CN114447298B - NiS (nickel-zinc sulfide) 2 Composite material, preparation method and application thereof - Google Patents

NiS (nickel-zinc sulfide) 2 Composite material, preparation method and application thereof Download PDF

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CN114447298B
CN114447298B CN202210018747.4A CN202210018747A CN114447298B CN 114447298 B CN114447298 B CN 114447298B CN 202210018747 A CN202210018747 A CN 202210018747A CN 114447298 B CN114447298 B CN 114447298B
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zif
carbon shell
pda
composite material
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CN114447298A (en
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赵毅
甘艳美
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Fujian Normal University
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a NiS 2 Composite material, preparation method and application thereof, and the composite material is Y-S NiS 2 @C 1 @C 2 ，C 1 Refer to the inner carbon shell layer, C 2 Refer to the outer carbon shell, niS 2 Representing NiS 2 The compound, Y-S, refers to a bell-shaped core-shell structure. The preparation method comprises the following steps: coating of NiS by dopamine DA polymerization 2 Nanoparticle to obtain NiS 2 Coating NiS with 2-methylimidazole zinc salt ZIF-8 2 The @ PDA obtains ZIF-8 wrapped NiS 2 Complex NiS 2 @PDA@ZIF-8; etching of NiS with tannic acid 2 PDA@ZIF-8 gives a bell-shaped composite Y-S NiS with voids inside 2 @PDA@ZIF-8; Y-S NiS 2 The annealing, carbonization and acid washing of the @ PDA @ ZIF-8 are carried out to remove zinc sulfide, and then Y-S NiS is obtained 2 @C 1 @C 2 The composite material is applied to a potassium ion battery.

Description

NiS (nickel-zinc sulfide) 2 Composite material, preparation method and application thereof
Technical Field
The invention belongs to the field of new energy, and in particular relates to a NiS 2 Composite materials, methods of making and uses thereof.
Background
In a potassium ion battery, nickel-based sulfide NiS 2 Is widely used for negative electrode materials due to its moderate cost and high theoretical capacity. However, the disadvantages of poor conductivity and large volume change result in poor electrical storage performance. Nanostructured NiS 2 And is an effective method for solving the above problems by compounding with a highly conductive carbon material (carbon nanotube, graphene, hard carbon, etc.).
For this purpose, kang et al designed a yolk shell (Y-S) structured Y-S Ni-Fe sulfate @ C nanosphere with internal void space to achieve good structural stability. (Chemical Engineering Journal, doi.org/10.1016/j.cej.2020.127963) after 250 cycles, it can maintain a capacity of 297 mA h g-1 at 0.1A g-1. However, as reported, the Y-S structure generally exhibits a large yolk size and limited contact points between yolk and shell. These factors will lead to poor electron/ion transport, reducing cycle performance and cycle life. Therefore, the integration of good structural integrity and superior charge transport is critical to the design of high performance potassium ion battery cathodes. In addition, the invention discovers that the sulfur-nitrogen co-doped C layer has a synergistic effect on the capacity improvement of the whole composite material, however, the traditional ex-situ synthesis method is to continuously dope hetero atoms on the basis of the existing carbon shell layer, so that the active substance can be subjected to phase change and collapse or deformation of the original structure, and the problems can be effectively avoided by adopting an in-situ one-step doping method.
Disclosure of Invention
The object of the present invention is to provide a NiS 2 Composite materials, methods of making and uses thereof.
The technical scheme of the invention is as follows:
NiS (nickel-zinc sulfide) 2 The composite material has the following structural general formula: Y-S NiS 2 @C 1 @C 2 Wherein C 1 Represents an inner carbon shell layer, C 2 Represents an outer carbon shell layer, niS 2 Representing NiS 2 The compound, Y-S, represents a core-shell structure having a bell shape. The method comprises the following characteristics:
has a bell-shaped core-shell structure, and the inner core is NiS 2 ，NiS 2 The outer surface is coated with a carbon layer, namely an inner carbon shell layer, wherein the inner carbon shell layer and the inner core NiS 2 The outer surface is tightly contacted, the outermost carbon shell is a hollow sphere carbon shell, and a hollow gap is reserved between the inner carbon shell and the outer carbon shell.
