WO2021189836A1 - Graphite negative electrode material for high-performance lithium ion battery and preparation method therefor - Google Patents

Graphite negative electrode material for high-performance lithium ion battery and preparation method therefor Download PDF

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WO2021189836A1
WO2021189836A1 PCT/CN2020/123705 CN2020123705W WO2021189836A1 WO 2021189836 A1 WO2021189836 A1 WO 2021189836A1 CN 2020123705 W CN2020123705 W CN 2020123705W WO 2021189836 A1 WO2021189836 A1 WO 2021189836A1
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graphite
graphite anode
temperature
ion batteries
anode material
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张小广
褚相礼
黄雨生
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江西正拓新能源科技股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C01B32/21—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C01B32/21—After-treatment
    • C01B32/23—Oxidation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—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
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention relates to a graphite negative electrode material for lithium ion batteries and a preparation method thereof, in particular to a high-performance graphite negative electrode material for lithium ion batteries and a preparation method thereof.
  • Lithium-ion batteries are mainly composed of transition metal oxides with lithium intercalation in the positive electrode material, highly graphitized carbon as the negative electrode material, separator polyolefin microporous membrane, and electrolyte materials.
  • lithium-ion batteries Compared with traditional lead-acid, nickel-cadmium, nickel-metal hydride and other secondary batteries, lithium-ion batteries have high working voltage, small size, light weight, high capacity density, no memory effect, no pollution, and self-discharge. The advantages of small size and long cycle life. Since the successful commercialization of lithium-ion batteries by a Japanese company in the last century, lithium-ion batteries have become the dominant power source for mobile phones, notebook computers and digital products, and their applications in the fields of electric vehicles and energy storage have become more and more extensive. At present, the large-scale commercial use of lithium-ion battery anode materials is mainly carbon materials, mainly including natural graphite, artificial graphite, etc. Natural graphite is inherently high-capacity, high-pressure and compact. With the continuous improvement of artificial graphite technology, It has a significant increase in capacity density, almost reaching the level of natural graphite
  • lithium-ion battery anode materials is mainly carbon materials, including natural graphite, artificial graphite, etc., but in fact, its theoretical specific capacity is low, about 300mAh/g, which cannot meet the requirements of high-capacity and high-power lithium-ion batteries. Demand.
  • the Chinese Patent Publication No. CN109616639A published a hard carbon-coated expanded microcrystalline graphite material and its preparation method and application in sodium ion batteries.
  • This technology uses microcrystalline graphite as the substrate and is coated by hard carbon after oxidation.
  • the resulting composite material has good conductivity and high sodium storage capacity.
  • its hard carbon has a large number of micropores, and the electrolyte is easy to enter the material through the coating layer and cause side reactions, which will inevitably affect the material Cycle performance.
  • the Chinese Patent Publication No. CN109755581A discloses "a flexible carbon material coating structure and its coating process".
  • This technology is to disperse the low-residue carbon precursor in a solvent through a surfactant, and then spray-dry the low-residue carbon precursor in a solvent.
  • the carbon precursor is deposited on the surface of the coated object, and then a layer of high residual carbon precursor is uniformly coated on the outer layer, and then the coated product is heated and cooled in an inert atmosphere, and finally dispersed and sieved , Demagnetization to obtain an elastic carbon material coating structure.
  • the elastic carbon material coating structure prepared by the coating process of the present invention has strong elasticity, and can avoid rupture due to drastic changes in the volume of the coated object.
  • the process uses one-time carbonization, and the hard carbon and soft carbon precursors have defects such as difficult-to-control process methods during the simultaneous carbonization process, which affects the performance of the carbonized graphite anode material.
  • the purpose of the present invention is to overcome the shortcomings of the prior art and provide a high-performance lithium ion battery graphite negative electrode material and a preparation method thereof; it uses natural graphite as a raw material, increases the capacity through oxidation treatment, and improves its rate performance through hard carbon coating , Improve its cycle performance through impregnation treatment, increase capacity through surface oxidation treatment of natural graphite, hard carbon coating makes it have high rate charging ability, and use impregnation treatment to repair defects left after oxidation and hard carbon coating to improve its cycle performance .
  • the present invention is to provide a method for preparing a high-performance lithium ion battery graphite negative electrode material. Natural graphite is used as a raw material, the capacity is increased through oxidation treatment, the rate performance is improved through hard carbon coating, and the cycle performance is improved through immersion treatment. Including the following steps:
  • Oxidation treatment is to fully stir and mix the natural graphite and the oxidant mixed solution, filter, dry, and perform high-temperature oxidation treatment under inert atmosphere conditions to obtain oxidized natural graphite;
  • step 3 low-temperature carbonization treatment, the graphite anode material precursor obtained in step 2) is subjected to low-temperature carbonization treatment in an inert atmosphere to obtain a carbonized graphite anode material precursor;
  • Pitch impregnation treatment place the precursor of carbonized graphite anode material in a pitch solvent under pressure, perform mixing and dissolution treatment, take out, filter, and dry, and become the precursor of pitch carbonized graphite anode material;
  • the oxidant is a mixture of peroxide and organic acid or a mixture of peroxide and inorganic acid to control natural graphite and peroxide and organic
  • the mass ratio of acid or natural graphite to peroxide salt and inorganic acid is 80-95:5-20:1-10; the temperature of high-temperature oxidation treatment is controlled at 500-600°C; the time is 2-4h.
  • the coating agent is any one or more of sucrose, phenolic resin, epoxy resin, and polyvinyl alcohol; controlling the The mass ratio of oxidized natural graphite to coating agent is 100:3-40.
  • the step 3) controls the low-temperature carbonization treatment temperature at 500-650°C, the time is 6-20h, and controls the low-temperature carbonization treatment heating rate at 5-8°C/min .
  • the step 4) pitch impregnation treatment the pitch is low-temperature pitch or medium-temperature pitch; the pressure is controlled to 0.2-1.5Mp, and the pressure is maintained under the condition of this pressure.
  • the pressing time is 0.2-3h.
  • the step 5) controls the pitch carbonized graphite anode material precursor material to pulverize the particle size of the material to be 1um-50um, and the high-temperature carbonization temperature is controlled to be 1200-1400°C ,
  • the carbonization time is 5-24h; the heating rate of high-temperature carbonization is controlled at 4-10°C/min.
  • the oxidant is a mixture of sodium peroxide and oxalic acid or a mixture of sodium peroxide and concentrated sulfuric acid.
  • the graphite negative electrode material for high-performance lithium ion battery prepared by the method for preparing graphite negative electrode material for high-performance lithium ion battery, wherein the graphite negative electrode material for high-performance lithium ion battery is coated with oxidized natural graphite and soft carbon by hard carbon Composition, control the quality ratio of natural graphite quality: hard carbon quality: soft carbon quality is 80-98:1-10:1-10.
  • the high-performance lithium ion battery graphite negative electrode material controls the particle size of the high-performance lithium ion battery graphite negative electrode material to be 2um-45um, and the specific surface area is 3-20m 2 /g.
  • the solvent is any one of toluene, xylene, quinoline or water.
  • the soft carbon in the present invention refers to amorphous carbon that can be graphitized at high temperature; while hard carbon refers to the pyrolysis carbon of high molecular polymer.
  • the inert atmosphere in the present invention refers to the atmospheric conditions in the presence of nitrogen and/or helium.
  • the invention discloses a method for preparing high-performance lithium ion battery graphite negative electrode material.
  • the surface oxidation treatment of natural graphite is used to increase the capacity, the hard carbon coating makes it have a high-rate charging ability, the immersion treatment repairs oxidation and the hard carbon coating is left behind.
  • the following defects improve the cycle performance of graphite anode materials for lithium-ion batteries; when used as anode materials for lithium-ion batteries, this material has high capacity, high pressure, excellent rate performance and cycle life.
  • the combination of natural graphite and hard carbon coating not only ensures the capacity density of graphite anode materials for lithium-ion batteries, but also greatly improves the rate performance of the materials;
  • the secondary carbonization process is adopted to make the prepared graphite anode material for lithium ion batteries have better cycle performance. Constant current charge and discharge at a rate of 0.2C, the lower limit voltage is 0.001V, the upper limit voltage is 2.0V, and the charge and discharge capacity The first efficiency is over 94%, and its cycle capacity retention rate is over 650mAh/g.
  • Figure 1 The SEM profile of a high-performance lithium ion battery graphite anode material prepared by the preparation method of the present invention, that is, the SEM profile of the composite material prepared in one embodiment; the figure shows the SEM profiles of two products;
  • Figure 2 Graphite half-cell test spectrum of the graphite negative electrode material for lithium ion batteries prepared by the method of the present invention, that is, composite material;
  • Fig. 3 Comparison of charge and discharge curves of graphite anode material for lithium ion batteries prepared by the method of the present invention and ordinary artificial graphite 5C charge and 1C discharge cycle test.
  • the present invention is a high-capacity and high-power graphite negative electrode material for lithium-ion batteries and a preparation method thereof, or high-performance lithium-ion battery graphite negative electrode material and a preparation method thereof.
  • Carbon composition, the method steps are as follows:
  • Oxidation treatment is to fully stir and mix natural graphite and oxidant, aqueous solutions of oxalic acid and sodium persulfate or a mixed solution of sodium peroxide and concentrated sulfuric acid, filter, dry, and perform high-temperature oxidation treatment under inert atmosphere conditions.
