CN110660986A - Tin-based composite material, preparation method and application thereof - Google Patents

Tin-based composite material, preparation method and application thereof Download PDF

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CN110660986A
CN110660986A CN201911087812.3A CN201911087812A CN110660986A CN 110660986 A CN110660986 A CN 110660986A CN 201911087812 A CN201911087812 A CN 201911087812A CN 110660986 A CN110660986 A CN 110660986A
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sno
precursor
tin
composite material
based composite
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CN110660986B (en
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苏发兵
李琼光
王艳红
谭强强
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Institute of Process Engineering of CAS
Langfang Institute of Process Engineering of CAS
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Institute of Process Engineering of CAS
Langfang Institute of Process Engineering of 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
    • H01M4/36—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
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • 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
    • H01M4/625—Carbon or graphite
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • 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

Abstract

The invention relates to a tin-based composite material, a preparation method and application thereof. The method comprises the following steps: (1) SnO2Mixing water solutions of nano particles, a carbon source and an organic reagent to obtain a mixed solution, and heating the mixed solution to obtain SnO2The @ C precursor; (2) SnO obtained in step (1)2Mixing the @ C precursor, the dispersing agent and the organic reagent to obtain precursor suspension, and carrying out mixed reaction on the metal salt solution, the imidazole solution and the precursor suspension to obtain SnO2@ C @ NC precursor; (3) SnO in the step (2)2And carbonizing the @ C @ NC precursor to obtain the tin-based composite material. The preparation method of the tin-based composite material solves the problemsThe key problem of preparing the tin-based composite material in the prior art is solved, the preparation process is simple, the preparation cost is low, the process is clean and pollution-free, the material performance is excellent, and different requirements of the market can be met.

Description

Tin-based composite material, preparation method and application thereof
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to a tin-based composite material, and a preparation method and application thereof.
Background
Because of the characteristics of high energy density, environmental friendliness, no memory effect and the like, the development of lithium ion batteries is receiving attention and becomes one of the secondary batteries with the widest application range at present. The graphite negative electrode material cannot meet the requirement of a high specific energy battery, so that a negative electrode material with high energy density and low preparation cost is urgently needed to be developed. The Sn-based negative electrode material has the advantages of high theoretical specific capacity, good safety performance, simple preparation process, low cost and the like, and is considered to be a new generation of negative electrode material of the lithium ion battery with good commercial prospect. But due to problems of volume expansion during lithium intercalation and SnO2The conductivity problem of (a) severely hinders the cycle performance and safety performance of the Sn-based negative electrode material.
At present, the performance of the composite material is improved by adopting a method of compounding tin dioxide and graphene. The invention patent CN108649203A discloses a preparation method of a tin dioxide/graphene composite material, which comprises the steps of firstly obtaining expanded graphite through pretreatment, then obtaining the tin dioxide/graphene composite material through high-pressure hydrothermal reaction and twice heat treatment, and the preparation method is complex in operation and process and simultaneously shows poor electrochemical performance. The invention patent CN108793233A discloses a preparation method of a multilayer hollow tin oxide material, expanded graphite is compounded with tin oxide through series processes of microwave, ultrasonic, copolymerization, crosslinking and the like to obtain the multilayer hollow tin oxide material, and the steps are complicated, so that the further application of the multilayer hollow tin oxide material is limited. The invention patent CN109167047A discloses a preparation method of a self-supporting three-dimensional graphene/tin composite material, but the high cost of the graphene oxide material limits the commercial development of the graphene oxide material. The invention patent CN107369819A discloses a preparation method of an egg-shaped double-carbon shell tin-based composite material, but the preparation process is repeatedThe use of the template method seriously hinders the mass production thereof. The invention patent CN108321376A discloses a CNF @ SnO2The preparation method of the nano composite material cannot meet the current requirement of the negative electrode material on the electrochemical performance.
Therefore, the development of a novel negative electrode material is needed in the field, so that the novel negative electrode material has the advantages of high capacity density, good conductivity, simple preparation process, low preparation cost and the like, and has a good application prospect.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a tin-based composite material, a preparation method and application thereof. The preparation method of the tin-based composite material solves the key problems of complex process flow, poor material performance and the like of the tin-based composite material prepared by the prior art, has low preparation cost and clean and pollution-free process, and can meet different requirements of the market.
One of the purposes of the invention is to provide a preparation method of a tin-based composite material, which comprises the following steps:
(1) SnO2Mixing water solutions of nano particles, a carbon source and an organic reagent to obtain a mixed solution, and heating the mixed solution to obtain SnO2The @ C precursor;
(2) SnO obtained in step (1)2Mixing the @ C precursor, the dispersing agent and the organic reagent to obtain precursor suspension, and carrying out mixed reaction on the metal salt solution, the imidazole solution and the precursor suspension to obtain SnO2@ C @ NC precursor;
(3) SnO in the step (2)2And carbonizing the @ C @ NC precursor to obtain the tin-based composite material.
The invention adopts a solution method to synthesize SnO2Precursor material of @ C, making SnO2The nano particles are confined in a carbon skeleton structure, and are beneficial to coating a ZIF material to obtain SnO2A precursor of @ C @ NC. Then carrying out carbonization treatment in inert atmosphere to obtain the final product SnO2@C@NC。
SnO in the present invention2@ C represents a carbon-coated core-shell structure,wherein SnO2Is core, C is shell; SnO2@ C @ NC stands for SnO coated by NC (N-doped C layer)2The structure of @ C.
The preparation method of the tin-based composite material provided by the invention has the advantages of simple process, low preparation cost, clean and pollution-free process and excellent material performance, and can meet different requirements of the market.
Preferably, said SnO in step (1)2The nanoparticles include any one or a combination of at least two of a nano spherical particle, a nano flaky particle, a nano ribbon-shaped particle, a nano box-shaped particle and a nano linear particle.
Preferably, the SnO2The size of the nanoparticles is 3-500 nm, preferably 10-80 nm, such as 5nm, 10nm, 50nm, 100nm, 120nm, 150nm, 180nm, 200nm, 220nm, 250nm, 280nm, 300nm, 320nm, 350nm, 380nm, 400nm, 420nm, 450nm or 480 nm.
SnO in the present invention2The oversize of the nano particles is not beneficial to coating of the ZIF material; SnO2The nano particles are too small, so that the agglomeration phenomenon is easy to occur, and the performance of the material is influenced.
Preferably, said SnO in step (1)2The nanoparticles are any one of amorphous materials, single crystal materials or polycrystalline materials.
Preferably, the organic reagents in step (1) and step (2) are independently selected from any one of methanol, ethanol, propanol, ethylene glycol, glycerol, acetone and carbon tetrachloride or the combination of at least two of the above.