The NiS 2 Is nano-particle with particle size of 100-150nm;
the volume size of the outermost carbon shell layer (the outermost hollow sphere carbon shell layer) is NiS 2 The volume of the nanoparticles is more than 1.5 times, more preferably 1.5-3 times;
the appearance of the outermost hollow sphere carbon shell layer is a hollow sphere-like body, and the hollow sphere-like body comprises one or more of a hollow ellipsoid, a hollow sphere, a hollow egg sphere and a hollow olive sphere;
the inner and outer surfaces of the outermost hollow sphere carbon shell are provided with porous structures;
the outermost hollow sphere carbon shell layer is composed of carbon;
s and N atoms are doped on carbon atoms of the outermost hollow sphere carbon shell layer; s, N are uniformly distributed inside and on the surface of the carbon shell;
the shape of the nano particles is curved spherical particles.
The NiS 2 The content by mass relative to the composite material is 41.4. 41.4 wt%, more preferably 30 to 70% by weight.
The invention provides NiS 2 The composite material is applied to a potassium ion battery.
The invention provides a composition containing NiS 2 The secondary battery of the composite material comprises a potassium ion battery, wherein the potassium ion battery comprises a positive electrode, a negative electrode and electrolyte; the negative electrode includes: a current collector and a negative electrode material supported on the current collector; wherein the negative electrode material contains the electrode material.
Providing NiS 2 The preparation method of the composite material comprises the following steps:
1. coating of NiS by dopamine polymerization 2 Nanoparticle to obtain NiS 2 @PDA;
2. Coating of NiS with 2-methylimidazole Zinc salt (ZIF-8) 2 The @ PDA obtains ZIF-8 wrapped NiS 2 Complex (NiS) 2 @PDA@ZIF-8)；
3. Etching of NiS with tannic acid 2 PDA@ZIF-8 gives a bell-like composite (Y-S NiS) with voids inside 2 @PDA@ZIF-8）；
4. Under the atmosphere of sulfur vapor, Y-S NiS 2 The annealing, carbonization and acid washing of the @ PDA @ ZIF-8 are carried out to remove zinc sulfide, and then Y-S NiS is obtained 2 @C 1 @C 2 The composite material is the NiS 2 A composite material.
Optionally, step 1 includes: niS is subjected to 2 Stirring the dispersion liquid of the nano particles and the dopamine solution for full polymerization reaction, and centrifuging to remove the mother materialWashing the precipitate with methanol to obtain NiS 2 Dispersion of PDA (polydopamine). The NiS 2 The nanoparticle size is 100-150nm.
Optionally, step 2 includes: niS is subjected to 2 The @ PDA methanol dispersion was uniformly dispersed in a zinc salt Zn (NO 3 ) 2 Adding dimethyl imidazole in methanol solution, fully reacting, filtering, washing, and drying to obtain ZIF-8 coated NiS 2 Complex (NiS) 2 @PDA@ZIF-8)。
Optionally, the zinc salt is one or more of zinc nitrate, zinc chloride and zinc sulfate.
Optionally, step 3 includes:
adding tannic acid water solution into NiS 2 Stirring and reacting in a dispersion solution of @ PDA @ ZIF-8, centrifuging, washing the precipitate, filtering and drying to obtain Y-S NiS with internal gaps 2 @PDA@ZIF-8。
The NiS 2 The solvent of the @ ZIF-8 dispersion is a water-alcohol mixed solvent, preferably a water-alcohol mixed solvent;
optionally, step 4 includes:
Y-S NiS 2 Sealing the @ PDA @ ZIF-8 and sulfur powder in a vacuum quartz tube according to a certain proportion, and placing the whole quartz tube at a high temperature for annealing and carbonizing, and then pickling to remove zinc sulfide to obtain the Y-S NiS2@ C product 1 @C 2 A composite material.
The Y-S NiS 2 The ratio of @ PDA @ ZIF-8 to the sulfur powder is such that the amount of sulfur element in the sulfur powder is greater than Y-S NiS 2 The amount in @ PDA @ ZIF-8, preferably in a mass ratio of 1:1; the annealing temperature is 500-800 ℃; the acid used for pickling is an acid solution capable of dissolving zinc sulfide.
