CN110311092B - SnO (stannic oxide)2carbon/V2O5Application of/graphene composite nano material as battery negative electrode material - Google Patents
SnO (stannic oxide)2carbon/V2O5Application of/graphene composite nano material as battery negative electrode material Download PDFInfo
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Abstract
The invention provides SnO2carbon/V2O5Application of graphene composite nano material as battery negative electrode material, wherein the composite nano material is prepared into SnO by respectively adopting hydrothermal synthesis method2Carbon Material and V2O5The SnO is obtained from the graphene composite material by a ball milling method2carbon/V2O5The preparation method of the graphene composite nano material is simple and feasible, and a new way is provided for the controllable synthesis of the multi-element nano composite; the composite nano material improves the electronic conductivity of the electrode material, particularly obviously improves the first reversible capacity and rate performance, enhances the charge-discharge performance of the electrode material under high rate, increases the discharge capacity of the electrode material, reduces the attenuation of the battery capacity, improves the anti-overcharge performance of the battery, prolongs the cycle life of the electrode material, has high electrochemical lithium storage capacity, good stable cycle performance and less energy loss, and has wide application prospect.
Description
The invention relates to a composite nano material for a high-performance lithium ion battery and a preparation method thereof, which are filed by divisional application, wherein the application number of the original application is 201611045014.0, and the application date is 2016, 11 and 24.
Technical Field
The invention belongs to the technical field of nano material applicationIn particular to SnO2carbon/V2O5The graphene composite nano material is applied as a battery cathode material.
Background
The research on the nano material is a leading field in the scientific research nowadays and is a hot spot of research of many scientists all over the world. The curiosity and the aspects which are not known by people of the nanometer material draw extensive attention of people; the research and application of the preparation of the nano material are more hot and difficult points at present and are also key points for developing high technology.
The nano material is a material with a size range of 1-100 nm. With a particle size of less than 100nm, the surface atomic number of the ion is comparable to its in vivo atomic number. The property causes the nanometer material to have the structural and energy state change caused by the effects of small size, large surface, quantum tunnel and the like which are different from the traditional bulk phase material, and generates a plurality of unique physical and chemical properties of light, electricity, magnetism, mechanics and the like. For example, noble metal nanoparticles have particular physical properties and are widely used in catalysis, biomarkers, optoelectronics, information storage, and surface enhanced raman scattering. The special properties make the catalyst have wide application prospect in the fields of photoelectron, micro-electron, nano-electron device preparation, high-performance catalyst and biology. Also due to these potential application values, a lot of research costs have been invested in the development of nanomaterials with the aim of finding new methods for synthesizing nanomaterials and developing nanomaterials with excellent properties.
As one-dimensional materials have unique physical and chemical properties compared with bulk materials and are widely noticed by people, ZnO, Sn0 have been used for the past few years2、In203、Ga203、V205、Ti02The one-dimensional nano material of transition metal oxide is widely researched, widely applied to various fields such as semiconductor preparation, photocatalytic material preparation, photoelectric conversion material, new energy material and the like, and plays an increasingly important role in our life.
The single-crystal one-dimensional material has excellent performance due to the unique property of the one-dimensional material, but sometimes the single-crystal material has defects of the single-crystal material, so that the current researchers are prompted to further research the doping, coating and modification of the one-dimensional nano material on the basis of synthesizing the one-dimensional nano material, and composite materials with different shapes can be prepared on the basis of preparing the one-dimensional material. Therefore, the synthesis of the novel one-dimensional nano composite material with unique appearance, high performance and high efficiency becomes a research hotspot of researchers.
