WO2006109497A1 - Procédé pour la production de microbilles de mésocarbone - Google Patents

Procédé pour la production de microbilles de mésocarbone Download PDF

Info

Publication number
WO2006109497A1
WO2006109497A1 PCT/JP2006/305873 JP2006305873W WO2006109497A1 WO 2006109497 A1 WO2006109497 A1 WO 2006109497A1 JP 2006305873 W JP2006305873 W JP 2006305873W WO 2006109497 A1 WO2006109497 A1 WO 2006109497A1
Authority
WO
WIPO (PCT)
Prior art keywords
component
carbonaceous component
mesocarbon microbeads
carbonaceous
mesocarbon
Prior art date
Application number
PCT/JP2006/305873
Other languages
English (en)
Japanese (ja)
Inventor
Chiharu Yamaguchi
Juji Mondori
Akihiro Mabuchi
Ken Fujiwara
Original Assignee
Osaka Gas 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 Osaka Gas Co., Ltd. filed Critical Osaka Gas Co., Ltd.
Priority to JP2007512474A priority Critical patent/JPWO2006109497A1/ja
Publication of WO2006109497A1 publication Critical patent/WO2006109497A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
    • C10C3/00—Working-up pitch, asphalt, bitumen
    • C10C3/005—Working-up pitch, asphalt, bitumen by mixing several fractions (also coaltar fractions with petroleum fractions)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
    • C10C3/00—Working-up pitch, asphalt, bitumen
    • C10C3/002—Working-up pitch, asphalt, bitumen by thermal means

