CN112701284A - Carbon-coated zinc sulfide @ carbon special-shaped hollow nano polyhedral material and preparation and application thereof - Google Patents
Carbon-coated zinc sulfide @ carbon special-shaped hollow nano polyhedral material and preparation and application thereof Download PDFInfo
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Abstract
The invention discloses a carbon-coated zinc sulfide @ carbon special-shaped hollow nano polyhedral material, a preparation method thereof and application thereof in a lithium ion battery cathode material. In the material, zinc sulfide nanoparticles and amorphous carbon are assembled into a zinc sulfide @ carbon special-shaped hollow nano polyhedron, the structure of the zinc sulfide @ carbon special-shaped hollow nano polyhedron is formed by alternately growing two cubes, and an amorphous carbon layer is coated on the surface of the zinc sulfide @ carbon special-shaped hollow nano polyhedron. The preparation method of the material comprises the following steps: firstly synthesizing special-shaped ZIF-8, then coating a layer of RF resin, and obtaining a final product by a one-step gas phase vulcanization and carbonization method. The invention can improve the conductivity and structural stability of ZnS, improve the electrochemical activity and the cycling stability of ZnS, and ensure that ZnS has high specific discharge capacity and good cycling performance. The carbon-coated ZnS @ carbon special-shaped hollow nano polyhedral material has important application value as a lithium ion battery cathode material.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a carbon-coated zinc sulfide @ carbon special-shaped hollow nano polyhedral material and preparation and application thereof.
Background
The lithium ion battery has the advantages of long cycle life, high energy density, green and clean performance and the like, and is ideal energy storage equipment for new energy automobiles and portable electronic equipment. The negative electrode material is one of the key factors for determining the performance of the lithium ion battery, and the graphite is used as the main negative electrode material of the commercial lithium ion battery, and the theoretical capacity is only 372mAh g-1And the rate capability is poor, further development of the lithium ion battery is severely restricted, and the development of the high-performance negative electrode material becomes an important direction for the research and development of the lithium ion battery.
The theoretical specific capacity of zinc sulfide (ZnS) is up to 963mAh g-1And the storage capacity is rich, the price is low, the environment is protected, the material is widely concerned in recent years, and the material is an ideal material for replacing graphite. The patent specification with the publication number of CN110112373A discloses a preparation method of taking ZIF8 vulcanized composite graphene as a lithium ion battery negative electrode material. According to the patent technology, the ZIF8 is prepared, then the ZnS hollow MOF material is prepared, and then the ZnS hollow MOF material composite graphene is obtained by compounding with graphene oxide, the ZIF8 material is vulcanized in the preparation process, a porous composite body of ZnS nano particles and carbon is prepared, and meanwhile, the conductivity of the composite graphene as a lithium ion battery is improved.
The electron conductivity of ZnS is not high, so that the multiplying power performance is poor; the severe volume expansion phenomenon can be generated in the process of lithium intercalation and deintercalation, so that the specific capacity is rapidly attenuated, and the cycling stability is poor; these problems have severely hampered the practical application of ZnS in lithium ion batteries.
Disclosure of Invention
Aiming at the technical problems and the defects in the field, the invention provides the carbon-coated zinc sulfide @ carbon special-shaped hollow nano polyhedral material which is environment-friendly, harmless, excellent in performance and mild in reaction conditions.
The carbon-coated zinc sulfide @ carbon special-shaped hollow nano polyhedron material is characterized in that zinc sulfide nanoparticles and amorphous carbon are assembled into a zinc sulfide @ carbon special-shaped hollow nano polyhedron, the zinc sulfide @ carbon special-shaped hollow nano polyhedron is structurally formed by two cubes which are grown in a staggered mode, and an amorphous carbon layer is coated on the surface of the zinc sulfide @ carbon special-shaped hollow nano polyhedron.
The size of the zinc sulfide nano particles is 3-10 nm;
the side length of the cube is 1-2 mu m;
the amorphous carbon layer is formed by carbonizing resorcinol-formaldehyde (RF) resin and has a thickness of 3-30 nm.
