CN112551503A - Modified soft carbon negative electrode material, lithium ion battery, negative electrode material and preparation method of negative electrode material - Google Patents
Modified soft carbon negative electrode material, lithium ion battery, negative electrode material and preparation method of negative electrode material Download PDFInfo
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Abstract
The invention discloses a modified soft carbon negative electrode material, a lithium ion battery, a negative electrode material and a preparation method thereof. The preparation method of the modified soft carbon negative electrode material comprises the following steps: sequentially carrying out activation treatment, washing, drying and heat treatment on the soft carbon carbonized precursor material; the soft carbon carbonization precursor material is obtained by carbonizing a soft carbon precursor material at 1250-1450 ℃; the mass ratio of the soft carbon carbonization precursor material to the activating agent in the activation treatment process is 100 (3-15); the activating agent is alkali inorganic compound containing alkali metal and/or inorganic salt containing chlorine; the temperature of the heat treatment is 500-700 ℃. The modified soft carbon negative electrode material improves the structure of the soft carbon, improves the amorphous degree of the soft carbon structure, increases the pore lithium storage sites of the soft carbon material, increases the channels for lithium desorption and insertion, and has high first reversible capacity, first coulombic efficiency and capacity retention rate after 100 weeks of circulation.
Description
Technical Field
The invention particularly relates to a modified soft carbon negative electrode material, a lithium ion battery, a negative electrode material and a preparation method thereof.
Background
The negative electrode material is one of four key materials of the lithium ion battery, and the quality of the rate capability directly determines the quick charge performance of the lithium ion battery. At present, commercial graphite cathode materials are difficult to meet the pace of requirements of high power, high capacity and the like of lithium ion batteries for electric tools for vehicles due to the low specific capacity (372mAh/g), poor high-rate charge and discharge performance and safety problems caused by lithium separation. In the development process of the negative electrode material, researchers find that soft carbon has an irregular disordered layer structure and a crystal face interlayer spacing larger than that of graphite, so that the soft carbon has high-rate charge-discharge performance and excellent low-temperature charge-discharge performance, and the problem of poor quick charge performance of the soft carbon is hopefully solved when the soft carbon is applied to a lithium ion battery. However, the conventional soft carbon has common defects: low reversible capacity (<250mAh/g) and low first efficiency (< 85%), so the soft carbon material has a large room for improvement in capacity and efficiency. In the prior art, a mode of increasing pore lithium storage sites or amorphous degree generally adopts an oxidation pore-forming mode or element doping, wherein the former generally has uneven reaction and difficult pore control; the element doping of the latter can only be carried out on the surface layer of the precursor material, and the reaction depth is limited so that the capacity increase is limited. In the prior art, the soft carbon material is improved by adopting the coating to improve the performance of the soft carbon material, but the improvement of the capacity by the coating is limited. Chinese patent document CN105449162B discloses a negative electrode material for a lithium ion battery and a negative electrode sheet thereof. The negative electrode material is formed by mixing natural graphite and artificial graphite which are coated by soft carbon according to a certain mass ratio, and the cycle performance of the matrix material is greatly improved on the premise of ensuring high specific capacity by adopting the negative electrode material prepared by the method. CN104852049A discloses a modified soft carbon negative electrode material for lithium ion batteries, in which graphene powder particles are doped inside soft carbon powder particles, and meanwhile, the graphene powder particles are dispersed and loaded in a nano coating material coating on the surface layer of the soft carbon powder particles to form a nano conductive carbon layer. The reversible specific capacity of the modified soft carbon negative electrode material prepared by the method is more than 360mAh/g, the efficiency is more than 85 percent, the modified soft carbon negative electrode material has excellent capability of rapidly inserting and removing lithium, and the rate capability and the cycle performance are greatly improved. CN105591084A discloses a negative active material and a preparation method thereof. The negative electrode material is formed by coating soft carbon on the surfaces of a soft carbon matrix, silicon particles dispersed in the soft carbon matrix and the soft carbon particles, and the prepared negative electrode active material has excellent first charge-discharge efficiency, capacity, rate capability and cycle performance. However, in the above prior arts, soft carbon is mostly coated on the surface of other matrix negative electrode materials (such as graphite, hard carbon, silicon carbon, etc.) or directly physically mixed to improve partial performances of the original matrix negative electrode. None of these methods has been directed to improving the inherent deficiencies of soft carbon materials, and thus fails to address the inherent problems of soft carbon, such as low capacity and low first-pass efficiency.