Lithium ion batteries (also called lithium ion secondary batteries or lithium ion storage batteries) have the advantages of high voltage, small volume, light weight, high energy density, good cycle performance, no memory effect and the like, and are considered to be one of the most promising energy sources in the 21 st century. The negative electrode material of the commercial lithium ion battery is generally a graphite material or a material taking carbon as a matrix, such as graphite, carbon nanotubes, carbon nanowires, mesophase microspheres and the like. Although the carbon material has better cycle performance when being used as a negative electrode material of a potassium ion battery, the theoretical capacity of the carbon material is 372mAh/g, and the application of the carbon material in a chemical power source with high energy density requirement is limited. Power type batteries required in fields such as electric vehicles must have high energy density, low cost, and better safety performance. Therefore, with the development of the electronic industry and the automobile field, the theoretical capacity of the carbon material as the negative electrode material of the lithium ion battery cannot meet the requirements of various fields, and the development of the negative electrode material of the lithium ion battery with high specific capacity, high charge and discharge rate and high cycle stability becomes a research hotspot at present.
In order to solve the problems of the lithium ion battery, the doping or coating of the electrode material of the lithium ion battery is usually adopted. In particular, in order to provide mobility and good conductivity to lithium ions, it is common to coat electrode materials of lithium ion batteries with carbon. Chinese patent CN 101212049A uses raw materials according to a certain molar ratio through in-phase reaction, a hydrothermal method andsynthesis of doped Li by sol-gel method3+yFe2-XMeX(P04)3Then mixing the prepared powder with carbon to obtain Li3+yFe2-XMeX(P04)3The specific discharge capacity of the material can reach 122mAh/g under the C/20 multiplying power, and the specific discharge capacity can reach 100mAh/g under the C/2 multiplying power. However, since carbon has limited electron transfer rate and conductivity, the charge and discharge performance of the lithium ion battery at a high rate is still not ideal. Therefore, the development of composite nano materials to meet the development requirements of the existing lithium battery electrode materials is the key point of the future technical research.
Disclosure of Invention
The invention aims to provide a composite nano material for a lithium ion battery, and particularly relates to SnO2carbon/V2O5A graphene composite nano material and a preparation method thereof.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
a preparation method of a composite nano material for a high-performance lithium ion battery comprises the following steps:
（1）SnO2preparation of the/carbon composite material: firstly, weighing 8-12 g of SnCl4·5H2Adding O into 40-60 ml of mixed solvent of absolute ethyl alcohol and water to prepare a solution A; and then adding a carbon source into the solution A to form a uniform and stable solution for later use, wherein the adding amount of the carbon source is 15-80 g, then adding the formed mixed solution into a reaction kettle, adding a certain amount of 0.5mol/L NaOH solution into the reaction kettle, and then placing the reaction kettle into a homogeneous reactor for heat treatment, wherein the heat treatment conditions are as follows: the temperature is 180-200 ℃, and the time is 12-24 hours; then washing and drying the product, and roasting the product for 2 to 10 hours at 450 to 550 ℃ in an inert atmosphere to obtain SnO2A carbon material;
（2）V2O5preparation of graphene composite material: adding 5-10 g of vanadium oxide into 30-40 mL of hydrogen peroxide solution with the mass fraction of 3-6%, and stirring until the vanadium oxide is completely dissolved to generate red peroxovanadic acidAdding 4-6 g of graphite oxide nanosheets into the solution, carrying out ultrasonic treatment for 1-2 h at room temperature, transferring the mixture into a reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction for 8-12 h at 110-120 ℃, carrying out centrifugal separation and washing on the product after the reaction is finished, drying at 80-100 ℃, and finally roasting for 3-5 h at 400-500 ℃ in a nitrogen atmosphere to obtain V2O5A graphene composite material;
（3）SnO2carbon/V2O5Preparing a graphene composite nano material: SnO prepared in step (1)2Carbon/carbon composite and step (2) V2O5Adding the graphene composite material into 20-30mL of absolute ethyl alcohol, performing ultrasonic treatment for 1-2 h at room temperature, adding zirconium balls with the particle size of 0.5-lOmm, wherein the weight ratio of the zirconium balls to the mixture is 1:5, performing ball milling for 12-24 h to form stable suspension, filtering the obtained stable suspension to obtain a filtrate, washing the filtrate, and drying in a vacuum environment to obtain the SnO2carbon/V2O5A graphene composite nanomaterial.
