CN110963489B

CN110963489B - Carbon negative electrode material, preparation method thereof and lithium ion battery

Info

Publication number: CN110963489B
Application number: CN201811143292.9A
Authority: CN
Inventors: 李子坤; 杨书展; 岳敏
Original assignee: BTR New Material Group Co Ltd
Current assignee: BTR New Material Group Co Ltd
Priority date: 2018-09-28
Filing date: 2018-09-28
Publication date: 2023-07-28
Anticipated expiration: 2038-09-28
Also published as: CN110963489A

Abstract

The invention provides a carbon negative electrode material, a preparation method thereof and a lithium ion battery. The carbon negative electrode material comprises composite particles mainly composed of a frame carrier and small particles positioned in the frame carrier, and nano particles adhered to the surfaces of the composite particles, wherein the frame carrier and the small particles are graphite materials, the nano particles are carbon materials, and the sources of the small particles are graphite tailings. The preparation method comprises the following steps: (1) raw material mixing, (2) polymerization, (3) graphitization treatment, and (4) coating treatment. The invention has the advantages of high energy density, stable structure, good orientation, good conductivity, high specific capacity, high compaction density and excellent cycle performance, and can meet the requirement of high energy density in lithium ion battery application.

Description

Carbon negative electrode material, preparation method thereof and lithium ion battery

Technical Field

The invention belongs to the technical field of energy storage materials, relates to a negative electrode material, and in particular relates to a carbon negative electrode material, a preparation method thereof and a lithium ion battery.

Background

Lithium ion batteries have been used in various aspects of people's daily life as a well-established electrochemical power system, but their performance has not yet been fully satisfactory for various applications. The most widely used lithium ion battery negative electrode material is graphite material which has a good layered structure, a stable discharge platform, small volume change in the lithium intercalation process and no voltage hysteresis, but the graphite negative electrode material has a capacity upper limit value and is difficult to break through; poor compatibility with electrolyte and poor liquid absorption capacity, resulting in poor battery cycling stability; the high-current charge and discharge performance and the multiplying power performance are improved; the material cost is high and needs to be further reduced.

In the production process of the graphite as a negative electrode material, raw materials such as various cokes, carbon microspheres, natural crystalline flake graphite and the like need to be subjected to multiple processes such as crushing, shaping, grading and the like, and the processes can cause the problems of reduced raw material utilization rate, dust environmental pollution, increased process cost and the like, so that the raw material utilization rate in the whole production process can reach 40% -50% in a combined way, and the rest 50% -60% can become "tails", which are composed of a plurality of micro powder, and the materials have the characteristics of small granularity, high specific surface area, irregular morphology, low tap density, poor processability, low compaction density, low specific capacity, low coulombic efficiency, poor electric conductivity, short cycle life and the like. Therefore, a proper method is needed to find out the "tailing" left in the production process, and reuse the tailing for the negative electrode material, so that the utilization value of the material is improved, the production cost of the negative electrode material is reduced, and the requirement of high performance of the lithium ion battery is met, which is a technical problem to be solved in the field.

CN107200322a discloses a method for preparing a negative electrode material for a lithium battery by utilizing special graphite tailing. The method comprises the following steps: s1, performing sphericizing treatment on special graphite tailing particles, then adding a binder and uniformly mixing to obtain a premix; s2, performing ultrasonic dispersion on graphene oxide in a solvent to obtain suspension dispersion liquid, standing, taking upper stable dispersion liquid, and uniformly spraying and mixing the upper stable dispersion liquid into the premix in the S1 to obtain a mixture; s3, compacting the mixture in the step S2 to obtain a briquette, roasting the briquette under the mixed atmosphere of nitrogen and hydrogen, cooling to room temperature, and sequentially carrying out crushing, demagnetizing and screening on the briquette to obtain the composite material.

CN107863511a discloses a method for preparing negative electrode powder for lithium batteries by recycling high-purity graphite corner material. The method comprises the following steps: sl. spheroidizing special graphite tailing particles, adding a binder, and uniformly mixing to obtain a premix; s2, mixing graphene oxide and nano silicon in proportion, performing ultrasonic dispersion in a solvent to obtain suspension dispersion liquid, standing, and uniformly spraying and mixing the upper stable dispersion liquid into premix in the S I to obtain a mixture, wherein the upper stable dispersion liquid can be regarded as a dispersion system of the graphene oxide and the nano silicon powder; and (3) compacting the mixture in the step (S2) to obtain a briquette, roasting the briquette under the mixed atmosphere of nitrogen and hydrogen, cooling to room temperature, and sequentially crushing, demagnetizing and screening the briquette to obtain the negative electrode material for the lithium battery.

Although the two schemes can realize high-value utilization of the graphite tailings to a certain extent, the types of the graphite tailings are limited to special graphite tailings, the universality is poor, and the performance of the obtained negative electrode material needs to be further improved.

CN104766954a discloses a method for recycling artificial graphite fine powder as a negative electrode material, which comprises the following steps: step A: taking tailing generated in the production process of the artificial graphite cathode material of the lithium battery as a raw material, adding a binder and a pore-forming agent, kneading and granulating at a certain temperature, rolling or pressing, and carbonizing at a high temperature; and (B) step (B): crushing, shaping and spheroidizing the carbonized material to obtain spherical or elliptic graphite powder meeting the requirement of a particle size range, graphitizing at high temperature, and adding the tailing collected again in the crushing/spheroidizing process into the step A to be used as a raw material for recycling; step C: and (3) performing granularity allocation on the spheroidized powder, and filling gaps among the particles. The scheme can utilize the tailing generated in the production process of the artificial graphite negative electrode material of the lithium battery, but the electrochemical performance of the obtained negative electrode material needs to be further improved.

Therefore, development of a method capable of effectively solving the problem of 'tailing' left in the production process of graphite negative electrode and obtaining high-performance negative electrode materials is of great significance to the field.

Disclosure of Invention

Aiming at the defects in the prior art, the invention aims to provide a carbon anode material, a preparation method thereof and a lithium ion battery. The carbon negative electrode material provided by the invention has the characteristics of stable structure, good orientation, good conductivity, high specific capacity, high compaction density, excellent cycle performance and the like, can meet the high energy density requirement in lithium ion battery application, and solves the problem of processing graphite tailings.

To achieve the purpose, the invention adopts the following technical scheme:

in a first aspect, the invention provides a carbon negative electrode material, which comprises composite particles mainly composed of a frame carrier and small particles positioned in the frame carrier, and nanoparticles adhered to the surfaces of the composite particles, wherein the frame carrier and the small particles are both graphite materials, the nanoparticles are carbon materials, and the small particles are from graphite tailings.

