CN115490228B - Coke micro powder-based graphite material, preparation method thereof and application thereof in lithium secondary battery - Google Patents
Coke micro powder-based graphite material, preparation method thereof and application thereof in lithium secondary battery Download PDFInfo
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Classifications
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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
- C01B32/205—Preparation
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M2004/026—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
Abstract
The invention belongs to the field of graphite cathode materials, and particularly relates to a method for preparing a graphite cathode material by using coke micro powder, wherein the coke micro powder with the particle size smaller than or equal to 5 mu m and a polymer with thermal crosslinking performance are subjected to heat treatment in an oxygen-containing atmosphere; the polymer with the thermal crosslinking performance is a polymer which has a network polymer structure and is grafted and modified with two or more active groups of hydroxyl, carboxyl, amido, alkoxy, epoxy and hydroxymethyl; the temperature of the heat treatment is 100-350 ℃; the air pressure in the heat treatment stage is 20-300 MPa; crushing the heat-treated product, and carrying out secondary granulation on the crushed heat-treated product and the carbon source A to obtain secondary particles; degreasing, roasting and graphitizing the secondary particles; and coating the graphitization treatment product with a carbon source B, and then carbonizing to obtain the Jiao Weifen-base graphite anode material. The invention also relates to the material prepared by the preparation method and application thereof in lithium secondary batteries. The method can obtain Jiao Weifen-base graphite with high performance, and realizes waste utilization.
Description
Technical Field
The invention belongs to the field of preparation of graphite cathodes, and particularly relates to the technical field of preparation of graphite cathodes by adopting coke micro powder waste.
Background
The lithium ion battery has been widely used in the consumer electronics field due to its advantages of high operating voltage, high energy density, long cycle life, etc., and has been expanding in application fields with the rapid growth of new energy automobiles and large-scale energy storage markets. The lithium ion battery cathode materials are mainly divided into two types of carbon materials and non-carbon materials, and graphite in the carbon materials can be specifically divided into natural graphite and artificial graphite. The artificial graphite has the advantages of high electronic conductivity, large lithium ion diffusion coefficient, high lithium intercalation capacity, low lithium intercalation potential and the like, and the artificial graphite has wide raw material sources, is mature in technology and industry matching, and is the main stream of the current lithium ion battery cathode material.
The raw materials of the artificial graphite mainly comprise petroleum coke and needle coke, the needle coke is generally adopted as the raw material of the cathode with high specific capacity, the petroleum coke with lower price is adopted as the raw material of the common cathode, and asphalt is adopted as the binder. The basic procedures of artificial graphite preparation mainly comprise crushing, granulating, graphitizing and sieving. In the prior art, the crushing is generally realized by air flow grinding in an air flow mill, and raw and auxiliary materials with the particle size of 5-10mm can be ground to be less than 20 mu m. After the airflow is milled, a cyclone dust collector is adopted to collect materials with the required particle size, and micropowder which does not meet the particle size requirement, for example, micropowder smaller than 5 mu m, is used as a byproduct, and is usually sold in a carburant and other modes at low cost, and the part of byproduct can reach 30% of the feeding amount, so that economic benefit loss and resource waste are brought.
No special research has been publicly reported for the treatment of micropowder. The particle size is too small and the distribution is wider, so that the production requirement of the graphite cathode can not be met, and secondary granulation is needed. The conventional granulating process adopts asphalt as a binder, and comprises the steps of dry mixing, low-temperature carbonization, ball milling screening and the like, so that false granulation is easy to occur, and the particles are broken and pulping performance is poor in the subsequent coating and rolling processes; meanwhile, the particle size of the micro powder is difficult to control, so that the problems of uneven granulation, low tap density, large specific surface area and the like are caused.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for preparing a graphite negative electrode by using coke micro powder, and aims to provide a method for preparing a high-performance graphite negative electrode by using coke micro powder waste.
The invention also provides a Jiao Weifen-base graphite anode material prepared by the preparation method, and aims to provide a graphite anode material prepared by the coke micro powder.
The third object of the invention is to provide the application of the Jiao Weifen-based graphite anode material in a lithium secondary battery.
A fourth object of the present invention is to provide a lithium secondary battery comprising the Jiao Weifen-based graphite negative electrode material, a negative electrode material thereof, and a negative electrode.
