CN114976007B - Method for controllably constructing sulfide coating layer - Google Patents

Method for controllably constructing sulfide coating layer Download PDF

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CN114976007B
CN114976007B CN202210648057.7A CN202210648057A CN114976007B CN 114976007 B CN114976007 B CN 114976007B CN 202210648057 A CN202210648057 A CN 202210648057A CN 114976007 B CN114976007 B CN 114976007B
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sulfide
metal
core
lithium
oxide
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CN114976007A (en
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曹安民
刘园
孙勇刚
万立骏
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Institute of Chemistry CAS
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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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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

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Abstract

The invention provides a method for controllably constructing a sulfide coating. The method comprises the steps of uniformly mixing a core particle material, a complexing agent, metal salt and a precipitation control agent in a solvent, reacting, and calcining to obtain the core-shell structure particles containing the metal sulfide coating layer. The invention provides a method which is simple, convenient and easy to operate, mild in condition, strong in universality, uniform and controllable. The method is based on a liquid phase method at room temperature, and realizes slow precipitation of metal ions through stabilizing metal salts by a complexing agent in a solution and regulating and controlling precipitation kinetics of the metal salts after complexing by a precipitation control agent, thereby achieving uniform, continuous, complete and thickness-controllable coating effect. The core-shell structure particles containing the metal sulfide coating layer prepared by the method can be used as alkali metal ion batteries by coating the coating layer with controllable thickness on the surface of the core particle material in situ.

Description

Method for controllably constructing sulfide coating layer
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a method for controllably constructing a sulfide coating layer.
Background
In recent years, the surface of a substrate is modified, and the construction of a uniform and complete coating layer has become one of important means for modifying materials. The surface coating modification is to utilize inorganic matters or organic matters to deposit on the surface of the material to construct a coating layer with different chemical components so as to form a core-shell composite structure. By changing the characteristics of the material surface interface, the improvement of the optical, electric, magnetic, catalytic and other performances is realized, so that the exploration of the coating method has great value in the aspects of scientific research and practical application.
The excellent physical and chemical properties of sulfide make it an ideal coating layer, which has been proved to improve the problem of low conductivity of electrode materials, and at the same time, as a coating layer, can inhibit volume expansion and alleviate pulverization of materials. However, uniform coating of sulfides is often difficult to achieve, and the prior art has achieved partial adsorption effects primarily by simple mixing, and uneven contact is difficult to achieve the desired results of uniform coating. Particularly for electrode materials having a large volume change during charge and discharge, such as: the uniform and complete coating layer of silicon, tin, antimony, oxides thereof and the like can play a better role in inhibiting pulverization of materials, so that better cycle stability can be realized. In the prior art, the mixing of micron-sized and submicron-sized sulfide particles and silicon is utilized, and although the circulation stability of the material is improved to a certain extent, the sulfide particles with different sizes are difficult to realize the ideal complete coating effect, and the improvement on the stability of the material is limited. Therefore, development of a sulfide coating method capable of achieving uniformity and complete controllability is very necessary for modification of electrode materials and improvement of performance.
Disclosure of Invention
The invention aims to provide a method for coating different materials with controllable in-situ thickness by using sulfide.
The invention provides a method for preparing a metal sulfide coating layer, which comprises the steps of uniformly mixing a core particle material, a complexing agent, metal salt and a precipitation control agent in a solvent, reacting, and calcining to obtain core-shell structure particles containing the metal sulfide coating layer.
According to an embodiment of the invention, the method comprises the steps of:
(1) Adding a complexing agent, metal salt and a precipitation control agent into a solvent to prepare a solution, and then adding a nuclear particle material to react to form an intermediate containing metal and a sulfur coating; or alternatively, the first and second heat exchangers may be,
uniformly mixing a nuclear particle material, a complexing agent, metal salt and a precipitation control agent in a solvent, and reacting to form an intermediate containing metal and a sulfur coating;
(2) And (3) calcining the intermediate prepared in the step (1) to obtain the core-shell structure particles containing the metal sulfide coating layer.
According to an embodiment of the invention, the solvent is selected from water, organic solvents, preferably organic solvents.
Preferably, the organic solvent is an alcohol solvent and/or a ketone solvent.
Further, the alcohol solvent is at least one selected from methanol, ethanol, ethylene glycol, propanol, isopropanol, propylene glycol and n-butanol, preferably ethanol.
