CN115159527A - Hard carbon coated silicon nanoparticle composite microsphere negative electrode material and preparation method and application thereof - Google Patents
Hard carbon coated silicon nanoparticle composite microsphere negative electrode material and preparation method and application thereof Download PDFInfo
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- CN115159527A CN115159527A CN202210527511.3A CN202210527511A CN115159527A CN 115159527 A CN115159527 A CN 115159527A CN 202210527511 A CN202210527511 A CN 202210527511A CN 115159527 A CN115159527 A CN 115159527A
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- 239000005543 nano-size silicon particle Substances 0.000 title claims abstract description 90
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- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
- C01B33/021—Preparation
- C01B33/027—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
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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
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
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- 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
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- H—ELECTRICITY
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- 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
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- 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
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Abstract
The invention discloses a hard carbon-coated silicon nanoparticle composite microsphere negative electrode material and a preparation method and application thereof, wherein the preparation method comprises the following steps: dissolving silicon tetrachloride and a hard carbon precursor in an alcohol solvent to form a mixed solution; pouring the mixed solution into a hydrothermal reaction kettle, sealing, putting the hydrothermal reaction kettle into an oven, and heating to carry out solvothermal reaction to obtain a reaction product; and (3) drying the reaction product, and then calcining in an inert atmosphere and/or a reducing atmosphere to obtain the hard carbon coated silicon nanoparticle composite microsphere negative electrode material. In the invention, the hard carbon spheres can buffer the volume expansion in the process of lithiation of silicon, and the silicon nanoparticles are wrapped by the hard carbon spheres, so that the silicon nanoparticles are prevented from being directly contacted with an electrolyte, the first coulombic efficiency of the nano silicon negative electrode material is improved, the loss of active lithium caused by continuous growth of SEI in the circulating process is reduced, and the circulating stability is obviously improved; in addition, the conductivity of the hard carbon spheres is superior to that of the silicon cathode material, and the multiplying power performance of the silicon cathode material is greatly improved.
Description
Technical Field
The invention relates to the technical field of negative electrode materials, in particular to a hard carbon-coated silicon nanoparticle composite microsphere negative electrode material and a preparation method and application thereof.
Background
The silicon negative electrode material is expected to replace a graphite negative electrode material with wide commercial application due to the advantages of high capacity, low de-intercalation lithium potential, environmental friendliness, rich reserves, low cost and the like. However, during the lithiation process of the silicon negative electrode, severe volume expansion exists, which causes silicon particles to be crushed and pulverized, more surfaces are exposed, an SEI film continuously grows to consume active lithium ions, and the cycle performance is seriously deteriorated. The loss of electric connection after the particles are broken and the increasing thickness of SEI film can cause the increase of the internal resistance of the battery cell and the deterioration of the cycle and dynamic performance of the battery cell. Meanwhile, the electrical conductivity of the silicon negative electrode material is lower than that of the graphite negative electrode material, so that the multiplying power performance of the battery cell is severely limited.
The nano-crystallization of the silicon negative electrode material, the compounding with the carbon material and the use of the silicon oxide are common means for improving the volume expansion, and can relieve the volume expansion to a certain extent, but the problems of low coulombic efficiency, low energy density and the like are easily introduced for the first time, and the improvement effect is often not as expected.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a hard carbon-coated silicon nanoparticle composite microsphere negative electrode material, and a preparation method and application thereof, and aims to solve the problem that the conventional silicon negative electrode material is easy to generate volume expansion, so that the battery cell has poor cycle performance, dynamic performance and rate capability.
The technical scheme of the invention is as follows:
a preparation method of a hard carbon-coated silicon nanoparticle composite microsphere negative electrode material comprises the following steps:
dissolving silicon tetrachloride and a hard carbon precursor in an alcohol solvent to form a mixed solution;
pouring the mixed solution into a hydrothermal reaction kettle, sealing, putting the hydrothermal reaction kettle into a drying oven, and heating to carry out solvothermal reaction to obtain a reaction product;
and (3) drying the reaction product, and calcining in an inert atmosphere and/or a reducing atmosphere to obtain the hard carbon-coated silicon nanoparticle composite microsphere cathode material.