Jiao Weifen has a too small particle size and a relatively wide distribution, and cannot meet the production requirements of graphite cathodes, and in the prior art, the coke micro powder is generally utilized in the form of byproducts such as low-value carburant and the like. The conventional granulation process with asphalt as a binder is easy to generate pseudo granulation, so that particles are broken and pulping performance is poor in the subsequent coating and rolling processes; meanwhile, the particle size of the micro powder is difficult to control, and the problems of uneven granulation, low tap density, large specific surface area and the like are caused, so that the coke micro powder is difficult to re-granulate, the particle size distribution is disordered, the structure is damaged, and the high-performance graphite negative electrode material, particularly the high-rate performance, is difficult to prepare in a recycling manner. Aiming at the technical problem, the invention provides the following improvement means:
a method for preparing graphite cathode material by using coke micro powder comprises the following steps:
step (1):
heat-treating the coke micro powder with the grain diameter less than or equal to 5 mu m and the polymer with heat-crosslinking performance in an oxygen-containing atmosphere;
the polymer with the thermal crosslinking performance is a polymer which has a network polymer structure and is grafted and modified with two or more active groups of hydroxyl, carboxyl, amido, alkoxy, epoxy and hydroxymethyl;
the temperature of the heat treatment is 100-350 ℃; the air pressure in the heat treatment stage is 20-300 MPa;
step (2):
crushing the heat-treated product, and carrying out secondary granulation on the crushed heat-treated product and the carbon source A to obtain secondary particles;
step (3):
degreasing, roasting and graphitizing the secondary particles;
step (4):
and coating the graphitization treatment product with a carbon source B, and then carbonizing to obtain the Jiao Weifen-base graphite anode material.
Aiming at the problems that the coke micron is easy to have uneven particle size distribution, the structure is damaged, granulation is difficult, and high-performance graphite cathode is difficult to prepare, through intensive research, the special polymer with heat crosslinking performance is innovatively adopted to carry out heat treatment under the oxygen-containing atmosphere, and further the combination of the oxygen-containing atmosphere pressure and the heat treatment temperature is matched, so that the coordination can be realized unexpectedly, the particle size distribution is improved, the microstructure is repaired, the problems of unsatisfactory pseudo granulation and tap density are solved, and the material after heat treatment is subjected to secondary granulation, graphitization and carbon coating treatment, so that the high-performance graphite material with high-rate performance can be obtained.
Jiao Weifen is micro powder of at least one of petroleum coke and needle coke;
preferably, the Jiao Weifen particle size distribution is 0.1-5 μm;
in the invention, the special polymer assists the heat treatment and the combined control of the oxygen-containing atmosphere, the oxygen-containing atmosphere pressure and the temperature in the heat treatment stage is the key for solving the problem that Jiao Weifen is difficult to prepare the high-performance graphite cathode.
Preferably, the polymer with thermal crosslinking performance is a polymer capable of being crosslinked to form a three-dimensional network structure under the condition of the step (1);
preferably, the polymer is at least one of urea resin, polyester resin, vinyl ester, acrylic resin, melamine resin, organic silicon resin, polyimide and polyurethane with thermal crosslinking performance;
preferably, the polymers are urea formaldehyde and melamine. The invention has surprisingly found that the polymer with the combination can be further cooperated with the heat treatment process, and the electrochemical performance of the Jiao Weifen base graphite material can be further improved unexpectedly. Preferably, in the polymer of the synergistic combination, the weight ratio of urea-formaldehyde resin to melamine is 1-2:1.
Preferably, the weight ratio of the coke micro powder to the polymer is 1:0.1 to 10, more preferably 1:0.2 to 0.5;
in the present invention, the oxygen-containing atmosphere may be pure oxygen or a mixture of oxygen and other gases. The mixed gas is, for example, an oxygen-nitrogen (inert gas) mixed gas.
In the present invention, the oxygen concentration of the oxygen-containing atmosphere is not particularly required, and for example, the oxygen content of the oxygen-containing atmosphere is 22 to 35% by volume;
in the present invention, the pressure in the heat treatment stage can be controlled by introducing the oxygen-containing atmosphere.
In the invention, in the step (1), the pressure of the heat treatment stage is 50-150 MPa; more preferably 80 to 100MPa.
