CN110660986B - 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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CN110660986B
CN110660986B CN201911087812.3A CN201911087812A CN110660986B CN 110660986 B CN110660986 B CN 110660986B CN 201911087812 A CN201911087812 A CN 201911087812A CN 110660986 B CN110660986 B CN 110660986B
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tin
sno
composite material
based composite
precursor
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CN110660986A (en
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苏发兵
李琼光
王艳红
谭强强
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Langfang Green Industry Technology Service Center
Institute of Process Engineering of CAS
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Langfang Green Industry Technology Service Center
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) SnO 2 Mixing water solutions of nano particles, a carbon source and an organic reagent to obtain a mixed solution, and heating the mixed solution to obtain SnO 2 The @ C precursor; (2) SnO obtained in step (1) 2 Mixing 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 SnO 2 @ C @ NC precursor; (3) the SnO in the step (2) 2 And carbonizing the @ C @ NC precursor to obtain the tin-based composite material. The preparation method of the tin-based composite material solves the key problem of preparing the tin-based composite material in the prior art, has the advantages of simple preparation process, low preparation cost, clean and pollution-free process and excellent material performance, and can meet different requirements of the market.

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 cathode material can not meet the requirement of the high specific energy battery, so that the development of a cathode material with energy density is urgently neededHigh and low cost. 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 SnO 2 The 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 large-scale production of the composite material is seriously hindered by using a template method for many times in the preparation process. The invention patent CN108321376A discloses a CNF @ SnO 2 The 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) SnO 2 Mixing water solutions of nano particles, a carbon source and an organic reagent to obtain a mixed solution, and heating the mixed solution to obtain SnO 2 A @ C precursor;
(2) SnO obtained in step (1) 2 Mixing 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 SnO 2 @ C @ NC precursor;
(3) SnO in the step (2) 2 And carbonizing the @ C @ NC precursor to obtain the tin-based composite material.
The invention adopts a solution method to synthesize SnO 2 Precursor material of @ C, making SnO 2 The nano particles are confined in a carbon skeleton structure, and are beneficial to coating a ZIF material to obtain SnO 2 A precursor of @ C @ NC. Then carrying out carbonization treatment in inert atmosphere to obtain the final product SnO 2 @C@NC。
SnO in the present invention 2 @ C stands for a carbon-coated core-shell structure, in which SnO 2 Is core, C is shell; SnO 2 @ C @ NC stands for SnO coated by NC (N-doped C layer) 2 The 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) 2 The 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 SnO 2 The nanoparticles have a size of 3 to 500nm, preferably 10 to 80nm, for example 5nm, 10nm, 50nm,100nm, 120nm, 150nm, 180nm, 200nm, 220nm, 250nm, 280nm, 300nm, 320nm, 350nm, 380nm, 400nm, 420nm, 450nm or 480nm and the like.
SnO in the present invention 2 The size of the nano particles is too large, so that the coating of the ZIF material is not facilitated; SnO 2 The 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 of step (1) 2 The 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) 2 The mass ratio of the nanoparticles to the carbon source is 1 (0.1-10), 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.
SnO in the present invention 2 The 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 too 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 includes any one of distilled water, ethanol, methanol, propanol, ethylene glycol and glycerol or a combination of at least two thereof.
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) 2 The 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 invention 2 The mass ratio of the @ C precursor to the dispersing agent is 1 (0.1-10), the mass ratio is too large, and SnO 2 The @ C precursor is too much, the dispersing agent is too little, and the dispersion of particles is not facilitated; too small a mass ratio, SnO 2 The @ 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 of imidazole, 2-methylimidazole, 4-methylimidazole, 2, 4-dimethylimidazole, 1-vinylimidazole, N-ethylimidazole, N-propylimidazole, N-acetylimidazole, 2-bromo-4-nitroimidazole and 4-nitroimidazole or a combination of at least two thereof.
