WO2013042223A1 - Matériau carboné pour batteries secondaires à lithium ion, matériau pour électrode négative de batteries secondaires à lithium ion, et batterie secondaire à lithium ion - Google Patents

Matériau carboné pour batteries secondaires à lithium ion, matériau pour électrode négative de batteries secondaires à lithium ion, et batterie secondaire à lithium ion Download PDF

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Publication number
WO2013042223A1
WO2013042223A1 PCT/JP2011/071462 JP2011071462W WO2013042223A1 WO 2013042223 A1 WO2013042223 A1 WO 2013042223A1 JP 2011071462 W JP2011071462 W JP 2011071462W WO 2013042223 A1 WO2013042223 A1 WO 2013042223A1
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lithium ion
ion secondary
secondary battery
carbon material
negative electrode
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PCT/JP2011/071462
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English (en)
Japanese (ja)
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晋平 阪下
要介 澤山
佐々木　龍朗
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住友ベークライト株式会社
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Priority to PCT/JP2011/071462 priority Critical patent/WO2013042223A1/fr
Publication of WO2013042223A1 publication Critical patent/WO2013042223A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a carbon material for a lithium ion secondary battery, a negative electrode material for a lithium ion secondary battery, and a lithium ion secondary battery.
  • a carbon material has been used for the negative electrode of a lithium ion secondary battery. This is because even if the charge / discharge cycle proceeds, dendritic lithium is hardly deposited on the negative electrode using the carbon material, and safety is guaranteed.
  • a carbon material includes a highly crystalline material such as graphite and an amorphous carbon material called hard carbon.
  • a material with high crystallinity such as graphite has advantages that the irreversible capacity is small and the charge / discharge efficiency is high, but there is a limit to the charge capacity and the discharge capacity, and there is a problem that it is difficult to increase the capacity.
  • the charge / discharge capacity refers to the respective electric capacities when charging and discharging are performed for the first time after the battery is created, and the charge / discharge efficiency refers to the efficiency expressed by the discharge capacity / charge capacity.
  • the interplanar spacing is evaluated by a diffraction peak measured using a general-purpose wide-angle X-ray diffractometer, and furthermore, a laminated structure of carbon hexagonal mesh planes (that is, crystal parts) in a carbon material by a Raman spectrum. And the technique which evaluated the ratio of an amorphous carbon component etc. is disclosed.
  • the crystal structure of graphite contained in an amorphous material cannot be found by wide-angle X-ray diffraction, and the high charge capacity, discharge capacity, and excellent charge / discharge efficiency of the present invention are not found.
  • the technology for coexisting amorphous / crystalline is not disclosed.
  • the present invention can solve the above-mentioned problems, and according to the present invention, a lithium ion battery having a high charge capacity and discharge capacity and excellent balance of charge capacity, discharge capacity and charge / discharge efficiency is provided. It is possible to provide a carbon material for a lithium ion secondary battery, a negative electrode material for a lithium ion secondary battery, and a lithium ion secondary battery.
  • the average interplanar spacing d of the (002) plane obtained by the wide-angle X-ray diffraction method is 3.40 mm or more and 3.90 mm or less
  • the c-axis direction Lithium ions having an amorphous structure with a crystallite size Lc of 8 to 50 mm and a graphite structure with a (002) plane spacing d of 3.25 to 3.40 mm.
  • Carbon material for secondary batteries is 3.40 mm or more and 3.90 mm or less.
  • A Light source: Synchrotron radiation
  • B Large Debye-Scherrer camera, camera radius: 286.48 mm
  • C Beam size: Length 0.3mm x width 3.0mm
  • E Incident X-ray: wavelength of 1.0 mm (12.4 keV)
  • a diffraction pattern measured by a wide-angle X-ray diffraction method under the following conditions (A) to (E) is calculated using the Bragg equation.
  • the (002) plane average plane distance d is 3.4 mm.
  • the peak of the diffraction pattern in which the crystallite size Lc in the c-axis direction is not less than 8 and not more than 50 and not more than 3.9 and has an interplanar spacing d of 3.25 to 3
  • A Light source: Synchrotron radiation
  • B Large Debye-Scherrer camera, camera radius: 286.48 mm
  • C Beam size: Length 0.3mm x width 3.0mm
  • E Incident X-ray: wavelength of 1.0 mm (12.4 keV)
  • a carbon material for a lithium ion secondary battery according to (1) or (2) above A carbon material for a lithium ion secondary battery having a specific surface area of 15 m 2 / g or less and 1 m 2 / g or more by a BET three-point method in nitrogen adsorption.
  • a carbon material for a lithium ion secondary battery containing 95 wt% or more of carbon atoms and containing 0.5 wt% or more and 5 wt% or less of nitrogen atoms as elements other than carbon atoms.
  • a negative electrode material for a lithium ion secondary battery comprising the carbon material for a lithium ion secondary battery according to any one of (1) to (4) above.