The preparation method of the hard carbon coated silicon nanoparticle composite microsphere negative electrode material comprises the following step of preparing a hard carbon coated silicon nanoparticle composite microsphere negative electrode material, wherein the hard carbon precursor is one or more of glucose, sucrose, a phenolic resin precursor solution, a urea-formaldehyde resin precursor solution, polyacrylonitrile, polyaniline, furfural and furfuryl alcohol.
The preparation method of the hard carbon-coated silicon nanoparticle composite microsphere negative electrode material comprises the step of preparing a hard carbon-coated silicon nanoparticle composite microsphere negative electrode material, wherein the alcohol solvent is one or more of ethanol, propanol, isopropanol and butanol.
The preparation method of the hard carbon-coated silicon nanoparticle composite microsphere anode material comprises the step of placing the hydrothermal reaction kettle into an oven to be heated for solvothermal reaction, wherein the solvothermal reaction is carried out at the temperature of 120-200 ℃ for 2-10 hours.
The preparation method of the hard carbon-coated silicon nanoparticle composite microsphere negative electrode material comprises the step of drying a reaction product and then calcining in an inert atmosphere and/or a reducing atmosphere, wherein the calcining temperature is 600-1800 ℃ and the calcining time is 0.5-10 hours.
The preparation method of the hard carbon coated silicon nanoparticle composite microsphere negative electrode material comprises the following steps of (1) preparing a hard carbon coated silicon nanoparticle composite microsphere negative electrode material, wherein the inert atmosphere is one or more of nitrogen, argon and helium; and/or the reducing atmosphere is one or two of acetylene and hydrogen.
The invention discloses a hard carbon-coated silicon nanoparticle composite microsphere negative electrode material, which is prepared by the preparation method of the hard carbon-coated silicon nanoparticle composite microsphere negative electrode material.
The hard carbon-coated silicon nanoparticle composite microsphere negative electrode material is characterized by comprising a hard carbon sphere and silicon nanoparticles embedded in the hard carbon sphere.
The hard carbon-coated silicon nanoparticle composite microsphere negative electrode material is characterized in that the diameter of the hard carbon-coated silicon nanoparticle composite microsphere negative electrode material is 0.5-5 mu m, the particle size of the silicon nanoparticles is 5-50nm, and the mass ratio of hard carbon spheres to the hard carbon-coated silicon nanoparticle composite microsphere negative electrode material is 20-90%.
The application of the hard carbon-coated silicon nanoparticle composite microsphere negative electrode material is characterized in that the hard carbon-coated silicon nanoparticle composite microsphere negative electrode material is used as an active substance on a lithium ion battery negative electrode plate.
Has the beneficial effects that: the invention provides a preparation method of a hard carbon-coated silicon nanoparticle composite microsphere negative electrode material. Compared with the prior art, the silicon exists in the form of nano particles with the size less than 50nm, the volume expansion is obviously improved, and meanwhile, the hard carbon spheres can buffer the volume expansion in the process of lithiation of the silicon; the silicon nano particles are wrapped by the hard carbon spheres, so that the silicon nano particles are prevented from being directly contacted with the electrolyte, the first coulombic efficiency of the nano silicon negative electrode material is improved, the loss of active lithium caused by the continuous growth of SEI (solid electrolyte interphase) in the circulating process is reduced, and the circulating stability is obviously improved; in addition, the conductivity of the hard carbon spheres is superior to that of the silicon cathode material, and the multiplying power performance of the silicon cathode material is greatly improved.
Drawings
Fig. 1 is a flowchart of a preferred embodiment of a method for preparing a hard carbon-coated silicon nanoparticle composite microsphere anode material according to the present invention.
Fig. 2 is an SEM image of the hard carbon-coated silicon nanoparticle composite microsphere negative electrode material prepared in example 1 of the present invention.
Fig. 3 is a TEM image of the hard carbon-coated silicon nanoparticle composite microsphere negative electrode material prepared in example 1 of the present invention.