Wherein the nano material is granular, the particle size is 30-100 nm, the pore diameter is 20-80 nm, and the pore volume is 0.6-1.3 cm3A specific surface area of 120 to 280 m/g2/g。
The vanadium oxide in the step (2) is selected from V0 and V02、V203、V205One or more of (a).
The carbon source in the step (1) is one or more of glucose, sucrose, phenolic resin and resorcinol.
The dosage of NaOH in the step (1) is nSnCl4·5H20/nNaOHAddition was carried out in a proportion of = 4.
The preparation method of the graphite oxide nanosheet in the step (2) comprises the following steps: dispersing 0.015-0.072 g of graphite powder into 20-25 mL of concentrated sulfuric acid at 0 ℃ in an ice bath, and adding KMnO under stirring4Added KMnO4The mass of the graphite powder is 3-4 times of that of graphite powder, stirring is carried out for 30-60 minutes, the temperature is raised to 30-35 ℃, 40-50 ml of deionized water is added, and stirring is carried out for 20-30Adding 10-15 ml of H with the mass concentration of 30% into the mixture for minutes2O2And stirring for 5-20 minutes, performing centrifugal separation, and repeatedly washing with HCl solution with the mass concentration of 5%, deionized water and acetone to obtain the graphite oxide nanosheet.
The volume ratio of the absolute ethyl alcohol to the water in the absolute ethyl alcohol/water mixed solvent in the step (1) is 2: 1.
in addition, the invention also claims SnO for the lithium ion battery prepared by the preparation method2carbon/V2O5A graphene composite nanomaterial.
The invention has the technical effects that: the invention realizes SnO for the first time2carbon/V2O5Firstly, a hydrothermal synthesis method is adopted to respectively obtain SnO2Carbon Material and V2O5The SnO is obtained from the graphene composite material by a ball milling method2carbon/V2O5The preparation method of the graphene composite nano material is simple and feasible, a new way is provided for the controllable synthesis of the multi-element nano composite, and the material obtained by the invention is granular, the particle size is 30-100 nm, the pore diameter is 20-80 nm, and the pore volume is 0.6-1.3 cm3A specific surface area of 120 to 280 m/g2Compared with the prior art that the unitary or binary or ternary composite nano material is used as a lithium ion battery material, the quaternary composite nano material is used as a whole, so that the electronic conductivity of the electrode material is improved, particularly the first reversible capacity and the rate performance are obviously improved, the charge-discharge performance of the electrode material under high rate is enhanced, the discharge capacity of the electrode material is increased, the thermal stability of the electrode material is improved, the attenuation of the battery capacity is reduced, the anti-overcharge performance of the battery is improved, and the cycle life of the electrode material is prolonged; the lithium ion battery has the advantages of small absolute volume change in the charging and discharging processes, high electrochemical lithium storage capacity, good stable cycle performance, less energy loss and very wide application prospect.
Drawings
FIG. 1 is an SEM image of a composite nanomaterial of example 3 of the present invention.
