CN111554905B - Preparation method, product and application of zinc oxide-based carbon composite nano material - Google Patents
Preparation method, product and application of zinc oxide-based carbon composite nano material Download PDFInfo
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Abstract
The invention discloses a preparation method, a product and application of a zinc oxide-based carbon composite nano material. The method comprises the following steps: (1) uniformly dispersing basic zinc carbonate particles in deionized water to prepare a basic zinc carbonate dispersion liquid with the concentration of 15-25 mg/ml; (2) adding a pH value buffer solution, adjusting the pH value to be 7.5-8.5, adding enough water-soluble polymer monomer for forming a carbon layer, performing polymerization reaction or polycondensation reaction to wrap a carbon crystal precursor polymer on the surface of basic zinc carbonate particles, and performing solid-liquid separation, cleaning and drying; (3) calcining and annealing under an oxygen-free atmosphere to obtain the zinc oxide-based carbon composite nanomaterial. The prepared product is hollow amorphous carbon sphere confinement zinc oxide nano-particles and can be applied to preparation of lithium ion battery cathode materials. The method has the advantages of mild reaction conditions, simple steps, high reactant yield, no need of introducing any sacrificial template, reduction of the production cost required by the template removing process, high yield and suitability for large-scale industrial production.
Description
Technical Field
The invention belongs to the field of nano material preparation, and particularly relates to a preparation method, a product and application of a zinc oxide-based carbon composite nano material.
Background
With the reduction of global non-renewable resources and increasingly severe environmental issues, the development of energy conversion and reserve materials is not slow. Especially in recent years the development of consumer electronics, space technology and military electronics has increased the need for small discrete mobile power supplies. Therefore, in the past decades, the design and development of Lithium Ion Batteries (LIBs) with high energy density, coulombic efficiency, cycle count, and cycle stability has been a matter of great interest. Breakthrough in the aspect of electrode materials is the key to successful development of next-generation lithium ion batteries, and a great deal of research work is focused on finding novel materials and diversified synthetic methods at present, and developing various new functional composite materials capable of improving the energy density and stability of electrodes.
Among the numerous alternatives to conventional and commercial cathode materials, ZnO is due to its high theoretical capacity (987mA h g)-1) Low cost and high natural reserve, and becomes a lithium ion battery cathode material with great commercial prospect. Even so, like other metal oxides, ZnO is inherently poor in conductivity, and undergoes volume expansion during charge-discharge cycles, which is disadvantageous to stability, thereby limiting its energy storage performance. The fact proves that the ZnO-based composite electrode can obviously improve the specific capacity, the coulombic efficiency and the cycling stability, and is an effective method for improving the electricity storage performance. However, significant challenges remain in the design and fabrication of ZnO-based composite electrode materials. To date, a number of methods have been used to prepare ZnO/carbon composite electrode materials, such as: MOF derivative carbonization, nanoparticle assembly, atomic layer deposition, solvothermal methods, electrostatic assembly, and the like. The reaction raw materials required for the carbonization of MOF derivatives are expensive; the poor consistency among batches needs to be strictly controlled under the nano-particle assembly reaction conditions, so that the yield is not high; the atomic layer deposition reaction conditions are harsh, the required equipment is expensive, and the method is not suitable for large-scale industrial production; the ZnO/carbon composite nano material prepared by the solvothermal method has incomplete appearance, incomplete carbon coverage and unstable performance, and is introduced to the surfaceThe performance is affected by the impurities of the activating agent, and the cost is increased by adding the impurity removal step; the ZnO/carbon composite nano material prepared by the electrostatic assembly method also has the problems of poor consistency, low yield and increased cost.
In short, the total cost of the electrode material prepared by the current preparation method of the ZnO-based composite material is higher for various reasons, and the electrode material is not suitable for industrial large-scale production.
Disclosure of Invention
Aiming at the defects or improvement requirements of the prior art, the invention provides a preparation method, a product and application of a zinc oxide-based carbon composite nano material, aiming at adopting raw materials with wide sources and low cost to uniformly embed ZnO nano particles into hollow amorphous carbon spheres through mild controllable room-temperature sol-gel reaction and medium-temperature thermal decomposition reaction, thereby solving the technical problems of high preparation cost, low yield or unsuitability for large-scale production of the conventional ZnO-based composite material.
