WO2011157013A1 - Composite hard carbon material of negative electrode for lithium ion battery and method for preparing the same - Google Patents

Composite hard carbon material of negative electrode for lithium ion battery and method for preparing the same Download PDF

Info

Publication number
WO2011157013A1
WO2011157013A1 PCT/CN2010/077329 CN2010077329W WO2011157013A1 WO 2011157013 A1 WO2011157013 A1 WO 2011157013A1 CN 2010077329 W CN2010077329 W CN 2010077329W WO 2011157013 A1 WO2011157013 A1 WO 2011157013A1
Authority
WO
WIPO (PCT)
Prior art keywords
hard carbon
metal
tin
hydroxide
cobalt
Prior art date
Application number
PCT/CN2010/077329
Other languages
French (fr)
Chinese (zh)
Inventor
岳敏
汪福明
闫惠青
邓明华
薛嘉渔
Original Assignee
深圳市贝特瑞新能源材料股份有限公司
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
Priority claimed from CN2010102037680A external-priority patent/CN101887966B/en
Priority claimed from CN2010102463052A external-priority patent/CN101916845B/en
Application filed by 深圳市贝特瑞新能源材料股份有限公司 filed Critical 深圳市贝特瑞新能源材料股份有限公司
Priority to KR1020127033140A priority Critical patent/KR20130030769A/en
Priority to JP2013514526A priority patent/JP5680191B2/en
Publication of WO2011157013A1 publication Critical patent/WO2011157013A1/en

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—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
    • H01M4/133—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
    • H01M4/13—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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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 invention relates to a battery anode material and a preparation method thereof, in particular to a lithium ion battery anode material and a preparation method thereof.
  • the carbon anode materials which have been successfully used in the prior art include artificial graphite, mesocarbon microbeads MCMB, and petroleum coke.
  • its specific capacity of 372mAh/g is too low.
  • the requirements are not met, and the fragile structure results in very limited stability and is highly sensitive to electrolytes.
  • people turn their attention to other carbon materials, such as soft carbon and hard carbon.
  • the high capacity, low cost and excellent cycle performance of hard carbon in its random order have attracted great interest.
  • Hard carbon refers to carbon that is difficult to graphitize and is a pyrolytic carbon of a high molecular polymer. Such carbon has a high specific capacity.
  • Sony developed a lithium ion battery using hard carbon obtained by thermal cracking of polyptanol PFA as a negative electrode material. However, its first charge and discharge efficiency is low, only about 45%.
  • the object of the present invention is to provide a lithium ion battery composite hard carbon anode material and a preparation method thereof, and the technical problem to be solved is to improve the large rate charge and discharge performance of the lithium ion battery, and have excellent high and low temperature charge and discharge performance and stability. Cyclic performance.
  • the present invention adopts the following technical solution: a lithium ion battery composite hard carbon anode material, the hard carbon substrate of the lithium ion battery composite hard carbon anode material is coated with a coating, and the precursor of the coating is organic Epoxy resin, phenolic resin, carboxymethyl cellulose, asphalt, ethyl methyl carbonate, polyvinyl alcohol, polystyrene, polymethyl methacrylate, polytetrafluoroethylene, polyvinylidene fluoride, polyacrylonitrile , styrene-butadiene rubber, polyvinyl chloride, polyethylene, polyethylene oxide, polypropylene oxide, polyethylene succinate, polyethylene sebacate, polyethylene glycol imine, polyacetylene, Polyparaphenylene, polyaniline, polypyrrole, polyacene, One or more of poly(m-phenylenediamine), polyphhenol, polyparaphenylenevinylene, polythiophene, polypropylene, polyimide,
  • the hard carbon matrix precursor of the present invention is one or more of thermoplastic resin acrylic resin, polyvinyl chloride, polycarbonate, epoxy resin, phenolic resin and polyoxymethylene, and pyrolyzes to form a hard carbon matrix; the precursor mass of the coating is 1 to 15% of the mass of the hard carbon matrix precursor; the lithium ion battery composite hard carbon anode material is in the form of massive particles having a porous structure, a pore diameter of 0.2 to 100 nm, a porosity of 9 to 19%, and a 002 crystal plane.
  • the layer spacing is between 0.338 and 0.475 nm, the particle size range is from 0.5 to 90 ⁇ m, the specific surface area is from 1.9 to 75.3 m 2 /g, the true density is from 1.54 to 2.35 g/cm 3 , and the tap density is from 0.88 to 1.43 g/cm. 3 , the content of its carbon C element is not less than 90.5%.
  • the hard carbon matrix precursor of the present invention comprises the following thermoplastic ratio: 25% to less than 100% of a thermoplastic resin, more than 0 to 75% of a curing agent, pyrolysis to form a hard carbon matrix; the curing agent is hexamethylenediamine, One or more of m-phenylenediamine, aniline formaldehyde resin, polyamide resin, phthalic anhydride, and benzenesulfonic acid.
  • the hard carbon matrix precursor of the present invention is composed of the following mass ratio: 25% to less than 100% Thermoplastic resin, a curing agent greater than 0 to 75% or less, a dopant greater than 0 to 15%, pyrolyzed to form a hard carbon a matrix;
  • the dopant is at least one of a simple substance of a metal, a non-metal element, a metal compound, and a non-metal compound;
  • the metal element is one or more of copper, lead, antimony, tin, cobalt, and nickel;
  • the compound is one or more of tin oxide, cobalt oxide, nickel oxide, sodium phosphate, sodium dihydrogen phosphate, tin acetate, tin chloride, cobalt carbonate, copper hydroxide, cobalt hydroxide, tin hydroxide and nickel hydroxide;
  • the non-metal element is more than one of silicon, sulfur and boron;
  • the non-metal compound is silicon dioxide,
  • the hard carbon matrix precursor of the present invention is composed of the following mass ratio: 85% to less than 100% of a thermoplastic resin, and more than 0 to less than or equal to 15% of the blend.
  • the dopant is more than one element of a metal element, a non-metal element, a metal compound and a non-metal compound
  • the metal element is a kind of copper, lead, antimony, tin, cobalt and nickel Above
  • the metal compound is tin oxide, cobalt oxide, nickel oxide, sodium phosphate, sodium dihydrogen phosphate, tin acetate, tin chloride, cobalt carbonate, copper hydroxide, cobalt hydroxide, tin hydroxide and nickel hydroxide.
  • the non-metal element is more than one of silicon, sulfur and boron; the non-metal compound is silicon dioxide, phosphorus pentoxide, boric acid, silicic acid, phosphoric acid, ammonium dihydrogen phosphate, ammonium phosphate, One or more of ammonium sulfate, silicone resin, and ethylene glycol borate.
  • the hard carbon matrix precursor of the invention is more than one kind of plant raw material pollen, rice husk, sugar cane rod, walnut shell, bamboo, distiller's grains and wood chips, pyrolysis forms a hard carbon matrix, and the precursor mass of the coating is a hard carbon matrix precursor. 1 to 25% of the mass; the surface of the hard carbon substrate and the coating are combined by a chemical bond or a van der Waals force, the hard carbon matrix has a particle size of 2 to 60 ⁇ m, and the surface has a honeycomb open-cell structure with a pore diameter of 1.0 to 55 nm; The particles are in the form of blocks and/or flakes having a particle diameter of 3.5 to 70 ⁇ m and a specific surface area of 7.5 to 20 m 2 /g.
  • the surface of the material has a honeycomb open-cell structure with a pore diameter of 0.5 to 50 nm and a porosity. 9 to 16%, the layer spacing d 002 of the 002 crystal plane is between 0.337 and 0.455 nm, the true density is 1.55 to 2.25 g/cm 3 , and the tap density is 0.91 to 1.45 g/cm 3 .
  • the content is not less than 94%.
  • the hard carbon matrix precursor of the present invention is composed of the following mass ratios: a plant material, a dopant composition of plant materials greater than 0 to 40% or less, pyrolysis Forming a hard carbon substrate; the dopant is one or more of the metal oxides tin oxide, cobalt oxide, and nickel oxide, or one or more of the metal salt sodium phosphate, tin chloride, cobalt carbonate, and sodium dihydrogen phosphate, or One or more of a metal base copper hydroxide, cobalt hydroxide, tin hydroxide, and nickel hydroxide, or a non-metal oxide silica and/or phosphorus pentoxide, or one or more of boric acid, silicic acid, and phosphoric acid, Or one or more of the non-metal salts of ammonium dihydrogen phosphate, ammonium phosphate, and ammonium sulfate, or one or more of the metal elements of copper, lead, antimony, tin, cobalt,
  • a method for preparing a composite hard carbon anode material for a lithium ion battery comprises the following steps: 1. curing a thermoplastic resin in air at room temperature for 3 to 50 hours to obtain a solid precursor; and second, a nitrogen flow rate of 0.1 to 0.4 m 3 /h, the precursor body at a temperature increase rate of 0.1 ⁇ 3 ° C / min to 150 ° C ⁇ 450 ° C, low temperature pre-burning 2 ⁇ 24h, naturally cooled to room temperature, pulverization, to obtain a powder size of 1 ⁇ 60 ⁇ m;
  • the nitrogen flow rate is 0.1-0.4 m 3 /h
  • the temperature rise rate of 0.3-10 ° C / min is 560-1500 ° C
  • the pyrolysis is 0.5-7.5 h
  • the temperature is naturally cooled to room temperature to obtain hard carbon
  • Ball milling or pulverization to obtain a hard carbon matrix having a particle size of 1 to 60 ⁇ m; 5.
  • thermoplastic resin is an acrylic resin More than one of polyvinyl chloride, polycarbonate, epoxy resin, phenolic resin and polyoxymethylene; the precursor of the coating is organic epoxy resin, phenolic resin, carboxymethyl cellulose, asphalt, ethyl methyl Carbonate, polyvinyl alcohol, polystyrene, polymethyl methacrylate, polytetrafluoroethylene, polyvinylidene fluoride, polyacrylonitrile, styrene butadiene rubber,
  • the method of the present invention cures a curing agent having a mass ratio of from 25% to less than 100% by weight of the thermoplastic resin of from greater than 0 to less than or equal to 75%.
  • a curing agent having a mass ratio of from 25% to less than 100% by weight of the thermoplastic resin of from greater than 0 to less than or equal to 75%.
  • the curing agent is hexamethylenediamine, m-phenylenediamine, aniline formaldehyde resin, polyamide resin, phthalic anhydride and benzenesulfonic acid More than one.
  • the dopant is added in a powder form at a mass ratio of more than 0 to 15% or less, and the rotation speed is 1000 to 3000 r/min, and the time is 26 to 120 min;
  • the dopant is one or more of a simple metal, a non-metal element, a metal compound, and a non-metal compound;
  • the metal element is one or more of copper, lead, antimony, tin, cobalt, and nickel; and the metal compound is tin oxide.
  • the non-metal element It is one or more of silicon, sulfur and boron; the non-metal compound is silicon dioxide, phosphorus pentoxide, boric acid, silicic acid, phosphoric acid, ammonium dihydrogen phosphate, ammonium phosphate, ammonium sulfate, silicone resin and ethylene More than one type of alcohol borate.
  • the method of the present invention cures, in a mass ratio of 25% to less than 100%, of a thermoplastic resin, adding a curing agent of more than 0 to 75% or less, and a blending of more than 0 to less than or equal to 15%.
  • Miscellaneous, mixing and stirring, the speed is 2000 ⁇ 4500r/min, the time is 10 ⁇ 120min, Curing in air at room temperature for 3 to 50 hours to obtain a precursor;
  • the dopant is more than one element of a metal element, a non-metal element, a metal compound and a non-metal compound;
  • the metal element is copper, lead, antimony, More than one of tin, cobalt and nickel;
  • the metal compound is tin oxide, cobalt oxide, nickel oxide, sodium phosphate, sodium dihydrogen phosphate, tin acetate, tin chloride, cobalt carbonate, copper hydroxide, cobalt hydroxide, More than one of tin hydroxide and nickel hydroxide
  • the dopant is added at a mass ratio of more than 0 to 15% or less, and the rotation speed is 1000-3000 r/min, and the time is 26-120 min;
  • the dopant is a metal element, One or more of a non-metal element, a metal compound, and a non-metal compound;
  • the metal element is one or more of copper, lead, antimony, tin, cobalt, and nickel; and the metal compound is tin oxide, cobalt oxide, nickel oxide, More than one of sodium phosphate, sodium dihydrogen phosphate, tin acetate, tin chloride, cobalt carbonate, copper hydroxide, cobalt hydroxide, tin hydroxide and nickel hydroxide;
  • the non-metal element is silicon, sulfur and boron One or more;
  • the non-metal compound is not one of silica, phosphorus pentoxide, boric acid, silicic acid, phosphoric acid, am
  • a method for preparing a composite hard carbon anode material for a lithium ion battery comprises the following steps: 1. a thermoplastic resin having a mass ratio of 85% to less than 100%, a dopant greater than 0 to 15% or less, mixing and stirring, and a rotation speed is 2000 ⁇ 4500r / min, the time is 10 ⁇ 120min, in air, at room temperature curing 1 ⁇ 6 h, to obtain a solid body before; two nitrogen flow rate of 0.1 ⁇ 0.4m 3 / h, the precursor to 0.1 to 7 °C / min heating rate to 150 ° C ⁇ 450 ° C, low temperature pre-burning 3 ⁇ 24h, natural cooling to room temperature; three, nitrogen flow rate of 0.1 ⁇ 0.4m 3 / h, with a temperature of 0.3 ⁇ 10 ° C / min to 560 ⁇ 1500 ° C, pyrolysis 0.5 ⁇ 7.5h, natural cooling to room temperature, to produce hard carbon; Fourth, the hard carbon ball milling or
  • the precursor of the coating is organic epoxy resin, phenolic resin, carboxymethyl cellulose, asphalt, ethyl methyl carbonate, polyvinyl alcohol, polystyrene, polymethyl methacrylate, poly Tetrafluoroethylene, poly Fluorine, polyacrylonitrile, styrene butadiene rubber, polyvinyl chloride, polyethylene, polyethylene oxide, polypropylene oxide, polyethylene succinate, polyethylene sebacate, polyethylene glycol Imine, polyacetylene, polyparaphenylene, polyaniline, polypyrrole, polyacene, poly-m-phenylenediamine, poly-phasic, poly-p-phenylene vinyl, polythiophene, polypropylene, polyimide and polyphenylene More than one type of thioether.
  • the invention discloses a preparation method of a composite hard carbon anode material for a lithium ion battery, comprising the following steps: 1. adding 80 to 300 ml of acid or alkali per 100 g of dry plant material, soaking for 3 to 50 hours; the plant material is pollen, rice husk, More than one kind of sugar cane rod, walnut shell, bamboo, distiller's grains and wood chips, the acid is hydrofluoric acid, boric acid, sulfuric acid, hydrochloric acid or nitric acid, the alkali is potassium hydroxide, calcium hydroxide or sodium hydroxide; second, washing, Wash with pure water, rotation speed 800 ⁇ 1400r / min, time 8 ⁇ 30min; Third, remove water, dry at 80 ⁇ 140 °C for 10 ⁇ 40h, naturally cool to room temperature; Fourth, low temperature pre-burn, in vacuum The degree is 0.03 MPa or less, or under the protective gas helium, nitrogen, argon, helium or nitrogen, the flow rate is 0.1-0.4
  • the crushing or ball milling produces a hard carbon matrix with a particle size of 2 ⁇ 65 ⁇ m; 1 to 25% of the mass of the matrix precursor, the precursor of the coating is added to the hard carbon matrix, mixed at a speed of 1000 to 4500 r/min, mixed for 2 to 40 minutes, then at a vacuum of 0.03 MPa or less, or in a protective gas Under helium, nitrogen, argon, helium or nitrogen, the flow rate is 0.1-0.4 m 3 /h, and the temperature is raised from 0. 1 to 10 ° C/min to 400-1300 ° C for 1 to 24 hours.
  • the precursor of the coating is organic epoxy resin, phenolic resin, carboxymethyl cellulose, asphalt, ethyl methyl carbonate, polyvinyl alcohol, polystyrene , polymethyl methacrylate, polytetrafluoroethylene, polyvinylidene fluoride, polyacrylonitrile, styrene butadiene rubber, polyvinyl chloride, polyethylene, polyethylene oxide, polypropylene oxide, polyethylene succinate Alcohol ester, polyethylene sebacate, polyethylene glycol imine, polyacetylene, polyparaphenylene, polyaniline, polypyrrole , more than one of polyacene, poly-m-phenylenediamine, poly-phasic, poly-p-phenylene vinyl, polythiophene, polypropylene, polyimide and polyphenylene sulfide; nine, over 200 mesh sieve, obtained A lithium ion battery composite hard carbon anode material having a particle size of
  • the method of the present invention adds 80-300 ml of acid or alkali per 100 g of dry plant raw materials, and immerses the precursor dry plant material or pulverizes it to obtain a powder having a particle size of 40-100 ⁇ m before soaking for 3 to 50 hours; After calcination and pulverization, the dopant is added at a ratio of the powdery mass of more than 0 to 40%, and the rotation speed is 1000 to 4500 r/min. The time is 20 to 95 min; the dopant is one or more of the metal oxides such as tin oxide, cobalt oxide and nickel oxide, or one or more of the metal salt sodium phosphate, tin chloride, cobalt carbonate and sodium dihydrogen phosphate.
  • the metal oxides such as tin oxide, cobalt oxide and nickel oxide, or one or more of the metal salt sodium phosphate, tin chloride, cobalt carbonate and sodium dihydrogen phosphate.
  • the method of the invention adds 80-300 ml of acid or alkali per 100 g of dry plant material, and the rotation speed is 1000-3000 r/min.
  • the time is 3 to 30 minutes, and then immersed for 3 to 50 hours; after the low temperature pre-burning and pulverizing,
  • the dopant is added at a ratio of the powdery mass greater than 0 to 40%, and the rotation speed is 1000-4500 r/min for 20-95 min; the dopants are metal oxide tin oxide, cobalt oxide and nickel oxide.
  • metal salt sodium phosphate, tin chloride, cobalt carbonate, and sodium dihydrogen phosphate or one or more of the metal base copper hydroxide, cobalt hydroxide, tin hydroxide, and nickel hydroxide.
  • non-metal oxide silica and/or phosphorus pentoxide or one or more of boric acid, silicic acid and phosphoric acid, or one or more of the non-metal salts ammonium dihydrogen phosphate, ammonium phosphate and ammonium sulfate, or silicone Resin and / or ethylene glycol borate, Or one or more of metal elemental copper, lead, antimony, tin, cobalt and nickel, or one or more of non-metal elemental silicon, sulfur and boron.
  • the method of the present invention adds 80-300 ml of acid or alkali per 100 g of dry plant raw materials, and soaks the precursor dry plant material by mechanical pulverization or jet milling before soaking for 3 to 50 hours to obtain a powder having a particle size of 40-100 ⁇ m;
  • the dopant is added at a ratio of the powder-like mass greater than 0 to 40%, and the rotation speed is 1000-4500 r/min.
  • the time is 20 to 95 min; the dopant is one or more of the metal oxides such as tin oxide, cobalt oxide and nickel oxide, or one or more of the metal salt sodium phosphate, tin chloride, cobalt carbonate and sodium dihydrogen phosphate.
  • the composite hard carbon anode material obtained by high temperature pyrolysis and coating of the hard carbon matrix precursor has a first reversible capacity of 455.2 mAh/g or more at a temperature of 0.2 C, and the first charge has a coulombic efficiency. 79.4% or more.
  • the hard carbon anode material has the advantages of high capacity, high first coulombic efficiency and high magnification, simple preparation process, easy operation and low cost, and is suitable for lithium ion power batteries.
  • Fig. 1 is a scanning electron micrograph of Example 1.
  • Example 2 is an XRD chart of Example 1.
  • Fig. 3 is a graph showing the first charge and discharge performance of Example 1 at different magnifications.
  • Figure 4 is a graph showing the cycle performance of Example 1 at 60 ° C, 0.2 C rate.
  • Figure 5 is a graph showing the cycle performance of Example 1 at -30 ° C, 0.2 C rate.
  • Figure 6 is a scanning electron micrograph of the material produced in Example 14.
  • Figure 7 is an XRD pattern of the material produced in Example 14.
  • Figure 8 is a graph showing the performance of the first charge (delithiation) discharge (lithium intercalation) of the material obtained in Example 14 at different magnifications.
  • Figure 9 is a graph showing the cycle performance of the material produced in Example 14 at 60 ° C, 0.2 C rate.
  • Figure 10 is a graph showing the cycle performance of the material produced in Example 14 at -30 ° C, 0.2 C rate.
  • Lithium ion battery composite hard carbon anode material of the invention hard carbon
  • the substrate is coated with a coating, and the precursor of the coating is organic epoxy resin, phenolic resin, carboxymethyl cellulose CMC, asphalt, ethyl methyl carbonate EMC, polyvinyl alcohol, polystyrene, poly Methyl methacrylate, polytetrafluoroethylene, polyvinylidene fluoride, polyacrylonitrile, styrene butadiene rubber SBR, polyvinyl chloride, polyethylene, polyethylene oxide, polypropylene oxide, polyethylene glycol succinate Ester, polyethylene azelaic acid, polyethylene glycol imine, polyacetylene, polyparaphenylene, polyaniline, polypyrrole, polyacene, One or more of poly(m-phenylenediamine), polyphhenol, polyparaphenylenevinylene, polythioph
  • the precursor mass of the coating is 1 to 15% of the mass of the hard carbon matrix precursor.
  • the lithium ion battery composite hard carbon anode material has a uniform phase distribution, a block shape, irregular fine particles, a porous structure, a pore diameter of 0.2 to 100 nm, and a porosity of 9 to 19% (in the bulk volume of the granular material, the particle The ratio of the interstitial volume to the total volume), the layer spacing d 002 of the 002 crystal plane is between 0.338 and 0.475 nm, the particle size ranges from 0.5 to 90 ⁇ m, the specific surface area is 1.9 to 75.3 m 2 /g, and the true density is 1.53.
  • the tap density is 0.88 ⁇ 1.43 g /cm 3
  • the content of the carbon C element is not less than 90.5%.
  • the first reversible capacity is above 455.2mAh/g, and the first charge has a coulombic efficiency of 79.4% or more.
  • the hard carbon matrix precursor is composed of the following mass ratio: 25% to less than 100% thermoplastic resin (25%) ⁇ thermoplastic resin ⁇ 100%), a curing agent greater than 0 to 75% or less (0 ⁇ curing agent ⁇ 75%), a dopant greater than 0 to 15% or less (0 ⁇ dopant ⁇ 15%)
  • the dopant is one or more of a simple metal, a non-metal element, a metal compound, and a non-metal compound.
  • the thermoplastic resin is chemically reacted with the curing agent, mixed with the dopant, and then pyrolyzed to form a hard carbon matrix.