The beneficial effects of the invention are as follows:
the invention designs an internal interface regulation strategy and designs the NiS 2 Carbon interface, coating NiS with carbon layer 2 Kernel, shortening NiS 2 The diffusion path of electrons and ions in the inner core enhances the diffusion path from the outer carbon shell to the NiS 2 Electron/ion transport by the core. In addition, carbon layer coated NiS 2 The inner core was defined within a ZIF-8 derived hollow carbon sphere with sufficient internal void space to give a unique bell-like structure. In view of the advantages of good stability of the Y-S structure and improved charge transmission by internal interface regulation, the Y-S NiS is prepared 2 @C 1 @C 2 The composite material is used as a secondary potassium ion battery anode material, and has high capacity, good cycle retention and excellent multiplying power performance. The material is used in a potassium ion battery, and the capacity after 1200 times of circulation is kept at 360mAh g under the current density of 1A g-1 -1 At the same time, the rate performance test is carried out when the charge and discharge current is increased from 0.1 Ag-1 to 20 Ag-1, the capacity is kept at 306mAh g-1 under 20 Ag-1, and the current returns to 0.1 Ag -1 When the capacity is still kept at 563 mAh g -1 Exhibits excellent rate performance.
The preparation method disclosed by the invention is simple to operate, short in period and easy to realize large-scale production.
Drawings
FIG. 1 is a carbon-based NiS of bell-like structure prepared in example 1 2 Composite material (Y-S NiS) 2 @C 1 @C 2 ) Transmission electron micrographs of (2) in the drawings: a is its low resolution map and b is its high resolution map.
FIG. 2 is a carbon-based NiS of bell-like structure prepared in example 1 2 Composite material (Y-S NiS) 2 @C 1 @C 2 ) Is an X-ray diffraction pattern of (2).
FIG. 3 is a carbon-based NiS with a bell-like structure prepared in example 1 2 Composite material (Y-S NiS) 2 @C 1 @C 2 ) The battery charge-discharge cycle performance diagram is a battery charge-discharge cycle performance diagram of a potassium ion battery anode material.
FIG. 4 is a carbon-based NiS with a bell-like structure prepared in example 1 2 Composite material (Y-S NiS) 2 @C 1 @C 2 ) Battery charge-discharge rate performance diagram of the anode material of the potassium ion battery, wherein: a is a discharge curve graph, and b is a multiplying power cycle charge-discharge curve graph.
FIG. 5 NiS in a bell-like structure prepared in example 1 2 Composite material (Y-S NiS) 2 @C 1 @C 2 ) The nitrogen isothermal adsorption curve a, b is shown as the pore size distribution curve.
FIG. 6 NiS in a bell-like structure prepared in example 1 2 Composite material (Y-S NiS) 2 @C 1 @C 2 ) Element two-dimensional imaging of (2), in the figure: a is a dark field phase diagram of a transmission electron microscope, b is a line scanning element distribution diagram, C is an N element two-dimensional distribution diagram, d is a Ni element two-dimensional distribution diagram, e is an S element two-dimensional distribution diagram, and f is a C element two-dimensional distribution diagram.
FIG. 7 is a hand bell-like structure of NiS prepared in example 3 2 Transmission electron micrographs of the composite material, in which: a is NiS 2 Representative transmission electron microscope low resolution image of composite material, b is NiS 2 A high resolution image of the composite material is representative of a transmission electron microscope.
FIG. 8 is a hand bell-like structure of NiS prepared in example 3 2 X-ray diffraction pattern of the composite material.
FIG. 9 is a NiS with a bell-like structure prepared in example 3 2 The composite material is a battery charge-discharge cycle performance graph of a potassium ion battery cathode material.
FIG. 10 is a NiS with bell-like structure prepared in example 3 2 The composite material is a battery charge-discharge rate performance graph of a potassium ion battery cathode material.
FIG. 11 is a NiS with a bell-like structure prepared in example 3 2 The nitrogen isothermal adsorption curve a and b of the composite material are pore size distribution curves.
FIG. 12 is a NiS with bell-like structure prepared in example 3 2 Two-dimensional imaging of elements of the composite material, in which: a is NiS 2 And b is a distribution diagram of each element.
Fig. 13 is a charge-discharge cycle curve of a potassium ion battery obtained by using nickel disulfide prepared in step 1) of this example as a negative electrode material of the potassium ion battery.