Definitions

  • the present invention relates to a method for producing mesocarbon microbeads (unfired and fired mesocarbon microbeads) useful for various carbon materials such as negative electrode materials for lithium secondary batteries and special carbon materials, mesocarbon microbeads, and
  • the present invention relates to a negative electrode for a lithium secondary battery.
  • Carbon materials (or carbon powder materials) obtained by carbonizing (carbonizing or firing) carbon precursors such as mesocarbon microbeads (MCMB) are used in various applications, such as negative electrode active materials (for example, Lithium ion secondary battery negative electrode active material) and conductive fillers are used in various applications.
  • negative electrode active materials for example, Lithium ion secondary battery negative electrode active material
  • conductive fillers are used in various applications.
  • lithium secondary batteries are attracting attention as small, lightweight, high-energy density lithium-ion secondary batteries as power sources for portable devices, and will continue to be applied to applications such as power sources mounted in automobiles and power storage. Demand growth is expected.
  • MCMB that has been fired (graphitized) has a structure similar to graphite, and therefore can intercalate and desorb lithium ions and is used as a high-capacity negative electrode material for lithium secondary batteries.
  • J. Power Sources 43-44 (1993) 233-239 Non-Patent Document 1
  • Non-Patent Document 2 The Electrochemical Society Extended Abstracts, Vol. 93-1 (1 993) 8
  • Carbon ⁇ .165 (1994 ) 261-267 Non-Patent Document 3
  • Fired (black lead) treated MCMB (fired MCMB) has a good balance of performance such as discharge capacity, efficiency, rate characteristics, bulk density and low reactivity with electrolyte, but natural graphite or artificial black lead
  • the discharge capacity tends to be inferior.
  • the firing capacity of such a fired MCMB increases to a certain extent as the firing temperature is increased.
  • the increase in firing temperature is limited in terms of equipment and costs, and is practically used. There is a limit.
  • the characteristics as a carbon material include the crystallinity, surface morphology, particle size, internal particle structure, and composition of the carbon material used. Depending on the carbon material, etc. There is growing interest in mesocarbon microbeads.
  • mesocarbon microbeads have been produced by heating pitches to about 300 to 500 ° C. and separating and recovering the generated mesocarbon microbeads by means such as solvent fractionation.
  • this method has a low production efficiency and the yield of MCMB obtained by separation is only about 10% of the weight of raw material tar.
  • the particle size of the obtained MCMB is not uniform and the surface smoothness is also lacking.
  • Patent Document 1 states that (i) coal tar is subjected to a temperature of 0.5 to 50 under conditions of a temperature of 300 to 500 ° C and a pressure of normal pressure to 20 kgZcm 2 'G. (Ii) a step of separating the solid content and the clarified liquid by centrifuging the obtained heat treatment reaction product at 150 to 450 ° C., and (iii) a step of washing the obtained solid content. A method for producing the carbon particulates provided is described. Japanese Patent Laid-Open No.
  • Patent Document 2 discloses a method for heat treating coal-based heavy oil, separating the produced crude mesocarbon microbeads, washing and purifying them, and drying them to obtain mesocarbon microbeads. It describes a method for producing mesocarbon microbeads by dispersing and classifying mesocarbon microbeads after drying with a force that does not cause destruction. However, in these methods, as described above, mesocarbon microbeads having a smooth particle surface cannot be obtained, and the yield is low.
  • Patent Document 3 by applying heat treatment to a pitch, an optically anisotropic small sphere formed in the pitch grows and merges to form a Baltamesov. Aze is finely dispersed in a silicone oil bath in a temperature range of 60 ° C to 160 ° C higher than the temperature at which the bulk mesophase has a viscosity of 200 boise, and then cooled to solidify the differentiated mesophase to bulk bulk mesophase. Manufactures mesocarbon microbeads. However, even with this method, as described above, mesophase beads with a smooth surface cannot be obtained.
  • optically anisotropic microspheres that is, mesocarbon-bon microbeads
  • a bulk mesophase precipitated and aggregated as a bulk mesophase
  • the resulting noromesophase is isolated and pulverized.
  • a pulverization process is required, and the number of processes increases and the manufacturing procedure becomes complicated.
  • heat treatment of the pulverized bulk mesophase in a silicone oil bath and then wash the silicone oil with alcohol, etc. Since it must be cleaned, waste liquid such as used silicone oil and alcohol used for cleaning is generated, which is disadvantageous in terms of cost and environment.
  • the pitches are heat-treated at 350 ° C. to 500 ° C. to produce mesocarbon spherules in the pitch.
  • the pitch is heat-treated to produce mesocarbon spherules, and then hydrocarbon oil having a boiling point of 300 ° C to the heat treatment temperature is 1Z4 to the heat-treated product.
  • Patent Document 5 discloses a method for treating crude mesocarbon microbeads produced by heat-treating petroleum heavy oil.
  • a method for coating a surface with a pitch component having a thickness of 0.1 to 1 ⁇ m is disclosed.
  • the MCMB surface be smoothed by the method of this document, but also when used as a negative electrode material for a lithium secondary battery, the primary QI component that reduces the discharge capacity and initial efficiency adheres to the MCMB surface. ing.
  • the MC component a, ⁇ , and ⁇ are adjusted to reduce volatilization and make the firing atmosphere a little oxidizing.
  • the crystallinity of MCMB decreases due to acid soot, and the cohesive component increases to obtain an agglomerated MCMB. Therefore, spherical MCMB cannot be obtained.
  • Example 1 170 parts by weight of petroleum-based FCC residual oil was mixed with 100 parts by weight of a coal-based pitch having a soft scoring point of 120 ° C, and hydrotreated at 420 ° C. It is described that a pitch-based material was obtained by heat-treating at 420 ° C and finely converting the heat-treated pitch to an average particle size of 10 ⁇ m and oxidizing it.
  • the product becomes a bulk mesophase, and spherical particles cannot be obtained. For this reason, it is difficult to increase the density as a carbon material, and the structure becomes non-uniform.
  • a pulverization process and an oxidation process are required, which complicates the process and increases costs.
  • Non-Patent Document 4 J. Anal. Appl. Prosis, Vol.68 / 69, (2003) (Non-Patent Document 4) includes a coal tar pitch for impregnation with a softening point SP of 95 ° C and an SP of 127 ° C.
  • a pitch with SP of 176 ° C or higher was synthesized by heat treatment, and the effects of mesophase formation and solid content (primary quinoline insoluble QI) in the initial stage were investigated.
  • the generated pitch is hydrogen-rich, so the mesophase phase and the isotropic phase may be easily separated by thermal filtration, and the mesophase pitch after separation may be different. It has been reported that plasticity can be expected and there is a possibility of improving impregnation. However, the softening point of the generated pitch is 176 ° C or higher, and it is practically difficult to efficiently separate the mesophase phase industrially by the method described in this document, and MCMB with almost no thermoplasticity is produced. Is not intended. Even if the product force obtained by the method of this document also separates the mesophase phase, spherical particles cannot be obtained.
  • Patent Document 7 Japanese Patent Application Laid-Open No. 61-271392 (Patent Document 7) and Japanese Patent Application Laid-Open No. 61-215692 (Patent Document 8) disclose that after a hydrogenation treatment by mixing a petroleum-based pitch with a coal-based pitch and heat-treating it.
  • Patent Document 9 discloses that a substantially isotropic premesophase pitch can be produced by substantially the same method to improve spinnability and infusibilities. Has been. Both of these methods produce high soft saddle-point pitch, which occupies most of the mesophase or premesophase structure, and use high-softening point coal pitch as a raw material, and high-soft point oil pitch as a hydrogenating agent.
  • the hydrogenating agent is removed by blowing a vacuum or an inert gas, and at the same time, the soft spot is improved.
  • the mesophase structure is separated, and it is difficult to separate the mesophase structure because the pitch is a high and soft point.
  • the solid content (primary QI content) for making the mesophase spherical causes yarn breakage during spinning. It is removed in the middle and spherical particles cannot be formed.
  • Patent Document 1 Japanese Patent Publication No. 27968 (Patents)
  • Patent Document 2 Japanese Patent Laid-Open No. 1 242691 (Claims)
  • Patent Document 3 Japanese Patent Publication No. 6-35581 (Claims)
  • Patent Document 4 Japanese Patent Publication No. 63-1241 (Claims, Examples)
  • Patent Document 5 Japanese Patent No. 3674623 (Claims)
  • Patent Document 6 Japanese Patent No. 2697482 (Claims, Examples)
  • Patent Document 7 Japanese Patent Application Laid-Open No. 61-271392 (Claims)
  • Patent Document 8 Japanese Patent Application Laid-Open No. 61-215692 (Claims)
  • Patent Document 9 Japanese Examined Patent Publication No. 62-23084 (Claims)
  • Non-Patent Document 1 Power Sources 43-44 (1993), pp. 233-239
  • Non-Patent Document 2 The Electrochemical Society Extended Abstracts, Vol.93— 1 (1993), p.8
  • Non-Patent Document 3 Carbon ⁇ .165 (1994), pp. 261-267
  • Non-Patent Document 4 J. Anal. Appl. Prosis, Vol. 68/69, (2003) pp. 409-424
  • Non-Patent Document 5 Annual Meeting of the Carbon Materials Society of Japan, 17th (1990), pp. 30-33
  • an object of the present invention is to provide a method for producing mesocarbon microbeads having a smooth surface.
  • Another object of the present invention is to provide a method capable of industrially producing mesocarbon microbeads having a smooth surface with high yield.
  • Still another object of the present invention is to provide a method for producing mesocarbon microbeads having a sharp particle size distribution and a smooth surface with high yield.
  • Another object of the present invention is to provide a crystalline high carbon material (fired mesocarbon microbeads) useful as a negative electrode active material for a lithium ion secondary battery.
  • the carbonaceous component (1) capable of producing mesocarbon microbeads (hereinafter sometimes referred to as MCMB) is the carbonaceous component.
  • MCMB mesocarbon microbeads
  • the present invention provides a heat treatment of a mixture of a carbonaceous component (1) capable of producing mesocarbon microbeads and a low-carbonaceous component (2) that is more aromatic than the carbonaceous component (1).
  • This is a method for producing mesocarbon microbeads including at least the above process. This way!
  • the ratio f / ⁇ of the fraction f is 0.95 or less (eg 0.9 or less).
  • the carbonaceous component (1) is , Coal tar and coal tar pitch force may be composed of at least one selected. Further, the carbonaceous component (1) may be a carbonaceous component having an f of about 0.9 to 0.99.
  • It may be a carbonaceous component in which the content of primary quinoline insoluble matter is about 1 to 7% by weight.
  • the carbonaceous component (2) may have a lower aromaticity than the carbonaceous component (1).
  • the carbonaceous component (2) may be hydrated, pitched or hydrogenated. It may consist of at least one selected from heavy oil.
  • the carbonaceous component (2) may be composed of ethylene bottom oil, decantyl, wasphaltene, and at least one selected from pitch force using these as raw materials.
  • the content ratio of the component (heptane-soluble component) that dissolves in heptane with respect to the mixed solvent containing heptane and dimethylformamide, which can be even if it is a fraction, in the ratio of the former Z latter (weight ratio) iZi
  • the carbonaceous component may be about% by weight.
  • the carbonaceous component (1) and the carbonaceous component (2) may each have a soft saddle point of 60 ° C. or less.
  • the quinoline insoluble content is
  • the carbonaceous component (2) is liquid at room temperature and f
  • the former Z latter (weight ratio) 90Z10-45Z55 may be sufficient.
  • the mixture may further contain a compatibilizing agent in order to improve the compatibility between the carbonaceous component (1) and the carbonaceous component (2).
  • the method may include at least a step of heat treatment as long as it includes a step of heat treatment.
  • firing treatment fired mesocarbon microbeads can be obtained.
  • the generated mesocarbon mic mouth bead is separated from the heat treated product (or reaction product, simply product, etc.), and the separated mesocarbon microbead is fired. Processed and calcined mesocarbon You can get microbeads.
  • mesocarbon microbeads obtained by the method of the present invention are spherical particles having a smooth surface.