Detailed Description
The invention provides a hard carbon-coated silicon nanoparticle composite microsphere negative electrode material and a preparation method and application thereof, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
The invention provides a preparation method of a hard carbon-coated silicon nanoparticle composite microsphere anode material, which comprises the following steps of:
s10, dissolving silicon tetrachloride and a hard carbon precursor in an alcohol solvent to form a mixed solution;
s20, pouring the mixed solution into a hydrothermal reaction kettle, sealing, and putting the hydrothermal reaction kettle into an oven to be heated for solvothermal reaction to obtain a reaction product;
and S30, drying the reaction product, and calcining in an inert atmosphere and/or a reducing atmosphere to obtain the hard carbon-coated silicon nanoparticle composite microsphere cathode material.
The invention provides a simple, efficient and easy-to-operate method for preparing a hard carbon-coated silicon nanoparticle composite microsphere negative electrode material, and the prepared hard carbon-coated silicon nanoparticle composite microsphere negative electrode material consists of a hard carbon sphere and silicon nanoparticles embedded in the hard carbon sphere. In the present invention, the silicon nanoparticles may exist in a size form with a particle size of less than 50nm, the volume expansion is significantly improved, and at the same time, the hard carbon spheres may buffer the volume expansion during the lithiation of silicon; the silicon nano particles are wrapped by the hard carbon spheres, so that the silicon nano particles are prevented from being directly contacted with the electrolyte, the first coulombic efficiency of the nano silicon negative electrode material is improved, the loss of active lithium caused by the continuous growth of SEI (solid electrolyte interphase) in the circulating process is reduced, and the circulating stability is obviously improved; in addition, the conductivity of the hard carbon spheres is superior to that of the silicon cathode material, and the multiplying power performance of the silicon cathode material is greatly improved.
In some embodiments, the hard carbon precursor may be one or more of any carbon-containing compound that generates a spherical hard carbon precursor at high temperature and high pressure, for example, one or more of glucose, sucrose, a phenol resin precursor solution, a urea resin precursor solution, polyacrylonitrile, polyaniline, furfural, and furfuryl alcohol, but is not limited thereto.
In some embodiments, the alcoholic solvent is one or more of ethanol, propanol, isopropanol, and butanol, but is not limited thereto.
In some embodiments, the hydrothermal reaction kettle is placed in an oven and heated to perform a solvothermal reaction, wherein the solvothermal reaction temperature is 120-200 ℃, and may be, for example, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, and the like; the solvothermal reaction time is 2 to 10 hours, and may be, for example, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, or the like. Preferably, the temperature of the solvothermal reaction is 140-60 ℃ and the time is 4-6h.
In some embodiments, after the reaction product is dried, in the step of performing the calcination treatment in the inert atmosphere and/or the reducing atmosphere, the calcination treatment temperature is 600 to 1800 ℃, for example, 600 ℃, 800 ℃, 1000 ℃, 1200 ℃, 1400 ℃, 1500 ℃, 1600 ℃, 1700 ℃, 1800 ℃, etc.; the time for the calcination treatment is 0.5 to 10 hours, and may be, for example, 0.5 hour, 2 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, or the like. Preferably, the temperature of the calcination treatment is 800200 ℃ and the time is 1-3h.
In some embodiments, the calcination treatment may be performed under a single inert atmosphere or a reducing atmosphere, or may be performed under a mixed atmosphere of an inert atmosphere and a reducing atmosphere. In this embodiment, the inert atmosphere is one or more of nitrogen, argon and helium; the reducing atmosphere is one or two of acetylene and hydrogen.
In some specific embodiments, when the calcination treatment is performed under a mixed atmosphere of an inert atmosphere and a reducing atmosphere, the volume ratio of the inert atmosphere to the reducing atmosphere is 90 to 95. Within the volume ratio range, the calcining treatment efficiency is higher, and the hard carbon-coated silicon nanoparticle composite microsphere negative electrode material with better rate capability and higher circulating capacity retention rate can be prepared. By way of example, the mixed atmosphere may be argon and acetylene in a volume ratio of 90.