Preferably, in step (1), the temperature of the heat treatment is 200 to 250 ℃.
The time of the heat treatment is not particularly limited, and may be, for example, 0.5 to 5 hours, preferably 2 to 5 hours.
In the present invention, the material obtained in the step (1) may be subjected to crushing treatment, followed by sieving as needed to obtain suitable particles.
In the invention, the product obtained in the step (1) and the carbon source A are further subjected to secondary granulation to obtain secondary particles. For example, the heat-treated product is coarsely crushed, medium crushed, finely crushed to d50=5 to 10 μm, and sieved with a mesh number of 150 to 500 mesh, and the undersize is taken out for subsequent secondary granulation.
In the step (2), the crushed product of the heat treatment has a particle size of 6 to 10 μm.
Preferably, the carbon source A is at least one of high-temperature asphalt, phenolic resin and epoxy resin;
preferably, the softening point of the high-temperature asphalt is 95-250 ℃;
preferably, the high-temperature asphalt is petroleum asphalt and/or coal tar asphalt;
preferably, carbon source a is 0.1 to 10wt.%, preferably 1 to 3wt.% of the heat treated product;
preferably, the secondary granulation is fusion granulation;
preferably, the temperature in the process of fusion granulation is 80-220 ℃, and the fusion time is 0.1-10 h;
preferably, the secondary particles after secondary granulation have a particle size of 15-20 μm.
In the invention, in the step (3), degreasing roasting and graphitizing treatment are carried out in a protective atmosphere;
preferably, the degreasing and roasting temperature is 500-800 ℃, preferably 600-700 ℃; preserving the temperature for 0.5 to 10 hours,
preferably, the graphitization roasting temperature is 2600-3000 ℃, and the time is 24-64 h, preferably 24-48 h.
After graphitization treatment, cooling and sieving with a 150-500 mesh sieve, and then carrying out the subsequent steps.
According to the invention, the graphitized material is coated with amorphous carbon, which is helpful for improving the performance of the Jiao Weifen-base graphite cathode.
Preferably, in the step (4), the carbon source B is a carbon source that can be melted at 150 to 200 ℃; preferably medium temperature bitumen;
preferably, the softening point of the medium-temperature asphalt is 65-90 ℃;
preferably, the medium temperature asphalt is petroleum asphalt and/or coal tar asphalt.
In the invention, the carbon source B can be coated on the surface of the graphitized product based on the existing means, and in the invention, preferably, in the step (4), the graphitized product and the melted carbon source B are subjected to pressure transformation treatment, and then cooled and solidified, so as to prepare the graphitized product coated by the carbon source B, wherein the pressure transformation treatment comprises pre-performed negative pressure treatment and pre-performed positive pressure treatment; preferably, the negative-positive pressure cycle is performed in multiple layers. According to the invention, on the basis of innovation of the steps (1-3), the coating process under variable pressure is further matched, so that the cooperation is realized, the repair of the coke micro powder structure is facilitated, and the performance of the subsequently obtained coke micro-based graphite anode material is further improved.
Preferably, in the pressure transformation treatment stage of the step (4), the negative pressure is lower than 80mbar, and the positive pressure is 0.1-0.5Mpa; the negative and positive pressure are maintained for 5-10 minutes.
In the present invention, the mass ratio of the graphitized product to the carbon source B may be adjusted as required, for example, may be 10 to 50:1, and more preferably 20 to 30:1;
preferably, the carbonization process is performed under a protective atmosphere;
preferably, the temperature of the carbonization process is 1000-1300 ℃, preferably 1100-1200 ℃;
preferably, the carbonization time is 3 to 6 hours.
In the present invention, the protective atmosphere involved in the degreasing and baking, graphitizing and carbonizing processes is at least one of nitrogen and inert gas, for example, ar.
The invention also provides a Jiao Weifen-based graphite anode material prepared by the method.