Detailed Description
The technical scheme of the invention is further explained by combining the embodiment as follows:
example 1
A preparation method of a composite nano material for a high-performance lithium ion battery comprises the following steps:
（1）SnO2preparation of the/carbon composite material: first, 8g of SnCl was weighed4·5H2Adding O into 40ml of mixed solvent of absolute ethyl alcohol and water to prepare solution A; then adding a carbon source glucose into the solution A to form a uniform and stable solution for standby, wherein the adding amount of the carbon source is 15g, then adding the formed mixed solution into a reaction kettle, adding a certain amount of 0.5mol/L NaOH solution into the reaction kettle, and then placing the reaction kettle into a homogeneous reactor for heat treatment, wherein the heat treatment conditions are as follows: the temperature is 180 ℃ and the time is 12 hours; then washing and drying the product, and roasting the product for 4 hours at 450 ℃ in an inert atmosphere to obtain SnO2A carbon material;
（2）V2O5preparation of graphene composite material: 5g of vanadium oxide V02Adding the mixture into 30mL of hydrogen peroxide solution with the mass fraction of 3%, stirring until vanadium oxide is completely dissolved to generate red peroxyvanadate solution, then adding 4g of graphite oxide nanosheet, carrying out ultrasonic treatment for 1h at room temperature, then transferring the mixture into a reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction for 8h at 110 ℃, after the reaction is finished, carrying out centrifugal separation and washing on the product, drying at 80 ℃, and finally roasting for 3h at 400 ℃ in a nitrogen atmosphere to obtain V2O5A graphene composite material;
（3）SnO2carbon/V2O5Preparing a graphene composite nano material: SnO prepared in step (1)2Carbon/carbon composite and step (2) V2O5Adding the graphene composite material into 20mL of absolute ethyl alcohol, performing ultrasonic treatment for 1h at room temperature, adding zirconium balls with the particle size of 0.5mm, wherein the weight ratio of the zirconium balls to the mixture is 1:5, performing ball milling for 12h to form stable suspension, and filtering the obtained stable suspension to obtain the graphene/graphene composite materialObtaining a filtered substance, washing the filtered substance, and then drying the filtered substance in a vacuum environment to obtain the SnO2carbon/V2O5A graphene composite nanomaterial;
the dosage of NaOH in the step (1) is nSnCl4·5H20/nNaOHAdding in a proportion of = 4; the volume ratio of the absolute ethyl alcohol to the water in the absolute ethyl alcohol/water mixed solvent in the step (1) is 2: 1.
example 2
A preparation method of a composite nano material for a high-performance lithium ion battery comprises the following steps:
（1）SnO2preparation of the/carbon composite material: first, 12g of SnCl was weighed4·5H2Adding O into 60ml of mixed solvent of absolute ethyl alcohol and water to prepare solution A; then adding a carbon source of sucrose into the solution A to form a uniform and stable solution for standby, wherein the adding amount of the carbon source is 80g, then adding the formed mixed solution into a reaction kettle, adding a certain amount of 0.5mol/L NaOH solution into the reaction kettle, and then placing the reaction kettle into a homogeneous reactor for heat treatment, wherein the heat treatment conditions are as follows: the temperature is 200 ℃, and the time is 24 hours; then washing and drying the product, and roasting the product for 2 to 10 hours at 550 ℃ in an inert atmosphere to obtain SnO2A carbon material;
（2）V2O5preparation of graphene composite material: 10g of vanadium oxide V are taken203Adding the mixture into 40mL of hydrogen peroxide solution with the mass fraction of 6%, stirring until vanadium oxide is completely dissolved to generate red peroxyvanadate solution, then adding 6g of graphite oxide nanosheet, carrying out ultrasonic treatment at room temperature for 2h, then transferring the mixture into a reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction at 120 ℃ for 12h, after the reaction is finished, carrying out centrifugal separation and washing on the product, drying at 100 ℃, and finally roasting at 500 ℃ for 5h in nitrogen atmosphere to obtain V2O5A graphene composite material;
（3）SnO2carbon/V2O5Preparing a graphene composite nano material: SnO prepared in step (1)2Carbon/carbon compositeMaterials and step (2) V2O5Adding the graphene composite material into 30mL of absolute ethyl alcohol, performing ultrasonic treatment for 2h at room temperature, adding zirconium balls with the particle size of lOmm, wherein the weight ratio of the zirconium balls to the mixture is 1:5, performing ball milling for 24 h to form stable suspension, filtering the obtained stable suspension to obtain a filtrate, washing the filtrate, and drying in a vacuum environment to obtain the SnO2carbon/V2O5A graphene composite nanomaterial;
the dosage of NaOH in the step (1) is nSnCl4·5H20/nNaOHAdding in a proportion of = 4; the volume ratio of the absolute ethyl alcohol to the water in the absolute ethyl alcohol/water mixed solvent in the step (1) is 2: 1.