In order to achieve the above objects, according to one aspect of the present invention, there is provided a method for preparing a zinc oxide-based carbon composite nanomaterial, comprising the steps of:
(1) uniformly dispersing basic zinc carbonate particles in deionized water to prepare a basic zinc carbonate dispersion liquid with the concentration of 15-25 mg/ml;
(2) adding a pH value buffer solution into the basic zinc carbonate dispersion liquid prepared in the step (1), adjusting the pH value to be 7.5-8.5, adding enough water-soluble polymer monomer for forming a carbon layer, performing polymerization reaction or polycondensation reaction to wrap a carbon-containing precursor polymer on the surface of basic zinc carbonate particles, and performing solid-liquid separation, cleaning and drying to obtain the basic zinc carbonate particles wrapped with amorphous carbon precursor polymers on the surface;
(3) and (3) calcining and annealing the basic zinc carbonate particles coated with the carbon crystal precursor polymer on the surface, which are obtained in the step (2), in an oxygen-free atmosphere to obtain the zinc oxide-based carbon composite nanomaterial.
Preferably, in the preparation method of the zinc oxide-based carbon composite nanomaterial, the basic zinc carbonate particles have a particle size of 1-2 microns, and are preferably obtained by performing a sol-gel reaction on zinc acetate and oxalic acid.
Preferably, in the preparation method of the zinc oxide-based carbon composite nanomaterial, the basic zinc carbonate particles are specifically prepared by the following steps:
(A) mixing oxalic acid solution with the concentration of 0.12-0.17mol/L and zinc acetate solution with the concentration of 0.8-1.2mol/L according to the volume ratio of 1:1, and carrying out sol-gel reaction to obtain a reaction product; the concentration and the proportion of reactants are controlled, so that the particle size of the final basic zinc carbonate particles can be effectively controlled, and the basic zinc carbonate particles with the particle size within a proper range can be obtained and directly applied to the preparation of the zinc oxide-based carbon composite nano material;
(B) and (C) cleaning and drying the reaction product obtained in the step (A) to obtain the basic zinc carbonate particles with the particle size of 1-2 microns.
Preferably, in the zinc oxide-based carbon composite nanomaterial preparation method, the water-soluble polymer monomer for forming the carbon layer is dopamine or glucose.
Preferably, in the preparation method of the zinc oxide-based carbon composite nanomaterial, the calcination temperature is 600-700 ℃, the calcination time is 5-7 hours, and the annealing rate is 2-10 ℃/min until the carbonization is complete.
According to another aspect of the present invention, there is provided a zinc oxide-based carbon composite nanomaterial, which is hollow amorphous carbon sphere confinement zinc oxide nanoparticles having an aggregated ZnO nanoparticle core and hollow amorphous carbon spheres wrapping the ZnO nanoparticle core.
Preferably, the zinc oxide-based carbon composite nanomaterial, wherein the ZnO nanoparticles are spherical and have an average diameter of between 100nm and 150 nm.
Preferably, the zinc oxide-based carbon composite nanomaterial is characterized in that the hollow amorphous carbon spheres wrapping the ZnO nanoparticles are spherical shell-shaped, and the average spherical shell thickness is between 80nm and 100 nm.
Preferably, the zinc oxide-based carbon composite nanomaterial is prepared according to the preparation method of the zinc oxide-based carbon composite nanomaterial provided by the invention.
According to another aspect of the invention, the invention provides an application of the zinc oxide-based carbon composite nano material in preparation of a negative electrode material of a lithium ion battery.
Generally, compared with the prior art, the technical scheme of the invention has the advantages of mild reaction conditions, simple steps, high reactant yield, no need of introducing any sacrificial template, reduction of the production cost required by the template removing process, high yield and suitability for large-scale industrial production.
