CN112382754A - Carbon nanofiber coated hollow zinc sulfide material and preparation method and application thereof - Google Patents
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Abstract
The invention relates to a carbon nanofiber coated hollow zinc sulfide material and a preparation method and application thereof, which solve the technical problems that the existing metal sulfide can suffer from larger volume expansion in the energy storage process, and the electrochemical stability of the material can be greatly influenced by common mechanical mixing. The invention also provides a preparation method and application thereof. The invention can be used in the field of battery electrode preparation.
Description
Technical Field
The invention relates to a battery material, a preparation method and application thereof, in particular to a carbon nanofiber coated hollow zinc sulfide material, and a preparation method and application thereof.
Background
The rapid development of current social economy and science and technology makes people put forward higher requirements on energy supply, and with the continuous consumption of non-renewable energy sources such as fossil fuel, novel energy storage devices such as fuel cells, primary batteries and secondary batteries are produced. Among them, the secondary battery has been rapidly developed in recent decades due to its advantages of high energy density, good cyclicity, small self-discharge, etc., and various energy storage devices such as lithium ion battery, sodium ion battery, etc. are derived, and are widely applied to various fields such as digital products, electric vehicles, large-scale energy storage power grids, etc., and cover aspects of our lives. The high-performance electrode material is an important factor for improving the energy density of the secondary battery, and the preparation of the flexible electrode can further widen the application field of the secondary battery, such as wearable devices and the like.
For electrode materials, carbon materials have excellent conductivity, but have a low specific capacity; the metal sulfide has higher specific capacity and poorer conductivity, and the combination of the metal sulfide and the metal sulfide is a common method for preparing the electrode at present.
However, metal sulfides undergo large volume expansion during energy storage, and ordinary mechanical mixing greatly affects the electrochemical stability of the material. Among the numerous metal sulfides, zinc sulfide has the advantages of no toxicity and small volume expansion, but the application of the zinc sulfide in electrode materials is limited due to relatively poor electrical conductivity.
Disclosure of Invention
The invention provides a flexible carbon nanofiber coated hollow zinc sulfide material with stable electrochemical performance, and a preparation method and application thereof, aiming at the technical problems that the existing metal sulfide can suffer from larger volume expansion in the energy storage process and the electrochemical stability of the material can be greatly influenced by common mechanical mixing.
The invention provides a flexible carbon nanofiber-coated hollow zinc sulfide material, wherein the exterior of the material is coated by uniform carbon, the interior of the material is of a hollow zinc sulfide structure, the diameter of a carbon nanofiber is 1.2-2.0 mu m, the size of the hollow zinc sulfide is 500-700nm, and the mass percentage of zinc sulfide in the carbon nanofiber-coated hollow zinc sulfide material is 23-50%.
The invention also provides a preparation method of the flexible carbon nanofiber-coated hollow zinc sulfide material, which adopts a zeolite imidazole organic framework ZIF-8 as a template, obtains the hollow zinc sulfide material by utilizing the difference of ion diffusion rates through electrostatic spinning and a hydrothermal method, and obtains the flexible carbon nanofiber-coated hollow zinc sulfide material through subsequent heat treatment.
Preferably, the preparation method of the flexible carbon nanofiber-coated hollow zinc sulfide material provided by the invention comprises the following steps:
(1) preparation of zeolitic imidazole organic framework ZIF-8: taking out ionizable Zn2+Dissolving the metal salt in an alcohol solvent, and stirring for dissolving; dissolving methylimidazole in alcohol solvent, and stirring for dissolving; mixing and stirring the two, standing, centrifuging, washing and drying to obtain a zeolite imidazole organic framework material ZIF-8;
(2) preparing a polyacrylonitrile-coated ZIF-8 nanofiber membrane: firstly, dispersing the ZIF-8 prepared in the step (1) into an N, N-dimethylformamide solvent, and carrying out intermittent ultrasonic treatment and stirring to uniformly disperse the ZIF-8 in the solvent; then dissolving 30-60% of surfactant based on the mass fraction of ZIF-8 in N, N-dimethylformamide solvent, and stirring for dissolving; then pouring the surfactant solution into the ZIF-8 dispersion liquid, and continuously stirring to obtain a uniformly dispersed solution A; dissolving polyacrylonitrile in N, N-dimethylformamide solvent, heating, stirring and dissolving to obtain solution B, adding solution A into solution B, and continuously stirring to obtain uniform and stable spinning solution; performing electrostatic spinning to obtain a polyacrylonitrile-coated ZIF-8 nanofiber membrane;
(3) preparing a polyacrylonitrile-coated hollow zinc sulfide nanofiber membrane: cutting the polyacrylonitrile-coated ZIF-8 nanofiber membrane obtained in the step (2), dispersing and soaking in an alcohol solvent, dissolving thioacetamide in the alcohol solvent, and stirring at room temperature; finally, adding the thioacetamide solution into the alcohol dispersion liquid of the fiber membrane, refluxing in an oil bath, separating, washing and drying a product to obtain the polyacrylonitrile-coated hollow zinc sulfide nanofiber membrane;
(4) and (3) heat treatment: pre-oxidizing the polyacrylonitrile-coated hollow zinc sulfide nanofiber membrane material obtained in the step (3) in an air atmosphere; and then carbonizing in an inert atmosphere to finally obtain the flexible carbon nanofiber coated hollow zinc sulfide material.
