CN116003132B - Monodisperse porous silica-carbon sphere material, method and battery anode material - Google Patents
Monodisperse porous silica-carbon sphere material, method and battery anode material Download PDFInfo
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 47
- 239000000463 material Substances 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000010405 anode material Substances 0.000 title claims abstract description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 73
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 42
- 239000002127 nanobelt Substances 0.000 claims abstract description 37
- 239000002243 precursor Substances 0.000 claims abstract description 21
- 229920000642 polymer Polymers 0.000 claims abstract description 20
- 239000000413 hydrolysate Substances 0.000 claims abstract description 18
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- ADKPKEZZYOUGBZ-UHFFFAOYSA-N [C].[O].[Si] Chemical compound [C].[O].[Si] ADKPKEZZYOUGBZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 27
- 235000012239 silicon dioxide Nutrition 0.000 claims description 26
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- 239000011259 mixed solution Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 17
- 238000000197 pyrolysis Methods 0.000 claims description 13
- 239000005751 Copper oxide Substances 0.000 claims description 12
- 229910000431 copper oxide Inorganic materials 0.000 claims description 12
- 229910021426 porous silicon Inorganic materials 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000003760 magnetic stirring Methods 0.000 claims description 11
- 239000012299 nitrogen atmosphere 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 8
- 230000009471 action Effects 0.000 claims description 6
- 238000006068 polycondensation reaction Methods 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 3
- 230000003301 hydrolyzing effect Effects 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 13
- 239000002077 nanosphere Substances 0.000 abstract description 8
- 238000005245 sintering Methods 0.000 abstract description 5
- 229910052681 coesite Inorganic materials 0.000 description 13
- 229910052906 cristobalite Inorganic materials 0.000 description 13
- 229910052682 stishovite Inorganic materials 0.000 description 13
- 229910052905 tridymite Inorganic materials 0.000 description 13
- 239000000047 product Substances 0.000 description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- 239000002074 nanoribbon Substances 0.000 description 6
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 3
- 238000000635 electron micrograph Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910018540 Si C Inorganic materials 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229940102396 methyl bromide Drugs 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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 application provides a monodisperse silicon-oxygen-carbon porous nanosphere material, a method and a battery anode material, wherein the method comprises the following steps: and adding the hollow silica nanobelt into the hydrolysate of the phenyl triethoxysiloxane to obtain a polymer precursor, sintering the polymer precursor at a high temperature, and cooling to obtain the porous silica carbon spheres. The preparation method of the monodisperse porous silica-carbon nanosphere material provided by the embodiment of the application is simple, and the monodisperse porous silica-carbon nanosphere material can be obtained, is used for a lithium ion battery anode material, and has good electrochemical performance.
Description
Technical Field
The application relates to the field of lithium electronic battery material preparation, in particular to a monodisperse porous silica-carbon sphere material, a method and a battery cathode material.
Background
To meet the ever-increasing battery demands of modern lifestyles, it is a very difficult task for researchers to study high performance batteries. For example, in applications such as electric vehicles and green grids, batteries are required to have high performance indicators such as high energy and power density, long cycle life, and good safety. However, the theoretical specific capacity of the commercial graphite anode material widely used at present is only 372mAh/g, and the commercial graphite anode material cannot meet the wider requirements of the modern society. Therefore, the search for alternative anode materials with higher specific capacities is a key place for further popularization of new energy automobiles.
As one branch of high-capacity anode materials, silicon-based anode materials such as elemental silicon, silicon alloys, and silicon oxides have received considerable attention due to their high specific capacity and good safety properties. Among these materials, elemental silicon has a very high theoretical specific capacity of 4200mAh/g. However, elemental silicon anode materials have a fatal disadvantage in that excessive volume expansion (> 300%) occurs during the lithium storage alloying reaction, which results in particularly poor cycle performance. In addition, amorphous silicon is also poor in electrical conductivity, so that the preparation of various silicon/carbon composite materials is becoming a hot spot of current research. However, these composites have low reversible capacity due to the presence of carbon in an amount that serves as a conductive additive and volume buffer. And because the material still can generate serious volume expansion and pulverization in the circulating process, the mechanical structure of the active material is collapsed, and the rapid reduction of the material capacity is more easily caused.
Disclosure of Invention
In view of the above, the application provides a monodisperse porous silica-carbon sphere material, a method and a battery anode material, and the porous silica-carbon sphere prepared by the method has the characteristics of smaller size, open micropore structure and the like, and shows good electrochemical performance as the lithium ion battery anode material.