Chinese patent document CN108448114A discloses a soft carbon negative electrode material of a lithium ion battery and a preparation method thereof, and specifically discloses a soft carbon precursor material obtained by carbonizing a crushed soft carbon raw material at 380-1530 ℃, and then mixing the soft carbon precursor material with a lithium-containing compound and/or an activating agent according to a mass ratio of 100: (1-2500) activating at 450-1650 ℃, and finally washing and drying to obtain the soft carbon negative electrode material. The soft carbon cathode material has low coulombic efficiency for the first time, and the activator used in the preparation process of the soft carbon cathode material is an expensive and active lithium-containing compound, or an acidic compound or an organic compound with strong corrosiveness, so that the soft carbon cathode material has high danger, excessively harsh preparation conditions and extremely high requirements on equipment.
Therefore, the development of an improvement method for improving the performance of the soft carbon material to improve the soft carbon capacity, the first efficiency and the cycle performance is still a common technical bottleneck faced by negative electrode enterprises in China at present.
Disclosure of Invention
The invention solves the technical problems that the modification of the soft carbon negative electrode material in the prior art is surface coating or physical direct mixing, the modification of the soft carbon material is not related to the defects of the soft carbon material, the amorphous degree of the carbon structure of the soft carbon material is lower, the number of pore lithium storage sites is less, the discharge capacity, the first coulombic efficiency and the capacity retention rate after circulation of the obtained soft carbon negative electrode material are lower, the preparation conditions of the modified soft carbon negative electrode material are harsh, and the requirement of the preparation process on equipment is high, and provides the modified soft carbon negative electrode material, the lithium ion battery and the negative electrode material and the preparation method thereof. The modified soft carbon negative electrode material has no special requirements on equipment in the preparation process, can be prepared by adopting common equipment, has no harsh preparation conditions, does not need to be coated and modified, and directly improves the structure of the soft carbon, so that the amorphous degree of the soft carbon structure is improved, the pore lithium storage sites of the soft carbon material are obviously increased, and the lithium removal and insertion channels are increased, thereby ensuring that the first reversible capacity, the first coulombic efficiency and the capacity retention rate after 100 weeks of circulation of the obtained soft carbon negative electrode material of the lithium ion battery are high.
The invention solves the technical problems through the following technical scheme.
The invention provides a preparation method of a modified soft carbon negative electrode material, which comprises the following steps:
sequentially carrying out activation treatment, washing, drying and heat treatment on the soft carbon carbonized precursor material;
wherein the soft carbon carbonization precursor material is obtained by carbonizing a soft carbon precursor material at 1250-1450 ℃; the mass ratio of the soft carbon carbonized precursor material to the activating agent in the activating treatment process is 100 (3-15); the activating agent is an alkali inorganic compound containing alkali metal and/or a chlorine-containing inorganic salt; the temperature of the heat treatment is 500-700 ℃.
In the present invention, the soft carbon precursor material can be conventional in the art, and the particle size of the soft carbon precursor material is preferably 2 to 20 μm, more preferably 5 to 15 μm, for example 8 μm.
In the present invention, the soft carbon precursor material is generally obtained by crushing and sieving a soft carbon raw material, as known to those skilled in the art.
The soft carbon material may be conventional in the art, and may specifically be a graphitized amorphous carbon material, such as one or more of pitch coke, needle coke, carbon fiber, and mesocarbon microbeads, for example, needle coke.
Wherein the content of volatile components in the soft carbon raw material is generally below 8%, preferably below 6%, such as 5%, more preferably below 1%.
Wherein, the magnetic foreign matters in the soft carbon raw material are Fe <80ppm, Co <5ppm, Ni <3ppm, Cr <5ppm, Zn <5ppm and Mn <3 ppm.
Wherein the crushing treatment may be an operation conventional in the art, typically planetary ball milling, mechanical crushing or jet milling, preferably jet milling.
Wherein the sieving process may be a conventional one in the art, and the sieving process is preferably a standard sieve having a size of not less than 200 mesh.
In the present invention, the carbonization treatment apparatus may be conventional in the art, and is preferably an atmosphere furnace, a rotary kiln, a roller kiln, a pusher kiln or a tubular carbonization furnace, such as a roller kiln.
In the present invention, the temperature of the carbonization treatment is preferably 1250 to 1350 ℃, for example 1300 ℃. The temperature of the carbonization treatment can be obtained by a temperature increase operation which is conventional in the art. In the heating operation, the heating rate may be conventional in the art, preferably 5 to 10 ℃/min, and more preferably 5 to 8 ℃/min.