Preferably, said step (1) ionizes to give Zn2+The metal salt of (a) is one or a combination of two or more of zinc acetate dihydrate or zinc nitrate hexahydrate; the alcohol solvent is one or more of absolute ethyl alcohol and absolute methyl alcohol.
Preferably, in the step (1), the Zn can be ionized2+The mass concentration of the metal salt dissolved in the alcohol solvent is 2.2-4.4 mg/mL; the mass concentration of the methylimidazole dissolved in the alcohol solvent is 12 mg/mL.
Preferably, the surfactant in the step (2) is one or more of F127 and PVP.
Preferably, in the step (2), the mass concentration of the ZIF-8 dispersed in the N, N-dimethylformamide solvent is 133-267 mg/mL; the surfactant accounts for 30-60% of the mass fraction of the ZIF-8.
Preferably, in the step (3), the concentration of the thioacetamide dissolved in the alcohol solvent is 25-35 mg/mL.
Preferably, in the step (4), pre-oxidation is carried out at 260-280 ℃ in an air atmosphere, the heating rate is 1-2 ℃/min, and the heat preservation time is 1-3 h; then carbonizing at 500-900 ℃ in an inert atmosphere at the heating rate of 1-10 ℃/min for 2-4 h; the inert atmosphere is nitrogen or argon.
The invention also provides application of the hollow zinc sulfide material coated by the flexible carbon nanofiber as a flexible electrode of a lithium ion battery or a sodium ion battery.
The invention has the following beneficial effects:
the invention provides a flexible carbon nanofiber-coated hollow-structure zinc sulfide material.In the spinning solution, nitrogen atoms of cyano groups in polyacrylonitrile and Zn on the surface of a zeolithium imidazole organic framework ZIF-82+Has stronger coordination function, and can effectively strengthen the interface combination between polyacrylonitrile and ZIF-8. The polyacrylonitrile coated ZIF-8 nano fiber membrane is directly subjected to hydrothermal reaction, and S can be used by utilizing the solubility difference of reactants and products2-By replacing the imidazole skeleton of ZIF-8 by Zn2+Outwardly and S2-The difference in the inward diffusion rates allows the formation of a hollow zinc sulfide structure that is tightly bound to the polyacrylonitrile layer. Finally, the flexible carbon nanofiber-coated hollow zinc sulfide material can be obtained through further heat treatment. Compared with the traditional sulfur powder vulcanization method, the low-temperature ion exchange method can obtain the hollow zinc sulfide structure, and the method is simple and environment-friendly.
The flexible carbon nanofiber coated hollow zinc sulfide material can be directly cut to be used as a self-supporting electrode to carry out electrochemical performance test, a copper foil is not needed to be used as a current collector, and the cost is reduced to a great extent.
Specifically, the present invention has the following advantages:
(1) different from the traditional method for preparing the sulfide carbon nanofiber composite material by using the sulfur powder high-temperature sulfide fiber membrane, which produces hydrogen sulfide waste gas pollution, the invention innovatively prepares the polyacrylonitrile-coated hollow zinc sulfide nanofiber membrane material by using the polyacrylonitrile-coated ZIF-8 nanofiber membrane through a low-temperature hydrothermal method, and is safer and more environment-friendly.
