the negative electrode has a large amount of lithium ion storage and release. Therefore, other members such as the positive electrode and the electrolytic solution constituting the battery of the present invention are not particularly limited, and various materials conventionally used or proposed for secondary batteries can be used. .
【００１６】たとえば、正極（活物質）としては、改質
ＭｎＯ2 、ＬｉＣｏＯ2 、ＬｉＮｉＯ2 、ＬｉＭｎ
Ｏ2 、ＬｉＭｎ2 Ｏ4 が例示される。For example, as the positive electrode (active material), modified MnO 2 , LiCoO 2 , LiNiO 2 , LiMn
O 2 and LiMn 2 O 4 are exemplified.
【００１７】また、電解液としては、プロピレンカーボ
ネート、エチレンカーボネート、ビニレンカーボネート
などの有機溶媒や、これらとジメチルカーボネート、ジ
エチルカーボネート、１，２−ジメトキシエタン、１，
２−ジエトキシエタン、エトキシメトキシエタンなどの
低沸点溶媒との混合溶媒に、ＬｉＰＦ6 、ＬｉＣｌ
Ｏ4 、ＬｉＣＦ3 ＳＯ3 などの電解液溶質を０．７〜
１．５Ｍ（モル／リットル）、就中１Ｍの割合で溶かし
た溶液が例示される。好適な電解液溶媒としては、エチ
レンカーボネートとジメチルカーボネートとの混合溶媒
及びビニレンカーボネートとジメチルカーボネートとの
混合溶媒が挙げられる。As the electrolytic solution, organic solvents such as propylene carbonate, ethylene carbonate, vinylene carbonate, etc., and dimethyl carbonate, diethyl carbonate, 1,2-dimethoxyethane, 1,
In a mixed solvent with a low boiling point solvent such as 2-diethoxyethane or ethoxymethoxyethane, LiPF 6 , LiCl
Electrolyte solution solutes such as O 4 and LiCF 3 SO 3 are added to 0.7-
An example is a solution of 1.5M (mol / liter), especially 1M. Suitable electrolytic solution solvents include a mixed solvent of ethylene carbonate and dimethyl carbonate and a mixed solvent of vinylene carbonate and dimethyl carbonate.
【００１８】[0018]
【作用】本発明方法において、層状構造を有する粘土鉱
物の層間に液状有機化合物を挿入し、高温で加熱する
と、当該液状有機化合物は高温、高圧下で焼成されるこ
ととなり、黒鉛化の進んだ炭素材料が生成する。また、
この本発明方法により製造した黒鉛化の進んだ炭素材料
を二次電池の負極に使用すると（本発明電池）、負極の
リチウム吸蔵放出量が多いため、容量が大きくなる。In the method of the present invention, when a liquid organic compound is inserted between layers of a clay mineral having a layered structure and heated at a high temperature, the liquid organic compound is fired at a high temperature and a high pressure, and the graphitization progresses. A carbon material is produced. Also,
When the graphitized carbon material produced by the method of the present invention is used for the negative electrode of the secondary battery (the battery of the present invention), the lithium storage and release amount of the negative electrode is large, so that the capacity becomes large.
【００１９】[0019]
【実施例】以下、本発明を実施例に基づいてさらに詳細
に説明するが、本発明は下記実施例により何ら限定され
るものではなく、その要旨を変更しない範囲において適
宜変更して実施することが可能なものである。EXAMPLES The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited by the examples described below, and various modifications may be made without departing from the scope of the invention. Is possible.
【００２０】（実施例）本発明方法により単３型（Ａ
Ａ）のリチウム二次電池（本発明電池）を作製した。(Example) AA type (A
A lithium secondary battery (invention battery) of A) was produced.
