CN111200118A - Preparation method of graphene-coated mesoporous silicon microsphere negative electrode material - Google Patents
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Abstract
The invention relates to a preparation method of a graphene-coated mesoporous silicon microsphere cathode material, which comprises the steps of mixing silicon dioxide microspheres coated with graphene on the surfaces with reducing metal, reacting for 4-12 hours at 600-800 ℃ in a protective atmosphere, and then washing with acid to obtain the graphene-coated mesoporous silicon microsphere cathode material.
Description
Technical Field
The invention relates to a preparation method of a graphene-coated mesoporous silicon microsphere negative electrode material, and belongs to the field of material preparation.
Background
Currently, commercial graphite anodes cannot meet the requirements of high performance battery systems due to their low theoretical capacity. Therefore, in order to meet the requirements of renewable energy storage and EV applications, next generation lithium ions are continuously developed into high energy density and high power batteries.
Si is due to its highest theoretical storage capacity (4200 mAhg)-1) And stable electrochemical potentials have received increased attention. However, since Si is in Li+The insertion/extraction process is accompanied by a large volume change (> 300%) resulting in damage to the electrode and a break in the mechanical integrity of its particles, with a rapid loss of capacity during its cycling. Therefore, more and more researchers have reduced the volume change and increased the conductivity of Si by changing the volume of Si or exploring Si — C composite. These attempts all improve the cycling and rate performance of Si.
In recent years, porous materials of silicon-based negative electrode materials (in particular, having a particle size of not more than 100nm) have been used because of their strong tendency to agglomerate and the more difficult Li+Transmission performance is receiving increasing attention. Generally, the porous structure can provide sufficient internal free space to effectively absorb the expansion of volume, thereby improving the cycle stability. Furthermore, the open structure of the porous material favors Li+Fast transmission and possess high rate capability. Cho et al (Nano letters.2008,8(11):3688-2As a template, a reversible capacity of 2800mAh g was obtained-1The porous silicon material with excellent cycle performance has the capacity retention rate of 72% after 100 charge-discharge cycles under 3C. However, the complicated preparation process and high cost may hinder the mass production thereof. Recently, there is a document [ Advanced Energy materials.2011,1(6): 1036-.]Reports that the two-step chemical vapor deposition method for preparing silicon nanoparticles with high internal porosity can obtain a capacity of about 1500mAh g-1. However, these most advanced techniques still cannot satisfy industrial applications, and the particle size and morphology of the material are difficult to control, and a material with strong comprehensive properties cannot be obtained.
It is known that the surface of the mesoporous Si material can be uniformly coated with a layer of carbon by a CVD method. However, for graphene, a high-temperature growth condition (greater than 1200 ℃) is required under the condition of no catalysis, but the morphology and the internal mesoporous structure of the mesoporous Si material are damaged by the high temperature.
Disclosure of Invention
Aiming at the problems, the invention aims to provide a preparation method of a graphene-coated mesoporous silicon microsphere cathode material, which is characterized by mixing silicon dioxide microspheres with surfaces coated with graphene and a reducing metal, reacting for 4-12 hours at 600-800 ℃ in a protective atmosphere, and then washing with acid to obtain the graphene-coated mesoporous silicon microsphere cathode material.
According to the invention, after the silicon dioxide microspheres coated with graphene on the surface are mixed with reducing metal (for example, at least one of metal aluminum, alkali metal and alkaline earth metal), the mixture reacts for 4-12 hours at 600-800 ℃ in a protective atmosphere, and in the reaction process, the silicon dioxide and the reducing metal react to generate silicon and oxide of the reducing metal, and the silicon dioxide and the reducing metal are uniformly mixed and still have a spherical shape due to the existence of the graphene coating layer. And removing the reducing metal oxide and the residual reducing metal in the reaction product after acid washing, wherein the intermediate microsphere only has a Si material and has a porous structure, and finally the graphene-coated mesoporous silicon microsphere cathode material is formed.
Preferably, the reducing metal is at least one of aluminum metal, alkali metal, and alkaline earth metal, preferably at least one of magnesium, aluminum, lithium, sodium, and potassium.
Preferably, the silicon dioxide microspheres coated with graphene on the surfaces are prepared by a plasma-assisted chemical vapor deposition method.
