CN114497475A - Zinc-containing nitrogen-doped porous carbon-coated zinc-based negative electrode material for lithium ion battery - Google Patents
Zinc-containing nitrogen-doped porous carbon-coated zinc-based negative electrode material for lithium ion battery Download PDFInfo
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 43
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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
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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
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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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
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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Abstract
The invention discloses a zinc-based negative electrode material coated by zinc-nitrogen-doped porous carbon for a lithium ion battery, which has a core-shell structure with ZnO nanoparticles as a core and a ZIF-8 carbide skeleton as a shell, and a preparation method of the zinc-based negative electrode material comprises the following process steps: s1, preparing ZnO nano particle seeds; s2, preparing ZnO nano particles, and dispersing the ZnO nano particles in a polyvinylpyrrolidone solution; s3, preparing a ZIF-8 coated ZnO (ZnO @ ZIF-8) material; s4, preparing the zinc-containing nitrogen-doped porous carbon-coated ZnO (ZnO @ nitrogen-doped porous carbon/Zn) lithium ion battery negative electrode material. The ZIF-8 carbon matrix provides a conductive network, can inhibit the aggregation of ZnO particles and buffer the volume expansion of ZnO in the lithium intercalation process, and can prevent the mechanical disintegration of the ZnO negative electrode material, thereby improving the cycle stability of the material.
Description
Technical Field
The invention belongs to the field of new energy materials and lithium ion batteries, and mainly relates to a zinc-containing nitrogen-doped porous carbon-coated zinc-based negative electrode material for a lithium ion battery.
Background
The lithium ion battery is one of the most popular secondary batteries in portable electronic products, has the best energy density, and is also the preferred power source for electric and hybrid vehicles. ZnO is an attractive material as a potential alternative to conventional graphite anodes in lithium ion batteries because it is estimated that the theoretical capacity of ZnO (978mAh/g) is better than graphite (372 mAh/g). High capacity negative electrodes (e.g., zinc based) typically suffer from severe capacity fade due to rapid aggregation of zinc particles and the large volume expansion caused during lithium ion intercalation, which results in negative electrode material pulverization and electrical separation of active materials. At present, main approaches for improving the capacity and the cycle performance of the lithium ion battery cathode material are carbon coating and ion doping.
Various carbon materials have been widely studied for lithium ion batteries to improve the performance of the negative electrode material. Metal organic framework Materials (MOFs) have proven to be the most promising template or precursor for the fabrication of nanostructured carbon due to their characteristics of diverse framework structure, high specific surface area, adjustable pore size, and open metal sites. In addition to the above advantages, MOFs can be synthesized directly and economically and efficiently by assembling various metal ions/clusters and organic ligands under mild conditions. Therefore, mass production can be simply performed by increasing the amount of raw materials without any processing equipment. In addition, nitrogen-doped carbon materials derived from nitrogen-containing MOFs have been noted to exhibit greater electronic conductivity. Zeolite azaimidazole framework (ZIF-8) is a nitrogen containing MOF with high stability, high surface area and high porosity, a good carbon precursor for preparing carbon matrices and enhancing the cycling stability of lithium ion battery electrode materials.
Disclosure of Invention
The ZnO with higher theoretical capacity is used for replacing the traditional graphite cathode of the lithium ion battery, so that the capacity of the cathode material of the lithium ion battery is improved. Meanwhile, ZnO is coated with carbon by using a nitrogen-containing MOFs material ZIF-8 as a precursor of porous carbon, so that the technical problems of low capacity and poor cycle performance of the cathode of the conventional lithium ion battery can be solved.