Preferably, the volume ratio of the organic reagent to water in the aqueous solution of the organic reagent in the step (1) is 1 (0.01-100), more preferably 1 (0.1-10), such as 1:0.02, 1:0.05, 1:0.1, 1:0.5, 1:0.8, 1:1, 1:2, 1:5, 1:8, 1:10, 1:15, 1:20, 1:30, 1:40, 1:50, 1:60, 1:70, 1:80, or 1: 90.
The volume ratio of the organic reagent to water is 1 (0.01-100), and the solution in the ratio range is beneficial to the uniform coating of the carbon layer.
Preferably, said SnO in step (1)2The mass ratio of the nano particles to the carbon source is 1 (0.1 to up to10) For example, 1:0.5, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5, 1:6, 1:6.5, 1:7, 1:7.5, 1:8, 1:8.5, 1:9, or 1:9.5, etc.
SnO in the present invention2The mass ratio of the nano particles to the carbon source is 1 (0.1-10), and a uniformly coated carbon layer cannot be formed due to an excessively large mass ratio; the mass ratio is too small to facilitate the increase of the capacity of the material.
Preferably, the carbon source in step (1) is a mixed material of a phenolic reagent and an aldehyde reagent, or a carbohydrate.
The carbon source in the invention selects the mixed material of the phenolic reagent and the aldehyde reagent or the carbohydrate, which is beneficial to simplifying the operation flow and reducing the preparation cost of the material.
Preferably, the phenolic reagent comprises any one of phenol, 2-aminophenol, 3-aminophenol, 4-aminophenol, nitrophenol and p-nitrophenol or a combination of at least two thereof.
Preferably, the aldehyde reagent is formaldehyde.
The mass ratio of the phenol reagent to the aldehyde reagent is preferably 1 (0.1 to 10), more preferably 1 (1 to 5), for example, 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.8, 1:1, 1:2, 1:3, 1:5, or 1:8.
Preferably, the carbon source is a mixed material of a phenol reagent and an aldehyde reagent, and the pH value of the mixed solution needs to be adjusted by using ammonia water before the mixed solution is heated.
Preferably, the pH value is 8-12, preferably 9-10, such as 8, 9, 10, 11 or 12.
Preferably, the carbohydrate comprises any one of or a combination of at least two of glucose, sucrose, maltose, cellulose, chitosan and lignin.
Preferably, the heating temperature in step (1) is 10 to 80 ℃, preferably 20 to 40 ℃, such as 15 ℃, 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃ or 70 ℃.
Preferably, the heating mode of the step (1) is water bath heating or oil bath heating.
Preferably, the heating time in step (1) is 5min to 72h, preferably 12 to 36h, such as 10min, 15min, 20min, 30min, 40min, 50min, 1h, 2h, 5h, 8h, 10h, 12h, 15h, 20h, 24h, 28h, 30h, 35h, 40h, 48h, 50h, 55h, 60h or 70 h.
Preferably, after the heating in step (1), the process further comprises the steps of filtering, washing and drying.
Preferably, the filtration mode is centrifugal filtration or suction filtration.
Preferably, the washing reagent comprises any one of distilled water, ethanol, methanol, propanol, ethylene glycol and glycerol or a combination of at least two of the above.
Preferably, the drying means is vacuum drying, forced air drying or freeze drying.
Preferably, the drying temperature is-50 to 200 ℃, such as-40 ℃, -20 ℃, -10 ℃, 50 ℃, 80 ℃, 100 ℃, 120 ℃, 150 ℃ or 180 ℃.
Preferably, the dispersant of step (2) comprises cetyltrimethylammonium bromide and/or polyethylene glycol.
Preferably, said SnO in step (2)2The mass ratio of the @ C precursor to the dispersant is 1 (0.1-10), for example, 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.8, 1:1, 1:2, 1:3, 1:5, 1:6, 1:8, or 1:9.
SnO in the present invention2The mass ratio of the @ C precursor to the dispersing agent is 1 (0.1-10), the mass ratio is too large, and SnO2The @ C precursor is too much, the dispersing agent is too little, and the dispersion of particles is not facilitated; too small a mass ratio, SnO2The @ C precursor is too little, and the dispersing agent is too much, so that the preparation cost is not reduced.
Preferably, the preparation process of the metal salt solution in the step (2) comprises: and mixing the metal salt with an organic solvent to obtain a metal salt solution.
Preferably, the preparation process of the imidazole solution in the step (2) comprises the following steps: mixing an imidazole reagent with an organic solvent to obtain an imidazole solution.
Preferably, the metal salt comprises a cobalt salt or a zinc salt.
Preferably, the cobalt salt comprises any one of cobalt nitrate, cobalt sulfate, cobalt chloride and cobalt acetate or a combination of at least two thereof.
Preferably, the zinc salt includes any one of zinc nitrate, zinc sulfate, zinc chloride and zinc acetate or a combination of at least two thereof.
Preferably, the imidazole reagent includes any one or a combination of at least two of imidazole, 2-methylimidazole, 4-methylimidazole, 2, 4-dimethylimidazole, 1-vinylimidazole, N-ethylimidazole, N-propylimidazole, N-acetylimidazole, 2-bromo-4-nitroimidazole, and 4-nitroimidazole.
Preferably, the organic solvent includes any one of methanol, ethanol, propanol, ethylene glycol, glycerol and acetone or a combination of at least two thereof.
Preferably, said SnO in step (2)2The mass ratio of the @ C precursor to the metal salt in the metal salt solution is 1 (1-50), for example, 1:5, 1:10, 1:15, 1:20, 1:25, 1:30, 1:35, 1:40, or 1: 45.
Preferably, said SnO in step (2)2The mass ratio of the @ C precursor to the imidazole reagent in the imidazole solution is 1 (1-60), for example, 1:5, 1:10, 1:15, 1:20, 1:25, 1:30, 1:35, 1:40, 1:45, 1:50, or 1: 55.
Preferably, the mixing reaction of the metal salt solution, the imidazole solution and the precursor suspension in the step (2) is performed in a manner that: stirring and mixing.
Preferably, the stirring and mixing is stirring and mixing at room temperature.
Preferably, the stirring and mixing time is 5min to 72h, preferably 12 to 36h, such as 10min, 15min, 20min, 30min, 40min, 50min, 1h, 2h, 5h, 8h, 10h, 12h, 15h, 20h, 24h, 28h, 30h, 35h, 40h, 48h, 50h, 55h, 60h or 70 h.
Preferably, the mixing reaction mode of the metal salt solution, the imidazole solution and the precursor suspension in the step (2) is as follows: the temperature of the hydrothermal reaction is 80 to 200 ℃, for example, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃ or 180 ℃.
Preferably, the hydrothermal reaction time is 5min to 72h, preferably 12 to 36h, such as 10min, 15min, 20min, 30min, 40min, 50min, 1h, 2h, 5h, 8h, 10h, 12h, 15h, 20h, 24h, 28h, 30h, 35h, 40h, 48h, 50h, 55h, 60h or 70 h.