  • step 2) Preparing the precursor of the graphite anode material, placing step 1) oxidized natural graphite in the coating agent and corresponding solvent, and thoroughly stir and mix into a mixture of oxidized natural graphite and the coating agent, the coating agent is sucrose, phenolic aldehyde One or more of resin, epoxy resin, and polyvinyl alcohol are dissolved and mixed in the corresponding solvent, and the mass ratio of the oxidized natural graphite to the coating agent is controlled to be 100:3-40; the oxidized natural graphite is mixed with the coating After the coating agent mixture is spray-dried, the graphite anode material precursor is obtained;
  • low-temperature carbonization treatment the graphite anode material precursor obtained in step 2) is subjected to low-temperature carbonization treatment in an inert atmosphere to obtain a carbonized graphite anode material precursor;
  • the low-temperature carbonization treatment temperature is controlled to 500-650°C, and the time is 6 -20h, control the heating rate of low-temperature carbonization to 5-8°C/min.
  • Pitch impregnation treatment place the precursor of carbonized graphite anode material in a pitch solvent under pressure, perform mixing and dissolution treatment, take out, filter, and dry, and become the precursor of pitch carbonized graphite anode material; control the pitch to be Low-temperature asphalt or medium-temperature asphalt; control the pressure to 0.2-1.5Mp, and hold the pressure for 0.2-3h under the condition of the pressure;
  • the quality of natural graphite in step 1) oxalic acid: sodium persulfate is 80-95:5-20:1-10, the treatment temperature is 500-600°C, and the holding time is 1-5h;
  • the graphite quality in step 2) the quality of the coating agent is 100:3-40;
  • the high-temperature carbonization temperature curve in step 3) is: the heating rate is 1-10°C/min, the sintering temperature is 500-900°C, and the sintering time is 5-24h;
  • the solvent is any one of toluene, xylene, quinoline or water;
  • the method of the present invention prepares the final product a high-capacity and high-power graphite anode material for lithium-ion batteries.
  • the graphite anode material has a particle size of 2um-45um and a specific surface area of 3-20m 2 /g.
  • the quality of natural graphite is: Hard carbon quality: The soft carbon quality is 80-98:1-10:1-10.
  • the graphite anode material for high-performance lithium ion batteries prepared by the method of the present invention has surface oxidation treatment of natural graphite to increase capacity, hard carbon coating to make it have high-rate charging ability, and impregnation treatment to repair defects left after oxidation and hard carbon coating , To improve its cycle performance.
  • the material is used as a negative electrode material of a lithium ion battery, it has high capacity, high compactness, excellent rate performance and cycle life.
  • the present invention is a high-capacity and high-power graphite negative electrode material for lithium ion batteries and a preparation method thereof, which is composed of hard carbon coated on oxidized natural graphite and surface-modified soft carbon.
  • the method steps are as follows:
  • Oxidation treatment is to fully stir and mix natural graphite and oxidant, oxalic acid and sodium persulfate aqueous solution mixed solution, filter, dry, and perform high-temperature oxidation treatment under inert atmosphere conditions to oxidize natural graphite; make natural graphite
  • the mass ratio of peroxide and organic acid or natural graphite to peroxide salt and inorganic acid is 80-95:5-20:1-10; the temperature of high-temperature oxidation treatment is controlled at 500-600°C; the time is 2-4h ;
  • the oxidant is a mixture of sodium persulfate and oxalic acid;
  • step 2) Preparing the precursor of the graphite anode material, placing step 1) oxidized natural graphite in the coating agent and corresponding solvent, and thoroughly stir and mix into a mixture of oxidized natural graphite and the coating agent, the coating agent is sucrose, phenolic aldehyde One or more of resin, epoxy resin, and polyvinyl alcohol are dissolved and mixed in the corresponding solvent, and the mass ratio of the oxidized natural graphite to the coating agent is controlled to be 100:3-40; the oxidized natural graphite is mixed with the coating After the coating agent mixture is spray-dried, the graphite anode material precursor is obtained;
  • low-temperature carbonization treatment the graphite anode material precursor obtained in step 2) is subjected to low-temperature carbonization treatment in an inert atmosphere to obtain a carbonized graphite anode material precursor;
  • the low-temperature carbonization treatment temperature is controlled to 500-650°C, and the time is 6 -20h, control the heating rate of low-temperature carbonization to 5-8°C/min.
  • Pitch dipping treatment place the precursor of carbonized graphite anode material in a pitch solvent or organic solution called pitch, mix and dissolve it under pressure, take it out, filter, and dry, and become the precursor of pitch carbonized graphite anode material;
  • the pitch is controlled to be low-temperature pitch or medium-temperature pitch;
  • the organic solvent is any one of toluene, xylene, and quinoline;
  • the pressure is controlled to be 0.2-1.5Mp, and the pressure holding time is 0.2- in the presence of pressure. 3h;
  • Oxidation treatment Add 1000g of natural graphite to 1000ml of water, add 10g of sodium persulfate and 50g of oxalic acid to form a mixed aqueous solution, stir for 1-2h at a temperature of 60°C, filter and dry in vacuum for 18-24h, and protect in a nitrogen atmosphere.
  • the pressure of the reactor is increased to 1.5Mp. Under this pressure condition, the pressure is maintained for 1 hour, and the material is taken out and filtered and dried.
  • the precursor of the pitch carbonized graphite anode material is marked as material C;
  • the active material is the lithium ion battery graphite anode material, conductive agent, super P carbon black, and carboxymethyl prepared by the present invention.
  • the lithium piece is used as the counter electrode to make a half-cell.
  • the battery model is still the existing CR2032 button cell, and the electrolyte is the same Use commonly used lithium ion battery electrolyte: such as 1.2-1.6mol/L lithium hexafluorophosphate (LiPF6)/ethylene carbonate (EC): dimethyl carbonate (DMC): ethyl methyl carbonate (EMC) is 12:12:76 The mixture.
  • a charge-discharge test was performed on the battery prepared by the present invention, the constant current charge-discharge at a rate of 0.2C, the lower limit voltage is 0.001V, and the upper limit voltage is 2.0V. See Figure 2 for charge and discharge curves. Its charge and discharge capacity is the first efficiency respectively.
  • the battery is subjected to a rate charge-discharge cycle test, and its cycle capacity retention rate is shown in Figure 3 of the curve.
  • the following embodiments are the same as Embodiment 1 except for the description in the embodiments.
  • the material C is crushed to a D50 particle size of 18um, it is placed in a box furnace, under the protection of a nitrogen atmosphere, the heating rate is increased to 1200°C at 2°C/min, and the temperature is kept for 5 hours.
  • the target product obtained by cooling and taking out is a graphite anode material for high-performance lithium-ion batteries.
  • the button cell assembly and testing are the same as in Example 1.
  • the present invention is a high-capacity and high-power graphite negative electrode material for lithium ion batteries and a preparation method thereof, which is composed of hard carbon coated on oxidized natural graphite and surface-modified soft carbon.
  • the method steps are as follows:
  • Oxidation treatment add 1000g of natural graphite to 1000ml of water, add 10g of sodium persulfate and corresponding sulfuric acid to form a mixed aqueous solution, stir for 1-2h at a temperature of 70°C, filter and dry in vacuum for 18-24h, and protect in a nitrogen atmosphere. Place it in the box furnace of the heating device, heat it up to 500°C, keep it for 2h, take it out naturally, and record it as material A, which is oxidized natural graphite.
  • the oxidized natural graphite to the coating agent 50g epoxy resin is dissolved in 2000L deionized water, 1000g material A is added to control the mass ratio of the oxidized natural graphite to the coating agent to be 100:3-40; it is a mixture of oxidized natural graphite and the coating agent, which will oxidize the natural stone
  • the ink and coating agent mixture is spray-dried to obtain the precursor, which is the precursor of the graphite anode material. 3), low-temperature carbonization, and the precursor of the carbonized graphite anode material in step 2) is placed in a box furnace, and protected in a nitrogen atmosphere.
  • the temperature rise rate of 6°C/min was increased to 500°C, and the temperature was kept for 6 hours.
  • the precursor of the carbonized graphite anode material was obtained, which was recorded as material B; 4).
  • the pitch impregnation treatment was prepared with a 10% mass concentration of medium temperature pitch toluene solution.
  • the pressure of the reactor is increased to 1.0Mp, the pressure is maintained for 2h, and the material is taken out and filtered and dried to obtain the precursor of the pitch carbonized graphite anode material, which is marked as material C;
  • the high-performance graphite negative electrode material for lithium ion batteries prepared by the method of the present invention is surface oxidation treatment of natural graphite to increase the capacity, hard carbon coating to make it have a high-rate charging ability, asphalt impregnation treatment to repair oxidation and hard carbon coating to leave behind Under the defect, improve its cycle performance.
  • the material is used as a negative electrode material for lithium-ion batteries, it has high capacity, high compactness, excellent rate performance and cycle life.

Abstract

Disclosed is a graphite negative electrode material for a high-performance lithium ion battery and a preparation method therefor. The preparation process therefor comprises the following steps: 1) subjecting natural graphite to a surface oxidation treatment; 2) coating the natural graphite, which has undergone the oxidation treatment, with hard carbon to obtain a precursor; 3) subjecting the precursor obtained in step 2) to a carbonization treatment; 4) subjecting the precursor, which has undergone the carbonization treatment, to an impregnation treatment; and 5) crushing the impregnated material, and then carbonizing same to obtain a high-capacity high-power graphite negative electrode material. The surface oxidation treatment increases the capacity of the natural graphite, the coating with the hard carbon endows same with a large rate charging capacity, and the impregnation treatment can repair any defects remaining after the oxidation and hard carbon coating, thereby improving the cycle performance thereof.

