CN112125304B - Metal oxide modified micro-nano silicon-graphite composite negative electrode material and preparation method thereof - Google Patents

Metal oxide modified micro-nano silicon-graphite composite negative electrode material and preparation method thereof Download PDF

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CN112125304B
CN112125304B CN202011019339.8A CN202011019339A CN112125304B CN 112125304 B CN112125304 B CN 112125304B CN 202011019339 A CN202011019339 A CN 202011019339A CN 112125304 B CN112125304 B CN 112125304B
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nano silicon
metal oxide
graphite composite
silicon
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CN112125304A (en
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李加新
黄永聪
黄伟健
林应斌
黄志高
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Fujian Normal University
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    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/20Graphite
    • C01B32/21After-treatment
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • CCHEMISTRY; METALLURGY
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    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00Silicon; Compounds thereof
    • C01B33/02Silicon
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/38Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386Silicon or alloys based on silicon
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • H01M4/625Carbon or graphite
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract

The invention belongs to the technical field of lithium ion battery electrode materials, and relates to a metal oxide modified micro-nano silicon-graphite composite anode material and a preparation method thereof. The method comprises the steps of firstly putting nano-silicon, metal salt, a certain amount of carbon source and a proper amount of graphite powder into a solvent, fully stirring and dissolving, then volatilizing the solvent to obtain a mixed solid, pre-oxidizing the dried mixture in air, and finally calcining the powder in an inert gas atmosphere to obtain the metal oxide modified micro-nano silicon-graphite composite negative electrode material. The invention provides a synthesis strategy for improving the conductivity and stability of a silicon-carbon negative electrode material by using metal oxide, and the synthesized silicon-carbon negative electrode material has uniform particle size distribution, high yield and excellent electrochemistry and is suitable for industrial production.

Description

Metal oxide modified micro-nano silicon-graphite composite negative electrode material and preparation method thereof
Technical Field
The invention belongs to the field of lithium ion battery electrode materials, and particularly relates to a metal oxide modified micro-nano silicon-graphite composite anode material and a preparation method thereof.
Technical Field
In recent years, with the rapid development of electronic technologies including 5G networks, the demand for lightweight and large-capacity lithium batteries for corresponding electronic products has sharply increased. The development of high performance lithium battery anode materials has been the trend. The industrial graphite with the theoretical specific capacity of 372mAh/g meets an obvious bottleneck in improving the energy density of the lithium battery. Therefore, silicon (Si) material has been a hot point of research due to its theoretical capacity of 4200mAh/g and lower discharge potential. However, it still faces the benefits of inherent material properties and technological development; the huge volume expansion rate (> 300%) causes structural degradation, unstable Solid Electrolyte Interface (SEI), fast capacity attenuation, and poor intrinsic conductivity seriously limits the diffusion rate of lithium in a silicon anode, further limiting the performance of the lithium ion battery. Some common strategies, including surface modification, nano-processing, introduction of carbon nanomaterials and designing of headspace, etc., have been used to address these issues. However, these processes inevitably reduce the compacted density and initial coulombic efficiency of the silicon-based composite anode, resulting in a material expansion rate of more than 10%, thereby slowing down the progress of industrialization. So far, no synthetic strategy capable of stably producing a low-cost, high-performance silicon-based material has been found.
Disclosure of Invention
In order to solve the problems of the silicon-based negative electrode material, the invention provides a metal oxide modified micro-nano silicon-graphite composite negative electrode material and a preparation method thereof, the preparation process is simple, and the silicon-carbon negative electrode material with stable structure and excellent electrochemical performance can be prepared.
The technical scheme adopted for realizing the purpose of the invention is as follows:
a preparation method of a metal oxide modified micro-nano silicon-graphite composite anode material comprises the following steps:
1) respectively dissolving nano-silicon, metal salt, a carbon source and graphite powder in a solvent, and fully stirring to obtain a mixed solution;
2) placing the mixed solution in a water bath kettle at the temperature of 60-90 ℃ and stirring for 0.5-2 hours to evaporate the solvent to obtain a mixture;
3) pre-oxidizing the mixture in air at 200-300 ℃ for 1-3 hours at a heating rate of 1-5 ℃/min;
4) placing the obtained product in an atmosphere furnace, and calcining in an inert atmosphere, wherein the calcining temperature is 600-1000 ℃, the heating rate is 2-10 ℃/min, and the calcining time is 0.5-5 hours; and after the calcination is finished, cooling to room temperature along with the furnace to obtain the micro-nano silicon-graphite composite negative electrode material.