In the invention, the frame carrier is a ridge beam for supporting the whole graphite particles, and the tails of the small particles are combined together to ensure that the particles are not scattered and broken in the processes of pole piece rolling, battery circulation and the like. The graphite tailing refers to the tailing left in the production process of the graphite anode material.

In the invention, the morphology of the small particles is not completely the same. The carbon anode material provided by the invention is formed by embedding small particle tails with different shapes into a thicker frame carrier to form larger composite particles, and the carbon anode material has isotropy in a macroscopic sense due to different shapes and orientations of the tails, so that the direction selectivity of the carbon anode material is eliminated in the lithium ion transmission process; the diffusion path of lithium ions is greatly shortened due to smaller particles; the small particle tailing is firmly adhered together by using the polymeric additive, so that the structural stability is better, the expansion of the pole piece is low in the charge and discharge process of the battery, and the cyclic stability is shown; meanwhile, the non-metal carbide and the tailing are adhered together by the polymeric additive, the non-metal carbide plays a catalytic role in the graphitization process, a complete crystal structure is formed, and the capacity of graphite for storing lithium ions and the pole piece compaction density are greatly improved. On the other hand, the nano conductive material with better conductivity is adopted for surface modification, and point contact among particles is communicated, so that the cathode material shows enhanced conductivity, reduced battery polarization and improved power characteristic. In view of the increase of specific capacity of the carbon negative electrode material, the compacted density of the electrode plate is increased, the electron conductivity is enhanced, the lithium ion diffusion performance is improved, and the like, the characteristic of high energy density is exhibited.

In the carbon anode material provided by the invention, nano particles are uniformly distributed on the surfaces of the composite particles consisting of the frame carrier and the small particles in the frame carrier.

The following preferred technical solutions are used as the present invention, but not as limitations on the technical solutions provided by the present invention, and the technical objects and advantageous effects of the present invention can be better achieved and achieved by the following preferred technical solutions.

As a preferred embodiment of the present invention, the small particles have an average particle size D50 of 1 to 10. Mu.m, for example, 1 μm, 2 μm, 4 μm, 6 μm, 8 μm or 10 μm, etc., but are not limited to the values recited, and other values not recited in the range of values are equally applicable.

Preferably, the average particle size D50 of the nanoparticles is from 1 to 1000nm, such as 1nm, 10nm, 100nm, 200nm, 500nm, 750nm or 1000nm, etc., but is not limited to the recited values, and other non-recited values within this range are equally applicable.

Preferably, the average particle size D50 of the carbon negative electrode material is 10.0 to 40.0 μm, for example, 10.0 μm, 15.0 μm, 20.0 μm, 25.0 μm, 30.0 μm, 35.0 μm, 40.0 μm, or the like, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.

Preferably, the carbon negative electrode material has a particle size distribution dispersion of 0.5 to 2.0, for example, 0.5, 1.0, 1.5, or 2.0, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.

Preferably, the sphericity S50 of the carbon negative electrode material is 0.8 to 0.9, for example, 0.8, 0.82, 0.84, 0.86, 0.88 or 0.9, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.

Preferably, the specific surface area of the carbon anode material is 2.0-20.0m ² /g, e.g. 2.0m ² /g、5.0m ² /g、10.0m ² /g、15.0m ² /g or 20.0m ² For example,/g, etc., but are not limited to the recited values, and other values not recited in this range are equally applicable.

The conductivity of the carbon anode material provided by the invention is more than or equal to 200S/cm, the first lithium removal specific capacity is more than or equal to 355mAh/g, the pole piece compaction density is more than or equal to 1.6g/cc, and the 500-week circulation capacity retention rate is more than or equal to 95%.

In a second aspect, the present invention provides a method for preparing a carbon negative electrode material according to the first aspect, the method comprising the steps of:

(1) Mixing graphite tailings, nonmetallic carbide and a polymerization additive to obtain a mixed material;

(2) Carrying out polymerization reaction on the mixed material in the step (1) in a protective atmosphere to obtain polymerized particles;

(3) Graphitizing the polymer particles in the step (2) in a protective atmosphere to obtain graphitized materials;

(4) And (3) coating the graphitized material in the step (3) by using a nano conductive material to obtain the carbon anode material.

In the preparation method provided by the invention, the tailing, the nonmetallic carbide and the polymeric additive are uniformly mixed, then the polymerization treatment and the high-temperature graphitization treatment are carried out under the protective atmosphere, then the crushing, the particle shaping and the screening are carried out, and finally the surface coating treatment is carried out by using the nano conductive material to obtain the carbon anode material. The graphite tailing finally forms small particles in the carbon anode material, the polymeric additive finally forms a frame carrier, and the nano conductive material finally forms nano particles on the surface of the carbon anode material.

The preparation method adopts a brand-new material design concept, takes the discarded tailing in the production process of the graphite anode material as a main raw material, reconstructs the anode material, fully utilizes the technological advantage of particle polymerization and the performance advantage of the nano conductive material, has simple production flow, accurate process control and no harsh condition, is easy to industrialize, greatly reduces the production cost of the carbon anode material, and improves the performance advantage of high energy density.

In the preparation method provided by the invention, the nonmetallic carbide has the following functions: in the graphitization process, the nonmetallic carbide can be decomposed and volatilized due to higher temperature, and the graphite crystal growth is facilitated in the volatilization process, so that the graphitization degree is improved.

As a preferable technical scheme of the invention, the graphite tailing in the step (1) comprises any one or a combination of at least two of raw coke, cooked coke, carbon microspheres, crystalline graphite, aphanitic graphite or spherical graphite micropowder. The carbon materials all belong to the tailing left in the production process of the graphite cathode material.

Preferably, the raw coke is any one or a combination of at least two of petroleum coke, pitch coke or coal coke.

Preferably, the cooked coke is any one or a combination of at least two of petroleum coke, pitch coke or coal coke.

Preferably, the carbon microspheres comprise petroleum pitch-based carbon microspheres and/or coal pitch-based carbon microspheres.

Preferably, the raw coke, cooked coke, or carbon microsphere has a volatile content of 1-20%, such as 1%, 4%, 6%, 8%, 10%, 12%, 14%, 16%, 18%, or 20%, etc., but is not limited to the recited values, and other non-recited values within the range are equally applicable.

Preferably, the raw, cooked or carbon microspheres each have an ash content of less than 0.5%, e.g., 0.5%, 0.4%, 0.3%, 0.2%, etc.

Preferably, the carbon content of the flake graphite, crystalline graphite, aphanitic graphite or spherical graphite fine powder is 90 to 99.9%, for example 90%, 92%, 94%, 96%, 98% or 99.9%, etc., but not limited to the recited values, and other non-recited values within the range are equally applicable.

Preferably, the average particle size D50 of the graphite tailings in step (1) is 1-10 μm, e.g. 1 μm, 2 μm, 4 μm, 6 μm, 8 μm or 10 μm etc., but is not limited to the values recited, and other non-recited values within this range are equally applicable.

