CN114242962A - Lithium orthosilicate and carbon-coated nano-silicon composite material and preparation method and application thereof - Google Patents
Lithium orthosilicate and carbon-coated nano-silicon composite material and preparation method and application thereof Download PDFInfo
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- YTZVWGRNMGHDJE-UHFFFAOYSA-N tetralithium;silicate Chemical compound [Li+].[Li+].[Li+].[Li+].[O-][Si]([O-])([O-])[O-] YTZVWGRNMGHDJE-UHFFFAOYSA-N 0.000 title claims abstract description 108
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
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- 239000007773 negative electrode material Substances 0.000 claims description 5
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- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
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- ZYJNJMHGRZIEST-UHFFFAOYSA-N dilithium dihydroxy(dioxido)silane Chemical compound [Si]([O-])([O-])(O)O.[Li+].[Li+] ZYJNJMHGRZIEST-UHFFFAOYSA-N 0.000 description 1
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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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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 discloses a lithium orthosilicate and carbon-coated nano-silicon composite material and a preparation method and application thereof, wherein the method comprises the following steps: sintering nano silicon in air atmosphere to generate a silicon oxide coating layer on the surface of the nano silicon; dispersing nano-silicon with a silicon oxide coating layer in an organic solvent, adding lithium hydroxide monohydrate, and stirring to obtain a first suspension; adding the carbon nano tube and polyvinylpyrrolidone into an organic solvent, and performing ultrasonic dispersion to obtain a second suspension; mixing the first suspension and the second suspension, and then stirring, heating and drying to obtain a precursor of the lithium orthosilicate and the carbon-coated nano-silicon composite material; and carrying out heat treatment on the precursor to obtain the lithium orthosilicate and carbon-coated nano silicon composite material. The composite material prepared by the invention has higher specific capacity, rate capability and cycling stability. The invention has low preparation cost and simple preparation method, and is easy for industrial production.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a lithium orthosilicate and carbon-coated nano silicon composite material as well as a preparation method and application thereof.
Background
Silicon has the advantages of high theoretical capacity, moderate working voltage, high utilization rate, environmental friendliness and the like, and is considered to be one of the best choices for replacing the widely used graphite cathode of the lithium ion battery. However, the silicon negative electrode material has problems of large volume change, low conductivity and ionic conductivity, unstable solid electrolyte interface, and the like, which leads to serious pulverization and capacity attenuation of silicon, and hinders practical application of the silicon negative electrode material. Among the numerous solutions, carbon compounding is a promising and effective solution, and is receiving increasing attention.
In the silicon/carbon composite negative electrode material, silicon is used as an active substance with high capacity, and carbon improves the conductivity and simultaneously slows down the expansion of the silicon. In order to solve the problems of poor conductivity and volume expansion of silicon materials, the modification method mainly comprises the steps of silicon particle size nanocrystallization, carbon coating and the like. The nano silicon powder is dispersed in the three-dimensional conductive network formed by the graphene, so that the close contact between the nano silicon powder and the graphene can be maintained, the diffusion path of lithium ions is shortened, and the electronic conduction of the electrode material is ensured not to be lost. The carbon coating limits the volume expansion of silicon in charge-discharge circulation to a certain extent, avoids the side reaction of silicon and electrolyte, and simultaneously improves the electronic conductivity of the material. Although the technical means can achieve the technical effects of improving the capacity and the conductivity of the cathode material and improving the structural stability and the cycling stability of the material, the preparation cost is high, the preparation process is complex, and the method is not suitable for large-scale production.
Therefore, how to prepare the silicon-based composite material with excellent electrochemical properties at low cost is an urgent problem to be solved for developing silicon cathode materials.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a lithium orthosilicate and carbon-coated nano silicon composite material, a preparation method and application thereof, and aims to solve the problem of high preparation cost of the existing silicon-based composite material.