Description

高性能锂离子电池石墨负极材料及其制备方法High-performance lithium ion battery graphite negative electrode material and preparation method thereof 技术领域：Technical field:
本发明涉及一种锂离子电池用的石墨负极材料及其制备方法，特别是一种高性能锂离子电池石墨负极材料及其制备方法。The invention relates to a graphite negative electrode material for lithium ion batteries and a preparation method thereof, in particular to a high-performance graphite negative electrode material for lithium ion batteries and a preparation method thereof.
背景技术:Background technique:
锂离子电池主要由正极材料嵌锂的过渡金属氧化物，负极材料为高度石墨化的碳、隔膜聚烯烃微孔膜和电解质材料等组成。Lithium-ion batteries are mainly composed of transition metal oxides with lithium intercalation in the positive electrode material, highly graphitized carbon as the negative electrode material, separator polyolefin microporous membrane, and electrolyte materials.
锂离子电池与传统的铅酸、镍镉、镍氢等二次电池相比，锂离子二次电池具有工作电压高、体积小、质量轻、容量密度高、无记忆效应、无污染、自放电小以及循环寿命长等优点。自上世纪由日本某公司成功将锂离子电池实现商品化以来，锂离子电池已成为手机、笔记本电脑和数码产品的主导电源，在电动汽车和储能等领域的应用亦越来越广泛。目前，大规模商业化使用的锂离子电池负极材料主要是碳材料，主要包括天然石墨、人造石墨等，天然石墨天生具有高容量、高压实的优点，随着人造石墨技术的不断提升亦使得其在能力密度上有明显提升，几乎达到天然石墨水平Compared with traditional lead-acid, nickel-cadmium, nickel-metal hydride and other secondary batteries, lithium-ion batteries have high working voltage, small size, light weight, high capacity density, no memory effect, no pollution, and self-discharge. The advantages of small size and long cycle life. Since the successful commercialization of lithium-ion batteries by a Japanese company in the last century, lithium-ion batteries have become the dominant power source for mobile phones, notebook computers and digital products, and their applications in the fields of electric vehicles and energy storage have become more and more extensive. At present, the large-scale commercial use of lithium-ion battery anode materials is mainly carbon materials, mainly including natural graphite, artificial graphite, etc. Natural graphite is inherently high-capacity, high-pressure and compact. With the continuous improvement of artificial graphite technology, It has a significant increase in capacity density, almost reaching the level of natural graphite
但是目前，大规模商业化使用的锂离子电池负极材料主要是碳材料，包括天然石墨、人造石墨等，但其实其理论比容量低，300mAh/g左右，无法满足高容量高功率的锂离子电池的需求。However, currently, the large-scale commercial use of lithium-ion battery anode materials is mainly carbon materials, including natural graphite, artificial graphite, etc., but in fact, its theoretical specific capacity is low, about 300mAh/g, which cannot meet the requirements of high-capacity and high-power lithium-ion batteries. Demand.
近年来，特别是5G时代的到来，电子产品对电池快充性能要求不断提升，需要负极材料满足5C充电要求，且倍率性能要求还在不断提升。目前，中间相炭微球，小粒径沥青焦、等方焦等能满足5C充电要求，但其容量压实偏低，满足不了能力密度要求。因此，急需开发出兼具能力密度与快充性能的高容量高功率的锂离子电池用的石墨负极材料。In recent years, especially with the advent of the 5G era, electronic products have continuously improved the requirements for battery fast charging performance, requiring negative electrode materials to meet the 5C charging requirements, and the rate performance requirements are still increasing. At present, mesophase carbon microspheres, small particle size pitch coke, etc. can meet the 5C charging requirements, but their capacity compaction is low and cannot meet the capacity density requirements. Therefore, there is an urgent need to develop graphite anode materials for high-capacity, high-power lithium-ion batteries that have both capacity density and fast charging performance.
如中国专利公告号为CN109616639A发表了一种硬碳包覆膨胀微晶石墨材料及其制备方法和在钠离子电池中的应用，该技术采用微晶石墨为基材，氧化后通过硬碳包覆，得到的复合材料导电性好，储钠能力高，但要是作为锂离子电池负极材料，其硬碳大量微孔的存在，电解液易通过包覆层加入材料内部并发生副反应，势必影响材料的循环性能。还有如中国专利公告号为CN109755581A公开了《一种弹性碳材料包覆结构及其包覆工艺》，该技术是将低残碳前驱体通过表面活性剂分散于溶剂中，而后通过喷雾干燥将低碳前驱体沉积于被包覆物表面，再在其外层均匀包覆一层高残碳前驱体，然后在惰性气氛下，将包覆后的产物加热、冷却，最后经打散、筛分、除磁得到弹性碳材料包覆结构。该发明包覆工艺制备的弹性碳材料包覆结构具有很强的弹性，可以避免因被包覆物体积剧烈变化而出现破裂。但该工艺采用的是一次碳化，硬碳与软碳前驱体在同时碳化的过程中存在难以控制的工艺方法的等缺陷，从而影响了碳化后的石墨负极材料的性能。For example, the Chinese Patent Publication No. CN109616639A published a hard carbon-coated expanded microcrystalline graphite material and its preparation method and application in sodium ion batteries. This technology uses microcrystalline graphite as the substrate and is coated by hard carbon after oxidation. , The resulting composite material has good conductivity and high sodium storage capacity. However, if it is used as a lithium-ion battery negative electrode material, its hard carbon has a large number of micropores, and the electrolyte is easy to enter the material through the coating layer and cause side reactions, which will inevitably affect the material Cycle performance. For example, the Chinese Patent Publication No. CN109755581A discloses "a flexible carbon material coating structure and its coating process". This technology is to disperse the low-residue carbon precursor in a solvent through a surfactant, and then spray-dry the low-residue carbon precursor in a solvent. The carbon precursor is deposited on the surface of the coated object, and then a layer of high residual carbon precursor is uniformly coated on the outer layer, and then the coated product is heated and cooled in an inert atmosphere, and finally dispersed and sieved , Demagnetization to obtain an elastic carbon material coating structure. The elastic carbon material coating structure prepared by the coating process of the present invention has strong elasticity, and can avoid rupture due to drastic changes in the volume of the coated object. However, the process uses one-time carbonization, and the hard carbon and soft carbon precursors have defects such as difficult-to-control process methods during the simultaneous carbonization process, which affects the performance of the carbonized graphite anode material.
因此，如何来提供一种锂离子电池用高容量高功率石墨负极材料及其制备方法，其可克服锂离子电池用石墨负极材料的容量压实偏低，满足不了能力密度要求的问题；同时制备出兼具能量密度与快充性能的高容量高功率的锂离子电池用的石墨负极材料及方法。Therefore, how to provide a high-capacity and high-power graphite negative electrode material for lithium-ion batteries and a preparation method thereof, which can overcome the problem of low capacity compaction of graphite negative electrode materials for lithium-ion batteries and insufficient capacity density requirements; A graphite anode material and method for high-capacity and high-power lithium-ion batteries with both energy density and fast charging performance are developed.
发明内容Summary of the invention
本发明目的在于克服现有技术的不足，提供一种高性能锂离子电池石墨负极材料及其制备方法；其是以天然石墨为原材料，通过氧化处理提升容量，通过硬碳包覆提升其倍率性能，通过浸渍处理提升其循环性能，通过表面氧化处理天然石墨提升容量，硬碳包覆使其具备大倍率充电能力，采用浸渍处理修复氧化及硬碳包覆后留下的缺陷，提升其循环性能。工业化生产成本低的，用于锂离子电池用的石墨负极材料。The purpose of the present invention is to overcome the shortcomings of the prior art and provide a high-performance lithium ion battery graphite negative electrode material and a preparation method thereof; it uses natural graphite as a raw material, increases the capacity through oxidation treatment, and improves its rate performance through hard carbon coating , Improve its cycle performance through impregnation treatment, increase capacity through surface oxidation treatment of natural graphite, hard carbon coating makes it have high rate charging ability, and use impregnation treatment to repair defects left after oxidation and hard carbon coating to improve its cycle performance . Low industrial production cost, graphite anode material for lithium-ion batteries.