Preferably, the specific surface area of the graphite tailing in the step (1) is 5-15m ² /g, e.g. 5m ² /g、7m ² /g、10m ² /g、12m ² /g, or 15m ² For example,/g, etc., but are not limited to the recited values, and other values not recited in this range are equally applicable.

Preferably, the nonmetallic carbide of step (1) is silicon carbide and/or boron carbide.

Preferably, the average particle size D50 of the nonmetallic carbide of step (1) is 5-60 μm, such as 5 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, or 60 μm, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.

Preferably, the specific surface area of the nonmetallic carbide of step (1) is 0.5-5m ² /g, e.g. 0.5m ² /g、1m ² /g、2m ² /g、3m ² /g、4m ² /g or 5m ² For example,/g, etc., but are not limited to the recited values, and other values not recited in this range are equally applicable.

Preferably, the purity of the nonmetallic carbide of step (1) is 98-99.5%, such as 98%, 98.5%, 99% or 99.5%, etc., but is not limited to the recited values, and other non-recited values within this range are equally applicable.

Preferably, the nonmetallic carbide(s) of step (1) are added in an amount of 1.0% -10.0%, such as 1.0%, 2.0%, 4.0%, 6.0%, 8.0% or 10.0% etc., based on the total weight of the mixture, but are not limited to the recited values, as other non-recited values within this range are equally applicable. If the nonmetallic carbide is excessively added, a large amount of volatile gas is generated in the graphitization process and is not thoroughly volatilized, the volatile gas is condensed again once encountering low temperature, impurities which are unfavorable for the performance of the anode material are generated, and meanwhile, more severe requirements are put forward on a graphitization furnace; if the addition of nonmetallic carbide is too little, the effect on graphitization is smaller, and the effect of improving the product performance is not achieved.

Preferably, the polymeric additive of step (1) comprises any one or a combination of at least two of asphalt, resin, polymeric material or polymer.

Preferably, the asphalt comprises any one or a combination of at least two of coal asphalt, petroleum asphalt, natural asphalt, or mesophase asphalt.

Preferably, the polymeric additive is added in an amount of 10.0% to 30.0%, such as 10.0%, 15.0%, 20.0%, 25.0% or 30.0% by weight of the total weight of the mixture, but is not limited to the recited values, as other non-recited values within this range are equally applicable. If the polymerization additive is added too much, the particle size generated by polymerization is too large, and too much additive component is not beneficial to the exertion of the comprehensive performance of the particles; if the addition of the polymerization additive is too small, the binder needed by the polymerization of the small particle tailings is insufficient, and the polymerization adhesion cannot be well carried out, so that the effect of the frame carrier cannot be achieved.

The mixing in the step (1) is carried out by using a mixer.

Preferably, the mixer comprises any one or a combination of at least two of a V-type mixer, a slot-type mixer, a drum mixer, a conical twin screw mixer or a twin conical mixer.

Preferably, the mixing time in step (1) is 10-180min, such as 10min, 20min, 50min, 80min, 100min, 120min, 140min, 160min or 180min, but is not limited to the recited values, and other non-recited values within the range are equally applicable.

As a preferred embodiment of the present invention, the polymerization reaction in the step (2) is carried out in a polymerization vessel.

The polymerization kettle comprises any one of a tin-free new optical powder VC-1500J type reaction kettle, a tin-free Qingxin powder VC-1000L reaction kettle, a Buddha Hengaojia VC-2000L reaction kettle, a Buddha Shuoxing VC-2000L reaction kettle and a Buddha Nordic mechanical VC-2000L reaction kettle. However, the polymerization vessel is not limited to the above, and any vessel having heating and stirring functions is suitable for the polymerization reaction of the present invention.

Preferably, the polymerization reaction temperature in step (2) is 300 to 800 ℃, for example 300 ℃, 400 ℃, 500 ℃, 600 ℃, 700 ℃, 800 ℃, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable. If the polymerization temperature is too high, the polymerization additive is easy to decompose and carbonize, so that the effect of polymerization and adhesion on the small particle tailings is lost; if the polymerization temperature is too low, the polymerization additive is kept in a solid state and cannot be softened or fluidized, thereby exerting no polymerization adhesion.

Preferably, the polymerization reaction in step (2) is carried out for a period of time ranging from 3 to 9 hours, such as 3 hours, 4 hours, 6 hours, 8 hours, or 9 hours, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.

Preferably, the polymerization reaction of step (2) is accompanied by stirring.

Preferably, the stirring speed is 10-40r/min; for example, 10r/min, 20r/min, 30r/min, 40r/min, etc., but is not limited to the recited values, and other values not recited in the range of values are equally applicable.

Preferably, the protective atmosphere of step (2) comprises any one or a combination of at least two of helium, neon, argon or nitrogen;

preferably, the gas flow rate of the protective atmosphere in the step (2) is 20-50L/min, for example, 20L/min, 30L/min, 40L/min or 50L/min, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.

As a preferred embodiment of the present invention, the protective atmosphere in the step (3) includes any one or a combination of at least two of helium, neon, argon or nitrogen.

Preferably, the graphitizing treatment of step (3) is performed with a graphitizing furnace. The inking furnace comprises an internal string graphitizing furnace or an Acheson graphitizing furnace.

Preferably, the graphitization treatment in step (3) is carried out at a temperature of 2500 to 3300 ℃, for example 2500 ℃, 2600 ℃, 2700 ℃, 2800 ℃, 2900 ℃, 3000 ℃, 3100 ℃, 3200 ℃, 3300 ℃ or the like, but the graphitization treatment is not limited to the values listed, and other values not listed in the range are equally applicable.

Preferably, the temperature rise time of the graphitization treatment in step (3) is 12-72 hours, for example 12 hours, 24 hours, 36 hours, 48 hours, 60 hours or 72 hours, etc., but is not limited to the recited values, and other non-recited values within the range are equally applicable.

Preferably, the graphitization treatment in step (3) is performed for a period of 15 to 30 days, for example, 15 days, 20 days, 25 days, 30 days, etc., but is not limited to the values recited, and other values not recited in the range are equally applicable.

In the graphitization treatment in the step (3), the temperature is raised to the temperature required by the graphitization treatment, and then the temperature is kept for heat preservation treatment.

As a preferred technical scheme of the invention, the preparation method further comprises the step (3'): and (3) crushing, particle shaping and screening the graphitized material obtained in the step (3) to obtain the spheroidic material.

Preferably, the crushing and particle shaping device comprises any one or a combination of at least two of a turbine crusher, an airflow vortex pulverizer, a super cyclone vortex mill, a winnowing crusher or a double-stick crusher.

Preferably, the screening uses a screen mesh number of 150-325 mesh.

