CN115611275B - Artificial graphite negative electrode active material, preparation and application thereof - Google Patents
Artificial graphite negative electrode active material, preparation and application thereof Download PDFInfo
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- 229910021383 artificial graphite Inorganic materials 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 52
- 239000000571 coke Substances 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 46
- 239000006183 anode active material Substances 0.000 claims abstract description 45
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000011282 treatment Methods 0.000 claims abstract description 36
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 31
- 238000005087 graphitization Methods 0.000 claims abstract description 29
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- 150000003624 transition metals Chemical class 0.000 claims abstract description 20
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 18
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000010000 carbonizing Methods 0.000 claims abstract description 7
- 238000003825 pressing Methods 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims description 25
- 230000008569 process Effects 0.000 claims description 21
- 239000001301 oxygen Substances 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 15
- 238000003763 carbonization Methods 0.000 claims description 8
- 239000011331 needle coke Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000002006 petroleum coke Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 3
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 3
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 3
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 3
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 claims description 3
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 3
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005695 Ammonium acetate Substances 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 229940043376 ammonium acetate Drugs 0.000 claims description 2
- 235000019257 ammonium acetate Nutrition 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000001513 hot isostatic pressing Methods 0.000 claims description 2
- 239000004005 microsphere Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000011295 pitch Substances 0.000 claims description 2
- 239000006253 pitch coke Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 37
- 239000000243 solution Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 10
- 238000005265 energy consumption Methods 0.000 description 9
- 239000010405 anode material Substances 0.000 description 7
- 239000011362 coarse particle Substances 0.000 description 7
- 239000010419 fine particle Substances 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 239000010426 asphalt Substances 0.000 description 5
- 238000004321 preservation Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 4
- 239000005539 carbonized material Substances 0.000 description 4
- 229940078494 nickel acetate Drugs 0.000 description 4
- 238000012216 screening Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 239000007770 graphite material Substances 0.000 description 2
- 239000002391 graphite-based active material Substances 0.000 description 2
- 238000000462 isostatic pressing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- -1 transition metal salt Chemical class 0.000 description 1
Classifications
-
- 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
- C01B32/205—Preparation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to the field of lithium secondary batteries, in particular to a preparation method of an artificial graphite negative electrode active material, which comprises the steps of carrying out heat treatment on a coke raw material under the atmosphere containing gaseous water to obtain a coke raw material A; wherein the temperature of the heat treatment is 300-600 ℃; dispersing the coke raw material A in a solution containing a transition metal source and an ammonium source, and carrying out pressurization treatment on the system by utilizing gas, wherein the pressure is 5-20 MPa, and the temperature is 50-160 ℃; pressurizing and then decompressing, and collecting to obtain a coke raw material B; mixing a small-particle-size coke raw material B with a carbon source, and carbonizing to obtain carbon C; carbonizing a large-particle-size coke raw material B to obtain carbon D; and (3) pressing and forming the carbon C and the carbon D, and then carrying out graphitization treatment to obtain the artificial graphite anode active material. The invention also comprises the material prepared by the preparation method and application thereof. The method can reduce graphitization treatment time and treatment cost, and can improve the performance of materials, particularly the rate capability.
Description
Technical Field
The invention belongs to the technical field of lithium battery electrode materials, and particularly relates to a low-energy-consumption catalytic graphitization preparation method of an artificial graphite negative electrode.
Background
Lithium ion batteries are a typical representation of new green rechargeable battery systems and have wide application in a variety of fields due to their excellent performance. Graphite has good conductivity, is suitable for a layered structure of intercalation-deintercalation of lithium, has good cycle performance, and becomes one of core raw materials of lithium ion batteries.
In recent years, with the rapid development of new energy automobiles with lithium batteries, the advantages of multiplying power and cycle characteristics of artificial graphite are increasingly outstanding, and the artificial graphite becomes a main raw material of a power battery, and is widely focused on cost while being applied in a large amount of commercialization, so that the artificial graphite becomes a hot spot for research.