本发明就是要提供一种高性能锂离子电池石墨负极材料的制备方法，以天然石墨为原材料，通过氧化处理提升容量，通过硬碳包覆提升其倍率性能，通过浸渍处理提升其循环性能，其包括如下步骤：The present invention is to provide a method for preparing a high-performance lithium ion battery graphite negative electrode material. Natural graphite is used as a raw material, the capacity is increased through oxidation treatment, the rate performance is improved through hard carbon coating, and the cycle performance is improved through immersion treatment. Including the following steps:
1)、氧化处理，是将天然石墨与氧化剂混合溶液进行充分搅拌混合，过滤、干燥，在惰性气氛条件下，进行高温氧化处理，为氧化天然石墨；1) Oxidation treatment is to fully stir and mix the natural graphite and the oxidant mixed solution, filter, dry, and perform high-temperature oxidation treatment under inert atmosphere conditions to obtain oxidized natural graphite;
2)、制石墨负极材料前驱体，将步骤1)氧化天然石墨置于包覆剂及相应溶剂中，进行充分搅拌混合为氧化天然石墨与包覆剂混合物，将氧化天然石墨与包覆剂混合物经喷雾干燥后，得到石墨负极材料前驱体；2) To prepare the precursor of the graphite anode material, place step 1) oxidized natural graphite in the coating agent and the corresponding solvent, and mix thoroughly to form a mixture of oxidized natural graphite and coating agent, and combine the oxidized natural graphite and coating agent mixture After spray drying, the graphite anode material precursor is obtained;
3)、低温碳化处理，将步骤2)所得石墨负极材料前驱体在惰性气氛中，进行低温碳化处理，得碳化石墨负极材料前驱体；3), low-temperature carbonization treatment, the graphite anode material precursor obtained in step 2) is subjected to low-temperature carbonization treatment in an inert atmosphere to obtain a carbonized graphite anode material precursor;
4)、沥青浸渍处理，将碳化石墨负极材料前驱体置于沥青溶剂中在压力存在的条件下，进行混合溶解处理，取出过滤、干燥，为沥青碳化石墨负极材料前驱体；4) Pitch impregnation treatment: place the precursor of carbonized graphite anode material in a pitch solvent under pressure, perform mixing and dissolution treatment, take out, filter, and dry, and become the precursor of pitch carbonized graphite anode material;
5)、二次碳化，制高性能锂离子电池用石墨负极材料，将步骤4)所得沥青碳化石墨负极材料前驱体物料进行粉碎后，在惰性气氛中，再进行高温碳化处理，即得到高性能锂离子电池用石墨负极材料。5) Secondary carbonization is used to prepare graphite anode materials for high-performance lithium ion batteries. After the precursor material of the pitch carbonized graphite anode material obtained in step 4) is pulverized, it is subjected to high-temperature carbonization in an inert atmosphere to obtain high-performance Graphite anode material for lithium ion batteries.
所述的高性能锂离子电池石墨负极材料的制备方法，其步骤1)所述氧化剂为过氧化物和有机酸的混合或过氧化物和无机酸的混合，控制天然石墨与过氧化物和有机酸或天然石墨与过氧化盐和无机酸的质量比为80-95：5-20：1-10；控制高温氧化处理的温度为500-600℃；时间为2-4h。In the method for preparing graphite anode materials for high-performance lithium-ion batteries, in step 1), the oxidant is a mixture of peroxide and organic acid or a mixture of peroxide and inorganic acid to control natural graphite and peroxide and organic The mass ratio of acid or natural graphite to peroxide salt and inorganic acid is 80-95:5-20:1-10; the temperature of high-temperature oxidation treatment is controlled at 500-600℃; the time is 2-4h.
所述的高性能锂离子电池石墨负极材料的制备方法，其步骤2)所述包覆剂为蔗糖、酚醛树酯、环氧树脂、聚乙烯醇中的任意一种或多种；控制所述氧化天然石墨与包覆剂的质量比为100：3-40。In the preparation method of the high-performance lithium ion battery graphite negative electrode material, in step 2) the coating agent is any one or more of sucrose, phenolic resin, epoxy resin, and polyvinyl alcohol; controlling the The mass ratio of oxidized natural graphite to coating agent is 100:3-40.
所述的高性能锂离子电池石墨负极材料的制备方法，其步骤3)控制低温碳化处理温度温度为500-650℃，时间为6-20h，控制低温碳化处理升温速率为5-8℃/min。In the preparation method of the graphite anode material for high-performance lithium-ion batteries, the step 3) controls the low-temperature carbonization treatment temperature at 500-650°C, the time is 6-20h, and controls the low-temperature carbonization treatment heating rate at 5-8°C/min .
所述的高性能锂离子电池石墨负极材料的制备方法，其步骤4)沥青浸渍处理，所述沥青为低温沥青或中温沥青；控制所述压力为0.2-1.5Mp，在此压力存在条件下保压时间为0.2-3h。In the preparation method of the graphite anode material for high-performance lithium ion batteries, the step 4) pitch impregnation treatment, the pitch is low-temperature pitch or medium-temperature pitch; the pressure is controlled to 0.2-1.5Mp, and the pressure is maintained under the condition of this pressure. The pressing time is 0.2-3h.
所述的高性能锂离子电池石墨负极材料的制备方法，其步骤5)控制沥青碳化石墨负极材料前驱体物料进行粉碎后的材料粒径为1um-50um，，控制高温碳化温度为1200-1400℃，碳化时间为5-24h；控制高温碳化的升温速率4-10℃/min。In the preparation method of the high-performance lithium ion battery graphite anode material, the step 5) controls the pitch carbonized graphite anode material precursor material to pulverize the particle size of the material to be 1um-50um, and the high-temperature carbonization temperature is controlled to be 1200-1400°C , The carbonization time is 5-24h; the heating rate of high-temperature carbonization is controlled at 4-10℃/min.
优选的，是所述氧化剂为过硫酸钠和草酸的混合或过氧化钠和浓硫酸的混合。Preferably, the oxidant is a mixture of sodium peroxide and oxalic acid or a mixture of sodium peroxide and concentrated sulfuric acid.
所述的高性能锂离子电池石墨负极材料的制备方法制备的高性能锂离子电池用石墨负极材料，其所述高性能锂离子电池用石墨负极材料由硬碳包覆于氧化天然石墨及软 碳构成，控制质量比为天然石墨质量：硬碳质量：软碳质量为80-98：1-10：1-10。The graphite negative electrode material for high-performance lithium ion battery prepared by the method for preparing graphite negative electrode material for high-performance lithium ion battery, wherein the graphite negative electrode material for high-performance lithium ion battery is coated with oxidized natural graphite and soft carbon by hard carbon Composition, control the quality ratio of natural graphite quality: hard carbon quality: soft carbon quality is 80-98:1-10:1-10.
所述的高性能锂离子电池石墨负极材料，其控制所述高性能锂离子电池用石墨负极材料的粒径为2um-45um，比表面积为3-20m 2/g。 The high-performance lithium ion battery graphite negative electrode material controls the particle size of the high-performance lithium ion battery graphite negative electrode material to be 2um-45um, and the specific surface area is 3-20m 2 /g.
所述溶剂为甲苯、二甲苯，喹啉或水中的任意一种。The solvent is any one of toluene, xylene, quinoline or water.
本发明所述的软碳是指在高温下能石墨化的无定型碳；而硬碳则是指高分子聚合物的热解碳。The soft carbon in the present invention refers to amorphous carbon that can be graphitized at high temperature; while hard carbon refers to the pyrolysis carbon of high molecular polymer.
本发明所述的惰性气氛是指在氮气和/或氦气存在的气氛条件。The inert atmosphere in the present invention refers to the atmospheric conditions in the presence of nitrogen and/or helium.
本发明公开的一种高性能锂离子电池石墨负极材料的制备方法，采用表面氧化处理天然石墨提升容量，硬碳包覆使其具备大倍率充电能力，浸渍处理修复氧化及硬碳包覆后留下的缺陷，提升锂离子电池石墨负极材料其循环性能；该材料作为锂离子电池负极材料时，其具备高容量、高压实、优异的倍率性能及循环寿命。The invention discloses a method for preparing high-performance lithium ion battery graphite negative electrode material. The surface oxidation treatment of natural graphite is used to increase the capacity, the hard carbon coating makes it have a high-rate charging ability, the immersion treatment repairs oxidation and the hard carbon coating is left behind. The following defects improve the cycle performance of graphite anode materials for lithium-ion batteries; when used as anode materials for lithium-ion batteries, this material has high capacity, high pressure, excellent rate performance and cycle life.
其与现有技术相比，本发明技术方案还具有如下的有益效果：Compared with the prior art, the technical solution of the present invention also has the following beneficial effects:
1.采用天然石墨与硬碳包覆相结合，既保证了锂离子电池用石墨负极材料的能力密度，极大提升了材料的倍率性能；1. The combination of natural graphite and hard carbon coating not only ensures the capacity density of graphite anode materials for lithium-ion batteries, but also greatly improves the rate performance of the materials;
2.是用压力沥青溶剂浸渍技术修复了天然石墨氧化及硬碳碳化留下的缺陷，大大提升了锂离子电池石墨负极材料的循环性能；2. It uses pressure pitch solvent impregnation technology to repair the defects left by natural graphite oxidation and hard carbonization, and greatly improves the cycle performance of graphite anode materials for lithium-ion batteries;
3.是采用二次碳化处理工艺方法，使制备的锂离子电池用石墨负极材料的循环性能更优，以0.2C倍率下恒流充放电，下限电压0.001V，上限电压2.0V，充放电容量首次效率达94％以上，其循环容量保持率达650mAh/g以上。3. The secondary carbonization process is adopted to make the prepared graphite anode material for lithium ion batteries have better cycle performance. Constant current charge and discharge at a rate of 0.2C, the lower limit voltage is 0.001V, the upper limit voltage is 2.0V, and the charge and discharge capacity The first efficiency is over 94%, and its cycle capacity retention rate is over 650mAh/g.
附图说明Description of the drawings
图1：本发明制备方法制备的一种高性能锂离子电池石墨负极材料的SEM图谱即一种实施方式制备的复合材料SEM图；图中显示为两种产品的SEM图谱；Figure 1: The SEM profile of a high-performance lithium ion battery graphite anode material prepared by the preparation method of the present invention, that is, the SEM profile of the composite material prepared in one embodiment; the figure shows the SEM profiles of two products;
图2：本发明方法制备的锂离子电池用的石墨负极材料即复合材料的半电池测试图谱；Figure 2: Graphite half-cell test spectrum of the graphite negative electrode material for lithium ion batteries prepared by the method of the present invention, that is, composite material;
图3：本发明方法制备的锂离子电池用石墨负极材料与普通人造石墨5C充电1C放电循环测试对比充放电曲线图。Fig. 3: Comparison of charge and discharge curves of graphite anode material for lithium ion batteries prepared by the method of the present invention and ordinary artificial graphite 5C charge and 1C discharge cycle test.