Some embodiments of the application provide a method for preparing monodisperse silicon-oxygen-carbon porous nanospheres. The application is described in terms of several aspects, embodiments and advantages of which can be referenced to one another.
In a first aspect, the present application provides a monodisperse porous silica-carbon sphere comprising: and adding the hollow silica nanobelt into the hydrolysate of the phenyl triethoxysiloxane to obtain a polymer precursor, sintering the polymer precursor at a high temperature, and cooling to obtain the porous silica carbon spheres.
As an embodiment of the first aspect, the preparation method includes: s1, adding phenyl triethoxysiloxane into a first mixed solution containing a hydrochloric acid solution with a first concentration, deionized water and ethanol, and stirring to obtain a hydrolysate of the phenyl triethoxysiloxane;
s2, uniformly dispersing the hollow porous silicon dioxide nano-belt in a second mixed solution containing ammonia water and deionized water, adding the hydrolysate of the phenyl triethoxysiloxane into the second mixed solution under magnetic stirring, and continuing stirring at room temperature to obtain a polymer precursor;
and S3, washing the polymer precursor with deionized water and ethanol, centrifugally separating, drying, placing in a nitrogen atmosphere, heating for pyrolysis, and cooling to room temperature to obtain the porous silica-carbon spheres.
According to the preparation method of the monodisperse porous silica-carbon spheres, the prepared porous silica-carbon spheres have the characteristics of smaller size, open micropore structure and the like, and the porous silica-carbon spheres are used as anode materials of lithium ion batteries and have good electrochemical performance.
As an example of the first aspect, the first mixed solution contains 0.5mL of a hydrochloric acid solution with a first concentration, 1.1mL of deionized water and 4mL of ethanol, and the volume of the phenyltriethoxysiloxane is 0.8mL.
As an embodiment of the first aspect, the method for preparing the hollow porous silica nanoribbon includes:
s21, taking a copper oxide nano-belt as a template, and performing hydrolytic polycondensation on tetraethyl orthosilicate under the action of a surfactant to obtain a porous silicon dioxide layer which is deposited on the surface of the copper oxide nano-belt;
s22, placing the copper oxide nano-belt deposited with the porous silicon dioxide layer into a hydrochloric acid solution with a second concentration, stirring, and removing the copper oxide template to obtain the hollow porous silicon dioxide nano-belt.
The method can prepare the hollow porous silica nanobelt to prevent agglomeration phenomenon during high-temperature sintering of the silica carbon material, thereby preparing the monodisperse nano/microsphere silica carbon material.
As an example of the first aspect, the concentration of the hydrochloric acid solution of the first concentration in S1 is 0.01mol/L.
As an example of the first aspect, in S22, the concentration of the second concentration hydrochloric acid solution is 1mol/L.
As an example of the first aspect, in S3, the temperature of the thermal pyrolysis is 850 to 950 ℃ and the temperature rate of the thermal pyrolysis is 5C/min in a nitrogen atmosphere.
As an example of the first aspect, the concentration of the aqueous ammonia is 28wt%.
In a second aspect, the present application provides a monodisperse porous silica-carbon sphere material, which is prepared by the preparation method of the embodiment of the first aspect, wherein the diameter of the silica-carbon porous nanosphere is between 50 and 200 nanometers, and an open pore structure is formed on the surface of the silica-carbon porous nanosphere. The porous silicon-oxygen-carbon sphere shows good electrochemical performance as a lithium ion battery cathode material.
In a third aspect, the application provides a lithium ion battery anode material, which comprises the monodisperse porous silica-carbon sphere material in the second aspect.
Drawings
FIG. 1 is a flow chart of a method of preparing monodisperse porous silica-carbon spheres according to an embodiment of the application;
FIG. 2 is a flow chart of a method of preparing a hollow porous silica nanoribbon according to one embodiment of the application;
FIG. 3 is an electron microscope image of a CuO nanoribbon deposited with a SiO2 layer according to an embodiment of the present application;
FIG. 4 is an electron microscope image of a hollow porous SiO2 nanoribbon according to an embodiment of the application;
FIG. 5 is an electron microscope image of monodisperse porous silica-carbon spheres at different scale in accordance with one embodiment of the application;
FIG. 6 is an electron micrograph of a conventional SiOC material.