Preferably, the mixing reaction further comprises the processes of filtering, washing and drying.
Preferably, the filtration mode is centrifugal filtration or suction filtration.
Preferably, the washing reagent comprises any one of distilled water, ethanol, methanol, propanol, ethylene glycol and glycerol or a combination of at least two of the above.
Preferably, the drying means is vacuum drying, forced air drying or freeze drying.
Preferably, the drying temperature is-50 to 200 ℃, such as-40 ℃, -20 ℃, -10 ℃, 50 ℃, 80 ℃, 100 ℃, 120 ℃, 150 ℃ or 180 ℃.
Preferably, the carbonization treatment in the step (3) is performed under an inert atmosphere.
Preferably, the gas in the inert atmosphere comprises any one of nitrogen, argon and helium or a combination of at least two thereof.
Preferably, the temperature of the carbonization treatment in the step (3) is 500 to 1200 ℃, such as 600 ℃, 700 ℃, 800 ℃, 900 ℃, 1000 ℃ or 1100 ℃.
Preferably, the carbonization treatment time in the step (3) is 30min to 12h, such as 50min, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h or 11 h.
Preferably, the carbonization treatment in step (3) is carried out in a fixed bed, a stirred bed, a fluidized bed or a tubular furnace.
As a preferred technical scheme, the preparation method of the tin-based composite material comprises the following steps:
(1) SnO with the size of 10-80 nm2Mixing nanoparticles, a carbon source and an aqueous solution of an organic reagent, wherein the volume ratio of the organic reagent to water in the aqueous solution of the organic reagent is 1 (0.1-10), and the SnO2The mass ratio of the nano particles to the carbon source is 1 (0.1-10), so as to obtain a mixed solution, and mixingHeating the mixed solution at 20-40 ℃ for 12-36 h, filtering, washing and drying at-50-200 ℃ to obtain SnO2The @ C precursor;
(2) SnO obtained in step (1)2Mixing the @ C precursor, the dispersing agent and the organic reagent to obtain a precursor suspension, stirring and mixing the metal salt solution, the imidazole solution and the precursor suspension at room temperature for 12-36 h, wherein the SnO is2The mass ratio of the @ C precursor to the metal salt in the metal salt solution is 1 (1-50), and the SnO2The mass ratio of the @ C precursor to the imidazole reagent in the imidazole solution is 1 (1-60), and SnO2The mass ratio of the @ C precursor to the dispersing agent is 1 (0.1-10), and filtering, washing and drying are carried out to obtain SnO2@ C @ NC precursor;
or SnO obtained in the step (1)2Mixing the @ C precursor, the dispersing agent and the organic reagent to obtain precursor turbid liquid, mixing the metal salt solution, the imidazole solution and the precursor turbid liquid, and carrying out hydrothermal reaction at the temperature of 80-200 ℃ for 12-36 h, wherein the SnO2The mass ratio of the @ C precursor to the metal salt in the metal salt solution is 1 (1-50), and the SnO2The mass ratio of the @ C precursor to the imidazole reagent in the imidazole solution is 1 (1-60), and SnO2The mass ratio of the @ C precursor to the dispersing agent is 1 (0.1-10), and filtering, washing and drying are carried out to obtain SnO2@ C @ NC precursor;
(3) SnO in the step (2)2And (3) carbonizing the @ C @ NC precursor at 500-1200 ℃ for 30 min-12 h to obtain the tin-based composite material.
As one of the preferred technical schemes, the invention provides a method for preparing ZIF-67 coated SnO by adopting a solution method2A method of a @ C precursor, comprising the steps of:
(1) SnO2Mixing nanoparticles, a carbon source and an aqueous solution of an organic reagent, wherein the volume ratio of the organic reagent to water in the aqueous solution of the organic reagent is 1 (0.1-10), and the SnO2The mass ratio of the nano particles to the carbon source is 1 (0.1-10), obtaining a mixed solution, heating the mixed solution at 20-40 ℃ for 12-36 h, filtering, washing and drying at-50-200 ℃ to obtain SnO2The @ C precursor;
(2) SnO2Dissolving the @ C precursor in organic solvent, adding dispersant, and ultrasonic dispersing to obtain SnO2The mass ratio of the @ C precursor to the dispersing agent is 1 (0.1-10), and SnO is obtained2The @ C precursor suspension is prepared by respectively dissolving cobalt salt and imidazole reagents in organic solvents to form a cobalt salt solution and an imidazole solution, and then mixing the cobalt salt solution and the imidazole solution with SnO2Mixing the suspension of the @ C precursor, stirring and reacting at room temperature, filtering, washing and drying to obtain SnO2@ C @ NC precursor;
(3) SnO in the step (2)2And (3) carbonizing the @ C @ NC precursor at 500-1200 ℃ for 30 min-12 h to obtain the tin-based composite material.
As the second preferred technical scheme, the invention provides a method for preparing ZIF-8 coated SnO by adopting a solution method2A method of a @ C precursor, comprising the steps of:
(1) SnO2Mixing nanoparticles, a carbon source and an aqueous solution of an organic reagent, wherein the volume ratio of the organic reagent to water in the aqueous solution of the organic reagent is 1 (0.1-10), and the SnO2The mass ratio of the nano particles to the carbon source is 1 (0.1-10), obtaining a mixed solution, heating the mixed solution at 20-40 ℃ for 12-36 h, filtering, washing and drying at-50-200 ℃ to obtain SnO2The @ C precursor;
(2) SnO2Dissolving the @ C precursor in organic solvent, adding dispersant, and ultrasonic dispersing to obtain SnO2The mass ratio of the @ C precursor to the dispersing agent is 1 (0.1-10), and SnO is obtained2The preparation method comprises the following steps of (1) dissolving zinc salt and an imidazole reagent in an organic solvent respectively to form a zinc salt solution and an imidazole solution, and then mixing the zinc salt solution and the imidazole solution with SnO2Mixing the suspension of the @ C precursor, stirring and reacting at room temperature, filtering, washing and drying to obtain SnO2@ C @ NC precursor;
(3) SnO in the step (2)2And (3) carbonizing the @ C @ NC precursor at 500-1200 ℃ for 30 min-12 h to obtain the tin-based composite material.