Preferably, the average particle size D50 of the spheroidal material is from 10 to 40 μm, such as 10 μm, 20 μm, 30 μm, 40 μm, etc., but is not limited to the recited values, as other non-recited values within the range of values are equally applicable.

In a preferred embodiment of the present invention, the amount of the nano conductive material added in the step (4) is 0.1% -10.0%, for example, 0.1%, 0.5%, 1.0%, 2.0%, 4.0%, 6.0%, 8.0% or 10.0% of the total weight of the mixture in the step (1), but is not limited to the recited values, and other non-recited values in the range of values are equally applicable. If the nano conductive material is excessively added, the specific surface area of the anode material is increased, and the side reaction with electrolyte is increased, so that the capacity of the battery and the cycle performance are not facilitated; if the addition of the nano conductive material is too small, the improvement range of the conductive performance of the negative electrode material is limited, and the electrochemical performance advantage of the material cannot be fully exerted.

Preferably, the nano conductive material of step (4) comprises acetylene black and/or ketjen black. The Ken black comprises Ken black EC-300J, ken black ECP or Ken black ECP-600JD of Japan LION obstetrical department. In addition to the above materials, a nano-conductive material such as Super-P, ensaco 350G produced by Swiss Temmit (TIMCAL) may also be used as the nano-conductive material in the present invention.

Preferably, the coating treatment of step (4) is performed in a coating apparatus.

Preferably, the coating apparatus comprises any one of a mixer, a mechanoconfusion machine or a spray dryer.

Preferably, the mixer comprises any one of a V-type mixer, a tank mixer, a drum mixer, a conical twin screw mixer, a double conical mixer or a triple eccentric mixer.

Preferably, the mechanical fusion machine comprises any one of a Shandong-Fangyuan LHS type fusion machine, a Wuxi Fuan powder ZJ-30 type mechanical fusion machine, a Minghai powder ZSJ type mechanical fusion machine, a Wuxi Qingxin powder ZSJ-600 type mechanical fusion machine, shanghai privet fusion mechanical equipment, a Wuxi Xin LiZJ type mechanical fusion machine, a Wuxi Xinguang powder mechanical fusion equipment or a Japan Mikroot AMS type mechanical fusion machine.

Preferably, when the cladding apparatus is a mixer or mechanoconfusion machine, the motor frequency of the cladding apparatus is 50-800Hz, such as 50Hz, 100Hz, 200Hz, 300Hz, 400Hz, 500Hz, 600Hz, 700Hz or 800Hz, etc.

Preferably, when the coating apparatus is a spray dryer, the solvent used for the coating treatment comprises any one or a combination of at least two of water, methanol, methylene chloride, n-heptane, toluene, n-hexane, pentane, gasoline, benzene, styrene, butyltoluene, vinyl toluene, trichloroethylene, carbon disulphide or tri-o-cresol phosphate.

Preferably, when the coating apparatus is a spray dryer, the temperature of the coating treatment is 50-350 ℃, e.g. 50 ℃, 100 ℃, 150 ℃, 200 ℃, 250 ℃, 300 ℃, or 350 ℃, etc.

Preferably, the time of the coating treatment in step (4) is 20-120min, such as 20min, 50min, 100min or 120 min.

As a further preferred technical solution of the preparation method according to the invention, the method comprises the following steps:

(1) Mixing graphite tailing, nonmetallic carbide and polymeric additive in a mixer for 10-180 min to obtain a mixed material;

wherein the addition amount of the nonmetallic carbide is 1.0-10.0% of the total weight of the mixed material, and the addition amount of the polymerization additive is 10.0-30.0% of the total weight of the mixed material;

(2) Carrying out polymerization reaction on the mixed material in the step (1) at the temperature of 300-800 ℃ and the stirring speed of 10-40r/min under the protective atmosphere with the gas flow of 20-50L/min, and reacting for 3-9h to obtain polymerized particles;

(3) Carrying out graphitization treatment on the polymer particles in the step (2) by using a graphitization furnace under a protective atmosphere at the temperature of 2500-3300 ℃, wherein the temperature rise time of the graphitization treatment is 12-72h, and the heat preservation time is 15-30 days, so as to obtain graphitized materials;

(3') crushing and shaping particles of the graphitized material obtained in the step (3), and sieving with a 150-325 mesh sieve to obtain a spheroidal material, wherein the average particle size D50 of the spheroidal material is 10-40 mu m;

(4) Coating the spherical-like material in the step (3') in coating equipment by using a nano conductive material for 20-120min to obtain the carbon anode material;

wherein the addition amount of the nano conductive material is 0.1% -10.0% of the total weight of the mixed material in the step (1), and the coating equipment comprises any one of a mixer, a mechanical fusion machine or a spray dryer; when the coating equipment is a mixer or a mechanical fusion machine, the motor frequency of the coating equipment is 50-800Hz; when the coating apparatus is a spray dryer, the temperature of the coating process is 50-350 ℃.

In a third aspect, the present invention provides a lithium ion battery comprising a carbon negative electrode material according to the first aspect.

In the lithium ion battery provided by the invention, the carbon anode material in the first aspect is taken as an anode active material and an adhesive additive to form an anode material. The carbon cathode material used as the active substance has higher specific capacity, higher compacted density of the pole piece and higher electronic conductivity, and the external conductive agent is omitted in the manufacturing of the lithium ion battery, so that more active substances are put into a limited battery space, and the energy density of the lithium ion battery is increased.

Compared with the prior art, the invention has the following beneficial effects:

(1) The carbon negative electrode material provided by the invention has the advantages of high energy density, stable structure, good orientation, good conductivity, high specific capacity, high compaction density and excellent cycle performance, and can meet the high energy density requirement in lithium ion battery application, the conductivity of the carbon negative electrode material provided by the invention is more than or equal to 200S/cm, the first lithium removal specific capacity is more than or equal to 355mAh/g, the pole piece compaction density is more than or equal to 1.6g/cc, and the 500-week cycle capacity retention rate is more than or equal to 95%.

(2) The preparation method provided by the invention uses the discarded tailing in the production process of the graphite anode material as the main raw material, reconstructs the anode material, fully utilizes the technological advantage of particle polymerization and the performance advantage of the nano conductive material, has simple production flow, accurate process control and no harsh condition, is easy to industrialize, greatly reduces the production cost of the carbon anode material, and improves the performance advantage of high energy density.

Drawings

FIG. 1 is a schematic structural diagram of a carbon negative electrode material prepared in example 1 of the present invention, wherein 1-small particles, 2-frame carriers, 3-nanoparticles;

FIG. 2 is an SEM image of a carbon negative electrode material prepared according to example 1 of the present invention;

FIG. 3 is a charge-discharge curve of the carbon negative electrode material prepared in example 1 of the present invention;

fig. 4 is a cycle chart of the carbon anode material prepared in example 1 of the present invention.