At present, the artificial graphite takes petroleum coke or needle coke as a main raw material, and the main production process flow of the artificial graphite anode material mainly comprises the following 4 steps: crushing raw materials, modifying the surface of powder particles, graphitizing, sieving, demagnetizing, packaging and the like. The graphitization process is to heat the material to 2800 ℃ in a protective medium (mostly nitrogen) in a high-temperature electric furnace, and change the space structure of the zoom material to ensure that the material has good volume density, electrical conductivity, thermal conductivity, corrosion resistance and machining property. In recent years, with the maturation and scale expansion of domestic needle coke technology, graphitization cost exceeds raw material cost, and the problem to be solved is urgent. The main graphitizing equipment of the negative electrode material is an Acheson furnace, and the powder is filled into a graphite crucible by referring to an electrode graphitizing process, and the powder heats up due to the effect of resistance, so that the carbon powder is converted into artificial graphite through high-temperature heat treatment at 2500-3000 ℃. However, the acheson graphitizing furnace has higher energy consumption, and only 30% of electric energy is used for graphitizing the product, so that the graphitizing process in the artificial graphite process has higher cost pressure. The graphitization process flow mainly comprises the processes of furnace bottom paving, furnace core building, anode material precursor and heat preservation material body charging, power transmission, cooling, furnace discharging, packaging and the like. One period of graphitization generally takes 20-30 days, wherein 40-100 hours for power transmission and temperature rise are key links of the graphitization process. Because the whole link needs high temperature and high energy consumption, the graphitization treatment of a single ton of materials needs 7000-14000 ℃ electricity, and the graphitization process accounts for about 50% of the cost of the artificial graphite cathode. Therefore, there is a need to develop new processes to reduce the graphitization treatment cost of artificial graphite and improve the properties of the prepared materials.
Disclosure of Invention
Aiming at the problems of high energy consumption and non-ideal electrochemical performance of the existing artificial graphite active material, the first aim of the invention is to provide a preparation method of an artificial graphite negative electrode active material, and the preparation method aims at providing a preparation method of artificial graphite with low energy consumption and high electrochemical performance.
The second object of the invention is to provide the artificial graphite anode material prepared by the preparation method.
The third object of the invention is to provide the application of the artificial graphite anode material prepared by the preparation method in a lithium secondary battery and the prepared lithium secondary battery.
A fourth object of the present invention is to provide a lithium secondary battery comprising the artificial graphite active material.
In the prior art, the artificial graphite material is generally obtained by crushing and screening petroleum coke or needle coke to obtain primary particles, and mixing the primary particles with asphalt, carbonizing, graphitizing and other processes. The graphitization process needs high temperature treatment for more than 24 hours at the temperature of more than 2800 ℃ to realize carbon atom rearrangement and high crystalline phase graphite acquisition, so as to improve the reversible lithium removal performance and high conductivity of the material. However, the graphitization process generally needs to be kept for more than 30 hours, the electricity consumption is extremely high, the preparation cost is high, and the prepared artificial graphite is generally low in tap and compaction density. To this end, the invention provides the following improved method:
The preparation method of the artificial graphite anode active material comprises the following steps:
Step (1):
Carrying out heat treatment on the coke raw material in an atmosphere containing gaseous water to obtain a coke raw material A; wherein the temperature of the heat treatment is 300-600 ℃;
step (2):
Dispersing the coke raw material A in a solution containing a transition metal source and an ammonium source, and carrying out pressurization treatment on the system by utilizing gas, wherein the pressure is 5-25 MPa, and the temperature is 50-160 ℃;
pressurizing and then decompressing, and collecting to obtain a coke raw material B;
Step (3):
Mixing a small-particle-size coke raw material B with a carbon source, and carbonizing to obtain carbon C;
carbonizing a large-particle-size coke raw material B to obtain carbon D;
The D50 of the small-particle-size coke raw material B is 5-12 mu m; the D50 of the large-particle-size coke raw material B is 1.5 times of the D50 of the small-particle-size coke raw material B;
step (4):
and (3) pressing and forming the carbon C and the carbon D, and then carrying out graphitization treatment to obtain the artificial graphite anode active material.
