CN107857271A - Preparation method and application of hollow silicon nanospheres - Google Patents
Preparation method and application of hollow silicon nanospheres Download PDFInfo
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- CN107857271A CN107857271A CN201711085365.9A CN201711085365A CN107857271A CN 107857271 A CN107857271 A CN 107857271A CN 201711085365 A CN201711085365 A CN 201711085365A CN 107857271 A CN107857271 A CN 107857271A
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 52
- 239000010703 silicon Substances 0.000 title claims abstract description 52
- 239000002077 nanosphere Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 90
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 44
- 239000000203 mixture Substances 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 20
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims abstract description 20
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 18
- 238000001354 calcination Methods 0.000 claims abstract description 16
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000005245 sintering Methods 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000000376 reactant Substances 0.000 claims abstract 3
- 239000002253 acid Substances 0.000 claims abstract 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 18
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 235000013312 flour Nutrition 0.000 claims description 14
- 238000005554 pickling Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 7
- 229910001416 lithium ion Inorganic materials 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 229910052814 silicon oxide Inorganic materials 0.000 claims 1
- 238000000227 grinding Methods 0.000 abstract description 2
- 239000011259 mixed solution Substances 0.000 abstract description 2
- 239000011863 silicon-based powder Substances 0.000 abstract 2
- 238000001816 cooling Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 238000004729 solvothermal method Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 22
- 230000002572 peristaltic effect Effects 0.000 description 5
- -1 stir Chemical compound 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000002210 silicon-based material Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 2
- 239000005052 trichlorosilane Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- XUGSDIOYQBRKGF-UHFFFAOYSA-N silicon;hydrochloride Chemical compound [Si].Cl XUGSDIOYQBRKGF-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- 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
- C01B33/023—Preparation by reduction of silica or free silica-containing material
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Silicon Compounds (AREA)
Abstract
The invention discloses a preparation method of hollow silicon nanospheres, which comprises the following steps: s1, carrying out solvothermal reaction on a mixed solution of cetyl trimethyl ammonium bromide, octane and ethyl orthosilicate to obtain an intermediate reactant, and sintering the intermediate reactant to obtain a hollow silicon dioxide ball; s2, mixing the hollow silica spheres with magnesium powder, grinding, calcining, and cooling to room temperature to obtain a silicon powder mixture; and S3, sequentially carrying out acid washing, water washing and drying on the silicon powder mixture to obtain the hollow silicon nanospheres. The invention also discloses the application field of the hollow silicon nanosphere. The invention improves the specific surface area of the silicon ball and the scalability of volume expansion, thereby improving the capacity and the cycle stability of the material.
Description
Technical field
The present invention relates to nano silicon material field, and in particular to a kind of preparation method and applications of hollow silicon nanosphere.
Background technology
Abundance of the silicon in the earth's crust is very high, is only second to oxygen, and suffers from semiconductor and energy industry important
Status.Silicon materials have the advantages that high theoretical capacity, high surface area and high-tap density and prepared simple.In semiconductor, lithium
The field such as ion battery and ultracapacitor suffers from preferable application prospect.However, due to the larger volume of silicon materials itself
The coefficient of expansion causes constantly to rupture and formed new SEI films, constantly consumes lithium ion, therefore, directly use as lithium from
The cyclical stability of sub- cell negative electrode material is poor.At present, the mode for improving silicon materials cyclical stability has a lot, common are
Carbon coating and hollow two ways.Wherein, hollow structure can allow silicon materials to have larger volume cushion space, slow down material
Cause the speed of efflorescence because of violent Volume Changes, thus ideal cyclical stability is shown as negative material.
At present, the method for preparing hollow silicon nanometer ball material has a lot.For example using silica spheres as template, monosilane is
Raw material, the first step equably grow elementary silicon layer in silica ball surface by CVD method, second step by
Handled in 10wt% hydrofluoric acid solution 10 minutes and remove silica core, by washing, dried, obtain with ideal battery
The hollow silicon nanosphere negative material of energy.However, preparing appeal material by this method has many limitations, wherein using
CVD preparation method determines its high cost and relatively low yield, thus is not suitable for and large-scale industrial production.