In some embodiments, the invention further provides a hard carbon-coated silicon nanoparticle composite microsphere anode material, wherein the hard carbon-coated silicon nanoparticle composite microsphere anode material is prepared by the preparation method of the hard carbon-coated silicon nanoparticle composite microsphere anode material. In this embodiment, the hard carbon-coated silicon nanoparticle composite microsphere negative electrode material is composed of a hard carbon sphere and silicon nanoparticles embedded in the hard carbon sphere, wherein the diameter of the hard carbon-coated silicon nanoparticle composite microsphere negative electrode material is 0.5-5 μm, the particle size of the silicon nanoparticles is 5-50nm, and the mass ratio of the hard carbon sphere to the hard carbon-coated silicon nanoparticle composite microsphere negative electrode material is 20-90%.
In some embodiments, the application of the hard carbon-coated silicon nanoparticle composite microsphere negative electrode material is also provided, and the hard carbon-coated silicon nanoparticle composite microsphere negative electrode material is used as an active substance on a negative electrode plate of a lithium ion battery. In the invention, because the silicon nanoparticles in the hard carbon-coated silicon nanoparticle composite microsphere negative electrode material can exist in a size form with the particle size of less than 50nm, the volume expansion is obviously improved, and meanwhile, the hard carbon sphere can buffer the volume expansion in the process of silicon lithiation; the silicon nano particles are wrapped by the hard carbon spheres, so that the silicon nano particles can be prevented from being directly contacted with the electrolyte, the first coulombic efficiency of the nano silicon negative electrode material is improved, the loss of active lithium caused by continuous growth of SEI (solid electrolyte interphase) in the circulating process is reduced, and the circulating stability is obviously improved; in addition, the conductivity of the hard carbon spheres is superior to that of the silicon cathode material, and the multiplying power performance of the silicon cathode material is greatly improved. Therefore, after the hard carbon-coated silicon nanoparticle composite microsphere negative electrode material is used as an active substance on a negative electrode plate of a lithium ion battery, the prepared lithium ion battery has better rate performance and higher first coulombic efficiency and cycle capacity retention rate.
The invention is further illustrated by the following specific examples:
example 1
1.2g of silicon tetrachloride and 2.0g of furfural are weighed and dissolved in 80mL of ethanol, and the solution is stirred for 2 hours on a magnetic stirrer to be uniformly mixed. Transferring the solution into a 100mL inner container of a hydrothermal reaction kettle, putting the hydrothermal reaction kettle into the hydrothermal reaction kettle, and sealing the hydrothermal reaction kettle by a cover. And (3) putting the hydrothermal reaction kettle into an oven with the temperature of 140 ℃ for heat preservation for 10 hours, and naturally cooling the hydrothermal reaction kettle to room temperature after the reaction is finished. And taking out the precipitated product in the hydrothermal reaction kettle, washing the product with deionized water and ethanol solution for three times respectively, and then drying the product in a vacuum oven at 80 ℃ for 12 hours. And (3) placing the dried product in a tubular furnace, heating to 800 ℃ in Ar atmosphere, preserving heat for 1h at 800 ℃, and naturally cooling to room temperature to obtain the hard carbon-coated silicon nanoparticle composite microsphere negative electrode material.
Example 2
1.5g of silicon tetrachloride and 2.0g of furfural are weighed and dissolved in 80mL of ethanol, and the solution is stirred for 2 hours on a magnetic stirrer to be uniformly mixed. Transferring the solution into a 100mL inner container of a hydrothermal reaction kettle, putting the hydrothermal reaction kettle into the hydrothermal reaction kettle, and sealing the hydrothermal reaction kettle by a cover. And (3) putting the hydrothermal reaction kettle into an oven with the temperature of 140 ℃ for heat preservation for 10 hours, and naturally cooling the hydrothermal reaction kettle to room temperature after the reaction is finished. And taking out the precipitated product in the hydrothermal reaction kettle, washing the product with deionized water and ethanol solution for three times respectively, and then drying the product in a vacuum oven at 80 ℃ for 12 hours. And (3) placing the dried product in a tube furnace, heating to 800 ℃ in Ar atmosphere, preserving heat for 1h at 800 ℃, and naturally cooling to room temperature to obtain the hard carbon-coated silicon nanoparticle composite microsphere cathode material.