【００２１】〔正極〕正極活物質としてのＬｉＣｏＯ2
と導電剤としての黒鉛とを重量比９：１で混合して得た
混合物を、ポリイミドの５重量％Ｎ−メチルピロリドン
（ＮＭＰ）溶液に分散させてスラリーを調製し、このス
ラリーをドクターブレード法にて正極集電体としてのア
ルミニウム箔の両面に塗布した後、３５０°Ｃで２時間
真空乾燥して正極を作製した。[Positive Electrode] LiCoO 2 as a positive electrode active material
And a graphite as a conductive agent were mixed at a weight ratio of 9: 1 to obtain a slurry, which was dispersed in a 5 wt% N-methylpyrrolidone (NMP) solution of polyimide to prepare a slurry. Was applied on both sides of an aluminum foil as a positive electrode current collector, and then vacuum dried at 350 ° C. for 2 hours to produce a positive electrode.
【００２２】〔負極〕１００°Ｃに保持したメソフェー
ズピッチ中にモンモリロナイトを一昼夜（２４時間）浸
漬して、モンモリロナイト１ｇ当たり、０．１ｇのメソ
フェーズピッチをモンモリロナイトの層間に挿入した。[Negative Electrode] Montmorillonite was immersed in mesophase pitch maintained at 100 ° C. for 24 hours, and 0.1 g of mesophase pitch was inserted between the layers of montmorillonite per 1 g of montmorillonite.
【００２３】次いで、この層間化合物を、窒素気流下、
３０００°Ｃで２４時間焼成し、フッ酸でモンモリロナ
イトを溶かした後、濾過し、濾物を中和し、乾燥して高
黒鉛化炭素材料（人造黒鉛）を得た。Next, this intercalation compound was treated under a nitrogen stream.
After calcination at 3000 ° C. for 24 hours, montmorillonite was dissolved with hydrofluoric acid, filtered, the filter cake was neutralized, and dried to obtain a highly graphitized carbon material (artificial graphite).
【００２４】この高黒鉛化炭素材料の粉末Ｘ線回折によ
るｄ002 及びＬｃは、それぞれ３．３５６Å、１０００
Åであった。[0024] d 002 and Lc by powder X-ray diffraction of the highly graphitized carbon material, respectively 3.356A, 1000
It was Å.
【００２５】次いで、このようにして得た高黒鉛化炭素
材料を、ポリイミドの５重量％Ｎ−メチルピロリドン
（ＮＭＰ）溶液に分散させてスラリーを調製し、このス
ラリーをドクターブレード法にて負極集電体としての銅
箔の両面に塗布した後、３５０°Ｃで２時間真空乾燥し
て負極を作製した。Next, the highly graphitized carbon material thus obtained is dispersed in a 5% by weight solution of polyimide in N-methylpyrrolidone (NMP) to prepare a slurry, and this slurry is collected by a doctor blade method as a negative electrode. After applying on both surfaces of a copper foil as an electric body, it was vacuum dried at 350 ° C. for 2 hours to produce a negative electrode.
【００２６】〔電解液〕エチレンカーボネートとジメチ
ルカーボネートとの等体積混合溶媒に、ＬｉＰＦ6 を１
Ｍの割合で溶かして電解液を調製した。[Electrolytic Solution] 1 volume of LiPF 6 was added to an equal volume mixed solvent of ethylene carbonate and dimethyl carbonate.
An electrolyte solution was prepared by dissolving the electrolyte solution at a ratio of M.
【００２７】〔電池の作製〕以上の正負両極及び電解液
を用いて単３型の本発明電池ＢＡ１を作製した。なお、
セパレータとしては、ポリプロピレン製の微多孔膜（ポ
リプラスチックス社製、商品名「セルガード」）を使用
し、これに先の電解液を注液した。[Production of Battery] AA-type battery BA1 of the present invention was produced using the positive and negative electrodes and the electrolytic solution described above. In addition,
As the separator, a polypropylene microporous film (manufactured by Polyplastics Co., trade name "Celgard") was used, and the above electrolytic solution was injected therein.