Detailed Description
The following description of the embodiments of the present application will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are some, but not all embodiments of the application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
In order to facilitate understanding of the present application, first, the technical problem to be solved by the present application will be described.
As a ceramic material of a novel structure, silicon oxygen carbon (SiOC) has good thermal stability, superior chemical properties and mechanical properties. Amorphous SiOC materials are typically prepared by pyrolysis of polymer precursors from siloxane transformations. The material consists of SiOC glass phase and free carbon (Cfree), and its chemical formula can be expressed as SiO 2(1-x) C x +yC free (0 < x < 1). And the material has an open micropore network structure, and can provide a shorter path for ion diffusion and electron conduction. SiOC network is composed of silicon-centered tetrahedral SiO 4-x C x (x=1-4) structural units consisting essentially of Si-O bonds and Si-C bonds randomly distributed.
SiOC has higher reversible specific capacity (generally 500-900 mAh/g) as a lithium ion battery anode material. Typically, the lithium storage properties of SiOC materials are related to factors such as chemical composition, microstructure, conductivity, particle size, morphology, and microporous structure. The free carbon content in the microstructure depends mainly on the kind of siloxane reagent in the raw material, the composition and structure of the carbon source-rich polymer precursor, and the temperature and atmosphere of pyrolysis, among other things. SiOC materials obtained by pyrolysis at high temperatures are generally large-sized bulk bodies, since severe sintering of the polymer precursor occurs during heating. The electrochemical properties of such materials are not very good.
In order to solve the technical problems, the application discloses a preparation method of monodisperse porous silica-carbon spheres, which is used for preparing a monodisperse porous nano/microsphere SiOC material (porous silica-carbon spheres), wherein the porous silica-carbon spheres material has excellent lithium storage performance.
The method for preparing the monodisperse porous silica carbon spheres according to the embodiment of the application is described below with reference to the accompanying drawings.
It should be noted that the source of the raw materials not mentioned in the present application may be commercially available or prepared by a conventional method, and the present application is not limited thereto.
A flow chart of a method of preparing monodisperse porous silica-carbon spheres as in fig. 1. The method comprises S1-S3.
S1, adding phenyl triethoxysiloxane (Phenyl triethoxysilane, phTES) into a first mixed solution containing a first concentration hydrochloric acid (HCl) solution, deionized water and ethanol, and stirring to obtain a hydrolysate of the phenyl triethoxysiloxane.
Wherein the concentration of the first concentration of HCl solution is low to ensure that the PhTES remains in a weak acid environment when hydrolyzed. For example, it may be less than 0.1mol/L, for example, 0.01mol/L, 0.05mol/L, or 0.1mol/L.
In one embodiment of the application, 0.8mL of phenyl triethoxysiloxane is added to a mixed solution containing 0.5mL of HCl solution, 1.1mL of deionized water, and 4mL of ethanol under magnetic stirring, and stirred at room temperature for 7h to yield a hydrolysate of PhTES, e.g., an ethoxy-containing silicone oligomer.
S2, uniformly dispersing the hollow porous silica nano-belt in a second mixed solution containing ammonia water and deionized water, adding a hydrolysate of phenyl triethoxysiloxane into the second mixed solution under magnetic stirring, and continuously stirring at room temperature to obtain a polymer precursor.
In one embodiment of the application, 40mg of hollow porous SiO is used 2 The nanoribbon was uniformly dispersed in a mixed solution of 0.5mL ammonia water and 14mL deionized water. The hydrolysate of PhTES in step S1, e.g. a sol of PhTES, is added rapidly to the mixed solution under magnetic stirring and stirring is continued for 48h at room temperature to obtain a polymer precursor of the hydrolysate of PhTES.
The concentration of the ammonia water may be, for example, about 28wt% of the concentration of the ordinary reagent-grade ammonia water.
In one embodiment of the present application, a method for preparing a hollow porous silica nanoribbon is shown with reference to fig. 2, and as shown in fig. 2, the method includes S21 to S22.
S21, taking a copper oxide (CuO) nano-belt as a template, and performing hydrolytic polycondensation on tetraethyl orthosilicate (Tetraethyl orthosilicate, TEOS) under the action of a surfactant to obtain a porous silicon dioxide layer deposited on the surface of the copper oxide nano-belt.
Wherein, the surfactant can be cetyl trimethyl ammonium bromide (Sixteen alkyl three methyl bromide, CTMAB), which can improve the activity of the surface of the CuO nano-belt and is favorable for depositing a silicon dioxide layer on the surface of the CuO nano-belt.
