CN117393742A - Lithium ion battery negative electrode graphite-based material and preparation method thereof - Google Patents

Lithium ion battery negative electrode graphite-based material and preparation method thereof Download PDF

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CN117393742A
CN117393742A CN202311700351.9A CN202311700351A CN117393742A CN 117393742 A CN117393742 A CN 117393742A CN 202311700351 A CN202311700351 A CN 202311700351A CN 117393742 A CN117393742 A CN 117393742A
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nano silicon
graphene oxide
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CN117393742B (en
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郭藩
裴德成
姜正海
郭华德
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Qingdao Taida Tianrun Carbon Material Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention provides a graphite-based material for a lithium ion battery cathode and a preparation method thereof, and belongs to the technical field of lithium ion batteries. Preparation of bath flower-shaped graphene oxide coated nano silicon by spray drying and surface deposition of SnO 2 And the lithium ion battery cathode graphite-based material is prepared by modification of fullerol and reduction of hydrazine hydrate. The negative electrode graphite-based material of the lithium ion battery prepared by the invention effectively solves the problems of poor multiplying power performance, low cycle efficiency and the like of a graphene material batteryThe problem of poor cycling stability caused by serious volume effect of Si material in the charging and discharging process is avoided, the reversible capacity of the battery is greatly improved, the specific capacity retention rate after a plurality of times of cycling is greatly improved, the discharging voltage is reduced, the production method is simple, no harsh condition is available, the industrialization is easy, the cost is low, and the application prospect is wide.

Description

Lithium ion battery negative electrode graphite-based material and preparation method thereof
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a graphite-based material for a negative electrode of a lithium ion battery and a preparation method thereof.
Background
The lithium ion battery is a clean renewable resource, and has the advantages of environmental friendliness, high energy density, long cycle life and the like compared with the traditional lead-acid, nickel-hydrogen and nickel-cadmium batteries. With the development of power automobiles, the energy density of lithium ion batteries is also increasingly required. The national ministry of industrial and information requires that the energy density of the lithium ion battery in China reaches 300wH/kg in 2020. While the traditional graphite material is difficult to realize when used as the negative electrode material of the lithium ion battery, the theoretical capacity of the graphite negative electrode material is only 372mAh/g, meanwhile, the density of the graphite negative electrode is low, and the theoretical volume specific capacity of the graphite negative electrode material is only 800mAh/cm 3 This limits the development of lithium ion batteries in terms of high mass specific capacity and high volume specific capacity.
Non-carbon materials such as silicon, metal oxides (e.g. SnO 2 、Fe 2 O 3 Etc.) as a negative electrode of a lithium ion battery, has a high mass specific capacity and a high density, and thus has a high volumetric specific capacity. Wherein SnO 2 Specific capacity is as high as 782mAh/g, but SnO 2 As an electrode material, the volume changes up to 260% during charge and discharge, which causes pulverization of the electrode, resulting in disconnection of the active material from the current collector. The Si-based negative electrode material has a mass specific capacity exceeding 3000mAh/g, but the volume expansion of the Si-based negative electrode material reaches 300% -400%, and the capacity exertion is seriously influenced in the charge and discharge process. Thus, non-carbon materials have limited their large-scale use in lithium ion battery cathodes due to severe volume expansion problems.
The introduction of carbon materials is critical to solving the problem of volume expansion of non-carbon anode materials during battery operation. The carbon skeleton loaded with the non-carbon active material is designed, a proper space is reserved to meet the volume expansion of the non-carbon material in the lithium intercalation process, and meanwhile, the reserved space is designed to improve the density of the composite material, so that the novel carbon-non-carbon composite structure is prepared, and the novel carbon-non-carbon composite structure has important significance for improving the mass specific capacity and the volume specific capacity of the lithium ion battery.
Graphene, as a typical two-dimensional flexible carbon material, has a large specific surface area and good conductivity. The graphene is combined with a non-carbon active material, and has good application prospect in lithium ion battery materials. Open graphene skeleton structures, although adequate to SnO 2 The volume expands during the lithium intercalation process, but reduces the density of the negative electrode material, thereby limiting the improvement of the volume performance thereof. The densification of the three-dimensional graphene macroscopic body can be realized by utilizing a capillary evaporation method of water in the process of removing the three-dimensional graphene hydrogel water. The non-carbon active material is loaded in the compact three-dimensional graphene macroscopic body, so that the density of the composite material can be remarkably increased, but the too compact graphene skeleton structure cannot fully meet the volume expansion of the non-carbon active material in the lithium intercalation process, so that the quality performance of the composite material is affected, and the volume performance of the cathode material is also reduced.
Disclosure of Invention
The invention aims to provide a graphite-based material for a lithium ion battery cathode and a preparation method thereof, which effectively solve the problems of poor multiplying power performance, low cycle efficiency and the like of a graphene material battery, solve the problem of poor cycle stability caused by serious volume effect of a Si material in the charge and discharge process, greatly improve the reversible capacity of the battery and the specific capacity retention rate after a plurality of cycles, reduce the discharge voltage, have simple production method, are easy to industrialize without severe conditions, have low cost and have wide application prospect.
The technical scheme of the invention is realized as follows:
the invention provides a preparation method of a graphite-based material for a lithium ion battery cathode, which comprises the steps of preparing bath flower-shaped graphene oxide coated nano silicon by spray drying, and depositing SnO on the surface of the nano silicon 2 And the lithium ion battery cathode graphite-based material is prepared by modification of fullerol and reduction of hydrazine hydrate.