The invention can improve the conductivity and structural stability of ZnS, improve the electrochemical activity and the cycling stability of ZnS, and ensure that ZnS has high specific discharge capacity and good cycling performance.
The invention also provides a preparation method of the carbon-coated zinc sulfide @ carbon special-shaped hollow nano polyhedral material, which comprises the following steps of firstly synthesizing special-shaped ZIF-8, then coating a layer of RF resin, and obtaining a final product through a one-step gas phase vulcanization and carbonization method, wherein the preparation method comprises the following steps:
(1) dissolving CTAB (cetyl trimethyl ammonium bromide) in deionized water, adding Zn (CH)3COO)2·2H2O, stirring is continued to obtain Zn (CH)3COO)2A solution; dissolving 2-methylimidazole in deionized water to obtain a 2-methylimidazole solution; pouring the 2-methylimidazole solution into the Zn (CH) under stirring3COO)2Continuously stirring in the solution; then heating the obtained mixed solution to 100-200 ℃, and preserving heat for 12 hours to perform solvothermal reaction; cooling to room temperature after the reaction is finished, centrifugally separating a product, washing with methanol, and drying at 60 ℃ to obtain a special-shaped zeolite imidazole ester framework material ZIF-8 (special-shaped ZIF-8 for short);
(2) dispersing the special-shaped zeolite imidazole ester framework material ZIF-8 prepared in the step (1) in deionized water, adding CTAB, stirring, then adding absolute ethyl alcohol and resorcinol, placing the solution in a 35 ℃ water bath, stirring for 35min, then dropwise adding a formaldehyde solution, continuously stirring for 12h in the 35 ℃ water bath, then aging for 8h at room temperature, finally centrifugally separating a product, cleaning with deionized water and ethanol, and drying at 60 ℃ to obtain an RF resin coated special-shaped ZIF-8;
(3) putting the RF resin-coated special-shaped ZIF-8 prepared in the step (2) into a porcelain boat, putting the porcelain boat at the downstream of a quartz tube furnace, putting sulfur powder into another porcelain boat according to the mass ratio of the RF resin-coated special-shaped ZIF-8 to the sulfur powder of 1:4, putting the porcelain boat at the upstream of the quartz tube furnace, and under the protection of argon gas, keeping the temperature for 2 ℃ for min-1Heating to the temperature of 400-700 ℃, and preserving heat for 2h to obtain the carbon-coated zinc sulfide @ carbon special-shaped hollow nano polyhedral material.
Preferably, in step (1), the Zn (CH) is added to 0.05g of CTAB3COO)2·2H2The dosage of O is 0.128g, and the dosage of 2-methylimidazole is 1.1 g.
Preferably, in the step (2), the CTAB is used in an amount of 0.25g, the absolute ethyl alcohol is used in an amount of 10mL, the resorcinol is used in an amount of 10-100mg, the formaldehyde solution is used in an amount of 10-200 μ L, and the mass concentration of formaldehyde in the formaldehyde solution is 37% relative to 0.08g of the heteroleptic imidazolate framework material ZIF-8.