Drawings
FIG. 1 is a transmission electron microscope photograph of hollow amorphous carbon sphere confinement zinc oxide nano-materials magnified with different magnifications;
FIG. 2 is a specific surface area adsorption-desorption isotherm of zinc oxide nanoparticles (ZnO) and hollow amorphous carbon sphere confinement zinc oxide nanoparticles (ZnO @ AC);
FIG. 3 is a Raman spectrum of zinc oxide nanoparticles (ZnO) and hollow amorphous carbon sphere-confined zinc oxide nanoparticles (ZnO @ AC);
fig. 4 is a long cycle test and a rate performance test (c) at 0.1 rate (a), 1 rate (b) of zinc oxide nanoparticles and hollow amorphous carbon sphere confinement zinc oxide nanoparticles.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The preparation method of the zinc oxide-based carbon composite nano material provided by the invention comprises the following steps:
(1) uniformly dispersing basic zinc carbonate particles in deionized water to prepare a basic zinc carbonate dispersion liquid with the concentration of 15-25 mg/ml; the particle size of the basic zinc carbonate particles is 1-2 microns, the basic zinc carbonate particles are preferably obtained by performing a sol-gel reaction on zinc acetate and oxalic acid, and the specific preparation steps of the basic zinc carbonate particles are as follows:
(A) mixing oxalic acid solution with the concentration of 0.12-0.17mol/L and zinc acetate solution with the concentration of 0.8-1.2mol/L according to the volume ratio of 1:1, and carrying out sol-gel reaction to obtain a reaction product; the concentration and the proportion of reactants are controlled, so that the particle size of the final basic zinc carbonate particles can be effectively controlled, and the basic zinc carbonate particles with the particle size within a proper range can be obtained and directly applied to the preparation of the zinc oxide-based carbon composite nano material; the zinc carbonate does not need a special impurity removal process, does not influence the performance of the final zinc oxide-based carbon composite nano material, and is suitable for being used as an electrode material, so that the raw material cost and the process cost are greatly reduced.
(B) Washing the reaction product obtained in the step (A) to obtain basic zinc carbonate particles with the particle size of 1-2 microns; the reaction product obtained in step (a) is preferably washed and then dried to accurately weigh the basic zinc carbonate particles.
(2) Adding a pH value buffer solution into the basic zinc carbonate dispersion liquid prepared in the step (1), adjusting the pH value to be 7.5-8.5, adding enough water-soluble polymer monomer for forming a carbon layer, enabling the mass ratio of the basic zinc carbonate to the mass of carbon elements in the monomer to be 1: 0.4-1: 0.8, enabling the monomer to perform polymerization reaction or polycondensation reaction to wrap a carbon-containing precursor polymer on the surface of basic zinc carbonate particles, and performing solid-liquid separation, cleaning and drying to obtain basic zinc carbonate particles wrapped with amorphous carbon precursor polymers on the surface; the water-soluble polymer monomer for forming the carbon layer is preferably dopamine, glucose;
(3) calcining, carbonizing and annealing the basic zinc carbonate particles coated with the amorphous carbon precursor polymer on the surface, which are obtained in the step (2), in an oxygen-free atmosphere to obtain the zinc oxide-based carbon composite nano material; the calcination temperature is 600-700 ℃, the calcination is carried out until the carbonization is completed, the calcination time is preferably 5-7 hours, and the annealing speed is 2-10 ℃/min.
Compared with the existing preparation method of the zinc oxide-based carbon composite nanomaterial, the preparation method of the zinc oxide-based carbon composite nanomaterial has the advantages that the reaction condition is mild, the process link is simple, the raw materials are easy to obtain, the energy consumption cost, the labor cost and the raw material cost in the preparation process are saved, and the total cost for preparing the zinc oxide-based carbon composite nanomaterial is greatly reduced; meanwhile, the preparation method of the zinc oxide-based carbon composite nanomaterial provided by the invention has the advantages of high reactant yield, good product consistency and regular appearance, is high in yield when used for preparing electrode materials, and is suitable for large-scale industrial production.
The zinc oxide-based carbon composite nanomaterial provided by the invention is hollow amorphous carbon sphere confinement zinc oxide nanoparticles, and the hollow amorphous carbon sphere confinement zinc oxide nanoparticles are provided with an aggregation type ZnO nanoparticle inner core and hollow amorphous carbon spheres wrapping the ZnO nanoparticle inner core; the ZnO nanoparticles are spherical, and the average diameter of the ZnO nanoparticles is between 100nm and 150 nm; the hollow amorphous carbon spheres wrapping the ZnO nanoparticles are spherical shell-shaped, and the average spherical shell thickness is between 80nm and 100 nm.
After 50 times of circulation, the zinc oxide-based carbon composite nano material still maintains 475mAh g under the current density of 0.1A g-1-1The capacity of (CE is 98.8%) is 8.3 times (57 mAh g) of pure zinc oxide nano-particles-1) At 0.1 to 20A g-1The current density of the zinc oxide-based carbon composite nanomaterial is tested for multiplying power performance, the discharge capacity of the zinc oxide-based carbon composite nanomaterial provided by the invention is always kept 8-10 times of the pure zinc oxide capacity, and the zinc oxide-based carbon composite nanomaterial can be applied to preparation of a lithium ion battery cathode material.