FIG. 14 is a diagram of the NiS 2 Schematic structural diagram of the composite material.
Detailed Description
Example 1:
1) Dispersing 0.3g PVP (MW 40000) in 20ml water and 20ml ethylAdding 1mmol of nickel acetate and 3mmol of sodium thiosulfate into the mixed solution of glycol, stirring and dissolving uniformly, transferring into a 100ml reaction kettle, placing into a hydrothermal box at 180 ℃, preserving heat for 12 hours, naturally cooling, centrifuging the obtained suspension, washing with water and ethanol, and finally dispersing the washed precipitate in methanol for later use to obtain NiS 2 Methanol dispersion of nanoparticles.
2) The obtained NiS with the size of 100-150nm 2 30mg of nanoparticle dispersion was dispersed in 15ml of Tris buffer (pH=8.5), 10mg of dopamine DA was added thereto, and the mixture was stirred at room temperature for 16 hours, centrifuged to remove the mother solution, and the precipitate was washed with methanol to obtain NiS 2 Methanol dispersion of PDA (polydopamine).
3) NiS is subjected to 2 10mg of methanol dispersion of PDA (Polydopamine) was added to a solution containing 0.5mmol of Zn (NO) 3 ) 2 After ultrasonic homogenization, adding a methanol solution containing 1mmol of dimethyl imidazole under stirring, standing for 24 hours after stirring for 1min, filtering, washing with methanol, and drying to obtain NiS coated with 2-methylimidazole zinc salt (ZIF-8) 2 Complex (NiS) 2 @PDA@ZIF-8)；
4) NiS is subjected to 2 Dispersing @ PDA @ ZIF-8 in a mixed solution of 0.4ml of water and 4.6ml of absolute ethyl alcohol, and uniformly carrying out ultrasonic treatment to obtain a mixed solution A; dispersing 50mg of tannic acid in 5ml of water to obtain a mixed solution B, pouring the mixed solution B into the solution A under stirring, standing for 10min, centrifuging to remove mother solution, washing precipitate with water and ethanol, filtering, and drying to obtain Y-S NiS with voids 2 @PDA@ZIF-8。
5) The obtained Y-S NiS 2 Sealing the tube by using the @ PDA @ ZIF-8 and sulfur powder according to the mass ratio of 1:1, placing the tube in a muffle furnace at 600 ℃ for 3 hours to obtain a carbonized product, pickling and stirring the carbonized product with 1M hydrochloric acid for 8 hours, filtering, washing with water, and drying to obtain the Y-S NiS 2 @C 1 @C 2 A composite material.
FIG. 1 is a Y-S NiS prepared in example 1 2 @C 1 @C 2 A representative Transmission Electron Micrograph (TEM) of the composite is a transmission electron micrograph. It can be seen from FIG. 1 that the composite material has a bell shapeCore-shell structure Y-S with inner core of NiS 2 ，NiS 2 The outer surface is coated with a carbon layer, namely an inner carbon shell layer, an inner carbon shell layer and an inner core NiS 2 The outer surface is tightly contacted, the outermost carbon shell is a hollow sphere carbon shell, and a hollow gap is reserved between the inner carbon shell and the outer carbon shell. NiS (NiS) 2 Is nano-particle with particle size of 100-150nm; niS (NiS) 2 The shape of the nano-particles is curved spherical particles, and the volume size of the outermost carbon shell layer (the outermost hollow spherical carbon shell layer) is NiS 2 And 1.5-3 times of the volume of the nano particles.
FIG. 2 is a Y-S NiS prepared in this example 2 @C 1 @C 2 X-ray diffraction patterns of the composite material can determine NiS 2 Is a phase of (2).