The invention provides a preparation method of a zinc-based negative electrode material coated by zinc-containing nitrogen-doped porous carbon for a lithium ion battery, which comprises the following steps:
s1, adding a zinc source into diethylene glycol, heating and refluxing under the stirring condition, cooling to room temperature, centrifuging the suspension, and taking a colloid product in the supernatant as a seed for next synthesis;
s2, adding a zinc source into diethylene glycol, heating to a certain temperature under stirring, adding a colloidal product in the supernatant into the solution, continuously heating and refluxing, cooling to room temperature, centrifugally collecting the product, dispersing the product into a polyvinylpyrrolidone solution, and stirring for a period of time to obtain ZnO nanoparticles;
s3, mixing a certain volume of ZnO/polyvinylpyrrolidone solution and 2-methylimidazole in a N, N-dimethylformamide solution according to a certain proportion, reacting at room temperature for a period of time, carrying out centrifugal washing on the obtained product, and carrying out vacuum drying to obtain a ZIF-8-coated ZnO (ZnO @ ZIF-8) material;
s4, the obtained ZnO @ ZIF-8 is loaded in a quartz boat, the obtained ZnO @ ZIF-8 is calcined in an inert gas atmosphere to carbonize the ZIF-8, and hydrogen elements in the ZIF-are removed, so that the zinc-containing nitrogen-doped porous carbon-coated ZnO (ZnO @ nitrogen-doped porous carbon/Zn) lithium ion battery cathode material is obtained.
Preferably, in S1, the zinc source is zinc acetate dihydrate; preferably, the stirring speed is 350-450 rpm, the heating reflux temperature is 155-165 ℃, and the reflux time is 1-2 h.
Preferably, in S2, the zinc source is zinc acetate dihydrate; preferably, the heating reflux temperature is 155-165 ℃, the reflux time is 1-2 h, the concentration of the polyvinylpyrrolidone solution is 5%, and the stirring time is 12-36 h.
Preferably, in S3, the volume of the ZnO solution modified by polyvinylpyrrolidone is 0.1-0.8 mL, the concentration of 2-methylimidazole is 160mmol, the reaction time is 24-36 h, the detergent is methanol, and vacuum drying is performed for 12-24 h.
Preferably, in S4, the inert gas is one or more of nitrogen and argon; preferably, the temperature is raised to 600-800 ℃ at the speed of 0.5-10 ℃/min, and the calcination is carried out, and the temperature is kept for 2-4 h.
The invention also provides the nitrogen-doped porous carbon-coated zinc-based negative electrode material for the lithium ion battery, which is prepared by the preparation method.
The invention also provides a lithium ion battery which comprises an anode, a cathode, a diaphragm and electrolyte, wherein the cathode adopts the zinc-based cathode material coated by the zinc-nitrogen-doped porous carbon for the lithium ion battery as a cathode active substance.
Has the advantages that: the zinc-nitrogen-doped porous carbon-coated zinc-based negative electrode material for the lithium ion battery, provided by the invention, can be used as a negative electrode active material of the lithium ion battery, so that the capacity of the negative electrode material of the lithium ion battery can be improved, and the space provided by the holes in the ZIF-8 porous carbon matrix can inhibit the aggregation of ZnO particles and buffer the volume expansion of ZnO in the lithium intercalation process, so that the mechanical disintegration of the ZnO negative electrode material in the application process of the battery can be prevented, and the cycle stability of the material is improved.
Drawings
FIG. 1 is a transmission electron microscope image of the ZnO material prepared in example 1.
FIG. 2 is a scanning electron microscope image of the ZnO @ ZIF-8 material prepared in example 1.
FIG. 3 is a transmission electron microscope image of the ZnO @ ZIF-8 material prepared in example 1.
FIG. 4 is an X-ray diffraction pattern of the ZnO @ ZIF-8 material prepared in example 1.
Fig. 5 is a graph of the cycling performance of the button cell assembled and formed in example 1.
Detailed Description
The present invention will be further illustrated with reference to the following specific embodiments, however, the scope of the present invention is not limited to the following examples.