S22, placing the copper oxide nano-belt deposited with the porous silicon dioxide layer into a hydrochloric acid solution with a second concentration, stirring, and removing the copper oxide template to obtain the hollow porous silicon dioxide nano-belt.
In one embodiment of the present application, the second concentration of hydrochloric acid solution is 0.5mol/L to 3mol/L, for example, 0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L, 3mol/L, etc., which can effectively remove the CuO template.
In one embodiment of the application, the copper oxide nanobelt deposited with the porous silicon dioxide layer is stirred in 1M HCl solution for reaction for 1h, and CuO template is removed to obtain hollow porous SiO 2 A nanobelt.
In S3, washing the polymer precursor with deionized water and ethanol, centrifugally separating, drying, placing in a nitrogen atmosphere, heating for pyrolysis, and cooling to room temperature to obtain the porous silica-carbon spheres.
Wherein the temperature of the heating pyrolysis in the nitrogen atmosphere is 850-950 ℃, preferably 900 ℃. In the nitrogen atmosphere, the polymer precursor can be better pyrolyzed into silicon-oxygen-carbon, so that the oxidation of the product is avoided, and the yield of the product is influenced. Meanwhile, in the application, the temperature rising rate is 5 ℃/min, which is more beneficial to the efficient pyrolysis of the polymer precursor into the silicon-oxygen-carbon.
According to the preparation method of the monodisperse porous silica-carbon spheres, the preparation process is simple, phenyl triethoxy siloxane and tetraethyl orthosilicate are used as raw materials, phTES hydrolysis-polycondensation reaction is utilized to prepare a polymer precursor, and then SiOC material is prepared through high-temperature pyrolysis. The hollow porous silica (SiO 2) nanobelt is introduced into the precursor to prevent the agglomeration phenomenon during high-temperature sintering of the SiOC material, so that the monodisperse porous silica-carbon sphere material is obtained. The porous silica-carbon sphere has an open porous structure, the diameter is 50-200 nanometers, and the specific surface area is large. Compared with the massive SiOC material obtained by the traditional preparation method, the SiOC ball material can limit the volume expansion in the lithium storage process, has higher conductivity, and effectively improves the lithium storage performance of the SiOC material.
In addition, the application also discloses a lithium ion battery anode material, which comprises the monodisperse porous silica-carbon sphere material prepared by the preparation method shown in figure 1. The material has higher conductivity, and effectively improves the lithium storage performance of SiOC materials.
The method for preparing the monodisperse porous silica carbon spheres according to the embodiment of the present application will be further described with reference to specific examples.
Example 1
(1) Adding 0.8mL of phenyl triethoxysiloxane into a mixed solution containing 0.5mL of 0.01M HCl solution, 1.1mL of deionized water and 4mL of ethanol under magnetic stirring, and stirring at room temperature for 7h to obtain a hydrolysate of PhTES;
(2) The porous SiO2 layer is deposited on the surface of the CuO nanobelt by hydrolysis and polycondensation of tetraethyl orthosilicate by taking the CuO nanobelt as a template and cetyl trimethyl ammonium bromide as a surfactant, and referring to FIG. 3, FIG. 3 shows an electron microscope image of the CuO nanobelt deposited with the SiO2 layer. Then, placing the CuO nanobelt deposited with the porous SiO2 layer into a 1M HCl solution for stirring reaction for 1h; and removing the CuO template to obtain the hollow porous SiO2 nanobelt, wherein the hollow porous SiO2 nanobelt is shown in FIG. 3, and an electron microscope image of the hollow porous SiO2 nanobelt is shown in FIG. 4.
(3) Uniformly dispersing 40mg of prepared SiO2 nanobelts in 0.5mL of a mixed solution of 28wt% ammonia water and 14mL of deionized water, quickly adding the hydrolysate (sol) of PhTES prepared in the step (1) into the mixed solution under magnetic stirring, continuing stirring at room temperature for 48 hours to obtain a product (polymer precursor), washing the product with deionized water and ethanol, centrifugally separating, drying, placing the dried product in a nitrogen atmosphere, heating to 900 ℃ at a heating rate of 5 ℃/min, pyrolyzing for 2 hours, and cooling to room temperature to obtain the monodisperse porous silica-carbon spheres.
Referring to fig. 5, fig. 5 shows electron microscopy images of monodisperse porous silica-carbon spheres at different size ratios. As shown in fig. 5, spherical silica carbon spheres were observed at a ratio of 1 micron to 0.5 micron, and surface porosity was observed at a ratio of 0.5 micron.
