CN110336003B - Porous silicon-based composite material and preparation method and application thereof - Google Patents
Porous silicon-based composite material and preparation method and application thereof Download PDFInfo
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- 229910021426 porous silicon Inorganic materials 0.000 title claims abstract description 61
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 10
- 239000002105 nanoparticle Substances 0.000 claims abstract description 9
- 239000011148 porous material Substances 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 20
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 19
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 239000007795 chemical reaction product Substances 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000003638 chemical reducing agent Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 239000006227 byproduct Substances 0.000 claims description 6
- 238000005530 etching Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000007773 negative electrode material Substances 0.000 claims description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 229910001626 barium chloride Inorganic materials 0.000 claims description 2
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 12
- 239000010703 silicon Substances 0.000 abstract description 10
- 229910052710 silicon Inorganic materials 0.000 abstract description 8
- 239000010406 cathode material Substances 0.000 abstract description 6
- 239000002210 silicon-based material Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 230000022131 cell cycle Effects 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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
-
- 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
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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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
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- Composite Materials (AREA)
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- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Silicon Compounds (AREA)
Abstract
The invention discloses a porous silicon-based composite material and preparation and application thereof. The porous silicon-based composite material is composed of a porous silicon network framework, and silicon nanoparticles and amorphous SiO supported on the porous silicon network frameworkxThe particle size of the porous silicon network skeleton is 2-50 μm, the pore diameter is 10-500 nm, the particle size of the silicon nanoparticles is 1-100 nm, and SiO is addedxThe particle diameter of the nano particles is 1-100 nm and 0<x is less than or equal to 2. The invention provides application of the porous silicon-based composite material as a lithium ion battery cathode material, and when the porous silicon-based composite material is applied to the lithium ion battery cathode material, the cycle stability of a silicon-based cathode can be obviously improved.
Description
Technical Field
The invention relates to the field of lithium ion battery cathode materials, in particular to a porous silicon-based composite material and a preparation method and application thereof.
Background
Emerging markets such as electric vehicles and plug-in hybrid vehicles have generated a tremendous demand for high energy density, long cycle life, and low cost lithium ion batteries. Graphite is the most commonly used negative electrode material for commercial lithium ion batteries due to its lower theoretical capacity (372mAh g)-1) And cannot meet the performance requirements of high energy density. Therefore, silicon has an extremely high theoretical capacity (4200mAh g)-1) And a relatively low charge-discharge potential (<0.5Vvs.Li/Li+) And the lithium ion battery has gained wide attention and is considered to be one of the most promising next-generation lithium ion battery cathode materials. However, the large volume change during lithium intercalation: (>300%) can lead to cracking, dusting, flaking off of the silicon material, and ultimately to capacity fade.
In order to overcome the problem of poor cycling stability of silicon-based negative electrodes, porous silicon materials are generally used to improve their lithium storage properties. Because of the multipleAbundant pore channels in the pore silicon structure can effectively relieve stress generated by volume expansion of silicon, so that the circulation stability is improved; moreover, the larger specific surface area is also beneficial to better infiltrating the active material by the electrolyte, and the diffusion distance of lithium ions is shortened, so that excellent rate performance is obtained. Many magnesiothermic reduction methods have been reported as a common preparation method of porous silicon, but the magnesiothermic reduction methods reported in the literature or patents generally have the problems of low yield, complicated method and the like, and need to use a strong corrosive acid solution such as hydrofluoric acid and the like, which has certain dangerousness. CN102259858A discloses a method for preparing porous silicon by magnesiothermic reduction, which uses oxide SiO of siliconx(x is 0.5-2) is taken as a raw material, a mixture of silicon and magnesium oxide is generated through a magnesiothermic reduction reaction, then the magnesium oxide is selectively dissolved by using acid, and finally the self-supporting porous silicon material is obtained, wherein a scanning electron microscope image shows that the product has a nano porous structure and uniform pore size distribution; and XRD diffraction spectrum analysis of the material shows that the product with the nano porous structure consists of cubic phase nano silicon crystals. Although the preparation method of the porous silicon reduces the cost and improves the yield, and the preparation method is simple in preparation process, environment-friendly, high in preparation efficiency and good in repeatability, the prepared porous silicon material is used as a lithium ion battery cathode material, and the cycle stability of the prepared porous silicon material still needs to be improved.