A preferred method of preparation, comprising the steps of:
(1) 0.05g of cetyltrimethylammonium bromide (CTAB) was dissolved in 42mL of deionized water, and 0.128g of Zn (CH) was added3COO)2·2H2O, continuously stirring for 30min to obtain Zn (CH)3COO)2A solution; dissolving 1.1g of 2-methylimidazole in 10mL of deionized water to obtain a 2-methylimidazole solution; the 2-methylimidazole solution is poured rapidly into Zn (CH) under stirring3COO)2Continuously stirring the solution for 1 hour; then pouring the obtained mixed solution into a stainless steel reaction kettle with 100mL of polytetrafluoroethylene lining, heating to 100 ℃ and 200 ℃, and preserving heat for 12 hours; cooling to room temperature after the solvothermal reaction is finished, centrifugally separating a product, washing with methanol, and drying in a 60 ℃ oven; obtaining a special-shaped zeolite imidazole ester framework material ZIF-8;
(2) dispersing 0.08g of the special-shaped zeolite imidazole ester framework structure material ZIF-8 prepared in the step (1) in 30mL of deionized water, adding 0.25g of CTAB, stirring for 2h, then adding 10mL of absolute ethanol and 10-100mg of resorcinol, placing the solution in a 35 ℃ water bath, stirring for 35min, then dropwise adding 10-200mL of formaldehyde solution, keeping the mass concentration of formaldehyde in the formaldehyde solution at 37%, continuously stirring in the 35 ℃ water bath for 12h, then aging at room temperature for 8h, finally centrifugally separating a product, washing with deionized water and ethanol, and drying at 60 ℃ to obtain an RF resin coated special-shaped ZIF-8;
(3) putting the RF resin-coated special-shaped ZIF-8 prepared in the step (2) into a porcelain boat, putting the porcelain boat at the downstream of a quartz tube furnace, putting sulfur powder into another porcelain boat according to the mass ratio of the RF resin-coated special-shaped ZIF-8 to the sulfur powder of 1:4, putting the porcelain boat at the upstream of the tube furnace, and under the protection of argon gas, keeping the temperature for 2 ℃ for min-1Heating to the temperature of 400-700 ℃, and preserving heat for 2h to obtain the carbon-coated zinc sulfide @ carbon special-shaped hollow nano polyhedral material.
The invention also provides application of the carbon-coated zinc sulfide @ carbon special-shaped hollow nano polyhedral material in a lithium ion battery cathode material.
The material of the invention is adopted to manufacture the cathode of the lithium ion battery: respectively weighing a carbon-coated ZnS @ carbon irregular hollow nano polyhedral material, an acetylene black conductive agent and a polyvinylidene fluoride (PVDF) binder in a mass ratio of 8:1:1, dissolving the PVDF in a proper amount of 1-methyl-2-pyrrolidone (NMP), stirring until the PVDF is completely dissolved, adding an evenly ground active material and acetylene black into the solution, and continuously stirring to ensure that the slurry is evenly mixed. And then uniformly coating the slurry on a wafer copper foil (with the diameter of 12mm), drying in a vacuum oven at 100 ℃, and finally flattening by using a pressure intensity of 10MPa on a tablet press to obtain the electrode plate.
And assembling the prepared electrode plate, a lithium plate and a diaphragm into the CR2025 button-type lithium ion battery in a glove box filled with high-purity argon. The electrolyte is 1mol L-1LiPF6The EC/DMC electrolyte adopts a new power battery test system to test the charge-discharge performance and the cycling stability of the lithium ion battery.
Compared with the prior art, the invention has the main advantages that:
1) the one-step gas phase vulcanization and carbonization method has simple process and high reaction efficiency, can realize the integration of vulcanization and carbonization, and has unique integration. The product obtained by one-step gas-phase vulcanization and carbonization of the special-shaped ZIF-8 is a mixture of ZnS nano-particles and carbon, and the existence of the carbon obviously improves the conductivity and the structural stability of the ZnS nano-particles and has great effect on improving the performance of the ZnS lithium battery. In contrast, the product of the conventional ZIF-8 hydrothermal sulfidation process is zinc sulfide only and does not contain carbon. In addition, the product obtained by the one-step gas phase vulcanization and carbonization method of the special-shaped ZIF-8 is a hollow structure, the hollow structure brings larger specific surface area of the material, and the electrochemical activity and specific capacity of ZnS are improved; the hollow structure is also beneficial to relieving the volume expansion of ZnS in charge-discharge cycle, and the structural stability and the cycle stability of the material are improved. In contrast, ZIF-8 conventional carbonization methods only achieve solid carbon structures. Therefore, the one-step gas-phase sulfurization and carbonization treatment of the shaped ZIF-8 can simultaneously obtain the advantages of the conventional hydrothermal sulfurization method and carbonization method and remove the defects of the conventional hydrothermal sulfurization method and carbonization method.