(2) Different from the traditional carbon-coated zinc sulfide nanoparticles, the invention not only utilizes the ZIF-8 precursor as the template to prepare the hollow zinc sulfide, but also introduces the electrostatic spinning technology to realize uniform carbon coating outside the zinc sulfide, thereby enhancing the conductivity of the material while protecting the structural stability of the zinc sulfide, and in addition, the constructed three-dimensional conductive network can effectively shorten the transmission path of electrons and improve the electrochemical performance of the material.
(3) The prepared carbon nanofiber-coated hollow zinc sulfide material has good flexibility, does not need a copper foil as a current collector, and can be used as a self-supporting flexible electrode; the unique structural design of the hollow zinc sulfide embedded carbon nanofiber can improve the electrochemical performance of the zinc sulfide-based material, and the zinc sulfide embedded carbon nanofiber is non-toxic and environment-friendly. Therefore, the electrode material is expected to be applied to the field of flexible wearable devices.
Drawings
FIG. 1a is an SEM image of the zeolitic imidazolate organic framework ZIF-8 prepared according to example 1 of the present invention.
FIG. 1b is an SEM image of the zeolitic imidazolate organic framework ZIF-8 prepared according to example 2 of the present invention.
FIG. 1c is an XRD pattern of the zeolitic imidazolate organic framework ZIF-8 prepared in example 1 of the present invention.
FIG. 2a is an SEM image of polyacrylonitrile coated ZIF-8 nanofiber membranes with different ZIF-8 contents prepared in example 3 of the present invention.
FIG. 2b is an SEM image of polyacrylonitrile-coated ZIF-8 nanofiber membranes with different ZIF-8 contents prepared in example 4 of the present invention.
FIG. 2c is an SEM image of polyacrylonitrile coated ZIF-8 nanofiber membranes with different ZIF-8 contents prepared in example 5 of the present invention.
FIG. 3 is an SEM image of a polyacrylonitrile-coated hollow zinc sulfide nanofiber membrane prepared in example 6 of the present invention.
Fig. 4a is an SEM image of the carbon nanofiber-coated hollow zinc sulfide material prepared in example 9 of the present invention.
FIG. 4b is a TEM image of the carbon nanofiber-coated hollow zinc sulfide material prepared in example 9 of the present invention.
Fig. 4c shows Mapping element distribution of the carbon nanofiber-coated hollow zinc sulfide material prepared in example 9 of the present invention.
Fig. 5 is a graph of rate performance of the carbon nanofiber-coated hollow zinc sulfide material prepared in example 9 of the present invention as a self-supporting electrode for a sodium ion battery.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
Preparation of zeolitic imidazole organic framework ZIF-8: 0.4g of zinc acetate dihydrate is weighed and dissolved in 90mL of ethanol, the mass concentration is 4.4mg/mL, the mixture is stirred for 5 hours at 25 ℃ and fully dissolved, 1.0g of dimethylimidazole is weighed and dissolved in 90mL of ethanol, the mixture is stirred for 5 hours at 25 ℃ and fully dissolved, then the ethanol solution of dimethylimidazole is poured into the ethanol solution of zinc acetate dihydrate, and the mixture is stirred for 5 minutes and then kept stand for 24 hours. The product is collected by centrifugation, washed with ethanol and water three times respectively, and dried for 12h at 60 ℃.
Example 2
Preparation of zeolitic imidazole organic framework ZIF-8: weighing 0.2g of zinc acetate dihydrate, dissolving the zinc acetate dihydrate into 90mL of ethanol with the mass concentration of 2.2mg/mL, stirring the mixture at 25 ℃ for 5 hours for full dissolution, weighing 1.0g of dimethylimidazole, dissolving the dimethylimidazole into 90mL of ethanol, stirring the mixture at 25 ℃ for 5 hours for full dissolution, pouring the ethanol solution of the dimethylimidazole into the ethanol solution of the zinc acetate dihydrate, stirring the mixture for 5 minutes, and standing the mixture for 24 hours. The product is collected by centrifugation, washed with ethanol and water three times respectively, and dried for 12h at 60 ℃.