As a further improvement of the invention, the method comprises the following steps:
s1, preparing the nano silicon coated by the bath flower-shaped graphene oxide: adding nano silicon powder into graphene oxide aqueous dispersion, uniformly dispersing by ultrasonic, and spray-drying to obtain bath flower-shaped graphene oxide coated nano silicon;
S2.SnO 2 preparing nano silicon coated by deposition bath flower-shaped graphene oxide: dissolving tin nitrate, urea and sodium dodecyl sulfate in a mixed solution of ethylene glycol and water, adding the bath flower-shaped graphene oxide coated nano silicon prepared in the step S1, uniformly dispersing by ultrasonic, heating, stirring, reacting, filtering, washing, drying and calcining to obtain SnO 2 Coating nano silicon by using deposition bath flower-shaped graphene oxide;
s3, preparing fullerol: dissolving C60 solid powder in m-xylene, dropwise adding alkali liquor, tetrabutylammonium hydroxide solution and hydrogen peroxide, stirring and mixing uniformly, separating liquid, collecting water phase, adding ethanol for precipitation, centrifuging, washing and drying to obtain fullerol;
s4, modification of fullerol: dissolving fullerols obtained in the step S3 in water, and adding SnO obtained in the step S2 2 The deposition bath flower-shaped graphene oxide coats nano silicon, and the preparation method comprises the steps of ultrasonic dispersion, stirring reaction, centrifugation, washing and drying to prepare the fullerol modified SnO 2 Coating nano silicon by using deposition bath flower-shaped graphene oxide;
s5, reduction: modifying the fullerol prepared in the step S4 into SnO 2 And reducing the deposition bath flower-shaped graphene oxide coated nano silicon in hydrazine hydrate steam to prepare the lithium ion battery cathode graphite-based material.
As a further improvement of the invention, in the step S1, the average grain diameter of the nano silicon powder is smaller than 100nm, the concentration of the graphene oxide aqueous dispersion is 0.5-1mg/mL, the solid-to-liquid ratio of the nano silicon powder to the graphene oxide aqueous dispersion is 1:3-5g/mL, the spray drying condition is that the air inlet temperature is 90-100 ℃, the air outlet temperature is 30-50 ℃, and the evaporation water quantity is 1700-2200mL/h.
As a further improvement of the invention, in the step S2, the mass ratio of tin nitrate, urea, sodium dodecyl sulfate and bath flower-shaped graphene oxide coated nano silicon is 5-7:12-15:4-7:15-20, the volume ratio of glycol and water in the mixed solution of glycol and water is 3-4:6-7, the temperature of the heating and stirring reaction is 80-90 ℃, the time is 2-4h, the temperature of the calcination is 400-450 ℃, and the time is 2-4h.
As a further improvement of the present invention, the C in step S3 60 The mass ratio of the solid powder to the alkali liquor to the tetrabutylammonium hydroxide solution to the hydrogen peroxide is 0.5-1:15-20:15-20:30-40, wherein the alkali liquor is 1-2g/mL NaOH or KOH solution, the concentration of the tetrabutylammonium hydroxide solution is 10-15wt%, the concentration of the hydrogen peroxide is 30-32wt%, and the stirring and mixing time is 2-4h.
As a further improvement of the present invention, the fullerols, snO in step S4 2 The mass ratio of the deposition bath flower-shaped graphene oxide coated nano silicon is 3-5:15-20, and the stirring reaction time is 10-12h.
As a further improvement of the invention, the pressure of the hydrazine hydrate steam in the step S5 is 0.45-0.55KPa, and the reduction time is 7-10h.
As a further improvement of the invention, the method specifically comprises the following steps:
s1, preparing the nano silicon coated by the bath flower-shaped graphene oxide: adding nano silicon powder with the average particle size smaller than 100nm into graphene oxide aqueous dispersion liquid with the average particle size of 0.5-1mg/mL, wherein the solid-liquid ratio of the nano silicon powder to the graphene oxide aqueous dispersion liquid is 1:3-5g/mL, uniformly dispersing by ultrasonic, and spray-drying to obtain flower-shaped graphene oxide coated nano silicon;
the spray drying condition is that the air inlet temperature is 90-100 ℃, the air outlet temperature is 30-50 ℃ and the evaporation water quantity is 1700-2200mL/h;
S2.SnO 2 preparing nano silicon coated by deposition bath flower-shaped graphene oxide: dissolving 5-7 parts by weight of tin nitrate, 12-15 parts by weight of urea and 4-7 parts by weight of sodium dodecyl sulfate in a mixed solution of 100 parts by weight of ethylene glycol and water, adding 15-20 parts by weight of the bath flower-shaped graphene oxide coated nano silicon prepared in the step S1, uniformly dispersing by ultrasonic, heating to 80-90 ℃, stirring and reacting for 2-4 hours, filtering, washing, drying, calcining for 2-4 hours at 400-450 ℃ to prepare SnO 2 Coating nano silicon by using deposition bath flower-shaped graphene oxide;
the volume ratio of the glycol to the water in the mixed solution of the glycol and the water is 3-4:6-7;
s3, preparing fullerol: 0.5 to 1 part by weight of C 60 Dissolving solid powder in 1Dropwise adding 15-20 parts by weight of 1-2g/mL NaOH or KOH solution, 15-20 parts by weight of 10-15wt% tetrabutylammonium hydroxide solution and 30-40 parts by weight of 30-32wt% hydrogen peroxide into 00 parts by weight of m-xylene solution, stirring and mixing for 2-4 hours, separating liquid, collecting water phase, adding ethanol until the ethanol content of the system is 60-70wt%, precipitating for 1-3 hours, centrifuging, washing and drying to obtain fullerol;
s4, modification of fullerol: dissolving 3-5 parts by weight of fullerol prepared in the step S3 into 100 parts by weight of water, and adding 15-20 parts by weight of SnO prepared in the step S2 2 The deposition bath flower-shaped graphene oxide coats nano silicon, the ultrasonic dispersion is uniform, the stirring reaction is carried out for 10 to 12 hours, the centrifugation, the washing and the drying are carried out, and the fullerol modified SnO is prepared 2 Coating nano silicon by using deposition bath flower-shaped graphene oxide;
s5, reduction: modifying the fullerol prepared in the step S4 into SnO 2 And (3) reducing the deposition bath flower-shaped graphene oxide coated nano silicon in hydrazine hydrate steam with the pressure of 0.45-0.55KPa for 7-10h to prepare the lithium ion battery negative electrode graphite-based material.
The invention further protects the graphite-based material of the lithium ion battery cathode prepared by the preparation method.
The invention further protects application of the graphite-based material of the lithium ion battery cathode in preparation of a lithium ion battery.
