CN116692871A - Method for preparing porous hollow silicon spheres by using hollow glass microspheres and application of porous hollow silicon spheres - Google Patents
Method for preparing porous hollow silicon spheres by using hollow glass microspheres and application of porous hollow silicon spheres Download PDFInfo
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- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 59
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000010703 silicon Substances 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 57
- 239000011521 glass Substances 0.000 title claims abstract description 55
- 239000004005 microsphere Substances 0.000 title claims abstract description 46
- 239000002245 particle Substances 0.000 claims abstract description 37
- 239000002253 acid Substances 0.000 claims abstract description 35
- 238000010438 heat treatment Methods 0.000 claims abstract description 35
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 29
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000006722 reduction reaction Methods 0.000 claims abstract description 24
- 238000005530 etching Methods 0.000 claims abstract description 23
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 14
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011324 bead Substances 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 238000000498 ball milling Methods 0.000 claims abstract description 10
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 10
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 8
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000004321 preservation Methods 0.000 claims description 22
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 8
- 239000010405 anode material Substances 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 238000011534 incubation Methods 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 16
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 16
- 230000008569 process Effects 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 4
- 230000008859 change Effects 0.000 abstract description 3
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 25
- 239000000377 silicon dioxide Substances 0.000 description 11
- 235000012239 silicon dioxide Nutrition 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 229920002125 Sokalan® Polymers 0.000 description 6
- 239000004584 polyacrylic acid Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000009831 deintercalation Methods 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000011946 reduction process Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229910052810 boron oxide Inorganic materials 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000001311 chemical methods and process Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229910021419 crystalline silicon Inorganic materials 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910021426 porous silicon Inorganic materials 0.000 description 2
- 239000012686 silicon precursor Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 235000008429 bread Nutrition 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011325 microbead Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- -1 silicon dioxide compound Chemical class 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
- C01B33/021—Preparation
- C01B33/023—Preparation by reduction of silica or free silica-containing material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The application relates to the technical field of chemical material preparation, in particular to a method for preparing porous hollow silicon spheres by using hollow glass microspheres and application thereof; the method comprises the following steps: heating and preserving heat of the hollow glass beads to generate amplitude modulation decomposition reaction to obtain treated hollow glass beads; acid etching is carried out on the treated hollow glass bead, and filtering is carried out, and then rapid heating is carried out, thus obtaining porous amorphous SiO 2 Particles; to porous amorphous SiO 2 Adding magnesium powder into the particles, performing ball milling, and performing a magnesian reduction reaction in an oxygen-free environment to obtain a mixture containing nano silicon and magnesium oxide; adding the mixture into hydrochloric acid, rinsing and filtering, and drying to obtain porous hollow silicon spheres; the method can overcome the defect that the Si anode is in Li in the prior art + In the process of taking off/insertingThe volume change of the lithium ion battery is maintained, the structure is stable, the cycle service life of the lithium ion battery can be prolonged, and meanwhile, the preparation process of the method is simple, the manufacturing cost is low, and the commercialization is facilitated.
Description
Technical Field
The application relates to the technical field of chemical material preparation, in particular to a method for preparing porous hollow silicon spheres by using hollow glass microspheres and application thereof.
Background
Because the capacity of the current commercial lithium ion battery anode material is limited, the graphite capacity of the cathode material is close to the theoretical capacity of 372 mAh.g -1 ) While Si material has a specific value of up to 3578 mAh.g -1 Specific capacity of (2) and 0.4V (vs Li/Li) + ) The Si material has the advantages of rich resources, environmental friendliness, no need of high purity and the like, but the silicon anode is prepared by the method that Li is the following raw materials + The release/intercalation process undergoes a significant phase change volume expansion (-300%) which limits the use of silicon on the negative electrode. Although Li is relieved by the elaborate design of porous Si structures, nanotubes, hollow sphere structures and the like + The Si negative electrode volume in the deintercalation/intercalation process is changed to maintain structural stability while the cycle life of the lithium ion battery is prolonged, but the process is complicated, the manufacturing cost is expensive, and the commercialization is not facilitated.