2) Compared with the conventional shape (cube, dodecahedron) of the ZIF-8, the special-shaped ZIF-8 has more surfaces and surface areas, so that the special-shaped hollow nano polyhedron derived from the special-shaped ZIF-8 also has more surfaces and surface areas, and the electrochemical activity and specific capacity of ZnS are remarkably improved.
3) A layer of RF resin is coated on the surface of the special-shaped ZIF-8, and is decomposed into amorphous carbon in one-step gas-phase vulcanization and carbonization treatment, and the amorphous carbon is coated on the surface of the ZnS @ carbon special-shaped hollow nano polyhedron. The carbon formed by carbonizing the RF resin has higher structural strength than the carbon formed by carbonizing organic matters such as polypyrrole, polyaniline and polydopamine, the structural strength and stability of the ZnS @ carbon special-shaped hollow nano polyhedron can be further improved, and the cycle performance of the material is further improved; the coating carbon can also improve the conductivity of internal materials and improve the specific capacity of ZnS; the surface of the special-shaped ZIF-8 is coated with the RF resin, and then the special-shaped ZIF-8 and the RF resin are subjected to one-step gas phase vulcanization and carbonization treatment together, so that the one-step gas phase vulcanization and carbonization method has higher integration, the process is very efficient, the treatment links are reduced, and the treatment cost is reduced.
Drawings
FIG. 1 is an SEM photograph of the shaped ZIF-8 prepared in example 1;
FIG. 2 is an SEM photograph of carbon-coated ZnS @ carbon heteromorphic hollow nanofabrohedrons prepared in example 1;
FIG. 3 is a TEM photograph of the carbon-coated ZnS @ carbon heteromorphic hollow nanocopolymer prepared in example 1;
FIG. 4 is a partial TEM photograph of a carbon-coated ZnS @ carbon heteromorphic hollow nanocopolymer prepared in example 1;
FIG. 5 shows the current density of the carbon-coated ZnS @ carbon heteromorphic hollow nano-polyhedron prepared in example 1 at 0.2A g-1Cycle performance map of (c).
Detailed Description
The invention is further described with reference to the following drawings and specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are conducted under conditions not specified, usually according to conventional conditions, or according to conditions recommended by the manufacturer.
Example 1
(1) 0.05g CTAB was dissolved in 42mL deionized water, and 0.128g Zn (CH) was added3COO)2·2H2O, continuously stirring for 30 min; dissolving 1.1g of 2-methylimidazole in 10mL of deionized water; the solution of 2-methylimidazole is poured rapidly over Zn (CH) with stirring3COO)2The solution is continuously stirred for 1 hour; then pouring the mixed solution into a stainless steel reaction kettle with a 100mL polytetrafluoroethylene lining, heating to 120 ℃, and preserving heat for 12 hours; cooling to room temperature after the reaction is finished, centrifugally separating the product, washing the product for a plurality of times by using methanol, and drying the product in a 60 ℃ drying oven; obtaining special-shaped ZIF-8;
(2) dispersing 0.08g of the special-shaped ZIF-8 prepared in the step (1) in 30mL of deionized water, adding 0.25g of CTAB, stirring for 2h, then adding 10mL of absolute ethanol and 36mg of resorcinol, placing the solution in a 35 ℃ water bath, stirring for 35min, then dropwise adding 60mL of formaldehyde solution, keeping stirring for 12h in the 35 ℃ water bath, then aging for 8h at room temperature, finally centrifugally separating a product, washing with deionized water and ethanol for several times, and drying at 60 ℃ to obtain the RF resin coated special-shaped ZIF-8;
(3) putting 0.05g of RF resin coated special-shaped ZIF-8 prepared in the step (2) into the porcelainPlacing the boat at the downstream of a quartz tube furnace, taking 0.2g of sulfur powder according to the mass ratio (RF resin coated special-shaped ZIF-8: sulfur powder) (1: 4) and placing the other boat at the upstream of the tube furnace under the protection of argon gas at 2 ℃ for min-1Heating to 600 ℃, and preserving heat for 2h to obtain the carbon-coated ZnS @ carbon special-shaped hollow nano polyhedron.