The invention has the following beneficial effects:
the lithium ion battery negative electrode material can meet the conditions of low and stable oxidation-reduction potential, large reversible capacity, compact and stable SEI film formation, no toxicity to environment, low manufacturing cost and the like. Graphene is a planar two-dimensional structure nanomaterial with a hexagonal honeycomb lattice and composed of carbon atoms, the C-C bond length of the nanomaterial is 0.141nm, and the theoretical density of the nanomaterial is about 0.77mg/m 2 The thickness is only the diameter of one carbon atom, the carbon atoms are hybridized in an sp2 mode, electrons can be smoothly transmitted between layers, so that the graphene material with the minimum known resistivity has unique advantages as a lithium ion battery anode material, but the research on the graphene independent electrode material is not ideal due to the fact that the two-dimensional microstructures are easy to stack. Mainly shows the aspects of poor rate performance, low cycle efficiency and the like of the battery.
According to the invention, graphene oxide is coated on the surface of nano silicon powder, a spray drying method is adopted, a solvent is rapidly evaporated, so that the volume of liquid drops is contracted, the graphene oxide coated nano silicon with the surface in a bath flower shape is obtained, the specific surface area of the material is greatly improved, meanwhile, a silicon and graphene composite material is formed, the theoretical charging specific capacity of silicon and lithium ions can be up to 4200 mA.h/g, the reversible capacity can also be up to 2753 mA.h/g, the material still has high specific capacity after a plurality of cycles, and the discharge voltage is low. Meanwhile, the silicon material is nanocrystallized and carbon coated to buffer huge volume change to a certain extent, so that the problem of poor cycling stability caused by serious volume effect of the Si material in the charging and discharging process is avoided, and meanwhile, the lithium ion and electron transmission capability of the silicon material can be effectively improved.
The invention further deposits metal oxide SnO on the high specific surface area of the bath flower-shaped graphene oxide coated nano silicon 2 The added urea is heated and decomposed to generate ammonia water, so that the reaction system becomes alkaline, thereby promoting the generation of hydroxide, and further calcining and dehydrating, and depositing metal oxide SnO in situ 2 Meanwhile, the metal oxides are not agglomerated in the graphene interlayer and are uniformly distributed on the surface of graphene, so that the reversible capacity of the battery is greatly improved, the specific capacity retention rate after a plurality of cycles is greatly improved, and the surface inactivation of the graphite nano sheet can be effectively prevented.
The invention adopts tetrabutyl ammonium hydroxide catalytic alkali method to prepare polyhydroxy fullerol, and fixes the polyhydroxy fullerol on SnO through hydrogen bond 2 The deposition bath flower-shaped graphene oxide coats the nano silicon, meanwhile, a pi-bond conjugated system of a matrix is reserved, the mechanical property and the electron transmission capacity of the material are improved through the formation of a composite structure, more lithium storage space is provided, the diffusion distance of lithium ions can be effectively shortened, and the rapid storage and transmission of lithium ions and electrons in the material are improved.
The lithium ion battery cathode graphite-based material prepared by the invention effectively solves the problems of poor multiplying power performance, low cycle efficiency and the like of a graphene material battery, and avoids the problem of poor cycle stability caused by serious volume effect of Si material in the charging and discharging process, thereby greatly improving the reversible capacity of the battery and the specific capacity retention rate after several times of cycles, reducing the discharging voltage, having simple production method, no harsh condition, easy industrialization, low cost and wide application prospect.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Nanometer silica powder with average grain size of 80nm is purchased from Shanghai Ala Biochemical technology Co., ltd;
graphene oxide aqueous dispersion, 0.5mg/mL, 1-5 layers of layers and 0.2-4 mu m of sheet diameter, purchased from Jiangsu Xianfeng nano materials science and technology Co., ltd;
fullerene, C 60 The solid powder has a purity of greater than 99% and is available from the scientific and technological company of carbon-rich graphene, suzhou.
Example 1
The embodiment provides a preparation method of a graphite-based material for a lithium ion battery cathode, which specifically comprises the following steps:
s1, preparing the nano silicon coated by the bath flower-shaped graphene oxide: adding nano silicon powder with the average particle size of 80nm into graphene oxide aqueous dispersion liquid with the average particle size of 0.5mg/mL, wherein the solid-to-liquid ratio of the nano silicon powder to the graphene oxide aqueous dispersion liquid is 1:3g/mL, performing 1000W ultrasonic dispersion for 20min, and performing spray drying to obtain bath flower-shaped graphene oxide coated nano silicon;
the spray drying condition is that the air inlet temperature is 90 ℃, the air outlet temperature is 30 ℃ and the evaporation water quantity is 1700mL/h;
S2.SnO 2 preparing nano silicon coated by deposition bath flower-shaped graphene oxide: 6 parts by weight of tin nitrate, 125 parts by weight of urea and 4 parts by weight of sodium dodecyl sulfate are dissolved in 100 parts by weight of mixed solution of ethylene glycol and water, and 15 parts by weight of bath flower-shaped oxidation prepared in the step S1 are addedGraphene coated nano silicon is subjected to 1000W ultrasonic dispersion for 20min, heated to 80 ℃, stirred for 2h, filtered, washed, dried and calcined at 400 ℃ for 2h to prepare SnO 2 Coating nano silicon by using deposition bath flower-shaped graphene oxide;
the volume ratio of the glycol to the water in the mixed solution of the glycol and the water is 3:6;
s3, preparing fullerol: 0.5 part by weight of C 60 Dissolving solid powder in 100 parts by weight of m-xylene solution, dropwise adding 20 parts by weight of 1g/mL NaOH solution, 15 parts by weight of 10wt% tetrabutylammonium hydroxide solution and 30 parts by weight of 30wt% hydrogen peroxide, stirring and mixing for 2 hours, separating liquid, collecting water phase, adding ethanol until the ethanol content of the system is 60wt%, precipitating for 1 hour, centrifuging, washing and drying to obtain fullerol;
s4, modification of fullerol: dissolving 3 parts by weight of fullerols obtained in the step S3 in 100 parts by weight of water, and adding 15 parts by weight of SnO obtained in the step S2 2 The deposition bath flower-shaped graphene oxide coats nano silicon, 1000W ultrasonic dispersion is carried out for 20min, stirring reaction is carried out for 10h, centrifugation, washing and drying are carried out, and the fullerol modified SnO is prepared 2 Coating nano silicon by using deposition bath flower-shaped graphene oxide;
s5, reduction: modifying the fullerol prepared in the step S4 into SnO 2 And (3) reducing the deposition bath flower-shaped graphene oxide coated nano silicon in hydrazine hydrate steam with the pressure of 0.55KPa for 7h to prepare the graphite-based material of the lithium ion battery cathode.