Similarly, Germany scientist in 2015 similarly reports a kind of hollow silicon with preferable charge-discharge performance and cyclical stability
Trichlorosilane and block copolymer P123, are dissolved in hydrochloric acid solution, room temperature are placed in after being sufficiently mixed by nanometer ball material first
Lower twenty four hours is from volatilization, the presoma (HSiO that will be obtained1.5) n drying, and obtain titanium dioxide in 1100 DEG C or so calcinings
Silicon composite, unnecessary titanium dioxide is removed by being handled in the mixed solution of 40wt% hydrofluoric acid and 37wt% hydrochloric acid
Silicon obtains hollow silicon nanometer ball material.However, such a method equally has larger limitation, due to trichlorosilane use into
This is higher, and easily decomposition safety coefficient is low, and therefore, it is difficult to accomplish scale production.
The content of the invention
Based on technical problem existing for background technology, the present invention propose a kind of hollow silicon nanosphere preparation method and its
Using the present invention is by improving the specific surface area of silicon ball and the scalability of volumetric expansion, so as to improve the capacity of material and follow
Ring stability.
A kind of preparation method of hollow silicon nanosphere proposed by the present invention, comprises the following steps：
S1, the mixed liquor of cetyl trimethylammonium bromide, octane and tetraethyl orthosilicate is subjected to solvent thermal reaction obtained
Intermediate reaction thing, intermediate reaction thing is sintered to obtain hollow silica ball；
S2, hollow silica ball mixed with magnesium powder, ground, calcining, be cooled to room temperature, obtain silica flour mixture；
S3, obtain hollow silicon nanosphere after silica flour mixture is carried out into pickling, washing, drying successively.
Preferably, S1 concrete operations are：Cetyl trimethylammonium bromide is dissolved in the mixed liquor of water and ammoniacal liquor, added
Enter octane, stir, tetraethyl orthosilicate is added dropwise by peristaltic pump, successively by stirring, heat up, be incubated, wash, dry, burn
Hollow silica ball is obtained after knot.
Preferably, in S1 concrete operations, the time of stirring is 0.5-3h.
Preferably, in S1 concrete operations, the temperature of insulation is 80-120 DEG C, time 12-36h.
Preferably, in S1 concrete operations, washed successively using deionized water and ethanol solution.
Preferably, in S1 concrete operations, dry temperature is 30-70 DEG C, time 6-10h.
Preferably, in S1, it is sintered in the atmosphere of gas and carries out.
Preferably, the gas is selected from least one of air, oxygen.
Preferably, in S1, the temperature of sintering is 500-700 DEG C, time 4-12h.
Preferably, in S1 concrete operations, quality volume (g/ml) ratio of cetyl trimethylammonium bromide and water is
0.5-0.8：31-35.
Preferably, in S1 concrete operations, water, ammoniacal liquor, octane, the volume ratio of tetraethyl orthosilicate are 31-35： 5-9：
8-12：2.5-5.5.
Preferably, in S1 concrete operations, the concentration of ammoniacal liquor is 0.5-3mol/L.
Preferably, in S2, calcine and carried out in the atmosphere of argon gas and hydrogen gas mixture.
Preferably, in the argon gas and hydrogen gas mixture, the volume fraction shared by hydrogen is 2-10%.
Preferably, in S2, the temperature of calcining is 500-900 DEG C, time 1-6h；Wherein, during calcining, heating
Speed influences magnesium powder and the reaction effect of profound silica, if heating rate is too fast, precursor mixture will be caused to be heated
Inequality, internal silica can not fully be reacted, and asked so as to be difficult to obtain the silicon nanometer of pure phase state, do not reached ideal
Effect, therefore it is 1-10 DEG C/min, preferably 3 DEG C/min to control programming rate.
Preferably, in S3, pickling is carried out using hydrochloric acid solution.