The following are examples:
example 1
A hollow amorphous carbon sphere confinement zinc oxide nano-material comprises ZnO nano-particles and hollow amorphous carbon spheres wrapping the ZnO nano-particles.
The ZnO nanoparticles are spherical and have an average diameter of 100nm to 150 nm.
The hollow amorphous carbon spheres wrapping the ZnO nanoparticles are spherical shell-shaped, and the average spherical shell thickness is between 80nm and 100 nm.
The preparation method of the hollow amorphous carbon sphere confinement zinc oxide nano material comprises the following steps: the preparation method of the hollow amorphous carbon sphere confinement zinc oxide nano material comprises the following steps:
(1) uniformly dispersing basic zinc carbonate particles in deionized water to prepare 50ml of basic zinc carbonate dispersion liquid with the concentration of 15-25 mg/ml;
the basic zinc carbonate particles are prepared according to the following method:
(A) uniformly dispersing oxalic acid in deionized water to prepare 100ml of oxalic acid aqueous solution, wherein the concentration of the oxalic acid aqueous solution is 0.12-0.17 mol/L;
(B) adding 100ml of zinc acetate aqueous solution with the concentration of 0.1mol/L into the basic zinc carbonate dispersion liquid prepared in the step (A), and stirring for 24 hours at room temperature;
(C) and (3) centrifugally washing the product obtained in the step (B) with deionized water for 3-5 times, and drying at 60 ℃ for 12 hours to obtain the basic zinc carbonate particles.
(2) Adding 50ml of Tris buffer solution with the concentration of 10mmol/L and 1g of dopamine powder into the basic zinc carbonate dispersion liquid prepared in the step (1) in sequence, and stirring for 24 hours at room temperature; when dopamine is selected as a carbon-containing polymer monomer, the mass ratio of the basic zinc carbonate to the dopamine is 1: 0.8-1: 1.2.
(3) Centrifugally cleaning the product obtained in the step (2) with deionized water for 5-7 times, and drying at 60 ℃ for 12 hours to obtain polydopamine-coated basic zinc carbonate particles;
(4) placing the polydopamine-coated basic zinc carbonate particles obtained in the step (3) in N2Annealing at 600 ℃ for 3 hours in gas to obtain the hollow amorphous carbon sphere confinement zinc oxide nano material.
Imaging the product by a transmission electron microscope, as shown in figure 1, judging that the structure of the hollow amorphous carbon sphere confinement zinc oxide nano material is consistent with that of a target product. The nitrogen adsorption-desorption isotherms and pore size distributions of the samples were observed by Brunauer-Emmett-teller (bet) measurements. As shown in FIG. 2, the pure ZnO NPs have a low porosity and a specific surface area of 23.445m2 g-1Pore volume of 0.3918m3 g-1. For the hollow amorphous carbon sphere confinement zinc oxide nano material, the specific surface area and the pore volume respectively reach 96.759m2 g-1And 0.5711m3 g-1Much higher than the specific surface area and pore volume of pure ZnO. The Raman spectra of the pure ZnO and hollow amorphous carbon sphere confinement zinc oxide nano-material are shown in figure 3. At 331cm-1、663cm-1、436cm-1、541cm-1、1098cm-1Respectively finding out the characteristic Raman signals of the wurtzite ZnO, and dividing the Raman signals into a group theoryThe results of the analyses were consistent. About 1348cm was observed in the hollow amorphous carbon sphere confinement zinc oxide nanomaterial-1And 1592cm-1Two strong peaks at (a) which belong to the D and G bands of the carbon material, respectively, these two typical modes confirm the presence and partial graphitization of the carbon.
