CN112320792A - Preparation method of negative electrode material for lithium ion battery and product thereof - Google Patents
Preparation method of negative electrode material for lithium ion battery and product thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a negative electrode material for a lithium ion battery and a product thereof. Dissolving copper salt, nickel salt, graphene oxide, polyvinylpyrrolidone and 2-methylimidazole in a solvent, and magnetically stirring; then carrying out solvothermal reaction, filtering, washing, vacuum drying, then carrying out pyrolysis, then adding into ethylene glycol solution of thioacetamide, then calcining under inert atmosphere, washing, drying the product, growing a metal organic framework on the surface of graphene by a solvothermal method, generating a porous carbon material on the surface of the graphene after calcining, and then calcining in the presence of an organic sulfur source to obtain the doped composite material.
Description
Technical Field
The invention relates to the field of lithium batteries, in particular to a preparation method of a negative electrode material for a lithium ion battery and a product thereof.
Background
As a novel chemical power supply, the lithium ion battery is widely applied due to the characteristics of high energy density, long cycle life, environment friendliness and the like, at present, graphite is used as a negative electrode material of practical application, the theoretical capacity is low, and the requirement of a novel electronic device on high capacity cannot be met, so that the research of the novel lithium ion battery with higher specific capacity and strong stability has great significance for large-scale production and application.
Graphene is a polymer made of carbon atoms in sp2Two-dimensional nano material composed of hybrid tracks has high conductivity (103-104 S.m)-1) Large specific surface area (about 2630 m)2·g-1) However, when a single graphene material is used as a negative electrode material of a lithium ion battery, the graphene material is easy to agglomerate, so that the advantage of high lithium storage efficiency due to high specific area is lost, and more research results show that the graphene-based composite material shows more excellent electrochemical performance than a single component material when used as the negative electrode material of the lithium ion battery.
Zhao et al prepared CoS nanoflowers encapsulated in reduced graphene oxide (rGO) by a self-assembly method, and the CoS @ rGO electrode provided a high reversible capacity of 620mA · h/g at a current density of 100 mA/g. rGO flakes greatly improved the kinetics of CoS by avoiding pulverization of the nanoparticles and maintaining the integrity of the electrode.
WU topic group uses in-situ etching method to etch Fe2O3The nano particles are successfully fixed on the surface of the graphene to prepare the gamma-Fe2O3The @ H-rGO composite material shows high reversible capacity and good rate capability when being used as a lithium ion battery cathode material.
The SONG topic group utilizes an improved hydrothermal method to design a graphene-doped self-assembled WS2Nanocellular (WS)2/rGONano-HC) composite negative electrode material, in the mixed structure, the nano honeycomb plane supported by the graphene has larger specific surface area and higher conductivity than the nano wire microporous ball, and when the material is used as the negative electrode material of the lithium ion battery, the specific surface area is 0.1 A.g-1The charging specific capacity can reach 953.1mAh g under the current density-1At a current density of 0.1 A.g-1At times, there may be a cycle life of 350 cycles.
Although the above results have been achieved by compounding with graphene, the above results still do not satisfy the requirement of high capacity of the actual novel electronic device, and the above research has not studied the stability in the large current charge-discharge cycle, so how to improve the high reversible capacity, rate capability and long-term stability under the large current charge-discharge condition is still a problem to be solved.
Disclosure of Invention
The present invention aims to solve the above-mentioned problems in the prior art, and provides a method for preparing a negative electrode material for a lithium ion battery and a product thereof. Dissolving copper salt, nickel salt, graphene oxide, polyvinylpyrrolidone and 2-methylimidazole in a solvent, and magnetically stirring; then transferring the mixed solution into a polytetrafluoroethylene stainless steel reaction kettle for solvothermal reaction; the preparation method comprises the steps of filtering, washing and vacuum drying, pyrolyzing an obtained product in an inert atmosphere, adding the pyrolyzed product into a glycol solution of thioacetamide, ultrasonically stirring, transferring the pyrolyzed product into a quartz boat, calcining in the inert atmosphere, washing and drying the product, growing a metal organic framework on the surface of graphene by a solvothermal method, calcining, generating a porous carbon material on the surface of the graphene, calcining in the presence of an organic sulfur source to obtain a doped composite material, and improving the electron transfer between the porous carbon and the graphene by the synergistic cooperation of the components of the negative electrode material prepared by the method, so that the conductivity of an electrode is improved, and the negative electrode material presents high reversible capacity, excellent rate performance and long-term stability and is an ideal material for the negative electrode material for a lithium ion battery.