Preferably, the concentration of the hydrochloric acid solution is 0.1-1mol/L.
Preferably, in S3, the size of hollow silicon nanosphere is 50-200nm.
Preferably, in S2, the weight ratio of hollow silica ball and magnesium powder is 1：1-4.
Lithium ion battery negative material prepared by a kind of hollow silicon nanosphere obtained with the preparation method.
The time of above-mentioned grinding is not construed as limiting, and is selected as the case may be.
The present invention improves the specific surface area of material and the space of Volume Changes in the hollow structure of silicon nanosphere so that
Silicon nanosphere is used as lithium ion battery negative material and shows higher charge/discharge capacity and preferable cyclical stability, greatly
Ground adds the energy density of battery.The preparation method of the present invention is simple to operation, and cost is relatively low, can apply to a variety of silicon nanometers
Material, adaptability is good, and suitable for mass production.
Brief description of the drawings
Fig. 1 is the testing result of lithium ion battery negative material charge-discharge performance and cyclical stability in test example of the present invention
Schematic diagram.
Embodiment
Below, technical scheme is described in detail by specific embodiment.
Embodiment 1
A kind of preparation method of hollow silicon nanosphere, comprises the following steps：
S1, the mixed liquor progress solvent thermal reaction by cetyl trimethylammonium bromide solution, octane and tetraethyl orthosilicate
Intermediate reaction thing is obtained, intermediate reaction thing is sintered to obtain hollow silica ball；
S2, hollow silica ball mixed with magnesium powder, ground, calcining, be cooled to room temperature, obtain silica flour mixture；
S3, obtain hollow silicon nanosphere after silica flour mixture is carried out into pickling, washing, drying successively.
Embodiment 2
A kind of preparation method of hollow silicon nanosphere, comprises the following steps：
S1, the mixed liquor progress solvent thermal reaction by cetyl trimethylammonium bromide solution, octane and tetraethyl orthosilicate
Intermediate reaction thing is obtained, intermediate reaction thing is sintered to obtain hollow silica ball；
S2, hollow silica ball mixed with magnesium powder, ground, calcining, be cooled to room temperature, obtain silica flour mixture；
S3, obtain hollow silicon nanosphere after silica flour mixture is carried out into pickling, washing, drying successively；
Wherein, S1 concrete operations are：Cetyl trimethylammonium bromide is dissolved in the mixed liquor of water and ammoniacal liquor, added
Octane, stirring, tetraethyl orthosilicate is added dropwise by peristaltic pump, successively by stirring, is heated up, is incubated, wash, dries, sintering
After obtain hollow silica ball；
In S1 concrete operations, the time of stirring is 1h；
In S1 concrete operations, the temperature of insulation is 120 DEG C, time 12h；
In S1 concrete operations, washed successively using deionized water and ethanol solution；
In S1 concrete operations, dry temperature is 70 DEG C, time 6h；
In S1, it is sintered in the atmosphere of gas and carries out；
The gas is air；
In S1, the temperature of sintering is 700 DEG C, time 4h；
In S1 concrete operations, the quality volume (g/ml) of cetyl trimethylammonium bromide and water is than being 0.8：31；
In S1 concrete operations, water, ammoniacal liquor, octane, the volume ratio of tetraethyl orthosilicate are 35：5：12： 2.5；
In S1 concrete operations, the concentration of ammoniacal liquor is 3mol/L；
In S2, calcine and carried out in the atmosphere of argon gas and hydrogen gas mixture；
In the argon gas and hydrogen gas mixture, the volume fraction shared by hydrogen is 2%；
In S2, the temperature of calcining is 500 DEG C, time 6h；
In S3, pickling is carried out using hydrochloric acid solution；
The concentration of the hydrochloric acid solution is 0.1mol/L；
In S3, the size of hollow silicon nanosphere is 200nm；
In S2, the weight ratio of hollow silica ball and magnesium powder is 1：1.