The hollow amorphous carbon sphere confinement zinc oxide nano material described in the embodiment 1 is applied as a lithium ion battery negative electrode material, so that the lithium storage performance of the hollow amorphous carbon sphere confinement zinc oxide nano material is evaluated. The experimental procedure was as follows:
the hollow amorphous carbon sphere confinement zinc oxide nano material prepared in the embodiment, conductive carbon black and a polyvinylidene fluoride (PVDF) adhesive are weighed and placed in an agate mortar to be ground into paste according to the mass percentage of 8:1:1, and then the uniformly mixed paste is uniformly coated on a clean copper foil by using a Doctor scraper technology. And (5) placing the mixture in a blowing drying box with the temperature of 80 ℃ for drying for 4 hours, and taking out the mixture. Finally, the dried pole pieces are cut and sliced into round pieces with the diameter of 16mm, and the mass of active substances of each round piece is about 2.3mg/cm-3And vacuum drying at 120 ℃ for 12 hours for later use. Pure metal lithium sheets are used as a positive electrode and a reference electrode, and 1mol/L Li PF6[ EC (ethylene carbonate) -DMC (1, 2-dimethyl carbonate) dissolved in the ratio of 1:1 by volume)]And (3) taking a polypropylene porous membrane Celgard2320 as a diaphragm as an electrolyte, assembling the components in a vacuum glove box filled with high-purity argon (the content of water and oxygen is lower than 1ppm), and packaging the components to form the CR2025 button cell. And taking out the packaged battery, wiping off the residual electrolyte on the surface of the battery, standing for 12 hours, and then carrying out electrochemical performance tests such as constant-current charge-discharge performance, cyclic voltammetry, long cycle, different-multiplying-power cycle and the like. As shown in fig. 4a, the negative electrode of the hollow amorphous carbon sphere confinement zinc oxide nano material is subjected to 50 cycles and then is subjected to 0.1A g-1At a current density of 475mAh g-1The capacity of (CE is 98.8%) is 8.3 times of pure zinc oxide nano-particles
Even at 1A g-1Under high current density (as shown in figure 4 b), the hollow amorphous carbon sphere confines the zinc oxide nano-material cathodeCan still provide 338mAh g after 200 cycles-1Capacity of (CE: 99.2%), which is 10 times that of pure ZnO
FIG. 4c shows a cross-section from 0.1 to 20A g-1The cathode of the zinc oxide nano material with circulating pure ZnO and hollow amorphous carbon spheres confined in various current densities has multiplying power performance. It can be seen that the variable current of the hollow amorphous carbon sphere confinement zinc oxide nano-material negative electrode is respectively 0.1, 0.2, 0.5, 1,2, 5, 10 and 20A g -1570, 436, 341, 289, 250, 160, 106 and 87mAh g can be provided-1Stable reversible capacity of (2). When the current is reduced to 0.1A g-1When the method is used, 511mAh g is recorded in the hollow amorphous carbon sphere confinement zinc oxide nano material cathode-1Is almost 90% of the capacity previously obtained at the same rate.
Example 2
A hollow amorphous carbon sphere confinement zinc oxide nano-material comprises ZnO nano-particles and hollow amorphous carbon spheres wrapping the ZnO nano-particles.
The ZnO nanoparticles are spherical and have an average diameter of 100nm to 150 nm.
The hollow amorphous carbon spheres wrapping the ZnO nanoparticles are spherical shell-shaped, and the average spherical shell thickness is between 80nm and 100 nm.
The preparation method of the hollow amorphous carbon sphere confinement zinc oxide nano material comprises the following steps: the preparation method of the hollow amorphous carbon sphere confinement zinc oxide nano material comprises the following steps:
(1) uniformly dispersing basic zinc carbonate particles in deionized water to prepare 50ml of basic zinc carbonate dispersion liquid with the concentration of 15-25 mg/ml;
the basic zinc carbonate particles are prepared according to the following method:
(A) uniformly dispersing oxalic acid in deionized water to prepare 100ml of oxalic acid aqueous solution, wherein the concentration of the oxalic acid aqueous solution is 0.12-0.17 mol/L;
(B) adding 100ml of zinc acetate aqueous solution with the concentration of 0.1mol/L into the basic zinc carbonate dispersion liquid prepared in the step (A), and stirring for 24 hours at room temperature;
(C) and (3) centrifugally washing the product obtained in the step (B) with deionized water for 3-5 times, and drying at 60 ℃ for 12 hours to obtain the basic zinc carbonate particles.
(2) 50ml of Tris buffer solution with the concentration of 10mmol/L is added into the solution according to the mass ratio of 1:1 adding glucose, stirring uniformly, placing in a hydrothermal reaction kettle, and keeping the temperature at 180 ℃ for 6-8 hours.
(3) Centrifugally cleaning the product obtained in the step (2) with deionized water for 5-7 times, and drying at 60 ℃ for 12 hours to obtain polydextrose-coated basic zinc carbonate particles;
(4) placing the polydopamine-coated basic zinc carbonate particles obtained in the step (3) in N2Annealing at 600 ℃ for 3 hours in gas to obtain the hollow amorphous carbon sphere confinement zinc oxide nano material.