As a third preferred technical scheme, the invention provides a method for preparing ZI by adopting a solvothermal methodF-67 coated SnO2A method of a @ C precursor, comprising the steps of:
(1) SnO2Mixing nanoparticles, a carbon source and an aqueous solution of an organic reagent, wherein the volume ratio of the organic reagent to water in the aqueous solution of the organic reagent is 1 (0.1-10), and the SnO2The mass ratio of the nano particles to the carbon source is 1 (0.1-10), obtaining a mixed solution, heating the mixed solution at 20-40 ℃ for 12-36 h, filtering, washing and drying at-50-200 ℃ to obtain SnO2The @ C precursor;
(2) SnO2Dissolving the @ C precursor in organic solvent, adding dispersant, and ultrasonic dispersing to obtain SnO2The mass ratio of the @ C precursor to the dispersing agent is 1 (0.1-10), and SnO is obtained2The @ C precursor suspension is prepared by respectively dissolving cobalt salt and imidazole reagents in organic solvents to form a cobalt salt solution and an imidazole solution, and then mixing the cobalt salt solution and the imidazole solution with SnO2Mixing the @ C precursor turbid liquid, carrying out hydrothermal reaction at 80-200 ℃ for 12-36 h, filtering, washing and drying to obtain SnO2@ C @ NC precursor;
(3) SnO in the step (2)2And (3) carbonizing the @ C @ NC precursor at 500-1200 ℃ for 30 min-12 h to obtain the tin-based composite material.
As a fourth preferred technical scheme, the invention provides a method for preparing ZIF-8 coated SnO by adopting a solvothermal method2A method of a @ C precursor, comprising the steps of:
(1) SnO2Mixing nanoparticles, a carbon source and an aqueous solution of an organic reagent, wherein the volume ratio of the organic reagent to water in the aqueous solution of the organic reagent is 1 (0.1-10), and the SnO2The mass ratio of the nano particles to the carbon source is 1 (0.1-10), obtaining a mixed solution, heating the mixed solution at 20-40 ℃ for 12-36 h, filtering, washing and drying at-50-200 ℃ to obtain SnO2The @ C precursor;
(2) SnO2Dissolving the @ C precursor in organic solvent, adding dispersant, and ultrasonic dispersing to obtain SnO2The mass ratio of the @ C precursor to the dispersing agent is 1 (0.1-10), and SnO is obtained2Suspending the @ C precursor in suspension with zinc saltRespectively dissolving imidazole reagent in organic solvent to obtain zinc salt solution and imidazole solution, and mixing them with SnO2Mixing the @ C precursor turbid liquid, carrying out hydrothermal reaction at 80-200 ℃ for 12-36 h, filtering, washing and drying to obtain SnO2@ C @ NC precursor;
(3) SnO in the step (2)2And (3) carbonizing the @ C @ NC precursor at 500-1200 ℃ for 30 min-12 h to obtain the tin-based composite material.
The second object of the present invention is to provide a tin-based composite material prepared by the method described in the first object.
Preferably, the tin-based composite material is a dodecahedron-like structure.
Preferably, the size of the tin-based composite material is 100nm to 20 μm, such as 200nm, 300nm, 500nm, 600nm, 800nm, 1 μm, 2 μm, 5 μm, 6 μm, 8 μm, 10 μm, 12 μm, 15 μm, 18 μm, or the like.
If the material is particles, the size is the particle size; if the material is irregularly shaped, the dimension is the farthest point distance.
Preferably, the specific surface area of the tin-based composite material is 5-200 m2G, e.g. 8m2/g、10m2/g、20m2/g、50m2/g、80m2/g、100m2/g、120m2/g、150m2G or 180m2And/g, etc.
Preferably, the tin-based composite material includes Sn element, C element, N element, O element, and Co element.
Or, the tin-based composite material comprises Sn element, C element, N element, O element and Zn element.
Preferably, the content of the Sn element in the Sn-based composite material is 3 to 50 wt%, preferably 5 to 20 wt%, such as 5 wt%, 8 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, or 45 wt%.
Preferably, the content of the element C in the tin-based composite material is 20 to 80 wt%, preferably 20 to 40 wt%, such as 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, or the like.
Preferably, the content of the N element in the tin-based composite material is 10 to 50 wt%, preferably 20 to 40 wt%, for example 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, or 45 wt%.
Preferably, the content of the O element in the tin-based composite material is 5 to 50 wt%, preferably 10 to 30 wt%, such as 10 wt%, 15 wt%, 18 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, or 45 wt%.
Preferably, the content of the Co element in the tin-based composite material is 5 to 50 wt%, preferably 10 to 30 wt%, such as 10 wt%, 15 wt%, 18 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, or 45 wt%.
Preferably, the content of Zn element in the tin-based composite material is 5 to 50 wt%, preferably 10 to 30 wt%, such as 10 wt%, 15 wt%, 18 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, or 45 wt%.
The third object of the present invention is to provide a lithium ion battery comprising the tin-based composite material of the second object.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention adopts a solution method to synthesize SnO2Precursor material of @ C, making SnO2The nano particles are confined in a carbon skeleton structure, and are beneficial to coating a ZIF material to obtain SnO2A precursor of @ C @ NC. Then carrying out carbonization treatment in inert atmosphere to obtain the final product SnO2@C@NC。
(2) The preparation method of the tin-based composite material provided by the invention has the advantages of simple process, low preparation cost, clean and pollution-free process and excellent material performance, and can meet different requirements of the market.
Drawings
FIG. 1 is an SEM image of a tin-based composite material prepared in example 1;
FIG. 2 is a TEM image of a tin-based composite material prepared in example 1;
FIG. 3 shows that the tin-based composite material prepared in example 1 has a density of 50mAg-1Cycling performance at current density;
FIG. 4 shows the commercial graphite of comparative example 1 at 50mAg-1Cycling performance at current density.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
(1) 1g of SnO having a size of 80nm2Dispersing the polycrystalline nano spherical particles in 800mL of ethanol water solution (the volume ratio of ethanol to distilled water is 1:3), and carrying out ultrasonic treatment for 15 min;
(2) adding 0.3g of phenol and 0.5g of formaldehyde solution, adding ammonia water to adjust the pH value to 9, and stirring in a water bath at 35 ℃ for 24 hours;
(3) after centrifugal filtration, washing with ethanol and distilled water for 3 times respectively, and blast drying at 80 ℃ to obtain SnO2The @ C precursor;
(4) 0.8g SnO2The @ C precursor and 0.8g of cetyltrimethylammonium bromide (CTAB) are dispersed in 150mL of methanol solvent and ultrasonically dispersed;
(5) respectively dissolving 5.0g of zinc nitrate hexahydrate and 6.26g of 2-methylimidazole in 150mL of methanol solution, and adding SnO together after complete dissolution2Stirring the precursor suspension for 24 hours at 25 ℃;
(6) after centrifugal filtration, washing with ethanol and distilled water for 3 times respectively, and vacuum drying at 80 deg.C to obtain SnO2@ C @ NC precursor.
(7) And carrying out carbonization treatment in a tubular furnace at 800 ℃ for 6 hours under the nitrogen atmosphere to obtain the tin-based composite material.
The tin-based composite material prepared above was subjected to a material crystal form test on an X' Pert PRO MPD type multifunctional X-ray diffractometer manufactured by Panalytical corporation (Pasacaceae) in the Netherlands.