In the step 1), the average particle size of the nano silicon is 100-300 nm; preferably, the nano silicon is one or a combination of two of nano silicon crystal and nano silicon amorphous, and is preferably monodisperse nano silicon particles.
The metal salt solution is one or more of zinc acetate, zirconium hydroxide, butyl titanate and other metal salts capable of generating metal oxides. Preferably, the nano silicon is monodisperse nano silicon particles.
The carbon source comprises one or two of polyacrylamide, polyacrylonitrile, polyaniline and chitosan.
The solvent comprises one of N, N-dimethylformamide and absolute ethyl alcohol.
The graphite powder is commercial graphite.
The inert atmosphere is argon.
In the metal oxide modified micro-nano silicon-graphite composite negative electrode material prepared by the invention, the content of silicon nanoparticles is 10-30 wt%, the content of carbon for carbon source pyrolysis is 5-15 wt%, the content of graphene is 25-45 wt%, and the content of metal oxide is 5-15 wt%.
The invention has the following advantages: firstly, the prepared micro-nano silicon-graphite composite lithium storage material has a micro-nano composite structure with graphite as an inner core and cracked carbon-silicon as a wrapping layer, and a multi-dimensional carbon support framework is used for stabilizing the structure and enhancing the conductivity; trace metal oxide is doped in the outer shell layer to enhance the interface compatibility of the silicon-graphite composite material in the circulation process, thereby enhancing the circulation stability. Secondly, on the technical originality, an electrostatic self-assembly technology is developed to carry out simple liquid phase stirring configuration on the precursor liquid, and the silicon content controllable and modulated high-capacity silicon-carbon material is realized to have a micro-nano composite structure to meet the commercial tap density requirement; the multi-dimensional carbon nano material is compositely coated/supported to improve the material conductivity and enhance the structural stability of the material; the necessary metal oxide modifications are introduced to promote interfacial compatibility during material cycling. Thirdly, in the cost advantage of preparation, the technology realizes the preparation of the micro-nano silicon-graphite composite lithium storage material by simple and convenient liquid phase stirring and sintering treatment, has the characteristics of less operation steps and low energy consumption, and fully embodies the cost advantage.
Drawings
FIG. 1 is a scanning electron micrograph and a transmission electron micrograph of a sample prepared in example 1 of the present invention.
FIG. 2 is a cycling curve at a current density of 0.3A/g for the sample prepared in example 1 of the present invention.
FIG. 3 is a cycling curve at a current density of 1.2A/g for the sample prepared in example 1 of the present invention.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and examples.
Example 1
Preparation method of metal oxide modified micro-nano silicon-graphite composite negative electrode material
0.8 g of commercial graphite and 0.8 g of silicon nanoparticles (100nm) were weighed and stirred in 150 ml of N, N-dimethylformamide. 0.4 g of zinc acetate was further dissolved in the above solution and stirred for 0.5 hours. Then 0.6 g of PAM (polyacrylamide, Mw 150000) was slowly added and stirred to form a mixed solution. The solution was then heated to 80 ℃ and stirred vigorously under a sealed environment for 1 hour. Subsequently, the sealing film was removed and the solution was continued to be stirred at 90 ℃ to evaporate the solvent. The mixture was stable in air at 260 ℃ for 2 hours with a heating rate of 2 ℃/min. And then annealing the obtained product in argon flow at 700 ℃ for 1 hour at the heating rate of 5 ℃/minute, naturally cooling the product to room temperature along with the furnace, taking out the powder and grinding the powder to obtain a final product (marked as a sample 1).
FIG. 1 is a scanning electron microscope image and a transmission electron microscope image of sample 1, which shows that the prepared sample 1 has a spherical complex with a uniform particle distribution and a morphology of about 10. + -. 3 μm.
0.1 gram of the final sample, 10% acetylene black and 10% sodium carboxymethylcellulose (CMC) were dissolved in deionized water to form a homogeneous slurryCoating the solution on a current collector, and vacuum drying at 100 ℃ for 12 hours to obtain the electrode. The volume ratio is 10%: 90% FEC (fluoroethylene carbonate) and 1.0mol/L LiPF 6 The mixed solution of EC/DEC/DMC is electrolyte, wherein LiPF 6 The conductive salt is EC (ethylene carbonate)/DEC (diethyl carbonate)/DMC (dimethyl carbonate) which is a composite solvent, and the volume ratio of the EC, the DEC and the DMC is 1: 1: 1. a metal lithium sheet is used as a negative electrode, a microporous polypropylene membrane (Cellgard 2400) is used as a diaphragm, the metal lithium sheet and the diaphragm are assembled into a CR2025 button cell, charging and discharging are respectively carried out at current densities of 0.3A/g and 1.2A/g, the voltage range of charging and discharging is 0.01-3.0V, and the cell test results are listed in Table 1.