Example 2
The embodiment provides a preparation method of a graphite-based material for a lithium ion battery cathode, which specifically comprises the following steps:
s1, preparing the nano silicon coated by the bath flower-shaped graphene oxide: adding nano silicon powder with the average particle size of 80nm into graphene oxide aqueous dispersion liquid with the average particle size of 0.5mg/mL, wherein the solid-to-liquid ratio of the nano silicon powder to the graphene oxide aqueous dispersion liquid is 1:5g/mL, performing 1000W ultrasonic dispersion for 20min, and performing spray drying to obtain bath flower-shaped graphene oxide coated nano silicon;
the spray drying condition is that the air inlet temperature is 100 ℃, the air outlet temperature is 50 ℃, and the evaporation water quantity is 2200mL/h;
S2.SnO 2 deposition bath flower-like graphene oxide coated nano siliconPreparation: dissolving 7 parts by weight of tin nitrate, 15 parts by weight of urea and 7 parts by weight of sodium dodecyl sulfate in a mixed solution of 100 parts by weight of ethylene glycol and water, adding 20 parts by weight of the bath flower-shaped graphene oxide coated nano silicon prepared in the step S1, performing 1000W ultrasonic dispersion for 20min, heating to 90 ℃, stirring for reacting for 4h, filtering, washing, drying, and calcining at 450 ℃ for 4h to prepare SnO 2 Coating nano silicon by using deposition bath flower-shaped graphene oxide;
the volume ratio of the glycol to the water in the mixed solution of the glycol and the water is 4:7;
s3, preparing fullerol: 1 part by weight of C 60 Dissolving solid powder in 100 parts by weight of m-xylene solution, dropwise adding 15 parts by weight of 2g/mL KOH solution, 20 parts by weight of 15wt% tetrabutylammonium hydroxide solution and 40 parts by weight of 32wt% hydrogen peroxide, stirring and mixing for 4 hours, separating liquid, collecting water phase, adding ethanol until the ethanol content of the system is 70wt%, precipitating for 3 hours, centrifuging, washing and drying to obtain fullerol;
s4, modification of fullerol: dissolving 5 parts by weight of fullerols obtained in the step S3 in 100 parts by weight of water, and adding 20 parts by weight of SnO obtained in the step S2 2 The deposition bath flower-shaped graphene oxide coats nano silicon, 1000W ultrasonic dispersion is carried out for 20min, stirring reaction is carried out for 12h, centrifugation, washing and drying are carried out, and the fullerol modified SnO is prepared 2 Coating nano silicon by using deposition bath flower-shaped graphene oxide;
s5, reduction: modifying the fullerol prepared in the step S4 into SnO 2 And (3) reducing the deposition bath flower-shaped graphene oxide coated nano silicon in hydrazine hydrate steam with the pressure of 0.45KPa for 10 hours to prepare the graphite-based material of the lithium ion battery cathode.
Example 3
The embodiment provides a preparation method of a graphite-based material for a lithium ion battery cathode, which specifically comprises the following steps:
s1, preparing the nano silicon coated by the bath flower-shaped graphene oxide: adding nano silicon powder with the average particle size of 80nm into graphene oxide aqueous dispersion liquid with the average particle size of 0.5mg/mL, wherein the solid-to-liquid ratio of the nano silicon powder to the graphene oxide aqueous dispersion liquid is 1:4g/mL, performing 1000W ultrasonic dispersion for 20min, and performing spray drying to obtain bath flower-shaped graphene oxide coated nano silicon;
the spray drying condition is that the air inlet temperature is 95 ℃, the air outlet temperature is 40 ℃ and the evaporation water quantity is 2000mL/h;
S2.SnO 2 preparing nano silicon coated by deposition bath flower-shaped graphene oxide: dissolving 6 parts by weight of tin nitrate, 13.5 parts by weight of urea and 5 parts by weight of sodium dodecyl sulfate in a mixed solution of 100 parts by weight of ethylene glycol and water, adding 17 parts by weight of the bath flower-shaped graphene oxide coated nano silicon prepared in the step S1, performing 1000W ultrasonic dispersion for 20min, heating to 85 ℃, stirring for reacting for 3h, filtering, washing, drying, and calcining at 420 ℃ for 3h to prepare SnO 2 Coating nano silicon by using deposition bath flower-shaped graphene oxide;
the volume ratio of the glycol to the water in the mixed solution of the glycol and the water is 3.5:6.5;
s3, preparing fullerol: 0.7 part by weight of C 60 Dissolving solid powder in 100 parts by weight of m-xylene solution, dropwise adding 17 parts by weight of 1.5g/mL NaOH solution, 17 parts by weight of 12wt% tetrabutylammonium hydroxide solution and 35 parts by weight of 31wt% hydrogen peroxide, stirring and mixing for 3 hours, separating liquid, collecting water phase, adding ethanol until the ethanol content of the system is 65wt%, precipitating for 2 hours, centrifuging, washing and drying to obtain fullerol;
s4, modification of fullerol: dissolving 4 parts by weight of fullerols obtained in the step S3 in 100 parts by weight of water, and adding 17 parts by weight of SnO obtained in the step S2 2 The deposition bath flower-shaped graphene oxide coats nano silicon, 1000W ultrasonic dispersion is carried out for 20min, stirring reaction is carried out for 11h, centrifugation, washing and drying are carried out, and the fullerol modified SnO is prepared 2 Coating nano silicon by using deposition bath flower-shaped graphene oxide;
s5, reduction: modifying the fullerol prepared in the step S4 into SnO 2 And (3) reducing the deposition bath flower-shaped graphene oxide coated nano silicon in hydrazine hydrate steam with the pressure of 0.5KPa for 8 hours to prepare the graphite-based material of the lithium ion battery cathode.