In the invention, the coke raw material is innovatively subjected to gaseous underwater heat treatment, then matched with the pressurizing treatment of transition metal source and ammonium source solution under the assistance of gas, and the large and small coke raw materials are graded and further matched with the control of technological parameters, so that the technological and parameter coordination can be realized, the graphitization difficulty can be effectively reduced, the artificial graphite anode active material can be obtained with low energy consumption, and more importantly, the material prepared in the aspect has unexpected advantages in the aspect of performance.
In the invention, the coke raw material is at least one of petroleum coke, needle coke and pitch coke.
In the invention, the gas-solid heat treatment of the gaseous underwater in the step (1), the gas-solid-liquid three-phase pressurization treatment in the step (2) and the subsequent grading treatment are key to synergistically improving the material performance.
Preferably, in the atmosphere, the volume content of the gaseous water is 20% or more, preferably 20 to 100%, and more preferably 50 to 90%.
In the present invention, in the step (1), the atmosphere further contains an oxygen-containing gas. According to the invention, the research surprisingly shows that the treatment of the coke raw material under the combined atmosphere of the oxygen-containing atmosphere and the gaseous water can be further cooperated, so that the suitability of the microstructure and the particles can be further improved, the graphitization difficulty can be further reduced, and the graphite anode material with high tap density and high performance can be obtained.
Preferably, the oxygen-containing gas is air or oxygen;
preferably, the volume content of the oxygen-containing atmosphere is 5-20%;
preferably, the atmosphere in the step (1) further contains at least one atmosphere of nitrogen and inert gas;
Preferably, in the step (1), the temperature of the heat treatment is 450-550 ℃; in the invention, the preferable atmosphere and temperature help to reduce graphitization difficulty and can further improve the capacity and rate performance of the prepared material.
Preferably, in step (1), the time of the heat treatment is 0.5 to 6 hours, preferably 1 to 3 hours.
In the invention, under the special gas-solid treatment of the step (1), the catalyst is further placed in a solution containing a transition metal source and an ammonium source, and pressurized treatment is carried out by utilizing gas, so that the gas-solid-liquid three-phase treatment can be facilitated, the process of the step (1) is further matched, the particle suitability is further improved, the graphitization difficulty is reduced, and the electrochemical performance of the material is improved.
Preferably, the transition metal source is at least one of salts, hydroxides and oxides of transition metals;
Preferably, the transition metal element is nickel and/or cobalt;
preferably, the transition metal source is at least one of nickel nitrate, cobalt nitrate, nickel hydroxide, cobalt hydroxide, nickel oxide, cobalt oxide and nickel oxalate;
Preferably, the ammonium source is at least one of ammonia water, ammonium chloride, nitrate, ammonium sulfate and ammonium acetate;
Preferably, in the solution in the step (2), the concentration of the transition metal source is 0.1-5 g/L, and the concentration of the ammonium source is 0.5-20 g/L;
Preferably, the weight ratio of the coke raw material A to the transition metal source of the solution is 100:1 to 10, more preferably 100:5 to 8.
Preferably, in the step (2), the gas is at least one of nitrogen, inert gas and oxygen-containing gas, preferably oxygen-containing gas. It was found that pressurization under a preferred oxygen-containing atmosphere helped further synergistically improve the properties of the material.
In the invention, under the combined control of solution components, the control of the gas pressurizing pressure and temperature in the treatment stage is further matched, and the material performance can be further improved in cooperation with the step (1).
Preferably, the temperature of the pressure treatment stage is 60 to 120 ℃, further preferably 80 to 120 ℃;
In the present invention, the pressure of the gas pressurization is greater than the self pressure of the heating in the kettle (p=nrt/V).
Preferably, the pressurizing pressure is 15-20 MPa;
Preferably, the pressure maintaining treatment is carried out for 4 to 12 hours under the pressure.
