CN112607741A - Titanium oxide coated porous hollow silicon ball, preparation method and application thereof - Google Patents
Titanium oxide coated porous hollow silicon ball, preparation method and application thereof Download PDFInfo
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 116
- 239000010703 silicon Substances 0.000 title claims abstract description 116
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 66
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 76
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 41
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 28
- 238000000576 coating method Methods 0.000 claims abstract description 20
- 239000011248 coating agent Substances 0.000 claims abstract description 19
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 16
- 229910003081 TiO2−x Inorganic materials 0.000 claims abstract description 15
- 230000009467 reduction Effects 0.000 claims abstract description 14
- 238000003980 solgel method Methods 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000007773 negative electrode material Substances 0.000 claims abstract description 7
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 6
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 6
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 6
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 27
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000000843 powder Substances 0.000 claims description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 19
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 18
- 238000006722 reduction reaction Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 14
- 238000001556 precipitation Methods 0.000 claims description 14
- 239000011812 mixed powder Substances 0.000 claims description 12
- 238000002791 soaking Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000005530 etching Methods 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 9
- 239000007810 chemical reaction solvent Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- 239000011780 sodium chloride Substances 0.000 claims description 9
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 2
- 230000008569 process Effects 0.000 abstract description 14
- 230000008859 change Effects 0.000 abstract description 10
- 239000002244 precipitate Substances 0.000 description 28
- 239000000243 solution Substances 0.000 description 12
- 229910001220 stainless steel Inorganic materials 0.000 description 12
- 239000010935 stainless steel Substances 0.000 description 12
- 238000009826 distribution Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000010586 diagram Methods 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 238000002336 sorption--desorption measurement Methods 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000010406 cathode material Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- 239000002210 silicon-based material Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000001198 high resolution scanning electron microscopy Methods 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- 231100000331 toxic Toxicity 0.000 description 4
- 230000002588 toxic effect Effects 0.000 description 4
- 229910003481 amorphous carbon Inorganic materials 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000005543 nano-size silicon particle Substances 0.000 description 2
- 239000002077 nanosphere Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229910003077 Ti−O Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000002120 nanofilm Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 239000002620 silicon nanotube Substances 0.000 description 1
- 229910021430 silicon nanotube Inorganic materials 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
- C01B33/021—Preparation
- C01B33/023—Preparation by reduction of silica or free silica-containing material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- H—ELECTRICITY
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
- C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
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Abstract
The invention provides a titanium oxide coated porous hollow silicon ball, a preparation method and application thereof. The preparation method comprises the following steps: s1, preparing hollow silica spheres containing the template agent by adopting a sol-gel method; s2, mixing the hollow SiO2Carrying out magnesiothermic reduction on the spheres to obtain hollow silicon spheres containing the template agent; s3, wrapping the surface of the hollow silicon ballCoated with TiO2‑xWherein x is 0-0.6, to obtain TiO2‑xA coated hollow silicon sphere; s4, calcining TiO2‑xAnd coating the hollow silicon spheres to obtain the titanium oxide coated porous hollow silicon spheres. The titanium oxide coated porous hollow silicon spheres prepared by the method well solve the problems of poor conductivity and large volume change in the circulating process of the hollow silicon spheres, have good point circulation performance, and are very suitable for being used as the negative electrode material of a lithium ion battery.
Description
Technical Field
The invention relates to the field of lithium ion battery materials, in particular to a titanium oxide coated porous hollow silicon ball, and a preparation method and application thereof.
Background
Silicon has a specific capacity 10 times higher than that of graphite and is rich in storage, and most possibly replaces graphite to become a next-generation lithium ion negative electrode material. However, the large volume change of silicon during cycling can cause particle pulverization and repeated formation of a solid electrolyte interfacial film, seriously affecting its cycle life. In addition, silicon has poor conductivity, which affects its rate capability. Therefore, structural modifications of silicon, such as surface coating of silicon, are often required.
Coating the silicon surface with carbon can improve the conductivity of the composite, and the carbon layer can act as a barrier to prevent direct contact of the silicon with the electrolyte. However, since the volume of silicon varies greatly during the cycle and the strength of amorphous carbon is low, the carbon layer tightly coated on the silicon surface is easily broken during the cycle, and thus a good coating effect cannot be achieved. In addition, high-temperature calcination is needed in the process of forming the carbon layer, and products such as SiC which are not favorable for electrochemical performance are easily generated.