The technical scheme of the invention is as follows:
a preparation method of a lithium orthosilicate and carbon-coated nano silicon composite material comprises the following steps:
sintering the nano silicon for 1-5 hours at the temperature of 300-600 ℃ in the air atmosphere to generate a silicon oxide coating layer on the surface of the nano silicon;
dispersing nano-silicon with a silicon oxide coating layer in an organic solvent, adding lithium hydroxide monohydrate, and stirring to obtain a first suspension;
adding the carbon nano tube and polyvinylpyrrolidone into an organic solvent, and performing ultrasonic dispersion to obtain a second suspension;
mixing the first suspension and the second suspension, and then stirring, heating and drying to obtain a precursor of the lithium orthosilicate and the carbon-coated nano-silicon composite material;
and carrying out heat treatment on the lithium orthosilicate and carbon-coated nano-silicon composite material precursor to obtain the lithium orthosilicate and carbon-coated nano-silicon composite material.
Further, the nano silicon is prepared by the following method: and ball-milling the micron silicon in absolute ethyl alcohol, and drying to obtain powdery nano silicon.
Further, the organic solvent is one or more of methanol, ethanol, ethylene glycol and propanol.
Further, the addition amount of the lithium hydroxide monohydrate is 10.5-17.5% of the mass of the nano silicon.
Further, the mass ratio of the carbon nano tube to the polyvinylpyrrolidone is 1:1, and the mass ratio of the carbon nano tube to the nano silicon is 1: 2.
Further, the step of performing heat treatment on the lithium orthosilicate and carbon-coated nano-silicon composite material precursor to obtain the lithium orthosilicate and carbon-coated nano-silicon composite material specifically comprises:
and putting the lithium orthosilicate and carbon-coated nano-silicon composite material precursor into a sintering furnace, and carrying out heat treatment for 1-5 hours at the temperature of 800-1000 ℃ in the inert gas atmosphere to obtain the lithium orthosilicate and carbon-coated nano-silicon composite material.
Further, the temperature is raised to 800-1000 ℃ at a temperature raising rate of 3-10 ℃/min.
Further, the inert gas is selected from one or more of nitrogen, helium and argon.
A lithium orthosilicate and carbon-coated nano-silicon composite comprising: nano silicon, lithium orthosilicate coated on the surface of the nano silicon and a carbon material coated on the surface of the lithium orthosilicate;
and/or the lithium orthosilicate and carbon-coated nano silicon composite material is prepared by the preparation method.
The invention relates to an application of a lithium orthosilicate and carbon-coated nano silicon composite material as a lithium ion battery cathode material.
Has the advantages that: the method comprises the steps of carrying out surface treatment on nano silicon, sintering the nano silicon in the air atmosphere to generate a silicon oxide coating layer, reacting with lithium hydroxide to obtain lithium orthosilicate coated nano silicon, and finally compounding with a carbon material to obtain the lithium orthosilicate and carbon-coated nano silicon composite material. The lithium orthosilicate and carbon-coated nano silicon composite material prepared by the simple method realizes that the lithium orthosilicate is uniformly coated on the surface of the nano silicon, and the carbon material forms a three-dimensional conductive network, so that the volume expansion of the nano silicon is effectively limited, the direct contact between the electrolyte and the nano silicon particles is reduced, and the electronic conductivity of the composite material is obviously improved. Therefore, the lithium orthosilicate and carbon-coated nano silicon composite material has higher specific discharge capacity, excellent rate performance and long cycle stability. Meanwhile, the lithium orthosilicate and carbon-coated nano-silicon composite material has low preparation cost and simple preparation method, and is easy for industrial production.
Drawings
FIG. 1 is an X-ray powder diffraction pattern of a lithium orthosilicate and carbon-coated nano-silicon composite obtained in example 1;
FIG. 2 is a Raman spectrum of the lithium orthosilicate and carbon-coated nano-silicon composite obtained in example 1 and comparative example 3;
FIG. 3 is a scanning electron microscope photograph of the lithium orthosilicate and carbon-coated nano-silicon composite obtained in example 1;
FIG. 4 is a TEM image of the lithium orthosilicate and carbon-coated nano-silicon composite obtained in example 1;
FIG. 5 is a graph showing the rate capability test of the lithium orthosilicate and carbon-coated nano-silicon composite materials obtained in example 1, example 3 and example 4;
FIG. 6 is a graph showing the discharge specific capacities of lithium orthosilicate and carbon-coated nano-silicon composite materials obtained in example 1, example 2 and comparative example 1 as a function of the number of cycles;
FIG. 7 is a graph showing the specific discharge capacity of lithium orthosilicate and carbon-coated nano-silicon composite materials obtained in example 1, example 3 and example 4 as a function of the number of cycles;
fig. 8 is an ac impedance test chart of the lithium orthosilicate and carbon-coated nano-silicon composite material obtained in example 1, example 2 and comparative example 1.