In the present invention, the carbonization time can be conventional in the art, preferably 2 to 6 hours, and more preferably 4 to 6 hours.
In the present invention, it is known to those skilled in the art that the carbonization treatment is performed under nitrogen and/or an inert atmosphere, preferably one or more of nitrogen, helium, neon, argon, krypton, and xenon, and more preferably nitrogen.
In the present invention, the equipment for carrying out the activation treatment may be conventional in the art, and is preferably carried out in an atmosphere furnace, a rotary furnace, a roller kiln, a pusher kiln or a tubular carbonization furnace, for example, a rotary furnace.
The temperature of the activation treatment may be conventional in the art, preferably 600 to 800 ℃, and more preferably 700 to 800 ℃. The temperature of the activation treatment may be obtained by a temperature-raising operation which is conventional in the art. In the heating operation, the heating rate can be conventional in the art, and is preferably 0.5-5 ℃/min.
The time of the activation treatment can be conventional in the art, and is preferably 1 to 3 hours, for example 2 hours.
In the invention, the activation treatment or the low-temperature heat treatment is too short, which can result in incomplete reaction and incomplete pore structure development; the time is too long, the production cost is increased, and the production efficiency is reduced.
Wherein, the activation treatment is performed under nitrogen and/or inert atmosphere, preferably one or more of nitrogen, helium, neon, argon, krypton and xenon, more preferably nitrogen, as known to those skilled in the art.
In the present invention, the alkali metal-containing basic inorganic compound may be conventional in the art, and is generally one or more of alkali metal-containing hydroxide, alkali metal-containing carbonate and alkali metal-containing bicarbonate, preferably one or more of potassium hydroxide, sodium hydroxide, potassium carbonate, potassium bicarbonate, sodium carbonate and sodium bicarbonate, and more preferably potassium hydroxide and/or potassium carbonate.
In the present invention, the chlorine-containing inorganic salt may be conventional in the art, and is preferably one or more of sodium chloride, potassium chloride, calcium chloride, zinc chloride and aluminum chloride, and is preferably zinc chloride.
In the present invention, the mass ratio of the soft carbon carbonization precursor material to the activating agent is preferably 100 (5-15), such as 100:6, 100:7, 100:8, 100:9, 100:10, 100:11, 100:12, 100:13, 100:14, and more preferably 100 (10-15).
In the present invention, it is known to those skilled in the art that the method further includes an operation of mixing the soft carbon carbonization precursor material and the activating agent before the activation treatment, for example, mixing the soft carbon carbonization precursor material and the activating agent uniformly. Preferably, the mixing is performed by stirring at 500-1500 rpm for 0.5-1.5 hours, for example, stirring at 1000rpm for 1 hour.
In the present invention, the washing conditions and operations may be conventional in the art, and it is sufficient to wash the material after the activation treatment to be neutral. The washing operation is preferably carried out as follows: stirring in hydrochloric acid solution, washing with water, and filtering.
The mass fraction of hydrochloric acid in the hydrochloric acid solution may be conventional in the art, preferably 10-30%, and more preferably 20-25%.
The operation and conditions of the stirring may be conventional in the art, among others. Preferably, the stirring temperature is 40-60 ℃. Preferably, the stirring time is 1 to 3 hours. Preferably, the stirring speed is 500-1000 rpm. For example, at 50 ℃ for 2 hours at 500 rpm.
In the present invention, the operation and conditions of the drying may be conventional in the art. Preferably, the drying equipment is a blast air or vacuum electrothermal drying oven. Preferably, the drying temperature is 80-120 ℃, for example, 100 ℃. Preferably, the drying time is 4 to 12 hours, such as 10 hours.
In the present invention, the apparatus for the heat treatment may be conventional in the art. Preferably, the equipment for carrying out the low-temperature treatment is an atmosphere furnace, a rotary furnace or a roller kiln.
Wherein the temperature of the heat treatment is preferably 550 ℃ to 700 ℃, such as 600 ℃ to 650 ℃. The temperature of the heat treatment may be obtained by a temperature-raising operation which is conventional in the art. In the heating operation, the heating rate can be conventional in the art, and is preferably 1-3 ℃/min.
Wherein, the time of the heat treatment can be conventional in the field, and is preferably 2-4 h.
Wherein, as known to those skilled in the art, the heat treatment is performed under nitrogen and/or an inert atmosphere, preferably one or more of nitrogen, helium, neon, argon, krypton and xenon, more preferably nitrogen.