The stress caused by volume expansion can be relieved by carrying out nano treatment on the silicon, so that pulverization of the material is avoided. The design of structures such as silicon nanoparticles, silicon nano-films, silicon nanotubes, silicon nanowires and the like is beneficial to reducing volume expansion. The hollow nanospheres have larger cavities and thin shells, and can relieve the stress caused by volume expansion and shorten the diffusion path of electrolyte and lithium ions. However large surface of hollow nanospheresThe area and the surface are in contact with an electrolyte solution to consume lithium ions and the SEI film is repeatedly generated. The common method for preparing hollow nano silicon spheres is chemical vapor deposition and solid SiO2As template, SiO at high temperature2Depositing the surface, and then depositing SiO2And etching off to obtain the hollow nanospheres. However, this method uses toxic and flammable silane as a raw material and is not environmentally friendly.
For the above reasons, there is a need to provide a new process for modifying silicon material, so as to better overcome the defects of poor conductivity and large volume change in the cycle process, and make it better serve as the negative electrode material of lithium ion battery. Meanwhile, toxic and flammable silane is required to be avoided as a raw material, so that the preparation process is more environment-friendly.
Disclosure of Invention
The invention mainly aims to provide a titanium oxide coated porous hollow silicon ball, a preparation method and application thereof, and aims to solve the problems of poor electrical cycle performance caused by poor conductivity and large volume change in a cycle process when a silicon material is used as a lithium ion battery cathode material in the prior art and the problem of insufficient environmental protection in the preparation process.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for preparing titanium oxide-coated porous hollow silicon spheres, comprising the steps of: s1, preparing hollow silica spheres containing the template agent by adopting a sol-gel method; s2, mixing the hollow SiO2Carrying out magnesiothermic reduction on the spheres to obtain hollow silicon spheres containing the template agent; s3, coating TiO on the surface of the hollow silicon ball2-xWherein x is 0-0.6, to obtain TiO2-xA coated hollow silicon sphere; s4, calcining TiO2-xAnd coating the hollow silicon spheres to obtain the titanium oxide coated porous hollow silicon spheres.
Further, step S1 includes: dissolving ammonia water and a template agent in a first reaction solvent to form a pre-reaction system; adding tetraethoxysilane into the pre-reaction system to carry out a first precipitation reaction to obtain a first product system; and (3) aging and centrifugally separating the first product system to obtain the hollow silica spheres containing the template agent.
Further, the template agent is cetyl trimethyl ammonium bromide; preferably, the volume ratio of the ammonia water to the ethyl orthosilicate is 1: 1-1: 2, 0.15-0.2 g of the template agent is used for each milliliter of ammonia water, and the mass concentration of the ammonia water is 28-35%.
Further, the temperature of the first precipitation reaction is 30-50 ℃, and the time of the first precipitation reaction is 24-36 hours; preferably, the first reaction solvent is a mixed solvent of ethanol and deionized water; preferably, the aging temperature in the aging step is 90-95 ℃.
Further, step S2 includes: mixing the hollow silica spheres, magnesium powder and sodium chloride to obtain mixed powder; placing the mixed powder in an inert environment for reduction reaction to obtain reduced powder; soaking the reduced powder in a hydrochloric acid solution, and then carrying out solid-liquid separation to obtain solid powder; and etching to remove the residual magnesium powder in the solid powder to obtain the hollow silicon ball containing the template agent.
Further, in step S2, the weight ratio of the hollow silica spheres, the magnesium powder and the sodium chloride is 1: 0.8-0.9: 10-12.
Further, the reduction reaction step comprises: heating the mixed powder in inert gas to 680-720 ℃, preserving heat for 4-5 h, and then cooling to room temperature; and then soaking the cooled powder in a hydrochloric acid solution, and performing centrifugal separation to obtain reduced powder.
Further, in the step of removing the residual magnesium powder by etching, hydrofluoric acid is used as an etchant.