Detailed Description

For better illustrating the present invention, the technical scheme of the present invention is convenient to understand, and the present invention is further described in detail below. The following examples are merely illustrative of the present invention and are not intended to represent or limit the scope of the invention as defined in the claims.

The following are exemplary but non-limiting examples of the invention:

example 1

The carbon negative electrode material is prepared according to the following method:

(1) Mixing graphite tailing, nonmetallic carbide and polymeric additive in a V-shaped mixer for 10min to obtain a mixed material;

wherein, each raw material parameter is shown in table 1. The addition amount of the nonmetallic carbide is 1.2 percent of the total weight of the mixed materials, and the addition amount of the polymeric additive is 10.2 percent of the total weight of the mixed materials;

(2) Under the argon atmosphere with the gas flow of 20L/min, using a tin-free new optical powder VC-1500J type reaction kettle to carry out polymerization reaction on the mixed material in the step (1) at the temperature of 300 ℃ and the stirring speed of 10r/min for 3h to obtain polymerized particles;

(3) Graphitizing the polymer particles in the step (2) by using an Acheson graphitizing furnace at the temperature of 2500 ℃ in an argon atmosphere, wherein the temperature rise time of the graphitizing treatment is 24 hours, and the heat preservation time is 20 days, so as to obtain graphitized materials;

(3') crushing and shaping particles of the graphitized material obtained in the step (3) by using a turbine crusher, and sieving by using a 150-mesh screen to obtain a spheroidal material, wherein the average particle size D50 of the spheroidal material is 11.5 mu m;

(4) Coating the spherical-like material in the step (3') in a V-shaped mixer by using a nano conductive material, wherein the coating time is 20min, and the motor frequency of coating equipment is 50Hz, so as to obtain the carbon anode material;

the specific types of the nano conductive materials are shown in table 1. The addition amount of the nano conductive material is 0.1% of the total weight of the mixture material in the step (1).

The carbon negative electrode material finally obtained in the embodiment comprises composite particles mainly composed of a frame carrier and small particles positioned in the frame carrier, and nano particles adhered to the surfaces of the composite particles, wherein the frame carrier and the small particles are graphite materials, the nano particles are carbon materials, and the source of the small particles is graphite tailing.

The performance test results of the carbon anode material finally obtained in this example are shown in table 2.

Fig. 1 is a schematic structural diagram of a carbon negative electrode material prepared in this embodiment, and it can be seen from this figure that the carbon negative electrode material prepared in this embodiment is formed by embedding small particles 1 with different morphologies into a thicker frame carrier 2 to form a larger composite particle, and the surface of the composite particle is uniformly adhered with nano particles 3.

Fig. 2 is an SEM image of the carbon negative electrode material prepared in this example, and it can be seen from this image that the morphology of the carbon negative electrode material particles prepared in this example is presented as small particle polymers of different shapes, and a large number of nanoparticles are adhered to the surface.

Fig. 3 is a charge-discharge graph of the carbon negative electrode material prepared in this example, and it can be seen from this graph that the first lithium removal specific capacity of the carbon negative electrode material reaches 355mAh/g or more.

Fig. 4 is a cycle chart of the carbon negative electrode material prepared in this example, from which it can be seen that the capacity retention of the carbon negative electrode material at 500 cycles is 95% or more. In this figure, since the battery structure is unstable in the early stage, fluctuation occurs in the cycle retention rate, and the case where the cycle retention rate is more than 100% occurs in the early stage.

Example 2

(1) Mixing graphite tailing, nonmetallic carbide and polymeric additive in a groove type mixer for 180min to obtain a mixed material;

wherein, each raw material parameter is shown in table 1. The addition amount of the nonmetallic carbide is 9.7 percent of the total weight of the mixed materials, and the addition amount of the polymeric additive is 28.9 percent of the total weight of the mixed materials;

(2) Under the nitrogen atmosphere with the gas flow of 50L/min, carrying out polymerization reaction on the mixed material in the step (1) by using a tin-free Qingxin powder VC-1000L reaction kettle at the temperature of 800 ℃ and the stirring speed of 40r/min for 9h to obtain polymerized particles;

(3) Graphitizing the polymer particles in the step (2) by using an internal serial graphitizing furnace at 2800 ℃ in nitrogen atmosphere, wherein the temperature rise time of the graphitizing treatment is 12h, and the heat preservation time is 25 days, so as to obtain graphitized materials;

(3') crushing and shaping particles of the graphitized material obtained in the step (3) by using an airflow vortex micronizer, and sieving by using a 325-mesh screen to obtain a spheroidal material, wherein the average particle size D50 of the spheroidal material is 38.3 mu m;

(4) Coating the spherical-like material, namely the Shandong Weifang, in the step (3') in an LHS type fusion machine for 120min by using a nano conductive material, wherein the motor frequency of coating equipment is 800Hz, so as to obtain the carbon anode material;

The specific types of the nano conductive materials are shown in table 1. The addition amount of the nano conductive material is 10% of the total weight of the mixture material in the step (1).

Example 3

(1) Mixing graphite tailing, nonmetallic carbide and polymeric additive in a roller mixer for 60min to obtain a mixed material;

wherein, each raw material parameter is shown in table 1. The addition amount of the nonmetallic carbide is 2.5 percent of the total weight of the mixed materials, and the addition amount of the polymeric additive is 15.8 percent of the total weight of the mixed materials;

(2) Under the helium atmosphere with the gas flow of 25L/min, carrying out polymerization reaction on the mixed material in the step (1) by using a Hengaojia VC-2000L reaction kettle at the temperature of 450 ℃ and the stirring speed of 20r/min for 5h to obtain polymerized particles;

(3) Graphitizing the polymer particles in the step (2) by using an Acheson graphitizing furnace at a temperature of 3000 ℃ in neon atmosphere, wherein the temperature rise time of the graphitizing treatment is 36h, and the heat preservation time is 30 days, so as to obtain graphitized materials;

(3') crushing and shaping particles of the graphitized material obtained in the step (3) by using a super cyclone vortex mill, and sieving by using a 200-mesh screen to obtain a spheroidal material, wherein the average particle size D50 of the spheroidal material is 15.6 mu m;

(4) Coating the spherical-like material in the step (3') in a conical double-screw mixer by using a nano conductive material, wherein the coating time is 30min, and the motor frequency of coating equipment is 100Hz, so as to obtain the carbon anode material;

the specific types of the nano conductive materials are shown in table 1. The addition amount of the nano conductive material is 0.8% of the total weight of the mixture material in the step (1).