  • Such mesocarbon microbeads (unfired mesocarbon microbeads) of the present invention have a wave number (for example, 3050 cm _ 1 ) corresponding to the C—H stretching vibration of aromatic carbon in the infrared absorption spectrum.
  • the absorption intensity is ⁇
  • the absorption intensity of the wave number corresponding to C—H stretching vibration of aliphatic carbon for example, 2920 cm— 1
  • the IlZ (II +12) value is 0.5-0. It may be about 8.
  • the mesocarbon microbeads are assumed to be spherical and the apparent specific surface area calculated by particle size force is S1, and the BET specific surface area is S2, the degree of unevenness represented by S2ZS1 is 1 to It may be about 5.
  • the present invention also includes spherical calcined mesocarbon microbeads obtained by calcining (graphitizing) the mesocarbon microbeads.
  • a calcined mesocarbon microbead may have a spherical shape and high crystallinity.
  • the value of the interplanar spacing d (002) may be about 0.3354-0.
  • Such a calcined mesocarbon microbead (carbon material) is useful for various materials such as a negative electrode active material of a lithium ion secondary battery having high crystallinity. Therefore, the present invention also includes a negative electrode for a lithium secondary battery (and a lithium secondary battery including the negative electrode) formed of the fired mesocarbon microbeads. The invention's effect
  • a mixture of a carbonaceous component capable of producing mesocarbon microbeads and a carbonaceous component having a lower aromaticity than the carbonaceous component is heat-treated, so that mesocarbon microbeads having a smooth surface are obtained.
  • mesocarbon microbeads having a sharp particle size distribution and a smooth surface can be produced with high yield.
  • Carbon materials obtained by carbonizing such mesocarbon microbeads fired mesocarbon microbeads
  • Is suitable as a raw material for various carbon materials with high crystallinity for example, a negative electrode active material for lithium ion secondary batteries and special carbon materials such as electrodes for electric discharge machining, or as a conductive filler for plastics. Can be used.
  • FIG. 1 is an electron micrograph of unfired MCMB obtained in Example 3.
  • FIG. 2 is an electron micrograph of unfired MCMB obtained in Example 4.
  • FIG. 3 is an electron micrograph of unfired MCMB obtained in Comparative Example 2.
  • a carbonaceous component (1) capable of producing mesocarbon microbeads is obtained in the presence of a carbonaceous component (2) having a lower aromaticity than the carbonaceous component (1).
  • Heat treatment produces mesocarbon microbeads.
  • any material capable of producing mesocarbon microbeads and capable of being carbonized (or graphitized) may be used.
  • aromatic compounds such as phthalene, azulene, indanthene, fluorene, phenanthrene, Two or more condensed polycyclic hydrocarbons such as anthracene, triphenylene, pyrene, taricene, naphthacene, picene, perylene, pentaphen, and pentacene; indole, isoindole, quinoline, isoquinoline, quinoxane, carbazole, atalidine, phenazine, A condensed heterocyclic compound in which a heterocyclic ring having 3 or more members such as phenanthridine and an aromatic hydrocarbon ring are condensed; anthracene oil, decrystallized anthracene oil, naphthalene oil, methylnaphthalene oil, tar
  • Aromatic oils for example, phenol resin, polyacrylo-tolyl resin, polysalt resin, etc.
  • pitches for example, coal-based pitch (coal tar pitch), petroleum-based pitch
  • the pitch is a component obtained by removing low-boiling components having a boiling point of less than 200 ° C by subjecting petroleum-based or coal-based heavy oil such as petroleum distillation residue, coal liquefied oil, coal tar, etc. to distillation operation! ⁇
  • coal tar pitch can be cited as a representative.
  • These carbonaceous components (1) may have a substituent, for example, an alkyl group, a hydroxyl group, an alkoxy group, a carboxyl group, and the like.
  • the carbonaceous component (1) is usually hydrogenated as the carbonaceous component (1) from the viewpoint of using a highly aromatic component that may be hydrogenated. In many cases, ingredients are used.
  • a ring assembly compound (such as a ring assembly hydrocarbon such as biphenyl or binaphthalene) may be used, and the ring assembly compound and the carbonaceous component (1) may be used in combination. Carbonaceous component (1) may be used alone or in combination of two or more Can be used in combination.
  • a carbonaceous component having a low low boiling point and low molecular weight non-aromatic hydrocarbon component for example, an aliphatic or alicyclic hydrocarbon component.
  • a carbonaceous component (1) from the viewpoint of cost and availability, heavy oil (especially non-hydrogenated coal-based heavy oil such as coal tar), pitches (particularly, And non-hydrogenated pitches such as coal tar pitch).
  • the carbonaceous component (1) may be a component that has been previously heat-treated (eg, heat-treated at about 300 to 500 ° C.), but is usually a carbonaceous component (1) that has not been heat-treated. There are many cases.
  • the carbonaceous component (1) may contain a primary QI component (quinoline insoluble component).
  • the content of such primary quinoline insoluble component (sometimes referred to as primary QI) is: For example, 0.1 to 7% by weight (for example, about 0.3 to 6.5% by weight) of the total carbonaceous component (1), preferably 0.8 to 4.5% by weight, and more preferably 1 to 4%. It may be about 1% to 7% by weight (for example, about 1.5 to 6.5% by weight, preferably about 1.8 to 6% by weight).
  • the primary quinoline insoluble matter contributes to the spheres of MCMB produced, while preventing MCMB from crystallizing and suppressing the aggregation (or coalescence) of MCMB. It is preferable to be contained in a moderate amount.
  • the carbonaceous component (1) is preferably a component having a low content of non-aromatic components.
  • the content of an aliphatic component is a component that is soluble in heptane (a component that is soluble in heptane or a component that is soluble in heptane, a component that is soluble in heptane).
  • the content (HS) of the heptane-soluble component to the total carbonaceous component (1) is, for example, 5% by weight or less (for example, 0 or the detection limit to about 4% by weight) It may be 3% by weight or less (for example, about 0 to 2.5% by weight), and more preferably 2% by weight or less (for example, about 0 to 1.8% by weight).
  • the soft spot (SP) of the carbonaceous component (1) can be selected from a range force of 80 ° C or less (about -80 ° C to 75 ° C), for example, 70 ° C or less (for example, — 50 ⁇ 65 ° C), preferably 60 ° C or less (eg 30 ° C to 55 ° C), more preferably 50 ° C or less (eg, about 10 ° C to 45 ° C), particularly 40 ° C or less (eg, about 0 to 35 ° C). It may be less than 30 ° C (eg, 20 ° C ⁇ 20 ° C)! /.
  • the carbonaceous component (1) may be solid or liquid (liquid) at room temperature (for example, about 15 to 25 ° C).
  • the carbonaceous component (1) is particularly liquid at room temperature or room temperature (for example, about 15 to 25 ° C.) since it is preferably liquid at the temperature at the time of separation and collection (for example, filtration temperature). Is preferred.
  • the liquid carbonaceous component (1) may be viscous (viscous material) as long as it has fluidity at room temperature.
  • MCMB can be produced without extremely high (eg, 95 ° C or higher, especially 130 ° C or higher), separation or recovery efficiency can be improved. Note that by increasing the pressure during heat treatment, the volatile matter and decomposition products during the reaction can be incorporated into the reaction system, and the rise of the soft spot of the reaction product can be suppressed to some extent. Is not only efficient and leads to cost increase, but also the surface condition of the obtained MCMB cannot be improved.
  • the aromatic carbon fraction (ratio of aromatic carbon atoms) f of the carbonaceous component (1) is usually 0.6.
  • a range force of about 88 to 0.995 can be selected, for example, 0.9 or more (for example, about 0.91 to 0.99), preferably 0.92 or more (for example, 0.93 to 0.98). Degree), more preferably 0.93 to 0.97, and usually 0.9 to 0.99.
  • the aromatic carbon fraction is the carbon atom [aromatic carbon and non-aromatic carbon (for example, aliphatic carbon (particularly alicyclic carbon, linear or branched aliphatic carbon such as alicyclic carbon, alkyl group, etc. Etc.) expressed as the abundance ratio of aromatic carbon to the sum of eg)]].
  • NMR ⁇ vector for example, 13 C NMR ⁇ vector
  • the aromatic carbon area intensity (p) and non-aromatic in the obtained spectrum are measured.
  • the carbon fraction (f) is expressed by the following equation.
  • the carbonaceous component (2) as a whole should have a lower aromaticity than the carbonaceous component (1) (specifically, it should have a lower aromatic carbon fraction), for example: (i) a relatively aromatic (Ii) Relatively low-aromatic carbonaceous components and high-aromatic carbonaceous components may be used.
  • the mixture may be a carbonaceous component having a low aromaticity as a whole as a mixture.
  • a carbonaceous component that has been hydrogenated (or hydrotreated or hydrogenated) can be suitably used as the carbonaceous component (2).
  • a relatively low molecular weight component for example, the above-described carbonizable component such as anthracene or a hydride thereof] is hydrogenated!
  • heavy oil petroleum heavy oil (petroleum distillation residue such as asphaltene, cracked heavy oil (ethylene bottom oil, decant oil), etc.), coal heavy oil (coal liquefied oil, coal tar, etc.) and These hydrides, etc.]
  • pitches that may be hydrogenated [petroleum pitch, ethylene bottom oil pitch, coal pitch (coal tar pitch, etc.), and hydrides thereof].
  • These components may be used alone or in combination of two or more.
  • a combination of heavy oil and hydride of heavy oil can be combined with hydrogen V, or can be combined with heavy oil or combined with pitch! /.
  • Preferred carbonaceous component (2) includes a heavy oil that may be hydrogenated [for example, hydrogenated Coal tar (hydride of coal tar), heavy petroleum oils (especially ethylene bottom oil), etc., pitches that may be hydrogenated (especially hydrides of coal tar pitch), etc. .
  • Particularly preferred carbonaceous components (2) include ethylene bottom oil, decant oil, and waxarte, and pitches using these as raw materials, and ethylene bottom oil, among others.
  • the carbonaceous component (2) contains a primary QI component (primary quinoline insoluble component)! /.
  • the content ratio (primary QI) of the primary QI component (primary quinoline insoluble component) is, for example, 0.2% by weight or less of the total carbonaceous component (2) (for example, 0 or detection limit to 0.2% by weight), It may be preferably 0.1% by weight or less (for example, 0 to 0.1% by weight), particularly 0.05% by weight or less (for example, 0 to 0.05% by weight).
  • the primary QI content Prior to the heat treatment, the primary QI content may be removed from the carbonaceous component (2) by means such as filtration.
  • the carbonaceous component (2) usually contains an aliphatic component (for example, an aliphatic or alicyclic hydrocarbon component). Similar to the above, the content of such an aliphatic component has a correlation with the heptane-soluble content, and the content ratio HS of the heptane-soluble content can be used as a guide for the content of the aliphatic component.
  • the content ratio (HS) of the entire carbonaceous component (2) soluble in heptane (HS) can be selected from the range of about 0.5 to 50% by weight, and 1 to 40% by weight (for example, 2 to 35% by weight) ), Preferably 3 to 30% by weight, more preferably about 4 to 25% by weight, and usually about 2 to 30% by weight.
  • the carbonaceous component (2) or mixture
  • contains an appropriate aliphatic component it will be combined with the primary quinoline insoluble matter (particularly the primary quinoline insoluble matter in the carbonaceous component (1)) (or In combination, MCMB aggregation (or coalescence) can be efficiently suppressed.
  • MCMB generally cannot maintain a spherical shape as the particle size increases, and tends to become a balta shape or a pulverized shape (or a crushed shape) in which the balta shape is pulverized, but the aliphatic component is moderately contained. If it is included, the particle surface can be smoothed while preventing the primary QI from adhering to the particle surface, and spherical MCMB can be obtained efficiently even when the particle size is increased.
  • HS is aromatic charcoal
  • FCC decant oil is composed of aromatic (aromatic) molecules with an aromatic carbon fraction of about 0.8 and saturated (aliphatic) molecules with an aromatic carbon fraction of 0. It is described that there is almost no aliphatic component when the fraction is 0.8 or more (Carbon Glossary of Terms, Carbon Materials Society of Japan, Ryogune Jofusha, p. 30).
  • the aliphatic component reduces the viscosity or softening point of the reaction product and has the effect of improving the dispersibility of the primary QI in the reaction product. It has the effect of promoting the precipitation of the resulting quinoline-insoluble matter (or secondary QI content, ie, aromatic molecules that are larger than the primary QI content).