Example 1
The invention provides a preparation method of a zinc-containing nitrogen-doped porous carbon-coated ZnO (ZnO @ nitrogen-doped porous carbon/Zn) negative electrode material for a lithium ion battery, which comprises the following steps:
s1: 5mmol of zinc acetate dihydrate were dissolved in 50mL of diethylene glycol and heated to 160 ℃ with stirring for 1h under reflux. After cooling to room temperature, centrifuging the suspension for 3h at 4000rpm, and taking a colloid product in the supernatant as a seed for next synthesis;
s2: 3mmol of zinc acetate dihydrate was dissolved in 30mL of diethylene glycol, and when the solution was heated to 140 ℃ with stirring at 400rpm, a volume of the colloidal product in the supernatant was added to the solution, followed by continued heating and reflux reaction at 160 ℃ for 1 h. After cooling to room temperature, the product was centrifuged and collected by washing 3 times with methanol solution, then dispersed in 5% polyvinylpyrrolidone solution and stirred for 24 h. Finally, washing the ZnO nanoparticles modified by the polyvinylpyrrolidone for 3 times by using a methanol solution, and dispersing the ZnO nanoparticles in 30mL of the methanol solution for later use;
s3: 0.1mL of polyvinylpyrrolidone ZnO suspension was collected by centrifugation and redispersed in 1.5mL of deionized water. This solution was then mixed with a solution of 2-methylimidazole (160mmol) in N, N-dimethylformamide (4.5mL) and reacted at room temperature for 24 h. Centrifuging the obtained product at 7000rpm for 5min, collecting, washing with methanol solution for 3 times, and vacuum drying for 12h to obtain ZIF-8-coated ZnO (ZnO @ ZIF-8) shell-core material;
s4: and (2) loading the obtained ZnO @ ZIF-8 shell-core material in a quartz boat, and heating for 3h at 600 ℃ in an argon atmosphere to obtain the zinc-containing nitrogen-doped porous carbon-coated ZnO (ZnO @ nitrogen-doped porous carbon/Zn) lithium ion battery cathode material.
The zinc-containing nitrogen-doped porous carbon-coated ZnO (ZnO @ nitrogen-doped porous carbon/Zn) negative electrode material prepared in example 1 was mixed with conductive carbon black and polyvinylidene fluoride in a mass ratio of 8:1:1, and then a proper amount of N-methylpyrrolidone was added, mixed uniformly, coated on a copper foil, and dried in a vacuum oven at 80 ℃. And rolling and cutting to obtain an electrode plate, taking a Li plate as a counter electrode, adopting an electrolyte as a mixed system containing 1M LiPF6/(EC + DMC) (the volume ratio is 1:1), and assembling and forming the button cell in a glove box filled with argon, and then testing the performance of the button cell.
As can be seen from fig. 1 to 4, in the negative electrode material of a ZnO (ZnO @ nitrogen-doped porous carbon/Zn) lithium ion battery, ZnO is completely coated, and after carbonization, a coating layer of zinc-containing nitrogen-doped porous carbon is formed, which is equivalent to coating ZnO particles in a cage-like structure, and in the process of lithium desorption from the ZnO particles, mechanical disintegration of the ZnO particles is prevented by limiting volume expansion of the ZnO particles, so that the cycle stability of the negative electrode material is improved.
Fig. 5 is a cycle performance chart of the button cell assembled and molded in example 1, and the result shows that the capacity retention rate of the button cell prepared from the negative electrode material is about 95% or more after 50 weeks of cycle.
