CN116544415B - Preparation of ZnO-ZnS@nitrogen doped porous carbon composite material, product and application thereof - Google Patents

Preparation of ZnO-ZnS@nitrogen doped porous carbon composite material, product and application thereof Download PDF

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CN116544415B
CN116544415B CN202310762764.3A CN202310762764A CN116544415B CN 116544415 B CN116544415 B CN 116544415B CN 202310762764 A CN202310762764 A CN 202310762764A CN 116544415 B CN116544415 B CN 116544415B
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porous carbon
zno
zns
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doped porous
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CN116544415A (en
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张义永
李雪
王飞
董鹏
张英杰
郑毅仁
杜宁
刘聪
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Yunnan Lichen New Material Technology Co ltd
Kunming University of Science and Technology
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Kunming University of Science and Technology
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    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a preparation method, a product and an application of a ZnO-ZnS@nitrogen doped porous carbon composite material, wherein a ZnO-ZnS heterostructure is grown in situ on a carbon substrate by taking porous carbon as a substrate. The zinc sulfide nanoparticles are anchored on the zinc oxide nanoplatelets, forming a composite material having a heterostructure. ZnS nano particles are vulcanized on the ZnO surface in situ by a vulcanization method, so that electron rearrangement and local electron configuration of a contact interface are triggered, and rapid transfer of accessory electrons is accelerated by massive formation of a heterojunction surface. Simultaneously, znS has better catalytic capability on LiPSs, and comprehensively enhances the adsorption effect on polysulfide. The preparation method has short preparation flow and simple operation, and is an excellent sulfur fixing material.

Description

Preparation of ZnO-ZnS@nitrogen doped porous carbon composite material, product and application thereof
Technical Field
The invention belongs to the technical field of lithium-sulfur batteries, and particularly relates to preparation of a ZnO-ZnS@nitrogen doped porous carbon composite material, a product and application thereof.
Background
With the rapid development of new energy technology, more and more electronic communication devices and new energy automobiles are applied to people's life, and thus, it is more important to develop secondary batteries having high energy density. The lithium-sulfur battery has the advantages of high theoretical specific capacity (1675 mAh/g), safety of sulfur, low price and the like, and is expected to become one of the next-generation excellent secondary batteries. However, the commercialization of Lithium Sulfur Batteries (LSBs), in which S and Li are present, has been faced with a number of problems 2 The low conductivity of S and polysulfide (LiPSs) shuttle effect are major problems.
Carbon materials become a widely used sulfur fixation carrier due to high conductivity and morphology diversity. However, carbon alone is not sufficient to impair shuttling of LiPSs due to weak adsorption. Therefore, metal compounds having a relatively strong polarity have been widely studied. The metal compound can effectively adsorb polysulfide and accelerate the conversion of polysulfide, so that the reasonable design of the multifunctional sulfur fixation carrier is important.
Disclosure of Invention
The invention aims at solving the related problems of a lithium sulfur battery, designs a preparation method, a product and application of a ZnO-ZnS@nitrogen doped porous carbon composite material, and enables a ZnO-ZnS heterostructure to grow in situ in a porous carbon substrate by a simple chemical deposition method. The prepared composite material has a unique three-dimensional structure, has more adsorption and catalytic sites, and is an excellent sulfur fixing material.
In order to achieve the above purpose, the present invention provides the following technical solutions:
the preparation method of the ZnO-ZnS@nitrogen doped porous carbon composite material comprises the following steps:
(1) After ball milling melamine and sodium citrate, annealing for 2 hours at 700-900 ℃ in an argon atmosphere, putting the obtained product into hydrochloric acid, stirring, carrying out suction filtration, washing to be neutral, and drying to obtain nitrogen-doped porous carbon;
(2) Grinding nitrogen-doped porous carbon into powder, ultrasonic treating in deionized water, and adding Zn (NO) 3 )6H 2 O, sodium citrate and polyvinylpyrrolidone (PVP), adding sodium hydroxide, stirring, standing, suction filtering, and freeze drying to obtain ZnO@NPC composite material;
(3) Na is added into ZnO@NPC composite material 2 And (3) stirring the solution S at room temperature, carrying out suction filtration and freeze-drying to obtain the ZnO/ZnS@porous carbon composite material.
Further, the Na 2 The ratio of the S to the nitrogen doped porous carbon is 1-4:5.