  • the primary QI component can be prevented from adhering to the generated MCMB surface, and the primary QI component of the reaction product force and the separation of MCMB can be improved, and the primary QI component contained in MCMB (small The content of (particles with a particle size) can be reduced and the arrangement can be facilitated, so that the degree of crystallization of the fired MCMB can be improved.
  • the aromatic carbon fraction f of the carbonaceous component (2) can be selected from the range of 0.5 to 0.9, for example
  • 0.5 to 0.85 preferably 0.6 to 0.82, more preferably 0.6 to 0.8, specially 0.6 to 0.78 (e.g. 0.7 It may be about .about.0.77), but usually about 0.6 to 0.8. f
  • the hydrogenation capacity of the carbonaceous component (1) may not be sufficient as described later.
  • the ratio of the aromatic carbon fraction of the carbonaceous component (2) to the aromatic carbon fraction of the carbonaceous component (1) is, for example, 0.95 or less (eg, 0.4 to 0.95), for example a2 al
  • 0.5 to 0.9 e.g. 0.5 to 0.88
  • 0.6 to 0.85 preferably 0.63 to 0.82, especially 0.65 to 0.81. It may be a degree, and may normally be from 0.61 to 0.86. If f / ⁇ is too large, the hydrogenation capacity of the carbonaceous component (1) will decrease, and a2 al
  • the compatibility between the carbonaceous component (1) and the carbonaceous component (2) decreases, and sludge is generated.
  • the sludge is mixed into the MB, phase separation occurs due to the large specific gravity difference, uniform mixing and uniform reaction become difficult, aliphatic components are decomposed and gummed during heat treatment, and further In subsequent firing, fusion of MCMB tends to occur, which is not preferable.
  • the presence or absence of sludge can be confirmed using a mixture of carbonaceous component (1) and carbonaceous component (2).
  • the soft spot (SP) of the carbonaceous component (2) is preferably relatively low like the carbonaceous component (1).
  • 80 ° C or less eg, 100 ° C to 75 ° C, preferably 70 ° C or less (eg, about 70 to 65 ° C)], preferably 60 ° C or less (eg, about 50 ° C to 55 ° C), and more preferably 50 ° C or less (
  • about 30 ° C to 45 ° C) especially 40 ° C or less (eg — about 20 ° C to 35 ° C), usually 30 ° C or less (eg, 40 ° C to 20 ° C degree).
  • the carbonaceous component (2) may be solid or liquid (liquid) at room temperature! /, Force Normal temperature or room temperature (for example, about 15 to 25 ° C) ) Is preferably liquid.
  • the liquid carbonaceous component (2) may be viscous (viscous) as long as it has fluidity at room temperature. If the carbonaceous component (2) (and both of the carbonaceous component (1)) is liquid, the compatibility between the carbonaceous component (1) and the carbonaceous component (2) can be further improved.
  • Difference (f f) is, for example, 0.05-0.4, preferably 0.1-0.35, more preferably
  • the carbonaceous component (1) capable of generating mesocarbon microbeads and the carbon A mesocarbon microbead having a smooth surface can be obtained by heat-treating a mixture of the carbonaceous component (2), which is more aromatic than the carbonaceous component (1).
  • hydrogen ((2) is converted from aromatic low carbonaceous component (2) to carbonaceous component (1).
  • the transition of active hydrogen effectively suppresses the increase in viscosity in the reaction system due to heat treatment, and as a result, promotes the development and generation of highly crystalline mesocarbon microbeads with smooth surfaces.
  • the primary QI is also considered to be hydrogenated.
  • the carbonaceous component (2) since the viscosity in the reaction system is effectively reduced and the carbonaceous component (2) is heat-treated while covering the carbonaceous component (1), it is spherical (almost spherical) and has a narrow particle size distribution. Carbon microbeads can be obtained efficiently. That is, by mixing the carbonaceous component (1) with a carbonaceous component (2) (for example, heavy oil, pitch, etc.) that is less aromatic than the carbonaceous component (1), the system can be reduced. Viscosity can be changed, and the carbonaceous component (2) is interposed between the produced MCMB particles, so that aggregation of MCMB particles can be efficiently suppressed or prevented.
  • a carbonaceous component (2) for example, heavy oil, pitch, etc.
  • the yield of mesocarbon microbeads increases as the proportion of the carbonaceous component (1) decreases, and conversely, the yield tends to decrease as the proportion of the carbonaceous component (1) increases. Therefore, the yield of mesocarbon microbeads can be controlled by changing the weight ratio of the carbonaceous component (1) and the carbonaceous component (2). If the proportion of the carbonaceous component (2) is too small, the mixing effect will be small, and if it is too large, the MCMB produced may be too large.
  • the mixture may contain a compatibilizing agent as necessary in order to improve the compatibility between the carbonaceous component (1) and the carbonaceous component (2).
  • a compatibilizing agent include aromatic compounds having an aliphatic hydrocarbon group (for example, alkylenes such as methylnaphthalene), aromatic compounds containing a hetero atom such as a nitrogen atom, a sulfur atom, and an oxygen atom ( For example, quinoline, N-methyl-2-pyrrolidone, etc.). These compatible agents may be used alone or in combination of two or more.
  • the ratio of the compatibilizer may be, for example, about 1 to: LO wt% with respect to the entire mixture.
  • compatibility with the compatibilizer The upper effect can be enhanced as the soft spot of the carbonaceous component (1) and the carbonaceous component (2) is lowered.
  • the content of primary quinoline-insoluble matter (sometimes referred to as primary QI or QA) is, for example, 0.05 to 6% by weight (for example, 0.1 to 5). % By weight), preferably 0.2 to 4% by weight, more preferably about 0.3 to 3% by weight, usually 0.4 to 3.5% by weight (eg 0.5 to 3%). (About weight%).
  • the primary QI component has the effect of suppressing the aggregation or coalescence of the produced MCMB, and is usually contained at least in the carbonaceous component (1), and is particularly contained only in the carbonaceous component (1). It may be done. Also, if the heat treatment conditions are the same, if the amount of primary QI is large, the particle size of the produced MCMB tends to be small.
  • the mixing of the carbonaceous component (1) and the carbonaceous component (2) can be performed by a conventional method, and in particular, both components are further mixed.
  • both components are preferably mixed in liquid form rather than in solid form. That is, the mixture is preferably prepared by mixing the liquid carbonaceous component (1) and the liquid carbonaceous component (2).
  • stirring using a stirrer
  • Mixing may be performed using agitation (circulation using a pump), vibration (vibration using ultrasonic waves, etc.), circulation (circulation using a pump, etc.).
  • the heat treatment of the mixture of the carbonaceous component (1) and the carbonaceous component (2), which is less aromatic than the carbonaceous component (1) is usually performed at a temperature of 300 to 500 ° C. when performed multi ingredients preferably ⁇ or three hundred twenty to four hundred eighty o C, more [this preferably ⁇ or 340-460 o C, may be performed in the range of about JP - this 350 to 450 o C.
  • the heat treatment temperature is less than 300 ° C, the formation of mesocarbon microbeads is not sufficiently achieved, while when the heat treatment temperature exceeds 500 ° C, the heat resistance of the reaction vessel or the plant is improved. It may be difficult to maintain stability and the like, and may lack industrial practicality.
  • the reaction system during the heat treatment may be depressurized, normal pressure, or pressurized.
  • the reaction system is often pressurized.
  • the pressure in the system under pressure is about 0.15 to about LOMPa, preferably about 0.2 to 8 MPa, more preferably about 0.25 to 6MPa, special It may be about 0.3 to 5 MPa.
  • the heat treatment time can be appropriately selected in consideration of the type of raw material to be used, the heat treatment temperature, etc., and a time sufficient for the production of mesocarbon microbeads, for example, 1 to: LOO time, preferably May be 2 to 50 hours, more preferably 3 to 30 hours, particularly preferably about 5 to 20 hours.
  • substitution in the reaction system with an inert gas may not be performed, but side reactions are suppressed and the produced mesocarbon microbeads are suppressed.
  • an inert gas nitrogen, helium, argon gas, etc.
  • the reaction may be batch-type, semi-batch-type, continuous-type! /, Or deviation! /.
  • the mixture after heat treatment contains quinoline insoluble matter produced by the reaction.
  • the quinoline insoluble matter produced by such a reaction is called the secondary quinoline insoluble matter (secondary QI fraction), which is produced in contrast to the quinoline insoluble matter (primary quinoline insoluble fraction, primary QI fraction) contained in the raw material. It consists of mesocarbon microbeads.
  • the content ratio of quinoline insoluble matter (secondary quinoline content) generated by such heat treatment that is, the content ratio of secondary quinoline insoluble matter (secondary QI or A QI) increases with the progress of heat treatment.
  • Secondary QI indicates that the particles are agglomerated or coalesced and the particle size increases.
  • secondary quinoline insoluble content is, for example, 3 to 30% by weight, preferably 5 to 25% by weight, more preferably 8 to It may be about 20% by weight (for example, 10 to 15% by weight).
  • ⁇ QI can be obtained by (QI X reaction yield of reaction product) (primary QI).
  • the ratio of ⁇ QI (content ratio of quinoline insoluble matter produced by heat treatment) to primary QI (QI of the entire mixture before heat treatment) is, for example, 0.5 -20, preferably 1-18, more preferably 2-15 (eg, 2.5-14), especially around 3-12.
  • the above ratio is correlated with the average particle size of MCMB and is often roughly proportional.
  • Primary QI can be adjusted at the raw material stage and A QI can be adjusted by heat treatment conditions. However, even if these are changed, the relationship between A QI / -order QI and average particle size is almost the same. Therefore, on If the ratio is too small, the particle size of MCMB may be reduced and productivity may be reduced. If the ratio is too large, the MCMB particle size may be too large.
  • the softening point (or viscosity) of the mixture is increased by the reaction.
  • Such an increase in the soft spot or viscosity is preferably adjusted to be as low as possible from the viewpoint of enhancing the separability of the produced MCMB.
  • the soft spot (SP) of the reaction product can be selected as a range force of 150 ° C or less, for example, 130 ° C or less (eg, about 30 to 120 ° C), preferably 110 ° C or less (eg, , About 50 to 100 ° C.), more preferably 95 ° C. or less (eg, about 60 to 90 ° C.), usually about 65 to 85 ° C.
  • the soft spot of such a reaction product can be adjusted by the soft spot of carbonaceous components (1) and (2) and heat treatment conditions (for example, heat treatment under pressure), but at least It is preferable to reduce the soft spot of the reaction product by using the carbonaceous components (1) and (2) having a low soft spot.
  • the reaction product after the heat treatment is a component (liquid component) containing the generated mesocarbon microbeads (unfired or raw mesocarbon microbeads, mesocarbon microbeads before firing).
  • a combination of the carbonaceous component (1) and the carbonaceous component (2) (particularly, a combination of the liquid carbonaceous component (1) containing the primary QI component and the liquid carbonaceous component (2)).
  • a spherical MCMB with a smooth surface that cannot be separated as particles in the bulk mesophase can be obtained.
  • the recovered or separated mesocarbon microbeads are mixed with a suitable solvent [eg, tar medium oil, tar light oil, organic solvent (eg, xylene, toluene, benzene, quinoline, Lahydrofuran, dimethyl sulfoxide, dimethylformamide, hexane, etc.)] and then dried (eg, vacuum dried).
  • a suitable solvent eg, tar medium oil, tar light oil, organic solvent (eg, xylene, toluene, benzene, quinoline, Lahydrofuran, dimethyl sulfoxide, dimethylformamide, hexane, etc.)
  • the remaining liquid component from which the mesocarbon microbeads are separated may be reused as necessary.
  • the remaining liquid component may be used in place of all or part of at least one of the carbonaceous component (1) and the carbonaceous component (2) in the production method of the present invention.
  • the yield of mesocarbon microbeads obtained by the method of the present invention is high, for example, 12.5% by weight or more (eg, 12.5-50% by weight), preferably 12.8% based on the dewatered raw material. % By weight (eg 12.8-40% by weight), more preferably 13% by weight (eg 13-35% by weight), in particular 13.5% by weight (eg 13.5-30% by weight) %).
  • % By weight (eg 12.8-40% by weight), more preferably 13% by weight (eg 13-35% by weight), in particular 13.5% by weight (eg 13.5-30% by weight) %).
  • the more an aliphatic planar unit has a larger amount of aliphatic carbon, which is a reactive site, the higher the reactivity for generating MCMB, but such a raw material does not exist in the past. I got it.