Example 2
The invention provides a preparation method of a zinc-containing nitrogen-doped porous carbon-coated ZnO (ZnO @ nitrogen-doped porous carbon/Zn) negative electrode material for a lithium ion battery, which comprises the following steps:
s1: 5mmol of zinc acetate dihydrate were dissolved in 50mL of diethylene glycol and heated to 160 ℃ with stirring for 1h under reflux. After cooling to room temperature, centrifuging the suspension for 3h at 4000rpm, and taking a colloid product in the supernatant as a seed for next synthesis;
s2: 3mmol of zinc acetate dihydrate is dissolved in 30mL of diethylene glycol, and when the solution is heated to 140 ℃ under stirring at 400rpm, a certain volume of the colloidal product in the supernatant is added to the solution, and then the reaction is continued to be heated under reflux at 160 ℃ for 1 h. After cooling to room temperature, the product was centrifuged and collected by washing 3 times with methanol solution, then dispersed in 5% polyvinylpyrrolidone solution and stirred for 24 h. Finally, washing the ZnO nanoparticles modified by the polyvinylpyrrolidone for 3 times by using a methanol solution, and dispersing the ZnO nanoparticles in 30mL of the methanol solution for later use;
s3: 0.2mL of polyvinylpyrrolidone ZnO suspension was collected by centrifugation and redispersed in 1.5mL of deionized water. This solution was then mixed with a solution of 2-methylimidazole (160mmol) in N, N-dimethylformamide (4.5mL) and reacted at room temperature for 24 h. Centrifuging the obtained product at 7000rpm for 5min, collecting, washing with methanol solution for 3 times, and vacuum drying for 12h to obtain ZIF-8-coated ZnO (ZnO @ ZIF-8) shell-core material;
s4: and (2) loading the obtained ZnO @ ZIF-8 shell-core material in a quartz boat, and heating for 3h at 600 ℃ in an argon atmosphere to obtain the zinc-containing nitrogen-doped porous carbon-coated ZnO (ZnO @ nitrogen-doped porous carbon/Zn) lithium ion battery cathode material.
The zinc-containing nitrogen-doped porous carbon-coated ZnO (ZnO @ nitrogen-doped porous carbon/Zn) negative electrode material prepared in example 2 is mixed with conductive carbon black and sodium carboxymethylcellulose according to the mass ratio of 8:1:1, then a proper amount of N-methyl pyrrolidone is added, the mixture is uniformly mixed, coated on a copper foil, and dried in a vacuum oven at 80 ℃. And rolling and cutting to obtain an electrode plate, taking a Li plate as a counter electrode, adopting an electrolyte as a mixed system containing 1M LiPF6/(EC + DMC) (the volume ratio is 1:1), and assembling and forming the button cell in a glove box filled with argon, and then testing the performance of the button cell.
Example 3
The invention provides a preparation method of a zinc-containing nitrogen-doped porous carbon-coated ZnO (ZnO @ nitrogen-doped porous carbon/Zn) negative electrode material for a lithium ion battery, which comprises the following steps:
s1: 5mmol of zinc acetate dihydrate were dissolved in 50mL of diethylene glycol and heated to 160 ℃ with stirring for 1h under reflux. After cooling to room temperature, centrifuging the suspension for 3h at 4000rpm, and taking a colloid product in the supernatant as a seed for next synthesis;
s2: 3mmol of zinc acetate dihydrate was dissolved in 30mL of diethylene glycol, and when the solution was heated to 140 ℃ with stirring at 400rpm, a volume of the colloidal product in the supernatant was added to the solution, followed by continued heating and reflux reaction at 160 ℃ for 1 h. After cooling to room temperature, the product was centrifuged and collected by washing 3 times with methanol solution, then dispersed in 5% polyvinylpyrrolidone solution and stirred for 24 h. Finally, washing the ZnO nanoparticles modified by the polyvinylpyrrolidone for 3 times by using a methanol solution, and dispersing the ZnO nanoparticles in 30mL of the methanol solution for later use;
s3: 0.4mL of polyvinylpyrrolidone ZnO suspension was collected by centrifugation and redispersed in 1.5mL of deionized water. This solution was then mixed with a solution of 2-methylimidazole (160mmol) in N, N-dimethylformamide (4.5mL) and reacted at room temperature for 24 h. Centrifuging the obtained product at 7000rpm for 5min, collecting, washing with methanol solution for 3 times, and vacuum drying for 12h to obtain ZIF-8-coated ZnO (ZnO @ ZIF-8) shell-core material;
s4: and (2) loading the obtained ZnO @ ZIF-8 shell-core material in a quartz boat, and heating for 3h at 600 ℃ in an argon atmosphere to obtain the zinc-containing nitrogen-doped porous carbon-coated ZnO (ZnO @ nitrogen-doped porous carbon/Zn) lithium ion battery cathode material.