【００２８】図１は作製した本発明電池ＢＡ１を模式的
に示す断面図であり、図示の電池ＢＡ１は、正極１、負
極２、これら両電極を離間するセパレータ３、正極リー
ド４、負極リード５、正極外部端子６、負極缶７などか
らなる。正極１及び負極２は、非水系電解液を注入され
たセパレータ３を介して渦巻き状に巻き取られた状態で
負極缶７内に収容されており、正極１は正極リード４を
介して正極外部端子６に、また負極２は負極リード５を
介して負極缶７に接続され、電池内部で生じた化学エネ
ルギーを電気エネルギーとして外部へ取り出し得るよう
になっている。FIG. 1 is a cross-sectional view schematically showing the produced battery BA1 of the present invention. The illustrated battery BA1 includes a positive electrode 1, a negative electrode 2, a separator 3 separating these two electrodes, a positive electrode lead 4, and a negative electrode lead 5. , Positive electrode external terminal 6, negative electrode can 7 and the like. The positive electrode 1 and the negative electrode 2 are housed in the negative electrode can 7 in a state of being spirally wound via the separator 3 in which the non-aqueous electrolyte solution is injected, and the positive electrode 1 is externally connected to the positive electrode via the positive electrode lead 4. The terminal 6 and the negative electrode 2 are connected to the negative electrode can 7 via the negative electrode lead 5 so that chemical energy generated inside the battery can be taken out as electric energy to the outside.
【００２９】（比較例）石油コークスを窒素雰囲気下に
おいて、大気圧下、３０００°Ｃで焼成して炭素材料を
得た。この炭素材料（ｄ002 ＝３．３７Å；Ｌｃ＝６５
０Å）を負極材料として使用したこと以外は、実施例と
同様にして、比較電池ＢＣ１を作製した。Comparative Example A carbon material was obtained by calcining petroleum coke at 3000 ° C. under a nitrogen atmosphere and atmospheric pressure. This carbon material (d 002 = 3.37Å; Lc = 65
Comparative battery BC1 was prepared in the same manner as in Example except that 0Å) was used as the negative electrode material.
【００３０】〔両電池の放電特性〕２００ｍＡで充電終
止電圧４．２Ｖまで充電した後、２００ｍＡで放電終止
電圧２．４Ｖまで放電して、両電池の放電特性を調べ
た。結果を図２に示す。[Discharge characteristics of both batteries] After being charged to a final charge voltage of 4.2 V at 200 mA, and then discharged to a final discharge voltage of 2.4 V at 200 mA, the discharge characteristics of both batteries were examined. The results are shown in Figure 2.
【００３１】図２は、両電池の放電特性を、縦軸に電池
電圧（Ｖ）を、また横軸に充放電容量（ｍＡｈ）をとっ
て示したグラフである。FIG. 2 is a graph showing the discharge characteristics of both batteries, with the vertical axis representing the battery voltage (V) and the horizontal axis representing the charge / discharge capacity (mAh).
【００３２】同図より、本発明方法により製造した高黒
鉛化炭素材料を負極に使用した本発明電池ＢＡ１は、大
気圧下で焼成して製造した炭素材料を負極に使用した比
較電池ＢＣ１に比し、容量が格段に大きいことが分か
る。From the figure, the battery BA1 of the present invention in which the highly graphitized carbon material produced by the method of the present invention is used for the negative electrode is higher than the comparative battery BC1 in which the carbon material produced by firing at atmospheric pressure is used for the negative electrode. However, it can be seen that the capacity is remarkably large.
【００３３】叙上の実施例では、本発明電池をリチウム
二次電池に適用する場合について説明したが、本発明は
リチウム二次電池に限られず、負極に炭素材料を使用す
る二次電池に広く適用し得るものである。In the above embodiments, the case where the battery of the present invention is applied to a lithium secondary battery has been described, but the present invention is not limited to the lithium secondary battery, and is widely applied to secondary batteries using a carbon material for the negative electrode. It is applicable.
【００３４】[0034]
【発明の効果】本発明方法によれば、高黒鉛化炭素材料
を極めて容易に製造することができる。また、本発明方
法により製造した高黒鉛化炭素材料を負極に使用した本
発明電池は、大きな容量を有する。以上の如く、本発明
は優れた特有の効果を奏する。According to the method of the present invention, a highly graphitized carbon material can be manufactured extremely easily. Further, the battery of the present invention using the highly graphitized carbon material produced by the method of the present invention for the negative electrode has a large capacity. As described above, the present invention has excellent unique effects.