  • the aromatic planar unit is enlarged and the structure is in a trade-off relationship with a large amount of aliphatic carbon. MC
  • the method of the present invention requires that the MCMB (raw MCMB) produced after the heat treatment is sufficient if it includes at least the step of heat treating the carbonaceous component (1) and the carbonaceous component (2). Furthermore, you may bake. By such firing treatment (graphitization treatment), fired MCMB (graphitized MCMB) can be obtained.
  • the present invention also includes spherical (especially true spherical) mesocarbon microbeads (MCMB) with very few deposits (or surface irregularities) attached to the surface.
  • MCMB spherical (especially true spherical) mesocarbon microbeads
  • Such MCMB is not particularly limited, but can be obtained, for example, by the above method (method using carbonaceous component (1) and carbonaceous component (2)).
  • the MCMB of the present invention is a spherical shape
  • the apparent specific surface area of MCMB calculated from the particle size is S1
  • the BET specific surface area of MCMB is S2
  • the degree of unevenness is, for example, 6 or less (for example, about 1 to 5.5), preferably 5 or less (for example, about 1.1 to 4.9), and more preferably 1.2 to 4.8 (for example, 1. about 3 to 4.5), usually 1 to 5, 4 or less [eg 1 to 3.7, preferably 1.2 to 3.6, more preferably Preferably, it can be set to 1.3 to 3.3, particularly 3 or less (for example, about 1.5 to 2.5).
  • the above irregularity is an index indicating the degree of adhesion of the deposit on the MCMB surface.
  • the irregularity is 1, it indicates that the MCMB is spherical.
  • the larger the irregularity the higher the surface irregularity (or the primary QI component, etc.). This indicates that there are many deposits).
  • the apparent specific surface area S 1 can be obtained by dividing the entire surface area of MCMB by the mass of MCMB.
  • the shape of the mesocarbon microbeads of the present invention is spherical (especially true spherical), and as described above, the surface has no deposit (or less deposit), It is smooth without large concaves and convexes.
  • the mesocarbon microbeads of the present invention show a sharp particle size distribution and the particle size is uniform).
  • the particle size distribution of the mesocarbon microbeads can be easily measured by a laser light diffraction method.
  • the particle size (D) In the cumulative frequency distribution, the particle size (D
  • the ratio (D ZD) can be expressed by a ratio of diameter (D), and the ratio (D ZD) is referred to as uniformity (D ZD).
  • column f is 5 to 200 ⁇ m, typically 6 to 150 ⁇ m, usually 8 to 120 / zm, preferably about 10 to 100 / ⁇ ⁇ . May be.
  • D is preferably 5-50 / ⁇ ⁇
  • the particle size distribution of the mesocarbon microbeads of the present invention is narrow.
  • the uniformity (D / D) is 2
  • the particle size can also be controlled by classification or the like.
  • the MCMB of the present invention is a spherical particle having a relatively small particle size, not a Balta shape. Therefore, the MCMB of the present invention has an appropriate aromatic carbon fraction.
  • the MCMB of the present invention is excellent in IR (infrared absorption spectrum).
  • Wave number corresponding to the C-H stretching vibration of aromatic carbon e.g., 3050 cm _1
  • the absorption intensity and II the absorption strength of the wave number corresponding to the C-H stretching vibration of aliphatic carbon (e.g., 2920 cm _1)
  • the value of 11 / (II +12) is 0.5 to 0.8, preferably 0.55 to 0.75, more preferably ⁇ or 0.57 to 0.7, usually 0. May be around 5 ⁇ 0.7! / ⁇ .
  • MCMB usually contains a small particle size component (primary QI component) in addition to the secondary QI component.
  • primary QI content plays an important role in MCMB generation and particle size control as described above, but primary QI content has low crystallinity when considering the use of negative electrode materials for lithium secondary batteries.
  • the MCMB does not contain as much as possible.
  • the content of primary QI in MCMB could not be removed efficiently.
  • the present invention as described above, the amount of primary QI contained in the MCMB is extremely reduced due to the effect of improving the dispersibility of the primary QI in the reaction product due to the aliphatic component.
  • the content ratio of particles having an average particle size of 1.85 m or less with respect to the entire MCMB is, for example, 7% by volume or less (for example, about 0 to 6.5% by volume), preferably Is 6% by volume or less (for example, about 0.3 to 5.5% by volume), more preferably 5% by volume or less (for example, about 0.5 to 4.5% by volume), usually 0.8 to 5% by volume.
  • % (For example, about 1 to 4.7% by volume).
  • the present invention also includes calcined mesocarbon microbeads (graphitized mesocarbon microbeads) having a smooth surface.
  • calcined mesocarbon microbeads can be obtained, for example, by calcining the mesocarbon microbeads (raw mesocarbon microbeads). That is, since the MCMB is a spherical (particularly true spherical) particle with extremely small surface irregularities, the shape is reflected even after firing, and the shape of the fired MCMB is spherical with a smooth surface. .
  • Such calcined MCM B is a spherical carbon material containing MCMB as a calcining component, and has a very high crystallinity.
  • the crystallinity of calcined MCMB is higher than when calcining only the carbonaceous component (1) without combining the carbonaceous component (2).
  • the MCMB should have a smooth and spherical surface and be appropriately hydrogenated with little primary QI. Therefore, MCMB with good crystallinity is likely to be produced by firing because of the good molecular mobility with few defects and strains in the aromatic ring.
  • the crystal structure of the graphitized mesocarbon microbeads has a value of plane spacing (crystallite spacing) d (002), for example, 0.335 to 0.340, preferably 0.335 to 0. It may be about 338 nm (for example, 0.335 to 0.336 nm), and usually about 0.3354 to 0.3357 nm.
  • plane spacing crystallite spacing
  • d plane spacing
  • Spherical fired MCMB has a small specific surface area, so that it can improve initial efficiency, packing density, safety, etc. when used for electrodes. For example, in lithium secondary battery applications, it is possible to increase the edge portion as the lithium inlet / outlet and improve the initial efficiency and rate characteristics.
  • the calcined MCMB of the present invention is a carbon material obtained by calcining (graphitizing or graphitizing) the mesocarbon microbeads (raw MCMB) as described above.
  • the produced mesocarbon microbeads (raw mesocarbon microbeads) are separated from the heat treated product, and the separated mesocarbon microbeads are fired.
  • calcined mesocarbon microbeads can be obtained.
  • Such a carbon material may be obtained by calcining (or graphitizing) the mesocarbon microbead as it is, and after carbonizing (or carbonizing or carbonizing). It may be obtained by firing treatment.
  • the carbonization temperature (or final temperature reached) may be, for example, about 450 to 1500 ° C, preferably about 500 to 1200 ° C, and more preferably about 500 to 1100 ° C.
  • Carbonization can usually be performed in a non-oxidizing atmosphere (especially in an inert atmosphere such as nitrogen, helium or argon gas) or in a vacuum.
  • Carbonization can be performed in a conventional fixed bed or fluidized bed type carbonization furnace (such as a lead hammer furnace, a tunnel furnace, or a single furnace).
  • the furnace heating method and type are not particularly limited!
  • the firing temperature (or final temperature reached) is, for example, 1700 to 3200 ° C, preferably 180 0 to 3100. C, more preferred ⁇ 1900-3000.
  • About C (for example, 1950-2900. C), 2000-2800. It may be about C, usually 2500-3200. It may be about C.
  • the firing treatment may be performed in the presence of a reducing agent (for example, coatas, graphite, charcoal, etc.) as necessary.
  • the firing treatment can be usually performed in a non-oxidizing atmosphere (particularly, an inert atmosphere such as helium, argon, neon gas) or in a vacuum, and can usually be performed in an inert atmosphere.
  • the firing treatment can be normally performed in a graphitization furnace, and the graphitization furnace is not particularly limited as long as it is a furnace that can reach a predetermined temperature.
  • an Acheson furnace Examples thereof include a direct current graphitization furnace and a vacuum furnace.
  • the firing treatment may be performed in the presence of a boron compound.
  • JP-A-11-283625 When fired in the presence of a boron compound, a fired MCMB with a high degree of graphite can be obtained. However, when the graphitization furnace (such as the Atchison furnace) is damaged or applied to the negative electrode material of a lithium battery, an overvoltage is generated. In order to increase the size, in the present invention, it is preferable to fire in the absence of a boron compound.
  • a boron compound such as the Atchison furnace
  • the final calcined product of mesocarbon microbeads is pulverized by a pulverizer (ball mill, hammer mill, etc.) to be used as a carbon material as a final product.
  • a pulverizer ball mill, hammer mill, etc.
  • the carbon material (fired mesocarbon microbeads) of the present invention has high crystallinity and is a special carbon material such as various materials, for example, electrode materials (for example, lithium secondary battery negative electrode materials and electric discharge machining electrodes). It can be used effectively as a single material or filler (plastic conductive filler, etc.).
  • the carbon material of the present invention can be suitably used as a constituent material of a negative electrode for a lithium secondary battery (further, a lithium secondary battery).
  • a lithium secondary battery a lithium secondary battery
  • the capacity can be improved as the crystallinity is improved, and the initial force, cycle characteristics, safety, rate characteristics, environmental load reduction, etc.
  • the characteristics of can be improved. In other words, by improving crystallinity, (i) improving conductivity, improving cycle characteristics, and (ii) reducing the amount of functional groups on the MCMB surface by hydrogenation, smoothness of the particle surface, primary QI, The small surface area improves efficiency and safety.
  • the present invention also includes a negative electrode (or negative electrode material) for a lithium secondary battery formed from the fired mesocarbon microbeads.
  • a negative electrode or negative electrode material for a lithium secondary battery formed from the fired mesocarbon microbeads.
  • the negative electrode current collector is not particularly limited, and a known current collector, for example, a conductor such as copper can be used.
  • a solvent that can dissolve or disperse the solder is usually used, and examples thereof include organic solvents such as N-methylpyrrolidone and N, N-dimethylformamide.
  • the organic solvents may be used alone or in combination of two or more.
  • the amount of the organic solvent used is not particularly limited as long as it becomes a paste, and is, for example, generally 60 to 150 parts by weight, preferably 60 to about LOO parts by weight with respect to 100 parts by weight of the negative electrode carbon material.
  • Examples of the noinder include fluorine-containing resin (polyvinylidene fluoride, polytetrafluoroethylene, etc.) and the like.
  • the amount of Noinda used is not particularly limited. For example, 3 to 20 parts by weight, preferably 100 parts by weight of the carbon material (baked product) May be about 5 to 15 parts by weight (for example, 5 to 10 parts by weight).
  • the method for preparing the paste is not particularly limited, and examples thereof include a method of mixing a mixed liquid (or dispersion liquid) of a binder and an organic solvent and a carbon material.
  • the negative electrode may be manufactured by using the carbon material obtained by the method of the present invention and a conductive material (carbonaceous material or conductive carbon material) in combination.
  • the use ratio of the conductive material is not particularly limited, but is usually about 1 to 10% by weight, preferably about 1 to 5% by weight, based on the total amount of the carbon material and the carbonaceous material obtained by the method of the present invention.
  • a conductive material for example, a carbonaceous material such as carbon black (for example, acetylene black, thermal black, furnace black)
  • conductivity as an electrode may be improved.
  • Conductive materials can be used alone or in combination of two or more.
  • the conductive material can be effectively used together with the carbon material by, for example, a method of mixing a paste containing a carbon material and a solvent and applying the paste to the negative electrode current collector.
  • the coating amount of the negative electrode current collector of the paste is not particularly limited, usually, 5 ⁇ 15MgZcm 2 mm, preferably 7 ⁇ 13MgZcm 2 approximately.
  • the thickness of the film applied to the negative electrode current collector is, for example, about 50 to 300 m, preferably about 80 to 200 m, and more preferably about 100 to 150 m.
  • the negative electrode current collector may be subjected to a drying treatment (for example, vacuum drying or the like).