  • a method for producing a negative electrode material for a lithium ion secondary battery A method for producing a negative electrode material for a lithium ion secondary battery.
  • a carbon material for a lithium ion secondary battery a negative electrode material for a lithium ion secondary battery, and lithium capable of providing a lithium ion battery having high charge / discharge efficiency and high charge capacity and discharge capacity.
  • An ion secondary battery is provided.
  • FIG. 2 is a diffraction pattern of synchrotron radiation in Example 1.
  • FIG. It is a schematic diagram of a lithium ion secondary battery.
  • the carbon material for a lithium ion secondary battery of the present invention is Under the following conditions (A) to (E), the average interplanar spacing d of the (002) plane obtained by the wide angle X-ray diffraction method is 3.40 mm or more and 3.90 mm or less, and the crystallites in the c-axis direction
  • the average interplanar spacing d of the (002) plane obtained by the wide angle X-ray diffraction method is 3.40 mm or more and 3.90 mm or less
  • the crystallites in the c-axis direction For a lithium ion secondary battery having an amorphous structure with a size Lc of 8 to 50 mm and a graphite structure with a (002) plane spacing d of 3.25 to 3.40 mm Carbon material.
  • A Light source: Synchrotron radiation
  • B Large Debye-Scherrer camera, camera radius: 286.48 mm
  • C Beam size: Length 0.3mm x width 3.0mm
  • E Incident X-ray: wavelength of 1.0 mm (12.4 keV)
  • the raw materials or precursors used for the carbon material for lithium ion secondary batteries are not particularly limited, but the petroleum-based tars and pitches produced as a by-product during ethylene production, coal tars produced during coal dry distillation, and low coal tars are low. Heavy components obtained by distilling off boiling components and pitches, petroleum-based or coal-based tars or pitches such as tars and pitches obtained by liquefaction of coal, and those obtained by crosslinking the tars, pitches, etc., and thermosetting A resin obtained by carbonizing a resin or a resin composition such as an adhesive resin or a thermoplastic resin is preferable, and a resin or a resin composition described below is particularly preferable.
  • the resin composition contains the above resin as a main component and can contain a curing agent, an additive and the like.
  • thermosetting resin is not particularly limited.
  • a phenol resin such as a novolac type phenol resin or a resol type phenol resin
  • an epoxy resin such as a bisphenol type epoxy resin or a novolac type epoxy resin
  • a melamine resin such as a bisphenol type epoxy resin or a novolac type epoxy resin
  • a melamine resin such as a bisphenol type epoxy resin or a novolac type epoxy resin
  • a melamine resin such as a bisphenol type epoxy resin or a novolac type epoxy resin
  • a melamine resin such as a bisphenol type epoxy resin or a novolac type epoxy resin
  • a melamine resin such as a bisphenol type epoxy resin or a novolac type epoxy resin
  • a melamine resin such as a bisphenol type epoxy resin or a novolac type epoxy resin
  • a melamine resin such as a bisphenol type epoxy resin or a novolac type epoxy resin
  • a melamine resin such as a bis
  • thermoplastic resin is not particularly limited.
  • polyethylene polystyrene, polyacrylonitrile, acrylonitrile-styrene (AS) resin, acrylonitrile-butadiene-styrene (ABS) resin, polypropylene, vinyl chloride, methacrylic resin, polyethylene terephthalate, Polyamide, polycarbonate, polyacetal, polyphenylene ether, polybutylene terephthalate, polyphenylene sulfide, polysulfone, polyethersulfone, polyetheretherketone, polyetherimide, polyamideimide, polyimide, polyphthalamide, and the like can be given.
  • thermosetting resin is preferable as the resin as the main component used in the carbon material of the present invention. Thereby, the remaining carbon rate of a carbon material can be raised more.
  • thermosetting resins it is preferably selected from novolac type phenol resins, resol type phenol resins, melamine resins, furan resins, aniline resins, and modified products thereof. Thereby, the freedom degree of design of a carbon material spreads and it can manufacture at low cost.
  • curing agent when using a thermosetting resin, can be used together.
  • curing agent used here for example, in the case of a novolak-type phenol resin, a hexamethylene tetramine, a resol type phenol resin, a polyacetal, paraform etc. can be used.
  • epoxy resins known as epoxy resins such as polyamine compounds such as aliphatic polyamines and aromatic polyamines, acid anhydrides, imidazole compounds, dicyandiamide, novolac-type phenol resins, bisphenol-type phenol resins, and resol-type phenol resins. Can be used. Even if it is a thermosetting resin that usually uses a predetermined amount of a curing agent, the resin composition used in the present invention may use a smaller amount than usual or may be used without using a curing agent. You can also.
  • an additive can be mix
  • the additive used here is not particularly limited.
  • a carbon material precursor carbonized at 200 to 800 ° C., an organic acid, an inorganic acid, a nitrogen-containing compound, an oxygen-containing compound, an aromatic compound, and a non-ferrous metal A metal element etc. can be mentioned.