The hollow glass microsphere is a novel material with wide application and excellent performance, the main component of the product is borosilicate, the granularity is generally 10-250 mu m, the wall thickness is 1-2 mu m, the product has the advantages of light weight, low heat conduction, high strength, good chemical stability, high dispersion and the like, and the chemical component of the product is SiO 2 、K 2 O、Al 2 O 3 And B 2 O 3 Etc. Thus the low value SiO is reduced by the magnesian reduction process 2 The conversion of the material into the negative Si material is a feasible path with low cost and large scale, and simultaneously the pseudo-crystal conversion of the magnesian reduction system can keep the precursor structure unchanged before and after reduction, and can lead various fine and complex SiO 2 The structural features are replicated onto the Si product.
Current methods for the magnesium reduction process include: (1) A method for preparing hollow nanometer silicon spheres by metal thermal reduction comprises the steps of mixing active metal powder with silicon dioxide nanospheres, ball milling, transferring into a crucible, heating to a thermal reduction reaction temperature under the protection of argon or vacuum condition, and naturally cooling after thermal insulation reaction to obtain an active metal oxide/silicon dioxide compound; mixing the prepared compound with acid liquor, stirring for reaction, and washing with water to obtain a hollow silicon sphere nano silicon dioxide composite material; the silicon precursor adopted by the method is silicon dioxide nanospheres, the structure is exquisite, the silicon precursor is a nanomaterial, the manufacturing cost is high, and the commercialization is not facilitated.
(2) A preparation method of micron-sized porous hollow silicon spheres comprises the steps of placing magnesium powder into an absolute ethanol solution of 3-mercaptopropyl triethoxysilane for a series of chemical modification, and coating silicon dioxide microsphere powder with the magnesium powder through magnetic stirring; and (3) treating the obtained powder, acid etching, drying and other steps to obtain the porous hollow silicon spheres. And applies it to silicon-based lithium ion batteries. The method aims at preparing magnesium powder coated silicon dioxide microsphere powder, and the synthetic hollow silicon sphere chemical process is complex and is not beneficial to commercialization.
(3) A carbon-coated hollow silicon dioxide composite material is prepared by using polyacrylic acid as a raw material to prepare polyacrylic acid microspheres, adding absolute ethyl alcohol, tetraethyl orthosilicate and ammonia water, depositing silicon dioxide generated in situ on the surfaces of the polyacrylic acid microspheres to form a silicon dioxide layer, coating the polyacrylic acid outside the polyacrylic acid, repeatedly flushing the polyacrylic acid by using deionized water until the hollow silicon dioxide microspheres are formed, and then applying the hollow silicon dioxide microspheres to a silicon-based lithium ion battery through carbon coating. The method is still complex in the chemical process of synthesizing the hollow silicon spheres, and is not beneficial to commercialization.
(4) A preparation method of hollow porous micron-sized silicon spheres, a silicon-based negative electrode material and a lithium ion battery comprises the steps of reducing hollow glass microspheres by using active metals, removing metal oxides by using acid to obtain the hollow porous micron-sized silicon spheres, and manufacturing the silicon-based negative electrode and the lithium ion battery based on the hollow porous micron-sized silicon spheres. This method does not describe hollow glass microspheres.
Therefore, how to provide a method for preparing porous hollow silicon spheres by using glass hollow microspheres, so as to realize the technical problems of simple process, low cost and easy commercialization while maintaining stable structure, which are needed to be solved at present
Disclosure of Invention
The application provides a method for preparing porous hollow silicon spheres by using glass hollow microspheres and application thereof, which are used for solving the technical problems that the prior art is difficult to realize simple process, low cost and easy commercialization while maintaining stable structure.
In a first aspect, the present application provides a method for preparing porous hollow silica spheres using glass cenospheres, the method comprising:
heating and preserving heat of the hollow glass beads to generate amplitude modulation decomposition reaction to obtain SiO 2 The treated glass hollow microspheres are alternately distributed with other oxide micro-areas;
acid etching is carried out on the treated glass hollow microspheres, filtering is carried out, and then rapid heating is carried out, thus obtaining porous amorphous SiO 2 Particles;
to said porous amorphous SiO 2 Adding magnesium powder into the particles, performing ball milling, and performing a magnesian reduction reaction in an oxygen-free environment to obtain a mixture containing nano silicon and magnesium oxide;
and adding the mixture into hydrochloric acid, rinsing, filtering, and drying to obtain the porous hollow silicon spheres.