【図１】単３型の本発明電池の断面図である。FIG. 1 is a sectional view of an AA battery of the present invention.
【図２】実施例及び比較例で作製した各リチウム二次電
池の放電特性を示すグラフである。FIG. 2 is a graph showing discharge characteristics of each lithium secondary battery manufactured in Examples and Comparative Examples.
【符号の説明】 ＢＡ１ 本発明電池 １ 正極 ２ 負極 ３ セパレータ[Explanation of reference numerals] BA1 battery 1 of the present invention 1 positive electrode 2 negative electrode 3 separator
Claims (3)
有する粘土鉱物の層間に挿入した後、前記液状有機化合
物を不活性ガス雰囲気下において２０００°Ｃ以上の温
度で焼成し、次いで前記粘土鉱物を溶剤に溶かして除去
することを特徴とする高黒鉛化炭素材料の製造方法。1. A liquid organic compound as a starting material is inserted between layers of a clay mineral having a layered structure, and the liquid organic compound is fired at a temperature of 2000 ° C. or higher in an inert gas atmosphere, and then the clay mineral. A method for producing a highly graphitized carbon material, which comprises dissolving and removing the solvent.
造方法。2. The method according to claim 1, wherein the solvent is hydrofluoric acid.
高黒鉛化炭素材料が、負極に使用されてなる二次電池。3. A secondary battery in which the highly graphitized carbon material manufactured by the manufacturing method according to claim 1 is used for a negative electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5047314A JPH06239607A (en) | 1993-02-12 | 1993-02-12 | Production of highly graphitized carbonaceous material and secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5047314A JPH06239607A (en) | 1993-02-12 | 1993-02-12 | Production of highly graphitized carbonaceous material and secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06239607A true JPH06239607A (en) | 1994-08-30 |
Family
ID=12771835
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5047314A Pending JPH06239607A (en) | 1993-02-12 | 1993-02-12 | Production of highly graphitized carbonaceous material and secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06239607A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6268086B1 (en) | 1995-04-10 | 2001-07-31 | Hitachi, Ltd. | Non-aqueous secondary battery and a method of manufacturing graphite powder |
| US6447955B1 (en) | 1993-03-30 | 2002-09-10 | Sanyo Electric Co., Ltd. | Lithium secondary battery with a negative electrode of heat-treated natural graphite |
| US7273681B2 (en) | 1995-04-10 | 2007-09-25 | Hitachi, Ltd. | Non-aqueous secondary battery having negative electrode including graphite powder |
| JP2013518022A (en) * | 2010-01-27 | 2013-05-20 | ヘレーウス クヴァルツグラース ゲゼルシャフト ミット ベシュレンクテル ハフツング ウント コンパニー コマンディートゲゼルシャフト | Porous carbon product and method for producing the same |
-
1993
- 1993-02-12 JP JP5047314A patent/JPH06239607A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6447955B1 (en) | 1993-03-30 | 2002-09-10 | Sanyo Electric Co., Ltd. | Lithium secondary battery with a negative electrode of heat-treated natural graphite |
| US6268086B1 (en) | 1995-04-10 | 2001-07-31 | Hitachi, Ltd. | Non-aqueous secondary battery and a method of manufacturing graphite powder |
| US6383467B1 (en) | 1995-04-10 | 2002-05-07 | Hitachi, Ltd. | Non-aqueous secondary battery and a method of manufacturing graphite powder |
| US6835215B2 (en) | 1995-04-10 | 2004-12-28 | Hitachi, Ltd. | Non-aqueous secondary battery and a method of manufacturing graphite powder |
| US7273681B2 (en) | 1995-04-10 | 2007-09-25 | Hitachi, Ltd. | Non-aqueous secondary battery having negative electrode including graphite powder |
| JP2013518022A (en) * | 2010-01-27 | 2013-05-20 | ヘレーウス クヴァルツグラース ゲゼルシャフト ミット ベシュレンクテル ハフツング ウント コンパニー コマンディートゲゼルシャフト | Porous carbon product and method for producing the same |
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