FIG. 1 is an SEM photograph of the prepared heteromorphic ZIF-8. The special-shaped ZIF-8 is uniform in size and smooth in surface, and is formed by staggered growth of 2 cubes, and the side length of each cube is about 1.2 mu m. FIG. 2 is an SEM photograph of a carbon-coated ZnS @ carbon heteromorphic hollow nano-polyhedron. The profiled polyhedrons still retain the original shape, and the coating with RF resin and the subsequent one-step vapor phase vulcanization and carbonization treatment do not destroy the polyhedral structure of the material. However, the surface of the shaped polyhedron appears to be covered with a transparent film, and the vulcanized and carbonized nanoparticles hidden under the transparent film can be seen. Fig. 3 is a TEM photograph of a carbon-coated ZnS @ carbon heteromorphic hollow nano-polyhedron, which clearly shows that the carbon-coated ZnS @ carbon heteromorphic hollow nano-polyhedron is formed by the staggered growth of 2 cubes. The interior has good permeability and shows a hollow structure. FIG. 4 is a partial TEM image showing the outermost layer of the coated amorphous carbon, about 5-7nm thick; the inner part is provided with a plurality of nano particles which are ZnS nano particles, the particle size is about 5nm, amorphous substance adhesion exists among the particles, the amorphous adhesion substance is carbon, and the amorphous adhesion substance and the ZnS nano particles are assembled into an inner shell and are wrapped by an outer amorphous carbon outer shell.
A lithium ion battery negative electrode was fabricated using the material of example 1: respectively weighing the carbon-coated ZnS @ carbon irregular-shaped hollow nano polyhedral material, the acetylene black conductive agent and the polyvinylidene fluoride (PVDF) binder in a mass ratio of 8:1:1, dissolving the PVDF in a proper amount of 1-methyl-2-pyrrolidone (NMP), stirring until the PVDF is completely dissolved, adding the uniformly ground active material and the acetylene black into the solution, and continuously stirring to ensure that the slurry is uniformly mixed. And then uniformly coating the slurry on a wafer copper foil (with the diameter of 12mm), drying in a vacuum oven at 100 ℃, and finally flattening by using a pressure intensity of 10MPa on a tablet press to obtain the electrode plate.
Assembling the prepared electrode plate, a lithium plate and a diaphragm into CR2025 in a glove box filled with high-purity argonButton type lithium cell. The electrolyte is 1mol L-1LiPF6The EC/DMC electrolyte adopts a Xinwei battery test system to test the charge-discharge performance and the cycle stability of the lithium battery, and the charge-discharge current density is 0.2A g-1The voltage range is 0.01-3.0V.
FIG. 5 shows the current density of 0.2A g for the carbon-coated ZnS @ carbon hollow heteromorphic nano-polyhedron of example 1-1Cycle performance map of (c). The 1 st Specific discharge Capacity (Specific Capacity) was 907mAh g-1After 58 cycles, the specific discharge capacity is attenuated to 758mAh g-1Then gradually increases until the discharge specific capacity of the 200 th cycle increases to 909mAh g-1. The average specific discharge capacity over 200 cycles was 819mAh g-1. The discharge capacity and the cycle performance of the carbon-coated ZnS @ carbon special-shaped hollow nano polyhedral material exceed the work of CN110112373A and Hui Ding (H.Ding, H.C.Huang, X.K.Zhang, L.Xie, J.Q.Fan, T.Jiang, E.Shi, N.Ma, F.C.Tsai, Chem Electrochem 6(2019) 5617-5626) and the like.