The invention adopts the following technical scheme:
a preparation method of a negative electrode material for a lithium ion battery comprises the following steps:
(1) dissolving copper salt, nickel salt, graphene oxide, polyvinylpyrrolidone and 2-methylimidazole in a solvent, and magnetically stirring;
(2) then transferring the mixed solution into a polytetrafluoroethylene stainless steel reaction kettle for solvothermal reaction;
(3) then filtering, washing and vacuum drying, and pyrolyzing the obtained product for 4-6 hours at the temperature of 750-850 ℃ in an inert atmosphere to obtain a product A;
(4) and then adding the product A into 20-30 mL of ethylene glycol solution of thioacetamide, ultrasonically stirring, transferring into a quartz boat, calcining for 1-3 h at 280-320 ℃ in an inert atmosphere, centrifugally washing the obtained black powder for multiple times by using deionized water and absolute ethyl alcohol, and drying in a vacuum drying oven to obtain the product.
Preferably, in the step (1), the copper salt is one or more of copper nitrate, copper acetate and copper chloride; the nickel salt is one or more of nickel nitrate, nickel acetate and nickel chloride; the solvent is one or more of N, N-dimethylformamide, ethanol and glycol;
preferably, in the step (1), the rotation speed of the magnetic stirring is 300-400 rpm, and the stirring time is 2-4 h.
Preferably, in the step (1), the ratio of the copper salt, the nickel salt, the graphene oxide, the polyvinylpyrrolidone, the 2-methylimidazole and the solvent is 1-2 mmol: 1-2 mmol: 0.4-0.8 g: 15-17 mmol; 0.4-0.8 g, 6-12 mL.
Preferably, in the step (2), the solvothermal condition is 150-200 ℃ for 10-20 h.
Preferably, in the step (3), the vacuum drying temperature is 100-140 ℃, and the drying time is 10-14 h; the inert atmosphere is one of nitrogen, helium and argon.
Preferably, in the step (4), the concentration of the ethylene glycol solution of thioacetamide is 0.5 mol/L; the inert atmosphere is one of nitrogen, helium and argon.
Preferably, in the step (4), the temperature rise rate of the calcination is 3-5 ℃/min; the drying is carried out at 60-100 ℃ for 10-14 h.
The invention provides a negative electrode material prepared based on the preparation method, wherein the negative electrode material is prepared by loading porous carbon containing Cu and Ni on the surface of graphene, and the graphene and the porous carbon are both N, S codoped.
The preparation method of the cathode material for the lithium ion battery and the product thereof have the following technical effects:
(1) graphene oxide is reduced into graphene by a solvothermal method, and other reducing reagents do not need to be added, so that the cost is saved.
(2) Because the surface of the graphene oxide contains active groups, metal ions are adsorbed on the surface of the graphene oxide through the adsorption of the active groups, an MOF material is formed on the surface of the graphene oxide under the solvothermal reaction, the porous carbon is formed through pyrolysis, the electron transmission between the graphene and the porous carbon is improved in the mode, and in the presence of Cu and Ni, the electron transmission between the graphene and the porous carbon is further promoted due to the synergistic effect of copper and nickel, the stability of the electrode is improved, and therefore the composite electrode material is improved in high reversible capacity, rate capability and long-term stability.
(3) N, S doping is carried out on thioacetamide, so that the graphene and the porous carbon are both N, S codoped, and N atoms are doped to improve the conductivity of the composite material. The S doping is beneficial to further enlarging the interlayer distance and forming a more active site, and an electron transfer channel is more unobstructed due to the doping, so that the volume change can be buffered, the charge transfer resistance can be reduced, the conductivity can be improved, and the electrochemical performance can be improved.
(4) The preparation method is simple and easy to control, and the prepared product has excellent performance and is beneficial to industrial production.