Further, the ketone solvent is selected from acetone.
According to an embodiment of the invention, the concentration of the complexing agent in the solution of step (1) is 0.02 to 0.2mol/L, preferably 0.02 to 0.1mol/L, for example 0.01mol/L, 0.02mol/L, 0.03mol/L, 0.04mol/L, 0.05mol/L, 0.1mol/L, 0.15mol/L, 0.2mol/L.
According to an embodiment of the present invention, the complexing agent is selected from at least one of ethylenediamine, propylenediamine, butylenediamine, preferably ethylenediamine.
According to an embodiment of the invention, the concentration of the metal salt in the solution of step (1) is 0.004-0.04 mol/L, preferably 0.01-0.04 mol/L, for example 0.005mol/L, 0.01mol/L, 0.02mol/L, 0.03mol/L, 0.04mol/L.
According to an embodiment of the present invention, the metal salt is a metal salt containing a metal element that undergoes coordinate precipitation with the precipitant. Preferably, the metal salt contains at least one of iron, copper, cerium or tantalum metal elements.
Preferably, the metal salt is selected from at least one of chloride, sulfate, nitrate, acetate and alkoxide of the corresponding metal element, for example, at least one of chloride, sulfate, nitrate, acetate and alkoxide of the metal element of iron, copper, cerium or tantalum.
According to an embodiment of the invention, the concentration of the precipitation control agent in the solution of step (1) is 0.01 to 1.0mol/L, preferably 0.01 to 0.1mol/L, for example 0.01mol/L, 0.02mol/L, 0.03mol/L, 0.04mol/L, 0.05mol/L, 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L, 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L, 1.0mol/L.
According to an embodiment of the present invention, the precipitation control agent is selected from at least one of thiodiacetic acid, thiodipropionic acid, dithioacetic acid, dithiopropionic acid, disulfonic acid, preferably thiodiacetic acid.
According to an embodiment of the invention, in step (1), the concentration of the core particulate material is between 0.1g/L and 150g/L, for example 1g/L, 10g/L, 20g/L, 30g/L, 40g/L, 50g/L, 60g/L, 70g/L, 80g/L, 90g/L, 100g/L, 110g/L, 120g/L, 130g/L, 140g/L, 150g/L.
According to an embodiment of the invention, the core particle material is selected from at least one of metal, non-metal, carbide, nitride, oxide, sulfide, phosphide, phosphate, lithium salt, organic particles.
Preferably, in the core particle material, the metal is selected from at least one of aluminum, ruthenium, rhodium, palladium, silver, platinum, gold, germanium, tin, antimony, and alloys thereof.
Preferably, the nonmetal is at least one selected from carbon, silicon, phosphorus, sulfur, selenium.
Preferably, the carbide is at least one selected from titanium carbide, vanadium carbide, chromium carbide, tantalum carbide, tungsten carbide, boron carbide, and silicon carbide.
Preferably, the nitride is at least one selected from titanium nitride, vanadium nitride, niobium nitride, tungsten nitride, boron nitride, silicon nitride, and phosphorus nitride.
Preferably, the oxide is at least one selected from silica, titania, vanadium pentoxide, manganese dioxide, manganic oxide, ferric oxide, tricobalt tetraoxide, nickel oxide, zirconium oxide, molybdenum oxide, indium tin oxide, lithium lanthanum zirconium oxide, and lithium lanthanum zirconium oxide.
Preferably, the sulfide is at least one selected from titanium disulfide, iron sulfide, cobalt sulfide, nickel sulfide, molybdenum sulfide, tin sulfide, and antimony sulfide.
Preferably, the phosphide is at least one selected from titanium phosphide, iron phosphide, cobalt phosphide, nickel phosphide, molybdenum phosphide and tin phosphide.
Preferably, the phosphate is at least one selected from the group consisting of phosphopeptide, titanium pyrophosphate, lithium phosphopeptide, lithium aluminum titanium phosphate, lithium vanadium phosphate, sodium vanadium phosphate, iron phosphate, lithium manganese iron phosphate, and lithium cobalt phosphate.
Preferably, the lithium salt is selected from at least one of lithium manganate, lithium cobaltate, lithium nickelate, lithium-rich lithium nickelate, for example NCM622.
Preferably, the organic matter is selected from at least one of phenolic resin, urea-formaldehyde resin, melamine value and polystyrene.