Comparative example 1
The difference from example 3 is that no nano silicon powder is added in step S1.
The method comprises the following steps:
s1, preparing bath flower-shaped graphene oxide: spray drying graphene oxide aqueous dispersion liquid of 0.5mg/mL to obtain flower-shaped graphene oxide;
the spray drying condition is that the inlet air temperature is 95 ℃, the outlet air temperature is 40 ℃ and the evaporation water quantity is 2000mL/h.
Comparative example 2
In comparison with example 3, the difference is that the graphene oxide aqueous dispersion in step S1 is replaced with an equal amount of water, and step S5 is not performed.
The method comprises the following steps:
s1, preparing nano silicon: adding nano silicon powder with the average particle size of 80nm into water, wherein the solid-to-liquid ratio of the nano silicon powder to the water is 1:4g/mL, performing 1000W ultrasonic dispersion for 20min, and performing spray drying to obtain nano silicon;
the spray drying condition is that the air inlet temperature is 95 ℃, the air outlet temperature is 40 ℃ and the evaporation water quantity is 2000mL/h;
S2.SnO 2 preparation of deposited nano-silicon: dissolving 6 parts by weight of tin nitrate, 13.5 parts by weight of urea and 5 parts by weight of sodium dodecyl sulfate in a mixed solution of 100 parts by weight of ethylene glycol and water, adding 17 parts by weight of nano silicon prepared in the step S1, performing 1000W ultrasonic dispersion for 20min, heating to 85 ℃, stirring for reacting for 3h, filtering, washing, drying, and calcining at 420 ℃ for 3h to prepare SnO 2 Nano silicon;
the volume ratio of the glycol to the water in the mixed solution of the glycol and the water is 3.5:6.5;
s3, preparing fullerol: 0.7 part by weight of C 60 Dissolving solid powder in 100 parts by weight of m-xylene solution, dropwise adding 17 parts by weight of 1.5g/mL NaOH solution, 17 parts by weight of 12wt% tetrabutylammonium hydroxide solution and 35 parts by weight of 31wt% hydrogen peroxide, stirring and mixing for 3 hours, separating liquid, collecting water phase, adding ethanol until the ethanol content of the system is 65wt%, precipitating for 2 hours, centrifuging, washing and drying to obtain fullerol;
s4, modification of fullerol: dissolving 4 parts by weight of fullerols obtained in the step S3 in 100 parts by weight of water, and adding 17 parts by weight of SnO obtained in the step S2 2 Depositing nano silicon, performing 1000W ultrasonic dispersion for 20min, stirring and reacting for 11h, centrifuging, washing and drying to obtain the fullerol modified SnO 2 And depositing nano silicon to obtain the negative electrode graphite-based material of the lithium ion battery.
Comparative example 3
In comparison with example 3, the difference is that spray drying is not performed in step S1, and conventional drying is employed.
The method comprises the following steps:
s1, preparing graphene oxide coated nano silicon: adding nano silicon powder with the average particle size of 80nm into graphene oxide aqueous dispersion liquid with the average particle size of 0.5mg/mL, wherein the solid-to-liquid ratio of the nano silicon powder to the graphene oxide aqueous dispersion liquid is 1:4g/mL, performing 1000W ultrasonic dispersion for 20min, and drying to obtain the graphene oxide coated nano silicon.
Comparative example 4
In comparison with example 3, the difference is that step S2 is not performed.
The method comprises the following steps:
s1, preparing the nano silicon coated by the bath flower-shaped graphene oxide: adding nano silicon powder with the average particle size of 80nm into graphene oxide aqueous dispersion liquid with the average particle size of 0.5mg/mL, wherein the solid-to-liquid ratio of the nano silicon powder to the graphene oxide aqueous dispersion liquid is 1:4g/mL, performing 1000W ultrasonic dispersion for 20min, and performing spray drying to obtain bath flower-shaped graphene oxide coated nano silicon;
the spray drying condition is that the air inlet temperature is 95 ℃, the air outlet temperature is 40 ℃ and the evaporation water quantity is 2000mL/h;
s2, preparing fullerol: 0.7 part by weight of C 60 Dissolving solid powder in 100 parts by weight of m-xylene solution, dropwise adding 17 parts by weight of 1.5g/mL NaOH solution, 17 parts by weight of 12wt% tetrabutylammonium hydroxide solution and 35 parts by weight of 31wt% hydrogen peroxide, stirring and mixing for 3 hours, separating liquid, collecting water phase, adding ethanol until the ethanol content of the system is 65wt%, precipitating for 2 hours, centrifuging, washing and drying to obtain fullerol;
s3, modification of fullerol: dissolving 4 parts by weight of fullerol prepared in the step S2 into 100 parts by weight of water, adding 17 parts by weight of the bath flower-shaped graphene oxide coated nano silicon prepared in the step S1, performing 1000W ultrasonic dispersion for 20min, stirring and reacting for 11h, centrifuging, washing and drying to prepare the fullerene modified bath flower-shaped graphene oxide coated nano silicon;
s4, reduction: and (3) reducing the fullerene alcohol modified bath flower-shaped graphene oxide coated nano silicon prepared in the step (S3) in hydrazine hydrate steam with the pressure of 0.5KPa for 8 hours to prepare the graphite-based material of the lithium ion battery cathode.
Comparative example 5
In comparison with example 3, the difference is that steps S3 and S4 are not performed.