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 of step (2) 2 The 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) 2 The 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: and (4) 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 nm 2 Mixing 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 SnO 2 The 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 SnO 2 The @ C precursor;
(2) SnO obtained in the step (1) 2 Mixing 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 is 2 The mass ratio of the @ C precursor to the metal salt in the metal salt solution is 1 (1-50), and the SnO 2 The mass ratio of the @ C precursor to the imidazole reagent in the imidazole solution is 1 (1-60), and SnO 2 The 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 SnO 2 @ C @ NC precursor;
or the like, or, alternatively,SnO obtained in step (1) 2 Mixing 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 SnO 2 The mass ratio of the @ C precursor to the metal salt in the metal salt solution is 1 (1-50), and the SnO 2 The mass ratio of the @ C precursor to the imidazole reagent in the imidazole solution is 1 (1-60), and SnO 2 The 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 SnO 2 @ C @ NC precursor;
(3) SnO in the step (2) 2 And (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 method 2 A method of a @ C precursor, comprising the steps of:
(1) SnO 2 Mixing 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 SnO 2 The 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 SnO 2 The @ C precursor;
(2) SnO 2 Dissolving the @ C precursor in organic solvent, adding dispersant, and ultrasonic dispersing to obtain SnO 2 The mass ratio of the @ C precursor to the dispersing agent is 1 (0.1-10), and SnO is obtained 2 The @ 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 SnO 2 Mixing the suspension of the @ C precursor, stirring and reacting at room temperature, filtering, washing and drying to obtain SnO 2 @ C @ NC precursor;
(3) SnO in the step (2) 2 And (3) carbonizing the @ C @ NC precursor at 500-1200 ℃ for 30 min-12 h to obtain the tin-based composite material.
As a preferred technical solutionSecondly, the invention provides a method for preparing ZIF-8 coated SnO by adopting a solution method 2 A method of a @ C precursor, comprising the steps of:
(1) SnO 2 Mixing 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 SnO 2 The 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 SnO 2 The @ C precursor;
(2) SnO is treated 2 Dissolving the @ C precursor in organic solvent, adding dispersant, and ultrasonic dispersing to obtain SnO 2 The mass ratio of the @ C precursor to the dispersing agent is 1 (0.1-10), and SnO is obtained 2 The 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 SnO 2 Mixing the suspension of the @ C precursor, stirring and reacting at room temperature, filtering, washing and drying to obtain SnO 2 @ C @ NC precursor;
(3) the SnO in the step (2) 2 And (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 ZIF-67 coated SnO by adopting a solvothermal method 2 A method of a @ C precursor, comprising the steps of:
(1) SnO 2 Mixing 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 SnO 2 The 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 SnO 2 The @ C precursor;
(2) SnO 2 Dissolving the @ C precursor in organic solvent, adding dispersant, and ultrasonic dispersing to obtain SnO 2 The mass ratio of the @ C precursor to the dispersing agent is 1 (0.1-10), and SnO is obtained 2 @ C precursorDissolving cobalt salt and imidazole reagent in organic solvent to form cobalt salt solution and imidazole solution, mixing them with SnO 2 Mixing the @ C precursor turbid liquid, carrying out hydrothermal reaction at 80-200 ℃ for 12-36 h, filtering, washing and drying to obtain SnO 2 @ C @ NC precursor;
(3) SnO in the step (2) 2 And (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 method 2 A method of a @ C precursor, comprising the steps of:
(1) SnO 2 Mixing 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 SnO 2 The 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 SnO 2 A @ C precursor;
(2) SnO 2 Dissolving the @ C precursor in organic solvent, adding dispersant, and ultrasonic dispersing to obtain SnO 2 The mass ratio of the @ C precursor to the dispersing agent is 1 (0.1-10), and SnO is obtained 2 The 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 SnO 2 Mixing the @ C precursor turbid liquid, carrying out hydrothermal reaction at 80-200 ℃ for 12-36 h, filtering, washing and drying to obtain SnO 2 @ C @ NC precursor;
(3) SnO in the step (2) 2 And (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 m 2 In terms of/g, e.g. 8m 2 /g、10m 2 /g、20m 2 /g、50m 2 /g、80m 2 /g、100m 2 /g、120m 2 /g、150m 2 G or 180m 2 In terms of/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%, etc.
