CN111261856B - Carbon sheet cage coated porous silicon material and preparation method and application thereof - Google Patents

Carbon sheet cage coated porous silicon material and preparation method and application thereof Download PDF

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CN111261856B
CN111261856B CN202010067000.9A CN202010067000A CN111261856B CN 111261856 B CN111261856 B CN 111261856B CN 202010067000 A CN202010067000 A CN 202010067000A CN 111261856 B CN111261856 B CN 111261856B
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porous silicon
silicon
carbon sheet
coated porous
sheet cage
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CN111261856A (en
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李新喜
方称辉
张国庆
杨晓青
刘龙
郑炳河
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Guangdong University of Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention belongs to the technical field of lithium batteries, and discloses a carbon sheet cage-coated porous silicon material, and a preparation method and application thereof. Adding aluminum-silicon alloy into an inorganic acid solution, stirring, filtering or centrifuging to obtain porous silicon, adding the porous silicon into a mixed solution of ethanol/deionized water containing a carbon source and a silicon dioxide source, stirring, and preserving heat at 150-170 ℃ to obtain a precursor; sintering the obtained precursor at 800-1000 ℃ in inert atmosphere to obtain C/SiO2Double-continuous coating of porous silicon with C/SiO2Adding the bicontinuous coated porous silicon into hydrofluoric acid, washing and drying to obtain the product. The carbon sheet cage-coated porous silicon material has excellent high reversible capacity, cycling stability and rate capability, and can be applied to the field of lithium batteries.

Description

Carbon sheet cage coated porous silicon material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of lithium batteries, and particularly relates to a carbon sheet cage-coated porous silicon material, and a preparation method and application thereof.
Background
Due to the advantages of environmental protection, no pollution and the like, the lithium ion battery is widely applied to the fields of portable consumer electronics, new energy automobiles, medical electronics and the like, and along with the wide application of the lithium ion battery, the demand of consumers on the energy density of the lithium ion battery is increased day by day. Under the condition that the energy density of the battery cannot be effectively improved by the positive electrode, the theoretical specific energy density of the negative electrode material is urgently improved. The most commonly used graphite negative electrode at present has a theoretical specific capacity of 372mAh/g, while the lithium intercalation theoretical capacity of the novel silicon-carbon negative electrode material at present is 4200mAh/g, and the material is one of the materials which are known to be the highest in theoretical specific energy density of the negative electrode at present and most possibly replace the graphite negative electrode at present.
However, the silicon-based material still has many problems as the negative electrode of the lithium ion battery, such as volume expansion, low first efficiency, electrolyte consumption caused by repeated growth of SEI film, low electron ion transmission efficiency, poor conductivity and the like, and the volume expansion is a main problem; because the lithium ions form alloy phase Li in the process of being inserted into the silicon cathode15Si4Etc., thereby generating a very significant volume expansion (more than 360%), while also creating a huge stress due to the intercalation/deintercalation of lithium ions; the following problems arise due to the above-mentioned effects: the active material is peeled off from the current collector; crushing and powdering the active material; the SEI film is continuously reproduced repeatedly. Meanwhile, a compact carbon layer is coated on the outer layer of the silicon, which affects the transmission of lithium ions and causes larger interface impedance. These above processes are all liable to cause structural collapse of the anode material and fading of the battery capacity. In order to solve the problems of the silicon-based negative electrode material, the problems can be greatly improved through modification, carbon coating, silicon-carbon compounding and the like of the silicon material.
Disclosure of Invention
In order to solve the defects and shortcomings in the prior art, the invention aims to provide a carbon sheet cage-coated porous silicon material, which is prepared by firstly preparing porous silicon by utilizing aluminum-silicon alloy and coating C/SiO outside the porous silicon material2The bi-continuous compound item is obtained by acid washing.
The invention also aims to provide a preparation method of the carbon sheet cage-coated porous silicon material.
The invention also aims to provide application of the carbon sheet cage-coated porous silicon material.
The purpose of the invention is realized by the following technical scheme:
a carbon sheet cage coated porous silicon material is prepared by adding aluminum-silicon alloy into inorganic acid solution, stirring, filtering or centrifuging to obtain porous silicon, adding the porous silicon into ethanol/deionized water mixed solution containing carbon source and silicon dioxide sourceStirring, and preserving heat at 150-170 ℃ to prepare a precursor; sintering the obtained precursor at 800-1000 ℃ in inert atmosphere to obtain C/SiO2Double-continuous coating of porous silicon with C/SiO2Adding the bicontinuous coated porous silicon into hydrofluoric acid, washing and drying to obtain the product.