  • the hard carbon matrix precursor is composed of the following mass ratio: 25% to less than 100% of a thermoplastic resin (25% ⁇ thermoplastic resin ⁇ 100%), and a curing agent greater than 0 to 75% or less (0 ⁇ curing agent ⁇ 75) %), adding a curing agent to the thermoplastic resin, After the polymerization chemical reaction, pyrolysis forms a hard carbon matrix.
  • the hard carbon matrix precursor consists of the following mass ratios: 85% to less than 100% of thermoplastic resin (85% ⁇ thermoplastic resin ⁇ 100%), more than 0 to less than or equal to 15% of dopant (0 ⁇ dopant ⁇ 15%), the thermoplastic resin is mixed with one or more of a dopant metal element, a non-metal element, a metal compound, and a non-metal compound, and pyrolyzed to form a hard carbon matrix.
  • the hard carbon matrix precursor is one or more of a thermoplastic resin acrylic resin, polyvinyl chloride, polycarbonate, epoxy resin, phenol resin, and polyoxymethylene. Pyrolysis forms a hard carbon matrix.
  • the curing agent is one or more of hexamethylenediamine, m-phenylenediamine, aniline formaldehyde resin, polyamide resin, phthalic anhydride, and benzenesulfonic acid.
  • the metal element is one or more of copper, lead, antimony, tin, cobalt and nickel.
  • the metal compound is at least one of tin oxide, cobalt oxide, nickel oxide, sodium phosphate, sodium dihydrogen phosphate, tin acetate, tin chloride, cobalt carbonate, copper hydroxide, cobalt hydroxide, tin hydroxide, and nickel hydroxide.
  • the non-metal element is one or more of silicon, sulfur and boron.
  • the non-metallic compounds are silica, phosphorus pentoxide, boric acid, silicic acid, phosphoric acid, ammonium dihydrogen phosphate, ammonium phosphate, ammonium sulfate, silicone resins, and More than one type of ethylene glycol borate.
  • the dopant is in the form of solid particles or a liquid, and has the effect of increasing the capacity and the first coulombic efficiency of the composite hard carbon anode material of the lithium ion battery of the present invention.
  • the curing agent is used to increase the capacity of the hard carbon and the first coulombic efficiency.
  • Using conventional thermoplastic resin, curing agent The metal element, the non-metal element, the metal compound or the non-metal compound, the coating, and the material of the invention are low in cost.
  • the method for preparing the lithium ion battery composite hard carbon anode material of the present invention comprises the following steps:
  • a solid or liquid curing agent of more than 0 to 75% or less is added to the granular or liquid thermoplastic resin, stirred uniformly, and cured in air at room temperature for 3 to 50 hours to obtain a solid precursor.
  • the doped metal element, the non-metal element, the metal compound or the non-metal compound may be mixed and stirred in the curing step, the rotation speed is 2000 to 4500 r/min, the time is 10 to 120 min, and the pre-burning may be performed at a low temperature.
  • the hard carbon matrix precursor is composed of a thermoplastic resin and a curing agent, the above-described step four doping is not performed.
  • the hard carbon matrix precursor is composed of a thermoplastic resin and a dopant
  • the first two are mixed and stirred in the first step, and the speed is 2000-4500 r/min, using a F-0.4 high-speed disperser of Changzhou Wujin Bafang Machinery Factory.
  • Time is 10 ⁇ 120min, solidified in air, normal temperature 3 ⁇ 50 h. Do not perform the above four doping.
  • the hard carbon matrix precursor is a thermoplastic resin
  • it is cured in the air in the first step at room temperature 3 to 50. h, the above step four doping is not performed.
  • the low temperature calcination, pyrolysis, and high temperature treatment can also be carried out under the protection of protective gas helium, argon or helium.
  • the hard carbon matrix precursor is a lithium ion battery composite hard carbon anode material prepared by using a thermoplastic resin, and is observed by a KYKY2800B scanning electron microscope of Beijing Zhongke Science and Technology Development Co., Ltd., and the shape is blocky, irregular, fine particles, and adopted.
  • the test phase distribution was uniform, and the porous structure was tested by the NOVA1000 specific surface area tester of QUANTA CHROME, USA, and the pore size distribution was 0.2-100 nm, and the porosity was 9-19%.
  • the d 002 value was tested between 0.338 and 0.475 nm using a PW3040/60 X'Pert X-ray diffractometer from the Dutch PANalytical Instruments.
  • the particle size range was 0.5-90 ⁇ m using a Mastersizer 2000 laser particle size analyzer from Malvern Instruments.
  • the specific surface area was 1.9 to 75.3 m 2 /g using the Tristar 3000 fully automatic surface area and porosity analyzer from Mike Instruments.
  • the true density of the Ultrapycnometer 1000 automatic true density analyzer from Conta Instruments was 1.54 to 2.35 g/cm 3 .
  • the FZS4-4 type tap density meter was used to measure the tap density of 0.88 ⁇ 1.43 g/cm 3 .
  • Test method for the amount of carbon residue 1. Put the test sample in a clean crucible and dry it in an oven at 110 ° C ⁇ 5 ° C for 1 h. 2. The clean porcelain ark is calcined in a muffle furnace at 950 °C ⁇ 50 °C for 1 h, cooled in air for 2 min, then the porcelain ark is placed in a desiccator for 30 min, cooled to room temperature, weighed, and weighed 0.0001g. 3. Repeat step 2 until the difference of continuous weighing does not exceed 0.0004 g, and the mass of ⁇ is recorded as m 1 . 4. Weigh approximately 1 g of the dried sample into a porcelain ark and weigh to 0.000 lg, denoted as m 2 . 5.
  • the porcelain ark with the sample is placed in a muffle furnace at 950 °C ⁇ 50 °C for 1.5 h, then the porcelain ark is taken out and cooled in the air for 2 min, then placed in a desiccator for 30 min, cooled to room temperature and then weighed. The amount is weighed to 0.0001 g. 6. Repeat step 5 until the difference between consecutive weighings does not exceed 0.0004 g, denoted as m 3 .
  • C% [(m 2 - m 3 ) / (m 2 - m 1 )] ⁇ 100%, where m 1 is the mass of the porcelain boat, m 2 is the porcelain boat and the test The quality of the sample, m 3 is the quality of the porcelain boat and ash.
  • the lithium ion battery hard carbon anode material prepared by the method of the invention has a C element content of not less than 90%.
  • the negative electrode materials prepared in Examples 1 to 13 were mixed with a binder polyvinylidene fluoride PVDF and a conductive agent Super-P in a mass ratio of 92:5:3, and N-methylpyrrolidone NMP was added as a dispersing agent.
  • the slurry was uniformly coated on a 10 ⁇ m thick copper foil, pressed into a sheet, and then made into a diameter of 1 cm. Round carbon film. Dry in a dry box at 120 ° C for 12 h for use. A lithium metal sheet is used as a counter electrode.
  • the artificial graphite As a negative electrode material, batteries of Comparative Examples 1 to 2 were prepared as described above.
  • the artificial graphite has a specific surface area of 10 m 2 /g, a crystal layer spacing d 002 of 0.3358 nm, a true density of 2.22 g/cm 3 , a tap density of 1.01 g/cm 3 , and a particle size of 1 to 60 ⁇ m.
  • the first reversible capacity and the first coulombic efficiency were tested in the same manner as above.
  • Examples 1 to 13 are shown in Table 1.
  • the preparation processes of Examples 1 to 13 are shown in Table 2.
  • the physical and chemical properties of Examples 1 to 13 are shown in Table 3.
  • Examples 1 to 13 and Comparative Examples 1 to 4 The electrical performance test results are shown in Table 4.
  • the material prepared in Example 1 has a block-shaped irregular shape, a relatively uniform size, and a microporous structure.
  • d002 0.388, which is larger than the general graphite material d002 layer due to the porous and irregular structure of the composite hard carbon.
  • the 40C/1C charge capacity retention rate is 95.2%
  • the 30C/1C charge capacity retention rate is 96.2%
  • the composite hard carbon material is microporous and non- The irregular structure is so excellent that it has a high rate of charge and discharge performance.
  • Example 1 As shown in Figure 4, at 600C, 0.2C The capacity retention rate at a rate of 300 cycles was 96%, and the material prepared in Example 1 had excellent high temperature cycle performance.
  • Example 1 As shown in Figure 5, at -300C, 0.2C The 100-week capacity retention rate at the magnification was 88%, and the material prepared in Example 1 had excellent low-temperature cycle performance.
  • the precursor mass of the coating is 1 to 25% of the mass of the hard carbon matrix precursor.
  • the surface of the hard carbon substrate is chemically adsorbed, chemically reacted or physically adsorbed, so that the surface of the hard carbon substrate and the coating are combined by chemical bonds or van der Waals forces.
  • the surface of the hard carbon substrate has a honeycomb opening structure and a pore diameter of 1.0 ⁇ .
  • particle size is 2 ⁇ 60 ⁇ m
  • the pore size will be reduced to 0.5 ⁇ 50nm after coating
  • the particle size will become 3.5 ⁇ 70 ⁇ m
  • the lithium ion battery composite hard carbon anode material the shape is block and / or sheet
  • the particles have a particle diameter of 3.5 to 70 ⁇ m and a specific surface area of 7.5 to 20 m 2 /g.
  • the surface of the material has a honeycomb open-cell structure, a pore diameter of 0.5 to 50 nm, a porosity of 9 to 16%, and a 002 crystal plane.
  • the layer spacing d 002 is between 0.337 and 0.455 nm, the true density is 1.55 to 2.25 g/cm 3 , the tap density is 0.91 to 1.45 g/cm 3 , and the C element content is not less than 94%.
  • the first reversible capacity is above 450 mAh/g, and the first charge has a coulombic efficiency of 81.3%.
  • the hard carbon matrix precursor is one or more of plant raw material pollen, rice husk, sugar cane stick, walnut shell, bamboo, distiller's grains and wood chips, and pyrolyzes to form a hard carbon matrix.
  • the hard carbon matrix precursor is composed of the following mass ratio: a plant material, a mixture of more than 0 to 40% or less of a dopant of the plant material, and pyrolysis to form a hard carbon matrix.
  • the plant material is more than one type of pollen, rice husk, sugar cane stalk, walnut shell, bamboo, vinasse and wood chips.
  • the dopant is a metal compound, a non-metal compound, a metal element or a non-metal element.
  • the metal compound is a metal oxide, a metal salt or a metal base.
  • the non-metallic compound is a non-metal oxide, an acid, a non-metal element organic or a non-metal salt.
  • the metal oxide is one or more of tin oxide, cobalt oxide and nickel oxide.
  • the metal salt is one or more of sodium phosphate, tin chloride, cobalt carbonate, and sodium dihydrogen phosphate.
  • the metal base is one or more of copper hydroxide, cobalt hydroxide, tin hydroxide, and nickel hydroxide.
  • the non-metal oxide is silica and/or phosphorus pentoxide.
  • the acid is one or more of boric acid, silicic acid, and phosphoric acid.
  • the non-metal salt is one or more of ammonium dihydrogen phosphate, ammonium phosphate, and ammonium sulfate.
  • the non-metallic element organics are silicone resins and/or ethylene glycol borate esters.
  • the metal element is one or more of copper, lead, antimony, tin, cobalt and nickel.
  • the non-metal element is one or more of silicon, sulfur and boron.
  • the first method for preparing the lithium ion battery composite hard carbon anode material of the present invention comprises the following steps:
  • the acid is hydrofluoric acid, boric acid, sulfuric acid, hydrochloric acid or nitric acid
  • the base is potassium hydroxide, calcium hydroxide or sodium hydroxide.
  • the dopant is a dopant when the aforementioned hard carbon matrix precursor is a plant material.
  • the doping step can also be carried out before the low temperature pre-burning.
  • the hard carbon is ball milled or pulverized to obtain a hard carbon matrix with a particle size of 2 to 65 ⁇ m.
  • the precursor of the coating is the aforementioned organic matter.
  • the second method for preparing the lithium ion battery composite hard carbon anode material of the present invention comprises the following steps: the aforementioned plant material
  • the above plant material is mechanically pulverized or air-jet pulverized to obtain a powdery substance having a particle size of 40 to 100 ⁇ m, and a general mechanical pulverizer or a jet mill is used.
  • the dopant is a dopant when the hard carbon matrix precursor is a plant material.
  • the hard carbon is ball milled or pulverized for 10 to 30 minutes to obtain a hard carbon matrix having a particle size of 2 to 60 ⁇ m.
  • the precursor of the coating is the aforementioned organic matter.
  • the third method for preparing the lithium ion battery composite hard carbon anode material of the present invention comprises the following steps:
  • the dopant is a dopant when the aforementioned hard carbon matrix precursor is a plant material.
  • the precursor of the coating is the aforementioned organic matter.
  • the fourth method for preparing the lithium ion battery composite hard carbon anode material of the present invention comprises the following steps:
  • the hard carbon is ball milled or pulverized for 20-90 min to obtain a hard carbon matrix with a particle size of 2 to 60 ⁇ m.
  • the precursor of the coating is the aforementioned organic matter.
  • the hard carbon matrix precursor is a lithium ion battery composite hard carbon anode material prepared by using a plant material, and the above apparatus is used to measure: the shape is a block and/or a sheet-like particle, and the surface thereof has a honeycomb opening structure, and the pore size distribution is 0.5. ⁇ 50nm, porosity is 9-16%, d 002 value is between 0.337 ⁇ 0.455nm, particle size range is 3.5 ⁇ 70 ⁇ m, specific surface area is 0.5-20m 2 /g, true density is 1.55 ⁇ 2.25g/cm 3 , The tap density is 0.91 to 1.45 g/cm 3 .
  • the surface of the hard carbon matrix and the coating are combined by chemical bonds or van der Waals forces.
  • van der Waals forces are intermolecular forces, while the sources of intermolecular forces are orientation forces, inducing forces and dispersive forces.
  • the dispersion force is dominant.
  • the force between the surface of the hard carbon substrate and the cladding is formed during the coating process.
  • Example 14 to 21 The formulations of Examples 14 to 21 are shown in Table 5.
  • the preparation process is shown in Table 6.
  • the physical and chemical properties test results are shown in Table 7.
  • the simulated batteries were prepared according to the above method.
  • the electrical property test results are shown in Table 8.
  • the particles are in the form of blocks and/or sheets, and the surface of the material has a honeycomb open-cell structure with a pore diameter of 0.5 to 40 nm and a porosity of 12%.
  • the composite hard carbon porous structure causes it to be larger than the general graphite material d 002 layer.
  • Comparative Example 3 using natural graphite as a negative electrode material, a battery of the comparative example was prepared as described above.
  • the natural graphite has a specific surface area of 8.3 m 2 /g, a crystal layer spacing d 002 of 0.3365 nm, a true density of 2.22 g/cm 3 , a tap density of 1.05 g/cm 3 , and a particle size of 1 to 60 ⁇ m.
  • the first reversible capacity and the first coulombic efficiency were tested in the same manner as above, and the electrical performance test is shown in Table 8.
  • Comparative Example 4 using natural graphite as a negative electrode material, a battery of the comparative example was prepared as described above.
  • the natural graphite has a specific surface area of 6.3 m 2 /g, a crystal layer spacing d 002 of 0.3358 nm, a true density of 2.23 g/cm 3 , a tap density of 1.14 g/cm 3 and a particle size of 1.1 to 58 ⁇ m.
  • the first reversible capacity and the first coulombic efficiency were tested in the same manner as above, and the electrical performance test is shown in Table 8.
  • Example First curing Second, low temperature pre-burning Third, the average particle size after crushing Fourth, doping 5. Pyrolysis temperature, time, nitrogen flow Sixth, the average particle size after crushing Seven, coating process 1 3h
  • the heating rate was 0.26 ° C / min, 400 ° C low temperature pre-burning, 6.5 h, nitrogen flow rate was 0.2 m 3 / h. 25 ⁇ m 3000r/min, 35min Heating rate 5 ° C / min, 1100 ° C pyrolysis 2.2 h, nitrogen flow 0.2 m 3 / h 16 ⁇ m 1500r/min rotation speed, mixing 50min, 3°C/min heating rate, 1200°C treatment for 2h, nitrogen flow rate is 0.2m 3 /h.
  • the heating rate was 0.4 ° C / min, and the temperature was pre-fired at 360 ° C for 9 h, and the nitrogen flow rate was 0.23 m 3 /h. 22 ⁇ m 2500r/min, 41min The heating rate is 3 °C/min, the pyrolysis is 1400 °C for 1.8 h, and the nitrogen flow rate is 0.30 m 3 /h. 15 ⁇ m The speed of 1800r/min was mixed for 45 min, the temperature rising rate of 2 °C/min was 1000 °C, the treatment was carried out for 4 h, and the nitrogen flow rate was 0.3 m 3 /h.
  • the heating rate was 1.0 ° C / min, and the temperature was preheated at 300 ° C for 10 h, and the nitrogen flow rate was 0.25 m 3 /h. 27 ⁇ m 1200r/min, 58min Heating rate 10 ° C / min, 1500 ° C pyrolysis 0.5 h, nitrogen flow 0.20 m 3 / h 13 ⁇ m 2000 r / min speed, mixing 36min, 0.1 ° C / min temperature increase rate to 500 ° C, 8 h treatment, nitrogen flow rate of 0.3 m 3 / h.
  • the heating rate was 3 ° C / min, the temperature was pre-fired at 250 ° C for 12.0 h, and the nitrogen flow rate was 0.18 m 3 /h. 30 ⁇ m 1800r/min, 40min Heating rate 4 ° C / min, 1000 ° C pyrolysis 2.0 h, nitrogen flow 0.15 m 3 / h 18 ⁇ m
  • the rotation speed of 1900r/min was mixed for 39 minutes, the temperature rising rate of 10 °C/min was 1500 °C, and the treatment was carried out for 3 hours, and the nitrogen flow rate was 0.4 m 3 /h.
  • the heating rate was 2 ° C / min, the temperature was pre-fired at 200 ° C for 14.5 h, and the nitrogen flow rate was 0.2 m 3 /h.
  • the speed of 1400r/min was mixed for 38 min, the temperature rising rate of 10 °C/min was 1300 °C, the treatment was 2.5 h, and the nitrogen flow rate was 0.4 m 3 /h.
  • the heating rate was 0.1 ° C / min, the temperature was preheated at 150 ° C for 24 h, and the nitrogen flow rate was 0.24 m 3 / h. 32 ⁇ m 2800r/min, 37min Heating rate 3.0 ° C / min, 950 ° C pyrolysis 2.0 h, nitrogen flow 0.4 m 3 / h 30 ⁇ m
  • the speed was 2000 r/min, mixed for 37 min, and the heating rate was 1.5 ° C/min to 800 ° C.
  • the nitrogen flow rate was 0.3 m 3 /h.
  • the heating rate was 3 ° C / min, the temperature was preheated at 350 ° C for 9.5 h, and the nitrogen flow rate was 0.2 m 3 /h. 28 ⁇ m 1000r/min, 120min Heating rate 1.8 ° C / min, 700 ° C pyrolysis 2.5 h, nitrogen flow 0.4 m 3 / h 30 ⁇ m 2500r/min rotation speed, mixing for 38 min, 7 °C/min heating rate to 1200 °C, treatment for 4 h, nitrogen flow rate of 0.32 m 3 / h.
  • the heating rate was 3.6 ° C / min, the temperature was preheated at 450 ° C for 3.0 h, and the nitrogen flow rate was 0.3 m 3 /h. 38 ⁇ m Heating rate 2.7 ° C / min, 650 ° C pyrolysis 5.5 h, nitrogen flow 0.4 m 3 / h 34 ⁇ m
  • the rotation speed of 2300r/min was mixed for 37 min, the temperature rising rate of 6 °C/min was 1000 °C, the treatment was 3 h, and the nitrogen flow rate was 0.35 m 3 /h.
  • the heating rate was 2.5 ° C / min, the temperature was pre-fired at 250 ° C for 10.5 h, and the nitrogen flow rate was 0.28 m 3 /h. 23 ⁇ m 1300r/min, 90min Heating rate 4.0 ° C / min, 1100 ° C pyrolysis 1.5 h, nitrogen flow 0.26 m 3 / h 28 ⁇ m 3000r/min rotation speed, mixing for 24 min, heating rate of 1.5 °C/min to 700 °C, treatment for 5 h, nitrogen flow rate of 0.2 m 3 /h.
  • the heating rate was 0.5 ° C / min, and the temperature was preheated at 360 ° C for 7 h, and the nitrogen flow rate was 0.21 m 3 /h. 19 ⁇ m 3200r/min, 30min
  • the heating rate is 0.3 ° C / min, 560 ° C pyrolysis 7.5 h, nitrogen flow rate 0.4 m 3 / h 26 ⁇ m 3500r/min rotation speed, mixing for 20 min, temperature rise rate of 5.0 °C/min to 800 °C, treatment for 4 h, nitrogen flow rate of 0.3 m 3 /h.
  • the heating rate was 3.3 ° C / min, the temperature was pre-fired at 280 ° C for 10.0 h, and the nitrogen flow rate was 0.4 m 3 /h. 32 ⁇ m 2500r/min, 43min Heating rate 8.0 ° C / min, 720 ° C pyrolysis 3.5 h, nitrogen flow rate 0.2 m 3 / h 30 ⁇ m 2000r/min rotation speed, mixing for 40min, heating rate of 1.5°C/min to 650°C, treatment for 8h, nitrogen flow rate of 0.3 m 3 /h.
  • the heating rate was 1.3 ° C / min, the temperature was pre-fired at 180 ° C for 15.0 h, and the nitrogen flow rate was 0.2 m 3 /h. 17 ⁇ m 1200r/min, 60min Heating rate 6.8 ° C / min, pyrolysis 1.5 h at 1200 ° C, nitrogen flow 0.4 m 3 / h 21 ⁇ m
  • the speed of 1700r/min was mixed for 56 min, the heating rate of 1.0 °C/min was increased to 600 °C, and the treatment was carried out for 6 h.
  • the nitrogen flow rate was 0.25 m 3 /h.
  • Example 1 505.6 85.1 501.5 486.1 479.5
  • Example 2 500.3 81.1 487.3 477.6 458.1
  • Example 3 578.9 84.3 565 548.1 519.8
  • Example 4 530.6 83.9 516.9 501.4 485.8
  • Example 5 530.6 86 521 500.2 474.2
  • Example 7 604.5 84.1 593 569.3 557.4
  • Example 8 462.4 80 458.1 439.2 421.2
  • Example 9 510.3 81.6 503.3 494.6 488.5
  • Example 10 462.4 83.8 458.1 439.2 421.2
  • Example 11 458.3 80.5 450.9 437.4 416.6
  • Example 12 455.2 79.9 449.7 438.9 411
  • Example 13 550.8 82 541.4 530.2 505.7 Comparative example 1 320.5 90.3 308.
  • 16 adopts method three 41 ⁇ m 90ml concentrated sulfuric acid speed 900r/min, time 6min, soak for 15h pH 5.1, speed 800r/min, time 30min Temperature 120 ° C, 24h The heating rate was 0.25 ° C / min, and the temperature was preheated at 500 ° C for 6 h, and the nitrogen flow rate was 0.25 m 3 /h. 30 ⁇ m 1000r/min, 95min The heating rate is 10 °C/min, pyrolysis at 1300 °C for 1 h, and the nitrogen flow rate is 0.40 m 3 /h.
  • 18 adopt method four 72 ⁇ m 110ml sodium hydroxide rotation speed 1300r/min, time 3min, soaking potassium solution for 18h pH 8.4, speed 1400r/min, time 8min Temperature 110 ° C, 27 h The heating rate was 2 ° C / min, and the temperature was preheated at 300 ° C for 10 h, and the nitrogen flow rate was 0.2 m 3 /h.
  • the heating rate is 4.5°C/min
  • the pyrolysis is 950°C for 3h
  • the nitrogen flow rate is 0.21m 3 /h.
  • the speed was 4500 r/min, mixed for 10 min
  • the temperature rising rate of 1 ° C/min was 700 ° C
  • pyrolysis treatment was 12 h
  • the vacuum degree was 0.03 MPa.
  • 19 adopts method three 50 ⁇ m 100ml hydrochloric acid speed 800r/min, time 7min, soak for 45h pH 5.8, speed 1250r/min, time 6min Temperature 140 ° C, 10h Temperature rise rate of 0.1 °C / min, 350 °C low temperature calcined 18h, the nitrogen flow 0.16 m 3 / h.