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%, etc.
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 method adopts a solution method to synthesize SnO 2 Precursor material of @ C, making SnO 2 The nano particles are confined in a carbon skeleton structure, and are beneficial to coating a ZIF material to obtain SnO 2 A precursor of @ C @ NC. Then carrying out carbonization treatment in inert atmosphere to obtain the final product SnO 2 @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 -1 Cycling performance at current density;
FIG. 4 shows the commercial graphite of comparative example 1 at 50mAg -1 Cycling 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 80nm 2 Polycrystalline nano-spherical particle dispersionIn 800mL ethanol water solution (the volume ratio of ethanol to distilled water is 1:3), 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 SnO 2 The @ C precursor;
(4) 0.8g SnO 2 The @ 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 dissolution 2 Stirring 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 ℃ to obtain SnO 2 @ 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 -1 The cycle performance at current density is shown to be 504.2mAhg in charge capacity after 40 weeks of discharge -1 And 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 70nm 2 Dispersing 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 SnO 2 The @ C precursor;
(4) 0.8g SnO 2 The @ C precursor and 0.8g of cetyltrimethylammonium bromide (CTAB) were dispersed in 150mL of methanol solvent, and ultrasonically dispersed;
(5) respectively dissolving 5.0g of cobalt nitrate hexahydrate and 6.0g of 4-methylimidazole in 150mL of methanol solution, and adding SnO into the methanol solution together after complete dissolution 2 Stirring 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 SnO 2 @ 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 60nm 2 Dispersing 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 SnO 2 The @ C precursor;
(4)0.8g SnO 2 @ 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 dissolution 2 Stirring the @ C 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 SnO 2 @ 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 50nm 2 Dispersing 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 SnO 2 The @ C precursor;
(4)0.9g SnO 2 dispersing a @ C precursor and 5g of polyethylene glycol (PEG) in 150mL of methanol solvent, and performing ultrasonic dispersion;
(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 dissolution 2 Stirring 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 SnO 2 @ 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 40nm 2 Single crystal nano linear particles are dispersed in 800mL of acetone waterPerforming ultrasonic treatment for 15min in the solution (the volume ratio of ethanol to distilled water is 1: 3);
(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 SnO 2 A @ C precursor;
(4)0.8g SnO 2 the @ 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 dissolution 2 In 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 SnO 2 @ 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 30nm 2 Dispersing 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 SnO 2 The @ C precursor;
(4)0.7g SnO 2 the @ 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 are respectively dissolved in 150mL of methanol solution, and SnO is added together after complete dissolution 2 Stirring 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 SnO 2 @ 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 20nm 2 Dispersing 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 SnO 2 The @ C precursor;
(4)0.6g SnO 2 the @ 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 together after complete dissolution 2 In 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 SnO 2 @ 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 10nm 2 Dispersing 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 SnO 2 The @ C precursor;
(4)0.5g SnO 2 dispersing 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-nitroimidazoleRespectively dissolving oxazole in 150mL of methanol solution, and adding SnO together after complete dissolution 2 In 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 SnO 2 @ 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 20nm 2 Dispersing 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 SnO 2 The @ C precursor;
(4)0.2g SnO 2 dispersing 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 dissolution 2 In 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 SnO 2 @ 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 40nm 2 Dispersing 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, ethanol and distilled water are respectively usedCleaning for 3 times, and blast drying at 70 deg.C to obtain SnO 2 The @ C precursor;
(4)0.1g SnO 2 dispersing 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 dissolved in 150mL of methanol solution respectively, and added with SnO after complete dissolution 2 In 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 SnO 2 @ 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) 2 The size of the polycrystalline nanosphere particles was 3 nm.
Example 12
The difference from example 1 is that SnO described in step (1) 2 The size of the polycrystalline nano-spherical particles is 500 nm.
Example 13
The difference from example 1 is that SnO described in step (1) 2 The size of the polycrystalline nano-spherical particles is 1 nm.