Further, in the step (1), the mass ratio of the melamine to the sodium citrate is (0.5-1) to (5-10). Preferably 1:10.
Further, in the step (2), the nitrogen-doped porous carbon, zn (NO) 3 )6H 2 The mass ratio of O, sodium citrate and polyvinylpyrrolidone is (0.1-0.5) to (1-2) to (1.5-2.5) to (1.5-2). Preferably 0.5:1:2:2.
Further, in step (3), the Na 2 The S solution is prepared by mixing Na 0.1-0.5g 2 S was dissolved in 30mL of deionized water. Preferably 0.2g, 0.1g, 0.4g, more preferably 0.2g.
The invention also provides the ZnO-ZnS@nitrogen doped porous carbon composite material prepared by the preparation method of the ZnO-ZnS@nitrogen doped porous carbon composite material, wherein the nitrogen doped porous carbon is taken as a substrate, and zinc oxide nano particles are anchored on a zinc sulfide nano sheet to form a flower-shaped ZnO-ZnS heterostructure.
The invention also provides application of the ZnO-ZnS@nitrogen doped porous carbon composite material in a positive electrode material of a lithium-sulfur battery. The preparation method of the lithium-sulfur battery positive electrode material comprises the following steps: and mixing the ZnO-ZnS@nitrogen doped porous carbon composite material with sublimed sulfur powder according to the mass ratio of 3:7, and heating at 155 ℃ for 12 hours in an argon atmosphere to obtain the ZnO-ZnS@porous carbon@sulfur anode material.
The invention also provides an application of the ZnO-ZnS@nitrogen doped porous carbon composite material in preparing a lithium-sulfur battery electrode.
The invention also provides an application of the ZnO-ZnS@nitrogen doped porous carbon composite material in preparing a lithium-sulfur battery.
Compared with the prior art, the invention has the following advantages and technical effects:
the invention prepares the ZnO/ZnS heterostructure@porous carbon composite material by growing a flower-shaped ZnO-ZnS heterostructure on porous carbon in situ. The prepared composite material has the following characteristics:
1. the porous carbon has a unique porous three-dimensional structure, the specific surface area of the material is increased, and the adsorption capacity can be improved by doping nitrogen, so that the problem of volume expansion in the cycling process of the lithium-sulfur battery can be relieved, and the utilization rate of sulfur can be improved.
2. The ZnO@porous carbon grows in situ in the porous carbon through a simple chemical deposition method, the polar adsorption capacity of the material is further enhanced by adding zinc oxide, the zinc oxide has strong chemical affinity to LiPSs, meanwhile, the assembly of the nano sheets has more adsorption sites, and the adsorption effect of the material is enhanced while the reaction kinetics of the lithium-sulfur battery is improved.
3. On the basis of the material of the last step, znO-ZnS@porous carbon grows ZnS nano ions on ZnO nano sheets in situ. ZnS nano particles are vulcanized on the ZnO surface in situ by a vulcanization method, so that electron rearrangement and local electron configuration of a contact interface are triggered, and a large number of heterojunction surfaces are formed to accelerate rapid transfer of nearby electrons. Simultaneously, znS has better catalytic capability on LiPSs, and comprehensively enhances the adsorption effect on polysulfide.
4. The prepared ZnO-ZnS@porous carbon@sulfur cathode material is prepared by the method that the ZnO-ZnS@porous carbon@sulfur cathode material is prepared at the current of 0.1C (1C=1675 mAh g) -1 ) The first-turn discharge specific capacity is 1354mAh g -1 After 100 circles, 908mAh g is maintained -1 Exhibiting excellent specific capacity and lower capacity fade.
5. The invention relates to a ZnO-ZnS@porous carbon anode sulfur-fixing material which has excellent conductivity and strong adsorption and catalytic capability on polysulfide by a chemical deposition method with short flow and easy preparation.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application, illustrate and explain the application and are not to be construed as limiting the application. In the drawings:
FIG. 1 is a scanning electron microscope image of the ZnO-ZnS@porous carbon composite material prepared in example 3;
FIG. 2 is a scanning electron microscope image of ZnO-ZnS flower ball prepared in example 3;
FIG. 3 is an electrochemical charge-discharge curve of the ZnO-ZnS@porous carbon composite material prepared in example 3 as a positive electrode material for a lithium-sulfur battery at a 0.1C rate;
FIG. 4 is a graph showing the magnification of porous carbon, znO@porous carbon, znO-ZnS@porous carbon as a sulfur host in a lithium sulfur battery in example 3;
FIG. 5 is an ultraviolet light spectrum absorption test of the ZnO-ZnS@porous carbon prepared in example 3 to verify its strong adsorption capacity to polysulfide;
fig. 6 is a graph of a symmetrical cell experiment of the ZnO-zns@porous carbon prepared in example 3 demonstrating its strong catalytic ability to polysulfides.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The "room temperature" as used herein is calculated as 25.+ -. 2 ℃ unless otherwise indicated.