Further, step S3 includes: adding ammonia water and hollow silicon spheres containing a template agent into a second reaction solvent to form a suspension; adding tetrabutyl titanate into the suspension for a second precipitation reaction to obtain a second product system; carrying out centrifugal separation on the second product system to obtain TiO2-xCoated hollow silicon spheres.
Furthermore, the weight ratio of the ammonia water to the tetrabutyl titanate is 1: 1.5-1: 2, 0.333-0.5 g of hollow silicon spheres containing the template agent is corresponding to each milliliter of ammonia water, and the mass concentration of the ammonia water is 28-35%.
Further, in step S4, the TiO is calcined2-xCoated hollow siliconThe steps of the ball include: adding TiO into the mixture2-xAnd heating the coated hollow silicon spheres to 500-900 ℃ in an inert atmosphere, and preserving the heat for 4-5 hours to obtain the titanium oxide coated porous hollow silicon spheres.
According to another aspect of the invention, the titanium oxide coated porous hollow silicon spheres prepared by the preparation method are also provided.
According to another aspect of the invention, the application of the titanium oxide coated porous hollow silicon ball as a lithium ion battery negative electrode material is also provided.
The invention provides a preparation method of a titanium oxide coated porous hollow silicon ball. Secondly, coating TiO on the surface of the hollow silicon ball2-xForm a surface coating with non-stoichiometric TiO2-xFinally, the template agent is removed by calcining to form the titanium oxide coated porous hollow silicon spheres. TiO22Small volume change (less than 4%) in the circulation process, good stability, and TiO2The strength is much higher than amorphous carbon. In addition, TiO in non-stoichiometric proportions2-xThe composite material has good structural stability, small energy gap and high conductivity, so that the electrochemical performance of the silicon-based material can be improved by compounding the composite material with porous hollow silicon spheres. Therefore, the titanium oxide coated porous hollow silicon spheres prepared by the method well solves the problems of poor conductivity and large volume change in the circulation process of the hollow silicon spheres, has good point circulation performance, and is very suitable for being used as a lithium ion battery cathode material. In addition, the silica spheres are prepared by using a sol-gel method, toxic and flammable silane is not used as a raw material, and the method is environment-friendly and more suitable for industrial application.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
fig. 1 shows (a) SEM photographs and (b) HRSEM photographs of the hollow silica spheres containing the template prepared in example 1 according to the present invention;
fig. 2 shows (a) SEM photographs and (b) HRSEM photographs of the hollow silicon spheres prepared in example 1 according to the present invention;
FIG. 3 shows XRD patterns of hollow silicon spheres and titania-coated porous hollow silicon spheres prepared in example 1 according to the present invention;
FIG. 4 shows titania-coated porous hollow silica spheres and TiO prepared in example 1 according to the present invention2XPS Ti2p spectra of (A), wherein FIG. 4(a) is the XPS Ti2p spectra of the titanium oxide coated porous hollow silicon spheres and FIG. 4(a) is the XPS Ti2p spectra of the TiO coated porous hollow silicon spheres2XPS Ti2p spectrum of;
FIG. 5 shows N of hollow silicon spheres and titanium oxide-coated porous hollow silicon spheres prepared in example 1 according to the present invention2Adsorption/desorption curves and pore size distribution diagrams, wherein FIG. 5(a) is N of hollow silicon spheres2An adsorption/desorption curve, in which FIG. 5(b) is a pore size distribution diagram of the hollow silicon spheres and FIG. 5(c) is an N-type pore size distribution diagram of the titanium oxide-coated porous hollow silicon spheres2An adsorption/desorption curve, and fig. 5(d) is a pore size distribution diagram of the titanium oxide-coated porous hollow silicon spheres;
fig. 6 shows a charge and discharge graph of the titania-coated porous hollow silica spheres prepared in example 1 according to the present invention.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
As described in the background art, in the prior art, when a silicon material is used as a negative electrode material of a lithium ion battery, the electrical cycle performance is not good due to poor conductivity and large volume change in the cycle process, and the preparation process is not environment-friendly.