6) Subjecting the product of step 5) Y-S NiS 2 @C 1 @C 2 The composite (70 wt%), conductive carbon black (15 wt%) and carboxymethyl cellulose (CMC 15 wt%) were added to an agate mortar for pulverizing and grinding, wherein deionized water was used as a dispersant. The flattened, dried nickel foam was prepared and weighed. And coating the slurry obtained after uniform grinding on a foam nickel current collector, vacuum drying at 80 ℃ for 12h, weighing the dried electrode slices, and obtaining the mass of the slurry on each electrode slice according to the mass difference before and after coating the current collector. After weighing, the electrode slice is dried in vacuum at 80 ℃ for 2h, and the dried electrode slice is put into a glove box to be assembled with a button cell;
7) Assembling the button cell in a glove box filled with argon, wherein a metal potassium sheet is used as a negative electrode, glass fiber is used as a diaphragm, and the manufactured electrode sheet is used as a positive electrode;
8) The constant current charge and discharge test mainly examines the charge and discharge specific capacity, the cycle performance and the multiplying power performance of the potassium ion half battery under different currents. The potassium ion semi-battery has no potassium ion in the positive electrode in the initial state, so the battery starts to perform constant current discharge, and the potassium ion in the metal potassium sheet is embedded into the positive electrode material; after the discharge is finished, the positive electrode material is in a potassium-rich state, and a charging test is started, so that the cycle test is performed. The test voltage of the button cell is 0.05-2.8V, and the charge-discharge current density is set to be 100 mA g-1-20 Ag-1 according to experimental conditions.
FIG. 3 is a Y-S NiS prepared in this example 2 @C 1 @C 2 The composite material is a battery charge-discharge cycle performance graph of a potassium ion battery cathode material. Its capacity after 1200 cycles is maintained at 360mAh g-1 at a current density of 1A g-1;
FIG. 4 is a Y-S NiS prepared in this example 2 @C 1 @C 2 The composite material is a battery charge-discharge rate performance graph of a potassium ion battery cathode material. The rate performance test was performed with the charge-discharge current increased from 0.1 ag-1 to 200 ag-1, and the capacities at current densities of 1,2,4,6, 10 and 20 ag-1 were 503, 469, 430, 395, 361 and 306mAh g-1, respectively, and were maintained at 563 mAh g-1, returning to 0.1 ag-1, showing excellent rate performance.
FIG. 5 is a Y-S NiS 2 @C 1 @C 2 The graph a and the graph b of the isothermal adsorption curve of the nitrogen of the composite material show pore size distribution curves. The specific surface area is 228.4 m2/g, the pore volume is 0.318 cm3/g, and the pore size distribution is 1nm-10nm; wherein the main pore size distribution is concentrated: 2nm pores and 4nm pores.
The bell-like structure feature, niS, can be seen in fig. 6 2 The outer layer of the nanoparticle is tightly covered with an inner carbon layer, a hollow space is reserved between the inner carbon layer and the outer carbon shell layer, and S, N elements are uniformly distributed on the outer carbon shell layer to form S, N co-doped carbon.
Example 2
This example differs from example 1 in that zinc sulphate is used instead of zinc nitrate in step 2) and Y-S NiS in step 4) 2 The annealing temperature is 500-800 ℃ according to the mass ratio of ZIF-8 to sulfur powder of 1:2, and the annealing temperature is naturally cooled to room temperature after the constant-speed temperature rise of 8 h-800 ℃ from 500 ℃. The carbonized product is Y-S NiS 2 @C 1 @C 2 A composite material.
Example 3 (comparative example)
1) Dispersing 0.3g PVP (MW: 40000) in a mixture of 20ml water and 20ml glycol, stirring to dissolve uniformly, adding 1mmol nickel acetate and 3mmol sodium thiosulfate, stirring to dissolve into uniform solution, transferring toPlacing in a 100ml reaction kettle, placing in a hydrothermal box at 180deg.C, preserving heat for 12 hr, naturally cooling, centrifuging the obtained suspension, washing with water and ethanol, and dispersing the washed precipitate in methanol to obtain NiS 2 Methanol dispersion of nanoparticles.
2) The obtained NiS with the size of 100-150nm 2 10mg of nanoparticle dispersion was added to a solution containing 0.5mmol of Zn (NO 3 ) 2 After ultrasonic homogenization, adding a methanol solution containing 1mmol of dimethyl imidazole under stirring, standing for 24 hours after stirring for 1min, filtering, washing with methanol, and drying to obtain NiS coated with 2-methylimidazole zinc salt (ZIF-8) 2 Complex (NiS) 2 @ZIF-8)；
3) NiS is subjected to 2 Dispersing ZIF-8 in a mixed solution of 0.4ml of water and 4.6ml of absolute ethyl alcohol, and carrying out ultrasonic homogenization to obtain a mixed solution A; dispersing 50mg of tannic acid in 5ml of water to obtain a mixed solution B, pouring the mixed solution B into the solution A under stirring, standing for 10min, centrifuging to remove mother solution, washing precipitate with water and ethanol, filtering, and drying to obtain Y-S NiS with voids 2 ZIF-8, "Y-S" structure means a core-shell structure with a bell shape.