Disclosure of Invention
The first purpose of the invention is to provide a porous silicon-based composite material, and the porous silicon skeleton of the porous silicon-based composite material is loaded with silicon nano-particles and amorphous SiOx(0<x is less than or equal to 2) nano particles.
The second purpose of the invention is to provide a preparation method of the porous silicon-based composite material, which is environment-friendly, simple to operate and high in yield.
The third purpose of the invention is to provide the application of the porous silicon-based composite material as the negative electrode material of the lithium ion battery, and the cycle stability of the silicon-based negative electrode is greatly improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides aThe porous silicon-based composite material is composed of a porous silicon network skeleton, and silicon nanoparticles and amorphous SiO supported on the porous silicon network skeletonxThe particle size of the porous silicon network skeleton is 2-50 μm, the pore diameter is 10-500 nm, the particle size of the silicon nanoparticles is 1-100 nm, and SiO is addedxThe particle diameter of the nano particles is 1-100 nm and 0<x≤2。
In a second aspect, the invention provides a preparation method of a porous silicon-based composite material, which comprises the following steps:
1) mixing SiOy(0<y is less than or equal to 2), and uniformly mixing the metal powder reducing agent and the molten salt according to the molar ratio of 1: 0.1-5: 0.1-10 to obtain a mixture; the SiOyMiddle, 0<y is less than or equal to 2, and the metal powder reducing agent is magnesium powder or aluminum powder;
2) transferring the mixture obtained in the step 1) to a tubular furnace, heating to 400-1000 ℃ under the protection of inert atmosphere, reacting for 0.2-12 hours, and cooling to room temperature to obtain a reaction product;
3) and (3) placing the reaction product in an aqueous solution of 0.1-10 mol/L acid for etching to remove reaction byproducts, wherein the acid is any one or a mixture of any more of hydrochloric acid, sulfuric acid, nitric acid, acetic acid and oxalic acid, and centrifuging, washing and drying to obtain the porous silicon-based composite material.
In the present invention, the SiOyIs any one or a mixture of silicon monoxide, silicon dioxide and non-stoichiometric silicon oxide.
In the invention, the molten salt is preferably NaCl, KCl or MgCl2、CaCl2、BaCl2、AlCl3Any one or a mixture of several of them in any proportion.
In the present invention, the SiOyThe mixing molar ratio of the metal powder reducing agent to the molten salt is preferably 1: 0.5-5: 5-10, and most preferably 1:1: 10.
In the step 2), the reaction temperature is preferably 600-800 ℃, and the reaction time is 2-8 hours; the reaction temperature is most preferably 700 ℃ and the reaction time is 5 h.
In step 2) of the present invention, the inert atmosphere is preferably argon, nitrogen or a mixture of argon and nitrogen in any proportion.
In a third aspect, the invention provides an application of the porous silicon-based composite material as a negative electrode material of a lithium ion battery. When the porous silicon-based composite material is applied to a lithium ion battery cathode material, the cycle stability of a silicon-based cathode can be remarkably improved.
Compared with the prior art, the invention has the beneficial effects that:
the preparation method of the porous silicon-based composite material unexpectedly loads silicon nanoparticles and amorphous SiO on a porous silicon frameworkxThe nano particles not only have higher yield, but also can obviously improve the cycling stability of the silicon-based negative electrode when being used as a negative electrode material of a lithium ion battery, and have excellent rate performance.
Drawings
Fig. 1 is an XRD pattern of the porous silicon-based composite material in example 1.
FIG. 2 is a TEM image of the porous silicon-based composite material of example 1.
Fig. 3 is a graph of the cell cycle performance of the porous silicon-based composite material of example 1.
Fig. 4 is a battery rate performance graph of the porous silicon-based composite material of example 1.
Fig. 5 is a graph of the cell cycle performance of the porous silicon-based composite material of example 2.
Fig. 6 is a graph of the cell cycle performance of the porous silicon-based composite material of example 3.