Further, preferably, the plasma-assisted chemical vapor deposition method includes: placing the silicon dioxide microspheres in plasma chemical vapor deposition equipment, vacuumizing, heating to 400-800 ℃, turning on a radio frequency power supply, adjusting the power supply to 100-300W, introducing a carbon source gas and an auxiliary gas, and reacting for 20-60 minutes to obtain the silicon dioxide microspheres with surfaces coated with graphene; preferably, the pressure of the vacuum is 0.1-100 Pa; preferably, the vacuum degree of the vacuum is 0.1-100 Pa.
Also, preferably, the carbon source gas is selected from at least one of methane, ethylene and difluoromethane, and the auxiliary gas is hydrogen and/or argon; preferably, the flow rate of the carbon source gas is 5 to 20sccm, and the flow rate of the auxiliary gas is 1 to 10 sccm.
Preferably, the particle size of the silica microspheres in the silica microspheres coated with graphene on the surface is 50nm to 1 μm, and preferably 100nm to 500 nm.
Preferably, the protective atmosphere is at least one of argon, nitrogen, helium and hydrogen.
Preferably, the acid solution used for acid washing is hydrochloric acid, nitric acid or sulfuric acid.
On the other hand, the invention also provides the graphene-coated mesoporous silicon microsphere negative electrode material prepared by the preparation method. Preferably, the particle size of the graphene-coated mesoporous silicon microsphere negative electrode material is 100 nm-1 μm, and preferably 300-500 nm.
The method utilizes a plasma enhanced chemical vapor deposition method to grow a graphene coating layer on the surface of spherical silicon oxide (silicon dioxide microspheres) at a lower temperature; then, protecting the shape structure of the internal silicon oxide microspheres from being damaged in the subsequent reduction process by utilizing the graphene coating layer; and finally, removing magnesium oxide by acid washing to obtain the silicon microspheres with the mesoporous structures inside.
Drawings
Fig. 1 is an electron micrograph of the graphene-coated mesoporous silicon microsphere prepared in example 1;
fig. 2 is an electron micrograph of the graphene-coated mesoporous silicon microsphere prepared in example 1;
fig. 3 is a charge-discharge curve of the graphene-coated silicon negative electrode material prepared in example 1 at a magnification of 0.1C.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
According to the invention, the structure of the graphene-coated mesoporous silicon microsphere negative electrode material comprises a mesoporous silicon microsphere and graphene coated on the surface of the mesoporous silicon microsphere. The preparation method is simple and is easy for large-scale application. The preparation method of the graphene-coated mesoporous silicon microsphere negative electrode material provided by the invention is exemplarily described below.
And (4) preparing the silica microspheres. Wherein, the size of the silicon dioxide microsphere particles can be 50-500 nm. In the present invention, the silica microspheres are commercially available or prepared by themselves. The corresponding preparation method can comprise the following steps: adding tetraethoxysilane, ethanol, ammonia water and water into a reaction container according to a certain proportion, reacting for 0.5-2 h, centrifugally cleaning, collecting white solid particles, and drying to obtain the silicon dioxide microspheres. Wherein, the ethyl orthosilicate, the water, the ethanol and the ammonia water can be prepared according to the volume ratio of 8:56 (50-150) to (4-24). In alternative embodiments, the silica microspheres may have a particle size of 50nm to 500 nm.
And (3) preparing the silicon dioxide microspheres coated with the graphene on the surfaces. Including but not limited to using plasma assisted chemical vapor deposition and the like.
The plasma-assisted chemical vapor deposition method may include: placing the silicon dioxide microspheres in plasma chemical vapor deposition equipment, vacuumizing, heating to 400-800 ℃, turning on a radio frequency power supply, adjusting the power supply to 100-300W, introducing carbon source gas and auxiliary gas, and reacting for 20-60 minutes to obtain the silicon dioxide microspheres with surfaces coated with graphene. Wherein the pressure of the vacuum is 0.1 to 100 Pa. The carbon source gas is at least one selected from the group consisting of methane, ethylene, difluoromethane and acetylene. The assist gas may be hydrogen and/or argon. The flow rate of the carbon source gas can be 5 to 20 sccm. The flow rate of the assist gas can be 1-10 sccm.