In the invention, the tap density of the Jiao Weifen-based graphite anode material is high (more than or equal to 0.9 g/cm) 3 ) The specific surface area is small (less than or equal to 5 m) 2 /g)。
Preferably, the tap density of the Jiao Weifen-based graphite anode material is 1-1.2 g/cm 3 . Specific surface area of 1-3 m 2 /g。
The invention also provides an application of the method for preparing Jiao Weifen-based graphite anode material, which is used as anode active material for preparing lithium secondary batteries;
preferably, it is used as a negative electrode active material for preparing a negative electrode of a lithium secondary battery;
preferably, the lithium secondary battery is a lithium ion battery.
According to the invention, the Jiao Weifen-based graphite material prepared by the method can be prepared into a required lithium secondary battery and a negative electrode material thereof based on the existing method and process.
The invention also provides a lithium secondary battery anode material which comprises the Jiao Weifen graphite material, a conductive agent and a binder. The components and amounts of the conductive agent and binder may be conventional.
The invention also provides a lithium secondary battery anode, which comprises a current collector and an anode active material compounded on the surface of the current collector, wherein the anode active material is the Jiao Weifen-based graphite anode material.
The invention also provides a lithium secondary battery, which comprises the Jiao Weifen-based graphite anode material prepared by the method; preferably, the negative electrode thereof is the negative electrode.
The invention innovatively adopts the special polymer to carry out heat treatment, and further cooperates with the combined control of the oxygen-containing atmosphere, the oxygen-containing atmosphere pressure and the temperature of the heat treatment, so that the synergy can be realized accidentally, the particle size distribution of Jiao Weifen can be reset, the damaged structure can be repaired, and the pseudo-granulation can be avoided. The electrochemical performance of the Jiao Weifen-based graphite negative electrode can be synergistically improved by further combining secondary granulation, graphitization and carbon coating processes, and particularly the rate capability of the prepared negative electrode is improved.
The invention has the beneficial effects that:
the special polymer with the thermal crosslinking performance is innovatively adopted to carry out heat treatment under the oxygen-containing atmosphere, and the combination of the air pressure of the oxygen-containing atmosphere and the heat treatment temperature is further matched, so that the coordination can be realized unexpectedly, the particle size distribution and the microstructure restoration can be improved, the problems of pseudo-granulation, non-ideal tap density and the like can be solved, the material after the heat treatment is further subjected to secondary granulation, graphitization and carbon coating treatment, and the graphite material with high performance such as high rate performance can be obtained.
According to the invention, on the basis of the cooperation of the steps (1) to (3), the pressure-variable carbon coating process is further matched, so that the electrochemical performance of the prepared material is further synergistically improved.
Drawings
FIG. 1 is an SEM image of Jiao Weifen-base artificial graphite prepared in example 1;
FIG. 2 is an electrochemical test chart of Jiao Weifen-based artificial graphite prepared in example 1;
Detailed Description
The invention is further illustrated below in connection with specific examples, which are not to be construed as limiting in any way.
In the embodiment and the comparative example, the petroleum coke micro powder and the needle Jiao Weifen which are adopted refer to small-particle-size powder which is a byproduct in the grinding process in the artificial graphite production process, and the particle size range is 0.1-5 mu m.
Electrochemical performance test: the graphite electrode (graphite active material, acetylene black and PVDF with the weight ratio of 90:5:5) is used as a working electrode, lithium metal is used as a negative electrode, and 1mol/L LiPF is used 6 The EC/DMC/EMC (volume ratio 1:1:1) is electrolyte, the PE-PP composite film is diaphragm, the CR2032 button cell is assembled in a dry glove box filled with argon, and the battery charge and discharge detection is carried out at 0.1C and 5C multiplying power in a voltage interval of 0.001-1.8V at room temperature (25 ℃).
In the following cases of the present invention, the oxygen-containing atmosphere is a mixed gas of oxygen and Ar.
Example 1
Step (1):
mixing petroleum coke micro powder with melamine resin according to a proportion of 1: and 0.4 is put into a mixer for uniform mixing, the mixing linear speed is 10m/S, and the mixing time is 20min. The mixed materials are subjected to heat treatment in an oxygen-containing atmosphere, wherein the temperature of the heat treatment stage is 200 ℃, the pressure is 100MPa, and the oxygen content of the oxygen-containing atmosphere is 25% by volume; the heat treatment time is 2 hours;
step (2):
drying the heat-treated material obtained in the step (1) in a forced air drying oven for 12 hours, then carrying out coarse crushing, medium crushing and fine crushing until D50=6μm, sieving with a 350-mesh sieve, and returning the oversize material to the crushing step; taking undersize, using high-temperature coal pitch as a binder, and performing secondary granulation in a fusion machine, wherein the softening point of the pitch is 120 ℃, and the addition amount is 2% (based on the coke raw material heat-treated in the step (1)); the fusion temperature was 200℃and the fusion time was 0.5h, obtaining secondary particles having a particle size of 18. Mu.m.