Detailed Description
The invention provides a lithium orthosilicate and carbon-coated nano-silicon composite material, 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 are not intended to limit the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The embodiment of the invention provides a preparation method of a lithium orthosilicate and carbon-coated nano silicon composite material, which comprises the following steps:
s1, sintering the nano silicon for 1-5 hours at the temperature of 300-600 ℃ in the air atmosphere to generate a silicon oxide coating layer on the surface of the nano silicon;
s2, dispersing the nano-silicon with the silicon oxide coating layer in an organic solvent, adding lithium hydroxide monohydrate, and stirring to obtain a first suspension;
s3, adding the carbon nano tube and the polyvinylpyrrolidone into an organic solvent, and performing ultrasonic dispersion to obtain a second suspension;
s4, mixing the first suspension and the second suspension, and then stirring, heating and drying to obtain a lithium orthosilicate and carbon-coated nano silicon composite material precursor;
s5, carrying out heat treatment on the lithium orthosilicate and carbon-coated nano-silicon composite material precursor to obtain the lithium orthosilicate and carbon-coated nano-silicon composite material.
In this embodiment, the nano-silicon is subjected to surface treatment, and is sintered in an air atmosphere to generate a silicon oxide coating layer, and then reacts with lithium hydroxide to obtain lithium orthosilicate-coated nano-silicon, and finally is compounded with a carbon material to obtain the lithium orthosilicate and carbon-coated nano-silicon composite material. Namely, the lithium orthosilicate and carbon-coated nano-silicon composite includes: the silicon-based composite material comprises a nano silicon substrate, lithium orthosilicate coated on the surface of the nano silicon substrate and a carbon material coated on the surface of the lithium orthosilicate.
In the lithium orthosilicate and carbon-coated nano-silicon composite material described in this embodiment, the lithium orthosilicate is a fast ion conductor, and the lithium orthosilicate coating layer can improve the ionic conductivity of the composite material, effectively alleviate the volume expansion effect of the nano-silicon particles in the charging and discharging processes, and can prevent the nano-silicon particles from directly contacting with the electrolyte to generate an excessively thick solid electrolyte interface film. The carbon nano tube and the polyvinylpyrrolidone are used as carbon sources, and the three-dimensional conductive network carbon material with a coating structure can be formed on the surface of the lithium orthosilicate coating layer after heat treatment. Therefore, the prepared lithium orthosilicate and carbon-coated nano-silicon composite material has higher specific capacity, rate capability and cycling stability. Meanwhile, the lithium orthosilicate and carbon-coated nano-silicon composite material of the embodiment has low preparation cost and simple preparation method, and is easy for industrial production.
The lithium orthosilicate and carbon-coated nano-silicon composite material provided by the embodiment is used as a lithium ion battery cathode material, the specific capacity of the lithium orthosilicate and carbon-coated nano-silicon composite material is superior to that of other carbon-coated nano-silicon composite materials, the voltage range is 0.01-3V, and the average specific discharge capacity is 1200.7mAh/g, 1098.08mAh/g, 937.37mAh/g, 822.9mAh/g and 734.16mAh/g respectively under the current densities of 0.1A/g, 0.2A/g, 0.5A/g, 1A/g and 2A/g.
In the embodiment, the nano silicon is used as a raw material and has low price; the thermal oxidation treatment in the air atmosphere is simple, and the preparation cost is low; lithium hydroxide is used as a lithium source for lithiation treatment, so that uniform dispersion at an atomic level is easily realized, and a uniform lithium orthosilicate lithium ion conductor coating layer can be prepared; the carbon nano tube and the polyvinylpyrrolidone are used as carbon sources, and a three-dimensional conductive network with a coating structure can be formed after heat treatment.