Mixing the silicon dioxide microspheres coated with graphene on the surface with reducing metal, reacting for 4-12 hours at 600-800 ℃ in a protective atmosphere, and then washing with acid to obtain the graphene-coated mesoporous silicon microsphere negative electrode material. The reducing metal is aluminum, an alkali metal, an alkaline earth metal, or the like, and examples thereof include magnesium, aluminum, lithium, sodium, and the like. The protective atmosphere may be at least one of argon, nitrogen, helium. The acid solution used for acid washing is hydrochloric acid, nitric acid or sulfuric acid.
In an embodiment of the invention, a graphene coating layer is directly grown on the surface of a silicon oxide microsphere by using a plasma enhanced chemical vapor deposition method, and then magnesium oxide is removed by magnesiothermic reduction and acid washing to obtain the graphene-coated mesoporous silicon microsphere. Specifically, graphene grows in situ on the surface of a silicon dioxide microsphere at a lower temperature (400 ℃ plus 800 ℃) by a plasma enhanced chemical vapor deposition method, the graphene is firstly coated on the silicon dioxide microsphere (spherical silicon oxide), and then a magnesiothermic reduction process is carried out, so that the damage of the magnesiothermic reduction reaction on the morphology of spherical particles is effectively avoided, and the graphene-coated mesoporous silicon microsphere cathode material is prepared.
As a detailed example of a preparation method of a graphene-coated mesoporous silicon microsphere negative electrode material, the preparation method comprises the following steps: firstly, spherical silicon oxide raw materials are placed in a ceramic boat and placed in a tube furnace, and vacuum pumping is carried out. Then the temperature of the tube furnace is raised at the rate of 2-10 ℃/min to the predetermined reaction temperature of 400-4(5-20sccm) and H2(1-10sccm), turning on the RF power supply, adjusting the power supply power to 100-300W, growing for 20-60min, and forming a graphene coating layer on the surface of the spherical silicon oxide. Mixing magnesium powder and graphene-coated silicon oxide particles, and reacting for 4-12h at the temperature of 600-800 ℃ under the protection of argon. And (3) soaking the reacted material in a hydrochloric acid solution for 1-24h, removing magnesium oxide in the material, filtering, cleaning and drying to obtain the graphene-coated mesoporous silicon microsphere negative electrode material. The carbon source may be methane, ethylene or difluoromethane. The reducing metal may be magnesium. The acidic solution can be strong acid solution such as hydrochloric acid, nitric acid, etc.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
Firstly, spherical silicon oxide raw material (preparation of silicon dioxide microspheres: mixingAdding ethyl silicate, ethanol, ammonia water and water into a reaction vessel according to a certain proportion, wherein the volume ratio of the ethyl orthosilicate, the water, the ethanol and the ammonia water can be 8:56:100:10, after 0.5 of reaction, centrifugally cleaning the precipitate, collecting white solid particles, then putting the sample into an oven at 60 ℃ for drying for 6h to obtain nanosphere powder with the size of 200 plus 500nm), putting the nanosphere powder into a ceramic boat, putting the ceramic boat into a tube furnace, and vacuumizing. Then the temperature of the tubular furnace is increased at the rate of 6 ℃/min until the preset reaction temperature reaches 800 ℃, and CH is introduced4(20sccm) and H2(10sccm) turning on the RF power supply, adjusting the power of the power supply to 300W, growing for 60min, and generating a graphene coating layer on the surface of the spherical silicon oxide. Mixing magnesium powder with graphene-coated silicon oxide particles, and reacting at 650 ℃ for 12 hours under the protection of argon. And (3) soaking the reacted material in a hydrochloric acid solution for 24 hours, removing magnesium oxide in the material, filtering, cleaning and drying to obtain the graphene-coated mesoporous silicon microsphere negative electrode material. FIGS. 1 and 2 are electron micrographs of the morphology of the material prepared in example 1, and the mesoporous microsphere obtained after the reaction and composed of nanoparticles has a diameter of 200-500nm, and a charge-discharge test of a layer of graphene material coated and grown on the surface of the microsphere shows that the capacity reaches 22000mAh/g or more, as shown in FIG. 3.