Step (3):
degreasing and roasting the granulated material at 650 ℃ in nitrogen atmosphere, and preserving heat for 2 hours; graphitizing the degreasing roasting material at 2800 ℃ for 48 hours, cooling, and sieving with a 350-mesh sieve to obtain graphitized material;
step (4): graphitized material modification:
melting medium-temperature coal tar pitch with a softening point of 80 ℃ at 160 ℃, adding the graphitized material in the step (3), wherein the mass ratio of the graphitized material to the pitch is 20:1, vacuumizing to the pressure of 80mbar, maintaining for 8min, pressurizing to 0.5Mpa by introducing the atmosphere, maintaining for 5min, and cooling to room temperature after treatment; and carbonizing the material at 1150 ℃ for 3 hours in nitrogen atmosphere to obtain the Jiao Weifen-base artificial graphite cathode.
The physical properties of the prepared artificial graphite material product are tested, and the tap density is 1.1g/cm 3 A specific surface area of 1.95m 2 /g; electrochemical performance tests were carried out with a first reversible capacity of 351mAh/g, a first coulombic efficiency of 95% and a reversible capacity retention of 92% at 5C/0.1C at a 0.1C magnification.
Example 2
The difference compared with example 1 is that the type and proportion of the polymer in the step (1) are changed, and the petroleum coke micro powder and the urea resin are mixed according to the ratio of 1:0.5, putting the mixture into a mixer for uniform mixing; other operations and parameters were the same as in example 1.
The physical properties of the prepared artificial graphite material product are tested, and the tap density is 1.08g/cm 3 Specific surface area of 2.05m 2 /g; electrochemical performance tests were carried out with a first reversible capacity of 355mAh/g, a first coulombic efficiency of 92% and a reversible capacity retention of 94% at 5C/0.1C at a 0.1C magnification.
Example 3
The difference from example 1 is only that the kinds and proportions of the polymers are changed, and the petroleum coke micro powder and polyurethane resin are mixed according to the ratio of 1:0.3, putting the mixture into a mixer for uniform mixing; other operations and parameters were the same as in example 1.
The physical properties of the prepared artificial graphite material product are tested, and the tap density is 1.06g/cm 3 Specific surface area of 2.12m 2 /g; electrochemical performance test was conducted with a first reversible capacity of 358mAh/g, a first coulomb efficiency of 93%, and a reversible capacity retention of 5C/0.1C at 0.1C magnification95％。
Example 4
The difference compared with example 1 is that the combination type of the polymer is changed, and the petroleum coke micro powder, urea-formaldehyde resin and melamine resin are mixed according to the following ratio of 1:0.2:0.2, putting the mixture into a mixer for uniform mixing;
the physical properties of the prepared artificial graphite material product are tested, and the tap density is 1.15g/cm 3 Specific surface area of 1.88m 2 /g; electrochemical performance tests were carried out with a first reversible capacity of 363mAh/g, a first coulombic efficiency of 96% and a reversible capacity retention of 96% at 5C/0.1C at a rate of 0.1C.
Example 5
The difference compared to example 1 is only that the heat treatment process of step (1), specifically the heat treatment stage, was changed such that the oxygen content of the oxygen-containing atmosphere was 35v%, the pressure was 80MPa and the temperature was 250 ℃.
The physical properties of the prepared artificial graphite material product are tested, and the tap density is 1.12g/cm 3 Specific surface area of 1.92m 2 /g; electrochemical performance tests were carried out with a first reversible capacity of 354mAh/g, a first coulombic efficiency of 93% and a reversible capacity retention of 93% at 5C/0.1C at a 0.1C magnification.