In conclusion, the negative electrode material for the lithium ion battery prepared by the invention has high reversible capacity, rate capability and long-term stability, and is an ideal material for the negative electrode material of the lithium ion battery.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. The components of the embodiments of the present invention generally shown may be arranged and designed in a wide variety of different configurations. Thus, the following detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of a negative electrode material for a lithium ion battery comprises the following steps:
(1) dissolving 1.5mmol of copper nitrate, 1.5mmol of nickel nitrate, 0.6g of graphene oxide, 16mmol of polyvinylpyrrolidone and 0.6g of 2-methylimidazole in 9mL of ethylene glycol, and carrying out magnetic stirring; wherein the rotating speed of magnetic stirring is 350rpm, and the stirring time is 3 h;
(2) then transferring the mixed solution into a polytetrafluoroethylene stainless steel reaction kettle to react for 16h at 180 ℃;
(3) then carrying out centrifugal filtration, washing for 3 times by deionized water, carrying out vacuum drying for 12h at 120 ℃, and carrying out pyrolysis on the obtained product for 5h at 800 ℃ in helium atmosphere to obtain a product A;
(4) then adding the product A into 25mL0.5mol/L glycol solution of thioacetamide, ultrasonically stirring, then transferring into a quartz boat, calcining for 2h at 300 ℃ under helium atmosphere, wherein the heating rate is 4 ℃/min. The obtained black powder is centrifugally washed 3 times by deionized water and absolute ethyl alcohol, and then dried for 12 hours in a vacuum drying oven at the temperature of 80 ℃ to obtain the product.
Example 2
A preparation method of a negative electrode material for a lithium ion battery comprises the following steps:
(1) dissolving 2mmol of copper acetate, 1mmol of nickel acetate, 0.8g of graphene oxide, 17mmol of polyvinylpyrrolidone and 0.8g of 2-methylimidazole in 12mL of ethanol, and carrying out magnetic stirring; the rotating speed of the magnetic stirring is 400rpm, and the stirring time is 2 hours;
(2) then transferring the mixed solution into a polytetrafluoroethylene stainless steel reaction kettle to react for 10 hours at 200 ℃;
(3) then carrying out centrifugal filtration, washing for 3 times by deionized water, carrying out vacuum drying for 10h at 140 ℃, and carrying out pyrolysis on the obtained product for 4h at 850 ℃ in an argon atmosphere to obtain a product A;
(4) then adding the product A into 30mL0.5mol/L glycol solution of thioacetamide, ultrasonically stirring, then transferring into a quartz boat, calcining for 1h at the temperature of 320 ℃ in argon atmosphere, and the heating rate is 5 ℃/min. The obtained black powder is centrifugally washed for 3 times by deionized water and absolute ethyl alcohol, and then dried 10 times in a vacuum drying oven at 100 ℃ to obtain the product.
Example 3
A preparation method of a negative electrode material for a lithium ion battery comprises the following steps:
(1) dissolving 1mmol of copper chloride, 2mmol of nickel chloride, 0.4g of graphene oxide, 15mmol of polyvinylpyrrolidone and 0.4g of 2-methylimidazole in 6mLN, N-dimethylformamide, and carrying out magnetic stirring; the rotating speed of the magnetic stirring is 300rpm, and the stirring time is 4 hours;
(2) then transferring the mixed solution into a polytetrafluoroethylene stainless steel reaction kettle to react for 20 hours at 150 ℃;
(3) then carrying out centrifugal filtration, washing for 3 times by deionized water, carrying out vacuum drying for 14h at 100 ℃, and carrying out pyrolysis on the obtained product for 6h at 750 ℃ in a nitrogen atmosphere to obtain a product A;
(4) then adding the product A into 20mL0.5mol/L ethylene glycol solution of thioacetamide, ultrasonically stirring, then transferring into a quartz boat, calcining for 3h at 280 ℃ in nitrogen atmosphere, and raising the temperature at 3 ℃/min. The obtained black powder is centrifugally washed for 3 times by deionized water and absolute ethyl alcohol, and then dried for 14 hours in a vacuum drying oven at 60 ℃ to obtain the product.
Comparative example 1
A preparation method of a negative electrode material for a lithium ion battery comprises the following steps:
(1) dissolving 3mmol of copper nitrate, 0.6g of graphene oxide, 16mmol of polyvinylpyrrolidone and 0.6g of 2-methylimidazole in 9mL of ethylene glycol, and carrying out magnetic stirring; wherein the rotating speed of magnetic stirring is 350rpm, and the stirring time is 3 h;
(2) then transferring the mixed solution into a polytetrafluoroethylene stainless steel reaction kettle to react for 16h at 180 ℃;
(3) then carrying out centrifugal filtration, washing for 3 times by deionized water, carrying out vacuum drying for 12h at 120 ℃, and carrying out pyrolysis on the obtained product for 5h at 800 ℃ in helium atmosphere to obtain a product A;
(4) then adding the product A into 25mL0.5mol/L glycol solution of thioacetamide, ultrasonically stirring, then transferring into a quartz boat, calcining for 2h at 300 ℃ under helium atmosphere, wherein the heating rate is 4 ℃/min. The obtained black powder is centrifugally washed 3 times by deionized water and absolute ethyl alcohol, and then dried for 12 hours in a vacuum drying oven at the temperature of 80 ℃ to obtain the product.