example 3
A preparation method of a composite nano material for a high-performance lithium ion battery comprises the following steps:
（1）SnO2preparation of the/carbon composite material: first, 10g of SnCl was weighed4·5H2Adding O into 50ml of mixed solvent of absolute ethyl alcohol and water to prepare solution A; then adding a carbon source phenolic resin into the solution A to form a uniform and stable solution for standby, wherein the adding amount of the carbon source is 45g, then adding the formed mixed solution into a reaction kettle, adding a certain amount of 0.5mol/L NaOH solution into the reaction kettle, and then placing the reaction kettle into a homogeneous reactor for heat treatment, wherein the heat treatment conditions are as follows: the temperature is 190 ℃ and the time is 18 hours; then washing and drying the product, and roasting the product for 6 hours at 500 ℃ in an inert atmosphere to obtain SnO2A carbon material;
（2）V2O5preparation of graphene composite material: taking 7g of vanadium oxide V205Adding the mixture into 35mL of hydrogen peroxide solution with the mass fraction of 4%, stirring until vanadium oxide is completely dissolved to generate red peroxyvanadate solution, then adding 5g of graphite oxide nanosheet, carrying out ultrasonic treatment at room temperature for 1.5h, then transferring the mixture into a reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction at 115 ℃ for 10h, after the reaction is finished, carrying out centrifugal separation and washing on the product, and drying at 90 DEG CDrying, and roasting at 450 deg.C in nitrogen atmosphere for 4 hr to obtain V2O5A graphene composite material;
（3）SnO2carbon/V2O5Preparing a graphene composite nano material: SnO prepared in step (1)2Carbon/carbon composite and step (2) V2O5Adding the graphene composite material into 25mL of absolute ethyl alcohol, performing ultrasonic treatment for 1.5h at room temperature, adding zirconium balls with the particle size of 5mm, wherein the weight ratio of the zirconium balls to the mixture is 1:5, performing ball milling for 18 h to form stable suspension, filtering the obtained stable suspension to obtain a filtrate, washing the filtrate, and drying in a vacuum environment to obtain the SnO2carbon/V2O5A graphene composite nanomaterial;
the dosage of NaOH in the step (1) is nSnCl4·5H20/nNaOHAdding in a proportion of = 4; the volume ratio of the absolute ethyl alcohol to the water in the absolute ethyl alcohol/water mixed solvent in the step (1) is 2: 1.
example 4
A preparation method of a composite nano material for a high-performance lithium ion battery comprises the following steps:
（1）SnO2preparation of the/carbon composite material: first, 9g of SnCl was weighed4·5H2Adding O into 43ml of mixed solvent of absolute ethyl alcohol and water to prepare solution A; then adding resorcinol as a carbon source into the solution A to form a uniform and stable solution for standby, wherein the adding amount of the carbon source is 50g, then adding the formed mixed solution into a reaction kettle, adding a certain amount of 0.5mol/L NaOH solution into the reaction kettle, and then placing the reaction kettle into a homogeneous reactor for heat treatment, wherein the heat treatment conditions are as follows: the temperature is 190 ℃ and the time is 20 hours; then washing and drying the product, and roasting the product for 8 hours at 480 ℃ in an inert atmosphere to obtain SnO2A carbon material;
（2）V2O5preparation of graphene composite material: adding 7g of vanadium oxide V0 into 36mL of hydrogen peroxide solution with the mass fraction of 5%, and stirring until the vanadium oxide is completely dissolved to generate redAdding 5g of graphite oxide nano-sheets into a colored peroxyvanadate solution, carrying out ultrasonic treatment for 1.2h at room temperature, transferring the mixture into a reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction for 10h at 115 ℃, carrying out centrifugal separation and washing on a product after the reaction is finished, drying at 90 ℃, and finally roasting for 3.5h at 420 ℃ in a nitrogen atmosphere to obtain V2O5A graphene composite material;
（3）SnO2carbon/V2O5Preparing a graphene composite nano material: SnO prepared in step (1)2Carbon/carbon composite and step (2) V2O5Adding the graphene composite material into 26mL of absolute ethyl alcohol, performing ultrasonic treatment for 1.2h at room temperature, adding zirconium balls with the particle size of 6mm, wherein the weight ratio of the zirconium balls to the mixture is 1:5, performing ball milling for 18 h to form stable suspension, filtering the obtained stable suspension to obtain a filtrate, washing the filtrate, and drying in a vacuum environment to obtain the SnO2carbon/V2O5A graphene composite nanomaterial;
the dosage of NaOH in the step (1) is nSnCl4·5H20/nNaOHAdding in a proportion of = 4; the volume ratio of the absolute ethyl alcohol to the water in the absolute ethyl alcohol/water mixed solvent in the step (1) is 2: 1.