The method comprises the following steps:
s1, preparing the nano silicon coated by the bath flower-shaped graphene oxide: adding nano silicon powder with the average particle size of 80nm into graphene oxide aqueous dispersion liquid with the average particle size of 0.5mg/mL, wherein the solid-to-liquid ratio of the nano silicon powder to the graphene oxide aqueous dispersion liquid is 1:4g/mL, performing 1000W ultrasonic dispersion for 20min, and performing spray drying to obtain bath flower-shaped graphene oxide coated nano silicon;
the spray drying condition is that the air inlet temperature is 95 ℃, the air outlet temperature is 40 ℃ and the evaporation water quantity is 2000mL/h;
S2.SnO 2 preparing nano silicon coated by deposition bath flower-shaped graphene oxide: dissolving 6 parts by weight of tin nitrate, 13.5 parts by weight of urea and 5 parts by weight of sodium dodecyl sulfate in a mixed solution of 100 parts by weight of ethylene glycol and water, adding 17 parts by weight of the bath flower-shaped graphene oxide coated nano silicon prepared in the step S1, performing 1000W ultrasonic dispersion for 20min, heating to 85 ℃, stirring for reacting for 3h, filtering, washing, drying, and calcining at 420 ℃ for 3h to prepare SnO 2 Coating nano silicon by using deposition bath flower-shaped graphene oxide;
the volume ratio of the glycol to the water in the mixed solution of the glycol and the water is 3.5:6.5;
s3, reduction: snO obtained in step S2 2 And (3) reducing the deposition bath flower-shaped graphene oxide coated nano silicon in hydrazine hydrate steam with the pressure of 0.5KPa for 8 hours to prepare the graphite-based material of the lithium ion battery cathode.
Comparative example 6
In comparison with example 3, the difference is that steps S2 to S4 are not performed.
The method comprises the following steps:
s1, preparing the nano silicon coated by the bath flower-shaped graphene oxide: adding nano silicon powder with the average particle size of 80nm into graphene oxide aqueous dispersion liquid with the average particle size of 0.5mg/mL, wherein the solid-to-liquid ratio of the nano silicon powder to the graphene oxide aqueous dispersion liquid is 1:4g/mL, performing 1000W ultrasonic dispersion for 20min, and performing spray drying to obtain bath flower-shaped graphene oxide coated nano silicon;
the spray drying condition is that the air inlet temperature is 95 ℃, the air outlet temperature is 40 ℃ and the evaporation water quantity is 2000mL/h;
s2, reduction: and (3) reducing the bath flower-shaped graphene oxide coated nano silicon prepared in the step (S1) in hydrazine hydrate steam with the pressure of 0.5KPa for 8 hours to prepare the graphite-based material of the negative electrode of the lithium ion battery.
Comparative example 7
In comparison with example 3, the difference is that step S5 is not performed.
The method comprises the following steps:
s1, preparing the nano silicon coated by the bath flower-shaped graphene oxide: adding nano silicon powder with the average particle size of 80nm into graphene oxide aqueous dispersion liquid with the average particle size of 0.5mg/mL, wherein the solid-to-liquid ratio of the nano silicon powder to the graphene oxide aqueous dispersion liquid is 1:4g/mL, performing 1000W ultrasonic dispersion for 20min, and performing spray drying to obtain bath flower-shaped graphene oxide coated nano silicon;
the spray drying condition is that the air inlet temperature is 95 ℃, the air outlet temperature is 40 ℃ and the evaporation water quantity is 2000mL/h;
S2.SnO 2 preparing nano silicon coated by deposition bath flower-shaped graphene oxide: dissolving 6 parts by weight of tin nitrate, 13.5 parts by weight of urea and 5 parts by weight of sodium dodecyl sulfate in a mixed solution of 100 parts by weight of ethylene glycol and water, adding 17 parts by weight of the bath flower-shaped graphene oxide coated nano silicon prepared in the step S1, performing 1000W ultrasonic dispersion for 20min, heating to 85 ℃, stirring for reacting for 3h, filtering, washing, drying, and calcining at 420 ℃ for 3h to prepare SnO 2 Coating nano silicon by using deposition bath flower-shaped graphene oxide;
the volume ratio of the glycol to the water in the mixed solution of the glycol and the water is 3.5:6.5;
s3, preparing fullerol: 0.7 part by weight of C 60 Dissolving solid powder in 100 parts by weight of m-xylene solution, dropwise adding 17 parts by weight of 1.5g/mL NaOH solution, 17 parts by weight of 12wt% tetrabutylammonium hydroxide solution and 35 parts by weight of 31wt% hydrogen peroxide, stirring and mixing for 3 hours, separating liquid, collecting water phase, adding ethanol until the ethanol content of the system is 65wt%, precipitating for 2 hours, centrifuging, washing and drying to obtain fullerol;
s4, modification of fullerol: 4 parts by weight of fullerols obtained in step S3Dissolving in 100 weight parts of water, adding 17 weight parts of SnO prepared in the step S2 2 The deposition bath flower-shaped graphene oxide coats nano silicon, 1000W ultrasonic dispersion is carried out for 20min, stirring reaction is carried out for 11h, centrifugation, washing and drying are carried out, and the fullerol modified SnO is prepared 2 The deposition bath flower-shaped graphene oxide coats nano silicon, and the nano silicon is the negative electrode graphite-based material of the lithium ion battery.
Test example 1
The lithium ion battery negative electrode graphite-based materials prepared in examples 1 to 3 and comparative examples 1 to 7 of the present invention were measured for specific surface area of a sample using ASAP2460 type full-automatic specific surface area and porosity analyzer manufactured by Micromeritics instruments, inc. of America. The results are shown in Table 1.
TABLE 1
Group of Specific surface area (m) 2 /g）
Example 1 126.1
Example 2 125.8
Example 3 127.0
Comparative example 1 115.7
Comparative example 2 45.6
Comparative example 3 62.2
Comparative example 4 117.5
Comparative example 5 113.2
Comparative example 6 110.6
Comparative example 7 122.7
As shown in the table above, the graphite-based materials for negative electrodes of lithium ion batteries prepared in examples 1 to 3 of the present invention have a relatively high specific surface area.
Test example 2
The graphite-based materials of the lithium ion battery cathodes prepared in the examples 1-3 and the comparative examples 1-7, the conductive additives of acetylene black, the binder of sodium carboxymethyl cellulose and styrene-butadiene rubber are dissolved in N-methylpyrrolidone according to the mass ratio of 94:2:1.5:2.5, the mixed materials are fully and uniformly mixed, the slurry is stirred until the slurry is sticky and not dripped, the slurry is coated on a copper sheet, and the copper sheet is dried. And stamping the dried Cu sheet into a circular pole piece with the diameter of 14mm on a tablet press to serve as a working electrode. LiPF at 1mol/L 6 Organic solvent (EC/DMC/DEC volume ratio 1:1:1) is used as electrolyte, celgard2300 polypropylene film is used as diaphragm, lithium sheet is used as positive electrode, and CR2032 button cell is assembled for electrochemical performance test. The electrochemical performance test of the test button cell was performed at room temperature of 25 ℃ and was subjected to a charge and discharge test using the LAND cell test system CT2001A model. The charge and discharge were performed at a constant current, the current density was set to 0.1C, and the cut-off voltages of the charge and discharge were 3.0V and 0.001V, respectively. The results are shown in Table 2.