  • the above additives may be used alone or in combination of two or more depending on the type and properties of the resin used.
  • the resin used for the carbon material of the present invention may contain nitrogen-containing resins described later as the main component resin. Moreover, when the nitrogen-containing resin is not contained in the main component resin, at least one kind of nitrogen-containing compound may be included as a component other than the main component resin, or the nitrogen-containing resin is included as the main component resin. In addition, a nitrogen-containing compound may be included as a component other than the main component resin. By carbonizing such a resin, a carbon material containing nitrogen can be obtained.
  • thermosetting resins include melamine resins, urea resins, aniline resins, cyanate resins, urethane resins, phenol resins modified with nitrogen-containing components such as amines, and epoxy resins.
  • thermoplastic resin include polyacrylonitrile, acrylonitrile-styrene (AS) resin, acrylonitrile-butadiene-styrene (ABS) resin, polyamide, polyetherimide, polyamideimide, polyimide, polyphthalamide, and the like.
  • thermosetting resin examples include phenol resin, epoxy resin, furan resin, and unsaturated polyester resin.
  • thermoplastic resin examples include polyethylene, polystyrene, polypropylene, vinyl chloride, methacrylic resin, polyethylene terephthalate, polycarbonate, polyacetal, polyphenylene ether, polybutylene terephthalate, polyphenylene sulfide, polysulfone, polyethersulfone, and polyetheretherketone. .
  • a nitrogen-containing compound when used as a component other than the main component resin, the type thereof is not particularly limited.
  • hexamethylenetetramine which is a curing agent for a novolac type phenol resin
  • aliphatic polyamine which is a curing agent for an epoxy resin.
  • a compound containing nitrogen such as an amine compound, ammonium salt, nitrate, nitro compound which does not function as a curing agent can be used.
  • the nitrogen-containing compound one type may be used or two or more types may be used in combination, whether or not the main component resin contains nitrogen-containing resins.
  • the resin composition used for the carbon material of the present invention or the nitrogen content in the resin is not particularly limited, but is preferably 5 to 65% by weight. More preferably, it is 10 to 20% by weight.
  • the carbon atom content in the carbon material finally obtained is 95 wt% or more, and the nitrogen atom content is 0.5 to 5 wt%. Is preferred.
  • the carbon atom content is more preferably 96 wt% or more.
  • the nitrogen atom by setting the nitrogen atom to 5 wt% or less, particularly 3 wt% or less, the electrical characteristics imparted to the carbon material are suppressed from becoming excessively strong, and the occluded lithium ions are electrically connected to the nitrogen atoms. Adsorption is prevented. Thereby, an increase in irreversible capacity can be suppressed and high charge / discharge characteristics can be obtained.
  • the nitrogen content in the carbon material of the present invention is not limited to the nitrogen content in the resin composition or the resin, but is subjected to a condition for carbonizing the resin composition or the resin, or a curing treatment or a pre-carbonization treatment before the carbonization treatment. In some cases, these conditions can also be adjusted by appropriately setting. For example, as a method of obtaining the carbon material having the nitrogen content as described above, the nitrogen content in the resin composition or the resin is set as a predetermined value, and conditions for carbonizing the resin composition, particularly the final temperature are adjusted. There are methods.
  • the method for preparing the resin composition used for the carbon material of the present invention is not particularly limited.
  • the above main component resin and other components are blended in a predetermined ratio, and these are melt mixed.
  • These components can be prepared by dissolving them in a solvent and mixing them, or by pulverizing and mixing these components.
  • the nitrogen content was measured by a thermal conductivity method.
  • a measurement sample is converted into a simple gas (CO 2 , H 2 O, and N 2 ) using a combustion method, and then the gasified sample is homogenized and then passed through a column. Thereby, these gas is isolate
  • PE2400 Perkin-Elmer company-made elemental-analysis measuring apparatus
  • the carbon material of the present invention is obtained by a wide angle X-ray diffraction method under the following conditions (A) to (E) (a diffraction pattern measured by a wide angle X-ray diffraction method is (Calculated using the Bragg equation) (002)
  • the average interplanar spacing d is 3.40 mm or more and 3.90 mm or less
  • the crystallite size Lc in the c-axis direction is 8 mm or more and 50 mm or less.
  • A Light source: Synchrotron radiation
  • B Large Debye-Scherrer camera, camera radius: 286.48 mm
  • C Beam size: Length 0.3mm x width 3.0mm
  • E Incident X-ray: wavelength of 1.0 mm (12.4 keV)
  • the surface spacing d of the (002) plane is derived from the diffraction angle (spectral reflection angle) ⁇ by a parabolic approximation method, that is, a parabola passing through any number of points near the peak top by the least square method, and the peak is peaked.
  • the carbon material of the present invention has an average interplanar spacing d of (002) plane of 3.40 mm or more and 3.90 mm or less, and the crystallite size in the c-axis direction It has an amorphous structure in which Lc is not less than 8% and not more than 50%, and also has a graphite structure in which the (002) plane spacing d is not less than 3.25 and less than 3.40%.