In step S1, in one embodiment, the nano-silicon is prepared by the following method: high-energy ball milling the micron silicon in absolute ethyl alcohol, and drying to obtain powdery nano silicon (the particle size is 50-200 nanometers). The nano silicon is obtained by high-energy ball milling of the micron silicon, and the nano silicon is used as a raw material and has low price.
In step S2, nano-silicon having a silicon oxide coating layer is dispersed in an organic solvent, lithium hydroxide monohydrate is added, and the mixture is stirred uniformly (for 5 to 15 minutes, for example, 10 minutes) to obtain a first suspension. In this step, the lithium source is uniformly dispersed in the first suspension.
In one embodiment, the addition amount of the lithium hydroxide monohydrate is 10.5-17.5% of the mass of the nano silicon. When the content is less than 10.5%, the electrochemical performance of the prepared lithium orthosilicate and carbon-coated nano silicon composite material is not obviously improved due to too small lithium source, and when the content is more than 17.5%, the lithium orthosilicate coating layer on the silicon surface is too thick, the capacity is difficult to exert, and the commercial application is not facilitated.
In one embodiment, the organic solvent is one or more of methanol, ethanol, ethylene glycol, propanol, and the like, without limitation.
In step S3, the carbon nanotubes and polyvinylpyrrolidone are added to the organic solvent, and ultrasonic dispersion is performed (for 20 to 40 minutes, for example, 30 minutes) to obtain a second suspension. The polyvinylpyrrolidone can uniformly disperse the carbon nanotubes in an organic solvent, amorphous carbon can be generated after subsequent heat treatment, the silicon nanoparticles are coated, and the carbon nanotubes are mutually bonded to form a conductive network with a coating structure.
In one embodiment, the mass ratio of the carbon nanotubes to the nano-silicon is 1: 2. Since the carbon nanotube has a low capacity, the capacity is low when the amount of the carbon nanotube is too large, and the cycle stability is deteriorated when the amount of the carbon nanotube is too small.
In one embodiment, the organic solvent is one or more of methanol, ethanol, ethylene glycol, propanol, and the like, without limitation.
In one embodiment, the mass ratio of the carbon nanotubes to the polyvinylpyrrolidone is 1: 1.
In step S4, in one embodiment, the stirring time is 5-15 minutes, such as 10 minutes. In one embodiment, the temperature for the heat drying is 100-.
In step S5, performing heat treatment on the lithium orthosilicate and carbon-coated nano-silicon composite precursor, in which lithium hydroxide reacts with silicon oxide on the surface of the nano-silicon to generate lithium orthosilicate, polyvinylpyrrolidone undergoes a carbonization reaction to generate amorphous carbon, coating the nano-silicon particles, and simultaneously bonding the carbon nanotubes to each other to form a conductive network with a coating structure, thereby obtaining the lithium orthosilicate and carbon-coated nano-silicon composite.
In one embodiment, the step of performing a heat treatment on the lithium orthosilicate and carbon-coated nano silicon composite precursor to obtain the lithium orthosilicate and carbon-coated nano silicon composite specifically includes:
and putting the lithium orthosilicate and carbon-coated nano-silicon composite material precursor into a sintering furnace, and carrying out heat treatment for 1-5 hours at the temperature of 800-1000 ℃ in the inert gas atmosphere to obtain the lithium orthosilicate and carbon-coated nano-silicon composite material.
In one embodiment, the temperature is raised to 800-1000 ℃ at a temperature rise rate of 3-10 ℃/min. For example, the temperature increase rate can be 3 deg.C/min, 5 deg.C/min, or 10 deg.C/min, etc. By controlling the heating rate during the heat treatment, the reaction process can be more stable, and the reaction can be more thoroughly carried out.
In one embodiment, after the heat treatment is finished, the lithium orthosilicate and the carbon-coated nano silicon composite material are obtained by sequentially cooling, grinding and sieving. Further, cooling is carried out at a certain cooling rate, wherein the cooling rate can be 5 ℃/min or 7 ℃/min and the like. By controlling the cooling rate, the reaction process can be more stable, and the reaction can be more thorough. It should be noted that the temperature rising rate and the temperature lowering rate may be the same or different.
In one embodiment, the inert gas is selected from one or more of nitrogen, helium, argon, and the like.