The obtained Y-S NiS 2 Sealing the tube by the ZIF-8 and the sulfur powder according to the mass ratio of 1:1, placing the tube in a muffle furnace at 600 ℃ for 3 hours to obtain a carbonized product, pickling the carbonized product with 1M hydrochloric acid, and stirring the carbonized product at room temperature for 8 hours until the zinc sulfide is completely removed, thereby obtaining the Y-S NiS 2 @ C composite. As can be seen from FIG. 7, the microstructure of the composite material is represented by a core-shell structure Y-S with a bell shape, the outer shell layer is a hollow sphere carbon shell, and the inside of the hollow sphere carbon shell is coated with NiS 2 The method comprises the steps of carrying out a first treatment on the surface of the Hollow sphere carbon shell and NiS 2 A hollow gap is reserved between the two. NiS (NiS) 2 Is nano-particle with particle size of 100-150nm; the volume size of the hollow sphere carbon shell layer is NiS 2 1.5 to 3 times of the nano particles.
FIG. 8 is a Y-S NiS prepared in this example 2 An X-ray diffraction pattern of the @ C composite; the phase of nickel disulfide is shown.
FIG. 9 is a Y-S NiS prepared in this example 2 The @ C composite material is a potassium ion battery negative electrodeBattery charge-discharge cycle performance graph of the electrode material. Its capacity after 500 cycles was maintained at 276 mAh g-1 at a current density of 1A g-1;
FIG. 10 is a Y-S NiS prepared in this example 2 The @ C composite material is a battery charge-discharge rate performance graph of a potassium ion battery anode material. The rate performance test was performed with the charge-discharge current increased from 0.1 ag-1 to 20 ag-1 and the capacities at current densities of 1,2,4,6, 10 and 20 ag-1 were 480, 434, 386, 358, 318 and 260 mAh g-1, respectively, and the capacity remained at 550 mAh g-1 when returned to 0.1 ag-1, showing excellent rate performance.
FIG. 11 is a Y-S NiS 2 The graph of the isothermal adsorption curve a and b of the nitrogen of the composite material at the temperature of@C is a pore size distribution curve. Its specific surface area is 181 m 2 Per gram, pore volume of 0.33 cm 3 /g, the pore size distribution of which is 0.4nm-35nm; wherein the main pore size distribution is concentrated in three intervals: 1-2nm;3-6nm;15-30nm.
Fig. 12 shows the bell-like structural feature with S, N elements uniformly distributed on the carbon shell, resulting in S, N co-doped carbon.
Fig. 13 shows the charge-discharge cycle curve of the potassium ion battery obtained by using nickel disulfide prepared in step 1) of the present example as the negative electrode material of the potassium ion battery, and it can be seen from the figure that the cycle performance is poor, i.e., the capacity fade is close to 0 in 50 cycles.

Claims (10)

1. NiS (nickel-zinc sulfide) 2 The composite material has the following structural general formula: Y-S NiS 2 @C 1 @C 2 Wherein C 1 Refer to the inner carbon shell layer, C 2 Refer to the outer carbon shell, niS 2 Representing NiS 2 The compound, Y-S refers to a bell-shaped core-shell structure; the bell-shaped core-shell structure comprises an inner core, an inner carbon shell and an outer carbon shell; the inner core is NiS 2 Kernel NiS 2 The outer surface is coated with an inner carbon shell layer, wherein the inner carbon shell layer and the inner core NiS 2 The outer surface is tightly contacted, the carbon shell layer outside the inner carbon shell layer is an outer carbon shell layer, the outer carbon shell layer is a hollow sphere carbon shell layer, and the inner layerA hollow gap is reserved between the carbon shell layer and the shell carbon shell layer.
2. The composite material of claim 1, wherein said NiS 2 Is a nanoparticle;
the size of the nano particles is 100-150nm;
the NiS 2 The shape of the nano particles is a curved spherical particle;
the NiS 2 Accounting for 30-70wt% of the total mass of the composite material.