Abstract

A composite hard carbon material of a negative electrode for a lithium ion battery and a method of preparing the same. The composite hard carbon material includes a hard carbon base and a coating outside the hard carbon base, wherein the hard carbon base is formed by pyrolysis of thermoplastic resin or plant material and the coating is formed by pyrolysis of organic substances. The method of preparing the composite hard carbon material includes producing, crushing and coating of the hard carbon base. At 0.2C the composite hard carbon material has a first reversible capacity above 455.2mAh/g and a first charging coulombic efficiency above 79.4%, therefore the composite hard carbon material has a charge and discharge performance of high capacity and high first coulombic efficiency.

Description

锂离子电池复合硬碳负极材料及其制备方法  Lithium ion battery composite hard carbon anode material and preparation method thereof 锂离子电池复合硬碳负极材料及其制备方法  Lithium ion battery composite hard carbon anode material and preparation method thereof
技术领域Technical field
本发明涉及一种电池负极材料及其制备方法,特别是一种锂离子电池负极材料及其制备方法。The invention relates to a battery anode material and a preparation method thereof, in particular to a lithium ion battery anode material and a preparation method thereof.
背景技术Background technique
随着信息时代多功能便携式电子设备的需求日益增长，以及电动车的快速发展，研发高比能量、高倍率、高安全性、长寿命、低成本的新型锂电池电极材料已经成为目前国际上重要的前沿研究领域。现有技术较为成功的碳负极材料有人造石墨、中间相碳微球MCMB、石油焦炭。但其372mAh/g的比容量过低 , 越来越不能满足要求,而且脆弱结构会导致很有限的稳定性,对电解液也高度敏感。因而,人们把注意力转移到其他碳材料上,例如软碳、硬碳。其中硬碳以其无规排序所具有的较高容量、低造价和优良循环性能引起了人们的极大兴趣。硬碳是指难石墨化的碳,是高分子聚合物的热解碳,这类碳具有较高的比容量。Sony公司于1991年开发了使用聚糠醇PFA热裂解制得的硬碳作为负极材料的锂离子电池。但是其首次充、放电效率低，仅为45%左右。With the increasing demand for multifunctional portable electronic devices in the information age and the rapid development of electric vehicles, the development of new lithium battery electrode materials with high specific energy, high magnification, high safety, long life and low cost has become an internationally important Frontier research areas. The carbon anode materials which have been successfully used in the prior art include artificial graphite, mesocarbon microbeads MCMB, and petroleum coke. However, its specific capacity of 372mAh/g is too low. , Increasingly, the requirements are not met, and the fragile structure results in very limited stability and is highly sensitive to electrolytes. Thus, people turn their attention to other carbon materials, such as soft carbon and hard carbon. Among them, the high capacity, low cost and excellent cycle performance of hard carbon in its random order have attracted great interest. Hard carbon refers to carbon that is difficult to graphitize and is a pyrolytic carbon of a high molecular polymer. Such carbon has a high specific capacity. In 1991, Sony developed a lithium ion battery using hard carbon obtained by thermal cracking of polyptanol PFA as a negative electrode material. However, its first charge and discharge efficiency is low, only about 45%.
发明内容Summary of the invention
本发明的目的是提供一种锂离子电池复合硬碳负极材料及其制备方法，要解决的技术问题是提高锂离子电池的大倍率充放电性能，兼有优良的高、低温充放电性能和稳定的循环性能。The object of the present invention is to provide a lithium ion battery composite hard carbon anode material and a preparation method thereof, and the technical problem to be solved is to improve the large rate charge and discharge performance of the lithium ion battery, and have excellent high and low temperature charge and discharge performance and stability. Cyclic performance.
本发明采用以下技术方案：一种锂离子电池复合硬碳负极材料，所述锂离子电池复合硬碳负极材料的硬碳基体外包覆有包覆物，所述包覆物的前躯体为有机物环氧树脂、酚醛树脂、羧甲基纤维素、沥青、乙基甲基碳酸酯、聚乙烯醇、聚苯乙烯、聚甲基丙烯酸甲酯、聚四氟乙烯、聚偏氟乙烯、聚丙烯腈、丁苯橡胶、聚氯乙烯、聚乙烯、聚环氧乙烷、聚环氧丙烷、聚丁二酸乙二醇酯、聚癸二酸乙二醇、聚乙二醇亚胺、聚乙炔、聚对苯、聚苯胺、聚吡咯、聚并苯、 聚间苯二胺、聚噬吩、聚对苯撑乙烯、聚噻吩、聚丙烯晴、聚酰亚胺和聚苯硫醚的一种以上，热解形成包覆物。The present invention adopts the following technical solution: a lithium ion battery composite hard carbon anode material, the hard carbon substrate of the lithium ion battery composite hard carbon anode material is coated with a coating, and the precursor of the coating is organic Epoxy resin, phenolic resin, carboxymethyl cellulose, asphalt, ethyl methyl carbonate, polyvinyl alcohol, polystyrene, polymethyl methacrylate, polytetrafluoroethylene, polyvinylidene fluoride, polyacrylonitrile , styrene-butadiene rubber, polyvinyl chloride, polyethylene, polyethylene oxide, polypropylene oxide, polyethylene succinate, polyethylene sebacate, polyethylene glycol imine, polyacetylene, Polyparaphenylene, polyaniline, polypyrrole, polyacene, One or more of poly(m-phenylenediamine), polyphhenol, polyparaphenylenevinylene, polythiophene, polypropylene, polyimide, and polyphenylene sulfide, pyrolyzed to form a coating.
本发明的硬碳 基体前驱物为热塑性树脂丙烯酸树脂、聚氯乙烯、聚碳酸酯、环氧树脂、酚醛树脂和聚甲醛的一种以上， 热解形成硬碳基体；包覆物前躯体质量为硬碳基体前驱物质量的1～15%；所述锂离子电池复合硬碳负极材料形状为块状细小颗粒，具有多孔结构，孔径为0.2～100nm，孔隙率为9～19%，002晶面的层间距在0.338～0.475nm之间，粒度范围为0.5～90μm，比表面积为1.9～75.3m2/g，真实密度为1.54～2.35g/cm3，振实密度为0.88～1.43g/cm3，其炭C元素的含量不少于90.5%。The hard carbon matrix precursor of the present invention is one or more of thermoplastic resin acrylic resin, polyvinyl chloride, polycarbonate, epoxy resin, phenolic resin and polyoxymethylene, and pyrolyzes to form a hard carbon matrix; the precursor mass of the coating is 1 to 15% of the mass of the hard carbon matrix precursor; the lithium ion battery composite hard carbon anode material is in the form of massive particles having a porous structure, a pore diameter of 0.2 to 100 nm, a porosity of 9 to 19%, and a 002 crystal plane. The layer spacing is between 0.338 and 0.475 nm, the particle size range is from 0.5 to 90 μm, the specific surface area is from 1.9 to 75.3 m 2 /g, the true density is from 1.54 to 2.35 g/cm 3 , and the tap density is from 0.88 to 1.43 g/cm. 3 , the content of its carbon C element is not less than 90.5%.
本发明的硬碳基体前驱物包括以下质量比：25%至小于100%的热塑性树脂，大于0至小于等于75%的固化剂，热解形成硬碳基体；所述固化剂为己二胺、间苯二胺、苯胺甲醛树脂、聚酰胺树脂、邻苯二甲酸酐和苯磺酸的一种以上。The hard carbon matrix precursor of the present invention comprises the following thermoplastic ratio: 25% to less than 100% of a thermoplastic resin, more than 0 to 75% of a curing agent, pyrolysis to form a hard carbon matrix; the curing agent is hexamethylenediamine, One or more of m-phenylenediamine, aniline formaldehyde resin, polyamide resin, phthalic anhydride, and benzenesulfonic acid.
本发明的硬碳基体前驱物由以下质量比组成：25%至小于100%的 热塑性树脂，大于0至小于等于75%的固化剂，大于0至小于等于15%的掺杂物，热解形成硬碳 基体；所述掺杂物是金属单质、非金属单质、金属化合物和非金属化合物的一种以上；所述金属单质为铜、铅、锑、锡、钴和镍的一种以上；所述金属化合物为氧化锡，氧化钴、氧化镍、磷酸钠、磷酸二氢钠、乙酸锡、氯化锡、碳酸钴、氢氧化铜、氢氧化钴、氢氧化锡和氢氧化镍的一种以上；所述非金属单质为硅、硫和硼的一种以上；所述非金属化合物为二氧化硅、五氧化二磷、硼酸、硅酸、磷酸、磷酸二氢铵、磷酸铵、硫酸铵、有机硅树脂和 乙二醇硼酸酯 的一种以上。 The hard carbon matrix precursor of the present invention is composed of the following mass ratio: 25% to less than 100% Thermoplastic resin, a curing agent greater than 0 to 75% or less, a dopant greater than 0 to 15%, pyrolyzed to form a hard carbon a matrix; the dopant is at least one of a simple substance of a metal, a non-metal element, a metal compound, and a non-metal compound; the metal element is one or more of copper, lead, antimony, tin, cobalt, and nickel; The compound is one or more of tin oxide, cobalt oxide, nickel oxide, sodium phosphate, sodium dihydrogen phosphate, tin acetate, tin chloride, cobalt carbonate, copper hydroxide, cobalt hydroxide, tin hydroxide and nickel hydroxide; The non-metal element is more than one of silicon, sulfur and boron; the non-metal compound is silicon dioxide, phosphorus pentoxide, boric acid, silicic acid, phosphoric acid, ammonium dihydrogen phosphate, ammonium phosphate, ammonium sulfate, silicone Resin and More than one type of ethylene glycol borate.
本发明的硬碳基体前驱物由以下质量比组成：85%至小于100%的 热塑性树脂，大于0至小于等于15%的 掺 杂物， 热解形成硬碳基体；所述掺杂物是金属单质、非金属单质、金属化合物和非金属化合物的一种以上；所述金属单质为铜、铅、锑、锡、钴和镍的一种以上；所述金属化合物为氧化锡，氧化钴、氧化镍、磷酸钠、磷酸二氢钠、乙酸锡、氯化锡、碳酸钴、氢氧化铜、氢氧化钴、氢氧化锡和氢氧化镍的一种以上；所述非金属单质为硅、硫和硼的一种以上；所述非金属化合物为二氧化硅、五氧化二磷、硼酸、硅酸、磷酸、磷酸二氢铵、磷酸铵、硫酸铵、有机硅树脂和乙二醇硼酸酯的一种以上。The hard carbon matrix precursor of the present invention is composed of the following mass ratio: 85% to less than 100% of a thermoplastic resin, and more than 0 to less than or equal to 15% of the blend. Sundries, Pyrolysis to form a hard carbon matrix; the dopant is more than one element of a metal element, a non-metal element, a metal compound and a non-metal compound; the metal element is a kind of copper, lead, antimony, tin, cobalt and nickel Above; the metal compound is tin oxide, cobalt oxide, nickel oxide, sodium phosphate, sodium dihydrogen phosphate, tin acetate, tin chloride, cobalt carbonate, copper hydroxide, cobalt hydroxide, tin hydroxide and nickel hydroxide. One or more; the non-metal element is more than one of silicon, sulfur and boron; the non-metal compound is silicon dioxide, phosphorus pentoxide, boric acid, silicic acid, phosphoric acid, ammonium dihydrogen phosphate, ammonium phosphate, One or more of ammonium sulfate, silicone resin, and ethylene glycol borate.
本发明的硬碳基体前驱物为植物原料花粉、稻谷壳、甘蔗杆、核桃壳、竹子、酒糟和木屑的一种以上 ， 热解 形成硬碳基体，包覆物前躯体质量为硬碳基体前驱物质量的1～25%；所述硬碳基体表面与包覆物之间依靠化学键或范德华力相结合，硬碳基体粒度为 2～60μm，表面具有蜂窝开孔结构，孔径为1.0～55nm；形状为块状和/或片状的颗粒，其粒径为3.5～70μm，其比表面积在7.5～20m2/g之间，材料表面具有蜂窝状开孔结构，孔径为0.5～50nm，孔隙率为9～16%，002晶面的层间距d002值在0.337～0.455nm之间，真实密度为1.55～2.25g/cm3，振实密度为0.91～1.45g/cm3，其C元素的含量不少于94%。The hard carbon matrix precursor of the invention is more than one kind of plant raw material pollen, rice husk, sugar cane rod, walnut shell, bamboo, distiller's grains and wood chips, pyrolysis forms a hard carbon matrix, and the precursor mass of the coating is a hard carbon matrix precursor. 1 to 25% of the mass; the surface of the hard carbon substrate and the coating are combined by a chemical bond or a van der Waals force, the hard carbon matrix has a particle size of 2 to 60 μm, and the surface has a honeycomb open-cell structure with a pore diameter of 1.0 to 55 nm; The particles are in the form of blocks and/or flakes having a particle diameter of 3.5 to 70 μm and a specific surface area of 7.5 to 20 m 2 /g. The surface of the material has a honeycomb open-cell structure with a pore diameter of 0.5 to 50 nm and a porosity. 9 to 16%, the layer spacing d 002 of the 002 crystal plane is between 0.337 and 0.455 nm, the true density is 1.55 to 2.25 g/cm 3 , and the tap density is 0.91 to 1.45 g/cm 3 . The content is not less than 94%.
本发明的硬碳基体前驱物由以下质量比组成：植物原料、占植物类原料大于0至小于等于40%的掺杂物混合组成，热解 形成硬碳基体；所述掺杂物为金属氧化物氧化锡、氧化钴和氧化镍的一种以上，或金属盐磷酸钠、氯化锡、碳酸钴和磷酸二氢钠的一种以上，或金属碱氢氧化铜、氢氧化钴、氢氧化锡和氢氧化镍的一种以上，或非金属氧化物二氧化硅和/或五氧化二磷，或硼酸、硅酸和磷酸的一种以上，或非金属盐磷酸二氢铵、磷酸铵和硫酸铵的一种以上，或金属单质铜、铅、锑、锡、钴和镍的一种以上，或非金属单质硅、硫和硼的一种以上The hard carbon matrix precursor of the present invention is composed of the following mass ratios: a plant material, a dopant composition of plant materials greater than 0 to 40% or less, pyrolysis Forming a hard carbon substrate; the dopant is one or more of the metal oxides tin oxide, cobalt oxide, and nickel oxide, or one or more of the metal salt sodium phosphate, tin chloride, cobalt carbonate, and sodium dihydrogen phosphate, or One or more of a metal base copper hydroxide, cobalt hydroxide, tin hydroxide, and nickel hydroxide, or a non-metal oxide silica and/or phosphorus pentoxide, or one or more of boric acid, silicic acid, and phosphoric acid, Or one or more of the non-metal salts of ammonium dihydrogen phosphate, ammonium phosphate, and ammonium sulfate, or one or more of the metal elements of copper, lead, antimony, tin, cobalt, and nickel, or one of non-metal elemental silicon, sulfur, and boron. the above
一种锂离子电池复合硬碳负极材料的制备方法，包括以下步骤：一、将热塑性树脂在空气中、常温下固化3～50 h，得到固态前躯体；二、氮气流量为0.1～0.4m3/h，将前躯体以0.1～3℃/min的升温速度到150℃～450℃，低温预烧2～24h，自然降温至室温，进行粉碎，得到粒度为1～60μm的粉末状；三、氮气流量为0.1～0.4m3/h，以0.3～10℃/min的升温速度到560～1500℃，热解0.5～7.5h，自然降温至室温 , 制得硬碳；四、将硬碳进行球磨或粉碎，得到粒度为1～60μm的硬碳基体；五、在硬碳基体中按硬碳基体前驱物质量的1～15%，加入包覆物的前躯体，以1400～3500r/min的转速混合20～50min，然后氮气流量为0.1～0.4m3/h，以1～7.5℃/min的升温速度到500～1500℃，时间为2～8h，进行包覆物热解处理，自然降温至室温 ,得到锂离子电池复合硬碳负极材料；所述热塑性树脂为丙烯酸树脂、聚氯乙烯、聚碳酸酯、环氧树脂、酚醛树脂和聚甲醛的一种以上；所述包覆物的前躯体为有机物环氧树脂、酚醛树脂、羧甲基纤维素、沥青、乙基甲基碳酸酯、聚乙烯醇、聚苯乙烯、聚甲基丙烯酸甲酯、聚四氟乙烯、聚偏氟乙烯、聚丙烯腈、丁苯橡胶、聚氯乙烯、聚乙烯、聚环氧乙烷、聚环氧丙烷、聚丁二酸乙二醇酯、聚癸二酸乙二醇、聚乙二醇亚胺、聚乙炔、聚对苯、聚苯胺、聚吡咯、聚并苯、 聚间苯二胺、聚噬吩、聚对苯撑乙烯、聚噻吩、聚丙烯晴、聚酰亚胺和聚苯硫醚的一种以上。A method for preparing a composite hard carbon anode material for a lithium ion battery comprises the following steps: 1. curing a thermoplastic resin in air at room temperature for 3 to 50 hours to obtain a solid precursor; and second, a nitrogen flow rate of 0.1 to 0.4 m 3 /h, the precursor body at a temperature increase rate of 0.1 ~ 3 ° C / min to 150 ° C ~ 450 ° C, low temperature pre-burning 2 ~ 24h, naturally cooled to room temperature, pulverization, to obtain a powder size of 1 ~ 60μm; The nitrogen flow rate is 0.1-0.4 m 3 /h, the temperature rise rate of 0.3-10 ° C / min is 560-1500 ° C, the pyrolysis is 0.5-7.5 h, and the temperature is naturally cooled to room temperature to obtain hard carbon; Ball milling or pulverization to obtain a hard carbon matrix having a particle size of 1 to 60 μm; 5. Adding 1 to 15% of the mass of the hard carbon matrix precursor in the hard carbon matrix, adding the precursor of the coating to 1400 to 3500 r/min. Mixing at a speed of 20 to 50 minutes, then a nitrogen flow rate of 0.1 to 0.4 m 3 /h, a temperature increase rate of 1 to 7.5 ° C / min to 500 to 1500 ° C, time of 2 to 8 h, thermal treatment of the coating, natural cooling To room temperature, a lithium ion battery composite hard carbon anode material is obtained; the thermoplastic resin is an acrylic resin More than one of polyvinyl chloride, polycarbonate, epoxy resin, phenolic resin and polyoxymethylene; the precursor of the coating is organic epoxy resin, phenolic resin, carboxymethyl cellulose, asphalt, ethyl methyl Carbonate, polyvinyl alcohol, polystyrene, polymethyl methacrylate, polytetrafluoroethylene, polyvinylidene fluoride, polyacrylonitrile, styrene butadiene rubber, polyvinyl chloride, polyethylene, polyethylene oxide, Polypropylene oxide, polyethylene succinate, polyethylene sebacate, polyethylene glycol imine, polyacetylene, polyparaphenylene, polyaniline, polypyrrole, polyacene, poly(diphenylene) One or more of an amine, a polyphex, a polyparaphenylene vinylene, a polythiophene, a polypropylene clear, a polyimide, and a polyphenylene sulfide.
本发明的方法固化按质量比在25%至小于100%的热塑性树脂中添加大于0至小于等于75%的固化剂， 搅拌均匀，在空气中、常温下固化3～50h，得到固态前躯体； 所述固化剂为己二胺、间苯二胺、苯胺甲醛树脂、聚酰胺树脂、邻苯二甲酸酐和苯磺酸的一种以上。The method of the present invention cures a curing agent having a mass ratio of from 25% to less than 100% by weight of the thermoplastic resin of from greater than 0 to less than or equal to 75%. Stir well, solidify in air at room temperature for 3 to 50 hours to obtain a solid precursor; the curing agent is hexamethylenediamine, m-phenylenediamine, aniline formaldehyde resin, polyamide resin, phthalic anhydride and benzenesulfonic acid More than one.
本发明的方法低温预烧并进行粉碎后，在粉末状内按质量比大于0至小于等于15%的比例，加入掺杂物，转速为1000～3000r/min，时间为26～120min；所述掺杂物是金属单质、非金属单质、金属化合物和非金属化合物的一种以上；所述金属单质为铜、铅、锑、锡、钴和镍的一种以上；所述金属化合物为氧化锡，氧化钴、氧化镍、磷酸钠、磷酸二氢钠、乙酸锡、氯化锡、碳酸钴、氢氧化铜、氢氧化钴、氢氧化锡和氢氧化镍的一种以上；所述非金属单质为硅、硫和硼的一种以上；所述非金属化合物为二氧化硅、五氧化二磷、硼酸、硅酸、磷酸、磷酸二氢铵、磷酸铵、硫酸铵、有机硅树脂和乙二醇硼酸酯的一种以上。After the method of the present invention is calcined at a low temperature and pulverized, the dopant is added in a powder form at a mass ratio of more than 0 to 15% or less, and the rotation speed is 1000 to 3000 r/min, and the time is 26 to 120 min; The dopant is one or more of a simple metal, a non-metal element, a metal compound, and a non-metal compound; the metal element is one or more of copper, lead, antimony, tin, cobalt, and nickel; and the metal compound is tin oxide. , one or more of cobalt oxide, nickel oxide, sodium phosphate, sodium dihydrogen phosphate, tin acetate, tin chloride, cobalt carbonate, copper hydroxide, cobalt hydroxide, tin hydroxide and nickel hydroxide; the non-metal element It is one or more of silicon, sulfur and boron; the non-metal compound is silicon dioxide, phosphorus pentoxide, boric acid, silicic acid, phosphoric acid, ammonium dihydrogen phosphate, ammonium phosphate, ammonium sulfate, silicone resin and ethylene More than one type of alcohol borate.
本发明的方法固化按质量比，在25%至小于100%的热塑性树脂中，添加大于0至小于等于75%的固化剂，大于0至小于等于15%的 掺 杂物，混合搅拌，转速为2000～4500r/min， 时间为10～120min， 在空气中、常温下固化3～50h，得到前躯体；所述掺杂物是金属单质、非金属单质、金属化合物和非金属化合物的一种以上；所述金属单质为铜、铅、锑、锡、钴和镍的一种以上；所述金属化合物为氧化锡，氧化钴、氧化镍、磷酸钠、磷酸二氢钠、乙酸锡、氯化锡、碳酸钴、氢氧化铜、氢氧化钴、氢氧化锡和氢氧化镍的一种以上；所述非金属单质为硅、硫和硼的一种以上；所述非金属化合物为二氧化硅、五氧化二磷、硼酸、硅酸、磷酸、磷酸二氢铵、磷酸铵、硫酸铵、有机硅树脂和乙二醇硼酸酯的一种以上。The method of the present invention cures, in a mass ratio of 25% to less than 100%, of a thermoplastic resin, adding a curing agent of more than 0 to 75% or less, and a blending of more than 0 to less than or equal to 15%. Miscellaneous, mixing and stirring, the speed is 2000~4500r/min, the time is 10~120min, Curing in air at room temperature for 3 to 50 hours to obtain a precursor; the dopant is more than one element of a metal element, a non-metal element, a metal compound and a non-metal compound; the metal element is copper, lead, antimony, More than one of tin, cobalt and nickel; the metal compound is tin oxide, cobalt oxide, nickel oxide, sodium phosphate, sodium dihydrogen phosphate, tin acetate, tin chloride, cobalt carbonate, copper hydroxide, cobalt hydroxide, More than one of tin hydroxide and nickel hydroxide; the non-metal element is one or more of silicon, sulfur and boron; the non-metal compound is silicon dioxide, phosphorus pentoxide, boric acid, silicic acid, phosphoric acid, One or more of ammonium dihydrogen phosphate, ammonium phosphate, ammonium sulfate, silicone resin, and ethylene glycol borate.
本发明的方法低温预烧后，按质量比大于0至小于等于15%的比例，加入掺杂物，转速为1000～3000r/min，时间为26～120min；所述掺杂物是金属单质、非金属单质、金属化合物和非金属化合物的一种以上；所述金属单质为铜、铅、锑、锡、钴和镍的一种以上；所述金属化合物为氧化锡，氧化钴、氧化镍、磷酸钠、磷酸二氢钠、乙酸锡、氯化锡、碳酸钴、氢氧化铜、氢氧化钴、氢氧化锡和氢氧化镍的一种以上；所述非金属单质为硅、硫和硼的一种以上；所述非金属化合物非为二氧化硅、五氧化二磷、硼酸、硅酸、磷酸、磷酸二氢铵、磷酸铵、硫酸铵、有机硅树脂和乙二醇硼酸酯的一种以上。After the method of the invention is pre-fired at a low temperature, the dopant is added at a mass ratio of more than 0 to 15% or less, and the rotation speed is 1000-3000 r/min, and the time is 26-120 min; the dopant is a metal element, One or more of a non-metal element, a metal compound, and a non-metal compound; the metal element is one or more of copper, lead, antimony, tin, cobalt, and nickel; and the metal compound is tin oxide, cobalt oxide, nickel oxide, More than one of sodium phosphate, sodium dihydrogen phosphate, tin acetate, tin chloride, cobalt carbonate, copper hydroxide, cobalt hydroxide, tin hydroxide and nickel hydroxide; the non-metal element is silicon, sulfur and boron One or more; the non-metal compound is not one of silica, phosphorus pentoxide, boric acid, silicic acid, phosphoric acid, ammonium dihydrogen phosphate, ammonium phosphate, ammonium sulfate, silicone resin, and ethylene glycol borate. More than one species.
一种锂离子电池复合硬碳负极材料的制备方法，包括以下步骤：一、按质量比将85%至小于100%的热塑性树脂，大于0至小于等于15%的掺杂物，混合搅拌，转速为2000～4500r/min，时间为10～120min，在空气中、常温下固化1～6 h，得到固态前躯体；二、氮气流量为0.1～0.4m3/h，将前躯体以0.1～7 ℃/min的升温速度到150℃～450℃，低温预烧3～24h，自然降温至室温；三、氮气流量为0.1～0.4m3/h，以0.3～10 ℃/min的升温速度到560～1500℃，热解0.5～7.5h，自然降温至室温,制得硬碳；四、将硬碳进行球磨或粉碎，得到粒度为1～60μm的硬碳基体；五、在硬碳基体中按硬碳基体前驱物质量的1～15%，加入包覆物的前躯体，以1400～3500r/min的转速混合20～50min，然后氮气流量为0.1～0.4m3/h，以1～7.5℃/min的升温速度到500～1500℃，时间为2～8h，进行包覆物热解处理，自然降温至室温 , 得到锂离子电池复合硬碳负极材料 ；所述热塑性树脂为丙烯酸树脂、聚氯乙烯、聚碳酸酯、环氧树脂、酚醛树脂和聚甲醛的一种以上；所述掺杂物是金属单质、非金属单质、金属化合物和非金属化合物的一种以上；所述金属单质为铜、铅、锑、锡、钴和镍的一种以上；所述金属化合物为氧化锡，氧化钴、氧化镍、磷酸钠、磷酸二氢钠、乙酸锡、氯化锡、碳酸钴、氢氧化铜、氢氧化钴、氢氧化锡和氢氧化镍的一种以上；所述非金属单质为硅、硫和硼的一种以上；所述非金属化合物非为二氧化硅、五氧化二磷、硼酸、硅酸、磷酸、磷酸二氢铵、磷酸铵、硫酸铵、有机硅树脂和乙二醇硼酸酯的一种以上；所述包覆物的前躯体为有机物环氧树脂、酚醛树脂、羧甲基纤维素、沥青、乙基甲基碳酸酯、聚乙烯醇、聚苯乙烯、聚甲基丙烯酸甲酯、聚四氟乙烯、聚偏氟乙烯、聚丙烯腈、丁苯橡胶、聚氯乙烯、聚乙烯、聚环氧乙烷、聚环氧丙烷、聚丁二酸乙二醇酯、聚癸二酸乙二醇、聚乙二醇亚胺、聚乙炔、聚对苯、聚苯胺、聚吡咯、聚并苯、 聚间苯二胺、聚噬吩、聚对苯撑乙烯、聚噻吩、聚丙烯晴、聚酰亚胺和聚苯硫醚的一种以上。A method for preparing a composite hard carbon anode material for a lithium ion battery comprises the following steps: 1. a thermoplastic resin having a mass ratio of 85% to less than 100%, a dopant greater than 0 to 15% or less, mixing and stirring, and a rotation speed is 2000 ~ 4500r / min, the time is 10 ~ 120min, in air, at room temperature curing 1 ~ 6 h, to obtain a solid body before; two nitrogen flow rate of 0.1 ~ 0.4m 3 / h, the precursor to 0.1 to 7 °C / min heating rate to 150 ° C ~ 450 ° C, low temperature pre-burning 3 ~ 24h, natural cooling to room temperature; three, nitrogen flow rate of 0.1 ~ 0.4m 3 / h, with a temperature of 0.3 ~ 10 ° C / min to 560 ~1500 ° C, pyrolysis 0.5 ~ 7.5h, natural cooling to room temperature, to produce hard carbon; Fourth, the hard carbon ball milling or pulverization, to obtain a hard carbon matrix with a particle size of 1 ~ 60μm; five, in the hard carbon matrix 1 to 15% of the mass of the hard carbon matrix precursor, added to the precursor of the coating, mixed at 1400 ~ 3500r / min for 20 ~ 50min, then nitrogen flow rate of 0.1 ~ 0.4m 3 / h, 1 ~ 7.5 ° C /min heating rate to 500 ~ 1500 ° C, time is 2 ~ 8h, the coating pyrolysis treatment, naturally cool to room temperature, To a lithium ion battery composite hard carbon anode material; the thermoplastic resin is one or more of an acrylic resin, a polyvinyl chloride, a polycarbonate, an epoxy resin, a phenol resin, and a polyoxymethylene; the dopant is a metal element, a non-metal One or more kinds of metal simple substance, metal compound and non-metal compound; the metal element is one or more of copper, lead, antimony, tin, cobalt and nickel; the metal compound is tin oxide, cobalt oxide, nickel oxide, phosphoric acid One or more of sodium, sodium dihydrogen phosphate, tin acetate, tin chloride, cobalt carbonate, copper hydroxide, cobalt hydroxide, tin hydroxide and nickel hydroxide; the non-metal element is one of silicon, sulfur and boron More than the above; the non-metal compound is not a kind of silica, phosphorus pentoxide, boric acid, silicic acid, phosphoric acid, ammonium dihydrogen phosphate, ammonium phosphate, ammonium sulfate, silicone resin and ethylene glycol borate. Above; the precursor of the coating is organic epoxy resin, phenolic resin, carboxymethyl cellulose, asphalt, ethyl methyl carbonate, polyvinyl alcohol, polystyrene, polymethyl methacrylate, poly Tetrafluoroethylene, poly Fluorine, polyacrylonitrile, styrene butadiene rubber, polyvinyl chloride, polyethylene, polyethylene oxide, polypropylene oxide, polyethylene succinate, polyethylene sebacate, polyethylene glycol Imine, polyacetylene, polyparaphenylene, polyaniline, polypyrrole, polyacene, poly-m-phenylenediamine, poly-phasic, poly-p-phenylene vinyl, polythiophene, polypropylene, polyimide and polyphenylene More than one type of thioether.
一种锂离子电池复合硬碳负极材料的制备方法，包括以下步骤： 一、按每100克干植物原料加入80～300ml酸或碱，浸泡3～50h；所述植物原料为花粉、稻谷壳、甘蔗杆、核桃壳、竹子、酒糟和木屑的一种以上，所述酸为氢氟酸、硼酸、硫酸、盐酸或硝酸，碱为氢氧化钾、氢氧化钙或氢氧化钠；二、洗涤，用纯水洗涤，转速800～1400r/min，时间8～30min ；三、除水烘干，在80～140 ℃条件下烘干10～40h，自然降温至室温；四、低温预烧，在真空度0.03MPa以下，或者在保护性气体氦气、氮气、氩气、氙气或氮气下进行，流量为0.1～0.4m3/h，以0.1～10 ℃/min的升温速度到200～500 ℃， 低温预烧3～20h，在炉内自然降温至室温；五、粉碎，得到粒度为1～60μm的粉末；六、在真空度0.03MPa以下，或者在保护性气体氦气、氮气、氩气、氙气或 氮气下进行，流量为0.1～0.4m3/h，以0.1～10℃/min的升温速度到500～1300℃，热解1～10h，炉内自然降温至室温；七、粉碎或球磨，得到粒度为2～65μm的硬碳基体；八、按硬碳基体前驱物质量的1～25%，在硬碳基体中加入包覆物的前躯体，以1000～4500r/min的转速，混合2～40min，然后在真空度0.03MPa以下，或者在保护性气体氦气、氮气、氩气、氙气或 氮气下进行，流量为0.1～0.4m3/h，以0. 1～10 ℃/min的升温速度到400～1300℃，时间为1～24h，进行热解处理，在炉内自然降温至室温；所述包覆物的前躯体为有机物环氧树脂、酚醛树脂、羧甲基纤维素、沥青、乙基甲基碳酸酯、聚乙烯醇、聚苯乙烯、聚甲基丙烯酸甲酯、聚四氟乙烯、聚偏氟乙烯、聚丙烯腈、丁苯橡胶、聚氯乙烯、聚乙烯、聚环氧乙烷、聚环氧丙烷、聚丁二酸乙二醇酯、聚癸二酸乙二醇、聚乙二醇亚胺、聚乙炔、聚对苯、聚苯胺、聚吡咯、聚并苯、 聚间苯二胺、聚噬吩、聚对苯撑乙烯、聚噻吩、聚丙烯晴、聚酰亚胺和聚苯硫醚的一种以上；九、过200目筛，得到粒度为3.5～70μm的锂离子电池复合硬碳负极材料。The invention discloses a preparation method of a composite hard carbon anode material for a lithium ion battery, comprising the following steps: 1. adding 80 to 300 ml of acid or alkali per 100 g of dry plant material, soaking for 3 to 50 hours; the plant material is pollen, rice husk, More than one kind of sugar cane rod, walnut shell, bamboo, distiller's grains and wood chips, the acid is hydrofluoric acid, boric acid, sulfuric acid, hydrochloric acid or nitric acid, the alkali is potassium hydroxide, calcium hydroxide or sodium hydroxide; second, washing, Wash with pure water, rotation speed 800 ~ 1400r / min, time 8 ~ 30min; Third, remove water, dry at 80 ~ 140 °C for 10 ~ 40h, naturally cool to room temperature; Fourth, low temperature pre-burn, in vacuum The degree is 0.03 MPa or less, or under the protective gas helium, nitrogen, argon, helium or nitrogen, the flow rate is 0.1-0.4 m 3 /h, and the temperature rising rate is 0.1-10 ° C/min to 200-500 ° C. Pre-burning at low temperature for 3~20h, naturally lowering to room temperature in the furnace; 5. Grinding to obtain powder with particle size of 1~60μm; 6. Under vacuum degree 0.03MPa, or in protective gas helium, nitrogen, argon, Under helium or nitrogen, the flow rate is 0.1-0.4m 3 /h, The temperature rising rate of 0.1～10°C/min is 500～1300°C, the pyrolysis is 1～10h, and the furnace naturally cools to room temperature; 7. The crushing or ball milling produces a hard carbon matrix with a particle size of 2～65μm; 1 to 25% of the mass of the matrix precursor, the precursor of the coating is added to the hard carbon matrix, mixed at a speed of 1000 to 4500 r/min, mixed for 2 to 40 minutes, then at a vacuum of 0.03 MPa or less, or in a protective gas Under helium, nitrogen, argon, helium or nitrogen, the flow rate is 0.1-0.4 m 3 /h, and the temperature is raised from 0. 1 to 10 ° C/min to 400-1300 ° C for 1 to 24 hours. The solution is naturally cooled to room temperature in the furnace; the precursor of the coating is organic epoxy resin, phenolic resin, carboxymethyl cellulose, asphalt, ethyl methyl carbonate, polyvinyl alcohol, polystyrene , polymethyl methacrylate, polytetrafluoroethylene, polyvinylidene fluoride, polyacrylonitrile, styrene butadiene rubber, polyvinyl chloride, polyethylene, polyethylene oxide, polypropylene oxide, polyethylene succinate Alcohol ester, polyethylene sebacate, polyethylene glycol imine, polyacetylene, polyparaphenylene, polyaniline, polypyrrole , more than one of polyacene, poly-m-phenylenediamine, poly-phasic, poly-p-phenylene vinyl, polythiophene, polypropylene, polyimide and polyphenylene sulfide; nine, over 200 mesh sieve, obtained A lithium ion battery composite hard carbon anode material having a particle size of 3.5 to 70 μm.