  • the average interplanar spacing d of the (002) plane in the amorphous structure is more preferably 3.45 mm or more and less than 3.85 mm. Furthermore, since the amorphous structure has a graphite structure, lithium ions can be smoothly occluded / desorbed, so that charge / discharge efficiency can be increased while having a high charge capacity and discharge capacity.
  • the wide-angle X-ray diffraction method is well known as a technique for analyzing the structure of carbon materials.
  • the wide-angle X-ray diffraction method using synchrotron radiation by SPring-8 of the High Brightness Optical Science Research Center is extremely By using a measurement method having high resolution, it was possible to identify a graphite structure present in amorphous carbon, which was not known conventionally. Based on this technology, the present inventors have been able to reach the development of a material that can achieve high charge capacity and high discharge capacity, which is the main feature of the present invention.
  • the carbon material of the present invention may have an average interplanar spacing d of the (002) plane of 3.40 mm or more and 3.90 mm or less, and particularly when it is 3.60 mm or more, occlusion of lithium ions. It is preferable that the shrinkage / expansion between the layers is less likely to occur, and the decrease in charge / discharge cycleability can be further suppressed. On the other hand, when the average interplanar spacing d of the (002) plane is 3.80 mm or less, it is preferable because occlusion / desorption of lithium ions is performed smoothly and a decrease in charge / discharge efficiency can be further suppressed.
  • the crystallite size Lc in the c-axis direction is preferably 8 to 50 mm.
  • Lc is calculated as follows.
  • the carbon material of the present invention preferably has a specific surface area of 15 m 2 / g or less and 1 m 2 / g or more according to the BET three-point method in nitrogen adsorption. More preferably, the specific surface area according to the BET three-point method in nitrogen adsorption is 10 m 2 / g or less and 1 m 2 / g or more. Reaction with a carbon material and electrolyte solution can be suppressed because the specific surface area by BET 3 point method in nitrogen adsorption is 15 m ⁇ 2 > / g or less.
  • the carbon material as described above can be manufactured as follows. First, a resin or resin composition to be carbonized is manufactured.
  • the apparatus for preparing the resin composition is not particularly limited. For example, when melt mixing is performed, a kneading apparatus such as a kneading roll, a single screw or a twin screw kneader can be used. Moreover, when performing melt
  • the resin composition thus obtained may be one obtained by physically mixing a plurality of types of components, or is applied during mixing (stirring, kneading, etc.) during preparation of the resin composition.
  • a part of the material may be chemically reacted with mechanical energy and thermal energy converted from the mechanical energy. Specifically, a mechanochemical reaction using mechanical energy or a chemical reaction using thermal energy may be performed.
  • the carbon material of the present invention is obtained by carbonizing the above resin composition or resin.
  • Carbonization refers to a step of heating the resin composition to increase the carbon atom content ratio.
  • the conditions for the carbonization treatment are not particularly limited.
  • the carbonization treatment can be performed at a temperature of 1 to 200 ° C./hour and a temperature increase of 0.1 to 50 hours, preferably 0.5 to 10 hours.
  • the atmosphere during the carbonization treatment is an inert atmosphere such as nitrogen or helium gas, or a substantially inert atmosphere where a trace amount of oxygen is present in the inert gas, or a reducing gas atmosphere. Is preferred.
  • thermal decomposition (oxidative decomposition) of resin can be suppressed and a desired carbon material can be obtained.
  • Conditions such as temperature and time during the carbonization can be adjusted as appropriate in order to optimize the characteristics of the carbon material.
  • a pre-carbonization treatment Prior to performing the carbonization treatment, a pre-carbonization treatment can be performed.
  • the pre-carbonization treatment refers to a process in which a heat treatment is performed at a temperature lower than that of the carbonization treatment to make the resin infusible.
  • the conditions for the pre-carbonization treatment are not particularly limited.
  • the pre-carbonization treatment can be performed at 200 to 600 ° C. for 1 to 10 hours.
  • the amorphous structure in which the average face spacing d of the (002) plane of the present invention is 3.40 mm or more and 3.90 mm or less and the crystallite size Lc in the c-axis direction is 8 mm or more and 50 mm or less.
  • a reducing gas As an example of a method for obtaining a carbon material for a lithium ion secondary battery having a graphite structure having a (002) plane spacing d of 3.25 mm or more and less than 3.40 mm, a reducing gas, The pre-carbonization treatment can be performed in the absence of an inert gas.
  • thermosetting resin or a polymerizable polymer compound when used as the resin constituting the carbon material, the resin composition or the resin can be cured before the pre-carbonization treatment.
  • a hardening processing method For example, it can carry out by the method of giving the heat quantity which can perform a hardening reaction to a resin composition, the method of thermosetting, or the method of using resin and a hardening
  • the pre-carbonization treatment can be performed substantially in the solid phase, the carbonization treatment or the pre-carbonization treatment can be performed in a state in which the resin structure is maintained to some extent, and the structure and characteristics of the carbon material can be controlled. become.