Example 14
The difference from example 1 is that SnO described in step (1) 2 The 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 -1 The cycle performance at current density is shown to be 308.2mAhg of charge capacity after 40 weeks of discharge -1 The capacity is far lower than that of the tin-based composite material prepared by the method provided by the invention, and unfilled white spheres 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) 2 The @ 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 -1 Cycle 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 -1 The charging capacity of the battery can reach 504.2mAhg at the 40 th week -1 The first week coulombic efficiency can reach 53.7%, and the 40 week capacity retention rate can reach 67.7%.
Can be obtained by table 1It is seen that inventive examples 11-14 have poorer electrochemical performance than example 1, wherein example 1 (size 80nm) has better performance within the preferred parameter range of the inventive size than the endpoint values of example 11(3nm) and example 12(500nm) which are not within the preferred parameter range; and examples 13-14 (values outside the parameter ranges) performed poorly relative to examples 11-12; SnO in example 13 2 The 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 14 2 The polycrystalline nano spherical particles are too large in size, which is not beneficial to coating of the ZIF material, and therefore, 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 high 2 The 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, SnO 2 The 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 2 2 @ C is excellent because of the core-shell structure of SnO 2 The @ C particle undergoes huge volume expansion in the charge-discharge cycle process, so that the particle structure is destroyed, the electrochemical performance of the material is further influenced, and the capacity is rapidly attenuated in the cycle process.
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 (74)

1. A method of preparing a tin-based composite material, the method comprising the steps of:
(1) SnO 2 Mixing aqueous solutions of nanoparticles, carbon source and organic reagent, the SnO 2 The mass ratio of the nano particles to the carbon source is 1 (0.1-10), obtaining a mixed solution, and heating the mixed solution to obtain SnO 2 The @ C precursor;
(2) SnO obtained in step (1) 2 Mixing 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 SnO 2 @ C @ NC precursor;
(3) SnO in the step (2) 2 Carbonizing the @ C @ NC precursor to obtain the tin-based composite material, wherein the chemical formula of the tin-based composite material is SnO 2 @C@NC。
2. The method of claim 1, wherein said SnO of step (1) is used 2 The 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.
3. The method of claim 1, wherein said SnO is 2 The size of the nano-particles is 3-500 nm.
4. The method of claim 3, wherein said SnO is 2 The size of the nano particles is 10-80 nm.
5. The method of claim 1, wherein said SnO of step (1) is used 2 The nanoparticles are any one of amorphous materials, single crystal materials or polycrystalline materials.
6. The method according to claim 1, wherein 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 a combination of at least two of them.
7. The method according to claim 1, wherein 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).
8. The method according to claim 7, wherein the volume ratio of the organic reagent to water in the aqueous solution of the organic reagent in the step (1) is 1 (0.1-10).
9. The method according to claim 1 or 2, wherein the carbon source in the step (1) is a mixture of a phenolic reagent and an aldehyde reagent, or a carbohydrate.
10. The method of claim 9, wherein the phenolic reagent comprises any one of phenol, 2-aminophenol, 3-aminophenol, 4-aminophenol and p-nitrophenol, or a combination of at least two thereof.
11. The method according to claim 9, wherein the aldehyde reagent is formaldehyde.
12. The method according to claim 9, wherein the mass ratio of the phenolic reagent to the aldehyde reagent is 1 (0.1 to 10).
13. The method according to claim 12, wherein the mass ratio of the phenolic reagent to the aldehyde reagent is 1 (1-5).
14. The method according to claim 9, wherein the carbon source is a mixture of a phenolic reagent and an aldehyde reagent, and the pH of the mixed solution is adjusted by using ammonia water before the mixed solution is heated.
15. The method of claim 14, wherein the pH is 8 to 12.
16. The method according to claim 15, wherein the pH is 9 to 10.
17. The method of claim 9, wherein the carbohydrate comprises any one of or a combination of at least two of glucose, sucrose, maltose, cellulose, chitosan, and lignin.