According to an exemplary aspect of the invention, the core particulate material is selected from at least one of silicon, silicon oxide, tin oxide, antimony oxide, preferably silicon or a derivative of silicon.
According to an embodiment of the present invention, in step (1), the reaction is performed under stirring.
According to an embodiment of the invention, in step (1), the temperature of the reaction is between 10 and 40 ℃, for example between 10 ℃, 20 ℃, 30 ℃, 40 ℃; the reaction time is 1 to 24 hours, for example, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 15 hours, 20 hours.
According to an embodiment of the invention, in step (2), the calcination temperature is 400-1000 ℃, for example 400 ℃, 500 ℃, 600 ℃, 700 ℃, 800 ℃, 900 ℃, 1000 ℃; the calcination time is 1 to 24 hours, for example, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 15 hours, 20 hours.
According to an embodiment of the present invention, in step (2), the calcined atmosphere is at least one selected from the group consisting of air, oxygen, nitrogen, argon, hydrogen-argon mixture and hydrogen-nitrogen mixture.
The invention also provides a core-shell structure particle containing the metal sulfide coating layer, which is prepared by the method, wherein the metal sulfide coating layer grows in situ on the surface of the core particle, and the metal sulfide coating layer is uniform, continuous and complete.
According to an embodiment of the present invention, the metal sulfide is selected from at least one of manganese sulfide, iron sulfide, copper sulfide, zinc sulfide, tin sulfide, cerium sulfide, tantalum sulfide.
Illustratively, the core-shell structured particles may be iron sulfide coated polystyrene nanoparticles, cerium sulfide coated aluminum nanoparticles, iron sulfide coated silicon nanoparticles, tantalum sulfide coated NCM622 particles.
According to an embodiment of the present invention, the thickness of the metal sulfide coating layer is 1 to 200nm. Preferably, the thickness of the coating layer is 1 to 50nm, for example, 10nm, 20nm, 30nm, 40nm, 50nm.
According to an embodiment of the invention, the average particle size of the core structure is 50nm to 10 μm, for example 50nm, 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1 μm, 10 μm or a range between any two of the values mentioned above.
According to an embodiment of the present invention, the content of the metal sulfide is 0.01% to 10%, for example, 0.01%, 0.05%, 0.1%, 0.5%, 1%, 5%, 10% based on the total weight of the core-shell material. Preferably, the molar ratio of metal to elemental sulfur is from 1:1 to 1:3, for example 1:1, 1:1.5, 1:2, 1:2.5, 1:3.
The invention also provides application of the core-shell structure particles in the energy storage field, and the core-shell structure particles are preferably used for alkali metal ion batteries.
According to an embodiment of the invention, the alkali metal ion battery is selected from any one of a lithium ion battery, a sodium ion battery or a potassium ion battery.
The invention also provides a high-energy storage device comprising the core-shell structured particles described above. Preferably, the high energy storage device is a lithium ion battery.
The invention has the beneficial effects that:
the method of the invention can be used as a modification means for in-situ thickness-controllable coating of nuclear particle materials.
The core-shell structure particles containing the metal sulfide coating layer prepared by the method can be used as alkali metal ion batteries by coating the coating layer with controllable thickness on the surface of the core particle material in situ.
The thickness of the metal sulfide coating layer obtained by the coating method is controllable, namely the self precipitation dynamics process of the metal sulfide is controlled, namely the degree of freedom of metal ions, the ionic strength of solution and the surface electrical property and adsorption capacity of the nuclear particle material are controlled, the self nucleation homogeneous growth trend is reduced, the in-situ growth of the metal sulfide on the surface of the nuclear is promoted, a uniform, continuous and complete metal sulfide coating layer is obtained, and the thickness of the metal sulfide coating layer can be adjusted by changing the quantity of initial metal salt or the nuclear particle material. The liquid phase method adopted by the invention has the advantages of simple coating method, mild reaction condition, strong universality and very high practicability and application prospect in the field of alkali metal ion batteries.
The invention realizes a layer of uniform metal sulfide coating layer on the surface of the nuclear particle material by utilizing the method of in-situ growth of the metal sulfide, can prevent side reaction between the nuclear particle material and electrolyte solution, can reduce the surface film impedance and charge transfer impedance of the nuclear particle material, accelerates the diffusion speed of lithium ions, and obviously improves the cycle performance and the multiplying power performance of the nuclear particle material. And the electrochemical performance of the material can be optimized by regulating and controlling the thickness of the metal sulfide coating layer, so that the optimal thickness of the metal sulfide coating layer and the optimal electrochemical performance can be determined.