Preferably, the average particle size D50 of the aluminum-silicon alloy is 1-5 μm, and the mass ratio of aluminum to silicon in the aluminum-silicon alloy is (4-9): 1.
preferably, the inorganic acid is more than one of hydrochloric acid, nitric acid or sulfuric acid; the concentration of the inorganic acid is 0.1-0.5 mol/L.
Preferably, the carbon source is more than one of glucose, sucrose, starch, citric acid or ascorbic acid; the silicon dioxide source is tetraethoxysilane or/and siloxane.
Preferably, the volume ratio of ethanol to deionized water in the mixed solution is (2-1): 1; the mass of the carbon source, the volume of the silicon dioxide source and the total volume ratio of the ethanol to the deionized water are 5: (2-20): (1000 to 1500); the volume ratio of the mass of the porous silicon to the mass of the carbon source to the volume of the silicon dioxide source is (0.5-1): (0.05-1): (0.2 to 1).
Preferably, the stirring time is 12-24 hours, the heat preservation time at 150-170 ℃ is 10-24 hours, and the sintering time is 1-4 hours.
Preferably, the mass fraction of the hydrofluoric acid is 1-10 wt%.
Preferably, the inert atmosphere is argon or nitrogen.
The preparation method of the carbon sheet cage coated porous silicon material comprises the following specific steps:
s1, adding aluminum-silicon alloy into an inorganic acid solution, stirring, and filtering or centrifuging to obtain porous silicon;
s2, adding porous silicon into a mixed solution of ethanol/deionized water containing a carbon source and a silicon dioxide source, stirring, and carrying out heat preservation at 150-170 ℃ to obtain a precursor;
s3, sintering the obtained precursor at 800-1000 ℃ in an inert atmosphere to obtain C/SiO2Bi-continuously coating porous silicon;
s4, mixing C/SiO2And adding the bicontinuous coated porous silicon into hydrofluoric acid, washing and drying to obtain the carbon sheet cage coated porous silicon material.
The carbon sheet cage coated porous silicon material is applied to the field of lithium batteries.
Compared with the prior art, the invention has the following beneficial effects:
1. the carbon sheet cage-coated porous silicon material has excellent high reversible capacity, circulation stability and rate capability. The porous silicon structure is prepared by utilizing the aluminum-silicon alloy, the porous silicon ball is composed of a plurality of ordered silicon strips, and the gap between the silicon strips can greatly relieve the problem of volume expansion caused by the silicon-carbon cathode in the circulation process; meanwhile, the carbon sheet cage can well relieve the problem of volume expansion of silicon in the charging and discharging process. The problem of volume change of the silicon-based material in the lithium ion extraction process in the prior art is effectively solved.
2. The carbon sheet cage is coated with the porous silicon material, and the carbon coated outside the carbon sheet cage can be used as a conductive matrix, so that the conductivity of the silicon-based material is increased; meanwhile, the mesoporous exists between the carbon sheets, so that the transmission distance of lithium ions is shortened, and the lithium ions can be conveniently inserted/removed.
3. The carbon sheet cage coated porous silicon material is prepared by melting aluminum-silicon alloy ingots serving as raw materials and then atomizing nitrogen to prepare powder, and the aluminum-silicon alloy is easy to prepare on a large scale and is commercialized.
4. The preparation method disclosed by the invention is low in equipment requirement, low in energy consumption, simple in steps, high in controllability and easy for industrial production.
Drawings
FIG. 1 is a scanning electron micrograph of the aluminum-silicon alloy obtained in example 3.
FIG. 2 is a SEM photograph of porous silicon obtained in example 3.
FIG. 3 is a C/SiO solid obtained in example 32Scanning electron microscope photographs of the bicontinuous coated porous silicon.
FIG. 4 is a scanning electron micrograph of carbon sheet cage-coated porous silicon prepared in example 3.
Fig. 5 is a plot of the first charge-discharge specific capacity of a battery pole piece prepared by coating porous silicon with the carbon sheet cage of example 3.
Fig. 6 is a graph of cycle performance testing of battery pole pieces prepared by coating porous silicon with the carbon sheet cage of example 3.
Detailed Description
The following examples are presented to further illustrate the present invention and should not be construed as limiting the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Example 1
1. Adding aluminum-silicon alloy (the average particle size D50 is 1-5 mu m, the mass ratio of aluminum to silicon is 4: 1) into hydrochloric acid (0.5mol/L), and magnetically stirring, filtering or centrifuging to obtain the porous silicon.