18. The method according to claim 1, wherein the heating temperature in the step (1) is 10 to 80 ℃.
19. The method according to claim 18, wherein the heating temperature in the step (1) is 20 to 40 ℃.
20. The method according to claim 1, wherein the heating in step (1) is carried out by water bath heating or oil bath heating.
21. The method of claim 1, wherein the heating in step (1) is performed for a time period of 5min to 72 hours.
22. The method according to claim 21, wherein the heating time in step (1) is 12 to 36 hours.
23. The method according to claim 1, wherein the heating in step (1) further comprises filtration, washing and drying.
24. The method of claim 23, wherein the filtration is by centrifugation or suction filtration.
25. The method of claim 23, wherein the washing is performed with a reagent comprising any one or a combination of at least two of distilled water, ethanol, methanol, propanol, ethylene glycol and glycerol.
26. The method of claim 23, wherein the drying is vacuum drying, forced air drying, or freeze drying.
27. The method of claim 23, wherein the drying temperature is-50 to 200 ℃.
28. The method of claim 1, wherein the dispersant of step (2) comprises cetyltrimethylammonium bromide and/or polyethylene glycol.
29. The method of claim 1, wherein said SnO of step (2) 2 The mass ratio of the @ C precursor to the dispersing agent is 1 (0.1-10).
30. The method of claim 1, wherein the step (2) of preparing the metal salt solution comprises: and mixing the metal salt with an organic solvent to obtain a metal salt solution.
31. The method according to claim 1, wherein the imidazole solution of step (2) is prepared by a process comprising: mixing an imidazole reagent with an organic solvent to obtain an imidazole solution.
32. The method of claim 30, wherein the metal salt comprises a cobalt salt or a zinc salt.
33. The method of claim 32, wherein the cobalt salt comprises any one of cobalt nitrate, cobalt sulfate, cobalt chloride, and cobalt acetate or a combination of at least two thereof.
34. The method of claim 32, wherein the zinc salt comprises any one of zinc nitrate, zinc sulfate, zinc chloride, and zinc acetate, or a combination of at least two thereof.
35. The method of claim 31, wherein the imidazole reagent comprises any one of imidazole, 2-methylimidazole, 4-methylimidazole, 2, 4-dimethylimidazole, 1-vinylimidazole, N-ethylimidazole, N-propylimidazole, N-acetylimidazole, 2-bromo-4-nitroimidazole, and 4-nitroimidazole, or a combination of at least two thereof.
36. The method of claim 30 or 31, wherein the organic solvent comprises any one of methanol, ethanol, propanol, ethylene glycol, glycerol and acetone or a combination of at least two thereof.
37. The method of claim 1, wherein said SnO of step (2) 2 The mass ratio of the @ C precursor to the metal salt in the metal salt solution is 1 (1-50).
38. The method according to claim 1, wherein said SnO in step (2) is prepared 2 The mass ratio of the @ C precursor to the imidazole reagent in the imidazole solution is 1 (1-60).
39. The preparation method according to claim 1, wherein 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.
40. The method of claim 39, wherein the mixing is performed at room temperature.
41. The method of claim 39, wherein the time for stirring and mixing is 5min to 72 hours.
42. The method of claim 41, wherein the time for stirring and mixing is 12 to 36 hours.
43. The preparation method according to claim 1, wherein the metal salt solution, the imidazole solution and the precursor suspension in the step (2) are mixed and reacted in a manner that: the temperature of the hydrothermal reaction is 80-200 ℃.
44. The method of claim 43, wherein the hydrothermal reaction is carried out for a time of 5min to 72 hours.
45. The preparation method according to claim 43, wherein the hydrothermal reaction time is 12-36 h.
46. The method of claim 1, wherein the mixing reaction further comprises filtering, washing and drying.
47. The method of claim 46, wherein the filtration is performed by centrifugation or suction filtration.
48. The method of claim 46, wherein the washing is performed with a reagent comprising any one or a combination of at least two of distilled water, ethanol, methanol, propanol, ethylene glycol and glycerol.