Optionally, the heated end point temperature T satisfies:
0.85Ts≤T≤Ts，
wherein, ts is the stable temperature of the amplitude modulation decomposition reaction.
Optionally, the particle size of the glass hollow microsphere is 10-30 μm, and the wall thickness of the glass hollow microsphere is 1-2 μm.
Optionally, the heat preservation time is 1-24 h.
Optionally, the end temperature of the rapid temperature rise is more than or equal to 1500 ℃.
Optionally, the porous amorphous SiO 2 The mass ratio of the particles to the magnesium powder is more than or equal to 1.
Optionally, the ball milling time is more than or equal to 2 hours; and/or the number of the groups of groups,
the particle size of the magnesium powder is less than or equal to 30 mu m.
Optionally, the magnesium reduction reaction comprises a heating stage and a heat preservation stage, wherein the end temperature of the heating stage is 500-800 ℃, and the time of the heat preservation stage is 2-6 h.
Optionally, the acid solution used for acid etching is hydrochloric acid, and the ratio of the mass of the glass hollow microsphere to the mass of the acid solution used for acid etching is more than or equal to 1g/mol.
In a second aspect, the application provides an application of a method for preparing porous hollow silicon spheres by using glass hollow microspheres, wherein the porous hollow silicon spheres obtained by the method in the first aspect are used for preparing a battery anode material.
Compared with the prior art, the technical scheme provided by the embodiment of the application has the following advantages:
compared with the traditional porous hollow silicon spheres, the method for preparing the porous hollow silicon spheres by using the glass hollow spheres provided by the embodiment of the application does not need to independently design the structure of the Si precursor hollow spheres, which is expensive and exquisite and complex in cost, and only needs to heat the glass hollow spheres until amplitude modulation decomposition reaction occurs, so that SiO is realized 2 The micro-regions are alternately distributed with other oxides, and impurities of the glass hollow microspheres are removed through acid etching treatment and rapid heating, so that pure porous amorphous SiO is obtained 2 The particles are subjected to magnesian reduction reaction to obtain porous amorphous SiO 2 The particles are converted into porous hollow silicon spheres, and the porous hollow silicon spheres can be obtained by the simple early-stage amplitude modulation decomposition reaction and the magnesian reduction reaction, so that the defect that the Si cathode is in Li in the prior art can be overcome + The volume change in the process of removing/inserting is kept stable in structure, the cycle service life of the lithium ion battery can be prolonged, and meanwhile, the preparation process of the method is simple, the manufacturing cost is low, and the commercialization is facilitated.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the application and together with the description, serve to explain the principles of the application.
In order to more clearly illustrate the embodiments of the application or the technical solutions of the prior art, the drawings which are used in the description of the embodiments or the prior art will be briefly described, and it will be obvious to a person skilled in the art that other drawings can be obtained from these drawings without inventive effort.
FIG. 1 is a schematic flow chart of a method for preparing porous hollow silica spheres by using hollow glass beads according to an embodiment of the present application;
FIG. 2 shows a porous amorphous SiO according to an embodiment of the present application 2 XRD pattern of particles;
FIG. 3 is an XRD pattern of porous hollow silicon spheres after acid etching provided in an embodiment of the present application;
FIG. 4 is a diagram showing N of a porous hollow silicon sphere after acid etching according to an embodiment of the present application 2 Desorption-adsorption drawing;
FIG. 5 is an electrochemical graph of a Si@C anode material provided by an embodiment of the application cycled 400 times at a current density of 0.2A/g.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present application more apparent, the technical solutions of the embodiments of the present application will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present application, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments of the present 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.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present application are commercially available or may be prepared by existing methods.