2. Preparing a sol-gel solution: to a mixture solution of 100mL of ethanol and water (50mL of ethanol, 50mL of deionized water) was added 0.1g of glucose and 0.2mL of a siloxane solution.
3. Slowly and uniformly adding 0.5g of porous silicon powder into the prepared sol-gel solution; stirring for 30 min; heating at 160 ℃ for 12h to prepare a precursor;
4. sintering the precursor in the step 3 at 1000 ℃ in an inert atmosphere (argon or nitrogen) to obtain C/SiO2And (3) coating porous silicon in a bicontinuous manner.
5. Mixing the C/SiO of step 42And adding the bicontinuous coated porous silicon into 5 wt% of hydrofluoric acid, washing and drying to obtain the carbon sheet cage coated porous silicon.
The carbon sheet cage obtained in this example was coated with porous silicon, a conductive agent (conductive carbon black or Super P), and a binder (sodium alginate or sodium carboxymethylcellulose) in an amount of 6:2:2, uniformly mixing, adding a solvent (water or ethanol) to prepare slurry, coating the slurry on a copper foil, and drying at 60 ℃ to obtain the electrode material of the carbon sheet cage coated porous silicon.
Example 2
1. Adding aluminum-silicon alloy powder (purchased from Gvain, the mass ratio of aluminum to silicon is 4: 1) with the average diameter of 1 mu m into 0.5mol/LHCl, magnetically stirring for 12h, washing for multiple times by deionized water and absolute ethyl alcohol, putting the obtained sample into a vacuum drying oven, and drying for 10h at the temperature of 50 ℃ to obtain the porous silicon.
2. Preparing a sol-gel solution: to a mixed solution of 100ml of ethanol and water (50ml of ethanol, 50ml of deionized water) was added 0.1g of sucrose (C)6H12O6) And 0.2mL of an ethyl orthosilicate (28% TEOS) solution.
3. Slowly and uniformly adding 0.5g of porous silicon powder into the prepared sol-gel solution; stirring for 30 min; heating at 160 ℃ for 12h to prepare a precursor;
4. heating the precursor to 800 ℃ at the speed of 5 ℃/min under argon, annealing for 2h, and cooling to room temperature to obtain SiO2the/C bicontinuous item coats the porous silicon.
5. According to the chemical equation 4HF + SiO2＝SiF4+2H2And calculating to obtain the amount of HF, slowly and uniformly adding the HF into the annealing sample, performing ultrasonic treatment for 0.5h, and repeatedly cleaning the HF with deionized water and absolute ethyl alcohol to obtain the carbon sheet cage-coated porous silicon.
The carbon sheet cage obtained in this example was coated with porous silicon, a conductive agent (conductive carbon black or Super P), and a binder (sodium alginate or sodium carboxymethylcellulose) in an amount of 6:2:2, uniformly mixing, adding a solvent (water or ethanol) to prepare slurry, coating the slurry on a copper foil, and drying at 60 ℃ to obtain the electrode material of the carbon sheet cage coated porous silicon.
Example 3
1. Adding aluminum-silicon alloy powder (purchased from Gvain, the mass ratio of aluminum to silicon is 4: 1) with the average diameter of 1 mu m into 0.5mol/LHCl, magnetically stirring for 12h, washing with deionized water and absolute ethyl alcohol for multiple times, putting the obtained sample into a vacuum drying oven, and drying for 10h at the temperature of 50 ℃ to obtain the porous silicon.
2. Preparing a sol-gel solution: to a mixed solution of 100ml of ethanol and water (50ml of ethanol, 50ml of deionized water) was added 0.1g of sucrose (C)6H12O6) And 1mL of an tetraethylorthosilicate (28% TEOS) solution.
3. Slowly and uniformly adding 0.5g of porous silicon powder into the prepared sol-gel solution; stirring for 30min, and heating at 160 deg.C for 12h to obtain precursor.
4. Heating the precursor to 900 ℃ at the speed of 5 ℃/min under the protection of pure argon, annealing for 2h, and then cooling to room temperature to obtain C/SiO2The bicontinuous term coats the porous silicon.
5. And (3) calculating according to a chemical equation to obtain the amount of HF, slowly and uniformly adding the HF into the annealing sample, performing ultrasonic treatment for 0.5h, and repeatedly cleaning with deionized water and absolute ethyl alcohol to obtain the carbon sheet cage-coated porous silicon.