The invention provides a method which is simple, convenient and easy to operate, mild in condition, strong in universality, uniform and controllable. The method is based on a liquid phase method at room temperature, and realizes slow precipitation of metal ions through stabilizing metal salts by a complexing agent in a solution and regulating and controlling precipitation kinetics of the metal salts after complexing by a precipitation control agent, thereby achieving uniform, continuous, complete and thickness-controllable coating effect. In addition, the method can realize controllable coating on different substrate surfaces.
Drawings
Fig. 1 is a transmission electron micrograph of iron sulfide coated polystyrene nanoparticles of example 1.
Fig. 2 is a transmission electron micrograph of cerium sulfide coated aluminum nanoparticles of example 2.
Fig. 3 is a transmission electron micrograph of iron sulfide coated silicon nanoparticles of example 3.
FIG. 4 is a graph showing the cycling performance of the iron sulfide coated silicon nanoparticle of example 3 at a charge-discharge current of 840 mA/g.
Fig. 5 is a transmission electron micrograph of tantalum sulfide coated NCM622 particles of example 4.
Detailed Description
The technical scheme of the invention will be further described in detail below with reference to specific embodiments. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods.
Example 1
Preparation of iron sulfide coated polystyrene nanoparticles with core-shell structure
Polystyrene nanoparticles having an average particle diameter of 700nm as a core, ethylenediamine as a complexing agent, 0.1g of ferric chloride as an iron salt, and 0.15g of thiodiacetic acid as a precipitation control agent were mixed in 35ml of ethanol, reacted for 5 hours at room temperature with stirring, centrifuged, washed, and dried to obtain sulfide-coated polystyrene nanoparticles containing sulfur and iron, and the obtained particles were calcined at 700℃under an argon atmosphere for 3 hours to obtain iron sulfide-coated polystyrene particles.
The polystyrene nanoparticle coated with the ferric sulfide has a core-shell structure, and a transmission electron microscope photo of the polystyrene nanoparticle is shown in figure 1. The material forming the core is polystyrene nano particles with the average particle diameter of 700nm, the material forming the shell is sulfide, the thickness of the shell is 50nm, and the surface of the polystyrene nano particles is uniformly covered with ferric sulfide.
Example 2
Preparation of cerium sulfide coated aluminum nanoparticles with core-shell structure
80mg of aluminum particles with the average particle diameter of 80nm, 0.15g of thiodiacetic acid, 0.2g of cerium nitrate and 100 mu L of ethylenediamine are mixed in 35ml of ethanol, reacted for 5 hours at room temperature under stirring, centrifuged, washed and dried, and the obtained particles are calcined for 3 hours under an argon atmosphere at 700 ℃ to obtain cerium sulfide coated aluminum particles.
The cerium sulfide coated aluminum particles have a core-shell structure, and a transmission electron microscope photo of the cerium sulfide coated aluminum particles is shown in fig. 2. The material forming the core is aluminum particles with the average particle diameter of 80nm, the material forming the shell is cerium sulfide, the thickness of the shell is 15nm, and the cerium sulfide uniformly covers the surfaces of the aluminum particles.
Example 3
1. Preparation of iron sulfide coated silicon particles with core-shell structure
60mg of silicon particles having an average particle diameter of 50nm, 0.15g of thiodiacetic acid, 0.1g of ferric chloride and 100. Mu.L of ethylenediamine were mixed in 35ml of ethanol, reacted at room temperature for 5 hours under stirring, centrifuged, washed and dried, and the obtained particles were calcined at 700℃under an argon atmosphere for 3 hours to obtain iron sulfide-coated silicon particles.
The silicon particles coated with the ferric sulfide are of a core-shell structure, and a transmission electron microscope photo of the silicon particles is shown in figure 3. The material constituting the core is silicon particles with an average particle diameter of 50nm, the material constituting the shell is iron sulfide, the thickness of the shell is 10nm, and the iron sulfide uniformly covers the surface of the silicon particles.