Fig. 2 and fig. 3 are the test results of the silicon-carbon negative electrode material obtained in example 1 at current densities of 0.3A/g and 1.2Ag g, respectively, and it can be seen that the silicon-carbon negative electrode material still has a capacity of 1105.6mAh/g and a capacity retention rate of 98.2% after being cycled 400 times at 0.3A/g, and at the same time still has a high reversible capacity of 660mAh/g after being cycled 2000 times at a high rate of 1.2A/g.
Example 2
Preparation method of metal oxide modified micro-nano silicon-graphite composite negative electrode material
1.0 g of commercial graphite and 0.8 g of silicon nanoparticles (200nm) were weighed and stirred in 150 ml of N, N-dimethylformamide. 0.5 g of zinc acetate was further dissolved in the above solution and stirred for 1 hour. Then 0.5 g of polyacrylonitrile (Mw 150000) was slowly added and stirred to form a mixed solution. The solution was then heated to 60 ℃ and stirred vigorously under a sealed environment for 3 hours. Subsequently, the sealing film was removed and the solution was continued to be stirred at 90 ℃ to evaporate the solvent. The mixture was stable in air at 220 ℃ for 2 hours with a heating rate of 2 ℃/min. And then annealing the obtained product in argon flow at 700 ℃ for 3 hours at the heating rate of 5 ℃/min, naturally cooling the product to room temperature along with the furnace, taking out the powder and grinding the powder to obtain the final product.
The scanning electron microscope shows that the prepared sample 2 has uniform particle distribution and approximately 10 +/-3 mu m of folded spherical shape.
The counter electrode, electrolyte, battery assembly and test methods of the battery were the same as in example 1, and the test results of the battery are shown in table 1.
Example 3
Preparation method of metal oxide modified micro-nano silicon-graphite composite anode material
1.0 g of commercial graphite and 0.6 g of silicon nanoparticles (100nm) and stirred in 150 ml of N-methylpyrrolidone. 0.3 g of zirconium hydroxide was further dissolved in the above solution and stirred for 1.5 hours. Then 0.4 g of polyaniline (Mw 100000) was slowly added and stirred to form a mixed solution. The solution was then heated to 60 ℃ and stirred vigorously under a sealed environment for 2 hours. Subsequently, the sealing film was removed and the solution was continued to be stirred at 80 ℃ to evaporate the solvent. The mixture was stable in air at 300 ℃ for 1.5 hours with a heating rate of 5 ℃/min. And then annealing the obtained product in argon flow at 800 ℃ for 2 hours at the heating rate of 5 ℃/min, naturally cooling to room temperature along with the furnace, taking out the powder and grinding to obtain the final product.
The scanning electron microscope shows that the prepared sample 3 has uniform particle distribution and approximately spherical morphology of about 10 +/-2 microns.
The counter electrode, electrolyte, battery assembly and test methods of the battery were the same as in example 1, and the test results of the battery are shown in table 1.
Example 4
Preparation method of metal oxide modified micro-nano silicon-graphite composite anode material
1.2 g of commercial graphite and 0.8 g of silicon nanoparticles (300nm) and stirred in 150 ml of N, N-dimethylformamide. 0.2 g of zinc acetate and 0.3 g of zirconium hydroxide were further dissolved in the above solution and stirred for 1 hour. Then, 0.2 g of polyacrylamide (Mw 150000), 0.4 g of polyacrylonitrile (Mw 15000) were slowly added and stirred to form a mixed solution. The solution was then heated to 90 ℃ and stirred vigorously under a sealed environment for 2 hours. Subsequently, the sealing film was removed and the solution was continued to be stirred at 90 ℃ to evaporate the solvent. The dry mixture was stabilized in air at 260 ℃ for 3 hours at a heating rate of 2 ℃/min. And then annealing the obtained product in argon flow at 900 ℃ for 1 hour at the heating rate of 3 ℃/minute, naturally cooling the product to room temperature along with the furnace, taking out the powder and grinding the powder to obtain the final product.
