WO2021189836A1 - Materiau d'électrode négative de graphite pour batterie au lithium-ion à haute performance et sa méthode de préparation - Google Patents

Materiau d'électrode négative de graphite pour batterie au lithium-ion à haute performance et sa méthode de préparation 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.

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Abstract

L'invention concerne un matériau d'électrode négative de graphite pour une batterie au lithium-ion à haute performance, ainsi que sa méthode de préparation. Le procédé de préparation comprend les étapes suivantes : 1) soumettre du graphite naturel à un traitement d'oxydation de surface; 2) revêtir le graphite naturel, qui a subi le traitement d'oxydation, avec du carbone dur pour obtenir un précurseur; 3) soumettre le précurseur obtenu à l'étape 2) à un traitement de carbonisation; 4) soumettre le précurseur, qui a subi le traitement de carbonisation, à un traitement d'imprégnation; et 5) broyer le matériau imprégné, puis le carboniser pour obtenir un matériau d'électrode négative de graphite haute puissance à haute capacité. Le traitement d'oxydation de surface augmente la capacité du graphite naturel, le revêtement avec le carbone dur lui confère une grande capacité de charge, et le traitement d'imprégnation peut réparer tout défaut restant après l'oxydation et le revêtement de carbone dur, ce qui permet d'améliorer les performances de cycle de celui-ci.
PCT/CN2020/123705 2020-03-25 2020-10-26 Materiau d'électrode négative de graphite pour batterie au lithium-ion à haute performance et sa méthode de préparation WO2021189836A1 (fr)

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008100002A1 (fr) * 2007-02-16 2008-08-21 Ls Mtron, Ltd. Matériau actif pour anode pour batterie ion-lithium rechargeable, procédé de fabrication et batterie ion-lithium fabriquée au moyen dudit matériau actif
CN102030326A (zh) * 2010-11-22 2011-04-27 中科恒达石墨股份有限公司 一种石墨负极材料制备方法
CN102255077A (zh) * 2010-05-21 2011-11-23 深圳市比克电池有限公司 锂离子电池负极材料及制备方法
CN102832378A (zh) * 2012-08-28 2012-12-19 浙江瓦力新能源科技有限公司 一种锂离子电池碳负极材料及其制备方法
CN104733705A (zh) * 2013-12-20 2015-06-24 上海杉杉科技有限公司 锂离子动力电池用负极材料及其制备方法
CN106252596A (zh) * 2016-08-05 2016-12-21 深圳市贝特瑞新能源材料股份有限公司 软碳石墨复合负极材料、制备方法及锂离子电池
CN109449420A (zh) * 2018-11-08 2019-03-08 安徽科达洁能新材料有限公司 一种表面微氧化以及液相包覆改性石墨负极材料及其制备方法
CN110775971A (zh) * 2019-10-15 2020-02-11 合肥国轩高科动力能源有限公司 一种天然石墨的改性方法、改性天然石墨及应用
CN111333064A (zh) * 2020-03-25 2020-06-26 江西正拓新能源科技股份有限公司 高性能锂离子电池石墨负极材料及其制备方法

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008100002A1 (fr) * 2007-02-16 2008-08-21 Ls Mtron, Ltd. Matériau actif pour anode pour batterie ion-lithium rechargeable, procédé de fabrication et batterie ion-lithium fabriquée au moyen dudit matériau actif
CN102255077A (zh) * 2010-05-21 2011-11-23 深圳市比克电池有限公司 锂离子电池负极材料及制备方法
CN102030326A (zh) * 2010-11-22 2011-04-27 中科恒达石墨股份有限公司 一种石墨负极材料制备方法
CN102832378A (zh) * 2012-08-28 2012-12-19 浙江瓦力新能源科技有限公司 一种锂离子电池碳负极材料及其制备方法
CN104733705A (zh) * 2013-12-20 2015-06-24 上海杉杉科技有限公司 锂离子动力电池用负极材料及其制备方法
CN106252596A (zh) * 2016-08-05 2016-12-21 深圳市贝特瑞新能源材料股份有限公司 软碳石墨复合负极材料、制备方法及锂离子电池
CN109449420A (zh) * 2018-11-08 2019-03-08 安徽科达洁能新材料有限公司 一种表面微氧化以及液相包覆改性石墨负极材料及其制备方法
CN110775971A (zh) * 2019-10-15 2020-02-11 合肥国轩高科动力能源有限公司 一种天然石墨的改性方法、改性天然石墨及应用
CN111333064A (zh) * 2020-03-25 2020-06-26 江西正拓新能源科技股份有限公司 高性能锂离子电池石墨负极材料及其制备方法

Cited By (33)

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