Example 4

(1) Mixing graphite tailing, nonmetallic carbide and polymeric additive in a conical double-screw mixer for 120min to obtain a mixed material;

wherein, each raw material parameter is shown in table 1. The addition amount of the nonmetallic carbide is 6.8 percent of the total weight of the mixed materials, and the addition amount of the polymeric additive is 24.7 percent of the total weight of the mixed materials;

(2) Under the neon atmosphere with the gas flow of 30L/min, polymerizing the mixed material in the step (1) at the temperature of 550 ℃ and the stirring speed of 30r/min by using a VC-2000L reaction kettle of the large-star of Buddha for 7h to obtain polymerized particles;

(3) Carrying out graphitization treatment on the polymer particles in the step (2) by using an inner string type graphitization furnace at the temperature of 3100 ℃ in neon atmosphere, wherein the temperature rise time of the graphitization treatment is 48 hours, and the heat preservation time is 15 days, so as to obtain graphitized materials;

(3') crushing and shaping particles of the graphitized material obtained in the step (3) by using a winnowing pulverizer, and sieving by using a 250-mesh screen to obtain a spheroidal material, wherein the average particle size D50 of the spheroidal material is 22.4 mu m;

(4) Coating the spherical-like material in the step (3') in a tin-free Qingxin powder ZSJ-600 mechanical fusion machine by using a nano conductive material for 50min, wherein the motor frequency of coating equipment is 600Hz, so as to obtain the carbon anode material;

the specific types of the nano conductive materials are shown in table 1. The addition amount of the nano conductive material is 1.5% of the total weight of the mixture material in the step (1).

Example 5

(1) Mixing graphite tailing, nonmetallic carbide and polymeric additive in a double cone mixer for 70min to obtain a mixed material;

wherein, each raw material parameter is shown in table 1. The addition amount of the nonmetallic carbide is 7.4 percent of the total weight of the mixed materials, and the addition amount of the polymeric additive is 21.5 percent of the total weight of the mixed materials;

(2) Under the helium atmosphere with the gas flow of 30L/min, carrying out polymerization reaction on the mixed material in the step (1) at the temperature of 750 ℃ and the stirring speed of 35r/min by using a mechanical VC-2000L reaction kettle of the bergamot for 8 hours to obtain polymerized particles;

(3) Graphitizing the polymer particles in the step (2) by using an Acheson graphitizing furnace at 3300 ℃ in helium atmosphere, wherein the temperature rise time of the graphitizing treatment is 48 hours, and the heat preservation time is 25 days, so as to obtain graphitized materials;

(3') crushing and shaping particles of the graphitized material obtained in the step (3) by using a double-roller crusher, and sieving by using a 270-mesh screen to obtain a spheroidal material, wherein the average particle size D50 of the spheroidal material is 35.0 mu m;

(4) Coating the spherical-like material in the step (3') by using a nano conductive material in a spray dryer, wherein a coating solvent is deionized water, the coating temperature is 50 ℃, and the coating time is 80 minutes, so as to obtain the carbon anode material;

the specific types of the nano conductive materials are shown in table 1. The addition amount of the nano conductive material is 3.9% of the total weight of the mixture material in the step (1).

Example 6

(1) Mixing graphite tailing, nonmetallic carbide and polymeric additive in a double cone mixer for 30min to obtain a mixed material;

wherein, each raw material parameter is shown in table 1. The addition amount of the nonmetallic carbide is 9.5 percent of the total weight of the mixed materials, and the addition amount of the polymeric additive is 15.4 percent of the total weight of the mixed materials;

(2) Under the neon atmosphere with the gas flow of 40L/min, carrying out polymerization reaction on the mixed material in the step (1) by using a tin-free Qingxin powder VC-1000L reaction kettle at the temperature of 250 ℃ and the stirring speed of 20r/min for 4 hours to obtain polymerized particles;

(3) Graphitizing the polymer particles in the step (2) at 3100 ℃ in helium atmosphere by using an internal serial graphitizing furnace, wherein the temperature rise time of the graphitizing is 60h, and the heat preservation time is 15 days, so as to obtain graphitized materials;

(3') crushing and shaping particles of the graphitized material obtained in the step (3) by using a super cyclone vortex mill, and sieving by using a 300-mesh screen to obtain a spheroidal material, wherein the average particle size D50 of the spheroidal material is 25.3 mu m;

(4) Coating the spherical-like material in the step (3') in a triple eccentric mixer by using a nano conductive material, wherein the coating time is 100min, and the motor frequency of coating equipment is 60Hz, so as to obtain the carbon anode material;

the specific types of the nano conductive materials are shown in table 1. The addition amount of the nano conductive material is 7.8% of the total weight of the mixture material in the step (1).

Example 7

(1) Mixing graphite tailing, nonmetallic carbide and polymeric additive in a groove type mixer for 60min to obtain a mixed material;

wherein, each raw material parameter is shown in table 1. The addition amount of the nonmetallic carbide is 4.5 percent of the total weight of the mixed materials, and the addition amount of the polymeric additive is 20.9 percent of the total weight of the mixed materials;

(2) Under the argon atmosphere with the gas flow of 45L/min, carrying out polymerization reaction on the mixed material in the step (1) by using a constant-Aujia VC-2000L reaction kettle at the temperature of 500 ℃ and the stirring speed of 35r/min for 6h to obtain polymerized particles;

(3) Graphitizing the polymer particles in the step (2) by using an internal serial graphitizing furnace at the temperature of 3100 ℃ in an argon atmosphere, wherein the temperature rise time of the graphitizing treatment is 72h, and the heat preservation time is 30 days, so as to obtain graphitized materials;

(3') crushing and shaping particles of the graphitized material obtained in the step (3) by using a turbine crusher, and sieving by using a 325-mesh screen to obtain a spheroidal material, wherein the average particle size D50 of the spheroidal material is 17.6 mu m;

(4) Coating the spherical-like material in the step (3') in a mechanical fusion machine of an AMS type of fine Sichuan Makrolon, wherein the coating time is 110min, and the motor frequency of coating equipment is 400Hz, so as to obtain the carbon anode material;

the specific types of the nano conductive materials are shown in table 1. The addition amount of the nano conductive material is 13.0% of the total weight of the mixture material in the step (1).