Scanning electron micrographs show that the particles of the prepared sample 4 are uniformly distributed and have a spherical shape with the appearance of approximately 10 +/-3 microns.
The counter electrode, electrolyte, battery assembly and test methods of the battery were the same as in example 1, and the test results of the battery are shown in table 1.
Example 5
Preparation method of metal oxide modified micro-nano silicon-graphite composite negative electrode material
0.8 g of commercial graphite and 1.2 g of silicon nanoparticles (100nm) were weighed and stirred in a mixed solution of 100 ml of N, N-dimethylformamide and 50 ml of anhydrous ethanol. 0.46 g of zinc acetate was further dissolved in the above solution and stirred for 2.5 hours. Then, 0.2 g of polyacrylamide (Mw 150000), 0.3 g of chitosan were slowly added and stirred to form a mixed solution. The solution was then heated to 90 ℃ and stirred vigorously for 3 hours in a sealed environment. Subsequently, the sealing film was removed and the solution was continued to be stirred at 90 ℃ to evaporate the solvent. The mixture was stable in air at 300 ℃ for 1.5 hours with a heating rate of 1 ℃/min. And then annealing the obtained product in argon flow at 1000 ℃ for 1.5 hours at the heating rate of 4 ℃/min, naturally cooling to room temperature along with the furnace, taking out the powder and grinding to obtain the final product.
The scanning electron microscope shows that the prepared sample 5 has uniform particle distribution and approximately 10 +/-3 mu m of folded spherical shape.
The counter electrode, electrolyte, battery assembly and test methods of the battery were the same as in example 1, and the test results of the battery are shown in table 1.
TABLE 1 summary of test results for examples 1-5
Figure BDA0002700119280000051
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (10)

1. A preparation method of a metal oxide modified micro-nano silicon-graphite composite anode material is characterized by comprising the following steps:
1) respectively dissolving nano-silicon, metal salt, a carbon source and graphite powder in a solvent, and fully stirring to obtain a mixed solution;
2) placing the mixed solution in a water bath kettle at the temperature of 60-90 ℃ and stirring for 0.5-2 hours to evaporate the solvent to obtain a mixture;
3) pre-oxidizing the mixture in air at 200-300 ℃ for 1-3 hours;
4) placing the obtained product in an atmosphere furnace, calcining in an inert atmosphere at the temperature of 600-1000 ℃ for 0.5-5 hours, and cooling to room temperature along with the furnace after the calcination is finished to obtain the metal oxide modified micro-nano silicon-graphite composite negative electrode material;
the metal oxide modified micro-nano silicon-graphite composite negative electrode material has a micro-nano composite structure with graphite as an inner core and cracked carbon-silicon as a wrapping layer.
2. The preparation method of the metal oxide modified micro-nano silicon-graphite composite anode material according to claim 1, wherein the average particle size of the nano silicon is 100-300 nm.
3. The preparation method of the metal oxide modified micro-nano silicon-graphite composite anode material according to claim 2, wherein the nano silicon is one or a combination of nano silicon crystal and nano silicon amorphous substance.
4. The preparation method of the metal oxide modified micro-nano silicon-graphite composite anode material according to claim 2, wherein the nano silicon is monodisperse nano silicon particles.
5. The preparation method of the metal oxide modified micro-nano silicon-graphite composite anode material according to claim 1, wherein the metal salt solution is one or more of zinc acetate, zirconium hydroxide and butyl titanate.
6. The preparation method of the metal oxide modified micro-nano silicon-graphite composite anode material according to claim 1, wherein the carbon source is one or more of polyacrylamide, polyacrylonitrile, polyaniline and chitosan.
7. The preparation method of the metal oxide modified micro-nano silicon-graphite composite anode material according to claim 1, wherein the solvent is one of N, N-dimethylformamide and absolute ethyl alcohol.
8. The preparation method of the metal oxide modified micro-nano silicon-graphite composite anode material according to claim 1, wherein the temperature rise rate in the step 3) is 1-5 ℃/min, the temperature rise rate in the step 4) is 2-10 ℃/min, and the inert atmosphere is argon.
9. The micro-nano silicon-graphite composite anode material obtained by the preparation method according to any one of claims 1 to 8.
10. The micro-nano silicon-graphite composite negative electrode material of claim 9, wherein the content of silicon nanoparticles in the micro-nano silicon-graphite composite negative electrode material is 10-30 wt%, the content of carbon for carbon source pyrolysis is 5-15 wt%, the content of graphite is 25-45 wt%, and the content of metal oxide is 5-15 wt%.
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