本发明的方法按每100克干植物原料加入80～300ml酸或碱，浸泡3～50h前，将前躯物干植物原料机械粉碎或气流粉碎，得到粒度为40～100μm的粉末；所述低温预烧粉碎后，按占粉末状质量大于0小于等于40%的比例，加入掺杂物，转速为1000～4500r/min， 时间为20～95min；所述掺杂物为金属氧化物氧化锡、氧化钴和氧化镍的一种以上，或金属盐磷酸钠、氯化锡、碳酸钴和磷酸二氢钠的一种以上，或金属碱氢氧化铜、氢氧化钴、氢氧化锡和氢氧化镍的一种以上，或非金属氧化物二氧化硅和/或五氧化二磷，或硼酸、硅酸和磷酸的一种以上，或非金属盐磷酸二氢铵、磷酸铵和硫酸铵的一种以上，或有机硅树脂和/或乙二醇硼酸酯，或金属单质铜、铅、锑、锡、钴和镍的一种以上，或非金属单质硅、硫和硼的一种以上。The method of the present invention adds 80-300 ml of acid or alkali per 100 g of dry plant raw materials, and immerses the precursor dry plant material or pulverizes it to obtain a powder having a particle size of 40-100 μm before soaking for 3 to 50 hours; After calcination and pulverization, the dopant is added at a ratio of the powdery mass of more than 0 to 40%, and the rotation speed is 1000 to 4500 r/min. The time is 20 to 95 min; the dopant is one or more of the metal oxides such as tin oxide, cobalt oxide and nickel oxide, or one or more of the metal salt sodium phosphate, tin chloride, cobalt carbonate and sodium dihydrogen phosphate. Or one or more of a metal base copper hydroxide, cobalt hydroxide, tin hydroxide, and nickel hydroxide, or a non-metal oxide silica and/or phosphorus pentoxide, or one or more of boric acid, silicic acid, and phosphoric acid. , or a non-metal salt of ammonium dihydrogen phosphate, ammonium phosphate and ammonium sulfate, or a silicone resin and / or ethylene glycol borate, or a metal element of copper, lead, antimony, tin, cobalt and nickel More than one kind, or one or more of non-metal elemental silicon, sulfur and boron.
本发明的方法按每100 克干植物原料加入80～300ml酸或碱，转速为1000～3000r/min， 时间为3～30min，然后 浸泡3～50h ；所述低温预烧粉碎后， 按占粉末状质量大于0小于等于40%的比例，加入掺杂物，转速为1000～4500r/min，时间为20～95min；所述掺杂物为金属氧化物氧化锡、氧化钴和氧化镍的一种以上，或金属盐磷酸钠、氯化锡、碳酸钴和磷酸二氢钠的一种以上，或金属碱氢氧化铜、氢氧化钴、氢氧化锡和氢氧化镍的一种以上，或非金属氧化物二氧化硅和/或五氧化二磷，或硼酸、硅酸和磷酸的一种以上，或非金属盐磷酸二氢铵、磷酸铵和硫酸铵的一种以上，或有机硅树脂和/或乙二醇硼酸酯， 或金属单质铜、铅、锑、锡、钴和镍的一种以上，或非金属单质硅、硫和硼的一种以上。The method of the invention adds 80-300 ml of acid or alkali per 100 g of dry plant material, and the rotation speed is 1000-3000 r/min. The time is 3 to 30 minutes, and then immersed for 3 to 50 hours; after the low temperature pre-burning and pulverizing, The dopant is added at a ratio of the powdery mass greater than 0 to 40%, and the rotation speed is 1000-4500 r/min for 20-95 min; the dopants are metal oxide tin oxide, cobalt oxide and nickel oxide. One or more of the metal salt sodium phosphate, tin chloride, cobalt carbonate, and sodium dihydrogen phosphate, or one or more of the metal base copper hydroxide, cobalt hydroxide, tin hydroxide, and nickel hydroxide. Or a non-metal oxide silica and/or phosphorus pentoxide, or one or more of boric acid, silicic acid and phosphoric acid, or one or more of the non-metal salts ammonium dihydrogen phosphate, ammonium phosphate and ammonium sulfate, or silicone Resin and / or ethylene glycol borate, Or one or more of metal elemental copper, lead, antimony, tin, cobalt and nickel, or one or more of non-metal elemental silicon, sulfur and boron.
本发明的方法按每100克干植物原料加入80～300ml酸或碱，浸泡3～50h前，将前躯物干植物原料机械粉碎或气流粉碎，得到粒度为40～100μm的粉末； 所述低温预烧前， 按占 粉末状 质量大于0小于等于40%的比例，加入掺杂物，转速为1000～4500r/min， 时间为20～95min；所述掺杂物为金属氧化物氧化锡、氧化钴和氧化镍的一种以上，或金属盐磷酸钠、氯化锡、碳酸钴和磷酸二氢钠的一种以上，或金属碱氢氧化铜、氢氧化钴、氢氧化锡和氢氧化镍的一种以上，或非金属氧化物二氧化硅和/或五氧化二磷，或硼酸、硅酸和磷酸的一种以上，或非金属盐磷酸二氢铵、磷酸铵和硫酸铵的一种以上，或金属单质铜、铅、锑、锡、钴和镍的一种以上，或非金属单质硅、硫和硼的一种以上。The method of the present invention adds 80-300 ml of acid or alkali per 100 g of dry plant raw materials, and soaks the precursor dry plant material by mechanical pulverization or jet milling before soaking for 3 to 50 hours to obtain a powder having a particle size of 40-100 μm; Before the low-temperature pre-sintering, the dopant is added at a ratio of the powder-like mass greater than 0 to 40%, and the rotation speed is 1000-4500 r/min. The time is 20 to 95 min; the dopant is one or more of the metal oxides such as tin oxide, cobalt oxide and nickel oxide, or one or more of the metal salt sodium phosphate, tin chloride, cobalt carbonate and sodium dihydrogen phosphate. Or one or more of a metal base copper hydroxide, cobalt hydroxide, tin hydroxide, and nickel hydroxide, or a non-metal oxide silica and/or phosphorus pentoxide, or one or more of boric acid, silicic acid, and phosphoric acid. Or one or more of the non-metal salts of ammonium dihydrogen phosphate, ammonium phosphate, and ammonium sulfate, or one or more of the metal elements of copper, lead, antimony, tin, cobalt, and nickel, or one of non-metal elemental silicon, sulfur, and boron. More than one species.
本发明与现有技术相比，利用硬碳基体前驱物经过高温热解、包覆，得到的复合硬碳负极材料，在0.2C时，首次可逆容量为455.2mAh/g以上，首充库伦效率为79.4%以上， 具有优良的嵌、脱锂能力和循环稳定性，硬碳负极材料具有高容量、高的首次库仑效率和高倍率优点，制备工艺简单、易于操作、成本低廉，适用于锂离子动力电池，各类便携式器件、电动工具、电动车用锂离子电池负极材料。Compared with the prior art, the composite hard carbon anode material obtained by high temperature pyrolysis and coating of the hard carbon matrix precursor has a first reversible capacity of 455.2 mAh/g or more at a temperature of 0.2 C, and the first charge has a coulombic efficiency. 79.4% or more, With excellent embedding and de-lithiating ability and cycle stability, the hard carbon anode material has the advantages of high capacity, high first coulombic efficiency and high magnification, simple preparation process, easy operation and low cost, and is suitable for lithium ion power batteries. Anode material for lithium ion batteries for portable devices, power tools, and electric vehicles.
附图说明DRAWINGS
图1是实施例1的 扫描电子显微镜图。Fig. 1 is a scanning electron micrograph of Example 1.
图2是实施例1的XRD图。2 is an XRD chart of Example 1.
图3是实施例1在不同倍率下的首次充放电性能曲线图。Fig. 3 is a graph showing the first charge and discharge performance of Example 1 at different magnifications.
图4是实施例1在60℃，0.2C倍率下的循环性能曲线图。Figure 4 is a graph showing the cycle performance of Example 1 at 60 ° C, 0.2 C rate.
图5是实施例1在-30℃,0.2C倍率下的循环性能曲线图。Figure 5 is a graph showing the cycle performance of Example 1 at -30 ° C, 0.2 C rate.
图6是实施例14制得的材料的扫描电子显微镜图。Figure 6 is a scanning electron micrograph of the material produced in Example 14.
图7是实施例14制得的材料的XRD图。Figure 7 is an XRD pattern of the material produced in Example 14.
图8是实施例14制得的材料在不同倍率下的首次充电（脱锂）放电(嵌锂)性能曲线图。Figure 8 is a graph showing the performance of the first charge (delithiation) discharge (lithium intercalation) of the material obtained in Example 14 at different magnifications.
图9是实施例14制得的材料在60℃，0.2C倍率下的循环性能曲线图。Figure 9 is a graph showing the cycle performance of the material produced in Example 14 at 60 ° C, 0.2 C rate.
图10是实施例14制得的材料在-30℃,0.2C倍率下的循环性能曲线图。Figure 10 is a graph showing the cycle performance of the material produced in Example 14 at -30 ° C, 0.2 C rate.
具体实施方式detailed description
下面结合附图和实施例对本发明作进一步详细说明。本发明的锂离子电池复合硬碳负极材料，硬碳 基体外包覆有包覆物，包覆物的前躯体为有机物环氧树脂、酚醛树脂、羧甲基纤维素CMC、沥青、乙基甲基碳酸酯EMC、聚乙烯醇、聚苯乙烯、聚甲基丙烯酸甲酯、聚四氟乙烯、聚偏氟乙烯、聚丙烯腈、丁苯橡胶SBR、聚氯乙烯、聚乙烯、聚环氧乙烷、聚环氧丙烷、聚丁二酸乙二醇酯、聚癸二酸乙二醇、聚乙二醇亚胺、聚乙炔、聚对苯、聚苯胺、聚吡咯、聚并苯、 聚间苯二胺、聚噬吩、聚对苯撑乙烯、聚噻吩、聚丙烯晴、聚酰亚胺和聚苯硫醚的一种以上，热解形成包覆物。The present invention will be further described in detail below with reference to the accompanying drawings and embodiments. Lithium ion battery composite hard carbon anode material of the invention, hard carbon The substrate is coated with a coating, and the precursor of the coating is organic epoxy resin, phenolic resin, carboxymethyl cellulose CMC, asphalt, ethyl methyl carbonate EMC, polyvinyl alcohol, polystyrene, poly Methyl methacrylate, polytetrafluoroethylene, polyvinylidene fluoride, polyacrylonitrile, styrene butadiene rubber SBR, polyvinyl chloride, polyethylene, polyethylene oxide, polypropylene oxide, polyethylene glycol succinate Ester, polyethylene azelaic acid, polyethylene glycol imine, polyacetylene, polyparaphenylene, polyaniline, polypyrrole, polyacene, One or more of poly(m-phenylenediamine), polyphhenol, polyparaphenylenevinylene, polythiophene, polypropylene, polyimide, and polyphenylene sulfide, pyrolyzed to form a coating.
一、硬碳 基体前驱物采用热塑性树脂时，包覆物前躯体质量为硬碳基体前驱物质量的1～15%。该锂离子电池复合硬碳负极材料相分布均匀，形状为块状、不规则的细小颗粒，具有多孔结构，孔径为0.2～100nm，孔隙率为9～19%（粒状材料堆积体积中 , 颗粒之间的空隙体积占总体积的比例），002晶面的层间距d002值在0.338～0.475nm之间，粒度范围为0.5～90μm，比表面积为1.9～75.3m2/g，真实密度为1.53～2.35g /cm3，振实密度为0.88～1.43 g /cm3，其炭C元素的含量不少于90.5%。在0.2C时，首次可逆容量为455.2mAh/g以上，首充库伦效率为79.4%以上。1. When the hard carbon matrix precursor is made of a thermoplastic resin, the precursor mass of the coating is 1 to 15% of the mass of the hard carbon matrix precursor. The lithium ion battery composite hard carbon anode material has a uniform phase distribution, a block shape, irregular fine particles, a porous structure, a pore diameter of 0.2 to 100 nm, and a porosity of 9 to 19% (in the bulk volume of the granular material, the particle The ratio of the interstitial volume to the total volume), the layer spacing d 002 of the 002 crystal plane is between 0.338 and 0.475 nm, the particle size ranges from 0.5 to 90 μm, the specific surface area is 1.9 to 75.3 m 2 /g, and the true density is 1.53. ～2.35g /cm 3 , the tap density is 0.88~1.43 g /cm 3 , and the content of the carbon C element is not less than 90.5%. At 0.2C, the first reversible capacity is above 455.2mAh/g, and the first charge has a coulombic efficiency of 79.4% or more.
所述硬碳基体前驱物由以下质量比组成：25%至小于100%的热塑性树脂（25% ≤热塑性树脂＜100%），大于0至小于等于75%的固化剂（0＜固化剂≤75%），大于0至小于等于15%的 掺 杂物（0＜掺杂物≤15%） ，掺杂物是金属单质、非金属单质、金属化合物和非金属化合物的一种以上， 热塑性树脂与固化剂聚合化学反应 后，与掺杂物混合，再热解形成硬碳基体。The hard carbon matrix precursor is composed of the following mass ratio: 25% to less than 100% thermoplastic resin (25%) ≤ thermoplastic resin <100%), a curing agent greater than 0 to 75% or less (0<curing agent ≤75%), a dopant greater than 0 to 15% or less (0<dopant ≤15%) The dopant is one or more of a simple metal, a non-metal element, a metal compound, and a non-metal compound. The thermoplastic resin is chemically reacted with the curing agent, mixed with the dopant, and then pyrolyzed to form a hard carbon matrix.
所述硬碳基体前驱物由以下质量比组成：25%至小于100%的热塑性树脂（25%≤热塑性树脂＜100%），大于0至小于等于75%的固化剂（0＜固化剂≤75%），在热塑性树脂内添加固化剂， 聚合化学反应后，热解形成硬碳基体。The hard carbon matrix precursor is composed of the following mass ratio: 25% to less than 100% of a thermoplastic resin (25% ≤ thermoplastic resin <100%), and a curing agent greater than 0 to 75% or less (0<curing agent ≤75) %), adding a curing agent to the thermoplastic resin, After the polymerization chemical reaction, pyrolysis forms a hard carbon matrix.
所述硬碳基体前驱物由以下质量比组成： 85%至小于100%的热塑性树脂（85%≤热塑性树脂＜100%），大于0至小于等于15%的掺杂物（0＜掺杂物 ≤15%），热塑性树脂与掺杂物金属单质、非金属单质、金属化合物和非金属化合物中的一种以上混合， 热解形成硬碳基体。The hard carbon matrix precursor consists of the following mass ratios: 85% to less than 100% of thermoplastic resin (85% ≤ thermoplastic resin <100%), more than 0 to less than or equal to 15% of dopant (0< dopant ≤ 15%), the thermoplastic resin is mixed with one or more of a dopant metal element, a non-metal element, a metal compound, and a non-metal compound, and pyrolyzed to form a hard carbon matrix.
所述硬碳基体前驱物为热塑性树脂丙烯酸树脂、聚氯乙烯、聚碳酸酯、环氧树脂、酚醛树脂和聚甲醛的一种以上， 热解形成硬碳基体。The hard carbon matrix precursor is one or more of a thermoplastic resin acrylic resin, polyvinyl chloride, polycarbonate, epoxy resin, phenol resin, and polyoxymethylene. Pyrolysis forms a hard carbon matrix.
固化剂为己二胺、间苯二胺、苯胺甲醛树脂、聚酰胺树脂、邻苯二甲酸酐和苯磺酸的一种以上。The curing agent is one or more of hexamethylenediamine, m-phenylenediamine, aniline formaldehyde resin, polyamide resin, phthalic anhydride, and benzenesulfonic acid.
金属单质为铜、铅、锑、锡、钴和镍的一种以上。The metal element is one or more of copper, lead, antimony, tin, cobalt and nickel.
金属化合物为氧化锡，氧化钴、氧化镍、磷酸钠、磷酸二氢钠、乙酸锡、氯化锡、碳酸钴、氢氧化铜、氢氧化钴、氢氧化锡和氢氧化镍的一种以上。The metal compound is at least one of tin oxide, cobalt oxide, nickel oxide, sodium phosphate, sodium dihydrogen phosphate, tin acetate, tin chloride, cobalt carbonate, copper hydroxide, cobalt hydroxide, tin hydroxide, and nickel hydroxide.
非金属单质为硅、硫和硼的一种以上。The non-metal element is one or more of silicon, sulfur and boron.
非金属化合物为二氧化硅、五氧化二磷、硼酸、硅酸、磷酸、磷酸二氢铵、磷酸铵、硫酸铵、有机硅树脂和 乙二醇硼酸酯 的一种以上。The non-metallic compounds are silica, phosphorus pentoxide, boric acid, silicic acid, phosphoric acid, ammonium dihydrogen phosphate, ammonium phosphate, ammonium sulfate, silicone resins, and More than one type of ethylene glycol borate.
所述 掺杂物呈固体颗粒或液态，具有提高本发明的 锂离子电池复合硬碳负极材料容量及首次库伦效率的作用。 所述固化剂用于提高硬碳的容量及首次库伦效率。采用常规的热塑性树脂 、 固化剂 、金属单质、非金属单质、金属化合物或非金属化合物、包覆物，本发明的材料的造价低。The dopant is in the form of solid particles or a liquid, and has the effect of increasing the capacity and the first coulombic efficiency of the composite hard carbon anode material of the lithium ion battery of the present invention. The curing agent is used to increase the capacity of the hard carbon and the first coulombic efficiency. Using conventional thermoplastic resin, curing agent The metal element, the non-metal element, the metal compound or the non-metal compound, the coating, and the material of the invention are low in cost.
硬碳基体前驱物采用热塑性树脂时， 本发明的锂离子电池复合硬碳负极材料的制备方法，包括以下步骤：When the hard carbon matrix precursor is a thermoplastic resin, the method for preparing the lithium ion battery composite hard carbon anode material of the present invention comprises the following steps:
（一）、固化，按质量比在25%至小于100% 的 粒状或液态的热塑性树脂中添加大于0至小于等于75%的固态或液态固化剂 ，搅拌均匀，在空气中、常温下固化3～50h，得到固态前躯体。(1), curing, according to the mass ratio of 25% to less than 100% A solid or liquid curing agent of more than 0 to 75% or less is added to the granular or liquid thermoplastic resin, stirred uniformly, and cured in air at room temperature for 3 to 50 hours to obtain a solid precursor.
（二）、低温预烧，以提高硬碳的产率、容量及首次库伦效率，产生多孔结构，将前躯体放入宜兴市飞达电炉有限公司的SXQ12-14-20型箱式电阻炉，以0.1～10℃/min的升温速度到150℃～400℃，低温预烧2～24h，在炉内自然降温至室温 , 低温预烧在氮气的保护下进行，氮气流量为0.18～0.4m3/h，得到固态蜂窝状的灰黑色物质。(2) Low-temperature pre-burning to increase the productivity, capacity and first-time coulomb efficiency of hard carbon, to produce a porous structure, and put the precursor into the SXQ12-14-20 box-type resistance furnace of Yixing Feida Electric Furnace Co., Ltd. At a heating rate of 0.1 to 10 ° C / min to 150 ° C ~ 400 ° C, low temperature pre-burning 2 ~ 24h, the furnace naturally cooled to room temperature, low temperature pre-burning under the protection of nitrogen, nitrogen flow rate of 0.18 ~ 0.4m 3 /h, to obtain a solid honeycomb-like gray-black substance.
（三）、粉碎，将固态蜂窝状的灰黑色物进行粉碎或球磨，得到粒度为1～60μm的粉末状，采用南京大学仪器厂的QM-1SP4型行星球磨机，以控制材料粒度的大小便于掺杂。(3), crushing, pulverizing or ball milling the solid honeycomb gray-black material to obtain a powder shape with a particle size of 1 to 60 μm, using the QM-1SP4 planetary ball mill of Nanjing University Instrument Factory to control the size of the material to facilitate the mixing. miscellaneous.
（四）、掺杂金属单质、非金属单质、金属化合物或非金属化合物， 在粉末状内按质量比大于0至小于等于15%的比例，加入金属单质、非金属单质、金属化合物和非金属化合物的一种以上，采用常州市武进八方机械厂F-0.4型高速分散机，转速为1000～3000r/min，时间为26～120min，得到改良的前躯体，以提高硬碳的容量及首次库伦效率 。掺杂金属单质、非金属单质、金属化合物或非金属化合物可以在固化步骤中，混合搅拌，转速为2000～4500r/min，时间为10～120min，也可在低温预烧后。(4) doping metal element, non-metal element, metal compound or non-metal compound, In the powder form, more than one metal element, non-metal element, metal compound and non-metal compound are added at a mass ratio of more than 0 to 15%, and the F-0.4 high-speed disperser of Changzhou Wujin Bafang Machinery Factory is used. , the speed is 1000 ~ 3000r / min, the time is 26 ~ 120min, the improved precursor is obtained to improve the hard carbon capacity and the first coulombic efficiency . The doped metal element, the non-metal element, the metal compound or the non-metal compound may be mixed and stirred in the curing step, the rotation speed is 2000 to 4500 r/min, the time is 10 to 120 min, and the pre-burning may be performed at a low temperature.
（五）、热解，将改良的前躯体放入宜兴市飞达电炉有限公司的SXQ12-14-20箱式电阻炉，以0.3～10℃/min的升温速度到560～1500℃，热解0.5～7.5h，在炉内自然降温至室温 , 制得硬碳，热解在氮气的保护下进行，氮气流量为0.1～0.4m3/h。(5) Pyrolysis, put the improved precursor into the SXQ12-14-20 box-type resistance furnace of Yixing Feida Electric Furnace Co., Ltd., to the temperature increase rate of 0.3~10 °C/min to 560~1500 °C, pyrolysis 0.5 to 7.5 hours, the furnace is naturally cooled to room temperature to obtain hard carbon, and the pyrolysis is carried out under the protection of nitrogen gas, and the flow rate of nitrogen is 0.1 to 0.4 m 3 /h.
（六）、粉碎，将硬碳进行球磨或粉碎，得到粒度为1～60μm的硬碳基体。(6), pulverization, ball milling or pulverizing the hard carbon to obtain a hard carbon matrix having a particle size of 1 to 60 μm.
（七）、包覆，在硬碳基体中按硬碳基体前驱物 质量的1～15%，加入包覆物的前躯体，在无锡新光粉体加工工艺有限公司的VC-150型混合机中，以1400～3500r/min的转速混合20～50min，然后放入宜兴市飞达电炉有限公司的SXQ12-14-20箱式电阻炉，以1～10℃/min的升温速度到500～1500℃，时间为2～8h，进行处理，在氮气的保护下进行，氮气流量为0.1～0.4m3/h，使硬碳材料的表面较为光滑，降低最终产品的比表面积，在炉内自然降温至室温,过200目筛，得到锂离子电池复合硬碳负极材料。(7), coating, in the hard carbon matrix according to the hardness of the hard carbon matrix precursor 1 to 15%, added to the precursor of the coating, in the VC-150 mixer of Wuxi Xinguang Powder Processing Technology Co., Ltd. Mixing at 1400~3500r/min for 20~50min, then put it into SXQ12-14-20 box type resistance furnace of Yixing Feida Electric Furnace Co., Ltd., to increase temperature of 1~10°C/min to 500～1500°C The time is 2-8h, and the treatment is carried out under the protection of nitrogen. The flow rate of nitrogen is 0.1-0.4m 3 /h, which makes the surface of the hard carbon material smooth, reduces the specific surface area of the final product, and naturally cools down in the furnace. At room temperature, passing through a 200 mesh sieve to obtain a lithium ion battery composite hard carbon anode material.
所述硬碳基体前驱物由热塑性树脂和固化剂构成时，不进行上述步骤四掺杂。When the hard carbon matrix precursor is composed of a thermoplastic resin and a curing agent, the above-described step four doping is not performed.
所述硬碳基体前驱物由热塑性树脂和掺杂物构成时，步骤一中先将两者混合搅拌，采用常州市武进八方机械厂F-0.4型高速分散机，转速为2000～4500r/min，时间为10～120min，在空气中、常温下固化3～50 h。不进行上述步骤四掺杂。When the hard carbon matrix precursor is composed of a thermoplastic resin and a dopant, the first two are mixed and stirred in the first step, and the speed is 2000-4500 r/min, using a F-0.4 high-speed disperser of Changzhou Wujin Bafang Machinery Factory. Time is 10 ~ 120min, solidified in air, normal temperature 3 ~ 50 h. Do not perform the above four doping.
所述硬碳基体前驱物为热塑性树脂时，在步骤一中在空气中、常温下固化3～50 h，并不进行上述步骤四掺杂。When the hard carbon matrix precursor is a thermoplastic resin, it is cured in the air in the first step at room temperature 3 to 50. h, the above step four doping is not performed.
所述低温预烧、热解、高温处理还可以在保护性气体氦气、氩气或氙气的保护下进行。The low temperature calcination, pyrolysis, and high temperature treatment can also be carried out under the protection of protective gas helium, argon or helium.
硬碳基体前驱物采用热塑性树脂制备的锂离子电池复合硬碳负极材料，采用北京中科科仪技术发展有限公司的KYKY2800B扫描电子显微镜观测形貌，形状为块状、不规则、细小颗粒，采用测试相分布均匀，采用美国QUANTA CHROME公司的NOVA1000比表面积测试仪测试为多孔结构，孔径分布为0.2～100nm，孔隙率为9～19%。采用荷兰帕纳科仪器公司的PW3040/60 X'Pert X-射线衍射仪测试d002值在0.338～0.475nm之间。采用英国马尔文仪器有限公司的Mastersizer 2000型激光粒度分析仪测试粒度范围为0.5～90μm。采用美国麦克仪器公司的Tristar3000全自动比表面积和孔隙度分析仪测试比表面积为1.9～75.3m2/g。采用美国康塔仪器公司的Ultrapycnometer1000型全自动真实密度分析仪测试真实密度为1.54～2.35g/cm3。采用北京中西远大科技有限公司的FZS4-4型振实密度仪，测试振实密度为0.88～1.43 g/cm3。The hard carbon matrix precursor is a lithium ion battery composite hard carbon anode material prepared by using a thermoplastic resin, and is observed by a KYKY2800B scanning electron microscope of Beijing Zhongke Science and Technology Development Co., Ltd., and the shape is blocky, irregular, fine particles, and adopted. The test phase distribution was uniform, and the porous structure was tested by the NOVA1000 specific surface area tester of QUANTA CHROME, USA, and the pore size distribution was 0.2-100 nm, and the porosity was 9-19%. The d 002 value was tested between 0.338 and 0.475 nm using a PW3040/60 X'Pert X-ray diffractometer from the Dutch PANalytical Instruments. The particle size range was 0.5-90 μm using a Mastersizer 2000 laser particle size analyzer from Malvern Instruments. The specific surface area was 1.9 to 75.3 m 2 /g using the Tristar 3000 fully automatic surface area and porosity analyzer from Mike Instruments. The true density of the Ultrapycnometer 1000 automatic true density analyzer from Conta Instruments was 1.54 to 2.35 g/cm 3 . The FZS4-4 type tap density meter was used to measure the tap density of 0.88~1.43 g/cm 3 .
残炭量的测试方法:1、在干净的坩埚内放入被测试样品，在110℃±5℃烘箱中干燥1h。2、将洁净的瓷方舟放在950℃±50℃的马弗炉里煅烧1h，在空气中冷却2min，然后将瓷方舟放入干燥器内冷却30min，冷至室温，称量，称准至0.0001g。3、重复步骤2，直至连续称量的差数不超过0.0004g为止，将坩埚质量记为m1。4、称量约1g干燥后的样品至瓷方舟中，称准至0.000lg，记为m2。5、将盛有试样的瓷方舟放入950℃±50℃的马弗炉里煅烧1.5h，然后取出瓷方舟在空气中冷却2min后，放入干燥器内冷却30min，冷却至室温后称量，称准至0.0001g。6、重复步骤5直至连续称量间的差数不超过0.0004g，记为m3。Test method for the amount of carbon residue: 1. Put the test sample in a clean crucible and dry it in an oven at 110 ° C ± 5 ° C for 1 h. 2. The clean porcelain ark is calcined in a muffle furnace at 950 °C ± 50 °C for 1 h, cooled in air for 2 min, then the porcelain ark is placed in a desiccator for 30 min, cooled to room temperature, weighed, and weighed 0.0001g. 3. Repeat step 2 until the difference of continuous weighing does not exceed 0.0004 g, and the mass of 坩埚 is recorded as m 1 . 4. Weigh approximately 1 g of the dried sample into a porcelain ark and weigh to 0.000 lg, denoted as m 2 . 5. The porcelain ark with the sample is placed in a muffle furnace at 950 °C ± 50 °C for 1.5 h, then the porcelain ark is taken out and cooled in the air for 2 min, then placed in a desiccator for 30 min, cooled to room temperature and then weighed. The amount is weighed to 0.0001 g. 6. Repeat step 5 until the difference between consecutive weighings does not exceed 0.0004 g, denoted as m 3 .
按下式计算C元素的含量：C%=[(m2-m3)/(m2-m1)]×100%，式中：m1为瓷舟质量， m2为瓷舟与试样的质量， m3为瓷舟与灰分的质量。本发明的方法制备的锂离子电池硬碳负极材料，C元素的含量不少于90%。Calculate the content of C element by the following formula: C% = [(m 2 - m 3 ) / (m 2 - m 1 )] × 100%, where m 1 is the mass of the porcelain boat, m 2 is the porcelain boat and the test The quality of the sample, m 3 is the quality of the porcelain boat and ash. The lithium ion battery hard carbon anode material prepared by the method of the invention has a C element content of not less than 90%.
将实施例1～13制备的负极材料，与粘结剂聚偏二氟乙烯PVDF、导电剂Super-P按照92：5：3的质量比混合，加入N-甲基吡咯烷酮NMP作为分散剂调成浆料，均匀涂覆在10μm厚的铜箔上，压制成片，然后制成直径lcm 圆形炭膜。在干燥箱中120℃下烘干12h备用。以金属锂片作为对极。使用1mol/LLiPF6的三组分混合溶剂按EC：DMC：EMC＝1：1：1的体积比例混合的电解液，聚丙烯微孔膜为隔膜。在充满氩气的手套箱中组装成模拟电池（德国布劳恩惰性气体手套箱***有限公司MB200B型）。模拟电池的充放电测试在在深圳新威电池检测设备有限公司BTS-5V 100mA电池检测***上，充放电电压限制在0.001～2.0伏，40C、30C、1C、0.2C，测试首次可逆容量和首次库仑效率。首次库仑效率计算式为：首次库仑效率=首次充电容量/首次放电容量。The negative electrode materials prepared in Examples 1 to 13 were mixed with a binder polyvinylidene fluoride PVDF and a conductive agent Super-P in a mass ratio of 92:5:3, and N-methylpyrrolidone NMP was added as a dispersing agent. The slurry was uniformly coated on a 10 μm thick copper foil, pressed into a sheet, and then made into a diameter of 1 cm. Round carbon film. Dry in a dry box at 120 ° C for 12 h for use. A lithium metal sheet is used as a counter electrode. An electrolyte solution in which a three-component mixed solvent of 1 mol/L of LiPF6 was mixed in a volume ratio of EC:DMC:EMC=1:1:1 was used, and a polypropylene microporous membrane was used as a separator. Simulated batteries were assembled in an argon-filled glove box (Blauen Inert Gas Glove Box System GmbH MB200B). The charge and discharge test of the analog battery is in Shenzhen Xinwei Battery Testing Equipment Co., Ltd. BTS-5V On the 100 mA battery detection system, the charge and discharge voltage is limited to 0.001 to 2.0 volts, 40C, 30C, 1C, and 0.2C, and the first reversible capacity and the first coulombic efficiency are tested. The first Coulomb efficiency calculation is: first coulomb efficiency = first charge capacity / first discharge capacity.
将人造石墨作为负极材料，按上述方法制备对比例1～2的电池。人造石墨的比表面积10m2/g，晶体层间距d002为0.3358nm，真实密度2.22g/cm3，振实密度1.01g/cm3，粒度1～60μm。按上述相同的方法，测试首次可逆容量和首次库仑效率。Using artificial graphite as a negative electrode material, batteries of Comparative Examples 1 to 2 were prepared as described above. The artificial graphite has a specific surface area of 10 m 2 /g, a crystal layer spacing d 002 of 0.3358 nm, a true density of 2.22 g/cm 3 , a tap density of 1.01 g/cm 3 , and a particle size of 1 to 60 μm. The first reversible capacity and the first coulombic efficiency were tested in the same manner as above.
实施例1～13的配方见表1，实施例1～13的制备工艺见表2，实施例1～13的物理及化学性能测试结果见表3，实施例1～13及对比例1～4的电性能测试结果见表4。The formulations of Examples 1 to 13 are shown in Table 1. The preparation processes of Examples 1 to 13 are shown in Table 2. The physical and chemical properties of Examples 1 to 13 are shown in Table 3. Examples 1 to 13 and Comparative Examples 1 to 4 The electrical performance test results are shown in Table 4.
如图1所示，实施例1制备的材料为块状不规则的形状，大小相对均匀，微孔结构。As shown in FIG. 1, the material prepared in Example 1 has a block-shaped irregular shape, a relatively uniform size, and a microporous structure.
如图2所示，d002=0.388，由于复合硬碳多孔、不规则结构致其比一般石墨类材料d002层间距要大。As shown in Fig. 2, d002=0.388, which is larger than the general graphite material d002 layer due to the porous and irregular structure of the composite hard carbon.
如图3所示，在常温下，40C、30C高倍率条件下，40C/1C充电容量保持率为95.2%，30C/1C充电容量保持率达到96.2%，由于复合硬碳材料是微孔、无序不规则结构以致具有高倍率充放电性能非常优异。As shown in Fig. 3, under normal conditions of 40C and 30C, the 40C/1C charge capacity retention rate is 95.2%, and the 30C/1C charge capacity retention rate is 96.2%, because the composite hard carbon material is microporous and non- The irregular structure is so excellent that it has a high rate of charge and discharge performance.
如图4所示，在600C ，0.2C 倍率下300周容量保持率为96%，实施例1制备的材料具有优异的高温循环性能。As shown in Figure 4, at 600C, 0.2C The capacity retention rate at a rate of 300 cycles was 96%, and the material prepared in Example 1 had excellent high temperature cycle performance.
如图5所示，在-300C ，0.2C 倍率下100周容量保持率为88%，实施例1制备的材料具有优异的低温循环性能。As shown in Figure 5, at -300C, 0.2C The 100-week capacity retention rate at the magnification was 88%, and the material prepared in Example 1 had excellent low-temperature cycle performance.