Example 8

wherein, each raw material parameter is shown in table 1. The addition amount of the nonmetallic carbide is 8.6 percent of the total weight of the mixed materials, and the addition amount of the polymeric additive is 8.0 percent of the total weight of the mixed materials;

(2) Carrying out polymerization reaction on the mixed material in the step (1) by using a VC-2000L reaction kettle with the flow rate of 30L/min under the nitrogen atmosphere at the temperature of 700 ℃ and the stirring speed of 25r/min for 8 hours to obtain polymerized particles;

(3) Graphitizing the polymer particles in the step (2) by using an Acheson graphitizing furnace at a temperature of 3000 ℃ in a nitrogen atmosphere, wherein the temperature rise time of the graphitizing treatment is 48 hours, and the heat preservation time is 20 days, so as to obtain graphitized materials;

(3') crushing and shaping particles of the graphitized material obtained in the step (3) by using a super cyclone vortex mill, and sieving by using a 250-mesh screen to obtain a spheroidal material, wherein the average particle size D50 of the spheroidal material is 32.3 mu m;

(4) Coating the spherical-like material in the step (3') by using a nano conductive material in a spray dryer, wherein a coating solvent is methanol, the coating temperature is 340 ℃, and the coating time is 90 minutes, so as to obtain the carbon anode material;

the specific types of the nano conductive materials are shown in table 1. The addition amount of the nano conductive material is 5.2% of the total weight of the mixture material in the step (1).

TABLE 1

Performance test method

The physical properties and electrochemical performance test methods of the carbon anode materials finally obtained in each example and comparative example of the present invention are as follows:

(1) Microscopic state:

the surface morphology of the carbon cathode material prepared by the embodiment of the invention is tested by adopting a KYKY-2800B scanning electron microscope of a Chinese department instrument.

(2) Particle size and particle size distribution dispersion:

the carbon negative electrode materials prepared in examples 1-7 of the present invention were tested to have an average particle size D50 of between 10.0 and 40.0 μm using a Malvern-Mastersizer 2000 laser particle size analyzer, UK. According to a calculation formula of the particle size distribution dispersion: particle size distribution dispersion= (D90-D10)/D50, resulting in carbon negative electrode materials prepared in examples 1-5 and examples 7 and 8 having a dispersion of 0.5-2.0.

(3) Sphericity degree:

the sphericity S50 of the carbon anode material prepared by each example of the invention is between 0.8 and 0.9 by using a German QICPIC granularity particle shape analyzer.

(4) Specific surface area:

the specific surface area of the carbon anode materials prepared in examples 1 to 6 of the present invention was measured to be 2.0 to 20.0m by the BET method using nitrogen adsorption, using a specific surface area/pore size analyzer of Kang Da Nova 1000e in U.S ² /g。

(5) Conductivity:

the conductivity of the carbon anode materials prepared in examples 1-6 and 8 of the present invention was measured to be 200S/cm or more by using a Mitsubishi chemical MCP-PD51 type four-probe conductivity tester in Japan.

(6) Simulation battery test:

A. the preparation method of the lithium ion simulation battery by using the carbon negative electrode material comprises the following steps:

(1) the carbon negative electrode material prepared by the method is used as a negative electrode active substance of a lithium ion battery, the carboxymethyl cellulose CMC is used as a thickener, the styrene butadiene rubber SBR is used as a binder, a conductive agent is not needed, and an electrode material is prepared, wherein the three materials are active substances according to the mass ratio: CMC: sbr=96.5:1.5:2. Adding proper deionized water, uniformly mixing into paste by a paste mixer, coating on the copper foil by a coating machine, coating the copper foil with the thickness of 200 mu m, drying, and punching into a pole piece with the diameter of 8.4 mm.

(2) The pure lithium sheet is used as a counter electrode, the pole piece is used as a working electrode, a Celgard 2400 PE/PP/PE composite diaphragm is adopted to assemble a die type (the diameter of a positive stainless steel gasket is 8.4mm, the diameter of a negative copper gasket is 11.4 mm) simulated battery in a Germany Braun glove box, and H is the same as the above ₂ O and O ₂ The bias voltage was below 1ppm. The electrolyte adopts 1M LiPF ₆ Solution of ec+dmc+emc.

B. The charge and discharge performance test of the simulated battery is carried out by using a Wuhan Jinnuo Land CT 2001A charge and discharge test cabinet and with sectional current density in the voltage range of 0.001-1.5V. The test method and data were calculated as follows:

first lithium intercalation specific capacity: charge to 0.005V at a current density of 0.1C, and then charge to a capacitance of 0.001V at a current density of 0.02C/mass of the anode active material;

first lithium removal specific capacity: the discharge was carried out at a current density of 0.1C to a capacity of 2.0V per mass of the negative electrode active material.

(7) Full cell test:

A. the preparation method of the lithium ion full battery by utilizing the carbon negative electrode material comprises the following steps:

(1) the carbon negative electrode material prepared by the method is used as a negative electrode active material of a lithium ion battery, a conductive agent is not needed, styrene butadiene rubber SBR is used as a binder, and carboxymethyl cellulose CMC is used as a thickener to prepare an electrode material; the three are active substances according to the mass ratio: CMC: sbr=96.5:1.5:2. Adding proper deionized water, uniformly mixing into paste by a paste mixer, coating on a copper foil by a coating machine, vacuum drying, and finally rolling to obtain the lithium ion full battery cathode.

(2) In ternary material LiNi _0.5 Co _0.2 Mn _0.3 O ₂ (abbreviated: NCM 523)Is a positive electrode material; in 1M LiPF ₆ Ec+dmc+emc as electrolyte; taking a Celgard 2400 PE/PP/PE composite membrane as a diaphragm; the full cell was assembled using the conventional 18650 type cell production process.

B. The charge and discharge test is carried out by using a Wuhan Jinnuo Land CT 2001A charge and discharge test cabinet at different current densities within the voltage range of 3.0-4.2V. The performance evaluation and test method is as follows:

pole piece compaction density evaluation: and carrying out rolling treatment with different pressures on the pole pieces after size mixing, coating and drying until the corresponding pole piece compaction density appears when the edge of the pole piece shines.

Evaluation of battery cycle performance: the full cell was charged with constant current at a current density of 1C, and then discharged with constant current at a current density of 1C, and the capacity retention rate at 500 weeks of cycling was calculated: the ratio of the 500 th-week discharge capacity to the 1 st-week discharge capacity of the battery is shown. The larger this ratio, the higher the cell cycle capacity retention, the better the cycle performance, and the better the electrochemical performance of the carbon negative electrode material.

TABLE 2

In summary, the above examples show that, since the polymerization temperature of the carbon negative electrode material obtained in example 6 is too low, the polymerization additive does not fully exert the polymerization effect in the polymerization kettle, so that the "tailing" and the nonmetallic carbide cannot be well adhered, and the dispersion phenomenon of the composite particles occurs, which finally affects the stability of the carbon negative electrode material in the lithium ion battery, and the cycle performance is poor.

The carbon negative electrode material obtained in example 7 has too much coating amount of the nano conductive material, a large amount of micro powder particles are accumulated on the surfaces of the particles, the specific surface area is larger, the point contact between the particles is too much, the contact resistance is increased, the electron transmission is not facilitated, the powder conductivity is reduced, and the internal resistance, the polarization and the multiplying power performance of the lithium ion battery under high current are not facilitated.