In order to solve the problem, the invention provides a preparation method of titanium oxide coated porous hollow silicon spheres, which comprises the following steps: s1, preparing hollow silica spheres containing the template agent by adopting a sol-gel method;s2, mixing the hollow SiO2Carrying out magnesiothermic reduction on the spheres to obtain hollow silicon spheres containing the template agent; s3, coating TiO on the surface of the hollow silicon ball2-xWherein x is 0-0.6, to obtain TiO2-xA coated hollow silicon sphere; s4, calcining TiO2-xAnd coating the hollow silicon spheres to obtain the titanium oxide coated porous hollow silicon spheres.
The preparation method provided by the invention comprises the steps of preparing the hollow silica spheres containing the template agent by a sol-gel method, and reducing the silica into silicon by a magnesiothermic reduction method to form the hollow silica spheres containing the template agent. Secondly, coating TiO on the surface of the hollow silicon ball2-xForm a surface coating with non-stoichiometric TiO2-xFinally, the template agent is removed by calcining to form the titanium oxide coated porous hollow silicon spheres. TiO22Small volume change (less than 4%) in the circulation process, good stability, and TiO2The strength is much higher than amorphous carbon. In addition, TiO in non-stoichiometric proportions2-xThe composite material has good structural stability, small energy gap and high conductivity, so that the electrochemical performance of the silicon-based material can be improved by compounding the composite material with porous hollow silicon spheres. Therefore, the present invention effectively utilizes TiO2-XThe prepared titanium oxide coated porous hollow silicon ball has the advantages that the titanium oxide coated porous hollow silicon ball is combined with the porous hollow silicon ball to form an internal buffer structure, the problems of poor conductivity and large volume change in the circulation process of the hollow silicon ball are well solved, the titanium oxide coated porous hollow silicon ball has good point circulation performance, and the titanium oxide coated porous hollow silicon ball is very suitable for being used as a lithium ion battery cathode material. In addition, the silica spheres are prepared by using a sol-gel method, toxic and flammable silane is not used as a raw material, and the method is environment-friendly and more suitable for industrial application.
In particular, the invention is to reduce the hollow silicon dioxide spheres into hollow silicon spheres by magnesium thermal reduction after the step of preparing the hollow silicon dioxide spheres. Compared with the coating of TiO2-xAnd then, the magnesium thermal reduction is carried out, so that the reduction effect on the silicon dioxide is better. And after magnesiothermic reduction, TiO2The coating effect of the coating layer is better.
The step of preparing the silica spheres by the sol-gel method may be a conventional process of sol-gel method, and in a preferred embodiment, the step S1 includes: dissolving ammonia water and a template agent in a first reaction solvent to form a pre-reaction system; adding tetraethoxysilane into the pre-reaction system to carry out a first precipitation reaction to obtain a first product system; and (3) aging and centrifugally separating the first product system to obtain the hollow silica spheres containing the template agent. The sol-gel precipitation reaction is more stable in the step, and the prepared silicon dioxide spheres have more uniform particle size, so that the electrical cycle performance of the final cathode material is further improved.
In a preferred embodiment, the templating agent is cetyltrimethylammonium bromide. Preferably, the volume ratio of the ammonia water to the ethyl orthosilicate is 1: 1-1: 2, 0.15-0.2 g of the template agent is used for each milliliter of ammonia water, and the mass concentration of the ammonia water is 28-35%. The relation of the use amount of the raw materials is controlled within the range, so that the conversion rate and the yield of the sol-gel precipitation reaction are improved, and the reaction efficiency is improved. More preferably, the temperature of the first precipitation reaction is 30-36 ℃, and the time of the first precipitation reaction is 24-36 hours; preferably, the first reaction solvent is a mixed solvent of ethanol and deionized water; preferably, the aging temperature in the aging step is 90-95 ℃.
In a preferred embodiment, step S2 includes: mixing the hollow silica spheres, magnesium powder and sodium chloride to obtain mixed powder; placing the mixed powder in an inert environment for reduction reaction to obtain reduced powder; soaking the reduced powder in a hydrochloric acid solution, and then carrying out solid-liquid separation to obtain solid powder; and etching to remove the residual magnesium powder in the solid powder to obtain the hollow silicon ball containing the template agent. Under the process, the silicon dioxide can be fully reduced into silicon, and hollow silicon spheres with stable structures are formed.