FIG. 1 is a scanning electron micrograph of an aluminum-silicon alloy obtained in example 3. As can be seen from FIG. 1, the Al-Si alloy is spherical, has uniform size, and has a diameter of 1-2 μm. FIG. 2 is a scanning electron micrograph of the porous silicon obtained in example 3. As can be seen from fig. 2, the outer layer of the silicon ball is composed of a plurality of silicon strips, and a certain gap is formed between the silicon strips. FIG. 3 is a C/SiO solid obtained in example 32Scanning electron micrograph of bicontinuous coated porous silicon, from FIG. 3, it can be seen that C/SiO2The bicontinuous phase is uniformly coated on the outer layer of the porous silicon. FIG. 4 is a scanning electron micrograph of carbon plate cage-coated porous silicon prepared in example 3. As can be seen from FIG. 4, SiO is removed2And then only the carbon sheet is coated on the outer layer of the porous silicon, and finally a carbon sheet cage is formed to be coated on the outer layer of the porous silicon.
Coating porous silicon on a carbon sheet cage, a conductive agent (SP) and a binder (sodium alginate) according to a mass ratio of 6:2:2, mixing the slurry to be proper, coating the slurry on a copper foil, and drying the copper foil in a vacuum drying oven at the temperature of 60 ℃ for 10 hours. The obtained pole pieces were assembled into a 2032R type button cell, and the used silicon-carbon electrolyte (purchased from Koledo Co., Ltd.) was subjected to electrochemical performance test, the test results are shown in FIG. 5 and FIG. 6.
The lithium ion battery is prepared by using the porous silicon coated by the carbon sheet cage in the example as a negative electrode material, and a cycle performance test is performed on the lithium ion battery, and fig. 5 is a diagram of the first charge-discharge specific capacity of the battery sheet prepared in example 3. As seen from FIG. 5, the first discharge specific capacity of the material is 2553.3mAh/g, the first charge specific capacity is 2185.3mAh/g, and the first coulombic efficiency is 85.6%. FIG. 6 is a graph of cycle performance testing of the battery pole pieces prepared in example 3. As can be seen from FIG. 6, under the condition of a current density of 1A/g, after 200 cycles, the specific charge capacity still has 1250mAh/g, and the material has activation in the process of cyclic charge and discharge. The prepared carbon sheet cage coated porous silicon has excellent high reversible capacity, cycle stability and rate capability when used as a negative electrode material. The porous structure is prepared on the outer layer of carbon in the obtained negative electrode material with the porous silicon coated by the carbon sheet cage, and the carbon sheet with the porous structure is tightly coated on the outer layer of the porous silicon; the carbon coated on the porous silicon outer layer can relieve the volume expansion of silicon in the circulation process, and the porous structure is arranged between the carbon sheets, so that the transmission distance of ions between lithium can be shortened, and the lithium ions can be conveniently inserted into/removed from the negative electrode prepared by coating the porous silicon on the carbon sheet cage.
Example 4
The difference from example 3 is that: in the step 1, the average grain size D50 of the aluminum-silicon alloy is 5 mu m, and the mass ratio of aluminum to silicon in the aluminum-silicon alloy is 9: 1; the inorganic acid is nitric acid (0.2mol/L), and the carbon source in the step 2 is starch; the silica source is a siloxane. The volume ratio of ethanol to deionized water in the mixed solution is 2: 1; the heat preservation temperature in the step 3 is 170 ℃, and the heat preservation time is 10 hours; the mass fraction of the hydrofluoric acid in the step 5 is 10 wt%.
Uniformly mixing the carbon sheet cage-coated porous silicon obtained in the embodiment, a conductive agent (conductive carbon black) and a binder (sodium carboxymethyl cellulose) according to a mass ratio of 6:2:2, adding ethanol to prepare slurry, coating the slurry on a copper foil, and drying at 60 ℃ to obtain the carbon sheet cage-coated porous silicon electrode material.
Example 5
The difference from example 3 is that: in the step 1, the average grain size D50 of the aluminum-silicon alloy is 3 mu m, and the mass ratio of aluminum to silicon in the aluminum-silicon alloy is 5: 1; the carbon source in the step 2 is citric acid; the silica source is a siloxane; the volume ratio of ethanol to deionized water in the mixed solution is 2: 1; the heat preservation temperature in the step 3 is 150 ℃, and the heat preservation time is 24 hours; the mass fraction of the hydrofluoric acid in the step 5 is 3 wt%.