具体实施方式：Detailed ways:
下面结合具体实施方式对本发明作进一步的说明，为了使本发明所解决的技术问题、技术方案及有益效果更加清楚明白，以下结合附图和实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。The present invention will be further described below in combination with specific embodiments. In order to make the technical problems, technical solutions and beneficial effects solved by the present invention clearer and clearer, the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described here are only used to explain the present invention, but not used to limit the present invention.
本发明一种锂离子电池用高容量高功率石墨负极材料及其制备方法，或叫高性能锂离子电池石墨负极材料及其制备方法，是由硬碳包覆于氧化天然石墨及表面修饰的软碳构成，方法步骤依次为：The present invention is a high-capacity and high-power graphite negative electrode material for lithium-ion batteries and a preparation method thereof, or high-performance lithium-ion battery graphite negative electrode material and a preparation method thereof. Carbon composition, the method steps are as follows:
1)、氧化处理，是将天然石墨与氧化剂与草酸及过硫酸钠的水溶液或过氧化钠和浓硫酸的混合溶液进行充分搅拌混合，过滤、干燥，在惰性气氛条件下，进行高温氧化处理，为氧化天然石墨；控制天然石墨与过氧化物和有机酸或天然石墨与过氧化盐和无机酸的质量比为80-95：5-20：1-10；控制高温氧化处理的温度为500-600℃；时间为2-4h；优选的是氧 化剂为过硫酸钠和草酸的混合；1) Oxidation treatment is to fully stir and mix natural graphite and oxidant, aqueous solutions of oxalic acid and sodium persulfate or a mixed solution of sodium peroxide and concentrated sulfuric acid, filter, dry, and perform high-temperature oxidation treatment under inert atmosphere conditions. To oxidize natural graphite; control the mass ratio of natural graphite to peroxide and organic acid or natural graphite to peroxide salt and inorganic acid to be 80-95:5-20:1-10; control the temperature of high-temperature oxidation treatment to 500- 600°C; time is 2-4h; preferably, the oxidant is a mixture of sodium persulfate and oxalic acid;
2)、制石墨负极材料前驱体，将步骤1)氧化天然石墨置于包覆剂及相应溶剂中，进行充分搅拌混合为氧化天然石墨与包覆剂混合物，所述包覆剂为蔗糖、酚醛树酯、环氧树脂、聚乙烯醇中的一种或多种溶解于相应溶剂中混合，控制所述氧化天然石墨与包覆剂的质量比为100：3-40；将氧化天然石墨与包覆剂混合物经喷雾干燥后，得到石墨负极材料前驱体；2) Preparing the precursor of the graphite anode material, placing step 1) oxidized natural graphite in the coating agent and corresponding solvent, and thoroughly stir and mix into a mixture of oxidized natural graphite and the coating agent, the coating agent is sucrose, phenolic aldehyde One or more of resin, epoxy resin, and polyvinyl alcohol are dissolved and mixed in the corresponding solvent, and the mass ratio of the oxidized natural graphite to the coating agent is controlled to be 100:3-40; the oxidized natural graphite is mixed with the coating After the coating agent mixture is spray-dried, the graphite anode material precursor is obtained;
3)、低温碳化处理，将步骤2)所得石墨负极材料前驱体在惰性气氛中，进行低温碳化处理，得碳化石墨负极材料前驱体；控制低温碳化处理温度温度为500-650℃，时间为6-20h，控制低温碳化升温速率为5-8℃/min。3), low-temperature carbonization treatment, the graphite anode material precursor obtained in step 2) is subjected to low-temperature carbonization treatment in an inert atmosphere to obtain a carbonized graphite anode material precursor; the low-temperature carbonization treatment temperature is controlled to 500-650°C, and the time is 6 -20h, control the heating rate of low-temperature carbonization to 5-8℃/min.
4)、沥青浸渍处理，将碳化石墨负极材料前驱体置于沥青溶剂中在压力存在的条件下，进行混合溶解处理，取出过滤、干燥，为沥青碳化石墨负极材料前驱体；控制所述沥青为低温沥青或中温沥青；控制所述压力为0.2-1.5Mp，在该压力存在的条件下保压时间为0.2-3h；4) Pitch impregnation treatment: place the precursor of carbonized graphite anode material in a pitch solvent under pressure, perform mixing and dissolution treatment, take out, filter, and dry, and become the precursor of pitch carbonized graphite anode material; control the pitch to be Low-temperature asphalt or medium-temperature asphalt; control the pressure to 0.2-1.5Mp, and hold the pressure for 0.2-3h under the condition of the pressure;
5)、二次碳化，制高性能锂离子电池用石墨负极材料，将步骤4)所得沥青碳化石墨负极材料前驱体物料进行粉碎后，在惰性气氛中，再进行高温碳化处理，控制沥青碳化石墨负极材料前驱体物料进行粉碎后的材料粒径为1um-50um，，控制高温碳化温度为1200-1400℃，碳化时间为5-24h；控制高温碳化的升温速率4-10℃/min；即得到高性能锂离子电池用石墨负极材料。5) Secondary carbonization to prepare graphite anode material for high-performance lithium ion batteries. After pulverizing the precursor material of pitch carbonized graphite anode material obtained in step 4), it is subjected to high temperature carbonization treatment in an inert atmosphere to control the pitch carbonized graphite After the negative electrode material precursor material is crushed, the particle size of the material is 1um-50um, and the high-temperature carbonization temperature is controlled to be 1200-1400°C, and the carbonization time is 5-24h; the heating rate of the high-temperature carbonization is controlled to 4-10°C/min; Graphite anode material for high-performance lithium-ion batteries.
作为优选，步骤1)中天然石墨质量：草酸：过硫酸钠质量为80-95：5-20：1-10，处理温度为500-600℃，保温时间为1-5h；Preferably, the quality of natural graphite in step 1): oxalic acid: sodium persulfate is 80-95:5-20:1-10, the treatment temperature is 500-600°C, and the holding time is 1-5h;
作为优选，步骤2)中石墨质量：包覆剂质量为100：3-40；Preferably, the graphite quality in step 2): the quality of the coating agent is 100:3-40;
作为优选，步骤3)中高温碳化温度曲线为：升温速率1-10℃/min，烧结温度为500-900℃，烧结时间为5-24h；Preferably, the high-temperature carbonization temperature curve in step 3) is: the heating rate is 1-10°C/min, the sintering temperature is 500-900°C, and the sintering time is 5-24h;
优选的是所述溶剂为甲苯、二甲苯、喹啉或水中的任意一种；Preferably, the solvent is any one of toluene, xylene, quinoline or water;
最终，本发明方法制备获得终产物一种锂离子电池用高容量高功率石墨负极材料，所述石墨负极材料粒径为2um-45um，比表面积为3-20m 2/g，其中天然石墨质量：硬碳质量：软碳质量为80-98：1-10：1-10。 Finally, the method of the present invention prepares the final product a high-capacity and high-power graphite anode material for lithium-ion batteries. The graphite anode material has a particle size of 2um-45um and a specific surface area of 3-20m 2 /g. The quality of natural graphite is: Hard carbon quality: The soft carbon quality is 80-98:1-10:1-10.
本发明方法制备获得的高性能锂离子电池用石墨负极材料，表面氧化处理天然石墨提升容量，硬碳包覆使其具备大倍率充电能力，浸渍处理修复氧化及硬碳包覆后留下的缺陷，提升其循环性能。该材料作为锂离子电池的负极材料时，其具备高容量、高压实、优异的倍率性能及循环寿命。The graphite anode material for high-performance lithium ion batteries prepared by the method of the present invention has surface oxidation treatment of natural graphite to increase capacity, hard carbon coating to make it have high-rate charging ability, and impregnation treatment to repair defects left after oxidation and hard carbon coating , To improve its cycle performance. When the material is used as a negative electrode material of a lithium ion battery, it has high capacity, high compactness, excellent rate performance and cycle life.