In order to further improve the reduction effect, in a preferred embodiment, in step S2, the weight ratio of the hollow silica spheres, the magnesium powder and the sodium chloride is 1: 0.8-0.9: 10-12. More preferably, the reduction step comprises: heating the mixed powder in inert gas to 680-720 ℃, preserving heat for 4-5 h, and then cooling to room temperature; and then soaking the cooled powder in a hydrochloric acid solution, and performing centrifugal separation to obtain reduced powder. The magnesium thermal reduction is carried out under the temperature and the conditions, and the reduction is more sufficient. And soaking the cooled powder in a hydrochloric acid solution to dissolve and remove the residual sodium chloride in the reaction.
In a preferred embodiment, in the step of removing the residual magnesium powder by etching, the etchant used is hydrofluoric acid. And residual magnesium carried in the hollow silicon spheres can be more fully etched and removed by adopting hydrofluoric acid.
In a preferred embodiment, step S3 includes: adding ammonia water and hollow silicon spheres containing a template agent into a second reaction solvent to form a suspension; adding tetrabutyl titanate into the suspension for a second precipitation reaction to obtain a second product system; carrying out centrifugal separation on the second product system to obtain TiO2-xCoated hollow silicon spheres. By adopting the step to coat the titanium oxide, the coating process is more stable, and a more uniform titanium oxide coating layer can be formed on the surface of the hollow silicon ball. More preferably, the weight ratio of the ammonia water to the tetrabutyl titanate is 1: 1.5-1: 2, 0.333-0.5 g of hollow silicon spheres containing the template agent is corresponding to each milliliter of ammonia water, and the mass concentration of the ammonia water is 28-35%.
In a preferred embodiment, in step S4, the TiO is calcined2-xThe steps of coating the hollow silicon spheres include: adding TiO into the mixture2-xAnd heating the coated hollow silicon spheres to 500-900 ℃ in an inert atmosphere, and preserving the heat for 4-5 hours to obtain the titanium oxide coated porous hollow silicon spheres. Under the calcination process, the template agent is removed more thoroughly.
The inert gas used in the above preparation method may be argon gas.
According to another aspect of the invention, the titanium oxide coated porous hollow silicon spheres prepared by the preparation method are provided. The titanium oxide coated porous hollow silicon ball has better conductivity and small volume change in the circulating process, and is very suitable for being used as a lithium ion battery cathode material.
According to another aspect of the invention, the application of the titanium oxide coated porous hollow silicon spheres as the negative electrode material of the lithium ion battery is also provided.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
Example 1
4ml of 28 mass% ammonia water and 0.6g of cetyltrimethylammonium bromide (CTAB) were added to a mixed solvent containing 120ml of anhydrous ethanol and 200ml of deionized water, and ultrasonication was carried out for 15min to completely dissolve CTAB. 4ml of Tetraethylorthosilicate (TEOS) were added dropwise to the above liquid with vigorous stirring and stirred in a water bath at 30 ℃ for 24h at 500 rpm. The precipitate after the reaction was centrifuged and washed 3 times with water and absolute ethanol to remove unreacted TEOS and residual ammonia. The centrifuged precipitate was then dispersed in 400ml of deionized water by sonication, aged in a water bath at 90 ℃ for 24h, and the precipitate was centrifuged and washed 3 times with deionized water. Dispersing the precipitate in 320ml of anhydrous ethanol by ultrasonic treatment, adding 900ml of HCI solution with the mass fraction of 37%, stirring for 3h in a water bath at 60 ℃ at the rotating speed of 500rpm, centrifugally separating the precipitate, and drying for 6h in an oven at 80 ℃ to obtain HSiO2The SEM photograph of the hollow silica spheres is shown in FIG. 1(a), and the HRSEM photograph is shown in FIG. 1 (b).