The electrical property is equivalent to that of the hollow amorphous carbon sphere confinement zinc oxide nano material prepared in the example 1.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (12)
1. A preparation method of a zinc oxide-based carbon composite nano material is characterized by comprising the following steps:
(1) uniformly dispersing basic zinc carbonate particles in deionized water to prepare a basic zinc carbonate dispersion liquid with the concentration of 15-25 mg/ml;
(2) adding a pH value buffer solution into the basic zinc carbonate dispersion liquid prepared in the step (1), adjusting the pH value to be 7.5-8.5, adding enough water-soluble polymer monomer for forming a carbon layer, enabling the mass ratio of the basic zinc carbonate to the mass of carbon elements in the monomer to be 1: 0.4-1: 0.8, carrying out polymerization reaction or polycondensation reaction to wrap carbon-containing precursor polymer on the surface of basic zinc carbonate particles, and carrying out solid-liquid separation, cleaning and drying to obtain basic zinc carbonate particles wrapped with amorphous carbon precursor polymer on the surface;
(3) and (3) calcining and annealing the basic zinc carbonate particles coated with the amorphous carbon precursor polymer on the surface, which are obtained in the step (2), in an oxygen-free atmosphere to obtain the zinc oxide-based carbon composite nanomaterial.
2. The method of preparing zinc oxide-based carbon composite nanomaterial according to claim 1, wherein the basic zinc carbonate particles have a particle size of between 1 and 2 μm.
3. The method for preparing zinc oxide-based carbon composite nanomaterial according to claim 1, wherein the basic zinc carbonate particles are obtained by performing a sol-gel reaction of zinc acetate and oxalic acid.
4. The method for preparing the zinc oxide-based carbon composite nanomaterial according to claim 1, wherein the basic zinc carbonate particles are prepared by the specific steps of:
(A) mixing oxalic acid solution with the concentration of 0.12-0.17mol/L and zinc acetate solution with the concentration of 0.8-1.2mol/L according to the volume ratio of 1:1, and carrying out sol-gel reaction to obtain a reaction product; the concentration and the proportion of reactants are controlled, so that the particle size of the final basic zinc carbonate particles can be effectively controlled, and the basic zinc carbonate particles with the particle size within a proper range can be obtained and directly applied to the preparation of the zinc oxide-based carbon composite nano material;
(B) and (C) cleaning and drying the reaction product obtained in the step (A) to obtain the basic zinc carbonate particles with the particle size of 1-2 microns.
5. The method of preparing a zinc oxide-based carbon composite nanomaterial according to claim 1, wherein the water-soluble polymer monomer for forming the carbon layer is dopamine or glucose.
6. The method for preparing zinc oxide-based carbon composite nanomaterial as defined in claim 1, wherein the calcination temperature is 600-700 ℃ and the calcination is carried out until the carbonization is completed.
7. The method for preparing a zinc oxide-based carbon composite nanomaterial according to claim 6, wherein the calcination time is 5 to 7 hours.
8. The method for preparing a zinc oxide-based carbon composite nanomaterial according to claim 1, wherein the annealing rate is 2 to 10 ℃/min.
9. The zinc oxide-based carbon composite nanomaterial is characterized in that the zinc oxide nanomaterial is hollow amorphous carbon sphere confinement zinc oxide nanoparticles, and the zinc oxide nanoparticle confinement zinc oxide nanoparticles are provided with an aggregation type ZnO nanoparticle inner core and hollow amorphous carbon spheres wrapping the ZnO nanoparticle inner core; the hollow amorphous carbon spheres wrapping the ZnO nanoparticles are spherical shell-shaped, and the average spherical shell thickness is between 80nm and 100 nm.
10. The zinc oxide-based carbon composite nanomaterial of claim 9, wherein the ZnO nanoparticles are spherical and have an average diameter of between 100nm and 150 nm.
11. The zinc oxide-based carbon composite nanomaterial of claim 9, characterized by being produced according to the zinc oxide-based carbon composite nanomaterial production method of any one of claims 1 to 5.
12. Use of the zinc oxide-based carbon composite nanomaterial according to any one of claims 9 to 11 in the preparation of a negative electrode material for a lithium ion battery.
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