Example 2
Firstly, spherical silicon oxide raw material (200- & ltSUB & gt 500- & gt) is placed in a ceramic boat and placed in a tube furnace, and vacuum pumping is carried out. Then the temperature of the tubular furnace is increased at the rate of 6 ℃/min until the preset reaction temperature reaches 600 ℃, and CH is introduced4(8sccm) and H2(2sccm) turning on the RF power supply, adjusting the power of the power supply to 200W, growing for 60min, and generating a graphene coating layer on the surface of the spherical silicon oxide. Mixing magnesium powder with graphene-coated silicon oxide particles, and reacting for 6 hours at 800 ℃ under the protection of argon. And (3) soaking the reacted material in a hydrochloric acid solution for 24 hours, removing magnesium oxide in the material, filtering, cleaning and drying to obtain the graphene-coated mesoporous silicon microsphere negative electrode material.
Example 3
Firstly, spherical silicon oxide raw material (particle size 200-. The tube furnace was then operated at 2 deg.CHeating up at a heating rate of/min to a predetermined reaction temperature of 400 ℃, and introducing CH4(5sccm) and H2(1sccm) turning on an RF power supply, adjusting the power of the power supply to 100W, growing for 60min, and generating a graphene coating layer on the surface of the spherical silicon oxide. Mixing magnesium powder with graphene-coated silicon oxide particles, and reacting for 20 hours at 600 ℃ under the protection of argon. And (3) soaking the reacted material in a hydrochloric acid solution for 1h, removing magnesium oxide in the material, filtering, cleaning and drying to obtain the graphene-coated mesoporous silicon microsphere negative electrode material.
Example 4
Firstly, spherical silicon oxide raw material (particle size 200-. Then the temperature of the tubular furnace is increased at the rate of 10 ℃/min until the preset reaction temperature reaches 700 ℃, and CH is introduced4(10sccm) and H2(1sccm) turning on the RF power supply, adjusting the power of the power supply to 200W, growing for 30min, and generating a graphene coating layer on the surface of the spherical silicon oxide. Mixing magnesium powder with graphene-coated silicon oxide particles, and reacting at 650 ℃ for 10 hours under the protection of argon. And (3) soaking the reacted material in a hydrochloric acid solution for 24 hours, removing magnesium oxide in the material, filtering, cleaning and drying to obtain the graphene-coated mesoporous silicon microsphere negative electrode material.
Example 5
Firstly, spherical silicon oxide raw material (particle size 200-. Then the temperature of the tubular furnace is increased at the rate of 6 ℃/min until the preset reaction temperature is 650 ℃, and CH is introduced4(20sccm) and H2(1sccm) turning on an RF power supply, adjusting the power of the power supply to 200W, growing for 60min, and generating a graphene coating layer on the surface of the spherical silicon oxide. Mixing magnesium powder with graphene-coated silicon oxide particles, and reacting for 6 hours at 650 ℃ under the protection of argon. And (3) soaking the reacted material in a hydrochloric acid solution for 20 hours, removing magnesium oxide in the material, filtering, cleaning and drying to obtain the graphene-coated mesoporous silicon microsphere negative electrode material.
Example 6
Firstly, spherical silicon oxide raw material (particle size 200-.Then the temperature of the tubular furnace is increased at the rate of 6 ℃/min until the preset reaction temperature reaches 800 ℃, and CH is introduced4(15sccm) and H2And (5sccm) turning on an RF power supply, adjusting the power of the power supply to 200W, growing for 20min, and generating a graphene coating layer on the surface of the spherical silicon oxide. Mixing magnesium powder with graphene-coated silicon oxide particles, and reacting for 1h at 650 ℃ under the protection of argon. And (3) soaking the reacted material in a hydrochloric acid solution for 1h, removing magnesium oxide in the material, filtering, cleaning and drying to obtain the graphene-coated mesoporous silicon microsphere negative electrode material.
Example 7
Firstly, spherical silicon oxide raw material (particle size 200-. Then the temperature of the tubular furnace is increased at the rate of 6 ℃/min until the preset reaction temperature reaches 800 ℃, and CH is introduced4(20sccm) and H2(10sccm) turning on the RF power supply, adjusting the power of the power supply to 300W, growing for 60min, and generating a graphene coating layer on the surface of the spherical silicon oxide. Mixing aluminum powder and graphene-coated silicon oxide particles, and reacting for 12 hours at 800 ℃ under the protection of argon. And (3) soaking the reacted material in a hydrochloric acid solution for 24 hours, removing alumina in the material, filtering, cleaning and drying to obtain the graphene-coated mesoporous silicon microsphere negative electrode material.