The zinc-containing nitrogen-doped porous carbon-coated ZnO (ZnO @ nitrogen-doped porous carbon/Zn) negative electrode material prepared in example 3 was mixed with a carbon nanotube and sodium carboxymethylcellulose in a mass ratio of 8:1:1, and then a proper amount of N-methylpyrrolidone was added, mixed uniformly, coated on a copper foil, and dried in a vacuum oven at 80 ℃. And rolling and cutting to obtain an electrode plate, taking a Li plate as a counter electrode, adopting an electrolyte as a mixed system containing 1M LiPF6/(EC + DMC) (the volume ratio is 1:1), and assembling and forming the button cell in a glove box filled with argon, and then testing the performance of the button cell.
Example 4
The invention provides a preparation method of a zinc-containing nitrogen-doped porous carbon-coated ZnO (ZnO @ nitrogen-doped porous carbon/Zn) cathode material for a lithium ion battery, which comprises the following steps:
s1: 5mmol of zinc acetate dihydrate were dissolved in 50mL of diethylene glycol and heated to 160 ℃ with stirring for 1h under reflux. After cooling to room temperature, centrifuging the suspension for 3h at 4000rpm, and taking a colloid product in the supernatant as a seed for next synthesis;
s2: 3mmol of zinc acetate dihydrate was dissolved in 30mL of diethylene glycol, and when the solution was heated to 140 ℃ with stirring at 400rpm, a volume of the colloidal product in the supernatant was added to the solution, followed by continued heating and reflux reaction at 160 ℃ for 1 h. After cooling to room temperature, the product was centrifuged and collected by washing 3 times with methanol solution, then dispersed in 5% polyvinylpyrrolidone solution and stirred for 24 h. Finally, washing the ZnO nanoparticles modified by the polyvinylpyrrolidone for 3 times by using a methanol solution, and dispersing the ZnO nanoparticles in 30mL of the methanol solution for later use;
s3: 0.8mL of polyvinylpyrrolidone ZnO suspension was collected by centrifugation and redispersed in 1.5mL of deionized water. This solution was then mixed with a solution of 2-methylimidazole (160mmol) in N, N-dimethylformamide (4.5mL) and reacted at room temperature for 24 h. Centrifuging the obtained product at 7000rpm for 5min, collecting, washing with methanol solution for 3 times, and vacuum drying for 12h to obtain ZIF-8-coated ZnO (ZnO @ ZIF-8) shell-core material;
s4: and (2) loading the obtained ZnO @ ZIF-8 shell-core material in a quartz boat, and heating for 3h at 600 ℃ in an argon atmosphere to obtain the zinc-containing nitrogen-doped porous carbon-coated ZnO (ZnO @ nitrogen-doped porous carbon/Zn) lithium ion battery cathode material.
The nitrogen-doped porous carbon-coated ZnO (ZnO @ nitrogen-doped porous carbon/Zn) negative electrode material prepared in example 4 was mixed with a carbon nanotube and polyvinyl alcohol in a mass ratio of 8:1:1, and then a proper amount of N-methylpyrrolidone was added, mixed uniformly, coated on a copper foil, and dried in a vacuum oven at 80 ℃. And rolling and cutting to obtain an electrode plate, taking a Li plate as a counter electrode, adopting an electrolyte as a mixed system containing 1M LiPF6/(EC + DMC) (the volume ratio is 1:1), and assembling and forming the button cell in a glove box filled with argon, and then testing the performance of the button cell.