  • metals, pigments, lubricants, antistatic agents, antioxidants, and the like can be added to the resin composition to impart desired properties to the carbon material. .
  • the present invention has an amorphous structure in which the average spacing d of (002) planes is 3.40 mm or more and 3.90 mm or less and the crystallite size Lc in the c-axis direction is 8 mm or more and 50 mm or less.
  • a carbon material for a lithium ion secondary battery having a graphite structure having a (002) plane spacing d of 3.25 mm or more and less than 3.40 mm in the presence of a reducing gas or an inert gas Then, it is naturally cooled (cooled) to 800 to 500 ° C., and then cooled to 200 ° C. or lower, preferably 100 ° C. or lower, at 20 ° C./hour or more and 500 ° C./hour or less. If cooling is performed under conditions within the above range, the cooling rate is faster than that of natural cooling, and a unique structure that appropriately includes a graphite structure in an amorphous structure can be obtained, whereby the carbon material of the present invention can be obtained. Guessed.
  • FIG. 2 is a schematic diagram showing the configuration of the embodiment of the secondary battery.
  • the secondary battery 10 includes a negative electrode 13 composed of a negative electrode material 12 and a negative electrode current collector 14, a positive electrode 21 composed of a positive electrode material 20 and a positive electrode current collector 22, an electrolyte solution 16, and a separator 18. Including.
  • the negative electrode 13 as the negative electrode current collector 14, for example, a copper foil or a nickel foil can be used.
  • the negative electrode material 12 uses the carbon material of the present invention.
  • the negative electrode material of the present invention is manufactured, for example, as follows. 1 to 30 parts by weight of a binder (fluorine polymer including polyethylene, polypropylene, etc., acrylic resin, polyimide, or rubbery polymer such as butyl rubber or butadiene rubber) with respect to 100 parts by weight of the carbon material, A viscosity adjusting solvent (N-methyl-2-pyrrolidone, dimethylformamide, water, etc.) 10 to 400 parts by weight and an appropriate amount of additives (dispersant, conductive material, etc.) were added and kneaded to form a paste.
  • the negative electrode material 12 can be obtained by molding the mixture into a sheet shape, a pellet shape, or the like by compression molding, roll molding, or the like. By laminating with the negative electrode current collector 14, the negative electrode 13 can be manufactured.
  • a binder fluorine polymer including polyethylene, polypropylene, etc., rubbery polymer such as acrylic resin, polyimide, butyl rubber, butadiene rubber, etc.
  • a suitable amount of a viscosity adjusting solvent N-methyl-2-pyrrolidone, dimethylformamide, water, etc. was added and kneaded, and the resulting slurry was used as the negative electrode material 12, and this was used as the negative electrode current collector 14.
  • the negative electrode 13 can also be produced by coating or molding.
  • the electrolytic solution 16 a solution obtained by dissolving a lithium salt serving as an electrolyte in a non-aqueous solvent is used.
  • a non-aqueous solvent a mixture of cyclic esters such as propylene carbonate, ethylene carbonate and ⁇ -butyrolactone, chain esters such as dimethyl carbonate and diethyl carbonate, chain ethers such as dimethoxyethane, and the like can be used. it can.
  • the electrolyte lithium metal salts such as LiClO 4 and LiPF 6 , tetraalkylammonium salts, and the like can be used. Further, the above salts can be mixed with polyethylene oxide, polyacrylonitrile, etc. and used as a solid electrolyte.
  • the separator 18 is not particularly limited.
  • a porous film such as polyethylene or polypropylene, a nonwoven fabric, or the like can be used.
  • cathode material 20 such as lithium cobalt oxide (LiCoO 2), lithium nickel oxide (LiNiO 2), composite oxides such as lithium manganese oxide (LiMn 2 O 4), Conductive polymers such as polyaniline and polypyrrole can be used.
  • the positive electrode current collector 22 for example, an aluminum foil can be used.
  • the positive electrode 21 in the present embodiment can be manufactured by a known positive electrode manufacturing method.
  • the present invention is not limited to the above-described embodiment, but includes modifications and improvements as long as the object of the present invention can be achieved.
  • the carbon material for a lithium ion secondary battery of the present invention is A diffraction pattern measured by the wide-angle X-ray diffraction method under the following conditions (A) to (E) is calculated by using the Bragg equation, and the average spacing d of (002) planes is 3.4 mm or more, 3 .9 ⁇ or less, having a diffraction pattern peak in which the crystallite size Lc in the c-axis direction is 8 ⁇ or more and 50 ⁇ or less, and the interplanar spacing d is 3.25 ⁇ or more and 3.45 ⁇ or less in the peak.
  • This is a carbon material for a lithium ion secondary battery having a (002) plane peak of a graphite structure.