The carbon negative electrode material obtained in example 8, because the amount of the polymerization additive is small, part of the small particle "tailing" in the polymerization process cannot be polymerized into the polymerization additive well, even the particles still exist as independent particles, so that the particles of the final carbon negative electrode material are small, the specific surface area is large, the compatibility with electrolyte in the lithium ion battery is poor, and the cycle performance of the battery is seriously affected.

The carbon anode materials obtained in examples 1 to 5 have good conductivity, energy density and electrochemical properties: conductivity is more than or equal to 200S/cm; the specific capacity of the first lithium removal is more than or equal to 355mAh/g; the compacted density of the pole piece is more than or equal to 1.6g/cc; the retention rate of the circulation capacity of 500 weeks is more than or equal to 95 percent. Therefore, the carbon negative electrode material for the lithium ion battery has the advantages of being stable in structure, good in orientation, good in conductivity, high in specific capacity, high in compaction density, excellent in cycle performance and the like, and can meet the high energy density requirement in the application of the lithium ion battery.

The applicant states that the detailed features and detailed methods of the present invention are described by way of the above examples, but the present invention is not limited to the detailed features and detailed methods described above, i.e., it is not meant that the present invention must rely on the detailed features and detailed methods to practice the present invention. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of selected components, addition of auxiliary components, selection of specific modes, etc. fall within the scope of the invention and the scope of the disclosure.

Claims

1. The carbon negative electrode material is characterized by comprising composite particles composed of a frame carrier and small particles positioned in the frame carrier, and nano particles adhered to the surfaces of the composite particles, wherein the frame carrier and the small particles are both graphite materials, the nano particles are carbon materials, and the small particles are from graphite tailings;

the preparation method of the carbon anode material comprises the following steps:

(2) Carrying out polymerization reaction on the mixed material in the step (1) at the temperature of 300-800 ℃ and the stirring speed of 10-40 r/min under the protective atmosphere with the gas flow of 20-50L/min for 3-9h to obtain polymerized particles;

2. The carbon negative electrode material according to claim 1, wherein the small particles have an average particle size D50 of 1-10 μm.

3. The carbon negative electrode material of claim 1, wherein the nanoparticle has an average particle size D50 of 1-1000 nm.

4. The carbon negative electrode material according to claim 1, wherein the average particle size D50 of the carbon negative electrode material is 10.0-40.0 μm.

5. The carbon negative electrode material according to claim 1, wherein the carbon negative electrode material has a particle size distribution dispersion of 0.5 to 2.0.

6. The carbon negative electrode material according to claim 1, wherein the sphericity S50 of the carbon negative electrode material is 0.8-0.9.

7. The carbon negative electrode material according to claim 1, wherein the specific surface area of the carbon negative electrode material is 2.0 to 20.0 m ² /g。

8. The carbon negative electrode material of claim 1, wherein the graphite tailing of step (1) comprises any one or a combination of at least two of green coke, mature coke, carbon microspheres, crystalline graphite, aphanitic graphite, or spherical graphite micropowder.

9. The carbon negative electrode material of claim 8, wherein the green coke is any one or a combination of at least two of petroleum coke, pitch coke, or coal coke.

10. The carbon negative electrode material of claim 8, wherein the cooked coke is any one or a combination of at least two of petroleum coke, pitch coke, or coal coke.

11. The carbon negative electrode material according to claim 8, wherein the carbon microspheres comprise petroleum pitch-based carbon microspheres and/or coal pitch-based carbon microspheres.

12. The carbon negative electrode material of claim 8, wherein the raw coke, the cooked coke, or the carbon microsphere each have a volatile of 1-20%.

13. The carbon negative electrode material of claim 8, wherein the raw coke, the cooked coke, or the carbon microsphere each have an ash content of 0.5% or less.

14. The carbon negative electrode material according to claim 8, wherein the carbon content of the crystalline graphite, the aphanitic graphite, or the spherical graphite fine powder is 90 to 99.9%.

15. The carbon negative electrode material of claim 1, wherein the average particle size D50 of the graphite tail of step (1) is 1-10 μιη.

16. The carbon negative electrode material of claim 1, wherein the graphite tailstock of step (1) has a specific surface area of 5-15 m ² /g。

17. The carbon negative electrode material according to claim 1, wherein the nonmetallic carbide of step (1) is silicon carbide and/or boron carbide.

18. The carbon negative electrode material according to claim 1, wherein the average particle size D50 of the nonmetallic carbide of step (1) is 5-60 μm.

19. The carbon negative electrode material according to claim 1, wherein the specific surface area of the nonmetallic carbide of step (1) is 0.5 to 5 m ² /g。

20. The carbon negative electrode material according to claim 1, wherein the purity of the nonmetallic carbide of step (1) is 98-99.5%.

21. The carbon negative electrode material of claim 1 wherein the polymeric additive of step (1) comprises any one or a combination of at least two of pitch, resin, polymeric material, or polymer.

22. The carbon negative electrode material of claim 21, wherein the pitch comprises any one or a combination of at least two of coal pitch, petroleum pitch, natural pitch, or mesophase pitch.

23. The carbon negative electrode material of claim 1, wherein the mixer of step (1) comprises any one or a combination of at least two of a V-type mixer, a slot-type mixer, a drum mixer, a conical twin screw mixer, or a double conical mixer.

24. The carbon negative electrode material according to claim 1, wherein the polymerization reaction of step (2) is performed in a polymerization vessel.

25. The carbon negative electrode material of claim 1 wherein the protective atmosphere of step (2) comprises any one or a combination of at least two of helium, neon, argon, or nitrogen.

26. The carbon negative electrode material of claim 1 wherein the protective atmosphere of step (3) comprises any one or a combination of at least two of helium, neon, argon, or nitrogen.

27. The carbon negative electrode material of claim 1, wherein the means for crushing and particle shaping comprises any one or a combination of at least two of a turbine mill, an air-flow vortex mill, a super-cyclone mill, a winnowing mill, or a double-stick mill.

28. The carbon negative electrode material according to claim 1, wherein the nano-conductive material of step (4) comprises acetylene black and/or ketjen black.

29. The carbon negative electrode material of claim 1, wherein the mixer of step (4) comprises any one of a V-type mixer, a slot-type mixer, a drum mixer, a conical twin screw mixer, a double conical mixer, or a triple eccentric mixer.

30. The carbon negative electrode material according to claim 1, wherein when the coating apparatus is a spray dryer, the solvent used for the coating treatment includes any one or a combination of at least two of water, methanol, methylene chloride, n-heptane, toluene, n-hexane, pentane, gasoline, benzene, styrene, butyltoluene, vinyl toluene, trichloroethylene, carbon disulfide, or tri-o-cresol phosphate.

31. A lithium ion battery comprising the carbon negative electrode material of any one of claims 1-30.