  • the carbon material (fired MCMB) of the present invention can constitute a lithium secondary battery as a negative electrode constituent material as described above.
  • the carbon material of the present invention can constitute a lithium secondary battery for enabling repeated charge and discharge.
  • a lithium secondary battery is a combination of the negative electrode (negative electrode containing the carbon material), a positive electrode capable of occluding and releasing lithium, and an electrolyte, and a separator (such as a commonly used porous polypropylene nonwoven fabric).
  • a separator such as a commonly used porous polypropylene nonwoven fabric.
  • Polyolefin-based porous membrane separators, etc.), current collectors, gaskets, sealing plates, cases, and other battery components can be used to assemble and manufacture by conventional methods.
  • the method described in JP-A-7-249411 can be referred to.
  • the positive electrode is not particularly limited, and a known positive electrode can be used.
  • the positive electrode can be composed of, for example, a positive electrode current collector, a positive electrode active material, a conductive agent, and the like.
  • Examples of the positive electrode current collector include aluminum.
  • Examples of positive electrode active materials include TiS, MoS, NbSe, and FeS.
  • Metal oxides such as 3 6 3 2 5 2 5 2 2 2 2 2 o; polyacetylene, polyarine, polyparaphenylene, polythiol ⁇
  • Conductive conjugated polymer substances such as polypyrrole and polypyrrole can be used.
  • metal oxides especially V 2 O, Mn 0, LiCoO 3) are used.
  • Examples of the electrolyte include propylene carbonate, ethylene carbonate, and ⁇
  • Aprotic solvents such as butyrolatatane, tetrahydrofuran, 2-methyltetrahydrofuran, dioxolane, 4-methyldioxolane, sulfolane, 1,2-dimethoxyethane, dimethyl sulfoxide, aceto-tolyl, ⁇ , ⁇ ⁇ ⁇ ⁇ dimethylformamide, diethylene glycol, dimethyl ether, etc. It can be illustrated.
  • the electrolyte is a solution of LiPF, LiClO, LiBF, LiAsF, LiSbF, LiAlO, LiAlCl, LiCl, Lil, etc. in these aprotic solvents.
  • electrolytes may be used alone or in combination of two or more.
  • Preferred electrolytes include strong solvents such as tetrahydrofuran, 2-methyltetrahydrofuran, dioxolane, 4-methyldioxolane as solvents that are stable even in a strong reducing atmosphere, and ether solvents that are stable in a reducing atmosphere, and the non-protonic solvents described above.
  • a mixed solvent of two or more includes a solution in which the above exemplified salt is dissolved.
  • the lithium secondary battery can have any shape or form such as a cylindrical shape, a rectangular shape, or a button shape.
  • the mesocarbon microbeads (fired MCMB) or carbon material of the present invention is a lithium secondary battery negative electrode material having high crystallinity, an electric discharge machining electrode, a capacitor electrode material, a high-density high-strength carbon material, or the like. It can be used suitably for applications such as a unitary material of special carbon materials or plastic conductive fillers.
  • a sample was prepared by adding about 0.5 mol% of acetyl acetone acetone salt as a relaxation agent to the carbonaceous component (1) or the carbonaceous component (2).
  • the measurement was performed by a gated proton decoupling method at a temperature of 150 ° C. using a 400 MHz FT-NMR apparatus (ECX-400) manufactured by JEOL Ltd. From the ratio of the area intensity of aromatic carbon and the area intensity of non-aromatic carbon in the obtained spectrum, the aromatic carbon fraction f
  • the soft saddle point SP was measured using a heat measuring device (FP83, manufactured by METTLER TOLEDO CO., LTD.).
  • toluene insoluble matter (TI) and primary quinoline insoluble matter (QI) were measured.
  • the QI produced by the reaction (A QI) is quinoline insoluble in the reaction product after heat treatment.
  • the value was calculated from the phosphorus insoluble content Q as the value (Q XY) -Q. Also, the ratio of A QI to Q (A QI
  • HS heptane soluble fraction
  • the electron microscope was an S-3000 Scanning Electron Microscope manufactured by Hitachi, Ltd., and the applied voltage was 20 kV. And in Examples 3 to 9 and Comparative Examples 2 to 15, from the obtained electron micrographs, the particle shape was evaluated according to the following criteria:
  • A The particle surface is smooth with deposits on the particle surface.
  • X-ray diffraction measurement was performed using RINT2000 manufactured by Rigaku Corporation at a tube voltage of 40 kV and a tube current of 200 mA.
  • D / D and D were measured using a particle analyzer (JEOL HELOS SYSTEM), and the amount of particle size of 1.85 / z m or less was calculated, and D / ⁇ was calculated.
  • the BET specific surface area S2 of the particles was measured using a nitrogen adsorption BET specific surface area measuring device (manufactured by Quantachrome, NOVA2000). Then, the unevenness degree (S2ZS1) was determined by dividing the BET specific surface area S2 by the apparent specific surface area S1 determined by the particle size distribution measurement.
  • the irregularity is 1, it means that the particle is a true spherical particle, and as the irregularity increases, the irregularity on the particle surface increases (that is, the smoothness of the particle surface decreases).
  • the mixture of the filtered carbonaceous component (1) and carbonaceous component (2) at 100 ° C was checked for contamination on the filter paper according to the quinoline insoluble content analysis method CFIS K-2425).
  • a spectroscope Thermo Nicole, AVATAR370FT-IR
  • the relative aromatic fraction was calculated from the aromatic C-H stretching peak (3050 cm—intensity 11 and the aliphatic C-H stretching peak (2920 cm_strength 12) from the obtained spectrum. Since mesocarbon microbeads are insoluble in solvents and do not soften, the relative aromatic fraction by IR was applied instead of the aromatic fraction by NMR measurement. The larger the value of IlZ ( ⁇ +12), the higher the relative aromatic fraction, as in the NMR measurement.
  • LiCoO was used for the positive electrode body.
  • N, N-dimethylformamide is used as the negative electrode body.
  • the slurry obtained on the copper plate roll was applied at a thickness of 100 to 140 / zm using a negative electrode molding machine, and vacuum dried at 200 ° C. to obtain a negative electrode body.
  • electrolyte Lithium perchlorate was dissolved at a ratio of ImolZL in a mixed solvent of ethylene carbonate and jetyl carbonate (weight ratio 1: 1) to obtain an electrolytic solution.
  • a lithium secondary battery was produced using a polypropylene nonwoven fabric as a separator. The discharge characteristics of the obtained lithium secondary battery were measured.
  • the mesocarbon microbead graphite obtained (fired) in the examples was obtained by holding the mesocarbon microbead in a nitrogen atmosphere under conditions of pressure 0. IMPa and temperature 1000 ° C. Carbonized for a period of time, and then in argon atmosphere, pressure 0. IMPa and temperature 2800 ° C (Example 1, Example 2 and Comparative Example 1) or 3000 ° C (Examples 3 to 9, Comparative Examples 2 to This was performed by firing under the condition of 12).
  • the ratio of the aromatic carbon fraction of the ethylene bottom oil to the aromatic carbon fraction of the tar tar 0.776), and the reaction was carried out by heat treatment at 430 ° C for 8 hours under pressure with nitrogen in an autoclave (0.5 MPa). The product was obtained in a yield of 63.6% by weight. The reaction product was washed with tar medium oil and tar light oil, respectively, to obtain mesocarbon microbeads at a yield of 14.5% by weight based on the dehydrated raw material.
  • the yield of the reaction product of coal tar and ethylene bottom oil was 51.4%, and the yield of mesocarbon microbeads was 15.6% by weight based on the dehydrated raw material.
  • Example 1 the conditions were the same as in Example 1 except that only coal tar was used.
  • the yield of the reaction product of coal tar was 69.9%, and the yield of mesocarbon microbeads was 12.2% by weight based on the dehydrated raw material.
  • the former Z, the latter 80Z20, with a weight ratio of 70 ° C, stirring for 1 hour, and heat treatment in an autoclave under pressure with nitrogen (0.5 MPa) at a rotation speed of 600 rpm and 430 ° C for 8 hours.
  • the reaction product was obtained in a yield of 63.6% by weight.
  • the yield of the reaction product of coal tar and ethylene bottom oil was 51.4%, and the yield of mesocarbon microbeads was 15.6% by weight based on the dehydrated raw material (dehydrated tar).
  • d (002) was 0.3354 nm, and the crystal structure was developed.
  • the discharge capacity was 358.8 mAhZg, and the initial efficiency was as high as 93.4%.
  • Example 3 mesocarbon microbeads were prepared in the same manner as Example 3 except that only coal tar was used.
  • the yield of the reaction product of coal tar was 69.9%, and the yield of mesocarbon microbeads was 12.2% by weight based on the dehydrated raw material (dehydrated tar).
  • Example 3 mesocarbon microbeads were prepared in the same manner as in Example 3 except that only the coal tar from which the obtained solid content was removed was used. Since the product was not spherical but crushed because of the absence of QI, the mesocarbon microbeads graphitized at 3000 ° C had a low crystallinity and low charge and discharge capacity. It was.
  • Example 3 mesocarbon microbeads were prepared in the same manner as in Example 3 except that only coal tar was used and heat treatment was performed at 450 ° C. for 4 hours. As a result of increasing the heat treatment temperature, the particle size became too large, and the mesocarbon microbeads could not keep a spherical shape and were in a pulverized state. Since the mesocarbon microbeads obtained in the examples (for example, Example 4) were spherical even if the particle diameter (D50) was larger, the aliphatic in ethylene bottom oil was used in addition to the primary QI. It is thought that the component contributes to spheroidization.
  • a mesocarbon microphone mouth bead was prepared in the same manner as in Example 3 except that only this solid content was used.
  • the graphite product graphitized at 3000 ° C is a graphitized product of the primary QI content itself, which has a small particle size, low crystallinity, low discharge capacity, and low charge / discharge yield.
  • Example 3 mesocarbon microbeads were prepared in the same manner as in Example 3 except that only ethylene bottom oil was used and heat treatment was performed at 400 ° C. There is no primary QI As a result, the product was not spherical but crushed. In addition, because the aromatic carbon content in the raw material was low, the crystallinity of the mesocarbon microbeads graphitized at 3000 ° C was low, and the discharge capacity and initial efficiency were also low. When the heat treatment temperature was 410 ° C or higher, the reaction system was coking and could not be stirred.
  • Example 3 mesocarbon microbeads were prepared in the same manner as in Example 3 except that only the pitch of this high softening point was used. Since the softening point of the reaction product (reaction oil) was 171.0 ° C, the primary QI and pitch components remained around the beads even after separation and washing, which was difficult to separate and wash the mesocarbon mic bead. There were many scattered.
  • Example 3 mesocarbon microbeads were prepared in the same manner as in Example 3 except that only coal tar was used and heat treatment was performed at a pressure of 1. IMPa. Even when the reaction pressure was increased, the particle size distribution, surface condition, etc. were almost the same as in Comparative Example 2.
  • Example 5 Mesocarbon microbeads were prepared in the same manner as in Example 5 except that only coal tar was used in Example 5.
  • a relatively good mesocarbon microbead was prepared in the same manner as in Example 5 except that 1.00 wt% and HS 1.3 wt% were used.
  • Example 8 Mesocarbon microbeads were prepared in the same manner as in Example 8 except that only coal tar was used in Example 8.
  • the mesocarbon microbeads were prepared in the same manner as in Example 3 except that the heat treatment was performed at 400 ° C.
  • the product was not a sphere but a crushed material due to the absence of QI.
  • the aromatic carbon fraction in the raw material is low, the mesocarbon microbeads graphitized at 3000 ° C.
  • the crystallinity of the laser was low, the discharge capacity was low, and the initial efficiency was low.
  • the heat treatment temperature was 410 ° C or higher, the reaction system was caulked and could not be stirred.
  • FIG. 1 shows an electron micrograph (285 times) of the unfired MCMB obtained in Example 3.
  • Fig. 2 shows an electron micrograph of the unfired MCMB obtained in Example 4 (160 times).
  • FIG. 3 shows an electron micrograph (660 ⁇ magnification) of the unfired MCMB obtained in Comparative Example 2, respectively.
  • the mesocarbon microbeads having a spherical shape with a narrow particle size distribution and a smooth surface were obtained with high yield.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Structural Engineering (AREA)
  • Civil Engineering (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Working-Up Tar And Pitch (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