  • A Light source: Synchrotron radiation
  • B Large Debye-Scherrer camera, camera radius: 286.48 mm
  • C Beam size: Length 0.3mm x width 3.0mm
  • E Incident X-ray: wavelength of 1.0 mm (12.4 keV)
  • the diffraction pattern measured by the wide-angle X-ray diffraction method under the following conditions (A) to (E) is calculated using the Bragg equation.
  • the (002) plane has an average interplanar spacing d of 3.4 mm or more and 3.9 mm or less, a crystallite size Lc in the c-axis direction of 8 mm or more and 50 mm or less, and a peak of the diffraction pattern,
  • This is a carbon material for a lithium ion secondary battery having a (002) plane peak with a graphite structure in which the interplanar spacing d is not less than 3.25 and not more than 3.45.
  • A Light source: Synchrotron radiation
  • B Large Debye-Scherrer camera, camera radius: 286.48 mm
  • C Beam size: Length 0.3mm x width 3.0mm
  • E Incident X-ray: wavelength of 1.0 mm (12.4 keV)
  • the carbon material of the present invention has an average interplanar spacing d of 3.4 to 3.9 mm and a crystal structure size Lc in the c-axis direction of 8 to 50 and diffraction based on an amorphous structure.
  • Lithium is a material having a pattern peak and having a (002) plane peak of a graphite structure in which the interplanar spacing d is 3.25 to 3.45 mm. Since it has an amorphous structure with an average plane spacing of a size that allows easy entry and exit, the charge capacity and discharge capacity can be increased.
  • the surface spacing d of the (002) plane in the amorphous structure is more preferably 3.45 mm or more and 3.85 mm or less.
  • the amorphous structure has a graphite structure, lithium ions can be smoothly occluded / desorbed, so that charge / discharge efficiency can be increased while having a high charge capacity and discharge capacity.
  • Wide-angle X-ray diffraction is well known as a technique for analyzing the structure of carbon materials.
  • a measurement method with extremely high resolution is used. It was possible to identify a graphite structure present in amorphous carbon, which was not known in the past. Based on this technology, the present inventors have been able to reach the development of a material that can achieve high charge capacity and high discharge capacity, which is the main feature of the present invention.
  • synchrotron radiation is used.
  • the electron energy a radiation facility (apparatus) capable of obtaining 1 GeV or more, more preferably 7 GeV or more can be used.
  • Such facilities include the PF of the High Energy Accelerator Research Organization in Japan, SPring-8 of the High Brightness Optical Science Research Center, the APS of Argonne National Laboratory in the United States, the USRLS in the European Union (EU), etc.
  • SPring-8, APS, and USRLS are preferable.
  • the carbon material of the present invention may have an average interplanar spacing d of the (002) plane of 3.4 mm or more and 3.9 mm or less, but particularly when it is 3.6 mm or more, occlusion of lithium ions. It is preferable that the shrinkage / expansion between the layers is less likely to occur, and the decrease in charge / discharge cycleability can be further suppressed. On the other hand, when the average interplanar spacing d of the (002) plane is 3.8 mm or less, it is preferable because lithium ions can be smoothly occluded and desorbed, and a decrease in charge / discharge efficiency can be further suppressed.
  • the crystallite size Lc in the c-axis direction is preferably 8 to 50 mm.
  • Lc is calculated as follows.
  • the carbon material of the present invention is obtained by carbonizing the above resin composition or resin.
  • the conditions for the carbonization treatment are not particularly limited. For example, the temperature is raised from room temperature at 1 to 200 ° C./hour, and kept at 800 to 3000 ° C. for 0.1 to 50 hours, preferably 0.5 to 10 hours. Can be done.
  • the atmosphere during the carbonization treatment is an inert atmosphere such as nitrogen or helium gas, or a substantially inert atmosphere where a trace amount of oxygen is present in the inert gas, or a reducing gas atmosphere. Is preferred. By doing in this way, thermal decomposition (oxidative decomposition) of resin can be suppressed and a desired carbon material can be obtained. Conditions such as temperature and time during the carbonization can be adjusted as appropriate in order to optimize the characteristics of the carbon material.
  • a pre-carbonization treatment Prior to performing the carbonization treatment, a pre-carbonization treatment can be performed.
  • the conditions for the pre-carbonization treatment are not particularly limited.
  • the pre-carbonization treatment can be performed at 200 to 600 ° C. for 1 to 10 hours.
  • the resin composition after the pulverization is performed. It is possible to prevent the object or resin from being re-fused during the carbonization treatment, and to obtain a desired carbon material efficiently.
  • the average spacing d of (002) planes calculated using the Bragg equation is 3.4 mm or more and 3.9 mm or less, and the crystallite size Lc in the c-axis direction is 8 mm or more and 50 mm or less.
  • a carbon material for a lithium ion secondary battery having a peak of the (002) plane of a graphite structure having a peak of the diffraction pattern and having an interplanar spacing d of 3.25 to 3.45 mm in the peak is obtained.