According to the invention, under the combined treatment of the steps (1) and (2), the large-particle-size and small-particle-size segmented carbonization grading treatment is further matched, so that the graphitization difficulty can be further synergistically reduced, and the electrochemical performance of the prepared material can be improved.
In the invention, the large-particle and small-particle coke raw material B can be obtained by classifying the coke raw material into large particles and small particles and then performing the treatment of the steps (1) and (2), or by pre-treating the composite-size coke raw material by the steps (1) and (2) and then re-classifying the coke raw material to form the large-particle and small-particle coke raw material B.
Preferably, the D50 of the small-particle-size coke raw material B is 6-10 μm;
the ratio of D50 of the large-grain-size coke raw material B to the small-grain-size coke raw material B is 1.5-2.5: 1, preferably 2 to 2.5:1;
Preferably, the carbon source is at least one of soft carbon source, preferably pitch, needle coke, petroleum coke, mesophase carbon microsphere, and the like;
preferably, the weight ratio of the small particle size coke raw material B to the carbon source is 100:2 to 8;
preferably, the carbonization process is performed under negative pressure;
Preferably, the negative pressure is 5 to 50Pa;
preferably, the carbonization temperature is 800-1250 ℃, preferably 900-1000 ℃;
preferably, the mass ratio of carbon C to carbon D is 1-9:1-9, preferably 1-5:1;
Preferably, carbon C and carbon D are pressed by hot isostatic pressing, and the pressure is preferably 50-300 MPa;
preferably, the graphitization temperature is 2800-3200 ℃;
Preferably, the graphitization time is 10 to 16 hours.
And carrying out conventional treatments such as crushing, screening, demagnetizing and the like after graphitizing treatment to obtain the artificial graphite anode active material.
The invention discloses a low-energy-consumption catalytic graphitization preparation method of an artificial graphite negative electrode, which comprises the following steps of:
Step (1): treating one or more of uncalcined petroleum coke, needle coke or asphalt coke as raw materials by using an abrasive to obtain coarse particles (CKL) with the particle size of 1.5-3 times of that of the XKL and fine particles (XKL) with the particle size of 5-12 mu m;
step (2): placing the coarse particles and the fine particles in the previous step in an atmosphere furnace respectively, and introducing gaseous water (steam) or a gaseous water-oxygen atmosphere mixed gas for heat treatment to obtain treatment materials, namely h-CKL and h-XKL respectively; the temperature of the heat treatment is 300-600 ℃ and the time is 0.5-6 h;
Step (3): uniformly dispersing the solution of the treatment material, the transition metal salt and the ammonium source in the step 2, pressurizing by adopting gas, and then performing desolventizing treatment and material drying after the system is cooled to normal pressure and normal temperature to obtain s-h-CKL and s-h-XKL respectively; the transition metal source is nickel nitrate, cobalt nitrate, nickel hydroxide, cobalt hydroxide, nickel oxide, cobalt oxide, nickel oxalate and the like.
Step (4): placing the s-h-CKL in an atmosphere furnace for vacuum carbonization treatment to obtain a carbonized material (CKL-C);
Step (5): granulating the s-h-XKL and asphalt in a fusion machine, and then performing vacuum carbonization treatment in a vacuum furnace to obtain carbonized material (XKL-C/C);
Step (6): and uniformly mixing CKL-C and XKL-C/C according to a certain proportion, compacting in an isostatic press, then placing in a graphitizing furnace for graphitizing, and finally carrying out conventional depolymerization, demagnetizing and screening to obtain the artificial graphite anode material.
The invention also provides the artificial graphite anode active material prepared by the preparation method.
The preparation method can endow the material with special physical and chemical properties, and can show excellent electrochemical properties.
The invention also provides application of the artificial graphite anode active material, and the artificial graphite anode active material is used as an anode active material. Preferably, it is used as a negative electrode active material for preparing a lithium secondary battery.