二、硬碳基体前驱物采用植物原料时，包覆物前躯体质量为硬碳基体前驱物质量的1～25%。包覆物与硬碳基体表面化学吸附、化学反应或物理吸附，使硬碳基体表面与包覆物之间依靠化学键或范德华力相结合，硬碳基体表面具有蜂窝开孔结构，孔径为1.0～55nm，粒度为2～60μm，通过包覆之后孔径会变小为0.5～50nm，粒度会变大为3.5～70μm，该锂离子电池复合硬碳负极材料，形状为块状和/或片状的颗粒，其粒径为3.5～70μm，其比表面积在7.5～20m2/g之间，材料表面具有蜂窝状开孔结构，孔径为0.5～50nm，孔隙率为为9～16%，002晶面的层间距d002值在0.337～0.455nm之间，真实密度为1.55～2.25g/cm3，振实密度为0.91～1.45g/cm3，其C元素的含量不少于94%。在0.2C时，首次可逆容量为450 mAh/g以上，首充库伦效率为81.3%。2. When the hard carbon matrix precursor is made of plant material, the precursor mass of the coating is 1 to 25% of the mass of the hard carbon matrix precursor. The surface of the hard carbon substrate is chemically adsorbed, chemically reacted or physically adsorbed, so that the surface of the hard carbon substrate and the coating are combined by chemical bonds or van der Waals forces. The surface of the hard carbon substrate has a honeycomb opening structure and a pore diameter of 1.0 ～. 55nm, particle size is 2 ~ 60μm, the pore size will be reduced to 0.5 ~ 50nm after coating, the particle size will become 3.5 ~ 70μm, the lithium ion battery composite hard carbon anode material, the shape is block and / or sheet The particles have a particle diameter of 3.5 to 70 μm and a specific surface area of 7.5 to 20 m 2 /g. The surface of the material has a honeycomb open-cell structure, a pore diameter of 0.5 to 50 nm, a porosity of 9 to 16%, and a 002 crystal plane. The layer spacing d 002 is between 0.337 and 0.455 nm, the true density is 1.55 to 2.25 g/cm 3 , the tap density is 0.91 to 1.45 g/cm 3 , and the C element content is not less than 94%. At 0.2C, the first reversible capacity is above 450 mAh/g, and the first charge has a coulombic efficiency of 81.3%.
所述硬碳基体前驱物为植物原料花粉、稻谷壳、甘蔗杆、核桃壳、竹子、酒糟和木屑的一种以上，热解形成硬碳基体。The hard carbon matrix precursor is one or more of plant raw material pollen, rice husk, sugar cane stick, walnut shell, bamboo, distiller's grains and wood chips, and pyrolyzes to form a hard carbon matrix.
所述硬碳基体前驱物由以下质量比组成：植物原料、与占植物原料大于0至小于等于40%的掺杂物混合组成，热解形成硬碳基体。植物原料是花粉、稻谷壳、甘蔗杆、核桃壳、竹子、酒糟和木屑的一种以上。The hard carbon matrix precursor is composed of the following mass ratio: a plant material, a mixture of more than 0 to 40% or less of a dopant of the plant material, and pyrolysis to form a hard carbon matrix. The plant material is more than one type of pollen, rice husk, sugar cane stalk, walnut shell, bamboo, vinasse and wood chips.
所述硬碳基体前驱物采用植物原料时，掺杂物为金属化合物、非金属化合物、金属单质或非金属单质。所述金属化合物为金属氧化物、金属盐或金属碱。所述非金属化合物为非金属氧化物、酸、非金属元素有机物或非金属盐。When the hard carbon matrix precursor is a plant material, the dopant is a metal compound, a non-metal compound, a metal element or a non-metal element. The metal compound is a metal oxide, a metal salt or a metal base. The non-metallic compound is a non-metal oxide, an acid, a non-metal element organic or a non-metal salt.
金属氧化物为氧化锡，氧化钴和氧化镍的一种以上。The metal oxide is one or more of tin oxide, cobalt oxide and nickel oxide.
金属盐为磷酸钠、氯化锡、碳酸钴和磷酸二氢钠的一种以上。The metal salt is one or more of sodium phosphate, tin chloride, cobalt carbonate, and sodium dihydrogen phosphate.
金属碱为氢氧化铜、氢氧化钴、氢氧化锡和氢氧化镍的一种以上。The metal base is one or more of copper hydroxide, cobalt hydroxide, tin hydroxide, and nickel hydroxide.
非金属氧化物为二氧化硅和/或五氧化二磷。The non-metal oxide is silica and/or phosphorus pentoxide.
酸为硼酸、硅酸和磷酸的一种以上。The acid is one or more of boric acid, silicic acid, and phosphoric acid.
非金属盐为磷酸二氢铵、磷酸铵和硫酸铵的一种以上。The non-metal salt is one or more of ammonium dihydrogen phosphate, ammonium phosphate, and ammonium sulfate.
非金属元素有机物为有机硅树脂和/或乙二醇硼酸酯。The non-metallic element organics are silicone resins and/or ethylene glycol borate esters.
金属单质为铜、铅、锑、锡、钴和镍的一种以上。The metal element is one or more of copper, lead, antimony, tin, cobalt and nickel.
非金属单质为硅、硫和硼的一种以上。The non-metal element is one or more of silicon, sulfur and boron.
硬碳基体前驱物采用植物原料时，本发明的锂离子电池复合硬碳负极材料的制备方法一，包括以下步骤：When the hard carbon matrix precursor adopts a plant material, the first method for preparing the lithium ion battery composite hard carbon anode material of the present invention comprises the following steps:
（一）、前躯物除杂浸泡处理，在前躯物植物原料中加入酸或碱，按每100克干植物原料加入80～300ml酸或碱，采用常州市武进八方机械厂的F-0.4型高速分散机，转速为1000～3000r/min，时间为3～30min，然后浸泡3～50 h。(1) Adding acid or alkali to the precursor material of the forebody, adding 80-300 ml of acid or alkali per 100 grams of dry plant material, using F-0.4 of Changzhou Wujin Bafang Machinery Factory High-speed disperser with a speed of 1000~3000r/min, time of 3~30min, then soaking 3~50 h.
植物原料如前述，酸为氢氟酸、硼酸、硫酸、盐酸或硝酸，碱为氢氧化钾、氢氧化钙或氢氧化钠。Plant material As described above, the acid is hydrofluoric acid, boric acid, sulfuric acid, hydrochloric acid or nitric acid, and the base is potassium hydroxide, calcium hydroxide or sodium hydroxide.
（二）、洗涤，用电导率为13μs/cm的纯水洗涤，使前躯物的pH值为5～9，采用张家港市华祥离心机制造有限公司的SS300型三足式人工卸料离心机离心机，转速800～1400r/min，时间8～30min。(2) Washing, washing with pure water with a conductivity of 13 μs/cm, so that the pH of the precursor is 5-9, using SS300 type three-legged manual discharge centrifugal centrifugation of Zhangjiagang Huaxiang Centrifuge Manufacturing Co., Ltd. Machine centrifuge, speed 800 ~ 1400r / min, time 8 ~ 30min.
（三）、除水烘干，在80～140℃条件下烘干10～40h，自然降温至室温，采用广州东之旭试验设备有限公司的DHG-9140型高温试验箱。(3), drying in water, drying at 80 ~ 140 ° C for 10 ~ 40h, natural cooling to room temperature, using DHG-9140 high temperature test chamber of Guangzhou Dongzhixu Test Equipment Co., Ltd.
（四）、低温预烧，以提高硬碳的产率、容量及首次库伦效率，产生基体表面蜂窝开孔结构，将烘干的前躯体放入宜兴市飞达电炉有限公司的SXQ12-14-20型箱式电阻炉，以0.1～10℃/min的升温速度到200～500℃，低温预烧3～20 h，在炉内自然降温至室温,低温预烧在真空度0.03MPa以下，或者在保护性气体氦气、氮气、氩气、氙气或氮气下进行，流量为0.1～0.4m3/h，得到固态蜂窝状的灰黑色物质。 (4) Low-temperature pre-burning to improve the yield, capacity and first-time coulomb efficiency of hard carbon, and to produce a honeycomb open-cell structure on the surface of the substrate, and put the dried precursor into SXQ12-14 of Yixing Feida Electric Furnace Co., Ltd. 20 type box type resistance furnace, with a heating rate of 0.1 ~ 10 °C / min to 200 ~ 500 ° C, low temperature pre-burning for 3 ~ 20 h, naturally cooled to room temperature in the furnace, low temperature pre-burning under vacuum degree 0.03MPa, or It is carried out under a protective gas of helium, nitrogen, argon, helium or nitrogen at a flow rate of 0.1 to 0.4 m 3 /h to obtain a solid honeycomb-like gray-black substance.
（五）、粉碎，将固态蜂窝状的灰黑色物进行粉碎或球磨，得到粒度为1～60μm的粉末，采用南京大学仪器厂的QM-1SP4型行星球磨机，控制材料粒度的大小便于掺杂。(5), crushing, solid-state honeycomb gray-black matter is pulverized or ball-milled to obtain a powder with a particle size of 1 to 60 μm. The QM-1SP4 planetary ball mill of Nanjing University Instrument Factory is used to control the particle size of the material to facilitate doping.
（六）、掺杂，在上述粉末内，按占粉末质量大于0小于等于40%的比例，加入掺杂物，采用常州市武进八方机械厂F-0.4型高速分散机，转速为1000～4500r/min，时间为20～95min，得到改良的前躯体，以提高硬碳的容量及首次库伦效率。(6) Doping, in the above powder, according to the proportion of powder mass greater than 0 or less than or equal to 40%, adding dopants, using F-0.4 high-speed disperser of Changzhou Wujin Bafang Machinery Factory, the rotation speed is 1000～4500r /min, time 20 to 95 min, improved precursors to improve hard carbon capacity and first coulombic efficiency.
掺杂物为前述硬碳基体前驱物采用植物原料时的掺杂物。The dopant is a dopant when the aforementioned hard carbon matrix precursor is a plant material.
掺杂步骤也可以放在低温预烧前进行。The doping step can also be carried out before the low temperature pre-burning.
（七）、热解，将改良的前躯体放入宜兴市飞达电炉有限公司的SXQ12-14-20箱式电阻炉内，以0.1～10℃/min的升温速度升温到500～1300℃，热解1～10h，炉内自然降温至室温,得到硬碳，热解在真空度0.03MPa以下，或者在保护性气体氦气、氮气、氩气、氙气或氮气下进行，流量为0.1～0.4m3/h。(7) Pyrolysis, put the improved precursor into the SXQ12-14-20 box-type resistance furnace of Yixing Feida Electric Furnace Co., Ltd., and heat up to 500-1300 °C at a heating rate of 0.1~10 °C/min. Pyrolysis 1 ~ 10h, the furnace naturally cools to room temperature, to obtain hard carbon, pyrolysis under vacuum of 0.03MPa, or under protective gas helium, nitrogen, argon, helium or nitrogen, the flow rate is 0.1 ~ 0.4 m 3 /h.
（八）、粉碎或球磨，采用南京大学仪器厂的QM-1SP4型行星球磨机，将硬碳进行球磨或粉碎，得到粒度为2～65μm的硬碳基体。(8), crushing or ball milling, using the QM-1SP4 planetary ball mill of Nanjing University Instrument Factory, the hard carbon is ball milled or pulverized to obtain a hard carbon matrix with a particle size of 2 to 65 μm.
（九）、包覆，按硬碳基体前驱物质量的1～25%，在硬碳基体中加入包覆物的前躯体，采用无锡新光粉体加工工艺有限公司的VC-150型混合机中，以1000～4500r/min的转速，混合2～40min，然后放入宜兴市飞达电炉有限公司的SXQ12-14-20箱式电阻炉，以0.1～10℃/min的升温速度到400～1300℃，时间为1～24h，进行热解处理，在炉内自然降温至室温, 热解处理在真空度0.03MPa以下，或者在保护性气体氦气、氮气、氩气、氙气或氮气下进行，流量为0.1～0.4m3/h，使硬碳材料的表面较为光滑，降低最终产品的比表面积，过200目筛，得到粒度为3.5～70μm的锂离子电池复合硬碳负极材料。(9), coating, according to the hardness of the hard carbon matrix precursor 1 to 25%, adding the precursor of the coating to the hard carbon matrix, using VC-150 mixer of Wuxi Xinguang Powder Processing Technology Co., Ltd. , at a speed of 1000 ~ 4500 r / min, mixed for 2 ~ 40min, and then put into the SXQ12-14-20 box-type resistance furnace of Yixing Feida Electric Furnace Co., Ltd., with a heating rate of 0.1 ~ 10 °C / min to 400 ~ 1300 °C, the time is 1 ~ 24h, pyrolysis treatment, naturally cool to room temperature in the furnace, The pyrolysis treatment is carried out under a vacuum of 0.03 MPa or under a protective gas of helium, nitrogen, argon, helium or nitrogen, and the flow rate is 0.1 to 0.4 m 3 /h, so that the surface of the hard carbon material is smooth, and the final product is lowered. The specific surface area is over a 200 mesh sieve to obtain a lithium ion battery composite hard carbon anode material having a particle size of 3.5 to 70 μm.
包覆物的前躯体为前述有机物。The precursor of the coating is the aforementioned organic matter.
硬碳基体前驱物采用植物原料时，本发明的锂离子电池复合硬碳负极材料的制备方法二，包括以下步骤：前述植物原料When the hard carbon matrix precursor adopts a plant raw material, the second method for preparing the lithium ion battery composite hard carbon anode material of the present invention comprises the following steps: the aforementioned plant material
（一）、粉碎，将前述植物原料，机械粉碎或气流粉碎，得到粒度为40～100μm的粉末状物质，采用通用的机械粉碎机或气流粉碎机。(1) pulverizing, the above plant material is mechanically pulverized or air-jet pulverized to obtain a powdery substance having a particle size of 40 to 100 μm, and a general mechanical pulverizer or a jet mill is used.
（ 二）、除杂浸泡处理，按每100克干植物原料加入80～300ml酸或碱，在上述粉末状物质中加入氢氟酸、硼酸、硫酸、盐酸、硝酸、氢氧化钾、氢氧化钙或氢氧化钠，采用常州市武进八方机械厂的F-0.4型高速分散机，转速为1000～3000r/min，时间为3～30min，然后浸泡3～50 h。( b) In addition to the soaking treatment, add 80-300 ml of acid or alkali per 100 g of dry plant material, and add hydrofluoric acid, boric acid, sulfuric acid, hydrochloric acid, nitric acid, potassium hydroxide, calcium hydroxide or the above powdery substance. Sodium hydroxide, using F-0.4 high-speed disperser of Changzhou Wujin Bafang Machinery Factory, the speed is 1000~3000r/min, the time is 3~30min, then soaking 3~50 h.
（三）、洗涤，用电导率为13μs/cm的纯水洗涤，控制前躯物的pH为5～9，采用张家港市华祥离心机制造有限公司的SS300型三足式人工卸料离心机，转速800～1400r/min，时间8～30min。(3) Washing, washing with pure water with conductivity of 13μs/cm, controlling the pH of the precursor to be 5-9, using SS300 type three-legged manual unloading centrifuge of Zhangjiagang Huaxiang Centrifuge Manufacturing Co., Ltd. The speed is 800~1400r/min and the time is 8~30min.
（四）、除水烘干，在80～140℃条件下烘干10～40h，自然降温至室温，采用广州东之旭试验设备有限公司的号DHG-9140型高温试验箱。(4), drying in water, drying at 80 ~ 140 ° C for 10 ~ 40h, natural cooling to room temperature, using the DHG-9140 high temperature test chamber of Guangzhou Dongzhixu Test Equipment Co., Ltd.
（五）、掺杂，按占烘干的料质量大于0小于等于40%的比例，加入掺杂物，在无锡新光粉体加工工艺有限公司的VC-150型混合机中，以1000～4500r/min的转速混合20～95min。(5) Doping, adding dopants according to the ratio of the mass of the dried material to more than 0 and less than or equal to 40%, in the VC-150 mixer of Wuxi Xinguang Powder Processing Technology Co., Ltd., 1000~4500r The speed of /min is mixed for 20 to 95 minutes.
所述掺杂物为前述硬碳基体前驱物采用植物原料时的掺杂物。The dopant is a dopant when the hard carbon matrix precursor is a plant material.
（六）、低温预烧，将掺杂后的前躯体放入宜兴市飞达电炉有限公司的SXQ12-14-20型箱式电阻炉，以0.1～10℃/min的升温速度到200～500℃，低温预烧3～20h，在炉内自然降温至室温,低温预烧在真空度0.03MPa以下，或者在保护性气体氦气、氮气、氩气、氙气或氮气下进行，流量为0.1～0.4m3/h。(6) Low temperature pre-burning, put the doped precursor into the SXQ12-14-20 box type resistance furnace of Yixing Feida Electric Furnace Co., Ltd., and increase the temperature to 0.1-10 °C/min to 200-500. °C, low temperature pre-burning for 3 to 20h, natural cooling to room temperature in the furnace, low temperature pre-burning under vacuum of 0.03MPa, or under protective gas helium, nitrogen, argon, helium or nitrogen, the flow rate is 0.1~ 0.4m3/h.
（七）、粉碎或球磨，采用南京大学仪器厂的QM-1SP4型行星球磨机，得到粒度为1～65μm的硬碳前躯体。(7), crushing or ball milling, using the QM-1SP4 planetary ball mill of Nanjing University Instrument Factory, to obtain a hard carbon precursor with a particle size of 1 ~ 65μm.
（八）、热解，将硬碳前躯体放入宜兴市飞达电炉有限公司的SXQ12-14-20箱式电阻炉，以0.1～10℃/min的升温速度到500～1300℃，热解1～10h，炉内自然降温至室温,得到硬碳基体，热解在真空度0.03MPa以下，或者在保护性气体氦气、氮气、氩气、氙气或氮气下进行，流量为0.1～0.4m3/h，得到硬碳。(8) Pyrolysis, put the hard carbon precursor into the SXQ12-14-20 box type resistance furnace of Yixing Feida Electric Furnace Co., Ltd., to the temperature increase rate of 0.1～10°C/min to 500～1300°C, pyrolysis 1~10h, the furnace naturally cools to room temperature, and a hard carbon matrix is obtained. The pyrolysis is carried out under a vacuum of 0.03 MPa or under a protective gas of helium, nitrogen, argon, helium or nitrogen, and the flow rate is 0.1-0.4 m3. /h, get hard carbon.
（九）、将硬碳进行球磨或粉碎10～30min，得到粒度为2～60μm硬碳基体。(9) The hard carbon is ball milled or pulverized for 10 to 30 minutes to obtain a hard carbon matrix having a particle size of 2 to 60 μm.
（十）、包覆，按硬碳基体前驱物质量的1～25%，在硬碳基体中加入包覆物的前躯体，采用无锡新光粉体加工工艺有限公司的VC-150型混合机中，以1000～4500r/min的转速，混合2～40min，然后放入宜兴市飞达电炉有限公司的SXQ12-14-20箱式电阻炉，以0.1～10℃/min的升温速度到400～1300℃，时间为1～24h，进行热解处理，在炉内自然降温至室温, 热解处理在真空度0.03MPa以下，或者在保护性气体氦气、氮气、氩气、氙气或氮气下进行，流量为0.1～0.4m3/h，使硬碳材料的表面较为光滑，降低最终产品的比表面积，过200目筛，得到粒度为3.5～70μm的锂离子电池复合硬碳负极材料。(10), coating, according to the hardness of the hard carbon matrix precursor 1 to 25%, adding the precursor of the coating to the hard carbon matrix, using VC-150 mixer of Wuxi Xinguang Powder Processing Technology Co., Ltd. , at a speed of 1000 ~ 4500 r / min, mixed for 2 ~ 40min, and then put into the SXQ12-14-20 box-type resistance furnace of Yixing Feida Electric Furnace Co., Ltd., with a heating rate of 0.1 ~ 10 °C / min to 400 ~ 1300 °C, the time is 1 ~ 24h, pyrolysis treatment, natural cooling to room temperature in the furnace, pyrolysis treatment under vacuum degree 0.03MPa, or under protective gas helium, nitrogen, argon, helium or nitrogen, The flow rate is 0.1-0.4 m 3 /h, which makes the surface of the hard carbon material smooth, reduces the specific surface area of the final product, and passes through a 200 mesh sieve to obtain a lithium ion battery composite hard carbon anode material having a particle size of 3.5 to 70 μm.
包覆物的前躯体为前述有机物。The precursor of the coating is the aforementioned organic matter.
硬碳基体前驱物采用植物原料时，本发明的锂离子电池复合硬碳负极材料的制备方法三，包括以下步骤：When the hard carbon matrix precursor adopts a plant raw material, the third method for preparing the lithium ion battery composite hard carbon anode material of the present invention comprises the following steps:
（一）、粉碎，将前躯物干植物类原料花粉、稻谷壳、甘蔗杆、核桃壳、竹子、酒糟和木屑的一种以上，机械粉碎或气流粉碎，得到粒度为40～100μm的粉末状物质，采用通用的机械粉碎机或气流粉碎机。(1) pulverizing, more than one kind of raw material pollen, rice husk, sugar cane rod, walnut shell, bamboo, distiller's grains and wood chips of the forebody, mechanically pulverized or air-pulverized to obtain a powder with a particle size of 40-100 μm. Substance, using a general mechanical pulverizer or jet mill.
（二）、除杂浸泡处理，按每100克干植物原料加入80～300ml酸或碱，在上述粉末状物质中加入氢氟酸、硼酸、硫酸、盐酸、硝酸、氢氧化钾、氢氧化钙或氢氧化钠，采用常州市武进八方机械厂的F-0.4型高速分散机，转速为1000～3000r/min，时间为3～30min，然后浸泡3～50h。(2) In addition to the soaking treatment, 80-300 ml of acid or alkali is added per 100 g of dry plant raw materials, and hydrofluoric acid, boric acid, sulfuric acid, hydrochloric acid, nitric acid, potassium hydroxide and calcium hydroxide are added to the above powdery substance. Or sodium hydroxide, using F-0.4 high-speed disperser of Changzhou Wujin Bafang Machinery Factory, the speed is 1000~3000r/min, the time is 3~30min, then soak for 3~50h.
（三）、洗涤，用电导率为13μs/cm的纯水洗涤，控制前躯物的pH为5～9，采用张家港市华祥离心机制造有限公司的SS300型三足式人工卸料离心机，转速800～1400r/min，时间8～30min。(3) Washing, washing with pure water with conductivity of 13μs/cm, controlling the pH of the precursor to be 5-9, using SS300 type three-legged manual unloading centrifuge of Zhangjiagang Huaxiang Centrifuge Manufacturing Co., Ltd. The speed is 800~1400r/min and the time is 8~30min.
（四）、除水烘干，在80～140℃条件下烘干10～40h，自然降温至室温，采用广州东之旭试验设备有限公司的DHG-9140型高温试验箱。(4) Drying in water, drying at 80 ~ 140 °C for 10 ~ 40h, natural cooling to room temperature, using DHG-9140 high temperature test chamber of Guangzhou Dongzhixu Test Equipment Co., Ltd.
（五）、低温预烧，将烘干的前躯体放入宜兴市飞达电炉有限公司的SXQ12-14-20型箱式电阻炉，以0.1～10℃/min的升温速度到200～500℃，低温预烧3～20h，在炉内自然降温至室温,低温预烧在真空度0.03MPa以下，或者在保护性气体氦气、氮气、氩气、氙气或氮气下进行，流量为0.1～0.4m3/h。(5) Low-temperature pre-burning, put the dried precursor into the SXQ12-14-20 box-type resistance furnace of Yixing Feida Electric Furnace Co., Ltd., and increase the temperature to 0.1-10 °C/min to 200-500 °C. , preheated at low temperature for 3~20h, naturally cooled to room temperature in the furnace, preheated at a low temperature of 0.03MPa or below, or under protective gas helium, nitrogen, argon, helium or nitrogen. The flow rate is 0.1~0.4. m 3 /h.
（六）、粉碎，将预烧的料进行粉碎或球磨，得到粒度为1～60μm的粉末状，采用南京大学仪器厂的QM-1SP4型行星球磨机。(6), pulverizing, pulverizing or ball milling the pre-calcined material to obtain a powder having a particle size of 1 to 60 μm, and adopting a QM-1SP4 planetary ball mill of Nanjing University Instrument Factory.
（七）、掺杂，按占预烧的料质量大于0小于等于40%的比例，加入掺杂物，在无锡新光粉体加工工艺有限公司的VC-150型混合机中，以1000～4500r/min的转速混合20～95min。(7) Doping, adding dopants according to the ratio of the mass of the pre-fired material greater than 0 to less than or equal to 40%, in the VC-150 mixer of Wuxi Xinguang Powder Processing Technology Co., Ltd., 1000~4500r The speed of /min is mixed for 20 to 95 minutes.
掺杂物为前述硬碳基体前驱物采用植物原料时的掺杂物。The dopant is a dopant when the aforementioned hard carbon matrix precursor is a plant material.
（八）、热解，将掺杂后的硬碳前躯体放入宜兴市飞达电炉有限公司的SXQ12-14-20箱式电阻炉，以0.1～10℃/min的升温速度到500～1300℃，热解1～10h，炉内自然降温至室温,得到硬碳基体，热解在真空度0.03MPa以下，或者在保护性气体氦气、氮气、氩气、氙气或氮气下进行，流量为0.1～0.4m3/h，得到硬碳。(8) Pyrolysis, put the doped hard carbon precursor into the SXQ12-14-20 box-type resistance furnace of Yixing Feida Electric Furnace Co., Ltd., and increase the temperature to 0.1-10 °C/min to 500-1300 °C, pyrolysis for 1 ~ 10h, the furnace naturally cools to room temperature, to obtain a hard carbon matrix, pyrolysis under vacuum of 0.03MPa, or under protective gas helium, nitrogen, argon, helium or nitrogen, the flow rate is From 0.1 to 0.4 m 3 /h, hard carbon is obtained.
（九）、粉碎或球磨，采用南京大学仪器厂的QM-1SP4型行星球磨机，将硬碳进行球磨或粉碎20～90min，得到粒度2～60μm的硬碳基体。(9), crushing or ball milling, using the QM-1SP4 planetary ball mill of Nanjing University Instrument Factory, the hard carbon is ball milled or pulverized for 20-90 min to obtain a hard carbon matrix with a particle size of 2 to 60 μm.
（十）、包覆，按硬碳基体前驱物质量的1～25%，在硬碳基体中加入包覆物的前躯体，采用无锡新光粉体加工工艺有限公司的VC-150型混合机中，以1000～4500r/min的转速，混合2～40min，然后放入宜兴市飞达电炉有限公司的SXQ12-14-20箱式电阻炉，以0.1～10℃/min的升温速度到400～1300℃，时间为1～24h，进行热解处理，在炉内自然降温至室温, 热解处理在真空度0.03MPa以下，或者在保护性气体氦气、氮气、氩气、氙气或氮气下进行，流量为0.1～0.4m3/h，使硬碳材料的表面较为光滑，降低最终产品的比表面积，过200目筛，得到粒度为3.5～70μm的锂离子电池复合硬碳负极材料。(10), coating, according to the hardness of the hard carbon matrix precursor 1 to 25%, adding the precursor of the coating to the hard carbon matrix, using VC-150 mixer of Wuxi Xinguang Powder Processing Technology Co., Ltd. , at a speed of 1000 ~ 4500 r / min, mixed for 2 ~ 40min, and then put into the SXQ12-14-20 box-type resistance furnace of Yixing Feida Electric Furnace Co., Ltd., with a heating rate of 0.1 ~ 10 °C / min to 400 ~ 1300 °C, the time is 1 ~ 24h, pyrolysis treatment, natural cooling to room temperature in the furnace, pyrolysis treatment under vacuum degree 0.03MPa, or under protective gas helium, nitrogen, argon, helium or nitrogen, The flow rate is 0.1-0.4 m 3 /h, which makes the surface of the hard carbon material smooth, reduces the specific surface area of the final product, and passes through a 200 mesh sieve to obtain a lithium ion battery composite hard carbon anode material having a particle size of 3.5 to 70 μm.
包覆物的前躯体为前述有机物。The precursor of the coating is the aforementioned organic matter.
硬碳基体前驱物采用植物原料时，本发明的锂离子电池复合硬碳负极材料的制备方法四，包括以下步骤：When the hard carbon matrix precursor adopts a plant raw material, the fourth method for preparing the lithium ion battery composite hard carbon anode material of the present invention comprises the following steps:
（一）、粉碎，将前躯物干植物类原料花粉、稻谷壳、甘蔗杆、核桃壳、竹子、酒糟和木屑的一种以上，机械粉碎或气流粉碎，得到粒度为40～100μm的粉末状，采用通用的机械粉碎机或气流粉碎机。(1) pulverizing, more than one kind of raw material pollen, rice husk, sugar cane rod, walnut shell, bamboo, distiller's grains and wood chips of the forebody, mechanically pulverized or air-pulverized to obtain a powder with a particle size of 40-100 μm. Use a general mechanical shredder or jet mill.
（二）、除杂浸泡处理，按每100克干植物原料加入80～300ml酸或碱，在粉末状中加入氢氟酸、硼酸、硫酸、盐酸、硝酸、氢氧化钾、氢氧化钙或氢氧化钠，采用常州市武进八方机械厂的F-0.4型高速分散机，转速为1000～3000r/min，时间为3～30min，然后浸泡3～50h。(2) In addition to the soaking treatment, add 80-300 ml of acid or alkali per 100 g of dry plant raw materials, and add hydrofluoric acid, boric acid, sulfuric acid, hydrochloric acid, nitric acid, potassium hydroxide, calcium hydroxide or hydrogen to the powder. Sodium oxide is used in the F-0.4 high-speed disperser of Changzhou Wujin Bafang Machinery Factory. The rotation speed is 1000-3000r/min, the time is 3~30min, and then immersed for 3~50h.
（三）、洗涤，用电导率为13μS/cm的纯水洗涤，控制前躯物的pH为5～9，采用张家港市华祥离心机制造有限公司的SS300型三足式人工卸料离心机，转速800～1400r/min，时间8～30min。(3) Washing, washing with pure water with conductivity of 13μS/cm, controlling the pH of the precursor to be 5-9, using SS300 type three-legged manual unloading centrifuge of Zhangjiagang Huaxiang Centrifuge Manufacturing Co., Ltd. The speed is 800~1400r/min and the time is 8~30min.
（四）、除水烘干，在80～140℃条件下烘干10～40h，自然降温至室温，采用广州东之旭试验设备有限公司的DHG-9140 型烘干箱。(4) Drying in water, drying at 80~140 °C for 10~40h, natural cooling to room temperature, using DHG-9140 of Guangzhou Dongzhixu Testing Equipment Co., Ltd. Type drying box.
（五）、低温预烧，将烘干的前躯体放入宜兴市飞达电炉有限公司的SXQ12-14-20型箱式电阻炉，以0.1～10℃/min的升温速度到200～500℃，低温预烧3～20h，在炉内自然降温至室温,低温预烧在真空度0.03MPa以下，或者在保护性气体氦气、氮气、氩气、氙气或氮气下进行，流量为0.1～0.4m3/h。(5) Low-temperature pre-burning, put the dried precursor into the SXQ12-14-20 box-type resistance furnace of Yixing Feida Electric Furnace Co., Ltd., and increase the temperature to 0.1-10 °C/min to 200-500 °C. , preheated at low temperature for 3~20h, naturally cooled to room temperature in the furnace, preheated at a low temperature of 0.03MPa or below, or under protective gas helium, nitrogen, argon, helium or nitrogen. The flow rate is 0.1~0.4. m 3 /h.
（六）、粉碎，将预烧的料进行粉碎或球磨，得到粒度为1～60μm的粉末状，采用南京大学仪器厂的QM-1SP4型行星球磨机。(6), pulverizing, pulverizing or ball milling the pre-calcined material to obtain a powder having a particle size of 1 to 60 μm, and adopting a QM-1SP4 planetary ball mill of Nanjing University Instrument Factory.
（七）、热解，将硬碳前躯体放入宜兴市飞达电炉有限公司的SXQ12-14-20箱式电阻炉，以0.1～10℃/min的升温速度到500～1300℃，热解1～10h，炉内自然降温至室温,得到硬碳基体，热解在真空度0.03MPa以下，或者在保护性气体氦气、氮气、氩气、氙气或氮气下进行，流量为0.1～0.4m3/h，得到硬碳。(7) Pyrolysis, put the hard carbon precursor into the SXQ12-14-20 box-type resistance furnace of Yixing Feida Electric Furnace Co., Ltd., to the temperature rise rate of 0.1～10°C/min to 500～1300°C, pyrolysis 1~10h, the furnace naturally cools to room temperature, and a hard carbon matrix is obtained. The pyrolysis is carried out under a vacuum of 0.03 MPa or under a protective gas of helium, nitrogen, argon, helium or nitrogen, and the flow rate is 0.1 to 0.4 m. 3 / h, get hard carbon.
（八）、粉碎或球磨，采用南京大学仪器厂的QM-1SP4型行星球磨机，将硬碳进行球磨或粉碎20～90min，得到粒度2～60μm的硬碳基体。(8), crushing or ball milling, using the QM-1SP4 planetary ball mill of Nanjing University Instrument Factory, the hard carbon is ball milled or pulverized for 20-90 min to obtain a hard carbon matrix with a particle size of 2 to 60 μm.
（九）、包覆，按硬碳基体前驱物质量的1～25%，在硬碳基体中加入包覆物的前躯体，采用无锡新光粉体加工工艺有限公司的VC-150型混合机中，以1000～4500r/min的转速，混合2～40min，然后放入宜兴市飞达电炉有限公司的SXQ12-14-20箱式电阻炉，以0.1～10℃/min的升温速度到400～1300℃，时间为1～24h，进行热解处理，在炉内自然降温至室温, 热解处理在真空度0.03MPa以下，或者在保护性气体氦气、氮气、氩气、氙气或氮气下进行，流量为0.1～0.4m3/h，过200目筛，得到粒度为3.5～70μm的锂离子电池复合硬碳负极材料。(9), coating, according to the hardness of the hard carbon matrix precursor 1 to 25%, adding the precursor of the coating to the hard carbon matrix, using VC-150 mixer of Wuxi Xinguang Powder Processing Technology Co., Ltd. , at a speed of 1000 ~ 4500 r / min, mixed for 2 ~ 40min, and then put into the SXQ12-14-20 box-type resistance furnace of Yixing Feida Electric Furnace Co., Ltd., with a heating rate of 0.1 ~ 10 °C / min to 400 ~ 1300 °C, the time is 1 ~ 24h, pyrolysis treatment, natural cooling to room temperature in the furnace, pyrolysis treatment under vacuum degree 0.03MPa, or under protective gas helium, nitrogen, argon, helium or nitrogen, The flow rate is 0.1 to 0.4 m 3 /h, and a 200-mesh sieve is passed to obtain a lithium ion battery composite hard carbon anode material having a particle size of 3.5 to 70 μm.
包覆物的前躯体为前述有机物。The precursor of the coating is the aforementioned organic matter.