  • An example of a method for this is to perform pre-carbonization in the absence of a reducing gas or an inert gas.
  • the said hardening process and / or pre carbonization process are performed, you may grind
  • variation in the thermal history during the carbonization treatment can be reduced, and the uniformity of the surface state of the carbon material can be improved.
  • the handleability of a processed material can be made favorable.
  • the average plane distance d of (002) planes calculated using the Bragg equation is 3.4 mm or more and 3.9 mm or less, and the crystallite size Lc in the c-axis direction is 8 mm or more and 50 mm or less.
  • a carbon material for a lithium ion secondary battery having a diffraction pattern peak and having a (002) plane peak of a graphite structure in which the interplanar spacing d is 3.25 to 3.45 mm.
  • the conditions may be appropriately selected according to the raw material to be used. For example, after carbonization, if necessary, it is naturally cooled to 800 to 500 ° C. in the presence of a reducing gas or an inert gas, and then 100 You may cool at 100 degrees C / hour until it becomes below ° C. By doing so, it is presumed that the cooling rate is in an appropriate state, a unique structure appropriately including a graphite structure is formed in the amorphous structure, and the carbon material of the present invention can be obtained.
  • a diffraction pattern measured by a wide-angle X-ray diffraction method is calculated using the Bragg equation without using graphite or graphitization catalyst as a raw material or precursor to be used.
  • Carbon content, nitrogen content The measurement was performed using an elemental analysis measuring device “PE2400” manufactured by PerkinElmer. The measurement sample is converted into CO 2 , H 2 O, and N 2 using a combustion method, and then the gasified sample is homogenized and then passed through the column. Thereby, these gases were separated stepwise, and the contents of carbon, hydrogen, and nitrogen were measured from the respective thermal conductivities.
  • the positive electrode was evaluated with a bipolar coin cell using lithium metal.
  • the electrolytic solution a solution obtained by dissolving 1 mol / liter of lithium perchlorate in a mixed solution of ethylene carbonate and diethyl carbonate having a volume ratio of 1: 1 was used.
  • Example 1 As a resin composition, phenol resin PR-217 (manufactured by Sumitomo Bakelite Co., Ltd.) was treated in the order of the following steps (a) to (f) to obtain a carbon material.
  • (b) Reducing gas replacement and inert gas replacement Then, after degreasing treatment at 500 ° C.
  • Example 2 In Example 1, an aniline resin (synthesized by the following method) was used instead of the phenol resin. 100 parts of aniline, 697 parts of 37% aqueous formaldehyde, and 2 parts of oxalic acid were placed in a three-necked flask equipped with a stirrer and a condenser, reacted at 100 ° C. for 3 hours, and dehydrated to obtain 110 parts of aniline resin. The obtained aniline resin had a weight average molecular weight of about 800.
  • the resin composition obtained by pulverizing and mixing 100 parts of the aniline resin and 10 parts of hexamethylenetetramine obtained as described above was treated in the same process as in Example 1 to obtain a carbon material.
  • Example 2 In Example 1, instead of phenol resin, in place of coal tar pitch (manufactured by JFE Shoji Co., Ltd.), the steps of (d), (e), and (f) were changed as follows.
  • the carbon material was obtained by performing the same process.
  • f No Natural cooling to 100 ° C under active gas (nitrogen) flow
  • Example 3 In Example 1, the process of (d), (e), (f) was changed as follows, and it processed in the process similar to Example 1, and obtained the carbon material.
  • D Inactive gas (nitrogen) substitution and flow from room temperature to 1000 ° C. at 100 ° C./hour
  • e Carbonization treatment at 1000 ° C. for 8 hours under inert gas (nitrogen) flow
  • f Natural cooling to 100 ° C under active gas (nitrogen) flow
  • Table 1 shows the evaluation results of the carbon materials obtained in the above Examples and Comparative Examples, and the measurement results of the charge capacity, discharge capacity, and charge / discharge efficiency when the carbon material is used as a negative electrode.
  • Examples 1 and 2 which are carbon materials for lithium ion secondary batteries having a graphite structure in which the (002) plane spacing d is 3.25 mm or more and less than 3.40 mm, both the charge capacity and the discharge capacity are High charge and discharge efficiency.
  • Comparative Example 1 having no amorphous halo pattern based on the amorphous structure, the efficiency was high, but both the charge capacity and the discharge capacity were low.
  • the charge capacity and discharge capacity are high.
  • the efficiency is lowered, and in Comparative Example 3, the discharge capacity and the efficiency are lower than in the example.
  • the interplanar spacing d of the graphite structure that is 3.25 mm or more and less than 3.40 mm in the example was not detected.
  • Example 3 As a resin composition, phenol resin PR-217 (manufactured by Sumitomo Bakelite Co., Ltd.) was treated in the order of the following steps (a) to (f) to obtain a carbon material.