实施例1：Example 1:
本发明一种锂离子电池用高容量高功率石墨负极材料及其制备方法，由硬碳包覆于氧化天然石墨及表面修饰的软碳构成，方法步骤依次为：The present invention is a high-capacity and high-power graphite negative electrode material for lithium ion batteries and a preparation method thereof, which is composed of hard carbon coated on oxidized natural graphite and surface-modified soft carbon. The method steps are as follows:
1)、氧化处理，是将天然石墨与氧化剂与草酸及过硫酸钠的水溶液混合溶液进行充分搅拌混合，过滤、干燥，在惰性气氛条件下，进行高温氧化处理，为氧化天然石墨；制天然石墨与过氧化物和有机酸或天然石墨与过氧化盐和无机酸的质量比为80-95：5-20：1-10；控制高温氧化处理的温度为500-600℃；时间为2-4h；优选的是氧化剂为过硫酸钠和草酸的混合；1) Oxidation treatment is to fully stir and mix natural graphite and oxidant, oxalic acid and sodium persulfate aqueous solution mixed solution, filter, dry, and perform high-temperature oxidation treatment under inert atmosphere conditions to oxidize natural graphite; make natural graphite The mass ratio of peroxide and organic acid or natural graphite to peroxide salt and inorganic acid is 80-95:5-20:1-10; the temperature of high-temperature oxidation treatment is controlled at 500-600℃; the time is 2-4h ; Preferably the oxidant is a mixture of sodium persulfate and oxalic acid;
2)、制石墨负极材料前驱体，将步骤1)氧化天然石墨置于包覆剂及相应溶剂中，进行充分搅拌混合为氧化天然石墨与包覆剂混合物，所述包覆剂为蔗糖、酚醛树酯、环氧树脂、聚乙烯醇中的一种或多种溶解于相应溶剂中混合，控制所述氧化天然石墨与包覆剂的质量比为100：3-40；将氧化天然石墨与包覆剂混合物经喷雾干燥后，得到石墨负极材料前驱体；2) Preparing the precursor of the graphite anode material, placing step 1) oxidized natural graphite in the coating agent and corresponding solvent, and thoroughly stir and mix into a mixture of oxidized natural graphite and the coating agent, the coating agent is sucrose, phenolic aldehyde One or more of resin, epoxy resin, and polyvinyl alcohol are dissolved and mixed in the corresponding solvent, and the mass ratio of the oxidized natural graphite to the coating agent is controlled to be 100:3-40; the oxidized natural graphite is mixed with the coating After the coating agent mixture is spray-dried, the graphite anode material precursor is obtained;
3)、低温碳化处理，将步骤2)所得石墨负极材料前驱体在惰性气氛中，进行低温碳化处理，得碳化石墨负极材料前驱体；控制低温碳化处理温度温度为500-650℃，时间为6-20h，控制低温碳化升温速率为5-8℃/min。3), low-temperature carbonization treatment, the graphite anode material precursor obtained in step 2) is subjected to low-temperature carbonization treatment in an inert atmosphere to obtain a carbonized graphite anode material precursor; the low-temperature carbonization treatment temperature is controlled to 500-650°C, and the time is 6 -20h, control the heating rate of low-temperature carbonization to 5-8℃/min.
4)、沥青浸渍处理，将碳化石墨负极材料前驱体置于沥青溶剂或叫沥青有机溶液中在压力存在的条件下，进行混合溶解处理，取出过滤、干燥，为沥青碳化石墨负极材料前驱体；控制所述沥青为低温沥青或中温沥青；所述有机溶剂为甲苯、二甲苯，喹啉中的任意一种；控制所述压力为0.2-1.5Mp，在压力存在条件下保压时间为0.2-3h；4) Pitch dipping treatment: place the precursor of carbonized graphite anode material in a pitch solvent or organic solution called pitch, mix and dissolve it under pressure, take it out, filter, and dry, and become the precursor of pitch carbonized graphite anode material; The pitch is controlled to be low-temperature pitch or medium-temperature pitch; the organic solvent is any one of toluene, xylene, and quinoline; the pressure is controlled to be 0.2-1.5Mp, and the pressure holding time is 0.2- in the presence of pressure. 3h;
5)、二次碳化，制高性能锂离子电池用石墨负极材料，将步骤4)所得沥青碳化石墨负极材料前驱体物料进行粉碎后，在惰性气氛中，再进行高温碳化处理，控制沥青碳化石墨负极材料前驱体物料进行粉碎后的材料粒径为1um-50um，，控制高温碳化温度为1200-1400℃，碳化时间为5-24h；控制高温碳化的升温速率4-10℃/min；即得到高性能锂离子电池用石墨负极材料，控制高性能锂离子电池用石墨负极材料的各组成为为天然石墨质量：硬碳质量：软碳质量为80-98：1-10：1-10。5) Secondary carbonization to prepare graphite anode material for high-performance lithium ion batteries. After pulverizing the precursor material of pitch carbonized graphite anode material obtained in step 4), it is subjected to high temperature carbonization treatment in an inert atmosphere to control the pitch carbonized graphite After the negative electrode material precursor material is crushed, the particle size of the material is 1um-50um, and the high-temperature carbonization temperature is controlled to be 1200-1400°C, and the carbonization time is 5-24h; the heating rate of the high-temperature carbonization is controlled to 4-10°C/min; Graphite anode materials for high-performance lithium-ion batteries, the composition of graphite anode materials for high-performance lithium-ion batteries is controlled to be natural graphite quality: hard carbon quality: soft carbon quality is 80-98:1-10:1-10.
具体是1)氧化处理将1000g天然石墨加入到1000ml水中，加入10g过硫酸钠及50g草酸形成混合水溶液于温度为60℃条件下搅拌1-2h，过滤后真空干燥18-24h，在氮气气氛保护下置于加热装置的箱式炉中，升温到600℃，并保温3h，自然降温取出，记为料A即氧化天然石墨下称料A；2)、制石墨负极材料前驱体，将包覆剂50g蔗糖溶于2000L去离子水中，加入1000g料A，喷雾干燥后得到前驱体即为石墨负极材料前驱体，3)、低温碳化处理，将步骤2)的石墨负极材料前驱体置于箱式炉中，在氮气气氛保护下，按5℃/min升温速率升至650℃，保温6h，自然降温取出，得碳化石墨负极材料前驱体，记为料B；4)、沥青浸渍处理，是配置10％质量浓度的低温沥青甲苯溶液置于高压釜中，加入料B，在惰性气体条件下，反应釜压力升到1.5Mp，于此压力条件下保压1h，取出物料过滤烘干，即得沥青碳化石墨负极材料前驱体记，为料C；Specifically: 1) Oxidation treatment: Add 1000g of natural graphite to 1000ml of water, add 10g of sodium persulfate and 50g of oxalic acid to form a mixed aqueous solution, stir for 1-2h at a temperature of 60℃, filter and dry in vacuum for 18-24h, and protect in a nitrogen atmosphere. Place it in the box furnace of the heating device, heat it up to 600℃, keep it for 3h, take it out naturally, record it as material A, which is oxidized natural graphite, and call it material A; 2) Make the precursor of graphite anode material, and coat Dissolve 50g of sucrose in 2000L of deionized water, add 1000g of material A, spray and dry the precursor, which is the precursor of the graphite anode material, 3), low-temperature carbonization treatment, place the precursor of the graphite anode material of step 2) in a box type In the furnace, under the protection of a nitrogen atmosphere, the temperature is increased to 650°C at a heating rate of 5°C/min, kept for 6 hours, and taken out naturally to obtain the precursor of the carbonized graphite anode material, which is marked as material B; 4), pitch impregnation treatment, which is the configuration A low-temperature asphalt toluene solution with a mass concentration of 10% is placed in an autoclave, and material B is added. Under inert gas conditions, the pressure of the reactor is increased to 1.5Mp. Under this pressure condition, the pressure is maintained for 1 hour, and the material is taken out and filtered and dried. The precursor of the pitch carbonized graphite anode material is marked as material C;
5)、二次碳化，将料C粉碎至D50粒径为18um后，将其置于箱式炉中，在氮气气氛保护下，按5℃/min升温速率升至1200℃，保温5h降温，取出得到目标产品即为高性能锂离子电池用石墨负极材料，控制制备成的高性能锂离子电池石墨负极材料的各质量比是天然石墨质量：硬碳质量：软碳质量为80-98：1-10：1-10。SEM图谱见附图1，图1中的两图片为本发明制备方法制备的两种产品的SEM图谱。5) Secondary carbonization. After pulverizing material C to a D50 particle size of 18um, place it in a box furnace, under the protection of a nitrogen atmosphere, increase to 1200°C at a heating rate of 5°C/min, and keep it for 5 hours to cool down. The target product obtained is the graphite anode material for high-performance lithium-ion batteries, and the mass ratio of the prepared high-performance lithium-ion battery graphite anode material is controlled to be natural graphite quality: hard carbon quality: soft carbon quality 80-98:1 -10: 1-10. The SEM spectra are shown in Fig. 1. The two pictures in Fig. 1 are the SEM spectra of the two products prepared by the preparation method of the present invention.
下面是利用本发明方法制备的高性能锂离子电池石墨负极材料制成的锂离子电池性能检测，活性材料即本发明制得的锂离子电池石墨负极材料、导电剂，super P碳黑、羧甲基纤维素钠(CMC)、丁苯橡胶(SBR)：去离子水，按照质量比85:12:6:5:100，2000-2600r/min速度搅拌3h后，涂覆于15-18um厚度铜箔上，涂覆厚度40-45um，经滚压、切片、烘烤后得到电池极片，以锂片作为对电极制作半电池，电池型号为还是采用现有的CR2032扣式电池，电解液同样使用常用的锂离子电池电解液：如1.2-1.6mol/L六氟磷酸锂(LiPF6)/碳酸亚乙 酯(EC)：碳酸二甲酯(DMC)：碳酸甲乙酯(EMC)为12:12:76的混合液。The following is the performance test of lithium ion battery made of high-performance lithium ion battery graphite anode material prepared by the method of the present invention. The active material is the lithium ion battery graphite anode material, conductive agent, super P carbon black, and carboxymethyl prepared by the present invention. Sodium cellulose base (CMC), styrene butadiene rubber (SBR): deionized water, in accordance with the mass ratio of 85:12:6:5:100, 2000-2600r/min speed stirred for 3h, then coated on 15-18um thick copper The foil is coated with a thickness of 40-45um. After rolling, slicing, and baking, the battery pole piece is obtained. The lithium piece is used as the counter electrode to make a half-cell. The battery model is still the existing CR2032 button cell, and the electrolyte is the same Use commonly used lithium ion battery electrolyte: such as 1.2-1.6mol/L lithium hexafluorophosphate (LiPF6)/ethylene carbonate (EC): dimethyl carbonate (DMC): ethyl methyl carbonate (EMC) is 12:12:76 The mixture.