Example 6
The only difference compared to example 1 is that the carbon coating modification process of step (4) is changed, and the process is:
melting medium-temperature coal tar pitch with a softening point of 90 ℃ at 200 ℃, adding graphitized materials, wherein the mass ratio of the graphitized materials to the pitch is 30:1, vacuumizing to a pressure of 70mbar, maintaining for 10min, then pressurizing to 0.1Mpa by introducing the atmosphere, maintaining for 10min, and cooling to room temperature after treatment; the subsequent process was the same as in example 1.
The physical properties of the prepared artificial graphite material product are tested, and the tap density is 1.05g/cm 3 Specific surface area of 2.36m 2 /g; electrochemical performance tests were carried out with a first reversible capacity of 360mAh/g, a first coulombic efficiency of 94% and a reversible capacity retention of 93% at 5C/0.1C at a 0.1C magnification.
Example 7
Step (1): mixing petroleum coke micro powder with melamine resin according to a proportion of 1: and 0.4 is put into a mixer for uniform mixing, the mixing linear speed is 30m/S, and the mixing time is 10min. The mixed materials are subjected to heat treatment in an oxygen-containing atmosphere, wherein the temperature of the heat treatment stage is 200 ℃, the pressure is 100MPa, and the oxygen content of the oxygen-containing atmosphere is 25% by volume; the heat treatment time is 5 hours;
step (2):
drying the heat-treated material obtained in the step (1) in a forced air drying oven for 12 hours, then carrying out coarse crushing, medium crushing and fine crushing until D50=10μm, sieving with a 350-mesh sieve, and returning the oversize material to the crushing step; taking undersize, using high-temperature coal pitch as a binder, and performing secondary granulation in a fusion machine, wherein the softening point of the pitch is 95 ℃ and the addition amount is 10%; the fusion temperature was 220℃and the fusion time was 10 hours, obtaining secondary particles having a particle size of 20. Mu.m.
Step (3):
degreasing and roasting the granulated material at 800 ℃ in nitrogen atmosphere, and preserving heat for 1h; graphitizing the degreasing roasting material for 24 hours at 3000 ℃, cooling, and sieving with a 350-mesh sieve to obtain a graphite material;
step (4): carbon coating modification:
melting medium-temperature coal tar pitch with a softening point of 80 ℃ at 160 ℃, adding graphitized materials, wherein the mass ratio of the graphitized materials to the pitch is 20:1, vacuumizing to 80mbar, maintaining for 8min, then pressurizing to 0.5Mpa by introducing the atmosphere, maintaining for 5min, and cooling to room temperature after treatment; and carbonizing the material at the high temperature of 1000 ℃ for 6 hours under the nitrogen atmosphere to obtain the Jiao Weifen-base artificial graphite cathode.
The physical properties of the prepared artificial graphite material product are tested, and the tap density is 1.06g/cm 3 Specific surface area of 2.25m 2 /g; electrochemical performance tests were carried out with a first reversible capacity of 347mAh/g, a first coulombic efficiency of 92% and a reversible capacity retention of 91% at 5C/0.1C at a rate of 0.1C.
Example 7:
the difference from example 1 is that only in the modification of step (4), the carbon coating is not performed by the gas-change process, and the difference is that: graphitized material and asphalt are uniformly mixed, graphitized material and medium-temperature coal asphalt with a softening point of 80 ℃ are uniformly mixed in a mixer according to a mass ratio of 20:1, and then carbonization is carried out, and the carbonization process is the same as that of example 1.
The physical properties of the prepared artificial graphite material product are tested, and the tap density is 0.90g/cm 3 Specific surface area of 4.6m 2 /g; electrochemical performance tests were carried out with a first reversible capacity of 316mAh/g, a first coulombic efficiency of 89% and a reversible capacity retention of 85% at 5C/0.1C at a 0.1C magnification.
Comparative example 1:
the only difference compared to example 1 is that in step 1, the melamine resin is replaced with an equal weight of novolac resin, and other operations and parameters are the same as in example 1.
The physical properties of the prepared artificial graphite material product are tested, and the tap density is 0.65g/cm 3 A specific surface area of 12.5m 2 /g; electrochemical performance tests were carried out with a first reversible capacity of 238mAh/g, a first coulombic efficiency of 73% and a reversible capacity retention of 81% at 5C/0.1C at a 0.1C magnification.