  • Example 4 In Example 3, an aniline resin (synthesized by the following method) was used instead of the phenol resin. 100 parts of aniline, 697 parts of 37% aqueous formaldehyde, and 2 parts of oxalic acid were placed in a three-necked flask equipped with a stirrer and a condenser, reacted at 100 ° C. for 3 hours, and dehydrated to obtain 110 parts of aniline resin. The obtained aniline resin had a weight average molecular weight of about 800.
  • the resin composition obtained by pulverizing and mixing 100 parts of the aniline resin and 10 parts of hexamethylenetetramine obtained as described above was treated in the same process as in Example 3 to obtain a carbon material.
  • Example 5 Inert gas (nitrogen) replacement and flow, from room temperature to 1100 ° C., heated at 100 ° C./hour (e) Inactive gas (nitrogen) flow, 1100 ° C. for 4 hours carbonization (f) No Natural cooling to 100 ° C or lower under active gas (nitrogen) flow
  • Table 2 shows the evaluation results of the carbon materials obtained in the above Examples and Comparative Examples and the measurement results of the charge capacity, discharge capacity, and charge / discharge efficiency when the carbon material is used as a negative electrode.
  • the average spacing d of (002) planes calculated using the Bragg equation is 3.4 mm or more and 3.9 mm or less, and the crystal in the c-axis direction A (002) plane peak of a graphite structure having a diffraction pattern peak with a child size Lc of 8 to 50 mm and a face spacing d of 3.25 to 3.45 mm in the peak.
  • both the charge capacity and discharge capacity were high, and the charge / discharge efficiency was also high.
  • Comparative Example 4 having no amorphous halo pattern based on the amorphous structure, the efficiency was high, but both the charge capacity and the discharge capacity were low. Further, in Comparative Example 5 having only the amorphous halo pattern based on the amorphous structure and not having the (002) plane peak of the graphite structure in the wide-angle X-ray diffraction method using synchrotron radiation of the present invention, the charge capacity and discharge capacity are high. Efficiency became low. In addition, in wide-angle X-ray diffraction using a conventional lab-scale apparatus, a peak on the (002) plane of the graphite structure in which the interplanar spacing d in the example was 3.25 mm or more and 3.45 mm or less was not detected.

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Abstract

Ce matériau carboné pour batteries secondaires à lithium ion présente une structure amorphe dans laquelle l'espacement entre plans moyens (d) du plan (002) tel que déterminé par la diffraction des rayons X aux grands angles se situe entre 3,40 Å et 3,90 Å (inclus) et la taille de cristallite (Lc) dans la direction de l'axe c se situe entre 8 Å et 50 Å (inclus), et une structure graphite dans laquelle l'espacement entre plans (d) du plan (002) est de 3,25 Å ou plus, mais est inférieure à 3,40 Å.
PCT/JP2011/071462 2011-09-21 2011-09-21 Matériau carboné pour batteries secondaires à lithium ion, matériau pour électrode négative de batteries secondaires à lithium ion, et batterie secondaire à lithium ion WO2013042223A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07315822A (ja) * 1994-05-03 1995-12-05 Moli Energy 1990 Ltd 炭素質挿入化合物および再充電可能電池用の負極
JPH1040914A (ja) * 1996-05-23 1998-02-13 Sharp Corp 非水系二次電池及び負極活物質の製造方法
JP2009200014A (ja) * 2008-02-25 2009-09-03 Sumitomo Bakelite Co Ltd 二次電池用炭素材、二次電池用電極、および二次電池
WO2011064936A1 (fr) * 2009-11-25 2011-06-03 住友ベークライト株式会社 Matériau en carbone pour batterie secondaire au lithium-ion, matériau d'électrode négative pour batterie secondaire au lithium-ion, et batterie secondaire au lithium-ion
JP2011222472A (ja) * 2010-03-25 2011-11-04 Sumitomo Bakelite Co Ltd リチウムイオン二次電池用炭素材、リチウムイオン二次電池用負極材およびリチウムイオン二次電池

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07315822A (ja) * 1994-05-03 1995-12-05 Moli Energy 1990 Ltd 炭素質挿入化合物および再充電可能電池用の負極
JPH1040914A (ja) * 1996-05-23 1998-02-13 Sharp Corp 非水系二次電池及び負極活物質の製造方法
JP2009200014A (ja) * 2008-02-25 2009-09-03 Sumitomo Bakelite Co Ltd 二次電池用炭素材、二次電池用電極、および二次電池
WO2011064936A1 (fr) * 2009-11-25 2011-06-03 住友ベークライト株式会社 Matériau en carbone pour batterie secondaire au lithium-ion, matériau d'électrode négative pour batterie secondaire au lithium-ion, et batterie secondaire au lithium-ion
JP2011222472A (ja) * 2010-03-25 2011-11-04 Sumitomo Bakelite Co Ltd リチウムイオン二次電池用炭素材、リチウムイオン二次電池用負極材およびリチウムイオン二次電池

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