The carbon-coated ZnS @ carbon special-shaped hollow nano polyhedral material has excellent lithium battery performance, including high specific discharge capacity and stable cycle performance, and is attributed to the comprehensive action of a special-shaped hollow nano polyhedral structure formed by mixing and assembling ZnS and carbon and the carbon coated on the surface.
Example 2
(1) 0.05g CTAB was dissolved in 42mL deionized water, and 0.128g Zn (CH) was added3COO)2·2H2O, continuously stirring for 30 min; dissolving 1.1g of 2-methylimidazole in 10mL of deionized water; the solution of 2-methylimidazole is poured rapidly over Zn (CH) with stirring3COO)2The solution is continuously stirred for 1 hour; then pouring the mixed solution into a stainless steel reaction kettle with a 100mL polytetrafluoroethylene lining, heating to 120 ℃, and preserving heat for 12 hours; cooling to room temperature after the reaction is finished, centrifugally separating the product, washing the product for a plurality of times by using methanol, and drying the product in a 60 ℃ drying oven; obtaining special-shaped ZIF-8;
(2) dispersing 0.08g of the special-shaped ZIF-8 prepared in the step (1) in 30mL of deionized water, adding 0.25g of CTAB, stirring for 2h, then adding 10mL of absolute ethanol and 54mg of resorcinol, placing the solution in a 35 ℃ water bath, stirring for 35min, then dropwise adding 90mL of formaldehyde solution, keeping the mass concentration of formaldehyde in the formaldehyde solution at 37%, continuously stirring in the 35 ℃ water bath for 12h, then aging for 8h at room temperature, finally centrifugally separating a product, washing with deionized water and ethanol for several times, and drying at 60 ℃ to obtain the RF resin coated special-shaped ZIF-8;
the subsequent process was the same as in example 1.
The structure of the product carbon-coated ZnS @ carbon special-shaped hollow nano polyhedral material is similar to that in example 1, and the main difference is that the thickness of the carbon coating layer is changed into 11-13 nm.
The same process as in example 1 was used to fabricate a negative electrode of a lithium ion battery, which was assembled into a lithium ion battery at a current density of 0.2A g-1And carrying out cyclic charge and discharge test within the voltage range of 0.01-3.0V. Specific discharge capacity of 1 st cycle was 892mAh g-1The specific discharge capacity is reduced to 736mAh g by the 65 th cycle-1Then the discharge capacity is gradually increased to 867mAh g after the 200 th cycle discharge specific capacity-1. Average specific discharge capacity of 791mAh g of 200 cycles-1。
Example 3
(1) 0.05g CTAB was dissolved in 42mL deionized water, and 0.128g Zn (CH) was added3COO)2·2H2O, continuously stirring for 30 min; dissolving 1.1g of 2-methylimidazole in 10mL of deionized water; the solution of 2-methylimidazole is poured rapidly over Zn (CH) with stirring3COO)2The solution is continuously stirred for 1 hour; then pouring the mixed solution into a stainless steel reaction kettle with a 100mL polytetrafluoroethylene lining, heating to 150 ℃, and preserving heat for 12 hours; cooling to room temperature after the reaction is finished, centrifugally separating the product, washing the product for a plurality of times by using methanol, and drying the product in a 60 ℃ drying oven; obtaining special-shaped ZIF-8;
the subsequent process was the same as in example 1.
The structure of the product carbon-coated ZnS @ carbon irregular hollow nano polyhedron material is similar to that in example 1, and the material is a hollow nano polyhedron formed by two cubes in a staggered growth mode, and the main difference is that the side length of each cube is changed to about 1.6 mu m.
The same process as in example 1 was used to fabricate a negative electrode of a lithium ion battery, which was assembled into a lithium ion battery,at a current density of 0.2A g-1And carrying out cyclic charge and discharge test within the voltage range of 0.01-3.0V. The 1 st specific cyclic discharge capacity is 863mAh g-1The specific discharge capacity is reduced to 701mAh g by the 50 th cycle-1Then the discharge capacity is gradually increased until the 200 th cycle discharge specific capacity is 830mAh g-1. Average specific discharge capacity 754mAh g of 200 cycles-1。
Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention as defined by the appended claims.