硬碳基体前驱物采用植物原料制备的锂离子电池复合硬碳负极材料，采用上述仪器，测得：形状为块状和/或片状颗粒，其表面具有蜂窝状开孔结构，孔径分布为0.5～50nm，孔隙率为9～16%，d002值在0.337～0.455nm之间，粒度范围为3.5～70μm，比表面积为0.5～20m2/g，真实密度为1.55～2.25g/cm3，振实密度为0.91～1.45 g/cm3。硬碳基体表面与包覆物之间依靠化学键或范德华力相结合，根据理论分析，范德华力是分子间作用力，而分子间作用力的来源是取向力、诱导力和色散力，对大多数分子来说，色散力是主要的。硬碳基体表面与包覆物之间的作用力在包覆过程形成。The hard carbon matrix precursor is a lithium ion battery composite hard carbon anode material prepared by using a plant material, and the above apparatus is used to measure: the shape is a block and/or a sheet-like particle, and the surface thereof has a honeycomb opening structure, and the pore size distribution is 0.5. ～50nm, porosity is 9-16%, d 002 value is between 0.337～0.455nm, particle size range is 3.5～70μm, specific surface area is 0.5-20m 2 /g, true density is 1.55～2.25g/cm 3 , The tap density is 0.91 to 1.45 g/cm 3 . The surface of the hard carbon matrix and the coating are combined by chemical bonds or van der Waals forces. According to theoretical analysis, van der Waals forces are intermolecular forces, while the sources of intermolecular forces are orientation forces, inducing forces and dispersive forces. For molecules, the dispersion force is dominant. The force between the surface of the hard carbon substrate and the cladding is formed during the coating process.
残炭量的测试方法按前述，计算C元素的含量：C%=[(m2-m3)/(m2-m1)]×100%，C元素的含量不少于94%。Test Method of Residual Carbon Amount The content of the C element was calculated as described above: C% = [(m 2 - m 3 ) / (m 2 - m 1 )] × 100%, and the content of the C element was not less than 94%.
实施例14～21的配方见表5，制备工艺见表6，物理及化学性能测试结果见表7，按上述方法制备模拟电池，电性能测试结果见表8。 The formulations of Examples 14 to 21 are shown in Table 5. The preparation process is shown in Table 6. The physical and chemical properties test results are shown in Table 7. The simulated batteries were prepared according to the above method. The electrical property test results are shown in Table 8.
如图6所示，形状为块状和/或片状的颗粒，材料表面具有蜂窝状开孔结构，孔径为0.5～40nm，孔隙率为12%。 As shown in Fig. 6, the particles are in the form of blocks and/or sheets, and the surface of the material has a honeycomb open-cell structure with a pore diameter of 0.5 to 40 nm and a porosity of 12%.
如图7所示，d002=0.385nm，复合硬碳多孔结构致其比一般石墨类材料d002层间距要大。As shown in Fig. 7, d 002 =0.385 nm, the composite hard carbon porous structure causes it to be larger than the general graphite material d 002 layer.
如图8所示，在常温下，40C、30C高倍率条件下，40C/1C充电容量保持率为95.3%，30C/1C充电容量保持率达到96.9%，由于复合硬碳材料是微孔、无序不规则结构以致具有高倍率充放电性能非常优异。 As shown in Fig. 8, under normal conditions, 40C/30C high capacity, 40C/1C charge capacity retention rate is 95.3%, 30C/1C charge capacity retention rate is 96.9%, because the composite hard carbon material is microporous, no The irregular structure is so excellent that it has a high rate of charge and discharge performance.
如图9所示，在60℃，0.2C 倍率下300周容量保持率为97.4%，制备的材料具有优异的高温循环性能。 As shown in Figure 9, at 60 ° C, 0.2 C The 300-week capacity retention rate at the rate of magnification is 97.4%, and the prepared material has excellent high-temperature cycle performance.
如图10所示，在-30℃，0.2C 倍率下100周容量保持率为88.2%，制备的材料具有优异的低温循环性能。 As shown in Figure 10, at -30 ° C, 0.2 C The 100-week capacity retention rate at the magnification was 88.2%, and the prepared material had excellent low-temperature cycle performance.
对比例3，将天然石墨作为负极材料，按上述方法制备对比例的电池。天然石墨的比表面积8.3m2/g，晶体层间距d002为0.3365nm，真实密度2.22g/cm3，振实密度1.05g/cm3，粒度1～60μm。按上述相同的方法，测试首次可逆容量和首次库仑效率，电性能测试见表8。Comparative Example 3, using natural graphite as a negative electrode material, a battery of the comparative example was prepared as described above. The natural graphite has a specific surface area of 8.3 m 2 /g, a crystal layer spacing d 002 of 0.3365 nm, a true density of 2.22 g/cm 3 , a tap density of 1.05 g/cm 3 , and a particle size of 1 to 60 μm. The first reversible capacity and the first coulombic efficiency were tested in the same manner as above, and the electrical performance test is shown in Table 8.
对比例4，将天然石墨作为负极材料，按上述方法制备对比例的电池。天然石墨的比表面积6.3m2/g，晶体层间距d002为0.3358nm，真实密度2.23g/cm3，振实密度1.14g/cm3，粒度1.1～58μm。按上述相同的方法，测试首次可逆容量和首次库仑效率，电性能测试见表8。Comparative Example 4, using natural graphite as a negative electrode material, a battery of the comparative example was prepared as described above. The natural graphite has a specific surface area of 6.3 m 2 /g, a crystal layer spacing d 002 of 0.3358 nm, a true density of 2.23 g/cm 3 , a tap density of 1.14 g/cm 3 and a particle size of 1.1 to 58 μm. The first reversible capacity and the first coulombic efficiency were tested in the same manner as above, and the electrical performance test is shown in Table 8.
表1实施例1～13配方Table 1 Example 1 to 13 formula
实施例 Example 热塑性树脂及比例 Thermoplastic resin and ratio 固化剂及比例 Curing agent and ratio 掺杂物及比例 Doping and proportion 包覆物及比例 Wrap and ratio
1 1 环氧树脂45% Epoxy resin 45% 聚酰胺树脂50% Polyamide resin 50% 磷酸钠5% Sodium phosphate 5% 沥青6% Asphalt 6%
2 2 酚醛树脂30% Phenolic resin 30% 间苯二胺55% M-phenylenediamine 55% 氢氧化锡15% Tin hydroxide 15% 乙基甲基碳酸酯EMC8% Ethyl methyl carbonate EMC 8%
3 3 丙烯酸树脂25% Acrylic resin 25% 苯胺甲醛树脂 65% Aniline formaldehyde resin 65% 硼酸10% Boric acid 10% 环氧树脂11% Epoxy resin 11%
4 4 聚甲醛50% POM 50% 邻苯二甲酸酐42% Phthalic anhydride 42% 有机硅树脂8% Silicone resin 8% 聚吡咯15% Polypyrrole 15%
5 5 酚醛树脂59% Phenolic resin 59% 聚甲醛35% POM 35% 五氧化二磷6% Phosphorus pentoxide 6% 聚噻吩10% Polythiophene 10%
6 6 聚碳酸酯70% Polycarbonate 70% 己二胺20% Hexamethylenediamine 20% 锡粉10% Tin powder 10% 聚环氧丙烷4% Polypropylene oxide 4%
7 7 聚氯乙烯树脂85% Polyvinyl chloride resin 85% 苯磺酸10% Benzenesulfonic acid 10% 磷酸铵5% Ammonium phosphate 5% 聚乙炔6% Polyacetylene 6%
8 8 丙烯酸树脂100% Acrylic resin 100% 聚丁二酸乙二醇酯10% Polybutylene succinate 10%
9 9 聚碳酸酯85% Polycarbonate 85% 氯化锡15% Tin chloride 15% 聚偏氟乙烯8% Polyvinylidene fluoride 8%
10 10 聚氯乙烯树脂25% Polyvinyl chloride resin 25% 间苯二胺75% M-phenylenediamine 75% 聚苯乙烯2% Polystyrene 2%
11 11 环氧树脂40% Epoxy resin 40% 己二胺60% Hexamethylenediamine 60% 聚对苯7% Polyparaphenylene 7%
12 12 丙烯酸树脂55% Acrylic resin 55% 苯磺酸45% Benzenesulfonic acid 45% 聚对苯撑乙烯10% Polyparaphenylene vinyl 10%
13 13 酚醛树脂75% Phenolic resin 75% 邻苯二甲酸酐25% Phthalic anhydride 25% 聚癸二酸乙二醇6% Polyethylene glycol diacetate 6%
表2实施例1～13制备工艺 Table 2 Preparation Process of Examples 1 to 13
实施例Example 一、 固化 First, curing 二、低温预烧Second, low temperature pre-burning 三、粉碎后平均粒度Third, the average particle size after crushing 四、掺杂Fourth, doping 五、热解温度、时间、氮气流量5. Pyrolysis temperature, time, nitrogen flow 六、粉碎 后平均粒度 Sixth, the average particle size after crushing 七、包覆工艺Seven, coating process
11 3h3h 升温速度0.26℃/min，400℃低温预烧，6.5h，氮气流量为0.2m3/h。The heating rate was 0.26 ° C / min, 400 ° C low temperature pre-burning, 6.5 h, nitrogen flow rate was 0.2 m 3 / h. 25μm25μm 3000r/min，35min 3000r/min, 35min 升温速度5℃/min，1100℃热解2.2h，氮气流量0.2m3/hHeating rate 5 ° C / min, 1100 ° C pyrolysis 2.2 h, nitrogen flow 0.2 m 3 / h 16μm16μm 1500r/min转速，混合50min， 3℃/min的升温速度，1200℃ 处理2h，氮气流量为0.2m3/h。1500r/min rotation speed, mixing 50min, 3°C/min heating rate, 1200°C treatment for 2h, nitrogen flow rate is 0.2m 3 /h.
22 4h4h 升温速度0.4℃/min，360℃低温预烧9h，氮气流量为0.23m3/h。The heating rate was 0.4 ° C / min, and the temperature was pre-fired at 360 ° C for 9 h, and the nitrogen flow rate was 0.23 m 3 /h. 22μm22μm 2500r/min，41min 2500r/min, 41min 升温速度3℃/min，1300℃热解1.8h，氮气流量0.30m3/hThe heating rate is 3 °C/min, the pyrolysis is 1400 °C for 1.8 h, and the nitrogen flow rate is 0.30 m 3 /h. 15μm15μm 1800r/min转速，混合45 min， 2℃/min的升温速度到1000℃ ，处理4 h，氮气流量为0.3m3/h。The speed of 1800r/min was mixed for 45 min, the temperature rising rate of 2 °C/min was 1000 °C, the treatment was carried out for 4 h, and the nitrogen flow rate was 0.3 m 3 /h.
33 6h6h 升温速度1.0℃/min，300℃低温预烧10h，氮气流量为0.25m3/h。The heating rate was 1.0 ° C / min, and the temperature was preheated at 300 ° C for 10 h, and the nitrogen flow rate was 0.25 m 3 /h. 27μm27μm 1200r/min，58min1200r/min, 58min 升温速度10℃/min，1500℃热解0.5h，氮气流量0.20m3/h Heating rate 10 ° C / min, 1500 ° C pyrolysis 0.5 h, nitrogen flow 0.20 m 3 / h 13μm13μm 2000r/min转速，混合36min， 0.1℃/min的升温速度到500℃，处理8 h，氮气流量为0.3m3/h。2000 r / min speed, mixing 36min, 0.1 ° C / min temperature increase rate to 500 ° C, 8 h treatment, nitrogen flow rate of 0.3 m 3 / h.
44 10h10h 升温速度3℃/min，250℃低温预烧12.0h，氮气流量为0.18m3/h。The heating rate was 3 ° C / min, the temperature was pre-fired at 250 ° C for 12.0 h, and the nitrogen flow rate was 0.18 m 3 /h. 30μm30μm 1800r/min，40min1800r/min, 40min 升温速度4℃/min，1000℃热解2.0h，氮气流量0.15m3/hHeating rate 4 ° C / min, 1000 ° C pyrolysis 2.0 h, nitrogen flow 0.15 m 3 / h 18μm18μm 1900r/min转速，混合39min， 10℃/min的升温速度到1500℃ ，处理3h，氮气流量为0.4m3/h。The rotation speed of 1900r/min was mixed for 39 minutes, the temperature rising rate of 10 °C/min was 1500 °C, and the treatment was carried out for 3 hours, and the nitrogen flow rate was 0.4 m 3 /h.
55 15h15h 升温速度2℃/min，200℃低温预烧14.5h，氮气流量为0.2 m3/h。The heating rate was 2 ° C / min, the temperature was pre-fired at 200 ° C for 14.5 h, and the nitrogen flow rate was 0.2 m 3 /h. 20μm20μm 2500r/min，26min2500r/min, 26min 升温速度3.5℃/min，800℃热解3.5h，氮气流量0.25m3/hHeating rate 3.5 ° C / min, 800 ° C pyrolysis 3.5 h, nitrogen flow 0.25 m 3 / h 22μm22μm 1400r/min转速，混合38 min，10℃/min的升温速度到1300℃ ，处理2.5 h，氮气流量为0.4m3/h。The speed of 1400r/min was mixed for 38 min, the temperature rising rate of 10 °C/min was 1300 °C, the treatment was 2.5 h, and the nitrogen flow rate was 0.4 m 3 /h.
66 24 h24 h 升温速度0.1℃/min，150℃低温预烧24h，氮气流量0.24m3/h。The heating rate was 0.1 ° C / min, the temperature was preheated at 150 ° C for 24 h, and the nitrogen flow rate was 0.24 m 3 / h. 32μm32μm 2800r/min，37min2800r/min, 37min 升温速度3.0℃/min，950℃热解2.0h，氮气流量0.4m3/hHeating rate 3.0 ° C / min, 950 ° C pyrolysis 2.0 h, nitrogen flow 0.4 m 3 / h 30μm30μm 2000r/min转速，混合37 min， 1.5℃/min的升温速度到800℃ ，处理6 h，氮气流量为0.3 m3/h。The speed was 2000 r/min, mixed for 37 min, and the heating rate was 1.5 ° C/min to 800 ° C. After 6 h of treatment, the nitrogen flow rate was 0.3 m 3 /h.
77 20 h20 h 升温速度3℃/min，350℃低温预烧9.5h，氮气流量0.2 m3/h。The heating rate was 3 ° C / min, the temperature was preheated at 350 ° C for 9.5 h, and the nitrogen flow rate was 0.2 m 3 /h. 28μm28μm 1000r/min，120min1000r/min, 120min 升温速度1.8℃/min，700℃热解2.5h，氮气流量0.4m3/hHeating rate 1.8 ° C / min, 700 ° C pyrolysis 2.5 h, nitrogen flow 0.4 m 3 / h 30μm30μm 2500r/min转速，混合38 min， 7℃/min的升温速度到1200℃ ，处理4 h，氮气流量为0.32 m3/h。2500r/min rotation speed, mixing for 38 min, 7 °C/min heating rate to 1200 °C, treatment for 4 h, nitrogen flow rate of 0.32 m 3 / h.
88 50 h50 h 升温速度3.6℃/min，450℃低温预烧3.0h，氮气流量为0.3 m3/h。The heating rate was 3.6 ° C / min, the temperature was preheated at 450 ° C for 3.0 h, and the nitrogen flow rate was 0.3 m 3 /h. 38μm38μm 升温速度2.7℃/min，650℃热解5.5h，氮气流量0.4m3/hHeating rate 2.7 ° C / min, 650 ° C pyrolysis 5.5 h, nitrogen flow 0.4 m 3 / h 34μm34μm 2300r/min转速，混合37 min，6℃/min的升温速度到1000℃ ，处理3 h，氮气流量为0.35 m3/h。The rotation speed of 2300r/min was mixed for 37 min, the temperature rising rate of 6 °C/min was 1000 °C, the treatment was 3 h, and the nitrogen flow rate was 0.35 m 3 /h.
99 40 h40 h 升温速度2.5℃/min，250℃低温预烧10.5h，氮气流量为0.28 m3/h。The heating rate was 2.5 ° C / min, the temperature was pre-fired at 250 ° C for 10.5 h, and the nitrogen flow rate was 0.28 m 3 /h. 23μm23μm 1300r/min，90min1300r/min, 90min 升温速度4.0℃/min，1100℃热解1.5h，氮气流量0.26m3/hHeating rate 4.0 ° C / min, 1100 ° C pyrolysis 1.5 h, nitrogen flow 0.26 m 3 / h 28μm28μm 3000r/min转速，混合24 min， 1.5℃/min的升温速度到700℃ ，处理5h，氮气流量为0.2 m3/h。3000r/min rotation speed, mixing for 24 min, heating rate of 1.5 °C/min to 700 °C, treatment for 5 h, nitrogen flow rate of 0.2 m 3 /h.
1010 12 h12 h 升温速度0.5℃/min，360℃低温预烧7 h，氮气流量为0.21m3/h。The heating rate was 0.5 ° C / min, and the temperature was preheated at 360 ° C for 7 h, and the nitrogen flow rate was 0.21 m 3 /h. 19μm19μm 3200r/min，30min 3200r/min, 30min 升温速度0.3℃/min，560℃热解7.5h，氮气流量0.4m3/hThe heating rate is 0.3 ° C / min, 560 ° C pyrolysis 7.5 h, nitrogen flow rate 0.4 m 3 / h 26μm26μm 3500r/min转速，混合20 min， 5.0℃/min的升温速度到800℃ ，处理4 h，氮气流量为0.3 m3/h。3500r/min rotation speed, mixing for 20 min, temperature rise rate of 5.0 °C/min to 800 °C, treatment for 4 h, nitrogen flow rate of 0.3 m 3 /h.
1111 20 h20 h 升温速度3.3℃/min，280℃低温预烧10.0h，氮气流量为0.4 m3/h。The heating rate was 3.3 ° C / min, the temperature was pre-fired at 280 ° C for 10.0 h, and the nitrogen flow rate was 0.4 m 3 /h. 32μm32μm 2500r/min，43min 2500r/min, 43min 升温速度8.0℃/min，720℃热解3.5h，氮气流量0.2m3/hHeating rate 8.0 ° C / min, 720 ° C pyrolysis 3.5 h, nitrogen flow rate 0.2 m 3 / h 30μm30μm 2000r/min转速，混合40min， 1.5℃/min的升温速度到650℃ ，处理8 h，氮气流量为0.3 m3/h。2000r/min rotation speed, mixing for 40min, heating rate of 1.5°C/min to 650°C, treatment for 8h, nitrogen flow rate of 0.3 m 3 /h.
1212 12 h12 h 升温速度1.3℃/min，180℃低温预烧15.0h，氮气流量为0.2 m3/h。The heating rate was 1.3 ° C / min, the temperature was pre-fired at 180 ° C for 15.0 h, and the nitrogen flow rate was 0.2 m 3 /h. 17μm17μm 1200r/min，60min1200r/min, 60min 升温速度6.8℃/min，1200℃热解1.5h，氮气流量0.4m3/hHeating rate 6.8 ° C / min, pyrolysis 1.5 h at 1200 ° C, nitrogen flow 0.4 m 3 / h 21μm21μm 1700r/min转速，混合56 min， 1.0℃/min的升温速度到600℃ ，处理6 h，氮气流量为0.25m3/h。The speed of 1700r/min was mixed for 56 min, the heating rate of 1.0 °C/min was increased to 600 °C, and the treatment was carried out for 6 h. The nitrogen flow rate was 0.25 m 3 /h.
1313 8 h8 h 升温速度2℃/min，230℃低温预烧12.5h，氮气流量为0.24m3/h。The heating rate was 2 ° C / min, pre-burned at 230 ° C for 12.5 h, and the nitrogen flow rate was 0.24 m 3 / h. 32μm32μm 1600r/min，49min1600r/min, 49min 升温速度.9℃/min，700℃热解3.8h，氮气流量0.4m3/hHeating rate of 9 ° C / min, 700 ° C pyrolysis 3.8 h, nitrogen flow 0.4 m 3 / h 35μm35μm 2000r/min转速，混合36 min， 7.5℃/min的升温速度到1100℃ ，处理2 h，氮气流量为0.3 m3/h。The speed of 2000r/min was mixed for 36 min, the heating rate of 7.5 °C/min was increased to 1100 °C, and the treatment was carried out for 2 h. The nitrogen flow rate was 0.3 m 3 /h.
表3实施例 1～13物理及化学性能测试结果Table 3 Examples 1 to 13 physical and chemical properties test results
实施例Example 孔径分布nmPore size distribution nm 孔隙率%Porosity% d002 nmd 002 nm 粒度范围 μm Particle size range μm 比表面积 m2/g Specific surface area m 2 /g 真实密度 g/cm3 True density g/cm 3 振实密度g/cm3 Tap density g/cm 3 C元素的含量%% of C element
11 2.2～552.2~55 1717 0.3880.388 1.8～621.8 to 62 18.418.4 1.721.72 1.101.10 95.195.1
22 1.4～411.4 to 41 1616 0.3790.379 0.55～630.55～63 75.375.3 2.352.35 1.431.43 95.595.5
33 0.2～200.2 to 20 99 0.3390.339 0.5～580.5 to 58 58.058.0 2.172.17 1.231.23 97.497.4
44 3.0～593.0 to 59 1515 0.3980.398 2.5～752.5 to 75 13.713.7 1.791.79 1.171.17 91.991.9
55 3.0～633.0 to 63 1515 0.4220.422 1.7～731.7-73 13.713.7 1.81.8 1.231.23 92.592.5
66 4.0～1004.0～100 1818 0.4750.475 3.5～743.5～74 10.410.4 1.691.69 1.111.11 90.590.5
77 2.1～632.1 to 63 1414 0.3880.388 3.3～653.3 to 65 13.813.8 1.811.81 1.241.24 93.593.5
88 0.2～380.2 to 38 1111 0.3380.338 6.5～756.5-75 6.96.9 1.591.59 1.031.03 96.796.7
99 0.7～460.7 to 46 1212 0.3420.342 2.8～592.8~59 18.618.6 2.282.28 1.341.34 93.393.3
1010 1.6～571.6 to 57 1010 0.3820.382 12～9012 to 90 1.91.9 1.531.53 0.880.88 94.194.1
1111 2.9～672.9 to 67 1717 0.390.39 4.8～674.8 to 67 9.39.3 1.711.71 1.101.10 93.493.4
1212 6.0～946.0～94 1919 0.4310.431 1.1～531.1 to 53 72.472.4 2.312.31 1.381.38 98.898.8
1313 1.1～401.1 to 40 1313 0.3770.377 1.8～571.8 to 57 28.828.8 2.012.01 1.301.30 94.594.5
表4实施例1～13和对比例1～2电性能测试结果Table 4 Examples 1 to 13 and Comparative Examples 1 to 2 Electrical property test results
序号Serial number 首次可逆容量 mAh/g First reversible capacity mAh/g 首充库伦效率 % First charge Coulomb efficiency % 首次可逆容量 mAh/g First reversible capacity mAh/g 首次可逆容量 mAh/g First reversible capacity mAh/g 首次可逆容量 mAh/g First reversible capacity mAh/g
0.2C0.2C 0.2C0.2C 1C1C 30C30C 40C40C
实施例1Example 1 505.6505.6 85.185.1 501.5501.5 486.1486.1 479.5479.5
实施例2Example 2 500.3500.3 81.181.1 487.3487.3 477.6477.6 458.1458.1
实施例3Example 3 578.9578.9 84.384.3 565565 548.1548.1 519.8519.8
实施例4Example 4 530.6530.6 83.983.9 516.9516.9 501.4501.4 485.8485.8
实施例5Example 5 529.4529.4 84.184.1 515.6515.6 495495 484.6484.6
实施例6Example 6 530.6530.6 8686 521521 500.2500.2 474.2474.2
实施例7Example 7 604.5604.5 84.184.1 593593 569.3569.3 557.4557.4
实施例8Example 8 462.4462.4 8080 458.1458.1 439.2439.2 421.2421.2
实施例9Example 9 510.3510.3 81.681.6 503.3503.3 494.6494.6 488.5488.5
实施例10Example 10 462.4462.4 83.883.8 458.1458.1 439.2439.2 421.2421.2
实施例11Example 11 458.3458.3 80.580.5 450.9450.9 437.4437.4 416.6416.6
实施例12Example 12 455.2455.2 79.979.9 449.7449.7 438.9438.9 411411
实施例13Example 13 550.8550.8 8282 541.4541.4 530.2530.2 505.7505.7
对比例1Comparative example 1 320.5320.5 90.390.3 308.7308.7 268.4268.4 257.2257.2
对比例2Comparative example 2 323.5323.5 92.4 92.4 315.6315.6 273.6273.6 263.8263.8
表5实施例14～21配方 Table 5 Formulations 14 to 21
实施例 Example 植物原料g Plant material g 掺杂物及占 植物原料 比例 Doping and proportion of plant materials 包覆物及占 植物原料 比例 Wrap and proportion of plant materials
14 14 花粉90g Pollen 90g 磷酸铵10% Ammonium phosphate 10% 酚醛树脂10% Phenolic resin 10%
15 15 稻谷壳85g Rice husk 85g 硅粉15% Silicon powder 15% 沥青6% Asphalt 6%
16 16 核桃壳70g Walnut shell 70g 氯化锡30% Tin chloride 30% 羧甲基纤维素13% Carboxymethyl cellulose 13%
17 17 酒糟100g Distiller's grains 100g 环氧树脂20% Epoxy resin 20%
18 18 甘蔗杆100g Sugar cane rod 100g 聚吡咯11% Polypyrrole 11%
19 19 核桃壳 40g 和竹子 20g Walnut shell 40g and bamboo 20g 硼酸40% Boric acid 40% 聚乙炔14% Polyacetylene 14%
20 20 酒糟 40g 和木屑 55g Distiller's grains 40g and sawdust 55g 有机硅树脂5% Silicone resin 5% 聚乙烯醇25% Polyvinyl alcohol 25%
21 twenty one 20g 甘蔗杆和60g稻谷壳 20g sugar cane pole and 60g rice husk 碳酸钴20% Cobalt carbonate 20% 聚酰亚胺9% Polyimide 9%
表6实施例14～21制备工艺
实施例 原料粒度 除杂 洗涤 烘干 掺杂 低温预烧 粉碎后平均粒度 掺杂 热解 粉碎 后平均粒度 包覆工艺
14采用方法二 100μm 80ml氢氟酸，转速1000r/min，时间6min 浸泡50h pH 6.7，转速1000r/min，时间20min 温度80℃，40h 2000r/min，68min 升温速度10℃/min， 480℃低温预烧3h，氮气流量为0.23 m3/h。 20μm 升温速度5℃/min，1000℃热解4h，氮气流量0.23m3/h 21μm 1000r/min转速，混合40min， 0.1℃/min的升温速度，400℃ 热解处理24h，氮气流量为0.15m3/h。
15采用方法二 63μm 130ml盐酸转速1100r/min，时间4min ,浸泡40h pH 5.2，转速1200r/min，时间15min 温度100℃，30h 3000r/min，35min 升温速度0.38℃/min， 400℃低温预烧7h，真空度为0.01MPa 25μm 升温速度6℃/min，1100℃热解1.5h，氮气流量0.21m3/h 25μm 1800r/min转速，混合34 min，5 ℃/min的升温速度到1000℃ ，热解处理3h，氮气流量为0.3m3/h。
16采用方法三 41μm 90ml浓硫酸转速900r/min，时间6min ,浸泡15h pH 5.1，转速800r/min，时间30min 温度120℃，24h 升温速度0.25℃/min，500℃低温预烧6h，氮气流量为0.25 m3/h。 30μm 1000r/min， 95min 升温速度10℃/min，1300℃热解1h，氮气流量0.40m3/h 30μm 2000r/min转速，混合30min， 6.5℃/min的升温速度到1100℃，热解处理2.5h，氮气流量为0.3m3/h。
17采用方法四 96μm 120ml硼酸转速1250r/min，时间4min ,浸泡14h 6.5，转速900r/min，时间25min 温度90℃，36h 升温速度8℃/min，230℃低温预烧20h，氮气流量为0.4 m3/h。 40μm 升温速度1℃/min，800℃热解4.5h，氮气流量0.18m3/h 26μm 3000r/min转速，混合24min， 0.3℃/min的升温速度到550℃，热解处理20h，氮气流量为0.4m3/h。
18采用方法四 72μm 110ml氢氧化钠转速1300r/min，时间3min ,浸泡钾溶液18h pH 8.4，转速1400r/min，时间8min 温度110℃，27h 升温速度2℃/min，300℃低温预烧10h，氮气流量为0.2 m3/h。 18μm 升温速度4.5℃/min， 950℃热解3h，氮气流量0.21m3/h 40μm 4500r/min转速，混合10min，1℃/min的升温速度到700℃，热解处理12h，真空度为0.03MPa。
19采用方法三 50μm 100ml盐酸转速800r/min，时间7min ,浸泡45 h pH 5.8，转速1250r/min，时间6min 温度140℃，10h 升温速度0.1℃/min，350℃低温预烧18h，氮气流量0.16 m3/h。 34μm 3500r/min，20min 升温速度5.0℃/min， 1200℃热解2h，氮气流量0.35m3/h 34μm 2500r/min转速，混合26 min， 3.5℃/min的升温速度到800℃，热解处理9h，氮气流量为0.3 m3/h。
20采用方法二 66μm 100ml硝酸转速1400r/min，时间3min ,浸泡6 h pH 5.5，转速1250r/min，时间6min 温度130℃，20h 2800r/min，50min 升温速度1.5℃/min，250℃低温预烧8h，氮气流量0.2 1m3/h。 26μm 升温速度0.1℃/min，500℃热解10h，真空度为0.02MPa 35μm 2500r/min转速，混合38 min， 10℃/min的升温速度到1300℃，热解处理1h，氮气流量为0.32 m3/h。
21采用方法一 300ml氢氧化钙采用方法二转速3000r/min，时间2min ,浸泡15h pH 5.5，转速950r/min，时间10min 温度120℃，36h 升温速度0.4℃/min，200℃低温预烧14h，氮气流量0.2 3m3/h。 20μm 3000r/min，60min 升温速度2.5℃/min，1150℃热解10h，氮气流量0.26m3/h 20μm 4500r/min转速，混合2 min，1.0℃/min的升温速度到600℃，热解处理3h，氮气流量为0.18 m3/h。
Table 6 Preparation Process of Examples 14-21
Example Material size Miscellaneous washing drying Doping Low temperature burn-in Average particle size after crushing Doping Pyrolysis Average particle size after crushing Coating process
14 adopt method two 100μm 80ml hydrofluoric acid, speed 1000r/min, time 6min soak for 50h pH 6.7, speed 1000r/min, time 20min Temperature 80 ° C, 40h 2000r/min, 68min The heating rate was 10 ° C / min, 480 ° C low temperature pre-burning 3 h, nitrogen flow rate was 0.23 m 3 / h. 20μm Heating rate 5 ° C / min, 1000 ° C pyrolysis 4 h, nitrogen flow 0.23 m 3 / h 21μm 1000 r/min rotation speed, mixing for 40 min, heating rate of 0.1 ° C / min, pyrolysis treatment at 400 ° C for 24 h, nitrogen flow rate of 0.15 m 3 / h.
15 adopts method two 63μm 130ml hydrochloric acid speed 1100r/min, time 4min, soak for 40h pH 5.2, speed 1200r/min, time 15min Temperature 100 ° C, 30 h 3000r/min, 35min The heating rate is 0.38 ° C / min, 400 ° C low temperature pre-burning for 7 h, the vacuum is 0.01 MPa 25μm Temperature rise rate of 6 ℃ / min, pyrolyzed 1.5h 1100 ℃, nitrogen flow rate of 0.21m 3 / h 25μm The speed of 1800r/min was mixed for 34 min, the temperature rising rate of 5 °C/min was 1000 °C, the pyrolysis treatment was 3 h, and the nitrogen flow rate was 0.3 m 3 /h.
16 adopts method three 41μm 90ml concentrated sulfuric acid speed 900r/min, time 6min, soak for 15h pH 5.1, speed 800r/min, time 30min Temperature 120 ° C, 24h The heating rate was 0.25 ° C / min, and the temperature was preheated at 500 ° C for 6 h, and the nitrogen flow rate was 0.25 m 3 /h. 30μm 1000r/min, 95min The heating rate is 10 °C/min, pyrolysis at 1300 °C for 1 h, and the nitrogen flow rate is 0.40 m 3 /h. 30μm 2000 r / min speed, mixing for 30 min, 6.5 ° C / min heating rate to 1100 ° C, pyrolysis treatment 2.5 h, nitrogen flow rate of 0.3 m 3 / h.
17 adopt method four 96μm 120ml boric acid rotation speed 1250r/min, time 4min, soaking for 14h 6.5, speed 900r/min, time 25min Temperature 90 ° C, 36 h The heating rate was 8 ° C / min, and the temperature was preheated at 230 ° C for 20 h, and the nitrogen flow rate was 0.4 m 3 /h. 40μm Heating rate 1°C/min, 800°C pyrolysis 4.5h, nitrogen flow 0.18m 3 /h 26μm 3000r/min rotation speed, mixing for 24min, heating rate of 0.3°C/min to 550°C, pyrolysis treatment for 20h, nitrogen flow rate of 0.4m 3 /h.
18 adopt method four 72μm 110ml sodium hydroxide rotation speed 1300r/min, time 3min, soaking potassium solution for 18h pH 8.4, speed 1400r/min, time 8min Temperature 110 ° C, 27 h The heating rate was 2 ° C / min, and the temperature was preheated at 300 ° C for 10 h, and the nitrogen flow rate was 0.2 m 3 /h. 18μm The heating rate is 4.5°C/min, the pyrolysis is 950°C for 3h, and the nitrogen flow rate is 0.21m 3 /h. 40μm The speed was 4500 r/min, mixed for 10 min, the temperature rising rate of 1 ° C/min was 700 ° C, pyrolysis treatment was 12 h, and the vacuum degree was 0.03 MPa.
19 adopts method three 50μm 100ml hydrochloric acid speed 800r/min, time 7min, soak for 45h pH 5.8, speed 1250r/min, time 6min Temperature 140 ° C, 10h Temperature rise rate of 0.1 ℃ / min, 350 ℃ low temperature calcined 18h, the nitrogen flow 0.16 m 3 / h. 34μm 3500r/min, 20min Heating rate 5.0 ° C / min, pyrolysis 2 h at 1200 ° C, nitrogen flow 0.35 m 3 / h 34μm 2500r/min rotation speed, mixing for 26 min, 3.5 ° C / min heating rate to 800 ° C, pyrolysis treatment 9 h, nitrogen flow rate of 0.3 m 3 / h.
20 adopts method two 66μm 100ml nitric acid speed 1400r/min, time 3min, soak 6h pH 5.5, speed 1250r/min, time 6min Temperature 130 ° C, 20h 2800r/min, 50min The heating rate was 1.5 ° C / min, calcined at 250 ° C for 8 h, and the nitrogen flow rate was 0.2 1 m 3 / h. 26μm The heating rate is 0.1 °C/min, the pyrolysis is 500 °C for 10 h, and the vacuum is 0.02 MPa. 35μm 2500r/min rotation speed, mixing for 38 min, temperature rise rate of 10 °C/min to 1300 °C, pyrolysis treatment for 1 h, nitrogen flow rate of 0.32 m 3 /h.
21 adopt method one 300ml calcium hydroxide adopts method two rotation speed 3000r/min, time 2min, soaking for 15h pH 5.5, speed 950r/min, time 10min Temperature 120 ° C, 36 h The heating rate was 0.4 ° C / min, the temperature was preheated at 200 ° C for 14 h, and the nitrogen flow rate was 0.2 3 m 3 / h. 20μm 3000r/min, 60min Heating rate 2.5 ° C / min, 1150 ° C pyrolysis 10 h, nitrogen flow 0.26 m 3 / h 20μm The speed of 4500r/min was mixed for 2 min, the heating rate of 1.0 °C/min was increased to 600 °C, the pyrolysis treatment was carried out for 3 h, and the nitrogen flow rate was 0.18 m 3 /h.
表7实施例14～21物理及化学性能测试结果 Table 7 Examples 14 to 21 physical and chemical properties test results
实施例Example 孔径分布nmPore size distribution nm 孔隙率%Porosity% d002 nmd 002 nm 粒度范围 μm Particle size range μm 比表面积 m2/g Specific surface area m 2 /g 真实密度 g/cm3 True density g/cm 3 振实密度g/cm3 Tap density g/cm 3 C元素的含量%% of C element
1414 0.5～400.5 to 40 1212 0.3900.390 3.5～583.5～58 8.58.5 2.082.08 1.321.32 94.994.9
1515 1.0～371.0 to 37 1515 0.3820.382 4.1～604.1 to 60 15.315.3 1．651.65 1.271.27 95.895.8
1616 0.2～300.2 to 30 99 0.3430.343 3.6～573.6~57 7.57.5 2.252.25 1.451.45 96.496.4
1717 3.0～483.0 to 48 1313 0.4480.448 4.5～704.5～70 18.718.7 1.971.97 1.041.04 94.594.5
1818 2.0～452.0 to 45 1010 0.3920.392 3.7～483.7~48 17.717.7 2.222.22 1.181.18 95.195.1
1919 4.0～604.0 to 60 1616 0.4550.455 4.4～684.4~68 20.020.0 1.551.55 0.910.91 96.596.5
2020 1.6～501.6 to 50 1111 0.3370.337 3.9～553.9~55 15.815.8 2.122.12 1.231.23 95.495.4
21twenty one 2.6～552.6~55 1414 0.4050.405 3.8～653.8-65 16.416.4 1.851.85 1.011.01 96.896.8
表8实施例14～21和对比例3～4电性能测试结果
序号 首次可逆容量 mAh/g 首充库伦效率 % 首次可逆容量 mAh/g 首次可逆容量 mAh/g 首次可逆容量 mAh/g
0.2C 0.2C 1C 30C 40C
实施例14 493.5 84.5 489.9 474.8 466.9
实施例15 556.0 81.3 545.0 524.2 501.4
实施例16 590.0 82.8 579.0 561.3 548.5
实施例17 450.3 83.8 438.3 424.6 411.5
实施例18 510.2 84.1 499.8 489.8 469.8
实施例19 530.5 86.2 520.0 504.4 483.6
实施例20 602.6 84.2 591.4 567.7 549.2
实施例21 520.1 83.3 508.9 493.3 475.6
对比例3 362.1 90.2 351.9 313.4 301.2
对比例4 361.5 91.8 351.4 314.6 303.8
Table 8 Examples 14 to 21 and Comparative Examples 3 to 4 Electrical Property Test Results
Serial number First reversible capacity mAh/g First charge Coulomb efficiency% First reversible capacity mAh/g First reversible capacity mAh/g First reversible capacity mAh/g
0.2C 0.2C 1C 30C 40C
Example 14 493.5 84.5 489.9 474.8 466.9
Example 15 556.0 81.3 545.0 524.2 501.4
Example 16 590.0 82.8 579.0 561.3 548.5
Example 17 450.3 83.8 438.3 424.6 411.5
Example 18 510.2 84.1 499.8 489.8 469.8
Example 19 530.5 86.2 520.0 504.4 483.6
Example 20 602.6 84.2 591.4 567.7 549.2
Example 21 520.1 83.3 508.9 493.3 475.6
Comparative example 3 362.1 90.2 351.9 313.4 301.2
Comparative example 4 361.5 91.8 351.4 314.6 303.8