The raw materials used in the following examples of the present invention were all obtained from Shanghai Ala Latin Biochemical technologies Co., ltd.
The "parts" in the present invention are all calculated as "parts by mass" unless otherwise specified.
The reasonable combination of the carbon material and the metal compound is favorable for synthesizing the excellent LSBs positive electrode material, on one hand, the porous carbon material can improve the conductivity of the material, and on the other hand, the porous physical property can effectively relieve the volume effect of the LSBs in the charging and discharging processes. The multi-metal compound heterostructure can improve carbon material adsorption and catalyze short plates with weak LiPSs, the heterojunction surface can effectively accelerate electron transfer so as to improve conductivity, meanwhile, the introduction of more active catalytic sites further improves the utilization rate of sulfur, and the shuttle effect of polysulfide is weakened. The technology is mainly characterized in that heterostructures with adsorption and catalytic properties are effectively dispersed in a porous carbon substrate to form a unique three-dimensional structure, so that the cycle life of the lithium-sulfur battery is prolonged. Specific:
the technical scheme of the invention is as follows: the preparation of the ZnO-ZnS heterostructure @ nitrogen-doped porous carbon composite material comprises the following steps:
(1) Synthesis of porous carbon substrates: 0.5-1g (preferably 1 g) of melamine and 5-10g (preferably 10 g) of sodium citrate are ground and mixed, and the mixture after ball milling is placed in a quartz crucible. The mixture is then placed in a tube furnace and annealed under an argon atmosphere for 2 hours at 700-900 c (preferably 700 c). After magnetically stirring the annealed product in 60ml of 4MHCL solution for 12 hours, washing and filtering the product with deionized water, washing the product to be neutral, and drying the product in a 50 ℃ oven for one night to obtain nitrogen doped porous carbon (marked as NPC).
(2) Synthesis of ZnO@porous carbon material: 0.1-0.5g (preferably 0.5 g) of porous carbon is taken, ground into powder, then placed in 60ml of deionized water, and sonicated for 30 minutes. Then 1-2g (preferably 1 g) of Zn (NO) is added 3 )6H 2 O, 1.5-2.5g (preferably 2 g) sodium citrate and 1.5-2g (preferably 2 g) PVP, dissolving, adding 0.7g NaOH, stirring for 3-6h (preferably 3 h), and standing at room temperature for 3h. Washing and filtering with deionized water, and drying the product after the suction filtration in a freeze dryer for one night to obtain a ZnO@NPC composite material;
(3) Synthesis of ZnO-ZnS@porous carbon material: 0.1-0.5g (preferably 0.2 g) of Na 2 S was dissolved in 30mL of deionized water, and ZnO@NPC prepared above was added thereto and stirred at room temperature for 6 hours. Washing and filtering the product by deionized water, and placing the product after the suction filtration in a freeze dryer for drying overnight to obtain the ZnO/ZnS@porous carbon composite material.
The invention also provides the ZnO-ZnS@nitrogen doped porous carbon composite material prepared by the preparation method of the ZnO-ZnS@nitrogen doped porous carbon composite material, wherein the nitrogen doped porous carbon is taken as a substrate, and zinc oxide nano particles are anchored on a zinc sulfide nano sheet to form a flower-shaped ZnO-ZnS heterostructure.
The invention also provides application of the ZnO-ZnS@nitrogen doped porous carbon composite material in a positive electrode material of a lithium-sulfur battery. The preparation method of the lithium-sulfur battery positive electrode material comprises the following steps: and mixing the ZnO-ZnS@nitrogen doped porous carbon composite material with sublimed sulfur powder according to the mass ratio of 3:7, and heating at 155 ℃ for 12 hours under an argon atmosphere to ensure that sulfur is uniformly distributed on the porous carbon, thereby obtaining the ZnO-ZnS@porous carbon@sulfur anode material.