对利用本发明制备的电池进行充放电测试，0.2C倍率下恒流充放电，下限电压0.001V，上限电压2.0V。充放电曲线见附图2。其充放电容量分别是首次效率。对电池进行倍率充放电循环测试，其循环容量保持率见曲线附图3。下述实施例中除实施例中说明外其余与实施例1相同。A charge-discharge test was performed on the battery prepared by the present invention, the constant current charge-discharge at a rate of 0.2C, the lower limit voltage is 0.001V, and the upper limit voltage is 2.0V. See Figure 2 for charge and discharge curves. Its charge and discharge capacity is the first efficiency respectively. The battery is subjected to a rate charge-discharge cycle test, and its cycle capacity retention rate is shown in Figure 3 of the curve. The following embodiments are the same as Embodiment 1 except for the description in the embodiments.
实施例2：Example 2:
将1000g天然石墨加入到1000ml水中，加入10g过硫酸钠及50g草酸的水溶液60℃搅拌2h，过滤后真空干燥24h，氮气气氛下置于箱式炉中，以6℃/min升温速率升温至600℃保温3h降温取出，记为物料A，将包覆剂酚醛树脂30g溶解在1500ml无水乙醇中，加入物料A，喷雾干燥后得前驱体，将前驱体置于箱式炉中，氮气气氛下以2℃/min升温至800℃，保温3h，记为物料B，配制10％质量浓度的沥青甲苯溶液置高压反应釜中，加入料B，反应釜压力升到1.5Mp，保压1h，取出物料过滤烘干(记为料C)，将料C粉碎D50粒径为18um后，将其置于箱式炉中，在氮气气氛保护下，2℃/min升温速率升至1200℃，保温5h降温取出得到目标产品为高性能锂离子电池石墨负极材料。扣式电池组装及测试同实例1。Add 1000g natural graphite to 1000ml water, add 10g sodium persulfate and 50g oxalic acid aqueous solution at 60℃ and stir for 2h, filter and vacuum dry for 24h, put it in a box furnace under nitrogen atmosphere, and heat up to 600 at a heating rate of 6℃/min Keep it at ℃ for 3h and take it out, record it as material A, dissolve 30g of phenolic resin as the coating agent in 1500ml absolute ethanol, add material A, spray and dry to obtain the precursor, put the precursor in a box furnace under nitrogen atmosphere Raise the temperature to 800°C at 2°C/min, keep the temperature for 3h, record it as material B, prepare a 10% mass concentration asphalt toluene solution and place it in the autoclave, add material B, increase the pressure of the reactor to 1.5Mp, keep the pressure for 1h, and take it out The material is filtered and dried (denoted as material C). After the material C is crushed to a D50 particle size of 18um, it is placed in a box furnace, under the protection of a nitrogen atmosphere, the heating rate is increased to 1200°C at 2°C/min, and the temperature is kept for 5 hours. The target product obtained by cooling and taking out is a graphite anode material for high-performance lithium-ion batteries. The button cell assembly and testing are the same as in Example 1.
实施例3：Example 3:
将1000g天然石墨加入到1000ml水中，加入10g过硫酸钠及50g草酸60℃搅拌2h，过滤后真空干燥24h，氮气气氛下置于箱式炉中，以5℃/min升温速率升温至600℃保温3h降温取出，记为物料A，将聚乙烯醇40g溶解在1000ml水中，加入物料A，喷雾干燥后得前驱体，将前驱体置于箱式炉中，氮气气氛下以2℃/min升温至900℃，保温3h(记为物料B)，配制10％质量浓度的沥青二甲苯溶液置高压反应釜中，加入料B，反应釜压力升到1.2Mp，保压1h，取出物料过滤烘干，记为料C，将料C粉碎D50粒径为18um后，将其置于箱式炉中，在氮气气氛保护下，8℃/min升温速率升至1300℃，保温5h降温取出得到目标产品。Add 1000g of natural graphite to 1000ml of water, add 10g of sodium persulfate and 50g of oxalic acid, stir for 2h at 60°C, filter and vacuum dry for 24h, place in a box furnace under nitrogen atmosphere, heat up to 600°C at a heating rate of 5°C/min Take it out after cooling for 3 hours, record it as material A, dissolve 40g of polyvinyl alcohol in 1000ml of water, add material A, and get the precursor after spray drying. Place the precursor in a box furnace and heat up to 2℃/min under a nitrogen atmosphere. 900℃, heat preservation for 3h (denoted as material B), prepare a 10% mass concentration of asphalt xylene solution and place it in a high-pressure reactor, add material B, increase the pressure of the reactor to 1.2Mp, hold the pressure for 1h, take out the material and filter and dry it. Record it as material C. After crushing material C with a D50 particle size of 18um, place it in a box furnace, under the protection of a nitrogen atmosphere, increase the temperature rise rate of 8°C/min to 1300°C, keep it for 5 hours and lower the temperature to obtain the target product.
实施例4：Example 4:
将1000g天然石墨加入到1000ml水中，加入10g过硫酸钠及50g草酸60℃搅拌2h，过滤后真空干燥24h，氮气气氛下置于箱式炉中，以5℃/min升温速率升温至600℃保温3h降温取出，记为物料A，将水性环氧树脂50g溶解在1500ml水中，加入物料A，喷雾干燥后得前驱体，将前驱体置于箱式炉中，氮气气氛下以2℃/min升温至800℃，保温3h，记为物料B，配制15％质量浓度的沥青甲苯溶液置高压反应釜中，加入料B，反应釜压力升到1.2Mp，保压1h，取出物料过滤烘干记为料C，将料C粉碎D50粒径为15um后，将其置于箱式炉中，氦气气氛保护下，7℃/min升温速率升至1400℃，保温5h降温取出得到目标产品。扣式电池组装及测试同实例1。Add 1000g of natural graphite to 1000ml of water, add 10g of sodium persulfate and 50g of oxalic acid, stir for 2h at 60°C, filter and vacuum dry for 24h, place in a box furnace under nitrogen atmosphere, heat up to 600°C at a heating rate of 5°C/min Take it out after cooling for 3 hours, record it as material A, dissolve 50g of water-based epoxy resin in 1500ml water, add material A, and get the precursor after spray drying. Place the precursor in a box furnace and heat up at 2℃/min under nitrogen atmosphere. Keep the temperature at 800℃ for 3h, record it as material B, prepare 15% mass concentration of asphalt toluene solution and place it in the autoclave, add material B, increase the pressure of the reactor to 1.2Mp, keep the pressure for 1h, take out the material, filter and dry it, record it as Material C. After crushing material C with a particle size of D50 of 15um, place it in a box furnace under helium atmosphere protection, increase the temperature rise rate of 7°C/min to 1400°C, keep it for 5 hours and lower the temperature to obtain the target product. The button cell assembly and testing are the same as in Example 1.
实施例5：Example 5:
本发明一种锂离子电池用高容量高功率石墨负极材料及其制备方法，由硬碳包覆于氧化天然石墨及表面修饰的软碳构成，方法步骤依次为：The present invention is a high-capacity and high-power graphite negative electrode material for lithium ion batteries and a preparation method thereof, which is composed of hard carbon coated on oxidized natural graphite and surface-modified soft carbon. The method steps are as follows:
1)氧化处理，将1000g天然石墨加入到1000ml水中，加入10g过硫酸钠及相应的硫酸形成混合水溶液于温度为70℃条件下搅拌1-2h，过滤后真空干燥18-24h，在氮气气氛保护下置于加热装置的箱式炉中，升温到500℃，并保温2h，自然降温取出，记为料A即氧化天然石墨下称料A；2)、制石墨负极材料前驱体，将包覆剂50g环氧树脂溶于2000L去离子水中，加入1000g料A，控制所述氧化天然石墨与包覆剂的质量比为100：3-40；为氧化天然石墨与 包覆剂混合物，将氧化天然石墨与包覆剂混合物经喷雾干燥后得到前驱体即为石墨负极材料前驱体，3)、低温碳化处理，将步骤2)的碳化石墨负极材料前驱体置于箱式炉中，在氮气气氛保护下，6℃/min升温速率升至500℃，保温6h降温取出，得碳化石墨负极材料前驱体，记为料B；4)、沥青浸渍处理，是配置10％质量浓度的中温沥青甲苯溶液置于高压釜中，加入料B，在惰性气体条件下，反应釜压力升到1.0Mp，保压2h，取出物料过滤烘干，即得沥青碳化石墨负极材料前驱体记，为料C；1) Oxidation treatment, add 1000g of natural graphite to 1000ml of water, add 10g of sodium persulfate and corresponding sulfuric acid to form a mixed aqueous solution, stir for 1-2h at a temperature of 70℃, filter and dry in vacuum for 18-24h, and protect in a nitrogen atmosphere. Place it in the box furnace of the heating device, heat it up to 500℃, keep it for 2h, take it out naturally, and record it as material A, which is oxidized natural graphite. 50g epoxy resin is dissolved in 2000L deionized water, 1000g material A is added to control the mass ratio of the oxidized natural graphite to the coating agent to be 100:3-40; it is a mixture of oxidized natural graphite and the coating agent, which will oxidize the natural stone The ink and coating agent mixture is spray-dried to obtain the precursor, which is the precursor of the graphite anode material. 3), low-temperature carbonization, and the precursor of the carbonized graphite anode material in step 2) is placed in a box furnace, and protected in a nitrogen atmosphere. The temperature rise rate of 6°C/min was increased to 500°C, and the temperature was kept for 6 hours. The precursor of the carbonized graphite anode material was obtained, which was recorded as material B; 4). The pitch impregnation treatment was prepared with a 10% mass concentration of medium temperature pitch toluene solution. In the autoclave, add material B, under the inert gas condition, the pressure of the reactor is increased to 1.0Mp, the pressure is maintained for 2h, and the material is taken out and filtered and dried to obtain the precursor of the pitch carbonized graphite anode material, which is marked as material C;
5)、二次碳化，将料C粉碎至D50粒径为25um后，将其置于箱式炉中，在氮气气氛保护下，4℃/min升温速率升至1300℃，保温10h降温，取出得到目标产品即为高性能锂离子电池用石墨负极材料，控制制备成的高性能锂离子电池石墨负极材料的各质量比是天然石墨质量：硬碳质量：软碳质量为80-98：1-10：1-10。5) Secondary carbonization. After crushing material C to D50 with a particle size of 25um, place it in a box furnace, and under the protection of nitrogen atmosphere, the temperature rise rate of 4℃/min is increased to 1300℃, the temperature is kept for 10h, and the temperature is reduced. The target product obtained is the graphite anode material for high-performance lithium-ion batteries, and the mass ratio of the prepared high-performance lithium-ion battery graphite anode material is controlled to be natural graphite quality: hard carbon quality: soft carbon quality 80-98:1 10:1-10.