Example 3
1.8g of silicon tetrachloride and 2.0g of furfural are weighed and dissolved in 80mL of ethanol, and the solution is stirred for 2 hours on a magnetic stirrer to be uniformly mixed. Transferring the solution into a 100mL inner container of a hydrothermal reaction kettle, putting the hydrothermal reaction kettle into the hydrothermal reaction kettle, and sealing the hydrothermal reaction kettle by a cover. And (3) putting the hydrothermal reaction kettle into an oven with the temperature of 140 ℃ for heat preservation for 10 hours, and naturally cooling the hydrothermal reaction kettle to room temperature after the reaction is finished. And taking out the precipitated product in the hydrothermal reaction kettle, washing the product with deionized water and ethanol solution for three times respectively, and then drying the product in a vacuum oven at 80 ℃ for 12 hours. And (3) placing the dried product in a tubular furnace, heating to 800 ℃ in Ar atmosphere, preserving heat for 1h at 800 ℃, and naturally cooling to room temperature to obtain the hard carbon-coated silicon nanoparticle composite microsphere negative electrode material.
Example 4
1.2g of silicon tetrachloride and 2.4g of furfural are weighed and dissolved in 80mL of ethanol, and stirred for 2 hours on a magnetic stirrer to uniformly mix the solution. Transferring the solution into a 100mL inner container of a hydrothermal reaction kettle, putting the hydrothermal reaction kettle into the hydrothermal reaction kettle, and sealing the hydrothermal reaction kettle by a cover. And (3) putting the hydrothermal reaction kettle into an oven with the temperature of 140 ℃ for heat preservation for 10 hours, and naturally cooling the hydrothermal reaction kettle to room temperature after the reaction is finished. And taking out the precipitated product in the hydrothermal reaction kettle, washing the product with deionized water and ethanol solution for three times respectively, and then drying the product in a vacuum oven at 80 ℃ for 12 hours. And (3) placing the dried product in a tube furnace, heating to 800 ℃ in Ar atmosphere, preserving heat for 1h at 800 ℃, and naturally cooling to room temperature to obtain the hard carbon-coated silicon nanoparticle composite microsphere cathode material.
Example 5
1.2g of silicon tetrachloride and 2.0g of furfural are weighed and dissolved in 80mL of ethanol, and the solution is stirred for 2 hours on a magnetic stirrer to be uniformly mixed. Transferring the solution into a 100mL inner container of a hydrothermal reaction kettle, putting the hydrothermal reaction kettle into the hydrothermal reaction kettle, and sealing the hydrothermal reaction kettle by a cover. And (3) placing the hydrothermal reaction kettle into a drying oven at 160 ℃ for heat preservation for 10 hours, and naturally cooling the hydrothermal reaction kettle to room temperature after the reaction is finished. And taking out the precipitate in the hydrothermal reaction kettle, washing with deionized water and ethanol solution for three times respectively, and drying in a vacuum oven at 80 ℃ for 12 hours. And (3) placing the dried product in a tube furnace, heating to 800 ℃ in Ar atmosphere, preserving heat for 1h at 800 ℃, and naturally cooling to room temperature to obtain the hard carbon-coated silicon nanoparticle composite microsphere cathode material.