The invention also provides an application of the ZnO-ZnS@nitrogen doped porous carbon composite material in preparing a lithium-sulfur battery electrode.
The invention also provides an application of the ZnO-ZnS@nitrogen doped porous carbon composite material in preparing a lithium-sulfur battery.
The following examples serve as further illustrations of the technical solutions of the invention.
Example 1
Synthesis of porous carbon substrates: 1g of melamine and 10g of sodium citrate were ground and mixed, and the mixture after ball milling was placed in a quartz crucible. The mixture was then placed in a tube furnace and annealed at 700 ℃ for 2 hours under an argon atmosphere. After magnetically stirring the annealed product in 60ml of 4M HCL solution for 12 hours, washing and filtering the product by deionized water, washing the product to be neutral, and drying the product in a 50 ℃ oven for one night to obtain nitrogen doped porous carbon (recorded as NPC).
Example 2
(1) Synthesis of porous carbon substrates: 1g of melamine and 10g of sodium citrate were ground and mixed, and the mixture after ball milling was placed in a quartz crucible. The mixture was then placed in a tube furnace and annealed at 700 ℃ for 2 hours under an argon atmosphere. After magnetically stirring the annealed product in 60ml of 4M HCL solution for 12 hours, washing and filtering the product by deionized water, washing the product to be neutral, and drying the product in a 50 ℃ oven for one night to obtain nitrogen doped porous carbon (recorded as NPC).
(2) Synthesis of ZnO@porous carbon material: 0.5g of NPC was taken, ground into powder and then placed in 60ml of deionized water, and sonicated for 30 minutes. Then 1g of Zn (NO) was added 3 )6H 2 O, 2.4g of sodium citrate and 2g of PVP, after dissolution, 0.7g of NaOH is added, and after stirring for 3 hours, the mixture is left to stand at room temperature for 3 hours. Washing and filtering with deionized water, and drying the product after the filtering in a freeze dryer for one night to obtain the ZnO@NPC composite material.
Example 3
(1) Synthesis of porous carbon substrates: 1g of melamine and 10g of sodium citrate were ground and mixed, and the mixture after ball milling was placed in a quartz crucible. The mixture was then placed in a tube furnace and annealed at 700 ℃ for 2 hours under an argon atmosphere. After magnetically stirring the annealed product in 60ml of 4M HCL solution for 12 hours, washing and filtering the product by deionized water, washing the product to be neutral, and drying the product in a 50 ℃ oven for one night to obtain nitrogen doped porous carbon (recorded as NPC).
(2) Synthesis of ZnO@porous carbon material: 0.5g of NPC was taken, ground into powder and then placed in 60ml of deionized water, and sonicated for 30 minutes. Then 1g of Zn (NO) was added 3 )6H 2 O, 2.4g of sodium citrate and 2g of PVP, after dissolution, 0.7g of NaOH is added, and after stirring for 3 hours, the mixture is left to stand at room temperature for 3 hours. Washing and filtering with deionized water, and drying the product after the filtering in a freeze dryer for one night to obtain the ZnO@NPC composite material.
(3) Synthesis of ZnO-ZnS@porous carbon material: 0.2g of Na 2 S was dissolved in 30mL of deionized water, and ZnO@NPC prepared above was added thereto and stirred at room temperature for 6 hours. Washing and filtering the product by deionized water, and placing the product after the suction filtration in a freeze dryer for drying overnight to obtain the ZnO/ZnS@porous carbon composite material.
Performance test:
the ZnO-ZnS@porous carbon material prepared in example 3 is fully ground and mixed with sublimed sulfur powder, mixed according to the mass ratio of 3:7, and heated at 155 ℃ for 12 hours under argon atmosphere to obtain the ZnO-ZnS@porous carbon@sulfur cathode material.
And (3) stirring and mixing 80 parts of the prepared sulfur/Ni heterostructure@porous carbon gel anode material, 10 parts of conductive carbon Super-p and 10 parts of binder PVDF, coating the mixed slurry on an aluminum foil current collector, wherein the thickness of the slurry coated on the current collector is 100 micrometers, and vacuum drying at 60 ℃ for 25 hours to remove the solvent, thereby finally obtaining the working electrode. The working electrode, the lithium sheet negative electrode, the diaphragm and the electrolyte are assembled into a battery in a half-battery assembly mode, and the assembly process is totally called to be carried out in a glove box passing through an argon atmosphere, wherein the oxygen content is 0.01, and the water content is 0.01. The lithium sulfur battery is subjected to electrochemical test, the voltage range is 1.6-2.8V, and the charge-discharge multiplying power is 0.1C, 0.2C, 0.5C, 1C and 2C.