Example 2
(1) Adding 0.8mL of phenyl triethoxysiloxane into a mixed solution containing 0.5mL of 0.05M HCl solution, 1.1mL of deionized water and 4mL of ethanol under magnetic stirring, and stirring at room temperature for 7h to obtain a hydrolysate of PhTES;
(2) The porous SiO2 layer is deposited on the surface of the CuO nanobelt by hydrolysis and polycondensation of tetraethyl orthosilicate by taking the CuO nanobelt as a template and cetyl trimethyl ammonium bromide as a surfactant. Then, placing the CuO nanobelt deposited with the porous SiO2 layer into a 1M HCl solution for stirring reaction for 1h; and removing the CuO template to obtain the hollow porous SiO2 nanobelt.
(3) Uniformly dispersing 40mg of prepared SiO2 nanobelts in 0.5mL of a mixed solution of 28wt% ammonia water and 14mL of deionized water, quickly adding the hydrolysate (sol) of PhTES prepared in the step (1) into the mixed solution under magnetic stirring, continuing stirring at room temperature for 48 hours to obtain a product (polymer precursor), washing the product with deionized water and ethanol, centrifugally separating, drying, placing the dried product in a nitrogen atmosphere, heating to 950 ℃ at a heating rate of 5 ℃/min, pyrolyzing for 2 hours, and cooling to room temperature to obtain the monodisperse porous silica-carbon spheres.
When the monodisperse porous silica carbon sphere material is subjected to multiplying power test, the highest charge reversible capacity can reach 901.2mAh/g at a current density of 100mA/g, and the initial capacity is 819.1mAh/g when the material is subjected to long-time circulation at the current density, and the capacity is still kept at 804.6mAh/g after 100 times of circulation (the capacity retention rate is 98.2%). The SiOC ball prepared by the application has higher lithium storage activity, can slow down volume expansion in the charge-discharge cycle process, improves the stability of the material in the long-cycle process, and can be effectively applied to the field of lithium ion batteries, in particular to the field of power batteries.
Comparative example: ordinary silicon-oxygen-carbon material and preparation method thereof
(1) To a mixed solution containing 0.5mL of 0.01M HCl solution, 1.1mL of deionized water and 4mL of ethanol, 0.8mL of PhTES (phenyltriethoxysiloxane) was added under magnetic stirring, and stirred at room temperature for 7 hours, to obtain a hydrolysate of PhTES.
(2) After obtaining the hydrolysate of PhTES, the hydrolysate (sol) was rapidly added to a mixed solution containing 0.5mL of aqueous ammonia (28 wt%) and 14mL of deionized water under magnetic stirring, and stirring was continued at room temperature for 48 hours to obtain the product, which was then washed with deionized water and ethanol, centrifuged, and dried. And finally, heating the dried product (polymer precursor) to 900 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere, pyrolyzing for 2 hours, and cooling to room temperature to obtain the silicon-oxygen-carbon material.
An electron micrograph of a conventional SiOC material is shown in FIG. 6. The SiOC material has a large block structure, and the volume of the SiOC material is far greater than that of the monodisperse porous silica-carbon spheres shown in FIG. 5. Obviously, the specific surface area of the porous silica-carbon sphere is far larger than that of the silica-carbon material prepared by the traditional common method.
It should be noted that in the examples and descriptions of this patent, relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.
While the application has been shown and described with reference to certain preferred embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the application.
Claims (6)
1. A method for preparing monodisperse porous silica-carbon spheres, wherein the diameter of the monodisperse porous silica-carbon spheres is 50-200 nm, and an open pore structure is formed on the surface of the porous silica-carbon spheres, the method comprising:
s1, adding phenyl triethoxysiloxane into a first mixed solution containing a first concentration hydrochloric acid solution, deionized water and ethanol, and stirring to obtain a hydrolysate of the phenyl triethoxysiloxane, wherein the concentration of the first concentration hydrochloric acid solution is less than 0.1mol/L;
s2, uniformly dispersing the hollow porous silicon dioxide nano-belt in a second mixed solution containing ammonia water and deionized water, adding the hydrolysate of the phenyl triethoxysiloxane into the second mixed solution under magnetic stirring, and continuing stirring at room temperature to obtain a polymer precursor;
s3, washing the polymer precursor with deionized water and ethanol, centrifugally separating, drying, placing in a nitrogen atmosphere, heating for pyrolysis, and cooling to room temperature to obtain the porous silica-carbon spheres;
the preparation method of the hollow porous silica nanobelt comprises the following steps:
s21, taking a copper oxide nano-belt as a template, and performing hydrolytic polycondensation on tetraethyl orthosilicate under the action of a surfactant to obtain a porous silicon dioxide layer which is deposited on the surface of the copper oxide nano-belt;
s22, placing the copper oxide nanobelt deposited with the porous silicon dioxide layer into a hydrochloric acid solution with a second concentration, stirring, and removing the copper oxide template to obtain the hollow porous silicon dioxide nanobelt, wherein the concentration of the hydrochloric acid solution with the second concentration is 0.5mol/L-3 mol/L.