In the present invention, it is known to those skilled in the art that a sieving treatment is usually further included after the heat treatment. The operation and conditions of the screening process may be conventional in the art. Preferably, the material is sieved through a standard screen mesh with more than 250 meshes, for example, a standard screen mesh with 300 meshes.
The invention also provides a modified soft carbon negative electrode material prepared by the preparation method.
In the invention, the average volume particle diameter D50 of the modified soft carbon negative electrode material is usually 5-15 μm, and the specific surface area is 5-10 m2G, interlayer spacing d of carbon crystallites002Is 0.353-0.365 nm.
The invention also provides a preparation method of the lithium ion battery cathode material, which is prepared by adopting the modified soft carbon cathode material.
Preferably, the preparation method of the lithium ion negative electrode material comprises the following steps: (1) adding a modified soft carbon negative electrode material and conductive carbon black into the polyvinylidene fluoride solution to obtain battery negative electrode slurry; (2) coating the battery negative electrode slurry on copper foil to obtain a pole piece; (3) and drying the pole piece to obtain the electrode.
In step (1), the solvent in the polyvinylidene fluoride solution can be conventional in the art, and preferably is N-methylpyrrolidone.
In the step (1), the mass fraction of polyvinylidene fluoride in the polyvinylidene fluoride solution can be conventional in the art, and is preferably 6-7%.
In step (1), as known to those skilled in the art, after the soft carbon negative electrode material and the conductive carbon black are added to the polyvinylidene fluoride solution, an operation of stirring is usually required, and the stirring operation is performed to uniformly stir the raw materials.
In the step (1), as known to those skilled in the art, the mass ratio of the polyvinylidene fluoride solution, the modified soft carbon negative electrode material and the conductive carbon black in the battery negative electrode slurry is generally 91.6:6.6: 1.8.
In step (3), the drying conditions may be conventional in the art, and preferably the drying is performed in a vacuum drying oven at 90-120 ℃ for 2-6 hours, for example, in a vacuum drying oven at 110 ℃ for 4 hours.
The invention also provides the lithium ion battery cathode material prepared by the preparation method.
The invention also provides a preparation method of the lithium ion battery, and the negative electrode material of the lithium ion battery is the lithium ion negative electrode material or is prepared by adopting the modified soft carbon negative electrode material.
Preferably, the preparation method of the lithium ion battery comprises the following steps: the lithium ion negative electrode material is used as a negative electrode, the metal lithium sheet is used as a counter electrode, and the solvent of the electrolyte in the lithium ion battery is 1:1:1 volume ratio of EC/DEC/DMC mixed solvent, 1mol/L of solute in electrolyte LiPF6And assembling in a glove box to obtain the lithium ion battery.
The invention also provides a lithium ion battery prepared by the preparation method.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows: the preparation process of the modified soft carbon negative electrode material is simple, coating modification is not needed, the soft carbon material is directly improved, the amorphous degree of the soft carbon structure is improved, the pore lithium storage sites of the soft carbon material are obviously increased, and the specific surface area of the obtained modified soft carbon negative electrode material is uniform and can be within the range of 5-10 mu m; interlayer spacing d of carbon crystallites002Can be between 0.353 and 0.365 nm; the first reversible capacity can be more than 300mAh/g (up to 327mAh/g), and the first coulombThe efficiency can be more than 85 percent (the highest can reach 87.5 percent), and the capacity retention rate after 100 weeks of circulation can be more than 95 percent (the highest can reach 96.1 percent); and the activating agents used in the activation treatment are all inorganic alkali or inorganic salt which is cheap and easy to obtain, the preparation cost is low, no special requirements on equipment are required, and the preparation conditions are not harsh.