FIG. 1 is a scanning electron microscope image of the ZnO-ZnS@porous carbon composite material prepared in example 3; as can be seen from the figure, the flower-like ZnO-ZnS heterostructures are uniformly distributed in a three-dimensional porous carbon substrate, forming a unique three-dimensional conductive network.
FIG. 2 is a scanning electron microscope image of ZnO-ZnS flower ball prepared in example 3; from the figure, the nano-sheets are self-assembled into flower-shaped ZnO-ZnS flower spheres, the diameters of the flower spheres are 1-3um, and a large number of nano-sheets are staggered to enable the flower spheres to have larger specific surface area.
Fig. 3 is an electrochemical charge-discharge curve of the ZnO-zns@porous carbon composite material prepared in example 3 as a positive electrode material for a lithium sulfur battery at 0.1C magnification. It can be seen that at 0.1C current (1c=1675 mAh g -1 ) The first-turn discharge specific capacity is 1354mAh g -1 The method comprises the steps of carrying out a first treatment on the surface of the After 100 circles, 908mAh g is maintained -1 The capacity fade rate was 0.329%, exhibiting excellent specific capacity and lower capacity fade.
Fig. 4 is a magnification graph of the porous carbon, zno@porous carbon, znO-zns@porous carbon of example 3 as a sulfur host in a lithium sulfur battery, and the result shows that the ZnO-zns@porous carbon exhibits more excellent magnification capability as a sulfur host.
Fig. 5 is an ultraviolet light spectrum absorption test for verifying strong adsorption ability to polysulfide of ZnO-zns@porous carbon prepared in example 3, and the result shows that ZnO-zns@porous carbon exhibits excellent adsorption ability to polysulfide.
Fig. 6 is a graph of a symmetrical cell experiment in which the ZnO-zns@porous carbon prepared in example 3 demonstrates its strong catalytic ability to polysulfides, and it can be seen that the ZnO-zns@porous carbon exhibits a stronger catalytic ability to polysulfides as a sulfur host.
Example 4
(1) Synthesis of porous carbon substrates: 1g of melamine and 10g of sodium citrate were ground and mixed, and the mixture after ball milling was placed in a quartz crucible. The mixture was then placed in a tube furnace and annealed at 700 ℃ for 2 hours under an argon atmosphere. After magnetically stirring the annealed product in 60ml of 4M HCL solution for 12 hours, washing and filtering the product by deionized water, washing the product to be neutral, and drying the product in a 50 ℃ oven for one night to obtain nitrogen doped porous carbon (recorded as NPC).
(2) Synthesis of ZnO@porous carbon material: 0.5g of NPC was taken, ground into powder and then placed in 60ml of deionized water, and sonicated for 30 minutes. Then 1g of Zn (NO) was added 3 )6H 2 O, 2.4g of sodium citrate and 2g of PVP, after dissolution, 0.7g of NaOH is added, and after stirring for 3 hours, the mixture is left to stand at room temperature for 3 hours. Washing and filtering with deionized water, and drying the product after the filtering in a freeze dryer for one night to obtain the ZnO@NPC composite material.
(3) Synthesis of ZnO-ZnS@porous carbon material: 0.1g of Na 2 S was dissolved in 30mL of deionized water, and ZnO@NPC prepared above was added thereto and stirred at room temperature for 6 hours. Washing and filtering the product by deionized water, and placing the product after the suction filtration in a freeze dryer for drying overnight to obtain the ZnO/ZnS@porous carbon composite material.
Performance test: the ZnO-ZnS@porous carbon composite material prepared by the embodiment is used as a positive electrode material for an electrochemical charge-discharge curve of a lithium-sulfur battery at a rate of 0.1C. It can be seen that the first-turn discharge specific capacity is 1262mAh g at 0.1C current -1 The capacity decay rate after 100 cycles is 0.411%.
Example 5
(1) Synthesis of porous carbon substrates: 1g of melamine and 10g of sodium citrate were ground and mixed, and the mixture after ball milling was placed in a quartz crucible. The mixture was then placed in a tube furnace and annealed at 700 ℃ for 2 hours under an argon atmosphere. After magnetically stirring the annealed product in 60ml of 4M HCL solution for 12 hours, washing and filtering the product by deionized water, washing the product to be neutral, and drying the product in a 50 ℃ oven for one night to obtain nitrogen doped porous carbon (recorded as NPC).