Example 8
Firstly, spherical silicon oxide raw material (particle size 200-. Then the temperature of the tubular furnace is increased at the rate of 6 ℃/min until the preset reaction temperature reaches 800 ℃, and CH is introduced4(20sccm) and H2(10sccm) turning on the RF power supply, adjusting the power of the power supply to 300W, growing for 60min, and generating a graphene coating layer on the surface of the spherical silicon oxide. And mixing the sodium metal with the graphene-coated silicon oxide particles, and reacting for 4 hours at 600 ℃ under the protection of argon. And (3) soaking the reacted material in a hydrochloric acid solution for 1h, removing sodium oxide in the material, filtering, cleaning and drying to obtain the graphene-coated mesoporous silicon microsphere negative electrode material.
Example 9
Firstly, spherical silicon oxide raw material (particle size 200-And (4) vacuumizing the furnace. Then the temperature of the tubular furnace is increased at the rate of 6 ℃/min until the preset reaction temperature reaches 800 ℃, and CH is introduced4(20sccm) and H2(10sccm) turning on the RF power supply, adjusting the power of the power supply to 300W, growing for 60min, and generating a graphene coating layer on the surface of the spherical silicon oxide. Mixing aluminum powder and graphene-coated silicon oxide particles, and reacting for 12 hours at 800 ℃ under the protection of argon. And (3) soaking the reacted material in a nitric acid solution for 24 hours, removing magnesium oxide in the material, filtering, cleaning and drying to obtain the graphene-coated mesoporous silicon microsphere negative electrode material.
Claims (9)
1. A preparation method of a graphene-coated mesoporous silicon microsphere negative electrode material is characterized by mixing silicon dioxide microspheres with surfaces coated with graphene and a reducing metal, then reacting for 4-12 hours at 600-800 ℃ in a protective atmosphere, and then washing with acid to obtain the graphene-coated mesoporous silicon microsphere negative electrode material.
2. The method according to claim 1, wherein the reducing metal is at least one of aluminum metal, alkali metal, and alkaline earth metal, preferably at least one of magnesium, aluminum, lithium, sodium, and potassium.
3. The preparation method according to claim 1 or 2, wherein the silica microspheres coated with graphene on the surfaces are prepared by a plasma-assisted chemical vapor deposition method.
4. The method of claim 3, wherein the plasma-assisted chemical vapor deposition method comprises: placing the silicon dioxide microspheres in plasma chemical vapor deposition equipment, vacuumizing, heating to 400-800 ℃, turning on a radio frequency power supply, adjusting the power supply to 100-300W, introducing a carbon source gas and an auxiliary gas, and reacting for 20-60 minutes to obtain the silicon dioxide microspheres with surfaces coated with graphene; preferably, the vacuum degree of the vacuum is 0.1-100 Pa.
5. The production method according to claim 4, wherein the carbon source gas is at least one selected from methane, ethylene, difluoromethane and acetylene, and the auxiliary gas is hydrogen and/or argon; preferably, the flow rate of the carbon source gas is 5 to 20sccm, and the flow rate of the auxiliary gas is 1 to 10 sccm.
6. The preparation method according to any one of claims 1 to 5, wherein the particle size of the silica microspheres in the silica microspheres coated with graphene is 50nm to 1 μm, preferably 100nm to 500 nm.
7. The method according to any one of claims 1 to 6, wherein the protective atmosphere is at least one of argon, nitrogen, helium, and hydrogen.
8. The production method according to any one of claims 1 to 7, wherein the acid solution used for the acid washing is hydrochloric acid, nitric acid, or sulfuric acid.
9. The graphene-coated mesoporous silicon microsphere negative electrode material prepared according to the preparation method of any one of claims 1 to 8.
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| CN116063082A (en) * | 2022-11-16 | 2023-05-05 | 哈尔滨工业大学（威海） | Silicon oxide coated graphene composite wave-absorbing material and preparation method thereof |
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