The prepared tin-based composite material is observed on the surface morphology of a JSM6700 type field emission scanning electron microscope produced by Japan electronic company.
The tin-based composite material prepared above was observed under a transmission electron microscope of lanthanum hexaboride model JEM-2100, manufactured by Japan K.K.
The prepared tin-based composite material is subjected to charge and discharge tests on a NEWARE BTS-5V/10mA type charge and discharge tester produced by New Wille electronics Limited in Shenzhen.
Fig. 1 is an SEM image of the tin-based composite material obtained in this example, and it can be seen that the material has a dodecahedron-like structure and a particle size of about 200 nm.
Fig. 2 is a TEM image of the tin-based composite material obtained in this example, and it can be seen that the material was assembled from a multilayer structure.
FIG. 3 shows that the tin-based composite material obtained by the present example has a density of 50mAg-1The cycle performance at current density is shown to be 504.2mAhg in charge capacity after 40 weeks of discharge-1And the capacity retention was 67.7%, the unfilled white beads in the figure represent coulombic efficiency.
Example 2
(1)0.8g of SnO having a size of 70nm2Dispersing the single crystal nano flaky particles in 700mL of ethanol water solution (the volume ratio of ethanol to distilled water is 1:3), and carrying out ultrasonic treatment for 15 min;
(2) adding 0.3g of phenol and 0.5g of formaldehyde solution, adding ammonia water to adjust the pH value to 9, and stirring in a water bath at 35 ℃ for 24 hours;
(3) after centrifugal filtration, washing with ethanol and distilled water for 3 times respectively, and blast drying at 80 ℃ to obtain SnO2The @ C precursor;
(4) 0.8g SnO2The @ C precursor and 0.8g of cetyltrimethylammonium bromide (CTAB) are dispersed in 150mL of methanol solvent and ultrasonically dispersed;
(5)5.0g of cobalt nitrate hexahydrate and 6.0g of 4-methylimidazole are dissolved in 150mL of methanol solution respectively, and SnO is added after complete dissolution2Stirring the precursor suspension for 24 hours at 25 ℃;
(6) after centrifugal filtration, the mixture was washed 3 times with ethanol and distilled water, respectively, at 80 deg.CVacuum drying to obtain SnO2@ C @ NC precursor;
(7) and carrying out carbonization treatment in a tubular furnace at 800 ℃ for 6 hours under the nitrogen atmosphere to obtain the tin-based composite material.
Example 3
(1) 1g of SnO having a size of 60nm2Dispersing the amorphous nano-ribbon particles in 800mL of ethanol water solution (the volume ratio of ethanol to distilled water is 1:3), and carrying out ultrasonic treatment for 15 min;
(2) adding 3g of 2-aminophenol and 0.3g of formaldehyde solution, adding ammonia water to adjust the pH value to 8, and stirring in a water bath at 10 ℃ for 5 min;
(3) after centrifugal filtration, washing with ethanol and distilled water for 3 times respectively, and vacuum drying at 50 deg.C to obtain SnO2The @ C precursor;
(4)0.8g SnO2@ C precursor and 0.08g hexadecyl trimethyl ammonium bromide (CTAB) are dispersed in 150mL methanol solvent and ultrasonically dispersed;
(5)5.0g of zinc sulfate and 6.26g of 2, 4-dimethylimidazole are respectively dissolved in 150mL of methanol solution, and SnO is added together after complete dissolution2Stirring the precursor suspension for 5min at 25 ℃;
(6) after centrifugal filtration, the mixture was washed with ethanol and distilled water for 3 times, and air-dried at 60 ℃. To obtain SnO2@ C @ NC precursor;
(7) and (3) carrying out carbonization treatment in a tubular furnace under the argon atmosphere, wherein the temperature is 500 ℃, and the time is 30min, so as to obtain the tin-based composite material.
Example 4
(1)0.8g SnO with size 50nm2Dispersing the single crystal nanometer box-shaped particles in 800mL of ethanol water solution (the volume ratio of ethanol to distilled water is 1:3), and carrying out ultrasonic treatment for 15 min;
(2) adding 0.3g of nitrophenol and 3g of formaldehyde solution, adding ammonia water to adjust the pH value to 12, and stirring in an oil bath at 40 ℃ for 72 hours;
(3) after centrifugal filtration, washing with ethanol and distilled water for 3 times respectively, and vacuum drying at 80 deg.C to obtain SnO2The @ C precursor;
(4)0.9g SnO2@ C precursor and 5g polyethylene glycol (PEG) dispersed thereinDispersing in 150mL of methanol solvent by ultrasonic;
(5)1.0g of cobalt chloride and 2.0g of 2.0g N-ethylimidazole were dissolved in 150mL of methanol solution, and SnO was added after complete dissolution2Stirring the precursor suspension for 60 hours at room temperature;
(6) after suction filtration, respectively washing with ethanol and distilled water for 3 times, and freeze-drying at-50 ℃ to obtain SnO2@ C @ NC precursor;
(7) and (3) carrying out carbonization treatment in a tubular furnace under the argon atmosphere, wherein the temperature is 600 ℃, and the time is 1h, so as to obtain the tin-based composite material.
Example 5
(1)0.6g SnO with size 40nm2Dispersing the single crystal nano linear particles in 800mL of acetone aqueous solution (the volume ratio of ethanol to distilled water is 1:3), and carrying out ultrasonic treatment for 15 min;
(2) adding 0.3g of 2-aminophenol and 1g of formaldehyde solution, adding ammonia water to adjust the pH value to 9, and stirring in a water bath at 35 ℃ for 50 hours;
(3) after centrifugal filtration, washing with ethanol and distilled water for 3 times respectively, and vacuum drying at 80 deg.C to obtain SnO2The @ C precursor;
(4)0.8g SnO2the @ C precursor and 2g of cetyltrimethylammonium bromide (CTAB) are dispersed in 150mL of glycol solvent and ultrasonically dispersed;
(5)1.5g of zinc acetate and 1.5g N-propylimidazole were dissolved in 150mL of methanol, and SnO was added after complete dissolution2In the @ C precursor suspension, carrying out solvothermal reaction for 5min at the temperature of 80 ℃;
(6) after centrifugal filtration, washing with ethanol and distilled water for 3 times respectively, and blast drying at 100 ℃ to obtain SnO2@ C @ NC precursor;
(7) and carrying out carbonization treatment in a tubular furnace at 700 ℃ for 3 hours under the nitrogen atmosphere to obtain the tin-based composite material.