Comparative example 2
A preparation method of a negative electrode material for a lithium ion battery comprises the following steps:
(1) dissolving 3mmol of nickel nitrate, 0.6g of graphene oxide, 16mmol of polyvinylpyrrolidone and 0.6g of 2-methylimidazole in 9mL of ethylene glycol, and carrying out magnetic stirring; wherein the rotating speed of magnetic stirring is 350rpm, and the stirring time is 3 h;
(2) then transferring the mixed solution into a polytetrafluoroethylene stainless steel reaction kettle to react for 16h at 180 ℃;
(3) then carrying out centrifugal filtration, washing for 3 times by deionized water, carrying out vacuum drying for 12h at 120 ℃, and carrying out pyrolysis on the obtained product for 5h at 800 ℃ in helium atmosphere to obtain a product A;
(4) then adding the product A into 25mL0.5mol/L glycol solution of thioacetamide, ultrasonically stirring, then transferring into a quartz boat, calcining for 2h at 300 ℃ under helium atmosphere, wherein the heating rate is 4 ℃/min. The obtained black powder is centrifugally washed 3 times by deionized water and absolute ethyl alcohol, and then dried for 12 hours in a vacuum drying oven at the temperature of 80 ℃ to obtain the product.
Comparative example 3
A preparation method of a negative electrode material for a lithium ion battery comprises the following steps:
(1) 1.5mmol of copper nitrate, 1.5mmol of nickel nitrate, 16mmol of polyvinylpyrrolidone and 0.6g of 2-methylimidazole are dissolved in 9mL of ethylene glycol and magnetically stirred; wherein the rotating speed of magnetic stirring is 350rpm, and the stirring time is 3 h;
(2) then transferring the mixed solution into a polytetrafluoroethylene stainless steel reaction kettle to react for 16h at 180 ℃;
(3) then carrying out centrifugal filtration, washing for 3 times by deionized water, carrying out vacuum drying for 12h at 120 ℃, and carrying out pyrolysis on the obtained product for 5h at 800 ℃ in helium atmosphere to obtain a product A;
(4) then adding the product A into 25mL0.5mol/L glycol solution of thioacetamide, ultrasonically stirring, then transferring into a quartz boat, calcining for 2h at 300 ℃ under helium atmosphere, wherein the heating rate is 4 ℃/min. The obtained black powder is centrifugally washed 3 times by deionized water and absolute ethyl alcohol, and then dried for 12 hours in a vacuum drying oven at the temperature of 80 ℃ to obtain the product.
Comparative example 4
A preparation method of a negative electrode material for a lithium ion battery comprises the following steps:
(1) dissolving 0.6g of graphene oxide in 9mL of ethylene glycol, and carrying out magnetic stirring; wherein the rotating speed of magnetic stirring is 350rpm, and the stirring time is 3 h;
(2) then transferring the mixed solution into a polytetrafluoroethylene stainless steel reaction kettle to react for 16h at 180 ℃;
(3) then centrifugally filtering, washing for 3 times by deionized water, and drying for 12 hours in vacuum at 120 ℃ to obtain a product A;
(4) then adding the product A into 25mL0.5mol/L glycol solution of thioacetamide, ultrasonically stirring, then transferring into a quartz boat, calcining for 2h at 300 ℃ under helium atmosphere, wherein the heating rate is 4 ℃/min. The obtained black powder is centrifugally washed 3 times by deionized water and absolute ethyl alcohol, and then dried for 12 hours in a vacuum drying oven at the temperature of 80 ℃ to obtain the product.