The embodiment of the invention provides a lithium orthosilicate and carbon-coated nano silicon composite material, which comprises the following components: nano silicon, lithium orthosilicate coated on the surface of the nano silicon and a carbon material coated on the surface of the lithium orthosilicate;
and/or the lithium orthosilicate and carbon-coated nano silicon composite material is prepared by the preparation method provided by the embodiment of the invention.
According to the lithium orthosilicate and carbon-coated nano silicon composite material prepared by the simple method, the lithium orthosilicate is uniformly coated on the surface of the nano silicon, and the carbon material forms a three-dimensional conductive network, so that the volume expansion of the nano silicon is effectively limited, the direct contact between the electrolyte and nano silicon particles is reduced, and the electronic conductivity of the composite material is obviously improved. Therefore, the lithium orthosilicate and carbon-coated nano silicon composite material has higher specific discharge capacity, excellent rate performance and long cycle stability.
The embodiment of the invention provides an application of the lithium orthosilicate and carbon-coated nano silicon composite material as a lithium ion battery negative electrode material.
The lithium orthosilicate and carbon-coated nano-silicon composite material provided by the invention, and the preparation method and application thereof are further explained by specific preparation examples and comparative examples.
Example 1
Preparing a precursor of the lithium orthosilicate and carbon-coated nano-silicon composite material: sintering 1g of nano-silicon powder for 3 hours at 450 ℃ in an air atmosphere, cooling, ultrasonically dispersing into 50ml of ethanol solvent, adding 0.14g of lithium hydroxide monohydrate, and uniformly stirring to obtain a first suspension; dispersing 0.5g of carbon nano tube and 0.5g of polyvinylpyrrolidone in 100ml of ethanol solution, and performing ultrasonic dispersion to obtain uniformly dispersed second suspension; and mixing the two suspensions, uniformly stirring, and heating and drying to obtain the lithium orthosilicate and carbon-coated nano silicon composite material precursor.
And (3) heat treatment: and putting the obtained lithium orthosilicate and carbon-coated nano-silicon composite material precursor into a tubular furnace, carrying out heat treatment for 3 hours at the temperature of 900 ℃ in the argon atmosphere, wherein the heating rate is 5 ℃/min, naturally cooling, grinding and sieving to obtain the powdery lithium orthosilicate and carbon-coated nano-silicon composite material.
Example 2
Preparing a precursor of the silicon oxide and the carbon-coated nano silicon composite material: sintering 1g of nano silicon powder for 3 hours at 450 ℃ in an air atmosphere, cooling, ultrasonically dispersing into 50ml of ethanol solvent, and uniformly stirring to form a first suspension; dispersing 0.5g of carbon nano tube and 0.5g of polyvinylpyrrolidone in 100ml of ethanol solution, and performing ultrasonic dispersion to obtain uniformly dispersed second suspension; and mixing the two suspensions, uniformly stirring, and heating and drying to obtain the silicon oxide and the carbon-coated nano-silicon composite material precursor.
And (3) heat treatment: and putting the obtained silicon oxide and the carbon-coated nano-silicon composite material precursor into a tubular furnace, carrying out heat treatment for 3 hours at the temperature of 900 ℃ in an argon atmosphere at the heating rate of 5 ℃/min, naturally cooling, grinding and sieving to obtain the powdery silicon oxide and the carbon-coated nano-silicon composite material.
Example 3
Preparing a precursor of the lithium orthosilicate and carbon-coated nano-silicon composite material: sintering 1g of nano-silicon powder for 3 hours at 450 ℃ in an air atmosphere, cooling, ultrasonically dispersing into 50ml of ethanol solvent, adding 0.105g of lithium hydroxide monohydrate, and uniformly stirring to obtain a first suspension; dispersing 0.5g of carbon nano tube and 0.5g of polyvinylpyrrolidone in 100ml of ethanol solution, and performing ultrasonic dispersion to obtain uniformly dispersed second suspension; and mixing the two suspensions, uniformly stirring, and heating and drying to obtain the lithium orthosilicate and carbon-coated nano silicon composite material precursor.