2. Preparation of iron sulfide coated silicon electrode
Mixing 0.16g of the prepared silicon particles coated with the ferric sulfide with 0.02g of acetylene black serving as a conductive additive, 0.4g of sodium alginate with the mass concentration of 5% of a binder and a little solvent water, pulping, smearing (taking a copper sheet as a current collector), and drying to obtain the silicon electrode coated with the ferric sulfide.
3. Assembled battery
The prepared silicon electrode coated with ferric sulfide is used as a working electrode, and is assembled with metallic lithium as a negative electrode to form a battery 3, wherein the electrolyte is carbonate electrolyte with the concentration of 1M, and the solvent is DMC: DEC: ec=1: 1:1 (W/W/W), the solute is LiPF 6 。
4. Battery testing
And (3) carrying out constant current charge and discharge test on the battery by using a charge and discharge instrument, wherein the test voltage interval is 0.005-1.5V, and the test temperature is 25 ℃. The specific capacity of the battery and the charge-discharge current are calculated by the mass of silicon.
Comparative example 1
The comparative battery 1 was assembled, except that the negative electrode material was a silicon particulate material that was not coated, and the rest was referred to example 3.
Fig. 4 shows the cycle performance of the batteries of example 3 and comparative example 1 at a charge/discharge current of 840mA/g, and it can be seen from the graph that the battery 3 of example 3 has a capacity of 768mAh/g after 100 cycles, while the comparative battery 1 has almost no capacity. This is because the negative electrode material of comparative example 1 is not coated, and the silicon negative electrode material is extremely susceptible to swelling and deformation. Therefore, the method can form a uniform and complete coating layer on the surface of the silicon anode material, is favorable for exerting the high capacity characteristic of the material and avoids the reduction of the circulation stability caused by pulverization of the material.
Example 4
Preparation of tantalum sulfide coated NCM622 particles with core-shell structure
600mg (average particle size: 500 nm) of NCM622 particles, 0.15g of thiodiacetic acid, 0.13g of tantalum chloride and 100. Mu.L of ethylenediamine were mixed in 35ml of ethanol, reacted at room temperature under stirring for 5 hours, centrifuged, washed and dried, and the obtained particles were calcined at 700℃under an argon atmosphere for 3 hours to obtain tantalum sulfide-coated NCM622 particles. The tantalum sulfide coated NCM622 particles were of core-shell structure and their transmission electron microscopy photographs were shown in FIG. 5. The material forming the core is NCM622 particles with the particle size of 100-500 nm, the material forming the shell is tantalum sulfide, the thickness of the shell is 20nm, and the tantalum sulfide uniformly covers the surfaces of the NCM622 particles.
The above description has been given of exemplary embodiments of the present invention. However, the present invention is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, or the like, which are within the spirit and principles of the present invention, should be made by those skilled in the art, and are intended to be included within the scope of the present invention.

Claims (15)

1. A method of forming a metal sulfide coating, the method comprising the steps of:
(1) Adding a complexing agent, metal salt and a precipitation control agent into a solvent to prepare a solution, and then adding a nuclear particle material to react to form an intermediate containing metal and a sulfur coating; or alternatively, the first and second heat exchangers may be,
uniformly mixing a nuclear particle material, a complexing agent, metal salt and a precipitation control agent in a solvent, and reacting to form an intermediate containing metal and a sulfur coating;
in the step (1), the temperature of the reaction is 10-40 ℃; the reaction time is 1-24 h;
(2) Calcining the intermediate prepared in the step (1) to obtain core-shell structure particles containing a metal sulfide coating layer; the calcining temperature is 400-1000 ℃; the calcination time is 1-24 h; the metal sulfide is at least one selected from manganese sulfide, iron sulfide, copper sulfide, zinc sulfide, tin sulfide, cerium sulfide and tantalum sulfide;
the core particle material is selected from at least one of metal, nonmetal, carbide, nitride, oxide, sulfide, phosphide, phosphate, lithium salt and organic particles;
the complexing agent is at least one selected from ethylenediamine, propylenediamine and butylenediamine;
the metal salt is a metal salt containing a metal element which is coordinately precipitated with the precipitation control agent;
the precipitation control agent is at least one selected from thiodiacetic acid, thiodipropionic acid, dithioacetic acid, dithiopropionic acid and disulfonic acid.
2. The method according to claim 1, wherein the solvent is selected from the group consisting of water, organic solvents;
the organic solvent is an alcohol solvent and/or a ketone solvent.