In the invention, the artificial graphite anode active material prepared by the invention can be prepared into a required battery and a component thereof based on the existing process, equipment and means.
For example, the artificial graphite material is used as a negative electrode active material for compounding with a conductive agent and a binder to prepare a negative electrode material. The conductive agent and the binder are all materials known in the industry.
In a further preferred application, the negative electrode material is applied to the surface of a negative electrode current collector to prepare a negative electrode. The negative electrode material of the present invention may be formed on the current collector by an existing conventional method, for example, by a coating method. The current collector is any material known in the industry.
In a further preferred application, the negative electrode and positive electrode, separator and electrolyte are assembled into a lithium secondary battery.
A lithium secondary battery comprising the artificial graphite anode material produced by the production method.
The lithium secondary battery comprises a negative electrode plate and a graphite negative electrode material.
Preferably, the lithium secondary battery is a lithium ion battery.
The beneficial effects are that:
(1) In the invention, the coke raw material is innovatively subjected to gaseous underwater heat treatment, then matched with a transition metal source and an ammonium source solution under the assistance of gas for pressurization treatment, and further matched with the control of technological parameters, so that the technological and parameter coordination can be realized, the graphitization difficulty can be effectively reduced, the artificial graphite anode active material can be obtained with low energy consumption, and more importantly, the prepared material has unexpected advantages in performance.
(2) The main raw materials and the materials are wide in sources and low in cost, and the adopted materials are mixed, fused and granulated, heat treated and graphitized, so that the method is simple and convenient in process, high in operability, easy to realize large-scale production and good in practical prospect.
Drawings
FIG. 1 is an SEM image of the activated material (h-CKL) obtained in step (2) of example 1.
FIG. 2 is an SEM image of the final material obtained in example 1.
Detailed Description
The following examples illustrate specific steps of the invention, but are not intended to limit the scope of the invention in any way. Various processes and methods not described in detail herein are conventional methods well known in the art.
Example 1
Step (1): subjecting uncalcined petroleum coke to air flow grinding to obtain coarse particles (CKL) with particle size of 14 μm and fine particles (XKL) with particle size of 6 μm respectively;
Step (2): placing the coarse particles and the fine particles in an atmosphere furnace respectively, heating the coarse particles and the fine particles to 550 ℃ (marked as T1), and then introducing gaseous water for heat preservation pretreatment for 2 hours to obtain two pretreated materials (h-CKL and h-XKL) respectively;
Step (3): respectively placing the pretreated materials in a nickel acetate solution and an ammonium oxalate solution, placing the solution in a pressure-resistant kettle, introducing nitrogen (pressurized gas) into the kettle, controlling the temperature to 120 ℃ (marked as T2), keeping the system pressure to 15MPa (marked as P1), maintaining for 5 hours, then decompressing, recovering the equivalent system to normal pressure and normal temperature, and performing water evaporation operation on the obtained slurry to respectively obtain two treated materials s-h-CKL and s-h-XKL; in the solution, the concentration of nickel acetate is 2g/L, the concentration of ammonium oxalate is 5g/L, and the weight ratio of the pretreatment material to the nickel acetate in the solution is 100:5;
Step (4): placing the s-h-CKL in an atmosphere furnace, heating to 1000 ℃ at a speed of 5 ℃/min under the protection of argon (marked as T3), vacuumizing the system to a pressure of 10Pa, preserving heat for 5 hours, and cooling to room temperature to obtain a carbonized material (CKL-C);
Step (5): mixing s-h-XKL with asphalt according to a mass ratio of 100:2, granulating in a fusion machine, and then performing vacuum carbonization treatment in a vacuum furnace, which is the same as that of the step (4), to obtain carbonized material (XKL-C/C);
Step (6): CKL-C and XKL-C/C are mixed according to the mass ratio of 1:1, after uniformly mixing, pressing and forming in an isostatic press under the pressure of 150MPa to obtain an isostatic pressing block, then placing the isostatic pressing block in a graphitizing furnace for graphitizing treatment, preserving the temperature for 12 hours at 2900 ℃, and finally carrying out conventional depolymerization, demagnetizing and screening to obtain the artificial graphite negative electrode material.