Example 6
(1)0.4g SnO with size of 30nm2Dispersing the amorphous nano flaky particles in 800mL of glycerol aqueous solution (the volume ratio of ethanol to distilled water is 1:3), and carrying out ultrasonic treatment for 15 min;
(2) adding 0.1g of glucose, and stirring in a water bath at 20 ℃ for 40 h;
(3) after centrifugal filtration, washing with ethanol and distilled water for 3 times respectively, and vacuum drying at 120 ℃ to obtain SnO2The @ C precursor;
(4)0.7g SnO2the @ C precursor and 4.0g of cetyltrimethylammonium bromide (CTAB) are dispersed in 150mL of ethanol solvent and ultrasonically dispersed;
(5)2.0g of cobalt nitrate hexahydrate and 3.5g N-acetylimidazole were dissolved in 150mL of methanol solution, and SnO was added together after complete dissolution2Stirring the precursor suspension for 30 hours at 25 ℃;
(6) after centrifugal filtration, respectively washing with ethanol and distilled water for 3 times, and blast drying at 140 ℃ to obtain SnO2@ C @ NC precursor;
(7) and (3) carrying out carbonization treatment in a stirred bed under the nitrogen atmosphere, wherein the temperature is 800 ℃ and the time is 5 hours, so as to obtain the tin-based composite material.
Example 7
(1)0.2g SnO with size of 20nm2Dispersing the polycrystalline nano box-shaped particles in 800mL of ethanol water solution (the volume ratio of ethanol to distilled water is 1:3), and carrying out ultrasonic treatment for 15 min;
(2) adding 3g of cellulose, and stirring in a water bath at 40 ℃ for 20 hours;
(3) after centrifugal filtration, respectively washing with ethanol and distilled water for 3 times, and blast drying at 160 ℃ to obtain SnO2The @ C precursor;
(4)0.6g SnO2the @ C precursor and 3g of cetyltrimethylammonium bromide (CTAB) are dispersed in 150mL of methanol solvent and ultrasonically dispersed;
(5)4.0g of zinc nitrate hexahydrate and 6.0g of 1-vinylimidazole are dissolved in 150mL of methanol solution respectively, and SnO is added after complete dissolution2In the @ C precursor suspension, carrying out solvothermal reaction for 10h at 200 ℃;
(6) after centrifugal filtration, washing with ethanol and distilled water for 3 times respectively, and vacuum drying at 50 deg.C to obtain SnO2@ C @ NC precursor;
(7) and (3) carrying out carbonization treatment in a fixed bed under the argon atmosphere, wherein the temperature is 900 ℃, and the time is 7 hours, so as to obtain the tin-based composite material.
Example 8
(1)0.3g SnO with size of 10nm2Dispersing the single crystal nano spherical particles in 800mL of ethanol water solution (the volume ratio of ethanol to distilled water is 1:3), and carrying out ultrasonic treatment for 15 min;
(2) adding 0.3g of nitrophenol and 3g of formaldehyde solution, adding ammonia water to adjust the pH value to 12, and stirring in an oil bath at 40 ℃ for 5 hours;
(3) after centrifugal filtration, washing with ethanol and distilled water for 3 times respectively, and freeze-drying at-20 ℃ to obtain SnO2The @ C precursor;
(4)0.5g SnO2dispersing a @ C precursor and 2g of polyethylene glycol (PEG) in 150mL of methanol solvent, and performing ultrasonic dispersion;
(5)5.0g of cobalt nitrate hexahydrate and 7.0g of 2-bromo-4-nitroimidazole were dissolved in 150mL of methanol solution respectively, and SnO was added after complete dissolution2In the @ C precursor suspension, carrying out solvothermal reaction for 3h at 110 ℃;
(6) after suction filtration, respectively washing with ethanol and distilled water for 3 times, and vacuum drying at 160 ℃ to obtain SnO2@ C @ NC precursor;
(7) and (3) carrying out carbonization treatment in a fluidized bed under the argon atmosphere, wherein the temperature is 1000 ℃, and the time is 9 hours, so as to obtain the tin-based composite material.
Example 9
(1)0.5g SnO with size of 20nm2Dispersing the amorphous nano flaky particles in 800mL of ethanol water solution (the volume ratio of ethanol to distilled water is 1:3), and carrying out ultrasonic treatment for 15 min;
(2) adding 0.3g of nitrophenol and 3g of formaldehyde solution, adding ammonia water to adjust the pH value to about 10, and stirring in an oil bath at 30 ℃ for 1 h;
(3) after centrifugal filtration, washing with ethanol and distilled water for 3 times respectively, and freeze-drying at-40 deg.C to obtain SnO2The @ C precursor;
(4)0.2g SnO2dispersing a @ C precursor and 0.2g of polyethylene glycol (PEG) in 150mL of methanol solvent, and performing ultrasonic dispersion;
(5)4.5g of cobalt nitrate hexahydrate and 7.0g of 4-nitroimidazole are respectively dissolved in 150mL of methanol solution, and SnO is added together after complete dissolution2In the @ C precursor suspension, carrying out solvothermal reaction for 30min at 120 ℃;
(6) after suction filtration, respectively washing with ethanol and distilled water for 3 times, and vacuum drying at 180 ℃ to obtain SnO2@ C @ NC precursor;
(7) and (3) carrying out carbonization treatment in a stirred bed under the argon atmosphere, wherein the temperature is 1100 ℃, and the time is 10 hours, so as to obtain the tin-based composite material.
Example 10
(1)0.7g SnO with size of 40nm2Dispersing the polycrystalline nano linear particles in 800mL of ethanol water solution (the volume ratio of ethanol to distilled water is 1:3), and carrying out ultrasonic treatment for 15 min;
(2) adding 3g maltose, stirring in oil bath at 30 deg.C for 10 min;
(3) after centrifugal filtration, washing with ethanol and distilled water for 3 times respectively, and blast drying at 70 ℃ to obtain SnO2The @ C precursor;
(4)0.1g SnO2dispersing a @ C precursor and 1g of polyethylene glycol (PEG) in 150mL of methanol solvent, and performing ultrasonic dispersion;
(5)6.0g of cobalt nitrate hexahydrate and 4.5g of 4-nitroimidazole are respectively dissolved in 150mL of methanol solution, and SnO is added together after complete dissolution2In the @ C precursor suspension, carrying out solvothermal reaction for 5min at 150 ℃;
(6) after suction filtration, washing with ethanol and distilled water for 3 times, respectively, and freeze-drying at-30 deg.C. To obtain SnO2@ C @ NC precursor;
(7) and (3) carrying out carbonization treatment in a fixed bed under the argon atmosphere, wherein the temperature is 1200 ℃, and the time is 12 hours, so as to obtain the tin-based composite material.
Example 11
The difference from example 1 is that SnO described in step (1)2The size of the polycrystalline nanosphere particles was 3 nm.
Example 12
The difference from example 1 is that SnO described in step (1)2The size of the polycrystalline nanosphere particles is 500 nm.
Example 13
The difference from example 1 is that SnO described in step (1)2The size of the polycrystalline nanosphere particles is 1 nm.