L'invention concerne un procédé servant à produire avec un rendement de production élevé des microbilles de mésocarbone qui ont une distribution étroite de la taille des particules, des formes sphériques et des surfaces lisses, en particulier un procédé pour la production de microbilles de mésocarbone en traitant thermiquement un mélange qui comprend un composant carboné (1) et un composant carboné (2) ayant une aromaticité inférieure à celle du composant (1) et qui a un rapport fa2/fa1 inférieur ou égal à 0,95, fa1 étant la fraction de carbone aromatique du composant (1) et fa2 étant la fraction de carbone aromatique du composant (2). Le composant (1) peut être constitué d'un élément sélectionné parmi le goudron de houille et des brais de houille alors que le composant (2) peut être constitué d'huile de fond de colonne de préparation d'éthylène, d'huile décantée, d'asphaltène, de brais préparés à partir de celles-ci ou similaire. La proportion en poids du composant (1) par rapport au composant (2) peut être de 99/1 à 30/70.
PCT/JP2006/305873 2005-03-30 2006-03-23 Procédé pour la production de microbilles de mésocarbone WO2006109497A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2007512474A JPWO2006109497A1 (ja) 2005-03-30 2006-03-23 メソカーボンマイクロビーズの製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2005099570 2005-03-30
JP2005-099570 2005-03-30