Fig. 7 is a graph of cell cycle performance for the porous silicon-based composite material of comparative example 1.
Fig. 8 is an SEM image of the porous silicon material prepared in comparative example 2.
Fig. 9 is a graph showing the battery cycle performance of the porous silicon material prepared in comparative example 2.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples, but the scope of the present invention is not limited thereto:
example 1:
(1) preparation of porous silicon-based composite material
Mixing SiOy(y is approximately equal to 1), uniformly mixing the precursor, the metal powder Mg and the molten salt NaCl according to the molar ratio of 1:1: 10; transferring the mixture to a tubular furnace, heating to 700 ℃ under the protection of inert atmosphere, reacting for 5 hours, and cooling to room temperature to obtain a reaction product; and placing the reaction product in 1mol/L hydrochloric acid solution for etching to remove reaction byproducts, and centrifuging, washing and vacuum drying at 80 ℃ to obtain the porous silicon-based composite material.
(2) Preparation of electrode sheet
Mixing the obtained porous silicon-based composite material, acetylene black and CMC binder according to a weight ratio of 7:1.5:1.5, preparing slurry, coating the slurry on a copper foil current collector, and drying at 60 ℃ for 10 hours under a vacuum condition to obtain the electrode slice. Using a metal lithium sheet as a counter electrode and using 1M LiPF6EC/DEC (V)EC:VDEC1:1) solution as electrolyte, to assemble a button cell. And carrying out charge-discharge cycle tests on the assembled lithium ion battery at different current densities within a voltage range of 0.01-1.0V.
FIG. 1 is an XRD spectrum of the porous silicon-based composite material obtained in this example, from which it can be seen that the broad peak corresponds to amorphous SiOxThe crystalline silicon peaks correspond to the silicon standard cards. FIG. 2 is a TEM image of the porous silicon-based composite material obtained in this example, and it can be observed that a plurality of nanoparticles are supported on the network skeleton of the porous silicon, wherein the nanoparticles can be observed in the silicon nanoparticle crystal particlesInterplanar spacing of (A), amorphous SiOxNo lattice fringes were observed for the nanoparticles. FIGS. 3 and 4 are graphs of cell performance of the resulting porous silicon-based composite material in this example, showing excellent cycling stability and rate performance at 4Ag-1Can still maintain 958mAh g at 500 weeks-1The reversible capacity of (a).
Example 2:
mixing SiOy(y is approximately equal to 2) precursor, metal powder Al and molten salt AlCl3Uniformly mixing according to the molar ratio of 1:5: 8; transferring the mixture into a tubular furnace, heating to 650 ℃ under the protection of inert atmosphere, reacting for 3 hours, and cooling to room temperature to obtain a reaction product; and placing the reaction product in a 0.1mol/L sulfuric acid solution for etching to remove reaction byproducts, and centrifuging, washing and drying in vacuum at 100 ℃ to obtain the porous silicon-based composite material.
An electrode, an assembled battery, and a charge-discharge cycle test were prepared as in example 1.
Example 3:
mixing SiOy(y is approximately equal to 1.5) uniformly mixing the precursor, the metal powder Mg and the molten salt KCl according to the molar ratio of 1:2: 7; transferring the mixture to a tubular furnace, heating to 500 ℃ under the protection of inert atmosphere, reacting for 3 hours, and cooling to room temperature to obtain a reaction product; and placing the reaction product in a 2mol/L nitric acid solution for etching to remove reaction byproducts, and centrifuging, washing and vacuum drying at 90 ℃ to obtain the porous silicon-based composite material.
An electrode, an assembled battery, and a charge-discharge cycle test were prepared as in example 1.
Comparative example 1:
mixing SiOy(y is approximately equal to 0.7) uniformly mixing the precursor and the metal powder Mg according to the molar ratio of 1: 0.1; transferring the mixture to a tubular furnace, heating to 800 ℃ under the protection of inert atmosphere, reacting for 0.2 hour, and cooling to room temperature to obtain a reaction product; and placing the reaction product in 10mol/L acetic acid solution for etching to remove reaction byproducts, and centrifuging, washing and vacuum drying at 90 ℃ to obtain the porous silicon-based composite material.