Claims (17)

  1. 一种锂离子电池复合硬碳负极材料，其特征在于：所述锂离子电池复合硬碳负极材料的硬碳基体外包覆有包覆物，所述包覆物的前躯体为有机物环氧树脂、酚醛树脂、羧甲基纤维素、沥青、乙基甲基碳酸酯、聚乙烯醇、聚苯乙烯、聚甲基丙烯酸甲酯、聚四氟乙烯、聚偏氟乙烯、聚丙烯腈、丁苯橡胶、聚氯乙烯、聚乙烯、聚环氧乙烷、聚环氧丙烷、聚丁二酸乙二醇酯、聚癸二酸乙二醇、聚乙二醇亚胺、聚乙炔、聚对苯、聚苯胺、聚吡咯、聚并苯、聚间苯二胺、聚噬吩、聚对苯撑乙烯、聚噻吩、聚丙烯晴、聚酰亚胺和聚苯硫醚的一种以上，热解形成包覆物。 A lithium-ion battery composite hard carbon anode material, characterized in that: the hard carbon substrate of the lithium ion battery composite hard carbon anode material is coated with a coating, and the precursor of the coating is an organic epoxy resin , phenolic resin, carboxymethyl cellulose, asphalt, ethyl methyl carbonate, polyvinyl alcohol, polystyrene, polymethyl methacrylate, polytetrafluoroethylene, polyvinylidene fluoride, polyacrylonitrile, butylbenzene Rubber, polyvinyl chloride, polyethylene, polyethylene oxide, polypropylene oxide, polyethylene succinate, polyethylene sebacate, polyethylene glycol imine, polyacetylene, polyparaphenyl , more than one of polyaniline, polypyrrole, polyacene, poly-m-phenylenediamine, poly-phasic, poly-p-phenylene vinyl, polythiophene, polypropylene, polyimide, and polyphenylene sulfide, pyrolysis A wrap is formed.
  2. 根据权利要求1所述的锂离子电池复合硬碳负极材料，其特征在于：所述硬碳基体前驱物为热塑性树脂丙烯酸树脂、聚氯乙烯、聚碳酸酯、环氧树脂、酚醛树脂和聚甲醛的一种以上，热解形成硬碳基体；包覆物前躯体质量为硬碳基体前驱物质量的1～15%；所述锂离子电池复合硬碳负极材料形状为块状细小颗粒，具有多孔结构，孔径为0.2～100nm，孔隙率为9～19%，002晶面的层间距在0.338～0.475nm之间，粒度范围为0.5～90μm，比表面积为1.9～75.3m2/g，真实密度为1.54～2.35g/cm3，振实密度为0.88～1.43 g/cm3，其炭C元素的含量不少于90.5%。The lithium ion battery composite hard carbon anode material according to claim 1, wherein the hard carbon matrix precursor is a thermoplastic resin acrylic resin, polyvinyl chloride, polycarbonate, epoxy resin, phenolic resin, and polyoxymethylene. More than one type, pyrolysis forms a hard carbon matrix; the precursor mass of the coating is 1 to 15% of the mass of the hard carbon matrix precursor; the lithium ion battery composite hard carbon anode material is in the form of massive particles having a porous shape The structure has a pore diameter of 0.2 to 100 nm, a porosity of 9 to 19%, a layer spacing of 002 crystal faces of 0.338 to 0.475 nm, a particle size range of 0.5 to 90 μm, a specific surface area of 1.9 to 75.3 m 2 /g, and a true density. It is 1.54 to 2.35 g/cm 3 , and the tap density is 0.88 to 1.43 g/cm 3 , and the content of the carbon C element is not less than 90.5%.
  3. 根据权利要求2所述的锂离子电池复合硬碳负极材料，其特征在于：所述硬碳基体前驱物包括以下质量比：25%至小于100%的热塑性树脂，大于0至小于等于75%的固化剂，热解形成硬碳基体；所述固化剂为己二胺、间苯二胺、苯胺甲醛树脂、聚酰胺树脂、邻苯二甲酸酐和苯磺酸的一种以上。The lithium ion battery composite hard carbon anode material according to claim 2, wherein the hard carbon matrix precursor comprises a thermoplastic resin having a mass ratio of 25% to less than 100%, and more than 0 to 75% or less. The curing agent is pyrolyzed to form a hard carbon matrix; the curing agent is one or more of hexamethylenediamine, m-phenylenediamine, aniline formaldehyde resin, polyamide resin, phthalic anhydride, and benzenesulfonic acid.
  4. 根据权利要求3所述的锂离子电池复合硬碳负极材料，其特征在于：所述硬碳基体前驱物由以下质量比组成：25%至小于100%的热塑性树脂，大于0至小于等于75%的固化剂，大于0至小于等于15%的掺杂物，热解形成硬碳基体；所述掺杂物是金属单质、非金属单质、金属化合物和非金属化合物的一种以上；所述金属单质为铜、铅、锑、锡、钴和镍的一种以上；所述金属化合物为氧化锡，氧化钴、氧化镍、磷酸钠、磷酸二氢钠、乙酸锡、氯化锡、碳酸钴、氢氧化铜、氢氧化钴、氢氧化锡和氢氧化镍的一种以上；所述非金属单质为硅、硫和硼的一种以上；所述非金属化合物为二氧化硅、五氧化二磷、硼酸、硅酸、磷酸、磷酸二氢铵、磷酸铵、硫酸铵、有机硅树脂和乙二醇硼酸酯的一种以上。The lithium ion battery composite hard carbon anode material according to claim 3, wherein the hard carbon matrix precursor is composed of the following mass ratio: 25% to less than 100% of a thermoplastic resin, and more than 0 to 75% or less. a curing agent, a dopant greater than 0 to 15% or less, pyrolyzed to form a hard carbon matrix; the dopant is one or more of a simple substance of a metal, a simple substance of a metal, a metal compound, and a non-metal compound; The elemental substance is more than one of copper, lead, antimony, tin, cobalt and nickel; the metal compound is tin oxide, cobalt oxide, nickel oxide, sodium phosphate, sodium dihydrogen phosphate, tin acetate, tin chloride, cobalt carbonate, One or more of copper hydroxide, cobalt hydroxide, tin hydroxide and nickel hydroxide; the non-metal element is one or more of silicon, sulfur and boron; the non-metal compound is silicon dioxide, phosphorus pentoxide And one or more of boric acid, silicic acid, phosphoric acid, ammonium dihydrogen phosphate, ammonium phosphate, ammonium sulfate, silicone resin, and ethylene glycol borate.
  5. 根据权利要求2所述的锂离子电池复合硬碳负极材料，其特征在于：所述硬碳基体前驱物由以下质量比组成：85%至小于100%的热塑性树脂，大于0至小于等于15%的掺杂物，热解形成硬碳基体；所述掺杂物是金属单质、非金属单质、金属化合物和非金属化合物的一种以上；所述金属单质为铜、铅、锑、锡、钴和镍的一种以上；所述金属化合物为氧化锡，氧化钴、氧化镍、磷酸钠、磷酸二氢钠、乙酸锡、氯化锡、碳酸钴、氢氧化铜、氢氧化钴、氢氧化锡和氢氧化镍的一种以上；所述非金属单质为硅、硫和硼的一种以上；所述非金属化合物为二氧化硅、五氧化二磷、硼酸、硅酸、磷酸、磷酸二氢铵、磷酸铵、硫酸铵、有机硅树脂和乙二醇硼酸酯的一种以上。The lithium ion battery composite hard carbon anode material according to claim 2, wherein the hard carbon matrix precursor is composed of the following mass ratio: 85% to less than 100% of a thermoplastic resin, and more than 0 to less than or equal to 15%. The dopant is pyrolyzed to form a hard carbon matrix; the dopant is one or more of a simple substance of a metal, a simple substance of a non-metal, a metal compound, and a non-metal compound; the metal element is copper, lead, antimony, tin, cobalt And one or more of nickel; the metal compound is tin oxide, cobalt oxide, nickel oxide, sodium phosphate, sodium dihydrogen phosphate, tin acetate, tin chloride, cobalt carbonate, copper hydroxide, cobalt hydroxide, tin hydroxide And one or more of nickel hydroxide; the non-metal element is one or more of silicon, sulfur and boron; and the non-metal compound is silicon dioxide, phosphorus pentoxide, boric acid, silicic acid, phosphoric acid, dihydrogen phosphate One or more of ammonium, ammonium phosphate, ammonium sulfate, silicone resin, and ethylene glycol borate.
  6. 根据权利要求1所述的锂离子电池复合硬碳负极材料，其特征在于：所述硬碳基体前驱物为植物原料花粉、稻谷壳、甘蔗杆、核桃壳、竹子、酒糟和木屑的一种以上，热解形成硬碳基体，包覆物前躯体质量为硬碳基体前驱物质量的1～25%；所述硬碳基体表面与包覆物之间依靠化学键或范德华力相结合，硬碳基体粒度为2～60μm，表面具有蜂窝开孔结构，孔径为1.0～55nm；形状为块状和/或片状的颗粒，其粒径为3.5～70μm，其比表面积在7.5～20m2/g之间，材料表面具有蜂窝状开孔结构，孔径为0.5～50nm，孔隙率为9～16%，002晶面的层间距d002值在0.337～0.455nm之间，真实密度为1.55～2.25g/cm3，振实密度为0.91～1.45g/cm3，其C元素的含量不少于94%。The lithium ion battery composite hard carbon anode material according to claim 1, wherein the hard carbon matrix precursor is one or more of plant material pollen, rice husk, sugar cane rod, walnut shell, bamboo, distiller's grains and wood chips. , pyrolysis forms a hard carbon matrix, the precursor mass of the coating is 1 to 25% of the mass of the hard carbon matrix precursor; the surface of the hard carbon substrate and the coating are combined by a chemical bond or van der Waals force, and the hard carbon matrix The particle size is 2 to 60 μm, the surface has a honeycomb open-cell structure, the pore diameter is 1.0-55 nm, and the shape is a block and/or a sheet-like particle having a particle diameter of 3.5 to 70 μm and a specific surface area of 7.5 to 20 m 2 /g. The surface of the material has a honeycomb open-cell structure with a pore size of 0.5 to 50 nm and a porosity of 9 to 16%. The layer spacing d 002 of the 002 crystal plane is between 0.337 and 0.455 nm, and the true density is 1.55 to 2.25 g/ Cm 3 , the tap density is 0.91 to 1.45 g/cm 3 , and the content of the C element is not less than 94%.
  7. 根据权利要求6所述的锂离子电池复合硬碳负极材料，其特征在于：所述硬碳基体前驱物由以下质量比组成：植物原料、占植物类原料大于0至小于等于40%的掺杂物混合组成，热解形成硬碳基体；所述掺杂物为金属氧化物氧化锡、氧化钴和氧化镍的一种以上，或金属盐磷酸钠、氯化锡、碳酸钴和磷酸二氢钠的一种以上，或金属碱氢氧化铜、氢氧化钴、氢氧化锡和氢氧化镍的一种以上，或非金属氧化物二氧化硅和/或五氧化二磷，或硼酸、硅酸和磷酸的一种以上，或非金属盐磷酸二氢铵、磷酸铵和硫酸铵的一种以上，或金属单质铜、铅、锑、锡、钴和镍的一种以上，或非金属单质硅、硫和硼的一种以上。The lithium ion battery composite hard carbon anode material according to claim 6, wherein the hard carbon matrix precursor is composed of the following mass ratio: plant material, and plant material having a doping ratio of more than 0 to 40% or less. Mixing composition, pyrolysis to form a hard carbon matrix; the dopant is more than one of metal oxide tin oxide, cobalt oxide and nickel oxide, or metal salt sodium phosphate, tin chloride, cobalt carbonate and sodium dihydrogen phosphate One or more, or one or more of metal alkali hydroxides, cobalt hydroxide, tin hydroxide, and nickel hydroxide, or non-metal oxide silica and/or phosphorus pentoxide, or boric acid, silicic acid, and One or more kinds of phosphoric acid, or one or more of the non-metal salts ammonium dihydrogen phosphate, ammonium phosphate, and ammonium sulfate, or one or more of the metal elements copper, lead, antimony, tin, cobalt, and nickel, or non-metal elemental silicon, More than one of sulfur and boron.
  8. 一种锂离子电池复合硬碳负极材料的制备方法，包括以下步骤：一、将热塑性树脂在空气中、常温下固化3～50 h，得到固态前躯体；二、氮气流量为0.1～0.4m3/h，将前躯体以0.1～3℃/min的升温速度到1500C～4500C，低温预烧2～24h，自然降温至室温，进行粉碎，得到粒度为1～60μm的粉末状；三、氮气流量为0.1～0.4m3/h，以0.3～10℃/min的升温速度到560～15000C，热解0.5～7.5h，自然降温至室温,制得硬碳；四、将硬碳进行球磨或粉碎，得到粒度为1～60μm的硬碳基体；五、在硬碳基体中按硬碳基体前驱物质量的1～15%，加入包覆物的前躯体，以1400～3500r/min的转速混合20～50min，然后氮气流量为0.1～0.4m3/h，以1～7.5℃/min的升温速度到500～15000C，时间为2～8h，进行包覆物热解处理，自然降温至室温,得到锂离子电池复合硬碳负极材料；所述热塑性树脂为丙烯酸树脂、聚氯乙烯、聚碳酸酯、环氧树脂、酚醛树脂和聚甲醛的一种以上；所述包覆物的前躯体为有机物环氧树脂、酚醛树脂、羧甲基纤维素、沥青、乙基甲基碳酸酯、聚乙烯醇、聚苯乙烯、聚甲基丙烯酸甲酯、聚四氟乙烯、聚偏氟乙烯、聚丙烯腈、丁苯橡胶、聚氯乙烯、聚乙烯、聚环氧乙烷、聚环氧丙烷、聚丁二酸乙二醇酯、聚癸二酸乙二醇、聚乙二醇亚胺、聚乙炔、聚对苯、聚苯胺、聚吡咯、聚并苯、聚间苯二胺、聚噬吩、聚对苯撑乙烯、聚噻吩、聚丙烯晴、聚酰亚胺和聚苯硫醚的一种以上。A method for preparing a composite hard carbon anode material for a lithium ion battery comprises the following steps: 1. curing a thermoplastic resin in air at room temperature for 3 to 50 hours to obtain a solid precursor; and second, a nitrogen flow rate of 0.1 to 0.4 m 3 /h, the precursor body is heated to a temperature of 1500C to 4500C at a temperature of 0.1 to 3 ° C / min, preheated at a low temperature for 2 to 24 hours, naturally cooled to room temperature, and pulverized to obtain a powder having a particle size of 1 to 60 μm; 0.1 to 0.4 m 3 /h, at a temperature increase rate of 0.3 to 10 ° C / min to 560 ~ 15000 C, pyrolysis 0.5 ~ 7.5 h, natural cooling to room temperature, to obtain hard carbon; Fourth, the hard carbon ball milling or crushing A hard carbon matrix having a particle size of 1 to 60 μm is obtained; 5. 1 to 15% of the mass of the hard carbon matrix precursor is added to the hard carbon matrix, and the precursor of the coating is added to mix at a speed of 1400 to 3500 r/min. ~50min, then the nitrogen flow rate is 0.1 ~ 0.4m 3 / h, the temperature increase rate of 1 ~ 7.5 ° C / min to 500 ~ 15000C, time is 2 ~ 8h, the coating pyrolysis treatment, naturally cool to room temperature, get Lithium ion battery composite hard carbon anode material; the thermoplastic resin is acrylic resin, poly More than one of ethylene, polycarbonate, epoxy resin, phenolic resin and polyoxymethylene; the precursor of the coating is organic epoxy resin, phenolic resin, carboxymethyl cellulose, asphalt, ethyl methyl carbonate Ester, polyvinyl alcohol, polystyrene, polymethyl methacrylate, polytetrafluoroethylene, polyvinylidene fluoride, polyacrylonitrile, styrene butadiene rubber, polyvinyl chloride, polyethylene, polyethylene oxide, polycyclic Oxypropane, polyethylene succinate, polyethylene sebacate, polyethylene glycol imine, polyacetylene, polyparaphenylene, polyaniline, polypyrrole, polyacene, poly(m-phenylenediamine), More than one of polyphaphene, polyparaphenylene vinylene, polythiophene, polypropylene fine, polyimide, and polyphenylene sulfide.
  9. 根据权利要求8所述的锂离子电池复合硬碳负极材料的制备方法，其特征在于：所述固化按质量比在25%至小于100%的热塑性树脂中添加大于0至小于等于75%的固化剂，搅拌均匀，在空气中、常温下固化3～50h，得到固态前躯体；所述固化剂为己二胺、间苯二胺、苯胺甲醛树脂、聚酰胺树脂、邻苯二甲酸酐和苯磺酸的一种以上。The method for preparing a lithium ion battery composite hard carbon anode material according to claim 8, wherein the curing is performed by adding a curing ratio of more than 0 to 75% or less in a thermoplastic resin having a mass ratio of 25% to less than 100%. The agent is stirred evenly and cured in air at room temperature for 3 to 50 hours to obtain a solid precursor; the curing agent is hexamethylenediamine, m-phenylenediamine, aniline formaldehyde resin, polyamide resin, phthalic anhydride and benzene. More than one type of sulfonic acid.
  10. 根据权利要求9所述的锂离子电池复合硬碳负极材料的制备方法，其特征在于：所述低温预烧并进行粉碎后，在粉末状内按质量比大于0至小于等于15%的比例，加入掺杂物，转速为1000～3000r/min，时间为26～120min；所述掺杂物是金属单质、非金属单质、金属化合物和非金属化合物的一种以上；所述金属单质为铜、铅、锑、锡、钴和镍的一种以上；所述金属化合物为氧化锡，氧化钴、氧化镍、磷酸钠、磷酸二氢钠、乙酸锡、氯化锡、碳酸钴、氢氧化铜、氢氧化钴、氢氧化锡和氢氧化镍的一种以上；所述非金属单质为硅、硫和硼的一种以上；所述非金属化合物为二氧化硅、五氧化二磷、硼酸、硅酸、磷酸、磷酸二氢铵、磷酸铵、硫酸铵、有机硅树脂和乙二醇硼酸酯的一种以上。The method for preparing a lithium ion battery composite hard carbon anode material according to claim 9, wherein the low temperature is pre-fired and pulverized, and the mass ratio in the powder is greater than 0 to 15% or less. Adding a dopant, the rotation speed is 1000-3000r/min, and the time is 26-120min; the dopant is more than one element of a simple metal, a non-metal element, a metal compound and a non-metal compound; the metal element is copper, More than one of lead, antimony, tin, cobalt and nickel; the metal compound is tin oxide, cobalt oxide, nickel oxide, sodium phosphate, sodium dihydrogen phosphate, tin acetate, tin chloride, cobalt carbonate, copper hydroxide, One or more kinds of cobalt hydroxide, tin hydroxide and nickel hydroxide; the non-metal element is one or more of silicon, sulfur and boron; the non-metal compound is silicon dioxide, phosphorus pentoxide, boric acid, silicon One or more of acid, phosphoric acid, ammonium dihydrogen phosphate, ammonium phosphate, ammonium sulfate, silicone resin, and ethylene glycol borate.
  11. 根据权利要求9所述的锂离子电池复合硬碳负极材料的制备方法，其特征在于：所述固化按质量比，在25%至小于100%的热塑性树脂中，添加大于0至小于等于75%的固化剂，大于0至小于等于15%的掺杂物，混合搅拌，转速为2000～4500r/min，时间为10～120min，在空气中、常温下固化3～50h，得到前躯体；所述掺杂物是金属单质、非金属单质、金属化合物和非金属化合物的一种以上；所述金属单质为铜、铅、锑、锡、钴和镍的一种以上；所述金属化合物为氧化锡，氧化钴、氧化镍、磷酸钠、磷酸二氢钠、乙酸锡、氯化锡、碳酸钴、氢氧化铜、氢氧化钴、氢氧化锡和氢氧化镍的一种以上；所述非金属单质为硅、硫和硼的一种以上；所述非金属化合物为二氧化硅、五氧化二磷、硼酸、硅酸、磷酸、磷酸二氢铵、磷酸铵、硫酸铵、有机硅树脂和乙二醇硼酸酯的一种以上。The method for preparing a lithium ion battery composite hard carbon anode material according to claim 9, wherein the curing is added in a ratio of from 2% to less than or equal to 75% by weight in the thermoplastic resin of 25% to less than 100% by mass. The curing agent, more than 0 to less than or equal to 15% of the dopant, mixing and stirring, the rotation speed is 2000 ~ 4500 r / min, the time is 10 ~ 120min, solidified in air, normal temperature for 3 ~ 50h, to obtain the precursor; The dopant is one or more of a simple metal, a non-metal element, a metal compound, and a non-metal compound; the metal element is one or more of copper, lead, antimony, tin, cobalt, and nickel; and the metal compound is tin oxide. , one or more of cobalt oxide, nickel oxide, sodium phosphate, sodium dihydrogen phosphate, tin acetate, tin chloride, cobalt carbonate, copper hydroxide, cobalt hydroxide, tin hydroxide and nickel hydroxide; the non-metal element It is one or more of silicon, sulfur and boron; the non-metal compound is silicon dioxide, phosphorus pentoxide, boric acid, silicic acid, phosphoric acid, ammonium dihydrogen phosphate, ammonium phosphate, ammonium sulfate, silicone resin and ethylene More than one type of alcohol borate
  12. 根据权利要求9所述的锂离子电池复合硬碳负极材料的制备方法，其特征在于：所述低温预烧后，按质量比大于0至小于等于15%的比例，加入掺杂物，转速为1000～3000r/min，时间为26～120min；所述掺杂物是金属单质、非金属单质、金属化合物和非金属化合物的一种以上；所述金属单质为铜、铅、锑、锡、钴和镍的一种以上；所述金属化合物为氧化锡，氧化钴、氧化镍、磷酸钠、磷酸二氢钠、乙酸锡、氯化锡、碳酸钴、氢氧化铜、氢氧化钴、氢氧化锡和氢氧化镍的一种以上；所述非金属单质为硅、硫和硼的一种以上；所述非金属化合物非为二氧化硅、五氧化二磷、硼酸、硅酸、磷酸、磷酸二氢铵、磷酸铵、硫酸铵、有机硅树脂和乙二醇硼酸酯的一种以上。The method for preparing a lithium ion battery composite hard carbon anode material according to claim 9, wherein after the low temperature calcination, the dopant is added at a mass ratio of greater than 0 to 15% or less, and the rotation speed is 1000~3000r/min, time is 26-120min; the dopant is more than one element of metal element, non-metal element, metal compound and non-metal compound; the metal element is copper, lead, antimony, tin, cobalt And one or more of nickel; the metal compound is tin oxide, cobalt oxide, nickel oxide, sodium phosphate, sodium dihydrogen phosphate, tin acetate, tin chloride, cobalt carbonate, copper hydroxide, cobalt hydroxide, tin hydroxide And one or more of nickel hydroxide; the non-metal element is more than one of silicon, sulfur and boron; the non-metal compound is not silicon dioxide, phosphorus pentoxide, boric acid, silicic acid, phosphoric acid, phosphoric acid One or more of ammonium hydrogen phosphate, ammonium phosphate, ammonium sulfate, silicone resin, and ethylene glycol borate.
  13. 一种锂离子电池复合硬碳负极材料的制备方法，包括以下步骤：一、按质量比将85%至小于100%的热塑性树脂，大于0至小于等于15%的掺杂物，混合搅拌，转速为2000～4500r/min，时间为10～120min，在空气中、常温下固化1～6h，得到固态前躯体；二、氮气流量为0.1～0.4m3/h，将前躯体以0.1～7℃/min的升温速度到1500C～4500C，低温预烧3～24 h，自然降温至室温；三、氮气流量为0.1～0.4m3/h，以0.3～10℃/min的升温速度到560～15000C，热解0.5～7.5h，自然降温至室温,制得硬碳；四、将硬碳进行球磨或粉碎，得到粒度为1～60μm的硬碳基体；五、在硬碳基体中按硬碳基体前驱物质量的1～15%，加入包覆物的前躯体，以1400～3500r/min的转速混合20～50min，然后氮气流量为0.1～0.4m3/h，以1～7.5℃/min的升温速度到500～15000C，时间为2～8h，进行包覆物热解处理，自然降温至室温,得到锂离子电池复合硬碳负极材料；所述热塑性树脂为丙烯酸树脂、聚氯乙烯、聚碳酸酯、环氧树脂、酚醛树脂和聚甲醛的一种以上；所述掺杂物是金属单质、非金属单质、金属化合物和非金属化合物的一种以上；所述金属单质为铜、铅、锑、锡、钴和镍的一种以上；所述金属化合物为氧化锡，氧化钴、氧化镍、磷酸钠、磷酸二氢钠、乙酸锡、氯化锡、碳酸钴、氢氧化铜、氢氧化钴、氢氧化锡和氢氧化镍的一种以上；所述非金属单质为硅、硫和硼的一种以上；所述非金属化合物非为二氧化硅、五氧化二磷、硼酸、硅酸、磷酸、磷酸二氢铵、磷酸铵、硫酸铵、有机硅树脂和乙二醇硼酸酯的一种以上；所述包覆物的前躯体为有机物环氧树脂、酚醛树脂、羧甲基纤维素、沥青、乙基甲基碳酸酯、聚乙烯醇、聚苯乙烯、聚甲基丙烯酸甲酯、聚四氟乙烯、聚偏氟乙烯、聚丙烯腈、丁苯橡胶、聚氯乙烯、聚乙烯、聚环氧乙烷、聚环氧丙烷、聚丁二酸乙二醇酯、聚癸二酸乙二醇、聚乙二醇亚胺、聚乙炔、聚对苯、聚苯胺、聚吡咯、聚并苯、聚间苯二胺、聚噬吩、聚对苯撑乙烯、聚噻吩、聚丙烯晴、聚酰亚胺和聚苯硫醚的一种以上。A method for preparing a composite hard carbon anode material for a lithium ion battery comprises the following steps: 1. a thermoplastic resin having a mass ratio of 85% to less than 100%, a dopant greater than 0 to 15% or less, mixing and stirring, and a rotation speed is 2000 ~ 4500r / min, the time is 10 ~ 120min, in air, at room temperature curing 1 ~ 6h, to obtain a solid body before; two nitrogen flow rate of 0.1 ~ 0.4m 3 / h, the precursor to 0.1 ~ 7 ℃ /min heating rate to 1500C ~ 4500C, low temperature pre-burning for 3 ~ 24h, natural cooling to room temperature; three, nitrogen flow rate of 0.1 ~ 0.4m 3 / h, with a temperature increase of 0.3 ~ 10 ° C / min to 560 ~ 15000C , pyrolysis 0.5 ~ 7.5h, natural cooling to room temperature, to produce hard carbon; Fourth, the hard carbon ball milling or pulverization, to obtain a hard carbon matrix with a particle size of 1 ~ 60μm; five, in the hard carbon matrix by hard carbon matrix 1 to 15% of the mass of the precursor, added to the precursor of the coating, mixed at 1400 ~ 3500r / min for 20 ~ 50min, then nitrogen flow rate of 0.1 ~ 0.4m 3 / h, 1 ~ 7.5 ° C / min The heating rate is up to 500～15000C, the time is 2～8h, the coating is pyrolyzed, and the temperature is naturally cooled to room temperature to obtain lithium. a sub-cell composite hard carbon anode material; the thermoplastic resin is one or more of an acrylic resin, a polyvinyl chloride, a polycarbonate, an epoxy resin, a phenol resin, and a polyoxymethylene; the dopant is a simple substance of a metal, a non-metal element And one or more of a metal compound and a non-metal compound; the metal element is one or more of copper, lead, antimony, tin, cobalt, and nickel; and the metal compound is tin oxide, cobalt oxide, nickel oxide, sodium phosphate, One or more kinds of sodium dihydrogen phosphate, tin acetate, tin chloride, cobalt carbonate, copper hydroxide, cobalt hydroxide, tin hydroxide and nickel hydroxide; the non-metal element is one or more of silicon, sulfur and boron The non-metallic compound is not more than one of silica, phosphorus pentoxide, boric acid, silicic acid, phosphoric acid, ammonium dihydrogen phosphate, ammonium phosphate, ammonium sulfate, silicone resin, and ethylene glycol borate; The precursor of the coating is organic epoxy resin, phenolic resin, carboxymethyl cellulose, asphalt, ethyl methyl carbonate, polyvinyl alcohol, polystyrene, polymethyl methacrylate, polytetrafluoroethylene. Ethylene, polyvinylidene fluoride , polyacrylonitrile, styrene butadiene rubber, polyvinyl chloride, polyethylene, polyethylene oxide, polypropylene oxide, polyethylene succinate, polyethylene sebacate, polyethylene glycol imine , polyacetylene, polyparaphenylene, polyaniline, polypyrrole, polyacene, poly-m-phenylenediamine, poly-phasic, poly-p-phenylene vinyl, polythiophene, polypropylene, polyimide and polyphenylene sulfide More than one.
  14. 一种锂离子电池复合硬碳负极材料的制备方法，包括以下步骤：一、按每100克干植物原料加入80～300ml酸或碱，浸泡3～50h；所述植物原料为花粉、稻谷壳、甘蔗杆、核桃壳、竹子、酒糟和木屑的一种以上，所述酸为氢氟酸、硼酸、硫酸、盐酸或硝酸，碱为氢氧化钾、氢氧化钙或氢氧化钠；二、洗涤，用纯水洗涤，转速800～1400r/min，时间8～30min；三、除水烘干，在80～140℃条件下烘干10～40h，自然降温至室温；四、低温预烧，在真空度0.03MPa以下，或者在保护性气体氦气、氮气、氩气、氙气或氮气下进行，流量为0.1～0.4m3/h，以0.1～10℃/min的升温速度到200～500℃，低温预烧3～20 h，在炉内自然降温至室温；五、粉碎，得到粒度为1～60μm的粉末；六、在真空度0.03MPa以下，或者在保护性气体氦气、氮气、氩气、氙气或氮气下进行，流量为0.1～0.4m3/h，以0.1～10℃/min的升温速度到500～1300℃，热解1～10h，炉内自然降温至室温；七、粉碎或球磨，得到粒度为2～65μm的硬碳基体；八、按硬碳基体前驱物质量的1～25%，在硬碳基体中加入包覆物的前躯体，以1000～4500r/min的转速，混合2～40min，然后在真空度0.03MPa以下，或者在保护性气体氦气、氮气、氩气、氙气或氮气下进行，流量为0.1～0.4m3/h，以0.1～10℃/min的升温速度到400～1300℃，时间为1～24h，进行热解处理，在炉内自然降温至室温；所述包覆物的前躯体为有机物环氧树脂、酚醛树脂、羧甲基纤维素、沥青、乙基甲基碳酸酯、聚乙烯醇、聚苯乙烯、聚甲基丙烯酸甲酯、聚四氟乙烯、聚偏氟乙烯、聚丙烯腈、丁苯橡胶、聚氯乙烯、聚乙烯、聚环氧乙烷、聚环氧丙烷、聚丁二酸乙二醇酯、聚癸二酸乙二醇、聚乙二醇亚胺、聚乙炔、聚对苯、聚苯胺、聚吡咯、聚并苯、聚间苯二胺、聚噬吩、聚对苯撑乙烯、聚噻吩、聚丙烯晴、聚酰亚胺和聚苯硫醚的一种以上；九、过200目筛，得到粒度为3.5～70μm的锂离子电池复合硬碳负极材料。A method for preparing a composite hard carbon anode material for a lithium ion battery comprises the following steps: 1. adding 80 to 300 ml of acid or alkali per 100 g of dry plant material, soaking for 3 to 50 hours; the plant material is pollen, rice husk, More than one kind of sugar cane rod, walnut shell, bamboo, distiller's grains and wood chips, the acid is hydrofluoric acid, boric acid, sulfuric acid, hydrochloric acid or nitric acid, the alkali is potassium hydroxide, calcium hydroxide or sodium hydroxide; second, washing, Wash with pure water, speed 800 ~ 1400r / min, time 8 ~ 30min; Third, remove water, dry at 80 ~ 140 ° C for 10 ~ 40h, naturally cool to room temperature; Fourth, low temperature pre-burn, in vacuum Degree 0.03MPa or less, or under protective gas helium, nitrogen, argon, helium or nitrogen, the flow rate is 0.1 ~ 0.4m3 / h, the temperature increase rate of 0.1 ~ 10 ° C / min to 200 ~ 500 ° C, low temperature Pre-burning for 3 to 20 h, naturally cooling to room temperature in the furnace; 5. Grinding to obtain a powder with a particle size of 1 to 60 μm; 6. Under a vacuum of 0.03 MPa, or in a protective gas, helium, nitrogen, argon, It is carried out under helium or nitrogen at a flow rate of 0.1 to 0.4 m 3 /h to 0.1 to 10 °C / min heating rate to 500 ~ 1300 ° C, pyrolysis 1 ~ 10h, the furnace naturally cools to room temperature; seven, pulverization or ball milling, to obtain a hard carbon matrix with a particle size of 2 ~ 65μm; eight, according to the hard carbon matrix precursor 1 to 25% of the mass, the precursor of the coating is added to the hard carbon matrix, mixed at a speed of 1000 to 4500 r/min, mixed for 2 to 40 minutes, then at a vacuum of 0.03 MPa or less, or in a protective gas, helium, Under nitrogen, argon, helium or nitrogen, the flow rate is 0.1-0.4 m 3 /h, at a temperature increase rate of 0.1-10 ° C / min to 400-1300 ° C, the time is 1-24 h, pyrolysis treatment, in the furnace Naturally cooled to room temperature; the precursor of the coating is organic epoxy resin, phenolic resin, carboxymethyl cellulose, asphalt, ethyl methyl carbonate, polyvinyl alcohol, polystyrene, polymethacrylic acid Methyl ester, polytetrafluoroethylene, polyvinylidene fluoride, polyacrylonitrile, styrene butadiene rubber, polyvinyl chloride, polyethylene, polyethylene oxide, polypropylene oxide, polyethylene glycol succinate, polyfluorene Diacid glycol, polyethylene glycol imine, polyacetylene, polyparaphenylene, polyaniline, polypyrrole, polycondensation , more than one of poly-m-phenylenediamine, poly-p-phene, poly-p-phenylene vinyl, polythiophene, polypropylene, polyimide and polyphenylene sulfide; nine, over 200 mesh sieve, the particle size is 3.5 ~ 70μm lithium ion battery composite hard carbon anode material.
  15. 根据权利要求14所述的锂离子电池复合硬碳负极材料的制备方法，其特征在于：所述按每100克干植物原料加入80～300ml酸或碱，浸泡3～50h前，将前躯物干植物原料机械粉碎或气流粉碎，得到粒度为40～100μm的粉末；所述低温预烧粉碎后，按占粉末状质量大于0小于等于40%的比例，加入掺杂物，转速为1000～4500r/min，时间为20～95min；所述掺杂物为金属氧化物氧化锡、氧化钴和氧化镍的一种以上，或金属盐磷酸钠、氯化锡、碳酸钴和磷酸二氢钠的一种以上，或金属碱氢氧化铜、氢氧化钴、氢氧化锡和氢氧化镍的一种以上，或非金属氧化物二氧化硅和/或五氧化二磷，或硼酸、硅酸和磷酸的一种以上，或非金属盐磷酸二氢铵、磷酸铵和硫酸铵的一种以上，或有机硅树脂和/或乙二醇硼酸酯，或金属单质铜、铅、锑、锡、钴和镍的一种以上，或非金属单质硅、硫和硼的一种以上。The method for preparing a lithium ion battery composite hard carbon anode material according to claim 14, wherein the precursor is added by adding 80 to 300 ml of acid or alkali per 100 g of dry plant material, and soaking for 3 to 50 hours. The dry plant material is mechanically pulverized or air-jet pulverized to obtain a powder having a particle size of 40 to 100 μm; after the low-temperature pre-compression pulverization, the dopant is added at a ratio of the powder-like mass of more than 0 to 40%, and the rotation speed is 1000 to 4500 rpm. /min, time is 20-95 min; the dopant is one or more of metal oxides such as tin oxide, cobalt oxide and nickel oxide, or one of metal salt sodium phosphate, tin chloride, cobalt carbonate and sodium dihydrogen phosphate More than one kind, or one or more of metal alkali copper hydroxide, cobalt hydroxide, tin hydroxide and nickel hydroxide, or non-metal oxide silica and/or phosphorus pentoxide, or boric acid, silicic acid and phosphoric acid More than one, or a non-metal salt of ammonium dihydrogen phosphate, ammonium phosphate, and ammonium sulfate, or a silicone resin and/or ethylene glycol borate, or a metal elemental copper, lead, antimony, tin, cobalt, and More than one type of nickel, or non-metal elemental silicon, sulfur One of boron above.
  16. 根据权利要求14所述的锂离子电池复合硬碳负极材料的制备方法，其特征在于：所述按每100克干植物原料加入80～300ml酸或碱，转速为1000～3000r/min，时间为3～30min，然后浸泡3～50h；所述低温预烧粉碎后，按占粉末状质量大于0小于等于40%的比例，加入掺杂物，转速为1000～4500r/min，时间为20～95min；所述掺杂物为金属氧化物氧化锡、氧化钴和氧化镍的一种以上，或金属盐磷酸钠、氯化锡、碳酸钴和磷酸二氢钠的一种以上，或金属碱氢氧化铜、氢氧化钴、氢氧化锡和氢氧化镍的一种以上，或非金属氧化物二氧化硅和/或五氧化二磷，或硼酸、硅酸和磷酸的一种以上，或非金属盐磷酸二氢铵、磷酸铵和硫酸铵的一种以上，或有机硅树脂和/或乙二醇硼酸酯，或金属单质铜、铅、锑、锡、钴和镍的一种以上，或非金属单质硅、硫和硼的一种以上。The method for preparing a lithium ion battery composite hard carbon anode material according to claim 14, wherein the amount of the acid or alkali is 80 to 300 ml per 100 g of dry plant material, and the rotation speed is 1000 to 3000 r/min. 3~30min, then immersed for 3~50h; after the low-temperature pre-compression pulverization, the dopant is added at a ratio of powder-like mass greater than 0 or less than or equal to 40%, and the rotation speed is 1000~4500r/min, and the time is 20-95min. The dopant is one or more of the metal oxides such as tin oxide, cobalt oxide and nickel oxide, or one or more of the metal salt sodium phosphate, tin chloride, cobalt carbonate and sodium dihydrogen phosphate, or metal alkali hydroxide More than one of copper, cobalt hydroxide, tin hydroxide and nickel hydroxide, or non-metal oxide silica and/or phosphorus pentoxide, or one or more of boric acid, silicic acid and phosphoric acid, or a non-metal salt One or more of ammonium dihydrogen phosphate, ammonium phosphate, and ammonium sulfate, or one or more of silicone resin and/or ethylene glycol borate, or metal elemental copper, lead, antimony, tin, cobalt, and nickel. One or more of metal elemental silicon, sulfur and boron.
  17. 根据权利要求14所述的锂离子电池复合硬碳负极材料的制备方法，其特征在于：所述按每100克干植物原料加入80～300ml酸或碱，浸泡3～50h前，将前躯物干植物原料机械粉碎或气流粉碎，得到粒度为40～100μm的粉末；所述低温预烧前，按占粉末状质量大于0小于等于40%的比例，加入掺杂物，转速为1000～4500r/min，时间为20～95min；所述掺杂物为金属氧化物氧化锡、氧化钴和氧化镍的一种以上，或金属盐磷酸钠、氯化锡、碳酸钴和磷酸二氢钠的一种以上，或金属碱氢氧化铜、氢氧化钴、氢氧化锡和氢氧化镍的一种以上，或非金属氧化物二氧化硅和/或五氧化二磷，或硼酸、硅酸和磷酸的一种以上，或非金属盐磷酸二氢铵、磷酸铵和硫酸铵的一种以上，或金属单质铜、铅、锑、锡、钴和镍的一种以上，或非金属单质硅、硫和硼的一种以上。The method for preparing a lithium ion battery composite hard carbon anode material according to claim 14, wherein the precursor is added by adding 80 to 300 ml of acid or alkali per 100 g of dry plant material, and soaking for 3 to 50 hours. The dry plant material is mechanically pulverized or air-jet pulverized to obtain a powder having a particle size of 40 to 100 μm; before the low-temperature calcination, the dopant is added at a ratio of the powdery mass of more than 0 to 40%, and the rotation speed is 1000 to 4500 r/ Min, the time is 20-95 min; the dopant is more than one of metal oxide tin oxide, cobalt oxide and nickel oxide, or a metal salt of sodium phosphate, tin chloride, cobalt carbonate and sodium dihydrogen phosphate Above, or one or more of metal alkali hydroxide, cobalt hydroxide, tin hydroxide and nickel hydroxide, or non-metal oxide silica and/or phosphorus pentoxide, or one of boric acid, silicic acid and phosphoric acid More than or more than one or more of the non-metal salts of ammonium dihydrogen phosphate, ammonium phosphate and ammonium sulfate, or one or more of the metal elements copper, lead, antimony, tin, cobalt and nickel, or non-metal elemental silicon, sulfur and boron More than one.
PCT/CN2010/077329 2010-06-18 2010-09-26 Composite hard carbon material of negative electrode for lithium ion battery and method for preparing the same WO2011157013A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
KR1020127033140A KR20130030769A (en) 2010-06-18 2010-09-26 Composite hard carbon material of negative electrode for lithium ion battery and method for preparing the same
JP2013514526A JP5680191B2 (en) 2010-06-18 2010-09-26 Composite hard carbon negative electrode material for lithium ion battery and manufacturing method thereof