利用本发明方法制备获得的高性能锂离子电池石墨负极材料，是经表面氧化处理天然石墨提升容量，硬碳包覆使其具备大倍率充电能力，沥青浸渍处理修复氧化及硬碳包覆后留下的缺陷，提升其循环性能。该材料作为锂离子电池负极材料时，其具备高容量、高压实、优异的倍率性能及循环寿命。The high-performance graphite negative electrode material for lithium ion batteries prepared by the method of the present invention is surface oxidation treatment of natural graphite to increase the capacity, hard carbon coating to make it have a high-rate charging ability, asphalt impregnation treatment to repair oxidation and hard carbon coating to leave behind Under the defect, improve its cycle performance. When the material is used as a negative electrode material for lithium-ion batteries, it has high capacity, high compactness, excellent rate performance and cycle life.

Claims (9)

  1. 一种高性能锂离子电池石墨负极材料的制备方法，以天然石墨为原材料，通过氧化处理提升容量，通过硬碳包覆提升其倍率性能，通过浸渍处理提升其循环性能，其特征是包括如下步骤：A method for preparing high-performance lithium ion battery graphite negative electrode material, using natural graphite as raw material, increasing capacity through oxidation treatment, increasing rate performance through hard carbon coating, and improving cycle performance through impregnation treatment, characterized by including the following steps :
    1)、氧化处理，是将天然石墨与氧化剂混合溶液进行充分搅拌混合，过滤、干燥，在惰性气氛条件下，进行高温氧化处理，为氧化天然石墨；1) Oxidation treatment is to fully stir and mix the natural graphite and the oxidant mixed solution, filter, dry, and perform high-temperature oxidation treatment under inert atmosphere conditions to obtain oxidized natural graphite;
    2)、制石墨负极材料前驱体，将步骤1)氧化天然石墨置于包覆剂及相应溶剂中，进行充分搅拌混合为氧化天然石墨与包覆剂混合物，将氧化天然石墨与包覆剂混合物经喷雾干燥后，得到石墨负极材料前驱体；2) To prepare the precursor of the graphite anode material, place step 1) oxidized natural graphite in the coating agent and the corresponding solvent, and mix thoroughly to form a mixture of oxidized natural graphite and coating agent, and combine the oxidized natural graphite and coating agent mixture After spray drying, the graphite anode material precursor is obtained;
    3)、低温碳化处理，将步骤2)所得石墨负极材料前驱体在惰性气氛中，进行低温碳化处理，得碳化石墨负极材料前驱体；3), low-temperature carbonization treatment, the graphite anode material precursor obtained in step 2) is subjected to low-temperature carbonization treatment in an inert atmosphere to obtain a carbonized graphite anode material precursor;
    4)、沥青浸渍处理，将碳化石墨负极材料前驱体置于沥青溶剂中在压力存在的条件下，进行混合溶解处理，取出过滤、干燥，为沥青碳化石墨负极材料前驱体；4) Pitch impregnation treatment: place the precursor of carbonized graphite anode material in a pitch solvent under pressure, perform mixing and dissolution treatment, take out, filter, and dry, and become the precursor of pitch carbonized graphite anode material;
    5)、二次碳化，制高性能锂离子电池用石墨负极材料，将步骤4)所得沥青碳化石墨负极材料前驱体物料进行粉碎后，在惰性气氛中，再进行高温碳化处理，即得到高性能锂离子电池用石墨负极材料。5) Secondary carbonization is used to prepare graphite anode materials for high-performance lithium ion batteries. After the precursor material of the pitch carbonized graphite anode material obtained in step 4) is pulverized, it is subjected to high-temperature carbonization in an inert atmosphere to obtain high-performance Graphite anode material for lithium ion batteries.
  2. 根据权利要求1所述的高性能锂离子电池石墨负极材料的制备方法，其特征是步骤1)所述氧化剂为过氧化物和有机酸的混合或过氧化物和无机酸的混合，控制天然石墨与过氧化物和有机酸或天然石墨与过氧化盐和无机酸的质量比为80-95：5-20：1-10；控制高温氧化处理的温度为500-600℃；时间为2-4h。The method for preparing graphite anode materials for high-performance lithium-ion batteries according to claim 1, characterized in that step 1) the oxidant is a mixture of peroxide and organic acid or a mixture of peroxide and inorganic acid to control natural graphite The mass ratio of peroxide and organic acid or natural graphite to peroxide salt and inorganic acid is 80-95:5-20:1-10; the temperature of high-temperature oxidation treatment is controlled at 500-600℃; the time is 2-4h .
  3. 根据权利要求1所述的高性能锂离子电池石墨负极材料的制备方法，其特征是步骤2)所述包覆剂为蔗糖、酚醛树酯、环氧树脂、聚乙烯醇中的任意一种或多种；控制所述氧化天然石墨与包覆剂的质量比为100：3-40。The method for preparing graphite anode materials for high-performance lithium-ion batteries according to claim 1, wherein step 2) the coating agent is any one of sucrose, phenolic resin, epoxy resin, and polyvinyl alcohol. Many; control the mass ratio of the oxidized natural graphite and the coating agent to 100:3-40.
  4. 根据权利要求1所述的高性能锂离子电池石墨负极材料的制备方法，其特征是步骤3)控制低温碳化处理温度温度为500-650℃，时间为6-20h，控制升温速率为5-8℃/min。The method for preparing graphite anode materials for high-performance lithium-ion batteries according to claim 1, characterized in that step 3) controls the low-temperature carbonization temperature to be 500-650°C, the time is 6-20h, and the temperature rise rate is controlled to be 5-8 ℃/min.
  5. 根据权利要求1所述的高性能锂离子电池石墨负极材料的制备方法，其特征是步骤4)沥青浸渍处理，所述沥青为低温沥青或中温沥青；控制所述压力为0.2-1.5Mp，在压力存在条件下保压时间为0.2-3h。The method for preparing graphite anode materials for high-performance lithium-ion batteries according to claim 1, characterized in that step 4) pitch impregnation treatment, the pitch is low-temperature pitch or medium-temperature pitch; the pressure is controlled to be 0.2-1.5Mp, The holding time under pressure is 0.2-3h.
  6. 根据权利要求1所述的高性能锂离子电池石墨负极材料的制备方法，其特征是步骤5)控制沥青碳化石墨负极材料前驱体物料进行粉碎后的材料粒径为1um-50um，，控制高温碳化温度为1200-1400℃，碳化时间为5-24h；控制高温碳化的升温速率4-10℃/min。The method for preparing graphite anode materials for high-performance lithium-ion batteries according to claim 1, characterized in that step 5) control the pitch carbonized graphite anode material precursor material to crush the particle size of the material to be 1um-50um, and control high-temperature carbonization The temperature is 1200-1400°C, and the carbonization time is 5-24h; the heating rate of high-temperature carbonization is controlled at 4-10°C/min.
  7. 根据权利要求1或2所述的高性能锂离子电池石墨负极材料的制备方法，其特征是所述氧化剂为过硫酸钠和草酸的混合或过氧化钠和浓硫酸的混合。The method for preparing a graphite anode material for a high-performance lithium ion battery according to claim 1 or 2, characterized in that the oxidant is a mixture of sodium persulfate and oxalic acid or a mixture of sodium peroxide and concentrated sulfuric acid.
  8. 根据权利要求1所述的高性能锂离子电池石墨负极材料的制备方法制备的高性能锂离子电池用石墨负极材料，其特征是所述高性能锂离子电池用石墨负极材料由硬碳包覆于氧化天然石墨及软碳构成，控制质量比为天然石墨质量：硬碳质量：软碳质量为80-98：1-10：1-10。The graphite anode material for high-performance lithium-ion batteries prepared by the method for preparing graphite anode materials for high-performance lithium-ion batteries according to claim 1, characterized in that the graphite anode material for high-performance lithium-ion batteries is coated with hard carbon Composed of oxidized natural graphite and soft carbon, the control quality ratio is natural graphite quality: hard carbon quality: soft carbon quality is 80-98:1-10:1-10.
  9. 根据权利要求8所述的高性能锂离子电池石墨负极材料，其特征是控制所述高性能锂离子电池用石墨负极材料的粒径为2um-45um，比表面积为3-20m 2/g。 The graphite anode material for high-performance lithium ion batteries according to claim 8, characterized in that the particle size of the graphite anode material for high-performance lithium ion batteries is controlled to be 2um-45um, and the specific surface area is 3-20m 2 /g.
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