Claims (6)
1. The carbon-coated zinc sulfide @ carbon special-shaped hollow nano polyhedron material is characterized in that zinc sulfide nanoparticles and amorphous carbon are assembled into a zinc sulfide @ carbon special-shaped hollow nano polyhedron, the zinc sulfide @ carbon special-shaped hollow nano polyhedron is formed by alternately growing two cubes, and an amorphous carbon layer is coated on the surface of the zinc sulfide @ carbon special-shaped hollow nano polyhedron.
2. The carbon-coated zinc sulfide @ carbon heteromorphic hollow nano-polyhedron material as claimed in claim 1, wherein the zinc sulfide nanoparticles have a size of 3-10 nm;
the side length of the cube is 1-2 mu m;
the amorphous carbon layer is formed by carbonizing resorcinol-formaldehyde resin and has a thickness of 3-30 nm.
3. The preparation method of the carbon-coated zinc sulfide @ carbon heteromorphic hollow nano polyhedral material as claimed in claim 1 or 2, which is characterized by comprising the following steps:
(1) dissolving CTAB in deionized water, adding Zn (CH)3COO)2·2H2O, stirring is continued to obtain Zn (CH)3COO)2A solution; dissolving 2-methylimidazole in deionized water to obtain a 2-methylimidazole solution; pouring the 2-methylimidazole solution into the Zn (CH) under stirring3COO)2Continuously stirring in the solution; then heating the obtained mixed solution to 100-200 ℃, and preserving heat for 12 hours to perform solvothermal reaction; after the reaction is finished, cooling to room temperature, centrifugally separating a product, washing with methanol, and drying at 60 ℃ to obtain a special-shaped zeolite imidazole ester framework material ZIF-8;
(2) dispersing the special-shaped zeolite imidazole ester framework material ZIF-8 prepared in the step (1) in deionized water, adding CTAB, stirring, then adding absolute ethyl alcohol and resorcinol, placing the solution in a 35 ℃ water bath, stirring for 35min, then dropwise adding a formaldehyde solution, continuously stirring for 12h in the 35 ℃ water bath, then aging for 8h at room temperature, finally centrifugally separating a product, cleaning with deionized water and ethanol, and drying at 60 ℃ to obtain an RF resin coated special-shaped ZIF-8;
(3) putting the RF resin-coated special-shaped ZIF-8 prepared in the step (2) into a porcelain boat, putting the porcelain boat at the downstream of a quartz tube furnace, putting sulfur powder into another porcelain boat according to the mass ratio of the RF resin-coated special-shaped ZIF-8 to the sulfur powder of 1:4, putting the porcelain boat at the upstream of the quartz tube furnace, and under the protection of argon gas, keeping the temperature for 2 ℃ for min-1Heating to the temperature of 400-700 ℃, and preserving heat for 2h to obtain the carbon-coated zinc sulfide @ carbon special-shaped hollow nano polyhedral material.
4. The method according to claim 3, wherein in the step (1), the Zn (CH) is added to 0.05g of CTAB3COO)2·2H2The dosage of O is 0.128g, and the dosage of 2-methylimidazole is 1.1 g.
5. The production method according to claim 3, wherein in the step (2), the CTAB is used in an amount of 0.25g, the absolute ethanol is used in an amount of 10mL, the resorcinol is used in an amount of 10 to 100mg, the formaldehyde solution is used in an amount of 10 to 200. mu.L, and the mass concentration of formaldehyde in the formaldehyde solution is 37% with respect to 0.08g of the heteroleptic zeolite imidazolate framework material ZIF-8.
6. The application of the carbon-coated zinc sulfide @ carbon specially-shaped hollow nano polyhedral material in the negative electrode material of the lithium ion battery according to claim 1 or 2.
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