According to GB/T24533-2009, a CR2025 button cell is assembled in a dry glove box filled with argon by taking the graphite electrode as a working electrode, lithium metal as a negative electrode, EC/EMC (volume ratio 1:1) of 1mol/L LiPF 6 as electrolyte and a PE-PP composite film as a diaphragm, and electrochemical performance detection is carried out at room temperature in a voltage range of 0.001-2.0V.
Example 2
Compared with the embodiment 1, the difference is that in the step (2), the gaseous water atmosphere is replaced by the gaseous water-oxygen composite gas, and the heat preservation pretreatment process is carried out, wherein the volume ratio of the gaseous water to the oxygen in the composite gas is 8:2.
Example 3
The only difference compared to example 1 is that the temperature of T1 is changed to 350 ℃; other operations and parameters were the same as in example 1.
Example 4
The only difference compared to example 1 is that the temperature of T1 is changed to 500 ℃; other operations and parameters were the same as in example 1.
Example 5
The difference compared with the embodiment 1 is that in the step (3), the solution is an aqueous solution of cobalt nitrate and ammonium nitrate, wherein the concentration of the cobalt nitrate is 2g/L, the concentration of the ammonium nitrate is 5g/L, and the weight ratio of the pretreated material to the cobalt nitrate in the solution is 100:5;
example 6
The only difference compared to example 1 is that in step (3), the pressurized air is air. Other operations and parameters were the same as in example 1.
Example 7
The difference compared to example 1 is only that in step (3), the pressure of P1 is 10MPa and the temperature is 80 ℃.
Example 8
The difference compared to example 1 is only that in step (3), the pressure of P1 is 20MPa and the temperature is 90 ℃.
Example 9
The difference compared with example 1 is only that in step (4), the temperature of T3 is 900 ℃, and in (5), the mass ratio of s-h-XKL to asphalt is 100:8, 8; step (6): CKL-C and XKL-C/C are mixed according to the mass ratio of 1:5, a step of; graphitization is carried out at 3000 ℃ for 10 hours.
Example 10
Compared with the embodiment 1, the difference is that in the step (2), the gaseous water atmosphere is replaced by the gaseous water-oxygen compound gas, and the heat preservation pretreatment process is performed, wherein the volume ratio of the gaseous water to the oxygen in the compound gas is 9:1, and the temperature of T1 is 450 ℃. In the step (3), the pressurized air is air.
Comparative example 1
The difference compared to example 1 is only that in step (2) nitrogen is used instead of the gaseous water, and other operations and parameters are the same as in example 1.
Comparative example 2
The difference compared to example 1 is only that in step (2) the temperature of T1 is 700 ℃, the other operations and parameters are the same as in example 1.
Comparative example 3
The only difference compared to example 1 is that the process of step (2) is replaced, and the step (2) is: mixing the coarse particles and the fine particles in the step (1) with 0.5M potassium hydroxide (the mass ratio of the potassium hydroxide to the coarse particles/the fine particles is 3:1) uniformly, placing the mixture in an atmosphere furnace, heating the mixture to 550 ℃ (marked as T1) under the protection of nitrogen, and carrying out heat preservation treatment for 2 hours to obtain two pretreated materials (h-CKL and h-XKL) respectively.
Comparative example 4
The difference compared with example 1 is that in step (3), nickel acetate is not added to the solution, the solid-to-liquid ratio of the pretreatment material and the solution is the same as in example 1, and other operations and parameters are the same as in example 1.
Comparative example 5
The difference compared with example 1 is that in step (3), no ammonium oxalate was added to the solution, and other operations and parameters were the same as in example 1.
Comparative example 6
The difference from example 1 is that in step (3), the pressurizing gas is not introduced to pressurize, and other operations and parameters are the same as in example 1.