Comparative example 2:
the only difference compared to example 1 is that the heat treatment process of step (1) is changed; the heat treatment process is not performed under an oxygen-containing atmosphere, i.e., nitrogen is used instead of the oxygen-containing atmosphere. Other operations and parameters were the same as in example 1.
The physical properties of the prepared artificial graphite material product are tested, and the tap density is 0.88g/cm 3 Specific surface area of 6.2m 2 /g; electrochemical performance tests were carried out with a first reversible capacity of 295mAh/g, a first coulombic efficiency of 86% and a reversible capacity retention of 85% at 5C/0.1C at a rate of 0.1C.
Comparative example 3:
the only difference compared to example 1 is that the heat treatment process of step (1) is changed; the method comprises the following steps of:
group A: the temperature of the heat treatment process is controlled at 80 ℃; the pressure was 10MPa. Other operations and parameters were the same as in example 1.
Group B: the temperature of the heat treatment process is controlled at 500 ℃; the pressure was 100MPa. Other operations and parameters were the same as in example 1.
The measurement was carried out by the procedure of example 1, and the result was:
in the group A, the physical property test is carried out on the prepared artificial graphite material product, and the tap density is 0.79g/cm 3 Specific surface area of 9.5m 2 /g; electrochemical performance tests were carried out with a first reversible capacity of 268mAh/g, a first coulombic efficiency of 83% and a reversible capacity retention of 76% at 5C/0.1C at a 0.1C magnification.
In group B, the first reversible capacity was 301mAh/g at a 0.1C magnification, the first coulombic efficiency was 84%, and the reversible capacity retention at 5C/0.1C was 80%.
Comparative example 4:
compared with example 1, the method is different in that the treatment of the step (1) is not carried out, the cathode is directly prepared by adopting the coke micro powder through the steps (2), (3) and (4), and the process conditions are the same as those of example 1;
the physical properties of the prepared artificial graphite material product are tested, and the tap density is 0.59g/cm 3 Specific surface area of 13.2m 2 /g; electrochemical performance tests were carried out with a first reversible capacity of 254mAh/g, a first coulombic efficiency of 63% and a reversible capacity retention of 67% at 5C/0.1C at a 0.1C magnification.
Claims (38)
1. The method for preparing the graphite anode material by the coke micro powder is characterized by comprising the following steps:
step (1):
heat-treating the coke micro powder with the grain diameter less than or equal to 5 mu m and the polymer with heat-crosslinking performance in an oxygen-containing atmosphere; jiao Weifen is small-particle-size powder which is a byproduct of the grinding process in the production process of artificial graphite;
the polymer with the thermal crosslinking performance is at least one of urea resin, polyester resin and melamine resin with the thermal crosslinking performance;
jiao Weifen and the weight ratio of the polymer is 1: 0.1-10;
the temperature of the heat treatment is 100-350 ℃; the air pressure in the heat treatment stage is 20-300 MPa;
step (2):
crushing the heat-treated product, and carrying out secondary granulation on the crushed heat-treated product and the carbon source A to obtain secondary particles;
step (3):
degreasing, roasting and graphitizing the secondary particles;
step (4):
and (3) performing pressure transformation treatment on the graphitized product and the molten carbon source B, performing carbonization treatment, and then cooling and solidifying to obtain the Jiao Weifen-based graphite anode material, wherein the pressure transformation treatment comprises negative pressure treatment and positive pressure treatment which are performed in advance.
2. The method for preparing a graphite anode material as claimed in claim 1, wherein Jiao Weifen is micro powder of at least one of petroleum coke and needle coke.
3. The method for preparing a graphite anode material as claimed in claim 1, wherein the particle size distribution of Jiao Weifen is 0.1-5 μm.
4. The method of preparing a graphite anode material of claim 1, wherein said polymer is urea formaldehyde resin and melamine.
5. The method for preparing a graphite anode material of claim 1, wherein the weight ratio of the coke breeze to the polymer is 1:0.2-0.5.
6. The method for preparing a graphite anode material of claim 1, wherein the oxygen-containing atmosphere has an oxygen content of 22-35 v%.
7. The method for preparing a graphite anode material according to claim 1, wherein in the step (1), the pressure of the heat treatment is 80 to 150 MPa.
8. The method for preparing a graphite anode material according to claim 1, wherein in the step (1), the temperature of the heat treatment is 200 to 250 ℃.