And (3) heat treatment: and putting the obtained lithium orthosilicate and carbon-coated nano-silicon composite material precursor into a tubular furnace, carrying out heat treatment for 3 hours at the temperature of 900 ℃ in the argon atmosphere, wherein the heating rate is 5 ℃/min, naturally cooling, grinding and sieving to obtain the powdery lithium orthosilicate and carbon-coated nano-silicon composite material.
Example 4
Preparing a precursor of the lithium orthosilicate and carbon-coated nano-silicon composite material: sintering 1g of nano-silicon powder for 3 hours at 450 ℃ in an air atmosphere, cooling, ultrasonically dispersing into 50ml of ethanol solvent, adding 0.175g of lithium hydroxide monohydrate, and uniformly stirring to obtain a first suspension; dispersing 0.5g of carbon nano tube and 0.5g of polyvinylpyrrolidone in 100ml of ethanol solution, and performing ultrasonic dispersion to obtain uniformly dispersed second suspension; and mixing the two suspensions, uniformly stirring, and heating and drying to obtain the lithium orthosilicate and carbon-coated nano silicon composite material precursor.
And (3) heat treatment: and putting the obtained lithium orthosilicate and carbon-coated nano-silicon composite material precursor into a tubular furnace, carrying out heat treatment for 3 hours at the temperature of 900 ℃ in the argon atmosphere, wherein the heating rate is 5 ℃/min, naturally cooling, grinding and sieving to obtain the powdery lithium orthosilicate and carbon-coated nano-silicon composite material.
Comparative example 1
Nano silicon powder is used.
Comparative example 2
Carbon nanotubes are used.
Comparative example 3
Weighing 4.2g of lithium hydroxide monohydrate, dissolving in 200ml of water, stirring uniformly, adding 1.5g of silicon dioxide after fully dissolving, fully stirring, drying at 105 ℃, and sintering at 900 ℃ for 3 hours in an air atmosphere to obtain the lithium orthosilicate.
In order to test that the composite material provided by the invention has energy storage characteristics and can be used as a lithium ion battery cathode material, the materials obtained in the examples and the comparative examples are subjected to tests of X-ray diffraction, Raman spectroscopy, a scanning electron microscope, a transmission electron microscope, the multiplying power performance of the composite material, the cycle performance of the composite material, an alternating current impedance spectrogram of the composite material and the like, and the test results are shown in fig. 1 to 8.
Specifically, fig. 1 is an X-ray diffraction pattern of the composite material obtained in example 1, and it can be seen from the pattern that the diffraction peak of the composite material coincides with the PDF card of pure silicon, indicating that the main component thereof is silicon, and the peak near 28 ° is a characteristic peak of the carbon nanotube. FIG. 2 shows the results of example 1 and comparative example 3The Raman spectrum of the obtained material in example 1 showed a D peak, a G peak and a 2D peak peculiar to the carbon material in addition to the characteristic peak of silicon, and was found to be 900cm-1The presence of lithium orthosilicate in the composite is evidenced by the appearance of a peak of lithium orthosilicate on the left and right. Fig. 3 is a scanning electron microscope photograph of the lithium orthosilicate and carbon-coated nano-silicon composite material obtained in example 1, and it can be seen that the carbon nanotubes uniformly twine the lithium orthosilicate-coated nano-silicon to form a good three-dimensional conductive network. Fig. 4 is a transmission electron microscope photograph of the lithium orthosilicate and carbon-coated nano-silicon composite material obtained in example 1, and the morphology thereof is observed to clearly see the lattice fringes of silicon and the uniform lithium orthosilicate coating layer on the silicon surface. FIG. 5 is a graph showing rate capability tests of the materials obtained in examples 1, 3 and 4, wherein the composite material prepared according to the present invention has average specific discharge capacities of 1200.7mAh/g, 1098.08mAh/g, 937.37mAh/g, 822.9mAh/g and 734.16mAh/g at current densities of 0.1A/g, 0.2A/g, 0.5A/g, 1A/g, 2A/g and 0.1A/g, respectively. FIG. 6 is a test chart of the cycle performance of the materials obtained in comparative example 1, example 1 and example 2, the composite material prepared in example 1 of the present invention still has a specific discharge capacity of 1239.0mAh/g after 400 charge and discharge cycles under a current density of 0.5A/g, and the first coulombic efficiency reaches 86.31%; the nano-silicon powder of comparative example 1 and the composite material prepared in example 2 have specific discharge capacities of 527.5mAh/g and 773.2mAh/g respectively after 400 charge-discharge cycles under the current density of 0.5A/g (the first cycle is activated by the current density of 0.1A/g). Therefore, the lithium orthosilicate and carbon-coated nano silicon composite material prepared in the embodiment 1 of the invention is used as a lithium ion battery anode material, and the specific capacity of the lithium orthosilicate and carbon-coated nano silicon composite material is superior to that of the silicon oxide and carbon-coated nano silicon composite material prepared in the embodiment 2. FIG. 7 is a graph showing the cycle performance test of the composites prepared in examples 1, 2 and 3 (the first cycle of the activation treatment with a current density of 0.1A/g), and the composite prepared in example 1 of the present invention has the best specific capacity and stability. FIG. 8 is a graph showing the AC impedance test of the composite materials prepared in comparative example 1, example 1 and example 2, and comparing example 1 with comparative example 1, the charge transfer is performedThe resistance is reduced from 138.4 omega to 77.2 omega, the method can obviously reduce the charge transfer resistance of the electrode, and the electronic conductivity of the composite material is improved.