Comparative example 7
The difference compared to example 1 is only that in step (3) the temperature of T2 is 180 ℃, other operations and parameters are also the same as in example 1.
Comparative example 8
The only difference compared to example 1 is that in step (6), only CKL-C was used for pressing and graphitization.
Comparative example 9
The only difference compared to example 1 is that in step (6) only XKL-C/C was used for pressing and graphitization.
The test results of the materials obtained in the above examples and comparative examples are as follows:
Therefore, the coke raw material is innovatively subjected to gaseous underwater heat treatment, then matched with the pressurizing treatment of a transition metal source and an ammonium source solution under the assistance of gas, and subjected to grading treatment of large and small coke raw materials and further matched with the control of technological parameters, so that the technological and parameter coordination can be realized, the graphitization difficulty can be effectively reduced, the artificial graphite anode active material can be obtained with low energy consumption, and more importantly, the prepared material has unexpected advantages in performance. On the basis, the electrochemical performance, particularly the rate capability, of the material can be further synergistically improved by further combining parameters such as modified atmosphere, pressurized air and the like.
Claims (32)
1. The preparation method of the artificial graphite anode active material is characterized by comprising the following steps of:
Step (1):
Carrying out heat treatment on the coke raw material in an atmosphere containing gaseous water to obtain a coke raw material A; wherein the temperature of the heat treatment is 300-600 ℃;
step (2):
dispersing a coke raw material A in a solution containing a transition metal source and an ammonium source, and pressurizing the system by utilizing gas, wherein the pressure is 5-25 MPa, and the temperature is 50-160 ℃;
pressurizing and then decompressing, and collecting to obtain a coke raw material B;
step (3):
Mixing a small-particle-size coke raw material B with a carbon source, and carbonizing to obtain carbon C;
carbonizing a large-particle-size coke raw material B to obtain carbon D;
The D50 of the small-particle-size coke raw material B is 5-12 mu m; the ratio of D50 of the large-particle-size coke raw material B to the small-particle-size coke raw material B is 1.5-2.5: 1, a step of;
step (4):
pressing and forming carbon C and carbon D, and then graphitizing to obtain the artificial graphite anode active material;
The graphitization temperature is 2800-3200 ℃; the graphitization time is 10-16 h.
2. The method for preparing an artificial graphite anode active material according to claim 1, wherein the coke raw material is at least one of petroleum coke, needle coke, and pitch coke.
3. The method for producing an artificial graphite anode active material according to claim 1, wherein in the step (1), the atmosphere further contains an oxygen-containing gas.
4. The method for preparing an artificial graphite anode active material according to claim 3, wherein in the step (1), the oxygen-containing gas is air or oxygen.
5. The method for preparing an artificial graphite anode active material according to claim 4, wherein in the step (1), the volume content of the oxygen-containing atmosphere is 5 to 20%.
6. The method for producing an artificial graphite anode active material according to claim 4, wherein the atmosphere in the step (1) further contains at least one atmosphere selected from nitrogen and an inert gas.
7. The method for preparing an artificial graphite anode active material according to claim 6, wherein the volume content of the gaseous water in the atmosphere is 20-50%.
8. The method for preparing an artificial graphite anode active material according to claim 1 or 3, wherein in the step (1), the heat treatment temperature is 450 to 550 ℃.
9. The method for preparing an artificial graphite anode active material according to claim 1 or 3, wherein in the step (1), the heat treatment time is 0.5 to 6 hours.
10. The method for preparing an artificial graphite anode active material according to claim 1, wherein the transition metal source is at least one of a salt, a hydroxide and an oxide of a transition metal.
11. The method for preparing an artificial graphite anode active material according to claim 10, wherein the element of the transition metal in the transition metal source is nickel and/or cobalt.
12. The method for preparing an artificial graphite anode active material according to claim 11, wherein the transition metal source is at least one of nickel nitrate, cobalt nitrate, nickel hydroxide, cobalt hydroxide, nickel oxide, cobalt oxide, and nickel oxalate.