Example 3
Preparing a polyacrylonitrile-coated ZIF-8 nanofiber membrane: 0.4g of ZIF-8 is weighed and dispersed in 3mL of N, N-dimethylformamide with the concentration of 133mg/mL, and the mixture is subjected to ultrasonic treatment and stirring for 6 hours. Then 0.2g F127 was weighed out and dissolved in 1mL of N, N-dimethylformamide and stirred for 3 h. And pouring the surfactant solution into the ZIF-8 dispersion liquid, continuously stirring for 4 hours to obtain a uniformly dispersed solution A, dissolving 0.8g of polyacrylonitrile powder in 4mL of N, N-dimethylformamide, stirring in a water bath at 60 ℃ for 5 hours to obtain a uniformly dispersed solution B, finally adding the solution A into the solution B, continuously stirring for 24 hours to obtain a uniform and stable spinning solution, and selecting proper technological parameters to perform electrostatic spinning to obtain the polyacrylonitrile-coated ZIF-8 nanofiber membrane.
Example 4
Preparing a polyacrylonitrile-coated ZIF-8 nanofiber membrane: 0.6g of ZIF-8 is weighed and dispersed in 3mL of N, N-dimethylformamide with the concentration of 200mg/mL, and the mixture is subjected to ultrasonic treatment and stirring for 6 hours. Then 0.3g F127 was weighed out and dissolved in 1mL of N, N-dimethylformamide and stirred for 3 h. And pouring the surfactant solution into the ZIF-8 dispersion liquid, continuously stirring for 4 hours to obtain a uniformly dispersed solution A, dissolving 0.6g of polyacrylonitrile powder in 2mL of N, N-dimethylformamide, stirring in a water bath at 60 ℃ for 5 hours to obtain a uniformly dispersed solution B, finally adding the solution A into the solution B, continuously stirring for 24 hours to obtain a uniform and stable spinning solution, and selecting proper technological parameters to perform electrostatic spinning to obtain the polyacrylonitrile-coated ZIF-8 nanofiber membrane.
Example 5
Preparing a polyacrylonitrile-coated ZIF-8 nanofiber membrane: 0.8g of ZIF-8 is weighed and dispersed in 3mL of N, N-dimethylformamide with the concentration of 267mg/mL, and the mixture is subjected to ultrasonic treatment and stirring for 6 hours. Then 0.4g F127 was weighed out and dissolved in 1mL of N, N-dimethylformamide and stirred for 3 h. And pouring the surfactant solution into the ZIF-8 dispersion liquid, continuously stirring for 4 hours to obtain a uniformly dispersed solution A, dissolving 0.53g of polyacrylonitrile powder in 1.3mL of N, N-dimethylformamide, stirring for 5 hours in a water bath at 60 ℃ to obtain a uniformly dispersed solution B, finally adding the solution A into the solution B, continuously stirring for 24 hours to obtain a uniform and stable spinning solution, and selecting proper technological parameters to perform electrostatic spinning to obtain the polyacrylonitrile-coated ZIF-8 nanofiber membrane.
Example 6
Preparing a polyacrylonitrile-coated hollow zinc sulfide nanofiber membrane: cutting the obtained composite nanofiber membrane into a proper size, weighing 125mg, dispersing and soaking in 60mL of ethanol solution; 1.5g of thioacetamide was dissolved in 60mL of ethanol at a concentration of 25mg/mL, and the mixture was stirred at room temperature for 1 hour. And finally, adding the thioacetamide solution into the ethanol dispersion liquid of the fiber membrane, carrying out oil bath reflux at 90 ℃ for 3 hours, separating, washing and drying the product to obtain the polyacrylonitrile-coated hollow zinc sulfide nanofiber membrane.
Example 7
Preparing a polyacrylonitrile-coated hollow zinc sulfide nanofiber membrane: cutting the obtained composite nanofiber membrane into a proper size, weighing 125mg, dispersing and soaking in 60mL of ethanol solution; 1.8g of thioacetamide was dissolved in 60mL of ethanol at a concentration of 30mg/mL, and the mixture was stirred at room temperature for 1 hour. And finally, adding the thioacetamide solution into the ethanol dispersion liquid of the fiber membrane, carrying out oil bath reflux at 90 ℃ for 3 hours, separating, washing and drying the product to obtain the polyacrylonitrile-coated hollow zinc sulfide nanofiber membrane.