(2) Synthesis of ZnO@porous carbon material: 0.5g of NPC was taken, ground into powder and then placed in 60ml of deionized water, and sonicated for 30 minutes. Then 1g of Zn (NO) was added 3 )6H 2 O, 2.4g of sodium citrate and 2g of PVP, after dissolution, 0.7g of NaOH is added, and after stirring for 3 hours, the mixture is left to stand at room temperature for 3 hours. Washing with deionized water, suction filtering, and cooling the productDrying in a freeze dryer for one night to obtain the ZnO@NPC composite material.
(3) Synthesis of ZnO-ZnS@porous carbon material: 0.4g of Na 2 S was dissolved in 30mL of deionized water, and ZnO@NPC prepared above was added thereto and stirred at room temperature for 6 hours. Washing and filtering the product by deionized water, and placing the product after the suction filtration in a freeze dryer for drying overnight to obtain the ZnO/ZnS@porous carbon composite material.
Performance test: the ZnO-ZnS@porous carbon composite material prepared by the embodiment is used as a positive electrode material for an electrochemical charge-discharge curve of a lithium-sulfur battery at a rate of 0.1C. It can be seen that the first-turn discharge specific capacity is 1165mAh g at 0.1C current -1 The capacity decay rate after 100 circles is 0.387%.
Example 6
The difference from example 3 is that step (1) is annealed at 900℃for 2h.
The ZnO-ZnS@porous carbon composite material prepared by the embodiment is used as a positive electrode material for an electrochemical charge-discharge curve of a lithium-sulfur battery at a rate of 0.1C. It can be seen that the specific capacity of the first-turn discharge is 1156mAh g at 0.1C current -1 The capacity decay rate after 100 cycles was 0.426%.
Comparative example 1
(1) Synthesis of porous carbon substrates: 2g of melamine and 10g of sodium citrate were ground and mixed, and the mixture after ball milling was placed in a quartz crucible. The mixture was then placed in a tube furnace and annealed at 700 ℃ for 2 hours under an argon atmosphere. After magnetically stirring the annealed product in 60ml of 4MHCL solution for 12 hours, washing and filtering the product with deionized water, washing the product to be neutral, and drying the product in a 50 ℃ oven for one night to obtain nitrogen doped porous carbon (marked as NPC).
(2) Synthesis of ZnO@porous carbon material: 1g of porous carbon was taken, ground into powder, and then placed in 60ml of deionized water, followed by sonication for 30 minutes. Then 1.5g of Zn (NO) was added 3 )6H 2 O, 2.4g of sodium citrate and 2g of PVP, after dissolution, 0.7g of NaOH is added, and after stirring for 3 hours, the mixture is left to stand at room temperature for 3 hours. Washing and suction filtering with deionized water, and drying the suction filtered product in a freeze dryer for one night to obtain the ZnO@NPC composite materialAnd (5) material.
(3) Synthesis of ZnO-ZnS@porous carbon material: 0.2g of Na 2 S was dissolved in 30mL of deionized water, and the ZnO@NPC prepared above was added thereto and stirred at room temperature for 6 hours. Washing and filtering the product by deionized water, and placing the product after the suction filtration in a freeze dryer for drying overnight to obtain the ZnO/ZnS@porous carbon composite material.
The ZnO-ZnS@porous carbon composite material prepared by the comparative example is used as a positive electrode material for an electrochemical charge-discharge curve of a lithium-sulfur battery at a rate of 0.1C. It can be seen that the specific capacity of the first-turn discharge is 1057mAh g at 0.1C current -1 The capacity attenuation rate after 100 cycles is 0.421%.
Comparative example 2
As in example 3, the difference is that in step (3), na 2 The mass of S was 1g.
The ZnO-ZnS@porous carbon composite material prepared by the comparative example is used as a positive electrode material for an electrochemical charge-discharge curve of a lithium-sulfur battery at a rate of 0.1C. It can be seen that the first-turn discharge specific capacity is 1022mAh g at 0.1C current -1 The capacity fade rate was 0.422%.
Comparative example 3
The difference from example 3 is that in the preparation of the cathode material, the material of ZnO-ZnS@porous carbon and sublimed sulfur powder are mixed in a mass ratio of 4:5.