13. The method for preparing an artificial graphite anode active material according to claim 1, wherein the ammonium source is at least one of ammonia water, ammonium chloride, ammonium nitrate, ammonium sulfate and ammonium acetate.
14. The method for preparing an artificial graphite anode active material according to claim 1, wherein in the solution in the step (2), the concentration of the transition metal source is 0.1 to 5g/L, and the concentration of the ammonium source is 0.5 to 20g/L.
15. The method for preparing an artificial graphite anode active material according to claim 1, wherein the weight ratio of the coke raw material a to the transition metal source of the solution is 100:1-10.
16. The method for producing an artificial graphite anode active material according to claim 1 or 5, wherein in the step (2), the gas is at least one of nitrogen, an inert gas, and an oxygen-containing gas.
17. The method for preparing an artificial graphite anode active material according to claim 1 or 5, wherein the temperature in the pressure treatment stage is 60 to 120 ℃.
18. The method for producing an artificial graphite anode active material according to claim 1 or 5 or the above, wherein the pressurizing pressure is 15 to 20mpa.
19. The method for preparing an artificial graphite anode active material according to claim 1 or 5, wherein the pressure is maintained for 4 to 12 hours.
20. The method for preparing an artificial graphite anode active material according to claim 1 or claim 1, wherein the D50 of the small-particle-size coke raw material B is 6 to 10 μm.
21. The method for preparing an artificial graphite anode active material according to claim 1 or claim 1, wherein the carbon source is at least one of pitch, needle coke, petroleum coke, and mesophase carbon microspheres.
22. The method for producing an artificial graphite anode active material according to claim 1 or claim 1, wherein the weight ratio of the small particle size coke raw material B to the carbon source is 100: 2-8.
23. The method for preparing an artificial graphite anode active material according to claim 1 or, wherein the carbonization process is performed under negative pressure.
24. The method for preparing an artificial graphite anode active material according to claim 1 or claim 1, wherein the negative pressure is 5 to 50pa.
25. The method for preparing an artificial graphite anode active material according to claim 1 or claim, wherein the carbonization temperature is 800 to 1250 ℃.
26. The method for preparing an artificial graphite anode active material according to claim 1 or claim 1, wherein the mass ratio of carbon C to carbon D is 1 to 9:1 to 9.
27. The method for preparing an artificial graphite anode active material according to claim 1 or claim 1, wherein carbon C and carbon D are pressed by hot isostatic pressing and the pressure is 50 to 300mpa.
28. An artificial graphite anode active material prepared by the preparation method of any one of claims 1 to 27.
29. Use of the artificial graphite anode active material according to claim 28 as an anode active material.
30. Use of the artificial graphite anode active material according to claim 29, as an anode active material for the preparation of a lithium secondary battery.
31. A lithium secondary battery comprising the artificial graphite negative electrode active material according to claim 28.
32. The lithium secondary battery according to claim 31, wherein the negative electrode of the lithium secondary battery comprises the artificial graphite negative electrode active material.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10255770A (en) * | 1997-03-14 | 1998-09-25 | Adokemuko Kk | Manufacture of graphite material for battery and battery |
| CN101882685A (en) * | 2010-03-31 | 2010-11-10 | 孙公权 | Magnesium-oxygen battery for seawater underwater |
| WO2022121136A1 (en) * | 2020-12-10 | 2022-06-16 | 广东凯金新能源科技股份有限公司 | Artificial graphite negative electrode material for high-rate lithium ion battery and preparation method therefor |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10255770A (en) * | 1997-03-14 | 1998-09-25 | Adokemuko Kk | Manufacture of graphite material for battery and battery |
| CN101882685A (en) * | 2010-03-31 | 2010-11-10 | 孙公权 | Magnesium-oxygen battery for seawater underwater |
| WO2022121136A1 (en) * | 2020-12-10 | 2022-06-16 | 广东凯金新能源科技股份有限公司 | Artificial graphite negative electrode material for high-rate lithium ion battery and preparation method therefor |
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