Drawings
Fig. 1 is an SEM image of the modified soft carbon anode material in example 1.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
Example 1 preparation of modified Soft carbon Anode materials
Crushing needle coke with the volatile content of 5% by airflow, sieving by a 200-mesh standard sieve to obtain needle coke powder with the particle size of 8.0 microns, then placing the needle coke powder in a roller kiln, introducing nitrogen protective gas, heating to 1300 ℃ at the speed of 5 ℃/min, carrying out carbonization treatment for 4 hours, and naturally cooling to room temperature to obtain a soft carbon carbonization precursor material; and mixing the soft carbon carbonization precursor material and potassium hydroxide according to the mass ratio of 100:5, wherein the mixing is carried out for 1h under the condition that the rotating speed is 1000 rpm. Then placing the mixture into a rotary furnace, heating the mixture to 800 ℃ at the speed of 5 ℃/min under the nitrogen atmosphere, carrying out activation treatment for 2h, and naturally cooling. And then, adding a hydrochloric acid solution with the mass fraction of 20%, stirring and reacting at the rotation speed of 500rpm at 50 ℃ for 2 hours, washing and filtering with pure water until the pH value of the filtrate is 7.0, drying at 100 ℃ for 10 hours in a drying box, finally placing in an atmosphere furnace in a nitrogen atmosphere, heating to 600 ℃ at the speed of 3 ℃/min, carrying out heat treatment for 2 hours, naturally cooling, and screening by using a 300-mesh standard sieve to obtain the modified soft carbon negative electrode material, wherein the SEM picture of the modified soft carbon negative electrode material is shown in figure 1.
The parameters in the preparation methods of the modified soft carbon negative electrode materials of examples 1 to 5 and comparative examples 1 to 4 are described in the following table 1, and the parameters not listed are the same as those in example 1.
TABLE 1 Process parameters for the examples and comparative examples
Example 6 preparation of lithium ion negative electrode material and lithium ion battery (lithium ion 2430 type button cell)
The preparation of the lithium ion negative electrode material and the lithium ion battery in the above embodiments 1 to 5 and comparative examples 1 to 4 specifically includes the following steps: firstly, preparing a polyvinylidene fluoride solution with the mass fraction of 6-7% by taking N-methyl pyrrolidone as a solvent, uniformly mixing the prepared modified soft carbon negative electrode material, polyvinylidene fluoride and conductive carbon black according to the mass ratio of 91.6:6.6:1.8, coating the mixture on a copper foil, and putting the coated electrode piece into a vacuum drying oven at the temperature of 110 ℃ for vacuum drying for 4 hours to obtain the lithium ion negative electrode material for later use.
Then assembled into a 2430 type button cell in an argon-filled German Michelona glove box, wherein the solvent of the electrolyte in the cell is EC/DMC/EMC mixed solvent with the volume ratio of 1:1:1, and the solute in the electrolyte is LiPF with 1mol/L6And finally obtaining the lithium ion 2430 button cell.
Effect example 1
The modified soft carbon negative electrode materials of examples 1 to 5 and comparative examples 1 to 4 were tested for particle size, specific surface area, and ash content, respectively, and the results are shown in table 2. The name and model of the instrument used for the test: particle size: malvern laser particle size analyzer MS 2000; specific surface area: kangta specific surface area determinator NOVA2000 e; ash content: the high-temperature electric furnace SX 2-2.5-12.
The modified soft carbon negative electrode materials in examples 1 to 5 and comparative examples 1 to 4 were subjected to first reversible capacity, first coulombic efficiency and rate cycle performance tests by a half-cell test method, and the results are listed in table 2.
The testing method of the half cell comprises the following steps: the electrochemical performance of the assembled lithium ion 2430 type button cell is tested on a LAND cell test system of Wuhanjinnuo electronics, Inc., and the charge-discharge voltage range is 5mV to 2.0V. The parameters of the obtained modified soft carbon negative electrode material are shown in table 2.
TABLE 2 Performance parameters of modified Soft carbon Anode materials in 1-5 examples and comparative examples 1-4, respectively
As shown in Table 2, the modified soft carbon negative electrode materials prepared in examples 1 to 5 have uniform specific surface areas and interlayer spacings d of carbon microcrystals within the range of 5 to 10 μm002The first reversible capacity is more than 300mAh/g (up to 327mAh/g), the first coulombic efficiency is more than 85 percent (up to 87.5 percent), and the capacity retention rate after 100 cycles is more than 95 percent (up to 96.1 percent).
Claims (10)
1. The preparation method of the modified soft carbon negative electrode material is characterized by comprising the following steps of:
sequentially carrying out activation treatment, washing, drying and heat treatment on the soft carbon carbonized precursor material;
wherein the soft carbon carbonization precursor material is obtained by carbonizing a soft carbon precursor material at 1250-1450 ℃;
the mass ratio of the soft carbon carbonization precursor material to the activating agent in the activation treatment process is 100 (3-15); the activating agent is an alkali inorganic compound containing alkali metal and/or a chlorine-containing inorganic salt; the temperature of the heat treatment is 500-700 ℃.