Example 8
Preparing a polyacrylonitrile-coated hollow zinc sulfide nanofiber membrane: cutting the obtained composite nanofiber membrane into a proper size, weighing 125mg, dispersing and soaking in 60mL of ethanol solution; 2.1g of thioacetamide was dissolved in 60mL of ethanol at a concentration of 35mg/mL, and the mixture was stirred at room temperature for 1 hour. And finally, adding the thioacetamide solution into the ethanol dispersion liquid of the fiber membrane, carrying out oil bath reflux at 90 ℃ for 3 hours, separating, washing and drying the product to obtain the polyacrylonitrile-coated hollow zinc sulfide nanofiber membrane.
Example 9
The heat treatment process comprises the following steps: pre-oxidizing the polyacrylonitrile-coated hollow zinc sulfide nanofiber membrane at 260 ℃ in air atmosphere at a heating rate of 1 ℃/min for 2 h; and then carbonizing at 800 ℃ in a nitrogen atmosphere, wherein the heating rate is 3 ℃/min, and the heat preservation time is 2h, so that the flexible carbon nanofiber coated hollow zinc sulfide material is obtained, and can be directly cut into pieces to be used as self-supporting electrodes for carrying out electrochemical performance tests.
As shown in attached figures 1a and 1b, examples 1 and 2 adopt different Zn2+The concentration of the ZIF-8 material used for synthesizing the ZIF-8 material can cause the finally prepared ZIF-8 materials to have different sizes, namely 500-600nm and 200-300nm respectively, when the ZIF-8 materials with different sizes are applied to the material, the ZIF-8 materials are finally converted into the carbon nanofiber coated hollow zinc sulfide, and the electrochemical performance of the material is basically only related to the content of the active substances within a certain size range of the zinc sulfide, so that the electrochemical performance of the materials applied to the material preparation in the examples 1 and 2 is not obviously different.
Examples 3, 4 and 5 show that different ZIF-8 are dispersed in N, N-dimethylformamide, and the ZIF-8 content in the fibers is different, and the morphology of the fibers is different as shown in fig. 2a, 2b and 2 c. Finally, the zinc sulfide content in the material is different, the electrochemical performance of the material is affected, and the performance difference is shown in figure 5.
Examples 6, 7, and 8 show that, by using different thioacetamide concentrations in an alcohol solvent, the selected thioacetamide concentration range in which thioacetamide is dissolved in the alcohol solvent is 25-35mg/mL, and subsequent characterization, the thioacetamide concentration in the selected range has no significant influence on the morphology and final electrochemical performance of the material, and the analysis reason may be that at a lower concentration, the ZIF-8 precursor is completely converted into zinc sulfide, and then the increase of the thioacetamide concentration has no significant influence on the performance.
However, the above description is only exemplary of the present invention, and the scope of the present invention should not be limited thereby, and the replacement of the equivalent components or the equivalent changes and modifications made according to the protection scope of the present invention should be covered by the claims of the present invention.
Claims (10)
1. The carbon nanofiber-coated hollow zinc sulfide material is characterized in that the carbon nanofiber-coated hollow zinc sulfide material is coated with uniform carbon, the interior of the material is of a hollow zinc sulfide structure, the diameter of the carbon nanofiber is 1.2-2.0 mu m, the size of the hollow zinc sulfide is 500-700nm, and the zinc sulfide accounts for 23-50% of the mass of the carbon nanofiber-coated hollow zinc sulfide material.
2. The method for preparing the carbon nanofiber-coated hollow zinc sulfide material as claimed in claim 1, wherein the carbon nanofiber-coated hollow zinc sulfide material is obtained by using a zeolithium imidazole organic framework ZIF-8 as a template, utilizing ion diffusion rate difference through electrostatic spinning and a hydrothermal method, and performing subsequent heat treatment.