An electrode, an assembled battery, and a charge-discharge cycle test were prepared as in example 1.
Comparative example 2
Porous silicon was prepared according to CN102259858A example 1:
(1) SiO powder and magnesium powder are mixed according to a molar ratio of 1:1, uniformly mixing under the protection of argon, putting the mixture into a tubular atmosphere furnace, heating the mixture to 500 ℃ in argon flow, reacting the mixture for 6 hours at constant temperature, and naturally cooling the mixture to room temperature;
(2) and (3) placing the obtained product in hydrochloric acid with the concentration of 0.1mol/L for fully soaking for 24 hours, removing magnesium oxide, filtering to obtain a solid product, fully cleaning by deionized water, fully cleaning by absolute ethyl alcohol, and drying to obtain porous silicon powder.
An electrode, an assembled battery, and a charge-discharge cycle test were prepared as in example 1.
Fig. 8 is an SEM image of the porous silicon material prepared in this comparative example, and it can be found that the sample is a porous silicon network skeleton, and the surface thereof has no nano-particle loading. Fig. 9 is a graph showing the cell performance of the porous silicon material prepared in this comparative example, and it can be found that the capacity fade is fast.
The foregoing is a detailed description of the present invention with reference to preferred embodiments, but it should not be construed that the present invention is limited to the embodiments. It will be apparent to those skilled in the art to which the invention pertains that numerous modifications and alterations can be made without departing from the spirit of the invention, and such modifications and alterations are intended to be included within the scope of the invention as defined in the appended claims.
Claims (9)
1. A porous silicon-based composite material is prepared from a porous silicon network skeleton, and silicon nanoparticles and amorphous SiO supported on the skeletonxThe particle size of the porous silicon network skeleton is 2-50 μm, the pore diameter is 10-500 nm, the particle size of the silicon nanoparticles is 1-100 nm, and SiO is addedxThe particle diameter of the nano particles is 1-100 nm and 0<x is less than or equal to 2; the preparation method comprises the following steps:
1) mixing SiOyUniformly mixing the metal powder reducing agent and the molten salt according to a molar ratio of 1: 0.1-5: 0.1-10 to obtain a mixture; the SiOyMiddle, 0<y is less than or equal to 2, and the metal powder reducing agent is magnesium powder or aluminum powder;
2) transferring the mixture obtained in the step 1) to a tubular furnace, heating to 400-1000 ℃ under the protection of inert atmosphere, reacting for 0.2-12 hours, and cooling to room temperature to obtain a reaction product;
3) and (3) placing the reaction product in an aqueous solution of 0.1-10 mol/L acid for etching to remove reaction byproducts, wherein the acid is any one or a mixture of any more of hydrochloric acid, sulfuric acid, nitric acid, acetic acid and oxalic acid, and centrifuging, washing and drying to obtain the porous silicon-based composite material.
2. The method of claim 1, wherein: the SiOyIs any one or a mixture of silicon monoxide, silicon dioxide and non-stoichiometric silicon oxide.
3. The method of claim 1, wherein: the molten salt is NaCl, KCl and MgCl2、CaCl2、BaCl2、AlCl3Any one or a mixture of several of them in any proportion.
4. The method according to any one of claims 1 to 3, wherein: the SiOyAnd the mixing molar ratio of the metal powder reducing agent to the molten salt is 1: 0.5-5: 5-10.
5. The method of claim 4, wherein: the SiOyThe mixing molar ratio of the metal powder reducing agent to the molten salt is 1:1: 10.
6. The method according to any one of claims 1 to 3, wherein: in the step 2), the reaction temperature is 600-800 ℃, and the reaction time is 2-8 hours.
7. The method of claim 6, wherein: in the step 2), the reaction temperature is 700 ℃, and the reaction time is 5 h.
8. The method according to any one of claims 1 to 3, wherein: in the step 2), the inert atmosphere is argon, nitrogen or a mixed gas of argon and nitrogen in any proportion.
9. The porous silicon-based composite material prepared by the preparation method according to claim 1 is applied as a lithium ion battery negative electrode material.
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