Publications (1)

Publication Number Publication Date
WO2006109497A1 true WO2006109497A1 (fr) 2006-10-19

Family

ID=37086784

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2006/305873 WO2006109497A1 (fr) 2005-03-30 2006-03-23 Procédé pour la production de microbilles de mésocarbone

Country Status (4)

Country Link
JP (1) JPWO2006109497A1 (fr)
CN (1) CN101184825A (fr)
TW (1) TW200710027A (fr)
WO (1) WO2006109497A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101830457A (zh) * 2010-05-20 2010-09-15 湖南大学 一种炭微球的制备方法及杂多酸在炭微球制备和石墨化中的应用
WO2011034152A1 (fr) * 2009-09-18 2011-03-24 Ｊｘ日鉱日石エネルギー株式会社 Matériau à base de carbone d'électrode négative pour batterie rechargeable au lithium et son procédé de fabrication
WO2011162387A1 (fr) * 2010-06-25 2011-12-29 Ｊｘ日鉱日石エネルギー株式会社 Composition de départ à base de charbon pour matériau d'électrode négative de batterie secondaire au lithium-ion
WO2012046802A1 (fr) * 2010-10-08 2012-04-12 Ｊｘ日鉱日石エネルギー株式会社 Matière de graphite à déformation de réseau utile dans des électrodes négatives d'accumulateur rechargeable au lithium-ion, et accumulateur rechargeable au lithium-ion
CN103440990A (zh) * 2013-08-29 2013-12-11 电子科技大学 一种制造电化学电容器复合电极材料的方法
KR102254549B1 (ko) * 2020-06-03 2021-05-20 정영운 신규한 조립구상흑연의 제조방법

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102653397A (zh) * 2011-03-01 2012-09-05 辽宁科技大学 一种煤焦油基中间相炭微球的制备方法
CN102181299B (zh) * 2011-04-01 2013-04-24 常州黑玛新型碳材料工程技术研究中心有限公司 一种中间相沥青的制备方法
CN102633245A (zh) * 2011-05-27 2012-08-15 天津市贝特瑞新能源材料有限责任公司 一种中间相炭微球d50的控制方法及生产中间相炭微球的装置
CN102849719A (zh) * 2011-06-29 2013-01-02 天津爱敏特电池材料有限公司 一种连续生产制备中间相炭微球的方法
CN102952561B (zh) * 2011-08-31 2014-03-12 上海宝钢化工有限公司 一种制作可调的高喹啉不溶物煤焦油的方法
US9284192B2 (en) * 2011-10-21 2016-03-15 Showa Denko K.K. Method for producing electrode material for lithium ion batteries
CN103650221B (zh) * 2011-10-21 2016-04-06 昭和电工株式会社 锂离子电池用电极材料的制造方法
JP6505020B2 (ja) * 2012-11-26 2019-04-24 ジョージア − パシフィック ケミカルズ エルエルシー ポリマ樹脂および炭素材料の調製
CN104518206B (zh) * 2013-09-26 2017-11-28 联想(北京)有限公司 一种充电电池、方法及设备
CN105036116B (zh) * 2015-08-06 2017-11-17 太原理工大学 煤油共液化残渣制备中间相沥青或中间相碳微球的方法
CN105199766B (zh) * 2015-10-22 2017-10-17 鞍山兴德材料科技股份有限公司 用于动力锂电池负极材料的中间相沥青焦原料的制备方法
CN105645379B (zh) * 2016-01-11 2018-03-02 神华集团有限责任公司 沥青硬炭材料、其制备方法及其应用
CN105905883A (zh) * 2016-04-15 2016-08-31 神华集团有限责任公司 一种中间相炭微球及其制备方法
CN106635102B (zh) * 2016-12-09 2021-03-23 山东益大新材料股份有限公司 一种超临界萃取油浆做原料生产负极材料焦的工艺及其应用
CN108587664B (zh) * 2018-03-29 2020-08-18 武汉科技大学 一种细镶嵌结构中间相沥青及其制备方法和其在高强高密石墨材料中的应用
CN113046110B (zh) * 2021-03-19 2021-11-23 北京旭阳科技有限公司 一种粘结剂沥青的制备方法、粘结剂沥青及炼铝用电极

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61215692A (ja) * 1985-03-22 1986-09-25 Sumitomo Metal Ind Ltd 高性能炭素繊維用に好適なメソフエ−ズピツチ及びその製造方法
JPH01242691A (ja) * 1988-03-24 1989-09-27 Osaka Gas Co Ltd メソカーボンマイクロビーズの製造方法
JPH07268352A (ja) * 1994-04-01 1995-10-17 Osaka Gas Co Ltd メソカーボンマイクロビーズの製造方法
JPH07278566A (ja) * 1994-04-15 1995-10-24 Osaka Gas Co Ltd メソカーボンマイクロビーズの製造方法及びメソカーボンマイクロビーズ

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61215692A (ja) * 1985-03-22 1986-09-25 Sumitomo Metal Ind Ltd 高性能炭素繊維用に好適なメソフエ−ズピツチ及びその製造方法
JPH01242691A (ja) * 1988-03-24 1989-09-27 Osaka Gas Co Ltd メソカーボンマイクロビーズの製造方法
JPH07268352A (ja) * 1994-04-01 1995-10-17 Osaka Gas Co Ltd メソカーボンマイクロビーズの製造方法
JPH07278566A (ja) * 1994-04-15 1995-10-24 Osaka Gas Co Ltd メソカーボンマイクロビーズの製造方法及びメソカーボンマイクロビーズ

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011034152A1 (fr) * 2009-09-18 2011-03-24 Ｊｘ日鉱日石エネルギー株式会社 Matériau à base de carbone d'électrode négative pour batterie rechargeable au lithium et son procédé de fabrication
US8617508B2 (en) 2009-09-18 2013-12-31 Jx Nippon Oil & Energy Corporation Carbon material for negative electrode of lithium secondary battery and method for producing the same
CN101830457A (zh) * 2010-05-20 2010-09-15 湖南大学 一种炭微球的制备方法及杂多酸在炭微球制备和石墨化中的应用
WO2011162387A1 (fr) * 2010-06-25 2011-12-29 Ｊｘ日鉱日石エネルギー株式会社 Composition de départ à base de charbon pour matériau d'électrode négative de batterie secondaire au lithium-ion
JP2012009328A (ja) * 2010-06-25 2012-01-12 Jx Nippon Oil & Energy Corp リチウムイオン二次電池負極材料用の原料炭組成物
CN102986065A (zh) * 2010-06-25 2013-03-20 吉坤日矿日石能源株式会社 锂离子二次电池负极材料用的原料炭组合物
WO2012046802A1 (fr) * 2010-10-08 2012-04-12 Ｊｘ日鉱日石エネルギー株式会社 Matière de graphite à déformation de réseau utile dans des électrodes négatives d'accumulateur rechargeable au lithium-ion, et accumulateur rechargeable au lithium-ion
JP2012084360A (ja) * 2010-10-08 2012-04-26 Jx Nippon Oil & Energy Corp 格子歪を有するリチウムイオン二次電池負極用黒鉛材料及びリチウムイオン二次電池
US9214666B2 (en) 2010-10-08 2015-12-15 Jx Nippon Oil & Energy Corporation Graphite material with lattice distortion for use in lithium-ion secondary battery negative electrodes, and lithium-ion secondary battery
CN103440990A (zh) * 2013-08-29 2013-12-11 电子科技大学 一种制造电化学电容器复合电极材料的方法
KR102254549B1 (ko) * 2020-06-03 2021-05-20 정영운 신규한 조립구상흑연의 제조방법

Also Published As

Publication number Publication date
JPWO2006109497A1 (ja) 2008-10-23
TW200710027A (en) 2007-03-16
CN101184825A (zh) 2008-05-21

Similar Documents

Publication Publication Date Title
WO2006109497A1 (fr) Procédé pour la production de microbilles de mésocarbone
CN107710467B (zh) 锂离子电池用负极材料和其用途
US10522821B2 (en) Graphite power for negative electrode active material of lithium-ion secondary battery
JP6476116B2 (ja) 炭素材料、電池電極用材料、及び電池
WO2014003135A1 (fr) Matière à base carbone, matière carbonée pour électrode de batterie et batterie
EP2403802A1 (fr) Particules de graphite composites et batterie secondaire au lithium les utilisant
US20110256449A1 (en) Organic coated fine particle powders
US10377633B2 (en) Carbon material, method for producing same, and use for same
US20190237763A1 (en) Graphite material and secondary battery electrode using same
TWI663125B (zh) 碳材料、其製造方法及其用途
DE112016000490T5 (de) Verfahren zum Herstellen von Graphitpulver für ein Negativelektrodenmaterial für eine Lithiumionen-Sekundärbatterie, negative Elektrode für eine Lithiumionen-Sekundärbatterie und Lithiumionensekundärbatterie
JP6746918B2 (ja) 非水系二次電池用炭素材、及び、リチウムイオン二次電池
JP4179720B2 (ja) 炭素材料および黒鉛材料の製造方法並びにリチウムイオン二次電池負極用材料
WO2019131863A1 (fr) Matériau d'électrode négative pour accumulateurs au lithium-ion
JPH10255791A (ja) 非水系二次電池
KR100272991B1 (ko) 리튬 2차전지 부극용 탄소재료의 제조방법
JP2000149947A (ja) リチウムイオン電池負極用グラファイト粉末
JP2009260112A (ja) 電気化学キャパシタ用正極活物質の製造方法
KR100255826B1 (ko) 2차 전지 부극용 탄소재료의 제조방법
JP2014191924A (ja) 非水系二次電池用炭素材の製造方法及びその製造方法によって得られた炭素材

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200680018802.9

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 2007512474

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: 7250/DELNP/2007

Country of ref document: IN

NENP Non-entry into the national phase

Ref country code: DE

NENP Non-entry into the national phase

Ref country code: RU

122 Ep: pct application non-entry in european phase

Ref document number: 06729821

Country of ref document: EP

Kind code of ref document: A1