Example 6
1.2g of silicon tetrachloride and 2.0g of furfural are weighed and dissolved in 80mL of ethanol, and the solution is stirred for 2 hours on a magnetic stirrer to be uniformly mixed. Transferring the solution into a 100mL inner container of a hydrothermal reaction kettle, putting the hydrothermal reaction kettle into the hydrothermal reaction kettle, and sealing the hydrothermal reaction kettle by a cover. And (3) placing the hydrothermal reaction kettle into a drying oven at 160 ℃ for heat preservation for 10 hours, and naturally cooling the hydrothermal reaction kettle to room temperature after the reaction is finished. And taking out the precipitated product in the hydrothermal reaction kettle, washing the product with deionized water and ethanol solution for three times respectively, and then drying the product in a vacuum oven at 80 ℃ for 12 hours. And (3) placing the dried product in a tubular furnace, heating to 800 ℃ in a mixed atmosphere consisting of Ar and hydrogen in a volume ratio of 95.
Comparative example 1
1.2g of silicon tetrachloride and 1g of conductive carbon black are weighed and placed in 80mL of ethanol, and ultrasonic dispersion is carried out for 30min to form uniformly dispersed suspension. Transferring the suspension into a 100mL inner container of a hydrothermal reaction kettle, putting the hydrothermal reaction kettle into the hydrothermal reaction kettle, and sealing the hydrothermal reaction kettle with a cover. And (3) putting the hydrothermal reaction kettle into an oven with the temperature of 140 ℃ for heat preservation for 10 hours, and naturally cooling the hydrothermal reaction kettle to room temperature after the reaction is finished. And taking out the precipitated product in the hydrothermal reaction kettle, washing the product with deionized water and ethanol solution for three times respectively, and then drying the product in a vacuum oven at 80 ℃ for 12 hours. And (3) placing the dried product in a tubular furnace, heating to 800 ℃ in Ar atmosphere, preserving heat for 1h at 800 ℃, and naturally cooling to room temperature to obtain the silicon-carbon composite negative electrode material.
Comparative example 2
1.2g of silicon tetrachloride is weighed and dissolved in 80mL of ethanol, and the solution is stirred for 2 hours on a magnetic stirrer to be uniformly mixed. Transferring the solution into a 100mL inner container of a hydrothermal reaction kettle, putting the hydrothermal reaction kettle into the hydrothermal reaction kettle, and sealing the hydrothermal reaction kettle by a cover. And (3) putting the hydrothermal reaction kettle into an oven with the temperature of 140 ℃ for heat preservation for 10 hours, and naturally cooling the hydrothermal reaction kettle to room temperature after the reaction is finished. And taking out the precipitate in the hydrothermal reaction kettle, washing with deionized water and ethanol solution for three times respectively, and drying in a vacuum oven at 80 ℃ for 12 hours. And (3) placing the dried product in a tubular furnace, heating to 800 ℃ in Ar atmosphere, preserving heat for 1h at 800 ℃, and naturally cooling to room temperature to obtain the nano-silicon negative electrode material.
The hard carbon-coated silicon nanoparticle composite microsphere negative electrode material prepared in the embodiment 1 is characterized by structure and appearance: and (3) observing morphology characteristics by adopting a Scanning Electron Microscope (SEM) and a Transmission Electron Microscope (TEM), and characterizing the carbon content in the composite material by thermogravimetric testing. As shown in fig. 2 and 3, it can be seen from fig. 2 that the sample prepared in example 1 is spherical particles, and the particle size of the particles is about 1 micron; as can be seen from fig. 3, the sample prepared in example 1 has a large number of black nanoparticles embedded therein, and HRTEM shows that the black particles are silicon nanoparticles.