2. The method according to claim 1, wherein the first mixed solution contains 0.5mL of the first concentration hydrochloric acid solution, 1.1mL of deionized water and 4mL of ethanol, and the volume of the phenyltriethoxysiloxane is 0.8mL.
3. The preparation method according to claim 1, wherein in S3, the temperature of the thermal pyrolysis is 850-950 ℃ in a nitrogen atmosphere, and the temperature rising rate during the thermal pyrolysis is 5 ℃.
4. A method of producing according to claim 3, wherein the concentration of the aqueous ammonia is 28wt%.
5. A monodisperse porous silicon-oxygen-carbon sphere material, characterized in that the material is prepared by the preparation method of any one of claims 1 to 4, the diameter of the porous silicon-oxygen-carbon sphere is 50-200 nanometers, and an open pore structure is formed on the surface of the porous silicon-oxygen-carbon sphere.
6. A lithium ion battery anode material comprising the monodisperse porous silicon-oxygen-carbon sphere material of claim 5.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20080061551A (en) * | 2006-12-28 | 2008-07-03 | 연세대학교 산학협력단 | Hydrophobicity control process of silica particle using trialkoxysilane comprising alkyl group, alkenyl group, or alkynyl group and silica particle thereby |
| CN104319402A (en) * | 2014-10-28 | 2015-01-28 | 上海交通大学 | Preparation method for multi-layer carbon hollow sphere anode material |
| CN106552614A (en) * | 2015-09-29 | 2017-04-05 | 云南民族大学 | The preparation method of hydrophobicity titanium dioxide/mesoporous silicon core shell composite photo-catalyst |
| JP2018052787A (en) * | 2016-09-30 | 2018-04-05 | Ｊｘｔｇエネルギー株式会社 | A hollow silica particle internally containing molybdenum oxide nanoparticles, a process for producing the same, and a catalyst containing the same |
| CN113461045A (en) * | 2021-07-05 | 2021-10-01 | 福建宸润生物科技有限公司 | Method for preparing virus-like hollow mesoporous copper oxide nanoparticles |
| CN114057488A (en) * | 2022-01-17 | 2022-02-18 | 河南科技学院 | Preparation method of porous SiOC ceramic and application of porous SiOC ceramic in negative electrode material of lithium ion battery |
-
2022
- 2022-12-29 CN CN202211712865.1A patent/CN116003132B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20080061551A (en) * | 2006-12-28 | 2008-07-03 | 연세대학교 산학협력단 | Hydrophobicity control process of silica particle using trialkoxysilane comprising alkyl group, alkenyl group, or alkynyl group and silica particle thereby |
| CN104319402A (en) * | 2014-10-28 | 2015-01-28 | 上海交通大学 | Preparation method for multi-layer carbon hollow sphere anode material |
| CN106552614A (en) * | 2015-09-29 | 2017-04-05 | 云南民族大学 | The preparation method of hydrophobicity titanium dioxide/mesoporous silicon core shell composite photo-catalyst |
| JP2018052787A (en) * | 2016-09-30 | 2018-04-05 | Ｊｘｔｇエネルギー株式会社 | A hollow silica particle internally containing molybdenum oxide nanoparticles, a process for producing the same, and a catalyst containing the same |
| CN113461045A (en) * | 2021-07-05 | 2021-10-01 | 福建宸润生物科技有限公司 | Method for preparing virus-like hollow mesoporous copper oxide nanoparticles |
| CN114057488A (en) * | 2022-01-17 | 2022-02-18 | 河南科技学院 | Preparation method of porous SiOC ceramic and application of porous SiOC ceramic in negative electrode material of lithium ion battery |
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