Embodiment 3
A kind of preparation method of hollow silicon nanosphere, comprises the following steps：
S1, the mixed liquor progress solvent thermal reaction by cetyl trimethylammonium bromide solution, octane and tetraethyl orthosilicate
Intermediate reaction thing is obtained, intermediate reaction thing is sintered to obtain hollow silica ball；
S2, hollow silica ball mixed with magnesium powder, ground, calcining, be cooled to room temperature, obtain silica flour mixture；
S3, obtain hollow silicon nanosphere after silica flour mixture is carried out into pickling, washing, drying successively；
Wherein, S1 concrete operations are：Cetyl trimethylammonium bromide is dissolved in the mixed liquor of water and ammoniacal liquor, added
Octane, stirring, tetraethyl orthosilicate is added dropwise by peristaltic pump, successively by stirring, is heated up, is incubated, wash, dries, sintering
After obtain hollow silica ball；
In S1 concrete operations, the time of stirring is 3h；
In S1 concrete operations, the temperature of insulation is 80 DEG C, time 36h；
In S1 concrete operations, washed successively using deionized water and ethanol solution；
In S1 concrete operations, dry temperature is 30 DEG C, time 10h；
In S1, it is sintered in the atmosphere of gas and carries out；
The gas is oxygen；
In S1, the temperature of sintering is 500 DEG C, time 12h；
In S1 concrete operations, the quality volume (g/ml) of cetyl trimethylammonium bromide and water is than being 0.5：35；
In S1 concrete operations, water, ammoniacal liquor, octane, the volume ratio of tetraethyl orthosilicate are 31：9：8： 5.5；
In S1 concrete operations, the concentration of ammoniacal liquor is 0.5mol/L；
In S2, calcine and carried out in the atmosphere of argon gas and hydrogen gas mixture；
In the argon gas and hydrogen gas mixture, the volume fraction shared by hydrogen is 10%；
In S2, the temperature of calcining is 900 DEG C, time 1h；
In S3, pickling is carried out using hydrochloric acid solution；
The concentration of the hydrochloric acid solution is 1mol/L；
In S3, the size of hollow silicon nanosphere is 50nm；
In S2, the weight ratio of hollow silica ball and magnesium powder is 1：4.
Embodiment 4
A kind of preparation method of hollow silicon nanosphere, comprises the following steps：
S1, the mixed liquor progress solvent thermal reaction by cetyl trimethylammonium bromide solution, octane and tetraethyl orthosilicate
Intermediate reaction thing is obtained, intermediate reaction thing is sintered to obtain hollow silica ball；
S2, hollow silica ball mixed with magnesium powder, ground, calcining, be cooled to room temperature, obtain silica flour mixture；
S3, obtain hollow silicon nanosphere after silica flour mixture is carried out into pickling, washing, drying successively；
Wherein, S1 concrete operations are：Cetyl trimethylammonium bromide is dissolved in the mixed liquor of water and ammoniacal liquor, added
Octane, stirring, tetraethyl orthosilicate is added dropwise by peristaltic pump, successively by stirring, is heated up, is incubated, wash, dries, sintering
After obtain hollow silica ball；
In S1 concrete operations, the time of stirring is 2h；
In S1 concrete operations, the temperature of insulation is 90 DEG C, time 20h；
In S1 concrete operations, washed successively using deionized water and ethanol solution；
In S1 concrete operations, dry temperature is 45 DEG C, time 7h；
In S1, it is sintered in the atmosphere of gas and carries out；
The gas is oxygen；
In S1, the temperature of sintering is 600 DEG C, time 6h；
In S1 concrete operations, the quality volume (g/ml) of cetyl trimethylammonium bromide and water is than being 0.7：32；
In S1 concrete operations, water, ammoniacal liquor, octane, the volume ratio of tetraethyl orthosilicate are 32：6：9：4；
In S1 concrete operations, the concentration of ammoniacal liquor is 2mol/L；
In S2, calcine and carried out in the atmosphere of argon gas and hydrogen gas mixture；
In the argon gas and hydrogen gas mixture, the volume fraction shared by hydrogen is 6%；
In S2, the temperature of calcining is 600 DEG C, time 4h；
In S3, pickling is carried out using hydrochloric acid solution；
The concentration of the hydrochloric acid solution is 0.5mol/L；
In S3, the size of hollow silicon nanosphere is 50-200nm；
In S2, the weight ratio of hollow silica ball and magnesium powder is 1：2.