1g of HSiO20.8g of magnesium powder and 10g of NaCl are ground for 30min to be uniformly mixed. And filling the mixed powder into a stainless steel tube, introducing Ar gas, and sealing the stainless steel tube. The stainless steel tube was then placed in a tube furnace under Ar atmosphere for 3 min. The temperature rising rate of (1) is from room temperature to 680 ℃, and the temperature is kept for 4 hours and then the temperature is cooled to room temperature. Soaking the powder in the stainless steel tube in 150ml of 1mol/L hydrochloric acid solution, centrifuging and separating precipitates after 5h, soaking the precipitates in 100ml of hydrofluoric acid solution with the mass fraction of 5% for etching for 30min, centrifuging and separating the precipitates, washing the precipitates for 3 times respectively by using deionized water and absolute ethyl alcohol, and finally drying the obtained precipitates in a vacuum oven at 80 ℃ for 6h to obtain MHSi hollow silicon spheres, wherein the SEM picture is shown in figure 2(a), and the HRSEM picture is shown in figure 2 (b).
Adding 0.3ml of 28 mass percent ammonia water and 100mg of MHSi into 100ml of absolute ethyl alcohol, carrying out ultrasonic treatment for 15min, stirring the suspension in a water bath at 45 ℃ at the rotating speed of 600rpm, dropwise adding 0.45ml of tetrabutyl titanate (TBOT) into the suspension within 10min, and then adjusting the rotating speed to 400rpm and continuing stirring for 12 h. And (3) centrifugally separating the precipitate after reaction, washing the precipitate for 3 times by using absolute ethyl alcohol and deionized water respectively, and drying the precipitate in a vacuum oven at the temperature of 100 ℃ for 6 hours. The dried precipitate was placed in a crucible and placed in a tube furnace under Ar atmosphere for 30 min. Heating the titanium oxide-coated porous hollow silica spheres to 500 ℃, 600 ℃, 700 ℃, 800 ℃ and 900 ℃ respectively at the heating rate from room temperature, preserving the heat for 4 hours, and then cooling the titanium oxide-coated porous hollow silica spheres to room temperature to obtain the final product, namely the titanium oxide-coated porous hollow silica spheres MHSi @ TiO 2.
FIG. 3 shows XRD patterns of the above hollow silicon spheres and titania-coated porous hollow silicon spheres; as can be seen from the figure, at 111, 220, 311, 400, 311, respectively corresponding to 26 °, 47 °, 56 °, 70 °, 76 °, the peak shape indicates that silicon exists in the form of elemental silicon in the composite material. The peak pattern of anatase titanium oxide is typical and is compared with a standard graph to prove the above conclusion.
FIG. 4 shows titanium oxide coated porous hollow silica spheres and TiO2Wherein FIG. 4(a) is an XPS Ti2p spectrum (diffraction energy curve) of the porous hollow silicon spheres coated with titanium oxide, and FIG. 4(a) is a TiO2XPS Ti2p spectra of (a); as can be seen from the figure, the typical bond of titanium oxide is Ti3+And Ti4+From the bond strength, the analysis shows that Si-Ti-O bond is formed with silicon, and the bonding force is strong.
FIG. 5 shows hollow silicon spheres and N of titania-coated porous hollow silicon spheres2Adsorption/desorption curves and pore size distribution diagrams, wherein FIG. 5(a) is N of hollow silicon spheres2An adsorption/desorption curve, in which FIG. 5(b) is a pore size distribution diagram of the hollow silicon spheres and FIG. 5(c) is an N-type pore size distribution diagram of the titanium oxide-coated porous hollow silicon spheres2An adsorption/desorption curve, and fig. 5(d) is a pore size distribution diagram of the titanium oxide-coated porous hollow silicon spheres; as can be seen from the figure, the particle size distribution is relatively uniform, the specific surface area is large, and the porous lithium ion battery is very suitable for the insertion and extraction of lithium ions and is in a porous state.
FIG. 6 is a graph showing charge and discharge curves of titania-coated porous hollow silica spheres prepared in example 1 according to the present invention; as can be seen from the figure, the capacity of the material reaches 2400mah/g, and after 50 weeks of circulation, the capacity is still maintained at 1600 mah/g.