Comparative example 1
The other steps are the same as example 1, except that the ZnO nanoparticles prepared in step S2 are used as the negative electrode material of the lithium ion battery for assembling the button cell, that is, the ZnO nanoparticles are not coated and carbonized, and are directly used as the negative electrode material of the lithium ion battery for assembling the button cell, and then the performance of the button cell is tested.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments can still be modified, or some technical features of the foregoing embodiments can be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (7)
1. A zinc-based negative electrode material coated by zinc-nitrogen-doped porous carbon for a lithium ion battery is characterized by having a core-shell structure with ZnO nanoparticles as a core and a ZIF-8 carbide skeleton as a shell.
2. The preparation method of the zinc-based negative electrode material coated with the zinc-nitrogen-doped porous carbon for the lithium ion battery according to claim 1 is characterized by comprising the following steps:
s1, adding a zinc source into diethylene glycol, heating and refluxing under the stirring condition, cooling to room temperature, centrifuging the suspension, and taking a colloid product in the supernatant as a seed for next synthesis;
s2, adding a zinc source into diethylene glycol, heating to a certain temperature under stirring, adding a colloidal product in the supernatant into the solution, continuously heating and refluxing, cooling to room temperature, centrifugally collecting the product, dispersing the product into a polyvinylpyrrolidone solution, and stirring for a period of time to obtain ZnO nanoparticles;
s3, mixing a certain volume of ZnO/polyvinylpyrrolidone solution and 2-methylimidazole in a N, N-dimethylformamide solution according to a certain proportion, reacting at room temperature for a period of time, carrying out centrifugal washing on the obtained product, and carrying out vacuum drying to obtain a ZIF-8-coated ZnO (ZnO @ ZIF-8) material;
s4, the obtained ZnO @ ZIF-8 is loaded in a quartz boat, the quartz boat is calcined in an inert gas atmosphere to carbonize the ZIF-8, and hydrogen elements in the ZIF-8 are removed, so that the ZnO (ZnO @ nitrogen doped porous carbon/Zn) lithium ion battery cathode material coated with zinc-nitrogen doped porous carbon is obtained.
3. The method for preparing the zinc-based negative electrode material coated with the zinc-nitrogen-doped porous carbon for the lithium ion battery according to claim 1, wherein in S1, the zinc source is zinc acetate dihydrate; the stirring speed is 350-450 rpm, the heating reflux temperature is 155-165 ℃, and the reflux time is 1-2 h.
4. The method for preparing the zinc-based negative electrode material coated with the zinc-nitrogen-doped porous carbon for the lithium ion battery according to claim 1, wherein in S2, the zinc source is zinc acetate dihydrate; the heating reflux temperature is 155-165 ℃, the reflux time is 1-2 h, the concentration of the polyvinylpyrrolidone solution is 5%, and the stirring time is 12-36 h.
5. The preparation method of the zinc-based negative electrode material coated with the zinc-nitrogen-doped porous carbon for the lithium ion battery according to claim 1, wherein in S3, 0.1-0.8 mL of ZnO/polyvinylpyrrolidone modification solution is dispersed in 1.5mL of deionized water, the concentration of 2-methylimidazole is 160mmol, the reaction time is 24-36 h, the detergent is methanol, and the vacuum drying is performed for 12-24 h.
6. The method for preparing the zinc-based negative electrode material coated with the zinc-nitrogen-doped porous carbon for the lithium ion battery according to claim 1, wherein in S4, the inert gas is one or more of nitrogen and argon; heating to 600-800 ℃ at the speed of 0.5-10 ℃/min, calcining, and keeping the temperature for 2-4 h.
7. A lithium ion battery comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, and is characterized in that the negative electrode adopts the zinc-based negative electrode material coated with zinc-nitrogen-doped porous carbon for the lithium ion battery according to claim 1 as a negative electrode active substance.
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