2. The method according to claim 1, wherein the particle size of the soft carbon precursor material is 2 to 20 μm, preferably 5 to 15 μm, and more preferably 8 μm;
and/or the soft carbon precursor material is obtained by crushing and screening a soft carbon raw material, wherein the soft carbon raw material is preferably a graphitized amorphous carbon material, and is more preferably one or more of pitch coke, needle coke, carbon fiber and mesocarbon microbeads.
3. The process according to claim 2, wherein the soft carbon raw material has a volatile content of 8% or less, preferably 6% or less;
and/or the magnetic foreign matters of the soft carbon raw material are Fe <80ppm, Co <5ppm, Ni <3ppm, Cr <5ppm, Zn <5ppm and Mn <3 ppm;
and/or the crushing treatment is planetary ball milling, mechanical crushing or airflow crushing;
and/or, the screening treatment is to pass through a standard screen with the size of not less than 200 meshes.
4. The method according to claim 1, wherein the temperature of the carbonization treatment is 1250 to 1350 ℃, preferably 1300 ℃;
and/or in the temperature rise operation of the carbonization treatment, the temperature rise rate is 5-10 ℃/min, preferably 5-8 ℃/min;
and/or the carbonization treatment time is 2-6 h, preferably 4-6 h;
and/or the temperature of the activation treatment is 600-800 ℃, preferably 700-800 ℃;
and/or in the temperature rise operation of the activation treatment, the temperature rise rate is 0.5-5 ℃/min;
and/or the activation treatment time is 1-3 h, preferably 2 h;
and/or, the alkali metal-containing basic inorganic compound is one or more of alkali metal-containing hydroxide, alkali metal-containing carbonate and alkali metal-containing bicarbonate, preferably one or more of potassium hydroxide, sodium hydroxide, potassium carbonate, potassium bicarbonate, sodium carbonate and sodium bicarbonate, more preferably potassium hydroxide and/or potassium carbonate;
and/or the chlorine-containing inorganic salt is one or more of sodium chloride, potassium chloride, calcium chloride, zinc chloride and aluminum chloride, preferably zinc chloride;
and/or the mass ratio of the soft carbon carbonization precursor material to the activating agent is 100 (5-15), preferably 100: (10-15);
and/or, before the activation treatment, the operation of mixing the soft carbon carbonization precursor material and the activating agent is further included, preferably, the mixing is performed under the condition of 500-1500 rpm for 0.5-1.5 hours, and more preferably, under the condition of 1000rpm for 1 hour;
and/or the washing is operations of stirring in a hydrochloric acid solution, water washing and filtering, preferably, the mass fraction of hydrochloric acid in the hydrochloric acid solution is 10-30%, more preferably 20-25%, the stirring temperature is 40-60 ℃, the stirring time is 1-3 hours, and the stirring speed is 500-1000 rpm;
and/or the drying temperature is 80-120 ℃, and the drying time is 4-12 hours;
and/or the temperature of the heat treatment is 550-700 ℃, preferably 600 ℃;
and/or the time of the heat treatment is 2-4 h;
and/or in the heating operation of the heat treatment, the heating rate is 1-3 ℃/min;
and/or, the heat treatment is followed by a screening treatment, preferably, the screening treatment is carried out by a standard screen with a mesh of more than 250.
5. A modified soft carbon negative electrode material prepared by the preparation method as claimed in any one of claims 1 to 4.
6. The modified soft carbon negative electrode material as claimed in claim 5, wherein the average volume particle diameter D50 of the modified soft carbon negative electrode material is 5 to 15 μm, and the specific surface area is 5 to 10m2G, interlayer spacing d of carbon crystallites002Is 0.353-0.365 nm.
7. A preparation method of a lithium ion battery cathode material, which is prepared by adopting the modified soft carbon cathode material as claimed in claim 5 or 6.
8. The negative electrode material of the lithium ion battery prepared by the preparation method of claim 7.
9. The preparation method of the lithium ion battery is characterized in that the negative electrode material of the lithium ion battery is the lithium ion negative electrode material of claim 8 or is prepared by adopting the modified soft carbon negative electrode material of claim 5 or 6;
preferably, the preparation method of the lithium ion battery comprises the following steps: the lithium ion negative electrode material is used as a negative electrode, the metal lithium sheet is used as a counter electrode, and the solvent of the electrolyte in the lithium ion battery is 1:1:1 volume ratio of EC/DEC/DMC mixed solvent, and 1mol/L LiPF solute of electrolyte in lithium ion battery6And assembling in a glove box to obtain the lithium ion battery.
10. A lithium ion battery prepared by the preparation method of claim 9.
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