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CN2010102037680A CN101887966B (en) 2010-06-18 2010-06-18 Preparation method of composite hard carbon cathode material of lithium ion battery
CN201010203768.0 2010-06-18
CN201010246305.2 2010-08-05
CN2010102463052A CN101916845B (en) 2010-08-05 2010-08-05 Hard carbon material for power and energy-storage battery and preparation method thereof

Publications (1)

Publication Number Publication Date
WO2011157013A1 true WO2011157013A1 (en) 2011-12-22

Family

ID=45347655

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2010/077329 WO2011157013A1 (en) 2010-06-18 2010-09-26 Composite hard carbon material of negative electrode for lithium ion battery and method for preparing the same

Country Status (3)

Country Link
JP (1) JP5680191B2 (en)
KR (1) KR20130030769A (en)
WO (1) WO2011157013A1 (en)

Cited By (44)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014034857A1 (en) * 2012-08-30 2014-03-06 株式会社クレハ Carbon material for nonaqueous electrolyte secondary battery and method for manufacturing same, and negative electrode using carbon material and nonaqueous electrolyte secondary battery
JP2014044899A (en) * 2012-08-28 2014-03-13 Toyota Industries Corp Negative electrode material for nonaqueous electrolyte secondary battery, method for producing the same, negative electrode for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery
WO2014038491A1 (en) * 2012-09-06 2014-03-13 株式会社クレハ Carbonaceous material for negative electrodes of nonaqueous electrolyte secondary batteries, and method for producing same
WO2014038492A1 (en) * 2012-09-06 2014-03-13 株式会社クレハ Carbonaceous material for negative electrode of nonaqueous-electrolyte secondary battery, process for producing same, and negative electrode and nonaqueous-electrolyte secondary battery obtained using said carbonaceous material
WO2014038494A1 (en) * 2012-09-06 2014-03-13 株式会社クレハ Material for negative electrode of non-aqueous electrolyte secondary battery
JP2014203828A (en) * 2013-04-03 2014-10-27 深▲セン▼市貝特瑞新能源材料股▲ふん▼有限公司 Graphite negative electrode material for lithium ion battery and method for producing the same
CN105940536A (en) * 2013-10-21 2016-09-14 株式会社可乐丽 Carbonaceous material for negative electrodes of nonaqueous electrolyte secondary batteries
JPWO2014128814A1 (en) * 2013-02-22 2017-02-02 株式会社豊田自動織機 NEGATIVE ELECTRODE ACTIVE MATERIAL, ITS MANUFACTURING METHOD, AND POWER STORAGE DEVICE
CN108598476A (en) * 2018-03-11 2018-09-28 贵州格瑞特新材料有限公司 A kind of negative electrode of lithium ion battery high first spherical hard carbon material of effect and preparation method thereof
CN110289418A (en) * 2013-06-12 2019-09-27 14族科技公司 High capacity hard carbon material comprising efficiency enhancers
CN110476280A (en) * 2017-03-24 2019-11-19 日产自动车株式会社 Anode for nonaqueous electrolyte secondary battery and the non-aqueous electrolyte secondary battery for having used the cathode
US10504635B2 (en) 2013-02-19 2019-12-10 Kuraray Co., Ltd. Carbonaceous material for nonaqueous electrolyte secondary battery negative electrode
CN112645300A (en) * 2019-11-07 2021-04-13 上海杉杉科技有限公司 Hard carbon negative electrode material, lithium ion battery and preparation method and application thereof
CN113003559A (en) * 2021-02-06 2021-06-22 常德速碳新能源科技有限公司 Preparation method of carbon negative electrode material for lithium ion battery
CN113258047A (en) * 2021-04-29 2021-08-13 湖南九华碳素高科有限公司 Lithium ion battery cathode material and preparation method and application method thereof
CN113871574A (en) * 2021-09-24 2021-12-31 远景动力技术(江苏)有限公司 Lithium ion battery negative plate and preparation method and application thereof
CN113889625A (en) * 2021-09-28 2022-01-04 上海普澜特夫精细化工有限公司 Modified hard carbon composite material and preparation method and application thereof
CN113880068A (en) * 2021-09-29 2022-01-04 蜂巢能源科技有限公司 Hard carbon composite material and preparation method and application thereof
CN114180551A (en) * 2021-12-03 2022-03-15 广东凯金新能源科技股份有限公司 Continuous processing preparation method for lithium ion hard carbon negative electrode material
CN114212770A (en) * 2021-12-29 2022-03-22 上海杉杉科技有限公司 Modified hard carbon material, preparation method thereof, electrode and application
CN114335531A (en) * 2021-12-13 2022-04-12 湖南大学 Sulfur-doped hard carbon material and preparation method and application thereof
CN114512646A (en) * 2022-01-24 2022-05-17 西南大学 Amorphous carbon material with multilayer gradient microstructure and preparation method and application thereof
US11355755B2 (en) 2015-10-30 2022-06-07 Kuraray Co., Ltd. Carbonaceous material for non-aqueous electrolyte secondary battery, negative electrode for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte
CN114804065A (en) * 2022-03-25 2022-07-29 中南大学 Hard carbon based on alpha-type cellulose material and preparation method and application thereof
CN114843480A (en) * 2022-05-23 2022-08-02 常州烯源谷新材料科技有限公司 Silicon-phosphorus co-doped hard carbon composite material and preparation method and application thereof
US11437621B2 (en) 2015-08-28 2022-09-06 Group14 Technologies, Inc. Materials with extremely durable intercalation of lithium and manufacturing methods thereof
CN115072703A (en) * 2022-08-02 2022-09-20 洛阳月星新能源科技有限公司 Composite negative electrode material and preparation method and application thereof
CN115159497A (en) * 2022-07-15 2022-10-11 山东大学 Hard carbon negative electrode material of sodium ion battery and preparation method and application thereof
CN115259132A (en) * 2022-07-29 2022-11-01 华南理工大学 Preparation method and application of ultrahigh first-effect hard carbon negative electrode material
US11495793B2 (en) 2013-03-14 2022-11-08 Group14 Technologies, Inc. Composite carbon materials comprising lithium alloying electrochemical modifiers
US11492262B2 (en) 2020-08-18 2022-11-08 Group14Technologies, Inc. Silicon carbon composites comprising ultra low Z
CN115321514A (en) * 2022-08-29 2022-11-11 惠州亿纬锂能股份有限公司 Hard carbon material and preparation method and application thereof
CN115626630A (en) * 2022-11-08 2023-01-20 湘潭大学 Biomass carbon negative electrode material for sodium ion battery and preparation method and application thereof
US11611070B2 (en) 2020-08-18 2023-03-21 Group14 Technologies, Inc. Highly efficient manufacturing of silicon-carbon composites materials comprising ultra low Z
US11611073B2 (en) 2015-08-14 2023-03-21 Group14 Technologies, Inc. Composites of porous nano-featured silicon materials and carbon materials
US11611071B2 (en) 2017-03-09 2023-03-21 Group14 Technologies, Inc. Decomposition of silicon-containing precursors on porous scaffold materials
CN115954442A (en) * 2022-10-12 2023-04-11 广东容钠新能源科技有限公司 Polymer film surface modified biomass hard carbon material, preparation method and application
US11639292B2 (en) 2020-08-18 2023-05-02 Group14 Technologies, Inc. Particulate composite materials
US20230147558A1 (en) * 2021-11-09 2023-05-11 Microvast Power Systems Co., Ltd. Negative electrode material and method of preparing the same
US11661517B2 (en) 2014-03-14 2023-05-30 Group14 Technologies, Inc. Methods for sol-gel polymerization in absence of solvent and creation of tunable carbon structure from same
US11707728B2 (en) 2013-11-05 2023-07-25 Group14 Technologies, Inc. Carbon-based compositions with highly efficient volumetric gas sorption
US11718701B2 (en) 2012-02-09 2023-08-08 Group14 Technologies, Inc. Preparation of polymeric resins and carbon materials
CN116799219A (en) * 2023-08-25 2023-09-22 浙江华宇钠电新能源科技有限公司 Tin-based oxide nanocrystalline modified hard carbon, sodium ion battery and vehicle
CN116812913A (en) * 2023-08-30 2023-09-29 乌海宝杰新能源材料有限公司 High-reversible-capacity hard carbon negative electrode material and preparation method thereof

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20140140323A (en) * 2013-05-29 2014-12-09 (주)포스코켐텍 Negative electrode active material for rechargeable lithium battery, method for preparing the same and rechargeable lithium battery including the same
JP5894688B2 (en) * 2014-02-28 2016-03-30 株式会社クレハ Non-aqueous electrolyte secondary battery carbonaceous material and manufacturing method thereof, non-aqueous electrolyte secondary battery negative electrode and non-aqueous electrolyte secondary battery
WO2015129200A1 (en) * 2014-02-28 2015-09-03 株式会社クレハ Method for manufacturing carbonaceous material for non-aqueous electrolyte secondary cell
JP5957631B2 (en) * 2014-02-28 2016-07-27 株式会社クレハ Method for producing carbonaceous material for non-aqueous electrolyte secondary battery
KR20160130431A (en) * 2014-03-31 2016-11-11 가부시끼가이샤 구레하 Negative-electrode material for nonaqueous-electrolyte secondary battery, negative-electrode mixture for nonaqueous-electrolyte secondary battery, negative electrode for nonaqueous-electrolyte secondary battery, nonaqueous-electrolyte secondary battery, and vehicle
TWI604655B (en) * 2014-08-08 2017-11-01 Kureha Corp Non-aqueous electrolyte secondary battery negative carbonaceous material
TWI599092B (en) 2014-08-08 2017-09-11 Kureha Corp Non-Aqueous Electrolyte Secondary Battery Negative Carbonaceous Material
TWI565654B (en) 2014-08-08 2017-01-11 Kureha Corp Production method of carbonaceous material for negative electrode of nonaqueous electrolyte secondary battery and carbonaceous material for negative electrode of nonaqueous electrolyte secondary battery
CN104409689A (en) * 2014-11-17 2015-03-11 天津大学 Polypyrrole coated hard carbon cathode material and preparation method thereof
JP6180681B1 (en) * 2015-09-30 2017-08-16 株式会社クレハ Non-aqueous electrolyte secondary battery negative electrode carbonaceous material and method for producing the same
US10720638B2 (en) 2016-10-19 2020-07-21 Tee One Co., Ltd. Carbon-silicon composite material, negative electrode, secondary battery, and carbon-silicon composite material producing method
JP2020004589A (en) * 2018-06-27 2020-01-09 株式会社クラレ Production method of carbonaceous material
KR20240037176A (en) * 2021-07-30 2024-03-21 주식회사 쿠라레 Carbonaceous material, negative electrode for power storage device, power storage device, and method for producing carbonaceous material

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2176452A1 (en) * 1996-05-13 1997-11-14 Qiming Zhong Method for reducing the surface area of carbonaceous powders
WO1997046314A1 (en) * 1996-06-07 1997-12-11 Motorola Inc. Carbon electrode material for electrochemical cells and method of making same
CN1304187A (en) * 1999-12-15 2001-07-18 北京有色金属研究总院 Composite graphite negative electrode material for lithium cell and its preparation method
US6316146B1 (en) * 1998-01-09 2001-11-13 Matsushita Electric Industrial Co., Ltd. Carbon materials for negative electrode of secondary battery and manufacturing process
CN1913200A (en) * 2006-08-22 2007-02-14 深圳市贝特瑞电子材料有限公司 Silicon carbone compound negative polar material of lithium ion battery and its preparation method
US20070122712A1 (en) * 2005-11-30 2007-05-31 Yong-Mook Kang Negative active material for a rechargeable lithium battery, a method of preparing the same, and a rechargeable lithium battery comprising the same

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2844302B2 (en) * 1994-02-18 1999-01-06 日本酸素株式会社 Carbon negative electrode material for lithium secondary battery and method for producing the same
JP2844303B2 (en) * 1994-02-18 1999-01-06 日本酸素株式会社 Lithium secondary battery
JPH07249411A (en) * 1994-03-11 1995-09-26 Osaka Gas Co Ltd Manufacture of negative electrode material for lithium secondary battery and lithium secondary battery
JP3091944B2 (en) * 1994-05-09 2000-09-25 旭有機材工業株式会社 Method for producing carbon particles for negative electrode of lithium ion secondary battery
GB2296125B (en) * 1994-12-16 1998-04-29 Moli Energy Pre-graphitic carbonaceous insertion compounds and use as anodes in rechargeable batteries
EP0758801B1 (en) * 1995-03-06 2003-11-19 Sony Corporation nonaqueous liquid electrolyte secondary cell
JPH09326254A (en) * 1996-06-05 1997-12-16 Mitsui Mining Co Ltd Negative electrode material for lithium ion secondary battery and manufacture therefor
JP3399315B2 (en) * 1997-09-30 2003-04-21 松下電器産業株式会社 Method for producing negative electrode for secondary battery, negative electrode for secondary battery, and secondary battery
KR100315232B1 (en) * 1999-02-24 2001-11-26 김순택 Negative active material for lithium secondary battery and method of preapring the same
JP3466576B2 (en) * 2000-11-14 2003-11-10 三井鉱山株式会社 Composite material for negative electrode of lithium secondary battery and lithium secondary battery
WO2005098998A1 (en) * 2004-03-30 2005-10-20 Kureha Corporation Material for negative electrode of nonaqueous electrolyte secondary battery, process for producing the same, negative electrode and battery
JP2008251445A (en) * 2007-03-30 2008-10-16 Isao Mochida Carbonaceous material for lithium-ion secondary battery anode and its manufacturing method
JP5407196B2 (en) * 2008-06-27 2014-02-05 三菱化学株式会社 Non-aqueous secondary battery composite graphite particles, negative electrode material containing the same, negative electrode and non-aqueous secondary battery
JP2010092845A (en) * 2008-09-10 2010-04-22 Sumitomo Chemical Co Ltd Non-aqueous electrolyte secondary cell

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2176452A1 (en) * 1996-05-13 1997-11-14 Qiming Zhong Method for reducing the surface area of carbonaceous powders
WO1997046314A1 (en) * 1996-06-07 1997-12-11 Motorola Inc. Carbon electrode material for electrochemical cells and method of making same
US6316146B1 (en) * 1998-01-09 2001-11-13 Matsushita Electric Industrial Co., Ltd. Carbon materials for negative electrode of secondary battery and manufacturing process
CN1304187A (en) * 1999-12-15 2001-07-18 北京有色金属研究总院 Composite graphite negative electrode material for lithium cell and its preparation method
US20070122712A1 (en) * 2005-11-30 2007-05-31 Yong-Mook Kang Negative active material for a rechargeable lithium battery, a method of preparing the same, and a rechargeable lithium battery comprising the same
CN1913200A (en) * 2006-08-22 2007-02-14 深圳市贝特瑞电子材料有限公司 Silicon carbone compound negative polar material of lithium ion battery and its preparation method

Cited By (80)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11718701B2 (en) 2012-02-09 2023-08-08 Group14 Technologies, Inc. Preparation of polymeric resins and carbon materials
US11725074B2 (en) 2012-02-09 2023-08-15 Group 14 Technologies, Inc. Preparation of polymeric resins and carbon materials
US11732079B2 (en) 2012-02-09 2023-08-22 Group14 Technologies, Inc. Preparation of polymeric resins and carbon materials
JP2014044899A (en) * 2012-08-28 2014-03-13 Toyota Industries Corp Negative electrode material for nonaqueous electrolyte secondary battery, method for producing the same, negative electrode for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery
KR101553515B1 (en) 2012-08-30 2015-09-15 가부시끼가이샤 구레하 Carbon material for nonaqueous electrolyte secondary battery and method for manufacturing same, and negative electrode using carbon material and nonaqueous electrolyte secondary battery
WO2014034857A1 (en) * 2012-08-30 2014-03-06 株式会社クレハ Carbon material for nonaqueous electrolyte secondary battery and method for manufacturing same, and negative electrode using carbon material and nonaqueous electrolyte secondary battery
JP5619321B2 (en) * 2012-08-30 2014-11-05 株式会社クレハ Non-aqueous electrolyte secondary battery carbonaceous material and method for producing the same, and negative electrode and non-aqueous electrolyte secondary battery using the carbonaceous material
US10573891B2 (en) 2012-08-30 2020-02-25 Kuraray Co., Ltd. Carbon material for nonaqueous electrolyte secondary battery and method for manufacturing same, and negative electrode using carbon material and nonaqueous electrolyte secondary battery
JPWO2014034857A1 (en) * 2012-08-30 2016-08-08 株式会社クレハ Non-aqueous electrolyte secondary battery carbonaceous material and method for producing the same, and negative electrode and non-aqueous electrolyte secondary battery using the carbonaceous material
TWI487181B (en) * 2012-09-06 2015-06-01 Kureha Corp Negative electrode for nonaqueous electrolyte secondary battery
KR20150030731A (en) * 2012-09-06 2015-03-20 가부시끼가이샤 구레하 Carbonaceous material for negative electrode of nonaqueous-electrolyte secondary battery, process for producing same, and negative electrode and nonaqueous-electrolyte secondary battery obtained using said carbonaceous material
KR20150021045A (en) * 2012-09-06 2015-02-27 가부시끼가이샤 구레하 Carbonaceous material for negative electrodes of nonaqueous electrolyte secondary batteries, and method for producing same
CN104428926A (en) * 2012-09-06 2015-03-18 株式会社吴羽 Negative electrode for non-aqueous electrolyte secondary battery
JPWO2014038492A1 (en) * 2012-09-06 2016-08-08 株式会社クレハ Non-aqueous electrolyte secondary battery negative electrode carbonaceous material and method for producing the same, negative electrode and nonaqueous electrolyte secondary battery using the carbonaceous material
CN104412425A (en) * 2012-09-06 2015-03-11 株式会社吴羽 Carbonaceous material for negative electrodes of nonaqueous electrolyte secondary batteries, and method for producing same
JPWO2014038491A1 (en) * 2012-09-06 2016-08-08 株式会社クレハ Non-aqueous electrolyte secondary battery negative electrode carbonaceous material and method for producing the same
JPWO2014038494A1 (en) * 2012-09-06 2016-08-08 株式会社クレハ Nonaqueous electrolyte secondary battery negative electrode material
WO2014038491A1 (en) * 2012-09-06 2014-03-13 株式会社クレハ Carbonaceous material for negative electrodes of nonaqueous electrolyte secondary batteries, and method for producing same
WO2014038494A1 (en) * 2012-09-06 2014-03-13 株式会社クレハ Material for negative electrode of non-aqueous electrolyte secondary battery
KR101665843B1 (en) * 2012-09-06 2016-10-12 가부시끼가이샤 구레하 Carbonaceous material for negative electrodes of nonaqueous electrolyte secondary batteries, and method for producing same
US9537176B2 (en) 2012-09-06 2017-01-03 Kureha Corporation Material for non-aqueous electrolyte secondary battery negative electrode
KR101700048B1 (en) * 2012-09-06 2017-01-26 가부시끼가이샤 구레하 Carbonaceous material for negative electrode of nonaqueous-electrolyte secondary battery, process for producing same, and negative electrode and nonaqueous-electrolyte secondary battery obtained using said carbonaceous material
WO2014038492A1 (en) * 2012-09-06 2014-03-13 株式会社クレハ Carbonaceous material for negative electrode of nonaqueous-electrolyte secondary battery, process for producing same, and negative electrode and nonaqueous-electrolyte secondary battery obtained using said carbonaceous material
US10504635B2 (en) 2013-02-19 2019-12-10 Kuraray Co., Ltd. Carbonaceous material for nonaqueous electrolyte secondary battery negative electrode
JPWO2014128814A1 (en) * 2013-02-22 2017-02-02 株式会社豊田自動織機 NEGATIVE ELECTRODE ACTIVE MATERIAL, ITS MANUFACTURING METHOD, AND POWER STORAGE DEVICE
US10230100B2 (en) 2013-02-22 2019-03-12 Kabushiki Kaisha Toyota Jidoshokki Negative-electrode active material, production process for the same and electric storage apparatus
US11495793B2 (en) 2013-03-14 2022-11-08 Group14 Technologies, Inc. Composite carbon materials comprising lithium alloying electrochemical modifiers
JP2014203828A (en) * 2013-04-03 2014-10-27 深▲セン▼市貝特瑞新能源材料股▲ふん▼有限公司 Graphite negative electrode material for lithium ion battery and method for producing the same
CN110289418A (en) * 2013-06-12 2019-09-27 14族科技公司 High capacity hard carbon material comprising efficiency enhancers
US20160268590A1 (en) * 2013-10-21 2016-09-15 Kuraray Co., Ltd. Carbonaceous material for negative electrodes of nonaqueous electrolyte secondary batteries
CN105940536A (en) * 2013-10-21 2016-09-14 株式会社可乐丽 Carbonaceous material for negative electrodes of nonaqueous electrolyte secondary batteries
US10381637B2 (en) * 2013-10-21 2019-08-13 Kuraray Co., Ltd. Carbonaceous material for negative electrodes of nonaqueous electrolyte secondary batteries
CN105940536B (en) * 2013-10-21 2019-03-15 株式会社可乐丽 Non-aqueous electrolyte secondary cell negative electrode carbonaceous material
US11707728B2 (en) 2013-11-05 2023-07-25 Group14 Technologies, Inc. Carbon-based compositions with highly efficient volumetric gas sorption
US11661517B2 (en) 2014-03-14 2023-05-30 Group14 Technologies, Inc. Methods for sol-gel polymerization in absence of solvent and creation of tunable carbon structure from same
US11611073B2 (en) 2015-08-14 2023-03-21 Group14 Technologies, Inc. Composites of porous nano-featured silicon materials and carbon materials
US11646419B2 (en) 2015-08-28 2023-05-09 Group 14 Technologies, Inc. Materials with extremely durable intercalation of lithium and manufacturing methods thereof
US11495798B1 (en) 2015-08-28 2022-11-08 Group14 Technologies, Inc. Materials with extremely durable intercalation of lithium and manufacturing methods thereof
US11437621B2 (en) 2015-08-28 2022-09-06 Group14 Technologies, Inc. Materials with extremely durable intercalation of lithium and manufacturing methods thereof
US11355755B2 (en) 2015-10-30 2022-06-07 Kuraray Co., Ltd. Carbonaceous material for non-aqueous electrolyte secondary battery, negative electrode for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte
US11611071B2 (en) 2017-03-09 2023-03-21 Group14 Technologies, Inc. Decomposition of silicon-containing precursors on porous scaffold materials
CN110476280A (en) * 2017-03-24 2019-11-19 日产自动车株式会社 Anode for nonaqueous electrolyte secondary battery and the non-aqueous electrolyte secondary battery for having used the cathode
CN108598476A (en) * 2018-03-11 2018-09-28 贵州格瑞特新材料有限公司 A kind of negative electrode of lithium ion battery high first spherical hard carbon material of effect and preparation method thereof
CN112645300A (en) * 2019-11-07 2021-04-13 上海杉杉科技有限公司 Hard carbon negative electrode material, lithium ion battery and preparation method and application thereof
CN112645300B (en) * 2019-11-07 2023-02-07 上海杉杉科技有限公司 Hard carbon negative electrode material, lithium ion battery, and preparation method and application of hard carbon negative electrode material
US11639292B2 (en) 2020-08-18 2023-05-02 Group14 Technologies, Inc. Particulate composite materials
US11611070B2 (en) 2020-08-18 2023-03-21 Group14 Technologies, Inc. Highly efficient manufacturing of silicon-carbon composites materials comprising ultra low Z
US11804591B2 (en) 2020-08-18 2023-10-31 Group14 Technologies, Inc. Highly efficient manufacturing of silicon-carbon composite materials comprising ultra low Z
US11492262B2 (en) 2020-08-18 2022-11-08 Group14Technologies, Inc. Silicon carbon composites comprising ultra low Z
US11498838B2 (en) 2020-08-18 2022-11-15 Group14 Technologies, Inc. Silicon carbon composites comprising ultra low z
CN113003559A (en) * 2021-02-06 2021-06-22 常德速碳新能源科技有限公司 Preparation method of carbon negative electrode material for lithium ion battery
CN113258047A (en) * 2021-04-29 2021-08-13 湖南九华碳素高科有限公司 Lithium ion battery cathode material and preparation method and application method thereof
CN113871574A (en) * 2021-09-24 2021-12-31 远景动力技术(江苏)有限公司 Lithium ion battery negative plate and preparation method and application thereof
CN113871574B (en) * 2021-09-24 2023-08-08 远景动力技术(江苏)有限公司 Lithium ion battery negative plate and preparation method and application thereof
CN113889625A (en) * 2021-09-28 2022-01-04 上海普澜特夫精细化工有限公司 Modified hard carbon composite material and preparation method and application thereof
CN113889625B (en) * 2021-09-28 2023-02-17 上海飞鸿创联新能源发展有限公司 Modified hard carbon composite material and preparation method and application thereof
CN113880068A (en) * 2021-09-29 2022-01-04 蜂巢能源科技有限公司 Hard carbon composite material and preparation method and application thereof
US20230147558A1 (en) * 2021-11-09 2023-05-11 Microvast Power Systems Co., Ltd. Negative electrode material and method of preparing the same
CN114180551A (en) * 2021-12-03 2022-03-15 广东凯金新能源科技股份有限公司 Continuous processing preparation method for lithium ion hard carbon negative electrode material
CN114335531A (en) * 2021-12-13 2022-04-12 湖南大学 Sulfur-doped hard carbon material and preparation method and application thereof
CN114212770A (en) * 2021-12-29 2022-03-22 上海杉杉科技有限公司 Modified hard carbon material, preparation method thereof, electrode and application
CN114512646A (en) * 2022-01-24 2022-05-17 西南大学 Amorphous carbon material with multilayer gradient microstructure and preparation method and application thereof
CN114804065A (en) * 2022-03-25 2022-07-29 中南大学 Hard carbon based on alpha-type cellulose material and preparation method and application thereof
CN114804065B (en) * 2022-03-25 2023-11-03 中南大学 Hard carbon based on alpha-cellulose material and preparation method and application thereof
CN114843480A (en) * 2022-05-23 2022-08-02 常州烯源谷新材料科技有限公司 Silicon-phosphorus co-doped hard carbon composite material and preparation method and application thereof
CN115159497A (en) * 2022-07-15 2022-10-11 山东大学 Hard carbon negative electrode material of sodium ion battery and preparation method and application thereof
CN115159497B (en) * 2022-07-15 2024-01-23 山东大学 Hard carbon negative electrode material of sodium ion battery and preparation method and application thereof
CN115259132A (en) * 2022-07-29 2022-11-01 华南理工大学 Preparation method and application of ultrahigh first-effect hard carbon negative electrode material
CN115259132B (en) * 2022-07-29 2023-08-29 广东容钠新能源科技有限公司 Preparation method and application of ultra-high first-effect hard carbon anode material
CN115072703B (en) * 2022-08-02 2024-01-30 洛阳月星新能源科技有限公司 Composite anode material and preparation method and application thereof
CN115072703A (en) * 2022-08-02 2022-09-20 洛阳月星新能源科技有限公司 Composite negative electrode material and preparation method and application thereof
CN115321514A (en) * 2022-08-29 2022-11-11 惠州亿纬锂能股份有限公司 Hard carbon material and preparation method and application thereof
CN115954442B (en) * 2022-10-12 2023-09-29 广东容钠新能源科技有限公司 Polymer film surface modified biomass hard carbon material, preparation method and application
CN115954442A (en) * 2022-10-12 2023-04-11 广东容钠新能源科技有限公司 Polymer film surface modified biomass hard carbon material, preparation method and application
CN115626630B (en) * 2022-11-08 2023-12-05 湘潭大学 Biomass carbon anode material for sodium ion battery and preparation method and application thereof
CN115626630A (en) * 2022-11-08 2023-01-20 湘潭大学 Biomass carbon negative electrode material for sodium ion battery and preparation method and application thereof
CN116799219B (en) * 2023-08-25 2023-12-15 浙江华宇钠电新能源科技有限公司 Tin-based oxide nanocrystalline modified hard carbon, sodium ion battery and vehicle
CN116799219A (en) * 2023-08-25 2023-09-22 浙江华宇钠电新能源科技有限公司 Tin-based oxide nanocrystalline modified hard carbon, sodium ion battery and vehicle
CN116812913A (en) * 2023-08-30 2023-09-29 乌海宝杰新能源材料有限公司 High-reversible-capacity hard carbon negative electrode material and preparation method thereof
CN116812913B (en) * 2023-08-30 2023-11-21 乌海宝杰新能源材料有限公司 High-reversible-capacity hard carbon negative electrode material and preparation method thereof

Also Published As

Publication number Publication date
JP5680191B2 (en) 2015-03-04
KR20130030769A (en) 2013-03-27
JP2013534024A (en) 2013-08-29

Similar Documents

Publication Publication Date Title
WO2011157013A1 (en) Composite hard carbon material of negative electrode for lithium ion battery and method for preparing the same
Ma et al. Recent advances in preparation and application of laser-induced graphene in energy storage devices
CN113078318B (en) Three-dimensional porous silicon-carbon composite material, preparation method and application thereof
WO2016074479A1 (en) Pyrolytic amorphous carbon material, preparation method and use thereof
Shi et al. High-performance flexible supercapacitor enabled by Polypyrrole-coated NiCoP@ CNT electrode for wearable devices
KR101832663B1 (en) three dimensional graphene structure having high density and capacity properties, manufacturing method thereof and electrode material comprising the same
CN103682350A (en) Preparation method of asphalt liquid phase coated modified artificial graphite lithium battery cathode material
Lim et al. Novel approach for controlling free-carbon domain in silicone oil-derived silicon oxycarbide (SiOC) as an anode material in secondary batteries
CN109742384A (en) A kind of biomass porous carbon is used as the method for kalium ion battery cathode
CN108807892A (en) A kind of preparation method of asphaltic base silicon-carbon nanometer sheet lithium cell negative pole material
CN109360962B (en) High-stability silicon-carbon negative electrode material for lithium battery and preparation method thereof
Gao et al. Shape-controlled porous carbon from calcium citrate precursor and their intriguing application in lithium-ion batteries
Long et al. Heterostructure Fe 2 O 3 nanorods@ imine-based covalent organic framework for long cycling and high-rate lithium storage
Shi et al. Flower-like TiO 2 and TiO 2@ C composites prepared via a one-pot solvothermal method as anode materials for lithium-ion batteries: higher capacity and excellent cycling stability
Ou et al. A carbon-covered silicon material modified by phytic acid with 3D conductive network as anode for lithium-ion batteries
CN110299511B (en) Nano composite negative plate, preparation method thereof and lithium ion battery
Song et al. A green synthesis of mn3o4/graphene nanocomposite as anode material for lithium-ion batteries
CN112520732A (en) Silicon-carbon composite negative electrode material and preparation method thereof
An et al. Partially carbonised melamine sponge coated with metal–organic framework-derived CuCo2O4/C composite as a flexible anode for lithium-ion batteries
Liu et al. Graphene aerogel-supported silicon@ carbon hybrids with double buffering structure as anode for lithium-ion battery
Zhou et al. In situ growth of polyphosphazene nanoparticles on graphene sheets as a highly stable nanocomposite for metal-free lithium anodes
Zhang et al. Tuning shell thickness of MnO/C core-shell nanowires for optimum performance of lithium-ion batteries
Tang et al. Fabrication of Si nanoparticles encapsulated into porous N-doped carbon for superior lithium storage performances
CN113764645A (en) Preparation method of hard carbon composite material with three-dimensional structure
Wang et al. CoO nanorod arrays on carbon nanotube foams fabricated by reducing carbon dioxide as high-performance electrode materials for Li-ion batteries

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10853122

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2013514526

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 20127033140

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 10853122

Country of ref document: EP

Kind code of ref document: A1