Example 2
2g of HSiO2, 2.6g of magnesium powder and 15g of KCl are ground for 30min to be uniformly mixed. And filling the mixed powder into a stainless steel tube, introducing Ar gas, and sealing the stainless steel tube. The stainless steel tube was then placed in a tube furnace under Ar atmosphere for 5 deg.C min. The temperature rising rate of (1) is from room temperature to 720 ℃, and the temperature is kept for 4h and then the temperature is cooled to room temperature. Soaking the powder in the stainless steel tube in 300ml of 1mol/L hydrochloric acid solution, centrifuging and separating the precipitate after 4h, soaking the precipitate in 200ml of hydrofluoric acid solution with the mass fraction of 5% for etching for 30min, centrifuging and separating the precipitate, washing the precipitate for 3 times by using deionized water and absolute ethyl alcohol respectively, and finally drying the obtained precipitate in a vacuum oven at 80 ℃ for 6h to obtain the MHSi hollow silicon ball.
Adding 0.5ml of 28 mass percent ammonia water and 200mg of MHSi into 100ml of absolute ethyl alcohol, carrying out ultrasonic treatment for 15min, stirring the suspension in a water bath at 60 ℃ at the rotating speed of 600rpm, dropwise adding 0.45ml of tetrabutyl titanate (TBOT) into the suspension within 10min, and then adjusting the rotating speed to 400rpm and continuing stirring for 12 h. And (3) centrifugally separating the precipitate after reaction, washing the precipitate for 3 times by using absolute ethyl alcohol and deionized water respectively, and drying the precipitate in a vacuum oven at the temperature of 100 ℃ for 6 hours. The dried precipitate was placed in a crucible and placed in a tube furnace under Ar atmosphere for 30 min. Heating the mixture from room temperature to 500 ℃, 600 ℃, 700 ℃, 800 ℃ and 900 ℃, preserving the heat for 5 hours, and then cooling the mixture to room temperature to obtain the final product titanium oxide coated porous hollow silica spheres MHSi @ TiO2。
The detection proves that the capacity of the material reaches 2100mah/g, and after 50-week circulation, the capacity is still maintained at 1500 mah/g.
Comparative example 1
3g of HSiO20.8g of magnesium powder and 16g of NaCl are ground for 30min to be uniformly mixed. And filling the mixed powder into a stainless steel tube, introducing Ar gas, and sealing the stainless steel tube. The stainless steel tube was then placed in a tube furnace under Ar atmosphere for 3 min. The temperature rising rate of (1) is from room temperature to 750 ℃, and the temperature is kept for 2h and then the temperature is cooled to room temperature. Into a stainless steel pipeSoaking the powder in 180ml of 1mol/L hydrochloric acid solution, centrifugally separating the precipitate after 4h, soaking the precipitate in 100ml of 5% hydrofluoric acid solution for etching for 25min, centrifugally separating the precipitate, washing the precipitate for 3 times by using deionized water and absolute ethyl alcohol respectively, and finally drying the obtained precipitate in a vacuum oven at 80 ℃ for 5h to obtain the MHSi hollow silicon spheres.
The hollow silicon spheres are washed in absolute ethyl alcohol for 3 minutes, put into an oven for drying for 1 hour, and sieved to obtain powder with the particle size D50 of about 20 microns, and the gram volume is tested by a half cell.
The detection proves that the capacity of the composite material is only 1200mah/g, and after circulation, the capacity loss is only 500 mah/g.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (13)
1. The preparation method of the titanium oxide coated porous hollow silicon spheres is characterized by comprising the following steps:
s1, preparing hollow silica spheres containing the template agent by adopting a sol-gel method;
s2, mixing the hollow SiO2Carrying out magnesiothermic reduction on the spheres to obtain hollow silicon spheres containing the template;
s3, coating TiO on the surface of the hollow silicon ball2-xWherein x is 0-0.6, to obtain TiO2-xA coated hollow silicon sphere;
s4, calcining TiO2-xAnd coating the hollow silicon spheres to obtain the titanium oxide coated porous hollow silicon spheres.
2. The method for preparing a composite material according to claim 1, wherein the step S1 includes:
dissolving ammonia water and the template agent in a first reaction solvent to form a pre-reaction system;
adding tetraethoxysilane into the pre-reaction system to carry out a first precipitation reaction to obtain a first product system;
and aging and centrifugally separating the first product system to obtain the hollow silica spheres containing the template agent.