Embodiment 5
A kind of preparation method of hollow silicon nanosphere, comprises the following steps：
S1, the mixed liquor progress solvent thermal reaction by cetyl trimethylammonium bromide solution, octane and tetraethyl orthosilicate
Intermediate reaction thing is obtained, intermediate reaction thing is sintered to obtain hollow silica ball；
S2, hollow silica ball mixed with magnesium powder, ground, calcining, be cooled to room temperature, obtain silica flour mixture；
S3, obtain hollow silicon nanosphere after silica flour mixture is carried out into pickling, washing, drying successively；
Wherein, S1 concrete operations are：Cetyl trimethylammonium bromide is dissolved in the mixed liquor of water and ammoniacal liquor, added
Octane, stirring, tetraethyl orthosilicate is added dropwise by peristaltic pump, successively by stirring, is heated up, is incubated, wash, dries, sintering
After obtain hollow silica ball；
In S1 concrete operations, the time of stirring is 0.5h；
In S1 concrete operations, the temperature of insulation is 100 DEG C, time 24h；
In S1 concrete operations, washed successively using deionized water and ethanol solution；
In S1 concrete operations, dry temperature is 50 DEG C, time 8h；
In S1, it is sintered in the atmosphere of gas and carries out；
The gas is oxygen；
In S1, the temperature of sintering is 550 DEG C, time 8h；
In S1 concrete operations, the quality volume (g/ml) of cetyl trimethylammonium bromide and water is than being 0.69：
33；
In S1 concrete operations, water, ammoniacal liquor, octane, the volume ratio of tetraethyl orthosilicate are 33：7：10： 3.6；
In S1 concrete operations, the concentration of ammoniacal liquor is 1mol/L；
In S2, calcine and carried out in the atmosphere of argon gas and hydrogen gas mixture；
In S2, the temperature of calcining is 700 DEG C, time 2h；
In S3, pickling is carried out using hydrochloric acid solution；
The concentration of the hydrochloric acid solution is 0.7mol/L；
In S3, the size of hollow silicon nanosphere is 50-200nm；
In the argon gas and hydrogen gas mixture, the volume fraction shared by hydrogen is 5%.
Test example 1
It is 0.2A g in electric current-1Under conditions of, detect lithium-ion electric prepared by the hollow silicon nanosphere obtained by embodiment 5
The charge-discharge performance and cyclical stability of pond negative material, as a result as shown in Figure 1.
As shown in Figure 1, hollow silicon nanosphere is as lithium ion battery negative material, shows higher capacity and preferably
Stable circulation performance.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art the invention discloses technical scope in, technique according to the invention scheme and its
Inventive concept is subject to equivalent substitution or change, should all be included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of hollow silicon nanosphere, it is characterised in that comprise the following steps：
S1, the mixed liquor of cetyl trimethylammonium bromide, octane and tetraethyl orthosilicate is subjected to solvent thermal reaction obtains centre
Reactant, intermediate reaction thing is sintered to obtain hollow silica ball；
S2, hollow silica ball mixed with magnesium powder, ground, calcining, be cooled to room temperature, obtain silica flour mixture；
S3, obtain hollow silicon nanosphere after silica flour mixture is carried out into pickling, washing, drying successively.
2. the preparation method of hollow silicon nanosphere according to claim 1, it is characterised in that S1 concrete operations are：By ten
Six alkyl trimethyl ammonium bromides are dissolved in the mixed liquor of water and ammoniacal liquor, are added octane, stirring, are added tetraethyl orthosilicate, pass through successively
Stirring is crossed, is heated up, is incubated, is washed, is dried, hollow silica ball is obtained after sintering；Preferably, in S1 concrete operations,
The time of stirring is 0.5-3h；Preferably, in S1 concrete operations, the temperature of insulation is 80-120 DEG C, time 12-36h；
Preferably, in S1 concrete operations, washed successively using deionized water and ethanol solution；Preferably, in the specific of S1
In operation, dry temperature is 30-70 DEG C, time 6-10h.