3. The method according to claim 2, wherein the alcohol solvent is selected from at least one of methanol, ethanol, ethylene glycol, propanol, isopropanol, propylene glycol, n-butanol;
the ketone solvent is selected from acetone.
4. The method of claim 1, wherein the concentration of the complexing agent in the solution of step (1) is 0.02-0.2 mol/L;
and/or, the complexing agent is ethylenediamine.
5. The method of claim 1, wherein the concentration of the metal salt in the solution of step (1) is 0.004-0.04 mol/L;
and/or the metal salt contains at least one of iron, copper, cerium or tantalum metal elements;
and/or the metal salt is selected from at least one of chloride, sulfate, nitrate, acetate and alkoxide of the corresponding metal element.
6. The method of claim 1, wherein the concentration of the precipitation control agent in the solution of step (1) is 0.01-1.0 mol/L;
and/or, the precipitation control agent is thiodiacetic acid.
7. The method according to claim 1, wherein in step (1), the concentration of the core particle material is 0.1g/L to 150g/L;
and/or, in the core particulate material, the metal is selected from at least one of aluminum, ruthenium, rhodium, palladium, silver, platinum, gold, germanium, tin, antimony, and alloys thereof;
and/or the nonmetal is at least one of carbon, silicon, phosphorus, sulfur and selenium;
and/or the carbide is at least one of titanium carbide, vanadium carbide, chromium carbide, tantalum carbide, tungsten carbide, boron carbide and silicon carbide;
and/or the nitride is at least one selected from titanium nitride, vanadium nitride, niobium nitride, tungsten nitride, boron nitride, silicon nitride and phosphorus nitride;
and/or the oxide is at least one selected from silicon dioxide, titanium dioxide, vanadium pentoxide, manganese dioxide, manganic oxide, ferric oxide, cobaltosic oxide, nickel oxide, zirconium oxide, molybdenum oxide, indium tin oxide, lithium lanthanum zirconium oxide and lithium lanthanum zirconium oxide;
and/or the sulfide is at least one selected from titanium disulfide, iron sulfide, cobalt sulfide, nickel sulfide, molybdenum sulfide, tin sulfide and antimony sulfide;
and/or the phosphide is at least one selected from titanium phosphide, iron phosphide, cobalt phosphide, nickel phosphide, molybdenum phosphide and tin phosphide;
and/or the phosphate is at least one selected from phosphopeptide, titanium pyrophosphate, lithium phosphopeptide, lithium aluminum titanium phosphate, lithium vanadium phosphate, sodium vanadium phosphate, ferric phosphate, lithium iron manganese phosphate and lithium cobalt phosphate;
and/or the lithium salt is at least one selected from lithium manganate, lithium cobaltate, lithium nickelate and lithium-rich lithium nickelate;
and/or the organic matter is selected from at least one of phenolic resin, urea-formaldehyde resin, melamine resin and polystyrene.
8. The method of claim 7, wherein the core particulate material is selected from at least one of silicon, silicon oxide, tin oxide, antimony oxide.
9. The process of claim 1, wherein in step (1), the reaction is carried out under stirring;
and/or in the step (2), the calcined atmosphere is at least one selected from air, oxygen, nitrogen, argon, hydrogen-argon mixture and hydrogen-nitrogen mixture.
10. A core-shell structured particle comprising a metal sulfide coating layer, wherein the core-shell structured particle is prepared by the method of any one of claims 1-9, wherein the metal sulfide coating layer grows in situ on the surface of the core particle, and the metal sulfide coating layer is uniform, continuous, and complete.
11. The core-shell structured particle of claim 10, wherein the metal sulfide is selected from at least one of manganese sulfide, iron sulfide, copper sulfide, zinc sulfide, tin sulfide, cerium sulfide, tantalum sulfide.
12. The core-shell structured particle of claim 10, wherein the metal sulfide coating layer has a thickness of 1-200 nm;
and/or the average particle diameter of the core structure is 50 nm-10 mu m;
and/or, taking the total weight of the core-shell material as a reference, the content of the metal sulfide is 0.01% -10%;
and/or the molar ratio of the metal to the sulfur element is 1:1-1:3.
13. The core-shell structured particle of claim 12, wherein the metal sulfide coating layer has a thickness of 1 to 50nm.
14. Use of the core-shell structured particles according to any one of claims 10 to 13 in the field of energy storage.
15. A high energy storage device comprising the core-shell structured particle of any one of claims 10-13.
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