TABLE 2
Group of Charging capacity (mAh/g) Discharge capacity (mAh/g) First charge and discharge efficiency (%) Irreversible capacity (mAh/g) Capacity retention after 200 cycles (%)
Example 1 778 801.2 97.10 23.2 95.52
Example 2 782 803.8 97.29 21.8 95.49
Example 3 790 808.4 97.72 18.4 96.17
Comparative example 1 725 757.8 95.67 32.8 91.84
Comparative example 2 734 781.0 93.98 47.0 87.47
Comparative example 3 697 750.8 92.84 53.8 89.15
Comparative example 4 710 780.9 90.92 70.9 84.57
Comparative example 6 678 736.2 92.10 58.2 87.02
Comparative example 6 662 743.7 89.01 81.7 82.28
Comparative example 7 702 747.4 93.92 45.4 84.05
As shown in the table above, the graphite-based materials for the negative electrode of the lithium ion battery prepared in examples 1-3 of the present invention have good electrochemical properties.
In comparative example 1, no nano silicon powder was added in step S1, compared with example 3. Comparative example 2 in comparison with example 3, the graphene oxide aqueous dispersion in step S1 was replaced with an equal amount of water, and step S5 was not performed. The specific surface area is reduced and the electrochemical performance is reduced. The invention forms a silicon and graphene composite material, silicon and lithium ions can form Li-Si, the theoretical charging specific capacity of the silicon and lithium ions can reach 4200 mA.h/g, the reversible capacity can also reach 2753 mA.h/g, the silicon and lithium ions still have high specific capacity after a plurality of cycles, and the discharge voltage is low. Meanwhile, the silicon material is nanocrystallized and carbon coated to buffer huge volume change to a certain extent, so that the problem of poor cycling stability caused by serious volume effect of the Si material in the charging and discharging process is avoided, and meanwhile, the lithium ion and electron transmission capability of the silicon material can be effectively improved.
Comparative example 3 in comparison with example 3, spray drying was not performed in step S1, and conventional drying was employed. The specific surface area is greatly reduced, and the electrochemical performance is reduced. According to the invention, graphene oxide is coated on the surface of the nano silicon powder, and a spray drying method is adopted, so that the solvent is rapidly evaporated, the volume of liquid drops is contracted, the graphene oxide coated nano silicon with the surface in a bath flower shape is obtained, and the specific surface area of the material is greatly improved.
Comparative example 4 compared to example 3, step S2 was not performed. Electrochemical performance is degraded. The invention deposits metal oxide SnO on the high specific surface area of the bath flower-shaped graphene oxide coated nano silicon 2 The added urea is heated and decomposed to generate ammonia water, so that the reaction system becomes alkaline, thereby promoting the generation of hydroxide, and further calcining and dehydrating, and depositing metal oxide SnO in situ 2 Meanwhile, the metal oxides are not agglomerated in the graphene interlayer and are uniformly distributed on the surface of graphene, so that the reversible capacity of the battery is greatly improved, the specific capacity retention rate after a plurality of cycles is greatly improved, and the surface inactivation of the graphite nano sheet can be effectively prevented.
Comparative example 5 in comparison with example 3, steps S3 and S4 were not performed. Comparative example 6 in comparison with example 3, steps S2 to S4 were not performed. The specific surface area is reduced and the electrochemical performance is reduced. The invention adopts tetrabutyl ammonium hydroxide catalytic alkali method to prepare polyhydroxy fullerol which is fixed on SnO through hydrogen bond 2 The deposition bath flower-shaped graphene oxide coats the nano silicon, meanwhile, a pi-bond conjugated system of a matrix is reserved, the mechanical property and the electron transmission capacity of the material are improved through the formation of a composite structure, more lithium storage space is provided, the diffusion distance of lithium ions can be effectively shortened, and the rapid storage and transmission of lithium ions and electrons in the material are improved.
Comparative example 7 compared to example 3, step S5 was not performed. Electrochemical performance is degraded. The lithium ion battery anode material should meet the conditions of low and stable oxidation-reduction potential, large reversible capacity, compact stable SEI film formation, no toxicity to environment, low manufacturing cost and the like, and the graphene is a planar two-dimensional structure nanomaterial with a hexagonal honeycomb lattice and composed of carbon atoms, the C-C bond length of the nanomaterial is 0.141nm, and the theoretical density of the nanomaterial is about 0.77mg/m 2 The thickness is only the diameter of one carbon atom, the carbon atoms are hybridized in an sp2 mode, electrons can be smoothly transmitted between layers, so that the graphene material with the minimum known resistivity has unique advantages when being used as a lithium ion battery anode material, and the performance of the graphene oxide which is not reduced is greatly reduced.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.

Claims (10)

1. A preparation method of a graphite-based material for a lithium ion battery cathode is characterized in that bath flower-shaped graphene oxide coated nano silicon is prepared by spray drying, and SnO is deposited on the surface of the nano silicon 2 And the lithium ion battery cathode graphite-based material is prepared by modification of fullerol and reduction of hydrazine hydrate.