example 5
And (3) carrying out application test by taking the silicon dioxide/vanadium pentoxide/carbon composite nano material obtained in the embodiment 3 as a battery negative electrode material.
SnO prepared in example 32carbon/V2O5The graphene composite nano material is used as a lithium ion battery cathode material, an electrode is prepared by adopting a coating method, and raw materials are SnO (stannic oxide) in mass ratio2carbon/V2O5Graphene composite nanomaterial: acetylene black: CMC = 70: 20: 15, preparing a negative electrode slurry by using water as a solvent, coating the negative electrode slurry on copper foil, fully drying and tabletting, and slicing to obtain a negative electrode sheet with the diameter of 13 mm. The battery negative plate is a lithium plate. In an inert gas-protected glove box, l.2mol/L LiPF6/EC/DMC/DEC (1:1:1) is used as electrolyte, Celgerd2300 is used as diaphragm, and the components are assembledA 2320-type button cell is formed. Testing an instrument: a charge and discharge instrument (Land); bruker D8-X-ray diffractometer. SnO on a blue tester2carbon/V2O5The charge and discharge performance of the graphene composite nano material battery is tested, and the charge and discharge conditions are as follows: SnO within the voltage range of 0.02-3.0 and at the current density of 100mA/g2carbon/V2O5The initial discharge capacity of the/graphene composite nano material is 1374 and 1225mAh/g respectively, and the initial discharge capacity of the/graphene composite nano material can be stabilized at 930 and 788mAh/g respectively after 50 cycles. The material is subjected to rate performance test under different current densities, SnO2carbon/V2O5The graphene composite nano material has very good reversibility, stability and recoverability.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (4)
1. SnO (stannic oxide)2carbon/V2O5The application of the graphene composite nano material as a battery cathode material is characterized in that SnO is2carbon/V2O5The graphene composite nano material is used as a lithium ion battery cathode material, an electrode is prepared by adopting a coating method, and raw materials are SnO (stannic oxide) in mass ratio2carbon/V2O5Graphene composite nanomaterial: acetylene black: CMC = 70: 20: 15, preparing a negative electrode slurry by taking water as a solvent, coating the negative electrode slurry on copper foil, fully drying and tabletting, and slicing to obtain a negative electrode sheet with the diameter of 13 mm; assembling a lithium sheet for a battery negative plate into a 2320-type button battery in a glove box protected by inert gas by using l.2mol/L LiPF6/EC/DMC/DEC (1:1:1) as electrolyte and Celgerd2300 as a diaphragm; testing an instrument: a charge and discharge instrument (Land); BrukerD 8-X-rayA diffractometer; SnO on a blue tester2carbon/V2O5The charge and discharge performance of the graphene composite nano material battery is tested, and the charge and discharge conditions are as follows: SnO within the voltage range of 0.02-3.0 and at the current density of 100mA/g2carbon/V2O5The initial discharge capacities of the graphene composite nano material are 1374 mAh/g and 1225mAh/g respectively, the initial discharge capacities can be stabilized at 930 mAh/g and 788mAh/g respectively after 50-circle circulation, the material is subjected to rate capability test under different current densities, and SnO2carbon/V2O5The graphene composite nano material has very good reversibility, stability and recoverability;
the preparation method of the composite nano material comprises the following steps:
（1）SnO2preparation of the/carbon composite material: first, 10g of SnCl was weighed45H2O is added into 50ml of mixed solvent of absolute ethyl alcohol and water to prepare solution A; then adding a carbon source phenolic resin into the solution A to form a uniform and stable solution for standby, wherein the adding amount of the carbon source is 45g, then adding the formed mixed solution into a reaction kettle, adding a certain amount of 0.5mol/L NaOH solution into the reaction kettle, and then placing the reaction kettle into a homogeneous reactor for heat treatment, wherein the heat treatment conditions are as follows: the temperature is 190 ℃ and the time is 18 hours; then washing and drying the product, and roasting the product for 6 hours at 500 ℃ in an inert atmosphere to obtain SnO2A carbon material;
（2）V2O5preparation of graphene composite material: taking 7g of vanadium oxide V2O5Adding the mixture into 35mL of hydrogen peroxide solution with the mass fraction of 4%, stirring until vanadium oxide is completely dissolved to generate red peroxyvanadate solution, then adding 5g of graphite oxide nanosheet, carrying out ultrasonic treatment for 1.5h at room temperature, then transferring the mixture into a reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction for 10h at 115 ℃, after the reaction is finished, carrying out centrifugal separation and washing on the product, drying at 90 ℃, and finally roasting for 4h at 450 ℃ in a nitrogen atmosphere to obtain V2O5A graphene composite material;
（3）SnO2carbon/V2O5Graphene complexesPreparing a nano material: SnO prepared in step (1)2Carbon/carbon composite and step (2) V2O5Adding the graphene composite material into 25mL of absolute ethyl alcohol, performing ultrasonic treatment for 1.5h at room temperature, adding zirconium balls with the particle size of 5mm, wherein the weight ratio of the zirconium balls to the mixture is 1:5, performing ball milling for 18 h to form stable suspension, filtering the obtained stable suspension to obtain a filtrate, washing the filtrate, and drying in a vacuum environment to obtain the SnO2carbon/V2O5A graphene composite nanomaterial;
wherein the nano material is granular, the particle size is 30-100 nm, the pore diameter is 20-80 nm, and the pore volume is 0.6-1.3 cm3A specific surface area of 120 to 280 m/g2/g。
2. The use of the composite nanomaterial of claim 1 as a battery negative electrode material, wherein the amount of NaOH in step (1) is nSnCl4· 5H20/nNaOHAddition was carried out in a proportion of = 4.
3. The application of the composite nano material as a battery negative electrode material according to claim 1, wherein the preparation method of the graphite oxide nano sheet in the step (2) comprises the following steps: dispersing 0.015-0.072 g of graphite powder into 20-25 mL of concentrated sulfuric acid at 0 ℃ in an ice bath, and adding KMnO under stirring4Added KMnO4Stirring for 30-60 minutes, raising the temperature to 30-35 ℃, adding 40-50 ml of deionized water, stirring for 20-30 minutes, adding 10-15 ml of H with the mass concentration of 30%2O2And stirring for 5-20 minutes, performing centrifugal separation, and repeatedly washing with HCl solution with the mass concentration of 5%, deionized water and acetone to obtain the graphite oxide nanosheet.
4. The application of the composite nano material as a battery negative electrode material according to claim 1, wherein the volume ratio of the absolute ethyl alcohol to the water in the absolute ethyl alcohol/water mixed solvent in the step (1) is 2: 1.
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