The ZnO-ZnS@porous carbon composite material prepared by the comparative example is used as a positive electrode material for an electrochemical charge-discharge curve of a lithium-sulfur battery at a rate of 0.1C. It can be seen that the initial discharge specific capacity is 1252mAh g at 0.1C current -1 The capacity fade rate was 0.382%.
The foregoing is merely a preferred embodiment of the present application, but the scope of the present application is not limited thereto, and any changes or substitutions easily conceivable by those skilled in the art within the technical scope of the present application should be covered in the scope of the present application. Therefore, the protection scope of the present application shall be subject to the protection scope of the claims.

Claims (9)

1. The preparation method of the ZnO-ZnS@nitrogen doped porous carbon composite material is characterized by comprising the following steps of:
(1) After ball milling melamine and sodium citrate, annealing for 2 hours at 700-900 ℃ in an argon atmosphere, putting the obtained product into hydrochloric acid, stirring, carrying out suction filtration, washing to be neutral, and drying to obtain nitrogen-doped porous carbon;
(2) Grinding nitrogen-doped porous carbon into powder, ultrasonic treating in deionized water, and adding Zn (NO) 3 )6H 2 O, sodium citrate and polyvinylpyrrolidone, adding sodium hydroxide, stirring, standing, suction filtering, and freeze drying to obtain a ZnO@nitrogen doped porous carbon composite material; the nitrogen doped porous carbon, zn (NO) 3 ) 2 6H 2 The mass ratio of O, sodium citrate and polyvinylpyrrolidone is 0.5:1:2:2;
(3) Na is added into the ZnO@nitrogen doped porous carbon composite material 2 Stirring the solution S at room temperature, carrying out suction filtration and freeze drying to obtain the ZnO-ZnS@nitrogen doped porous carbon composite material;
the ZnO-ZnS@nitrogen-doped porous carbon composite material takes nitrogen-doped porous carbon as a substrate, and zinc sulfide nano particles are anchored on a zinc oxide nano sheet to form a flower-shaped ZnO-ZnS heterostructure.
2. The method for preparing a ZnO-zns@nitrogen doped porous carbon composite material according to claim 1, wherein the Na 2 The ratio of the S to the nitrogen doped porous carbon is 1-4:5.
3. The method for preparing a ZnO-zns@nitrogen doped porous carbon composite material according to claim 1, wherein in the step (1), the mass ratio of melamine to sodium citrate is 1:10.
4. The method for producing a ZnO-zns@nitrogen-doped porous carbon composite material according to claim 1, wherein in step (3), the Na 2 The S solution is prepared by mixing Na 0.1-0.5g 2 S was dissolved in 30mL of deionized water.
5. A ZnO-zns@nitrogen doped porous carbon composite material prepared by the preparation method of the ZnO-zns@nitrogen doped porous carbon composite material according to any one of claims 1 to 4.
6. The use of the ZnO-zns@nitrogen doped porous carbon composite material of claim 5 in preparing a lithium sulfur battery positive electrode material.
7. The use according to claim 6, wherein the preparation method of the positive electrode material of the lithium-sulfur battery comprises the following steps: and mixing the ZnO-ZnS@nitrogen doped porous carbon composite material with sublimed sulfur powder according to the mass ratio of 3:7, and heating at 155 ℃ for 12 hours in an argon atmosphere to obtain the ZnO-ZnS@porous carbon@sulfur anode material.
8. Use of the ZnO-zns@nitrogen doped porous carbon composite material of claim 5 in the preparation of lithium sulfur battery electrodes.
9. Use of the ZnO-zns@nitrogen doped porous carbon composite material of claim 5 in the preparation of a lithium sulfur battery.
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CN102345162A (en) * 2011-04-19 2012-02-08 中国科学院合肥物质科学研究院 One-dimensional axial type nano zinc oxide / zinc sulfide heterojunction and preparation method thereof
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CN102345162A (en) * 2011-04-19 2012-02-08 中国科学院合肥物质科学研究院 One-dimensional axial type nano zinc oxide / zinc sulfide heterojunction and preparation method thereof
CN104868102A (en) * 2015-06-10 2015-08-26 中南大学 Sodium ion battery zinc sulfide based negative electrode material and preparation method thereof
CN106299307A (en) * 2016-09-30 2017-01-04 上海空间电源研究所 A kind of lithium-sulfur cell high-performance positive electrode and preparation method thereof
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