Comparative example 5
A preparation method of a negative electrode material for a lithium ion battery comprises the following steps:
(1) dissolving 1.5mmol of copper nitrate, 1.5mmol of nickel nitrate, 0.6g of graphene oxide, 16mmol of polyvinylpyrrolidone and 0.6g of 2-methylimidazole in 9mL of ethylene glycol, and carrying out magnetic stirring; wherein the rotating speed of magnetic stirring is 350rpm, and the stirring time is 3 h;
(2) then transferring the mixed solution into a polytetrafluoroethylene stainless steel reaction kettle to react for 16h at 180 ℃;
(3) then carrying out centrifugal filtration, washing for 3 times by deionized water, carrying out vacuum drying for 12h at 120 ℃, and carrying out pyrolysis on the obtained product for 5h at 800 ℃ in helium atmosphere to obtain the product.
Comparative example 6
A preparation method of a negative electrode material for a lithium ion battery comprises the following steps:
(1) 1.5mmol of copper nitrate, 1.5mmol of nickel nitrate, 0.6g of graphene oxide and 0.6g of 2-methylimidazole are dissolved in 9mL of ethylene glycol and magnetically stirred; wherein the rotating speed of magnetic stirring is 350rpm, and the stirring time is 3 h;
(2) then transferring the mixed solution into a polytetrafluoroethylene stainless steel reaction kettle to react for 16h at 180 ℃;
(3) then carrying out centrifugal filtration, washing for 3 times by deionized water, carrying out vacuum drying for 12h at 120 ℃, and carrying out pyrolysis on the obtained product for 5h at 800 ℃ in helium atmosphere to obtain a product A;
(4) then adding the product A into 25mL0.5mol/L glycol solution of thioacetamide, ultrasonically stirring, then transferring into a quartz boat, calcining for 2h at 300 ℃ under helium atmosphere, wherein the heating rate is 4 ℃/min. The obtained black powder is centrifugally washed 3 times by deionized water and absolute ethyl alcohol, and then dried for 12 hours in a vacuum drying oven at the temperature of 80 ℃ to obtain the product.
The materials of examples 1-3 and comparative examples 1-6 are used as the negative electrode material of the lithium ion battery and are tested by the test method in CN 111106322A. Specifically, a synthetic negative electrode material is used as an active component, a 2016 type battery shell, a metal lithium sheet (phi 16mm multiplied by 1mm) and 1.0MLiPF are selected6The mixed solution of Ethylene Carbonate (EC) and diethyl carbonate (DEC) (volume ratio of 1:1) is used as electrolyte, and Celgard2300 microporous polypropylene coal membrane is used as battery diaphragm. The materials are assembled into a button cell in a glove box filled with Ar gas, and the test is carried out after the working electrode is fully soaked by the electrolyte. The method comprises the following five steps:
(1) size mixing
The material used has a large specific surface and is easy to adsorb moisture in the air, so the material for preparing the electrode is firstly dried fully in a vacuum drying oven at 120 ℃ to remove the surface moisture. Then adding the active substance, the conductive additive (acetylene black) and the binder (PVDF) into a dispersant N-methyl pyrrolidone (NMP) according to the mass ratio of 80:10:10, mixing and grinding to uniformly mix the materials, and preparing viscous slurry.
(2) Coating film
The resulting viscous paste was uniformly coated on a copper foil (thickness about 100 μm). The specific operation is as follows: 1) the copper foil of moderate size is cut and laid flat on a table top. 2) Removing stains on the surface of the copper foil. 3) The slurry was dispersed on a copper foil and uniformly spread on the copper foil using a die. 4) The copper foil coated with the slurry was dried in a vacuum drying oven at 120 ℃ for 12 hours.
(3) Roller compaction
After the completion of drying, the copper foil coated with the slurry was rolled with a small-sized rolling machine to prevent the electrode material from falling off from the surface of the copper foil.
(4) Tabletting
And cutting the rolled film into a plurality of circular electrode slices with the diameter of 12mm by using a manual slicer. In order to prevent the coating film from falling off during charge and discharge cycles, it was pressed into a sheet by an oil press. And taking out and weighing after drying, and waiting for battery loading.
(5) Assembled battery
The process of assembling the button cells was carried out in a glove box filled with Ar gas. The battery is assembled according to the sequence of negative battery shell/electrolyte/working electrode plate/electrolyte/diaphragm/lithium plate/positive battery shell. And standing for 24 hours, and carrying out electrochemical test after the electrolyte is fully soaked.