3. The composite material of claim 1, wherein the outer carbon shell is a hollow sphere-like carbon shell, and the morphology of the outer carbon shell is a hollow sphere-like body;
the hollow sphere-like body is selected from one or more of a hollow ellipsoid, a hollow sphere, a hollow egg sphere or a hollow olive sphere;
the inner and outer surfaces of the hollow sphere carbon shell layer are provided with porous structures;
the main component of the hollow sphere carbon shell layer is carbon;
s and N atoms are doped on carbon atoms of the hollow sphere carbon shell; s, N are uniformly distributed in the hollow sphere carbon shell and on the surface of the hollow sphere carbon shell;
the volume of the outer carbon shell layer is NiS 2 The volume of the nano particles is more than 1.5 times.
4. Use of the composite material according to any one of claims 1-3 as a negative electrode material for a potassium ion battery.
5. A potassium ion battery comprises a positive electrode, a negative electrode and electrolyte; characterized in that the anode comprises: a current collector and a negative electrode material supported on the current collector; wherein the negative electrode material contains the composite material according to any one of claims 1 to 3.
6. NiS (nickel-zinc sulfide) 2 The preparation method of the composite material comprises the following steps:
1) Coating of NiS by dopamine DA polymerization 2 Nanoparticle to obtain NiS 2 @PDA;
2) Coating NiS with 2-methylimidazole zinc salt ZIF-8 2 The @ PDA obtains ZIF-8 wrapped NiS 2 Complex NiS 2 @PDA@ZIF-8；
3) Etching of NiS with tannic acid 2 PDA@ZIF-8 gives a bell-shaped composite Y-S NiS with voids inside 2 @PDA@ZIF-8；
4) Under the atmosphere of sulfur vapor, Y-S NiS 2 The annealing, carbonization and acid washing of the @ PDA @ ZIF-8 are carried out to remove zinc sulfide, and then Y-S NiS is obtained 2 @C 1 @C 2 Composite material, wherein C 1 Refer to the inner carbon shell layer, C 2 Refer to the outer carbon shell, niS 2 Representing NiS 2 The compound, Y-S refers to a bell-shaped core-shell structure; namely NiS 2 A composite material.
7. The method of claim 6, wherein step 1) comprises: niS is subjected to 2 Adding the dispersion liquid of the nano particles into a dopamine DA solution, stirring, fully polymerizing, centrifuging to remove mother solution, and washing the precipitate with methanol to obtain NiS 2 Methanol dispersion at PDA; the NiS 2 The nanoparticle size is 100-150nm.
8. The method of claim 6, wherein step 2) comprises: niS is subjected to 2 The @ PDA methanol dispersion was uniformly dispersed in a zinc salt Zn (NO 3 ) 2 Adding dimethyl imidazole in methanol solution, fully reacting, filtering, washing, and drying to obtain ZIF-8 coated NiS 2 Complex NiS 2 @PDA@ZIF-8；
The zinc salt is one or more of zinc nitrate, zinc chloride and zinc sulfate.
9. The method of claim 6, wherein step 3) comprises: adding tannic acid water solution into NiS 2 Stirring and reacting in a dispersion liquid of @ PDA @ ZIF-8, and centrifugingWashing the precipitate, filtering and drying to obtain Y-S NiS with internal voids 2 @PDA@ZIF-8；
The NiS 2 The solvent of the @ ZIF-8 dispersion is a hydroalcoholic mixed solvent.
10. The method of claim 6, wherein step 4) comprises: Y-S NiS 2 Sealing the @ PDA @ ZIF-8 and sulfur powder in a vacuum quartz tube according to a certain proportion, and placing the whole quartz tube at a high temperature for annealing and carbonizing, and then pickling to remove zinc sulfide to obtain the Y-S NiS product 2 @C 1 @C 2 A composite material;
the Y-S NiS 2 The ratio of @ PDA @ ZIF-8 to the sulfur powder is such that the amount of sulfur element in the sulfur powder is greater than Y-S NiS 2 Amount in @ PDA @ ZIF-8;
the annealing carbonization temperature is 500-800 ℃;
the acid for pickling is an acid solution for dissolving zinc sulfide.
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