The carbon sheet cage obtained in this example was coated with porous silicon, a conductive agent (conductive carbon black), and a binder (sodium alginate) in an amount of 5: 1: 2, uniformly mixing, adding water to prepare slurry, coating the slurry on a copper foil, and drying at 50 ℃ to obtain the electrode material of the carbon sheet cage coated porous silicon.
Example 6
The difference from example 3 is that: in the step 1, the average grain size D50 of the aluminum-silicon alloy is 2 μm, and the mass ratio of aluminum to silicon in the aluminum-silicon alloy is 6: 1; the carbon source in the step 2 is ascorbic acid; the carbon source in the step 2 is citric acid; the silica source is a siloxane; the volume ratio of ethanol to deionized water in the mixed solution is 1.5: 1; the temperature of the heat preservation in the step 3 is 155 ℃, and the heat preservation time is 20 hours; the mass fraction of the hydrofluoric acid in the step 5 is 8 wt%.
The carbon sheet obtained in this example was coated with porous silicon, a conductive agent (Super P), and a binder (sodium carboxymethyl cellulose) in a mass ratio of 6:2: 1, uniformly mixing, adding ethanol to prepare slurry, coating the slurry on a copper foil, and drying at 70 ℃ to obtain the electrode material of the carbon sheet cage coated porous silicon.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations and simplifications are intended to be included in the scope of the present invention.

Claims (7)

1. A carbon sheet cage coated porous silicon material is characterized in that the carbon sheet cage coated porous silicon material is prepared by adding aluminum-silicon alloy into inorganic acid solution, stirring, filtering or centrifuging to obtain porous silicon, adding the porous silicon into ethanol/deionized water mixed solution containing a carbon source and a silicon dioxide source, stirring, and preserving heat at 150-170 ℃ for 10-24 hours to obtain a precursor; sintering the obtained precursor at 800-1000 ℃ in inert atmosphere to obtain C/SiO2Double-continuous coating of porous silicon with C/SiO2Adding the double-continuous coated porous silicon into hydrofluoric acid, and performingWashing and drying to obtain the product; the average particle size D50 of the aluminum-silicon alloy is 1-5 mu m, and the mass ratio of aluminum to silicon in the aluminum-silicon alloy is (4-9): 1; the mass concentration of the hydrofluoric acid is 1-10 wt%; the volume ratio of ethanol to deionized water in the mixed solution is (2-1) to 1; the volume of the silicon dioxide source and the total volume ratio of ethanol to deionized water are (2-20): (1000 to 1500); the volume ratio of the mass of the porous silicon to the mass of the carbon source to the volume of the silicon dioxide source is (0.5-1) g, (0.05-1) g, (0.2-1) mL.
2. The carbon sheet cage-coated porous silicon material as claimed in claim 1, wherein the inorganic acid is one or more of hydrochloric acid, nitric acid or sulfuric acid; the concentration of the inorganic acid is 0.1-0.5 mol/L.
3. The carbon sheet cage-coated porous silicon material as claimed in claim 1, wherein the carbon source is one or more of glucose, sucrose, starch, citric acid or ascorbic acid; the silicon dioxide source is tetraethoxysilane or/and siloxane.
4. The carbon sheet cage-coated porous silicon material as claimed in claim 1, wherein the stirring time is 12-24 hours, and the sintering time is 1-4 hours.
5. The carbon sheet cage-coated porous silicon material of claim 1, wherein the inert atmosphere is argon or nitrogen.
6. The preparation method of the carbon sheet cage-coated porous silicon material as claimed in any one of claims 1 to 5, comprising the following specific steps:
s1, adding the aluminum-silicon alloy into an inorganic acid solution, stirring, and filtering or centrifuging to obtain porous silicon;
s2, adding porous silicon into a mixed solution of ethanol/deionized water containing a carbon source and a silicon dioxide source, stirring, and preserving heat at 150-170 ℃ to obtain a precursor;
s3 before obtainingSintering the precursor at 800-1000 ℃ in an inert atmosphere to obtain C/SiO2Bi-continuously coating porous silicon;
s4, mixing C/SiO2And adding the bicontinuous coated porous silicon into hydrofluoric acid, washing and drying to obtain the carbon sheet cage coated porous silicon material.
7. Use of the carbon sheet cage-coated porous silicon material as claimed in any one of claims 1 to 5 in the field of lithium batteries.
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