3. the preparation method of hollow silicon nanosphere according to claim 1 or claim 2, it is characterised in that in S1, be sintered in gas
Carried out in atmosphere；Preferably, the gas is selected from least one of air, oxygen；Preferably, in S1, the temperature of sintering is
500-700 DEG C, time 4-12h.
4. according to the preparation method of any one of the claim 1-3 hollow silicon nanospheres, it is characterised in that in S1 specific behaviour
In work, quality volume (g/ml) ratio of cetyl trimethylammonium bromide and water is 0.5-0.8：31-35；Preferably, S1's
In concrete operations, water, ammoniacal liquor, octane, the volume ratio of tetraethyl orthosilicate are 31-35：5-9：8-12：2.5-5.5；Preferably, exist
In S1 concrete operations, the concentration of ammoniacal liquor is 0.5-3mol/L.
5. according to the preparation method of any one of the claim 1-4 hollow silicon nanospheres, it is characterised in that in S2, calcine
Carried out in the atmosphere of argon gas and hydrogen gas mixture；Preferably, in the argon gas and hydrogen gas mixture, the volume shared by hydrogen
Fraction is 2-10%.
6. according to the preparation method of any one of the claim 1-5 hollow silicon nanospheres, it is characterised in that in S2, calcining
Temperature is 500-900 DEG C, time 1-6h.
7. according to the preparation method of any one of the claim 1-6 hollow silicon nanospheres, it is characterised in that in S3, using salt
Acid solution carries out pickling；Preferably, the concentration of the hydrochloric acid solution is 0.1-1mol/L.
8. according to the preparation method of any one of the claim 1-7 hollow silicon nanospheres, it is characterised in that in S3, hollow silicon
The size of nanosphere is 50-200nm.
9. according to the preparation method of any one of the claim 1-8 hollow silicon nanospheres, it is characterised in that in S2, hollow two
The weight of silicon oxide ball and magnesium powder ratio is 1：1-4.
A kind of 10. lithium ion battery prepared by hollow silicon nanosphere obtained with any one of the claim 1-9 preparation methods
Negative material.
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| CN102145890A (en) * | 2011-04-30 | 2011-08-10 | 南京大学 | Preparation method of hollow spherical silicon nanomaterial |
| CN102432024A (en) * | 2011-09-14 | 2012-05-02 | 中山大学 | Hollow mesoporous silica microsphere, preparation method and application thereof |
| CN105070890A (en) * | 2015-07-20 | 2015-11-18 | 北京化工大学 | Titanium oxide-coated porous hollow silicon ball composite electrode material and preparation method therefor |
| CN106865494A (en) * | 2017-04-10 | 2017-06-20 | 山西大学 | A kind of preparation method of hollow nano silicon spheres/graphene composite negative pole |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102145890A (en) * | 2011-04-30 | 2011-08-10 | 南京大学 | Preparation method of hollow spherical silicon nanomaterial |
| CN102432024A (en) * | 2011-09-14 | 2012-05-02 | 中山大学 | Hollow mesoporous silica microsphere, preparation method and application thereof |
| CN105070890A (en) * | 2015-07-20 | 2015-11-18 | 北京化工大学 | Titanium oxide-coated porous hollow silicon ball composite electrode material and preparation method therefor |
| CN106865494A (en) * | 2017-04-10 | 2017-06-20 | 山西大学 | A kind of preparation method of hollow nano silicon spheres/graphene composite negative pole |
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| CN110581270A (en) * | 2019-08-21 | 2019-12-17 | 北京化工大学 | Preparation method and application of hollow nano silicon sphere negative electrode material |
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