3. The method of claim 2, wherein the template agent is cetyltrimethylammonium bromide; preferably, the volume ratio of ammonia water to the tetraethoxysilane is 1: 1-1: 2, 0.15-0.2 g of the template agent is used for each milliliter of ammonia water, and the mass concentration of the ammonia water is 28-35%.
4. The preparation method according to claim 2 or 3, wherein the temperature of the first precipitation reaction is 30-50 ℃, and the time of the first precipitation reaction is 24-36 h; preferably, the first reaction solvent is a mixed solvent of ethanol and deionized water; preferably, the aging temperature in the aging step is 90-95 ℃.
5. The production method according to any one of claims 1 to 4, wherein the step S2 includes:
mixing the hollow silica spheres, magnesium powder and sodium chloride to obtain mixed powder;
placing the mixed powder in an inert environment for reduction reaction to obtain reduced powder;
soaking the reduced powder in a hydrochloric acid solution, and then carrying out solid-liquid separation to obtain solid powder;
and etching to remove the residual magnesium powder in the solid powder to obtain the hollow silicon ball containing the template agent.
6. The method according to claim 5, wherein in step S2, the weight ratio of the hollow silica spheres to the magnesium powder to the sodium chloride is 1: 0.8-0.9: 10-12.
7. The method of claim 5, wherein the reduction step comprises: heating the mixed powder to 680-720 ℃ in inert gas, preserving heat for 4-5 h, and then cooling to room temperature; and then soaking the cooled powder in a hydrochloric acid solution, and performing centrifugal separation to obtain the reduced powder.
8. The method according to claim 7, wherein an etchant used in the step of removing the residual magnesium powder by etching is hydrofluoric acid.
9. The production method according to any one of claims 1 to 8, wherein the step S3 includes:
adding ammonia water and the hollow silicon spheres containing the template agent into a second reaction solvent to form a suspension;
adding tetrabutyl titanate into the suspension for a second precipitation reaction to obtain a second product system;
carrying out centrifugal separation on the second product system to obtain TiO2-xAnd (3) coating the hollow silicon spheres.
10. The preparation method according to claim 9, wherein the weight ratio of ammonia water to tetrabutyl titanate is 1: 1.5-1: 2, 0.333-0.5 g of the hollow silica spheres containing the template agent is used per ml of ammonia water, and the mass concentration of the ammonia water is 28-35%.
11. The method according to any one of claims 1 to 10, wherein the TiO is calcined in step S42-xThe step of coating the hollow silicon spheres comprises: subjecting the TiO to a reaction2-xAnd heating the coated hollow silicon spheres to 500-900 ℃ in an inert atmosphere, and preserving the heat for 4-5 hours to obtain the titanium oxide coated porous hollow silicon spheres.
12. The titanium oxide-coated porous hollow silicon spheres prepared by the preparation method of any one of claims 1 to 11.
13. Use of the titanium oxide-coated porous hollow silicon spheres of claim 12 as a negative electrode material for lithium ion batteries.
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| CN113363455A (en) * | 2021-06-04 | 2021-09-07 | 广东工业大学 | Composite two-dimensional micron-sized silicon wafer and preparation method thereof |
| CN113488625A (en) * | 2021-07-08 | 2021-10-08 | 中国恩菲工程技术有限公司 | Silicon-carbon composite material and preparation method and application thereof |
| CN117239105A (en) * | 2023-11-14 | 2023-12-15 | 比亚迪股份有限公司 | Silicon anode material and preparation method thereof, anode piece, battery and electric equipment |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113363455A (en) * | 2021-06-04 | 2021-09-07 | 广东工业大学 | Composite two-dimensional micron-sized silicon wafer and preparation method thereof |
| CN113488625A (en) * | 2021-07-08 | 2021-10-08 | 中国恩菲工程技术有限公司 | Silicon-carbon composite material and preparation method and application thereof |
| CN117239105A (en) * | 2023-11-14 | 2023-12-15 | 比亚迪股份有限公司 | Silicon anode material and preparation method thereof, anode piece, battery and electric equipment |
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