9. The method for preparing a graphite anode material of claim 1, wherein in step (2), the crushed product of the heat treatment has a particle size of 5 to 12 μm.
10. The method of claim 1, wherein carbon source a is at least one of a high temperature pitch, a phenolic resin, and an epoxy resin.
11. The method for preparing a graphite anode material of claim 10, wherein said high temperature pitch has a softening point of 95-250 ℃.
12. The method for preparing a graphite anode material of claim 11, wherein said high temperature pitch is petroleum pitch and/or coal tar pitch.
13. The method for preparing a graphite anode material of claim 1, wherein carbon source a is 0.1-10 wt.% of the heat-treated product.
14. The method of preparing a graphite anode material of claim 13, wherein carbon source a is 1-3 wt.% of said heat treated product.
15. The method of preparing a graphite anode material of claim 1, wherein the secondary granulation is fusion granulation.
16. The method for preparing a graphite anode material according to claim 1, wherein the temperature in the process of fusion granulation is 80-220 ℃ and the fusion time is 0.1-10 h.
17. The method for preparing a graphite anode material as claimed in claim 1, wherein the secondary particles after secondary granulation have a particle size of 15 to 20 μm.
18. The method for preparing a graphite anode material of claim 1, wherein in step (3), degreasing firing and graphitization treatment are performed under a protective atmosphere.
19. The method for preparing a graphite anode material according to claim 1, wherein the degreasing and baking temperature is 500-800 ℃, and the temperature is kept for 0.5-10 hours.
20. The method for preparing a graphite anode material according to claim 1, wherein the graphitization and calcination are performed at 2600-3000 ℃ for 24-64 hours.
21. The method for preparing a graphite anode material of claim 1, wherein in step (4), carbon source B is a carbon source that can be melted at 150 to 200 ℃.
22. The method for preparing a graphite anode material of claim 21, wherein in step (4), carbon source B is medium temperature pitch.
23. The method for preparing a graphite anode material of claim 22, wherein said medium temperature pitch has a softening point of 65-90 ℃.
24. The method of claim 22, wherein the medium temperature pitch is petroleum pitch and/or coal pitch.
25. The method for preparing a graphite anode material of claim 1, wherein the mass ratio of graphitized product to carbon source B is 10-50:1.
26. The method of preparing a graphite anode material of claim 1, wherein the carbonization process is performed in a protective atmosphere.
27. The method for preparing a graphite anode material of claim 1, wherein the carbonization process is performed at a temperature of 1000-1300 ℃.
28. The method for preparing a graphite anode material of claim 1, wherein the carbonization process is carried out at a temperature of 1100-1200 ℃.
29. The method for preparing a graphite anode material of claim 1, wherein the carbonization time is 3-6 hours.
30. A Jiao Weifen-based graphite anode material prepared by the method of any one of claims 1-29.
31. The Jiao Weifen-base graphite anode material prepared by the method of claim 30, wherein the tap density of the Jiao Weifen-base graphite anode material is not less than 0.9g/cm 3 Specific surface area is less than or equal to 5m 2 /g。
32. The Jiao Weifen-base graphite anode material prepared by the method of claim 30, wherein the Jiao Weifen-base graphite anode material has a tap density of 1-1.2 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Specific surface area of 1-3 m 2 /g。
33. Use of the method according to any one of claims 1 to 29 for preparing Jiao Weifen-based graphite anode material, wherein Jiao Weifen-based graphite anode material is used as anode active material for preparing lithium secondary battery.
34. The use according to claim 33 as negative electrode active material for the preparation of a negative electrode for a lithium secondary battery.
35. The use of claim 33, wherein the lithium secondary battery is a lithium ion battery.
36. A negative electrode of a lithium secondary battery, comprising a current collector and a negative electrode active material compounded on the surface of the current collector, wherein the negative electrode active material is a Jiao Weifen-based graphite negative electrode material prepared by the method according to any one of claims 1-29.
37. A lithium secondary battery, characterized by comprising the Jiao Weifen-based graphite anode material prepared by the method of any one of claims 1-29.
38. The lithium secondary battery according to claim 37, wherein the negative electrode of the lithium secondary battery is the negative electrode according to claim 36.
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