3. The method for preparing the carbon nanofiber-coated hollow zinc sulfide material as claimed in claim 2, comprising the steps of:
(1) preparation of zeolitic imidazole organic framework ZIF-8: taking out ionizable Zn2+Dissolving the metal salt in an alcohol solvent, and stirring for dissolving; dissolving methylimidazole in alcohol solvent, and stirring for dissolving; mixing and stirring the two, standing, centrifuging, washing and drying to obtain a zeolite imidazole organic framework material ZIF-8;
(2) preparing a polyacrylonitrile-coated ZIF-8 nanofiber membrane: firstly, dispersing the ZIF-8 prepared in the step (1) into an N, N-dimethylformamide solvent, and carrying out intermittent ultrasonic treatment and stirring to uniformly disperse the ZIF-8 in the solvent; then dissolving 30-60% of surfactant based on the mass fraction of ZIF-8 in N, N-dimethylformamide solvent, and stirring for dissolving; then pouring the surfactant solution into the ZIF-8 dispersion liquid, and continuously stirring to obtain a uniformly dispersed solution A; dissolving polyacrylonitrile in N, N-dimethylformamide solvent, heating, stirring and dissolving to obtain solution B, adding solution A into solution B, and continuously stirring to obtain uniform and stable spinning solution; performing electrostatic spinning to obtain a polyacrylonitrile-coated ZIF-8 nanofiber membrane;
(3) preparing a polyacrylonitrile-coated hollow zinc sulfide nanofiber membrane: cutting the polyacrylonitrile-coated ZIF-8 nanofiber membrane obtained in the step (2), dispersing and soaking in an alcohol solvent, dissolving thioacetamide in the alcohol solvent, and stirring at room temperature; finally, adding the thioacetamide solution into the alcohol dispersion liquid of the fiber membrane, refluxing in an oil bath, separating, washing and drying a product to obtain the polyacrylonitrile-coated hollow zinc sulfide nanofiber membrane;
(4) and (3) heat treatment: pre-oxidizing the polyacrylonitrile-coated hollow zinc sulfide nanofiber membrane material obtained in the step (3) in an air atmosphere; and then carbonizing in an inert atmosphere to obtain the carbon nanofiber coated hollow zinc sulfide material.
4. The method for preparing a carbon nanofiber coated hollow zinc sulfide material as claimed in claim 3, wherein the step (1) can ionize Zn2+The metal salt of (a) is one or a combination of two or more of zinc acetate dihydrate or zinc nitrate hexahydrate; the alcohol solvent is one or more of absolute ethyl alcohol and absolute methyl alcohol.
5. The method for preparing a carbon nanofiber-coated hollow zinc sulfide material as claimed in claim 3, wherein in the step (1), Zn is ionizable to be extracted2+The mass concentration of the metal salt dissolved in the alcohol solvent is 2.2-4.4 mg/mL; the mass concentration of the methylimidazole dissolved in the alcohol solvent is 12 mg/mL.
6. The carbon nanofiber coated hollow zinc sulfide material of claim 3, wherein the surfactant of step (2) is one or more of F127, PVP.
7. The carbon nanofiber-coated hollow zinc sulfide material as claimed in claim 3, wherein in the step (2), the mass concentration of the ZIF-8 dispersed in the N, N-dimethylformamide solvent is 133-267 mg/mL; the surfactant accounts for 30-60% of the mass fraction of the ZIF-8.
8. The carbon nanofiber-coated hollow zinc sulfide material according to claim 3, wherein the thioacetamide is dissolved in an alcohol solvent at a concentration of 25-35mg/mL in the step (3).
9. The carbon nanofiber-coated hollow zinc sulfide material as claimed in claim 1, wherein in the step (4), pre-oxidation is performed at 260-280 ℃ in an air atmosphere, the heating rate is 1-2 ℃/min, and the heat preservation time is 1-3 h; then carbonizing at 500-900 ℃ in an inert atmosphere at the heating rate of 1-10 ℃/min for 2-4 h; the inert atmosphere is nitrogen or argon.
10. The use of the carbon nanofiber-coated hollow zinc sulfide material of claim 1 as a flexible electrode for a lithium ion battery or a sodium ion battery.
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Cited By (3)
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| CN112366312A (en) * | 2020-10-19 | 2021-02-12 | 杭州职业技术学院 | Carbon-assembled zinc sulfide hollow nano polyhedral honeycomb material and preparation and application thereof |
| CN113381012A (en) * | 2021-07-02 | 2021-09-10 | 北京化工大学 | MXene-based metal sulfide and preparation method and application thereof |
| CN115843172A (en) * | 2021-09-18 | 2023-03-24 | 安徽璜峪电磁技术有限公司 | Hollow carbon-loaded metal nickel particle, preparation method and application of microwave absorption |
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