2. The method of manufacturing according to claim 1, comprising the steps of:
s1, preparing the nano silicon coated by the bath flower-shaped graphene oxide: adding nano silicon powder into graphene oxide aqueous dispersion, uniformly dispersing by ultrasonic, and spray-drying to obtain bath flower-shaped graphene oxide coated nano silicon;
S2.SnO 2 preparing nano silicon coated by deposition bath flower-shaped graphene oxide: dissolving tin nitrate, urea and sodium dodecyl sulfate in a mixed solution of ethylene glycol and water, adding the bath flower-shaped graphene oxide coated nano silicon prepared in the step S1, uniformly dispersing by ultrasonic, heating, stirring, reacting, filtering, washing, drying and calcining to obtain SnO 2 Coating nano silicon by using deposition bath flower-shaped graphene oxide;
s3, preparing fullerol: dissolving C60 solid powder in m-xylene, dropwise adding alkali liquor, tetrabutylammonium hydroxide solution and hydrogen peroxide, stirring and mixing uniformly, separating liquid, collecting water phase, adding ethanol for precipitation, centrifuging, washing and drying to obtain fullerol;
s4, modification of fullerol: dissolving fullerols obtained in the step S3 in water, and adding SnO obtained in the step S2 2 The deposition bath flower-shaped graphene oxide coats nano silicon, and the preparation method comprises the steps of ultrasonic dispersion, stirring reaction, centrifugation, washing and drying to prepare the fullerol modified SnO 2 Coating nano silicon by using deposition bath flower-shaped graphene oxide;
s5, reduction: repairing the fullerols prepared in the step S4Decorative SnO 2 And reducing the deposition bath flower-shaped graphene oxide coated nano silicon in hydrazine hydrate steam to prepare the lithium ion battery cathode graphite-based material.
3. The preparation method of claim 2, wherein in the step S1, the average particle size of the nano silicon powder is smaller than 100nm, the concentration of the graphene oxide aqueous dispersion is 0.5-1mg/mL, the solid-to-liquid ratio of the nano silicon powder to the graphene oxide aqueous dispersion is 1:3-5g/mL, the spray drying condition is that the air inlet temperature is 90-100 ℃, the air outlet temperature is 30-50 ℃, and the evaporation water amount is 1700-2200mL/h.
4. The preparation method of claim 2, wherein in the step S2, the mass ratio of tin nitrate, urea, sodium dodecyl sulfate and bath-flower-shaped graphene oxide coated nano silicon is 3-5:5-7:2-4:12-15:4-7:15-20, the volume ratio of glycol and water in the mixed solution of glycol and water is 3-4:6-7, the temperature of the heating and stirring reaction is 80-90 ℃, the time is 2-4h, the temperature of the calcination is 400-450 ℃, and the time is 2-4h.
5. The method according to claim 2, wherein said C in step S3 60 The mass ratio of the solid powder to the alkali liquor to the tetrabutylammonium hydroxide solution to the hydrogen peroxide is 0.5-1:15-20:15-20:30-40, wherein the alkali liquor is 1-2g/mL NaOH or KOH solution, the concentration of the tetrabutylammonium hydroxide solution is 10-15wt%, the concentration of the hydrogen peroxide is 30-32wt%, and the stirring and mixing time is 2-4h.
6. The method according to claim 2, wherein the fullerols, snO in step S4 2 The mass ratio of the deposition bath flower-shaped graphene oxide coated nano silicon is 3-5:15-20, and the stirring reaction time is 10-12h.
7. The preparation method according to claim 2, wherein the pressure of the hydrazine hydrate vapor in step S5 is 0.45-0.55KPa, and the time for the reduction is 7-10h.
8. The preparation method according to claim 2, characterized by comprising the following steps:
s1, preparing the nano silicon coated by the bath flower-shaped graphene oxide: adding nano silicon powder with the average particle size smaller than 100nm into graphene oxide aqueous dispersion liquid with the average particle size of 0.5-1mg/mL, wherein the solid-liquid ratio of the nano silicon powder to the graphene oxide aqueous dispersion liquid is 1:3-5g/mL, uniformly dispersing by ultrasonic, and spray-drying to obtain flower-shaped graphene oxide coated nano silicon;
the spray drying condition is that the air inlet temperature is 90-100 ℃, the air outlet temperature is 30-50 ℃ and the evaporation water quantity is 1700-2200mL/h;
S2.SnO 2 preparing nano silicon coated by deposition bath flower-shaped graphene oxide: dissolving 5-7 parts by weight of tin nitrate, 12-15 parts by weight of urea and 4-7 parts by weight of sodium dodecyl sulfate in a mixed solution of 100 parts by weight of ethylene glycol and water, adding 15-20 parts by weight of the bath flower-shaped graphene oxide coated nano silicon prepared in the step S1, uniformly dispersing by ultrasonic, heating to 80-90 ℃, stirring and reacting for 2-4 hours, filtering, washing, drying, calcining for 2-4 hours at 400-450 ℃ to prepare SnO 2 Coating nano silicon by using deposition bath flower-shaped graphene oxide;
the volume ratio of the glycol to the water in the mixed solution of the glycol and the water is 3-4:6-7;
s3, preparing fullerol: 0.5 to 1 part by weight of C 60 Dissolving solid powder in 100 weight parts of m-xylene solution, dropwise adding 15-20 weight parts of 1-2g/mL NaOH or KOH solution, 15-20 weight parts of 10-15 weight percent tetrabutylammonium hydroxide solution and 30-40 weight parts of 30-32 weight percent hydrogen peroxide, stirring and mixing for 2-4 hours, separating liquid, collecting water phase, adding ethanol until the ethanol content of the system is 60-70 weight percent, precipitating for 1-3 hours, centrifuging, washing and drying to obtain fullerol;
s4, modification of fullerol: dissolving 3-5 parts by weight of fullerol prepared in the step S3 into 100 parts by weight of water, and adding 15-20 parts by weight of SnO prepared in the step S2 2 Coating nano silicon with deposition bath flower-shaped graphene oxide, uniformly dispersing by ultrasonic, stirring and reacting for 10-12h, centrifuging, washing and drying to obtain fullerolModified SnO 2 Coating nano silicon by using deposition bath flower-shaped graphene oxide;
s5, reduction: modifying the fullerol prepared in the step S4 into SnO 2 And (3) reducing the deposition bath flower-shaped graphene oxide coated nano silicon in hydrazine hydrate steam with the pressure of 0.45-0.55KPa for 7-10h to prepare the lithium ion battery negative electrode graphite-based material.
9. A lithium ion battery negative electrode graphite-based material prepared by the preparation method of any one of claims 1-8.
10. Use of the negative electrode graphite-based material of a lithium ion battery according to claim 9 for preparing a lithium ion battery.
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