49. The method of claim 46, wherein the drying is vacuum drying, forced air drying, or freeze drying.
50. The method of claim 46, wherein the drying temperature is-50 to 200 ℃.
51. The method according to claim 1, wherein the carbonization treatment in the step (3) is performed under an inert atmosphere.
52. The method of claim 51, wherein the gas in the inert atmosphere comprises any one of argon and helium or a combination of at least two thereof.
53. The method according to claim 1, wherein the carbonization temperature in the step (3) is 500 to 1200 ℃.
54. The preparation method according to claim 1, wherein the carbonization treatment time in the step (3) is 30min to 12 h.
55. The method according to claim 1, wherein the carbonization treatment in the step (3) is carried out in a fixed bed, a stirred bed, a fluidized bed, or a tube furnace.
56. The method of claim 1, comprising the steps of:
(1) SnO with the size of 10-80 nm 2 Mixing nano particles, 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 SnO is 2 The 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 SnO 2 The @ C precursor;
(2) SnO obtained in step (1) 2 Mixing 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 is 2 The mass ratio of the @ C precursor to the metal salt in the metal salt solution is 1 (1-50), and the SnO is 2 The mass ratio of the @ C precursor to the imidazole reagent in the imidazole solution is 1 (1-60), and SnO 2 The 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 SnO 2 @ C @ NC precursor;
or SnO obtained in the step (1) 2 Mixing 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 SnO 2 The mass ratio of the @ C precursor to the metal salt in the metal salt solution is 1 (1-50), and the SnO 2 The mass ratio of the @ C precursor to the imidazole reagent in the imidazole solution is 1 (1-60), and SnO 2 The 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 SnO 2 @ C @ NC precursor;
(3) the SnO in the step (2) 2 Carbonizing the @ C @ NC precursor at 500-1200 ℃ for 30 min-12 h to obtain the tin-based composite material, wherein the chemical formula of the tin-based composite material is SnO 2 @C@NC。
57. A tin-based composite material prepared by the method of any one of claims 1 to 56.
58. The tin-based composite material of claim 57, wherein the tin-based composite material is a dodecahedron-like structure.
59. The tin-based composite material of claim 57, wherein the tin-based composite material has a size of 100nm to 20 μm.
60. The tin-based composite material of claim 57, wherein the tin-based composite material has a specific surface area of from 5m to 200m 2 /g。
61. The tin-based composite material of claim 57, wherein the tin-based composite material comprises an elemental Sn, an elemental C, an elemental N, an elemental O, and an elemental Co;
or, the tin-based composite material comprises Sn element, C element, N element, O element and Zn element.
62. The tin-based composite material of claim 61, wherein the tin-based composite material comprises from 3 to 50 wt% of the Sn element.
63. The tin-based composite material of claim 62, wherein the tin-based composite material comprises 5 to 20 wt% of Sn.
64. The tin-based composite material of claim 61, wherein the tin-based composite material comprises 20 to 80 wt% of the element C.
65. The tin-based composite material of claim 64, wherein the tin-based composite material has a C element content of 20 to 40 wt%.
66. The tin-based composite material of claim 61, wherein the tin-based composite material comprises 10 to 50 wt% of the N element.
67. The tin-based composite material of claim 66, wherein the tin-based composite material comprises 20 to 40 wt% of the N element.
68. The tin-based composite material of claim 61, wherein the tin-based composite material has an elemental O content of 5 to 50 wt%.
69. The tin-based composite material of claim 68, wherein the tin-based composite material comprises 10 to 30 wt% of the element O.
70. The tin-based composite material of claim 61, wherein the tin-based composite material comprises 5 to 50 wt% of Co.
71. The tin-based composite material of claim 70, wherein the tin-based composite material comprises 10 to 30 wt% of Co.
72. The tin-based composite material of claim 61, wherein the tin-based composite material has a Zn element content of 5 to 50 wt%.
73. The tin-based composite material of claim 72, wherein the tin-based composite material has an elemental Zn content of 10 to 30 wt%.
74. A lithium ion battery comprising the tin-based composite material according to any one of claims 57 to 73.
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