The negative electrode materials prepared in the above examples 1 to 6 and comparative examples 1 to 2 were assembled and electrically connected for electrical property characterization: the negative electrode material, conductive carbon black and binder polyacrylic acid (PAA, 25% aqueous solution) were mixed in 80:10: mixing at a ratio of 10, grinding thoroughly, and dispersing in a homogenizer for 15min to obtain viscous active substance slurry. And uniformly coating the slurry on a copper foil by adopting a blade coating method, and transferring the coated negative pole piece into a vacuum oven at 80 ℃ for drying for 12 hours. The dried pole pieces were rolled and punched into circular pole pieces 12mm in diameter and weighed. After weighing, the pole piece is immediately transferred into a glove box protected by Ar atmosphere to be assembled with CR2016 type electricity deduction, and the electrolyte is 1mol/L LiPF 6 Dissolved in EC: DEC =1:1 (volume ratio), 10% fec was added by volume ratio, a metal lithium piece was used as a negative electrode, and Celgard2300 was used as a separator. A LAND battery test system is adopted to carry out charging and discharging tests, the charging and discharging voltage range is 0.001-2V, and the test results are shown in Table 1:
table 1 characterization of electrical properties
The data in table 1 show that the gram capacity of the silicon negative electrode can be reduced by the hard carbon-coated silicon nanoparticle composite microsphere negative electrode material provided by the invention, but the cycling stability of the silicon negative electrode material can be remarkably improved, so that the silicon negative electrode material can still maintain higher gram capacity at the later cycle stage. Meanwhile, the problems of first coulombic efficiency, rate capability and the like can be improved, and the requirement of the lithium ion battery on a high-performance cathode material is met.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (10)
1. A preparation method of a hard carbon-coated silicon nanoparticle composite microsphere anode material is characterized by comprising the following steps:
dissolving silicon tetrachloride and a hard carbon precursor in an alcohol solvent to form a mixed solution;
pouring the mixed solution into a hydrothermal reaction kettle, sealing, putting the hydrothermal reaction kettle into an oven, and heating to carry out solvothermal reaction to obtain a reaction product;
and (3) drying the reaction product, and then calcining in an inert atmosphere and/or a reducing atmosphere to obtain the hard carbon coated silicon nanoparticle composite microsphere negative electrode material.
2. The preparation method of the hard carbon-coated silicon nanoparticle composite microsphere anode material as claimed in claim 1, wherein the hard carbon precursor is one or more of glucose, sucrose, a phenolic resin precursor solution, a urea resin precursor solution, polyacrylonitrile, polyaniline, furfural and furfuryl alcohol.
3. The preparation method of the hard carbon-coated silicon nanoparticle composite microsphere anode material as claimed in claim 1, wherein the alcohol solvent is one or more of ethanol, propanol, isopropanol and butanol.
4. The preparation method of the hard carbon-coated silicon nanoparticle composite microsphere anode material as claimed in claim 1, wherein in the step of heating the hydrothermal reaction kettle in an oven to carry out the solvothermal reaction, the temperature of the solvothermal reaction is 120-200 ℃ and the time is 2-10h.
5. The preparation method of the hard carbon-coated silicon nanoparticle composite microsphere anode material as claimed in claim 1, wherein in the step of calcining the reaction product in an inert atmosphere and/or a reducing atmosphere after drying, the calcining temperature is 600-1800 ℃ and the calcining time is 0.5-10h.
6. The preparation method of the hard carbon-coated silicon nanoparticle composite microsphere anode material as claimed in claim 1, wherein the inert atmosphere is one or more of nitrogen, argon and helium; and/or the reducing atmosphere is one or two of acetylene and hydrogen.
7. A hard carbon-coated silicon nanoparticle composite microsphere negative electrode material is characterized by being prepared by the preparation method of the hard carbon-coated silicon nanoparticle composite microsphere negative electrode material disclosed by any one of claims 1 to 6.
8. The hard carbon-coated silicon nanoparticle composite microsphere anode material of claim 7, wherein the hard carbon-coated silicon nanoparticle composite microsphere anode material consists of hard carbon spheres and silicon nanoparticles embedded inside the hard carbon spheres.
9. The hard carbon-coated silicon nanoparticle composite microsphere anode material of claim 8, wherein the diameter of the hard carbon-coated silicon nanoparticle composite microsphere anode material is 0.5-5 μm, the particle size of the silicon nanoparticles is 5-50nm, and the mass ratio of the hard carbon spheres to the hard carbon-coated silicon nanoparticle composite microsphere anode material is 20-90%.
10. The use of the hard carbon-coated silicon nanoparticle composite microsphere negative electrode material according to claims 7 to 9, wherein the hard carbon-coated silicon nanoparticle composite microsphere negative electrode material is used as an active material on a negative electrode plate of a lithium ion battery.
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