Example 14
The difference from example 1 is that SnO described in step (1)2The size of the polycrystalline nanosphere particles was 550 nm.
Example 15
The difference from example 1 is that the mass of phenol in step (2) was 0.03 and the mass of the formaldehyde solution was 0.05 g.
Example 16
The difference from example 1 is that the mass of the phenol in the step (2) is 6 and the mass of the formaldehyde solution is 10 g.
Comparative example 1
Commercial graphite (beiibri, model 918) is selected as a negative electrode material of the lithium ion battery to assemble the button type half battery.
FIG. 4 shows the commercial graphite obtained by the present comparative example at 50mAg-1The cycle performance at current density is shown to be 308.2mAhg of charge capacity after 40 weeks of discharge-1The capacity is far lower than that of the tin-based composite material prepared by the method provided by the invention, and unfilled white balls in the figure represent coulombic efficiency.
Comparative example 2
The difference from example 1 is that the SnO obtained in step (3) is not subjected to steps (4) to (6)2The @ C precursor is directly carbonized.
And (3) performance testing:
the materials obtained in the examples and comparative examples were applied to a negative electrode of a lithium ion battery, according to the active material: conductive carbon black: mixing the binder at a mass ratio of 50:30:20, taking deionized water as a solvent for slurry mixing, coating the slurry on a copper foil, performing vacuum drying at 120 ℃ to assemble the button type half cell, and performing charge and discharge tests on a NEWARE BTS-5V/10mA type charge and discharge tester produced by Shenzhen, New Wille electronics Limited.
(1) And (3) electrochemical performance testing: the half cell is at 50mAg-1Cycle performance (40-cycle capacity retention is the ratio of 40-cycle charge capacity to first-cycle charge capacity) and first-cycle coulombic efficiency were tested at current density for 40 cycles.
TABLE 1
Figure BDA0002265951790000221
Figure BDA0002265951790000231
As can be seen from Table 1, the tin-based composite material obtained by the invention has excellent electrochemical performance, and particularly, the first-cycle charge capacity of the material obtained in example 1 can reach 745.1mAhg-1The charging capacity of the charging capacitor can reach 504.2mAhg in the 40 th week-1The first week coulombic efficiency can reach 53.7%, and the 40 week capacity retention rate can reach 67.7%.
As can be seen from Table 1, the electrochemical performance of examples 11-14 of the present invention is inferior to that of example 1, wherein example 1 (size 80nm) is superior to that of examples 11(3nm) and 12(500nm) which are end values not within the preferred parameter range of the present invention; and examples 13-14 (outside the parameter ranges) performed poorly relative to examples 11-12; SnO in example 132The polycrystalline nano spherical particles are too small in size, so that the agglomeration phenomenon is easy to occur, and the performance of the material is influenced; SnO in example 142The polycrystalline nano spherical particles are too large in size, so that the coating of the ZIF material is not facilitated, and the performance is poor.
As can be seen from Table 1, examples 15 to 16 of the present invention are inferior in electrochemical properties to example 1, and in example 15, the carbon source (phenol and formaldehyde solution) is too low in mass, SnO is not high2The mass ratio of the nano particles to the carbon source is 1:0.08, and the carbon source cannot form a uniformly coated carbon layer due to an excessively large mass ratio; in example 16, the carbon source (phenol and formaldehyde solution) was too large in mass, SnO2The mass ratio of the nano particles to the carbon source is 1:16, which is not beneficial to improving the capacity of the material.
As can be seen from table 1, inventive example 1 is superior in performance to commercial graphite (comparative example 1); inventive example 1 vs. SnO obtained in comparative example 22@ C is excellent because of the core-shell structure of SnO2The @ C particles undergo huge volume expansion in the charge-discharge cycle process, so that the particle structure is destroyed and the influence is further exertedThe electrochemical properties of the material are affected such that the capacity decays rapidly during cycling.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (10)

1. A method of preparing a tin-based composite material, the method comprising the steps of:
(1) SnO2Mixing water solutions of nano particles, a carbon source and an organic reagent to obtain a mixed solution, and heating the mixed solution to obtain SnO2The @ C precursor;
(2) SnO obtained in step (1)2Mixing the @ C precursor, the dispersing agent and the organic reagent to obtain precursor suspension, and carrying out mixed reaction on the metal salt solution, the imidazole solution and the precursor suspension to obtain SnO2@ C @ NC precursor;
(3) SnO in the step (2)2And carbonizing the @ C @ NC precursor to obtain the tin-based composite material.
2. The method of claim 1, wherein said SnO of step (1) is used2The nano particles comprise any one or the combination of at least two of nano spherical particles, nano flaky particles, nano strip-shaped particles, nano box-shaped particles and nano linear particles;
preferably, the SnO2The size of the nano particles is 3-500 nm, preferably 10-80 nm;
preferably, said SnO in step (1)2The nano particles are any one of amorphous materials, single crystal materials or polycrystalline materials;
preferably, the organic reagents in step (1) and step (2) are respectively and independently selected from any one of methanol, ethanol, propanol, ethylene glycol, glycerol, acetone and carbon tetrachloride or the combination of at least two of the two;
preferably, the volume ratio of the organic reagent to the water in the aqueous solution of the organic reagent in the step (1) is 1 (0.01-100), and more preferably 1 (0.1-10).
3. The method according to claim 1 or 2, wherein said SnO in step (1)2The mass ratio of the nano particles to the carbon source is 1 (0.1-10);
preferably, the carbon source in the step (1) is a mixed material of a phenolic reagent and an aldehyde reagent, or a carbohydrate;
preferably, the phenolic reagent comprises any one of phenol, 2-aminophenol, 3-aminophenol, 4-aminophenol, nitrophenol and p-nitrophenol or a combination of at least two thereof;
preferably, the aldehyde reagent is formaldehyde;
preferably, the mass ratio of the phenolic reagent to the aldehyde reagent is 1 (0.1-10), preferably 1 (1-5);
preferably, the carbon source is a mixed material of a phenol reagent and an aldehyde reagent, and before the mixed solution is heated, ammonia water is needed to adjust the pH value of the mixed solution;
preferably, the pH value is 8-12, and preferably 9-10;
preferably, the carbohydrate comprises any one of or a combination of at least two of glucose, sucrose, maltose, cellulose, chitosan and lignin;
preferably, the heating temperature in the step (1) is 10-80 ℃, and preferably 20-40 ℃;
preferably, the heating mode of the step (1) is water bath heating or oil bath heating;
preferably, the heating time in the step (1) is 5min to 72 hours, and preferably 12 to 36 hours;
preferably, after the heating in the step (1), the process further comprises the processes of filtering, washing and drying;
preferably, the filtration mode is centrifugal filtration or suction filtration;
preferably, the washing reagent comprises any one or a combination of at least two of distilled water, ethanol, methanol, propanol, ethylene glycol and glycerol;
preferably, the drying manner is vacuum drying, forced air drying or freeze drying;
preferably, the drying temperature is-50 to 200 ℃.