Assembled button-type simulated battery at 0.5A.g-1The charge and discharge test was performed at the current density of (1). The first charge and discharge capacity and the discharge capacity after 500 charge and discharge tests of examples 1 to 3 and comparative examples 1 to 6 are shown in Table 1.
TABLE 1
| First reversible capacity/mAh.g-1 | Reversible capacity/mAh.g after 500 times of charge and discharge-1 | |
| Example 1 | 1484.3 | 1313.4 |
| Example 2 | 1432.4 | 1243.5 |
| Example 3 | 1454.3 | 1267.3 |
| Comparative example 1 | 1332.4 | 1078.4 |
| Comparative example 2 | 1325.5 | 1069.4 |
| Comparative example 3 | 905.3 | 687.5 |
| Comparative example 4 | 895.3 | 682.1 |
| Comparative example 5 | 1103.4 | 859.3 |
| Comparative example 6 | 1389.3 | 1189.6 |
As can be seen from table 1, the copper and the nickel have a synergistic effect, and the graphene and the porous carbon also have a synergistic effect, so that the reversible capacity, the rate capability and the long-term stability are remarkably improved through the synergistic effect, and the cathode material is an ideal material for a cathode material of a lithium ion battery.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (9)
1. A preparation method of a negative electrode material for a lithium ion battery is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) dissolving copper salt, nickel salt, graphene oxide, polyvinylpyrrolidone and 2-methylimidazole in a solvent, and performing magnetic stirring to obtain a mixed solution;
(2) then transferring the mixed solution into a polytetrafluoroethylene stainless steel reaction kettle for solvothermal reaction;
(3) then filtering, washing and vacuum drying, and pyrolyzing the obtained product for 4-6 hours at the temperature of 750-850 ℃ in an inert atmosphere to obtain a product A;
(4) and then adding the product A into 20-30 mL of ethylene glycol solution of thioacetamide, ultrasonically stirring, transferring into a quartz boat, calcining for 1-3 h at 280-320 ℃ in an inert atmosphere, centrifugally washing the obtained black powder for multiple times by using deionized water and absolute ethyl alcohol, and drying in a vacuum drying oven to obtain the product.
2. The method for preparing the negative electrode material for the lithium ion battery according to claim 1, wherein the method comprises the following steps: in the step (1), the copper salt is one or more of copper nitrate, copper acetate and copper chloride; the nickel salt is one or more of nickel nitrate, nickel acetate and nickel chloride; the solvent is one or more of N, N-dimethylformamide, ethanol and glycol.
3. The method for preparing the negative electrode material for the lithium ion battery according to claim 1, wherein the method comprises the following steps: in the step (1), the rotation speed of the magnetic stirring is 300-400 rpm, and the stirring time is 2-4 h.
4. The method for preparing the negative electrode material for the lithium ion battery according to claim 1, wherein the method comprises the following steps: in the step (1), the ratio of the copper salt, the nickel salt, the graphene oxide, the polyvinylpyrrolidone, the 2-methylimidazole and the solvent is 1-2 mmol: 1-2 mmol: 0.4-0.8 g: 15-17 mmol; 0.4-0.8 g, 6-12 mL.
5. The method for preparing the negative electrode material for the lithium ion battery according to claim 1, wherein the method comprises the following steps: in the step (2), the solvothermal condition is 150-200 ℃ for reaction for 10-20 h.
6. The method for preparing the negative electrode material for the lithium ion battery according to claim 1, wherein the method comprises the following steps: in the step (3), the temperature of the vacuum drying is 100-140 ℃, and the drying time is 10-14 h; the inert atmosphere is one of nitrogen, helium and argon.
7. The method for preparing the negative electrode material for the lithium ion battery according to claim 1, wherein the method comprises the following steps: in the step (4), the concentration of the ethylene glycol solution of thioacetamide is 0.5 mol/L; the inert atmosphere is one of nitrogen, helium and argon.
8. The method for preparing the negative electrode material for the lithium ion battery according to claim 1, wherein the method comprises the following steps: in the step (4), the temperature rise rate of the calcination is 3-5 ℃/min; the drying is carried out at 60-100 ℃ for 10-14 h.
9. The negative electrode material prepared by the method for preparing a negative electrode material for a lithium ion battery according to any one of claims 1 to 8, wherein: the negative electrode material is prepared by loading porous carbon containing Cu and Ni on the surface of graphene, and the graphene and the porous carbon are both N, S codoped.
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