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 lithium orthosilicate and carbon-coated nano silicon composite material is characterized by comprising the following steps:
sintering the nano silicon for 1-5 hours at the temperature of 300-600 ℃ in the air atmosphere to generate a silicon oxide coating layer on the surface of the nano silicon;
dispersing nano-silicon with a silicon oxide coating layer in an organic solvent, adding lithium hydroxide monohydrate, and stirring to obtain a first suspension;
adding the carbon nano tube and polyvinylpyrrolidone into an organic solvent, and performing ultrasonic dispersion to obtain a second suspension;
mixing the first suspension and the second suspension, and then stirring, heating and drying to obtain a precursor of the lithium orthosilicate and the carbon-coated nano-silicon composite material;
and carrying out heat treatment on the lithium orthosilicate and carbon-coated nano-silicon composite material precursor to obtain the lithium orthosilicate and carbon-coated nano-silicon composite material.
2. The method for preparing a lithium orthosilicate and carbon-coated nano-silicon composite material according to claim 1, wherein the nano-silicon is prepared by the following method: and ball-milling the micron silicon in absolute ethyl alcohol, and drying to obtain powdery nano silicon.
3. The method of claim 1, wherein the organic solvent is one or more of methanol, ethanol, ethylene glycol, and propanol.
4. The method of claim 1, wherein the lithium hydroxide monohydrate is added in an amount of 10.5 to 17.5% by mass of the nano-silicon.
5. The method of claim 1, wherein the mass ratio of the carbon nanotubes to the polyvinylpyrrolidone is 1:1, and the mass ratio of the carbon nanotubes to the nano-silicon is 1: 2.
6. The method for preparing the lithium orthosilicate and carbon-coated nano-silicon composite material according to claim 1, wherein the step of performing the heat treatment on the lithium orthosilicate and carbon-coated nano-silicon composite material precursor to obtain the lithium orthosilicate and carbon-coated nano-silicon composite material specifically comprises:
and putting the lithium orthosilicate and carbon-coated nano-silicon composite material precursor into a sintering furnace, and carrying out heat treatment for 1-5 hours at the temperature of 800-1000 ℃ in the inert gas atmosphere to obtain the lithium orthosilicate and carbon-coated nano-silicon composite material.
7. The method for preparing lithium orthosilicate and carbon-coated nano-silicon composite material according to claim 6, wherein the temperature is raised to 800-1000 ℃ at a temperature raising rate of 3-10 ℃/min.
8. The method of claim 6, wherein the inert gas is selected from one or more of nitrogen, helium, and argon.
9. A lithium orthosilicate and carbon-coated nano-silicon composite material, comprising: nano silicon, lithium orthosilicate coated on the surface of the nano silicon and a carbon material coated on the surface of the lithium orthosilicate;
and/or the lithium orthosilicate and carbon-coated nano silicon composite material is prepared by the preparation method of any one of claims 1 to 7.
10. Use of the lithium orthosilicate and carbon-coated nano-silicon composite material according to claim 9 as a negative electrode material for lithium ion batteries.
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