4. The production method according to any one of claims 1 to 3, wherein the dispersant in the step (2) comprises cetyltrimethylammonium bromide and/or polyethylene glycol;
preferably, said SnO in step (2)2The mass ratio of the @ C precursor to the dispersing agent is 1 (0.1-10);
preferably, the preparation process of the metal salt solution in the step (2) comprises: mixing metal salt with an organic solvent to obtain a metal salt solution;
preferably, the preparation process of the imidazole solution in the step (2) comprises the following steps: mixing an imidazole reagent with an organic solvent to obtain an imidazole solution;
preferably, the metal salt comprises a cobalt salt or a zinc salt;
preferably, the cobalt salt comprises any one of cobalt nitrate, cobalt sulfate, cobalt chloride and cobalt acetate or a combination of at least two of the foregoing;
preferably, the zinc salt includes any one or a combination of at least two of zinc nitrate, zinc sulfate, zinc chloride and zinc acetate;
preferably, the imidazole reagent comprises any one or a combination of at least two of imidazole, 2-methylimidazole, 4-methylimidazole, 2, 4-dimethylimidazole, 1-vinylimidazole, N-ethylimidazole, N-propylimidazole, N-acetylimidazole, 2-bromo-4-nitroimidazole and 4-nitroimidazole;
preferably, the organic solvent includes any one of methanol, ethanol, propanol, ethylene glycol, glycerol and acetone or a combination of at least two thereof.
5. The production method according to any one of claims 1 to 4, wherein the SnO in step (2)2The mass ratio of the @ C precursor to the metal salt in the metal salt solution is 1 (1-50);
preferably, said SnO in step (2)2The mass ratio of the @ C precursor to the imidazole reagent in the imidazole solution is 1 (1-60);
preferably, the mixing reaction of the metal salt solution, the imidazole solution and the precursor suspension in the step (2) is performed in a manner that: stirring and mixing;
preferably, the stirring and mixing is stirring and mixing at room temperature;
preferably, the stirring and mixing time is 5 min-72 h, preferably 12-36 h;
preferably, the mixing reaction mode of the metal salt solution, the imidazole solution and the precursor suspension in the step (2) is as follows: the temperature of the hydrothermal reaction is 80-200 ℃;
preferably, the time of the hydrothermal reaction is 5min to 72 hours, preferably 12 to 36 hours;
preferably, after the mixing reaction, the processes of filtering, washing and drying are also included;
preferably, the filtration mode is centrifugal filtration or suction filtration;
preferably, the washing reagent comprises any one or a combination of at least two of distilled water, ethanol, methanol, propanol, ethylene glycol and glycerol;
preferably, the drying manner is vacuum drying, forced air drying or freeze drying;
preferably, the drying temperature is-50 to 200 ℃.
6. The production method according to any one of claims 1 to 5, wherein the carbonization treatment in the step (3) is performed under an inert atmosphere;
preferably, the gas in the inert atmosphere comprises any one of nitrogen, argon and helium or a combination of at least two of them;
preferably, the temperature of the carbonization treatment in the step (3) is 500-1200 ℃;
preferably, the carbonization treatment time in the step (3) is 30 min-12 h;
preferably, the carbonization treatment in step (3) is carried out in a fixed bed, a stirred bed, a fluidized bed or a tubular furnace.
7. The method of any one of claims 1 to 6, wherein the method comprises the steps of:
(1) SnO with the size of 10-80 nm2Mixing nanoparticles, a carbon source and an aqueous solution of an organic reagent, wherein the volume ratio of the organic reagent to water in the aqueous solution of the organic reagent is 1 (0.1-10), and the SnO2The mass ratio of the nano particles to the carbon source is 1 (0.1-10), obtaining a mixed solution, heating the mixed solution at 20-40 ℃ for 12-36 h, filtering, washing and drying at-50-200 ℃ to obtain SnO2The @ C precursor;
(2) SnO obtained in step (1)2Mixing the @ C precursor, the dispersing agent and the organic reagent to obtain a precursor suspension, stirring and mixing the metal salt solution, the imidazole solution and the precursor suspension at room temperature for 12-36 h, wherein the SnO is2The mass ratio of the @ C precursor to the metal salt in the metal salt solution is 1 (1-50), and the SnO2The mass ratio of the @ C precursor to the imidazole reagent in the imidazole solution is 1 (1-60), and SnO2The mass ratio of the @ C precursor to the dispersing agent is 1 (0.1-10), and filtering, washing and drying are carried out to obtain SnO2@ C @ NC precursor;
or SnO obtained in the step (1)2Mixing the @ C precursor, the dispersing agent and the organic reagent to obtain precursor turbid liquid, mixing the metal salt solution, the imidazole solution and the precursor turbid liquid, and carrying out hydrothermal reaction at the temperature of 80-200 ℃ for 12-36 h, wherein the SnO2The mass ratio of the @ C precursor to the metal salt in the metal salt solution is 1 (1-50), and the SnO2The mass ratio of the @ C precursor to the imidazole reagent in the imidazole solution is 1 (1-60), and SnO2The mass ratio of the @ C precursor to the dispersing agent is 1 (0.1-10), and filtering, washing and drying are carried out to obtain SnO2@ C @ NC precursor;
(3) SnO in the step (2)2And (3) carbonizing the @ C @ NC precursor at 500-1200 ℃ for 30 min-12 h to obtain the tin-based composite material.
8. A tin-based composite material, characterized in that it is obtained by the process according to any one of claims 1 to 7.
9. The tin-based composite material of claim 8, wherein the tin-based composite material is a dodecahedron-like structure;
preferably, the size of the tin-based composite material is 100 nm-20 μm;
preferably, the specific surface area of the tin-based composite material is 5-200 m2/g；
Preferably, the tin-based composite material includes Sn element, C element, N element, O element, and Co element;
or, the tin-based composite material comprises Sn element, C element, N element, O element and Zn element;
preferably, in the tin-based composite material, the content of Sn element is 3-50 wt%, preferably 5-20 wt%;
preferably, in the tin-based composite material, the content of the C element is 20-80 wt%, and preferably 20-40 wt%;
preferably, in the tin-based composite material, the content of the N element is 10-50 wt%, preferably 20-40 wt%;
preferably, in the tin-based composite material, the content of the O element is 5-50 wt%, preferably 10-30 wt%;
preferably, in the tin-based composite material, the content of Co element is 5-50 wt%, preferably 10-30 wt%;
preferably, the content of Zn element in the tin-based composite material is 5-50 wt%, preferably 10-30 wt%.
10. A lithium-ion battery, characterized in that it comprises a tin-based composite material according to claim 8 or 9.
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