As shown in fig. 1, an embodiment of the present application provides a method for preparing a porous hollow silicon sphere by using hollow glass beads, the method comprising:
s1, heating and preserving heat of the hollow glass microspheres to generate amplitude modulation decomposition reaction to obtain SiO 2 Micro-scale with other oxidesThe treated glass hollow microspheres are distributed at intervals;
s2, carrying out acid etching on the treated glass hollow microspheres, filtering, and then carrying out rapid heating to obtain porous amorphous SiO 2 Particles;
s3, the porous amorphous SiO is oriented to 2 Adding magnesium powder into the particles, performing ball milling, and performing a magnesian reduction reaction in an oxygen-free environment to obtain a mixture containing porous silicon and magnesium oxide;
s4, adding the mixture into hydrochloric acid, rinsing, filtering, and drying to obtain the porous hollow silicon spheres.
In some alternative embodiments, the heated end temperature T satisfies:
0.85Ts≤T≤Ts，
wherein, ts is the stable temperature of the amplitude modulation decomposition reaction.
In the embodiment of the application, the relation between the specific terminal temperature T of heating and the stable temperature of amplitude modulation reaction is controlled, and the optimal and fastest temperature of the amplitude modulation decomposition reaction is 10% below Ts, so that the hollow glass bead can be promoted to carry out the amplitude modulation decomposition reaction under the proper temperature condition within the temperature range.
In some alternative embodiments, the glass hollow microspheres have a particle size of 10 μm to 30 μm and a wall thickness of 1 μm to 2 μm.
In the embodiment of the application, the specific particle size and specific wall thickness of the glass hollow microspheres are controlled, so that the glass hollow microspheres can fully react in amplitude modulation decomposition reaction, thereby enabling SiO (silicon dioxide) 2 And the porous hollow silicon spheres with proper particle size and wall thickness can be finally obtained.
In some alternative embodiments, the incubation time is 1h to 24h.
In the embodiment of the application, the specific time of heat preservation is controlled, so that the amplitude modulation decomposition reaction is fully carried out, thereby obtaining SiO 2 The glass hollow micro beads are treated in a manner of being alternately distributed with other oxide micro areas, so that later acid etching is facilitatedIn-process pair K 2 O、Al 2 O 3 And part B 2 O 3 Is completely removed.
In some alternative embodiments, the rapid temperature increase is at an endpoint temperature greater than or equal to 1500 ℃.
In the embodiment of the application, the specific end point temperature of rapid temperature rise is controlled, and the oxide of residual boron can be sublimated directly through high temperature, so that pure porous amorphous SiO is obtained 2 And (3) particles.
In some alternative embodiments, the porous amorphous SiO 2 The mass ratio of the particles to the magnesium powder is more than or equal to 1.
In the embodiment of the application, porous amorphous SiO is controlled 2 The specific mass ratio of the particles to the magnesium powder can enable the content of the magnesium powder to be enough, so that the magnesium reduction reaction can be smoothly carried out, and the mixture of the nano silicon and the magnesium oxide can be obtained.
In some alternative embodiments, the ball milling time is greater than or equal to 2 hours; and/or the number of the groups of groups,
the particle size of the magnesium powder is less than or equal to 30 mu m.
In the embodiment of the application, the specific time of ball milling is controlled, so that porous amorphous SiO can be obtained 2 The particles and the magnesium powder are fully mixed, and simultaneously, the magnesian reduction reaction can be induced.
The specific particle size of the magnesium powder is controlled, so that the magnesium powder and the porous amorphous SiO can be promoted 2 The particles are fully mixed, and meanwhile, the subsequent magnesian reduction reaction can be fully carried out, so that a mixture of enough nano silicon and magnesium oxide is obtained.
In some alternative embodiments, the magnesium reduction reaction includes a heating stage having an end temperature of 500 ℃ to 800 ℃ and a holding stage having a time of 2 hours to 6 hours.
In the embodiment of the application, the specific end temperature of the heating stage and the specific time of the heat preservation stage of the magnesia reduction reaction are controlled, so that the magnesia reduction reaction can be fully carried out, and a sufficient mixture of nano silicon and magnesia is obtained.
In some alternative embodiments, the acid solution used for the acid etching is hydrochloric acid, and the ratio of the mass of the hollow glass bead to the mass of the acid solution used for the acid etching is more than or equal to 1g/mol.
In the embodiment of the application, the specific acid solution for acid etching and the ratio of the mass of the glass hollow microsphere to the mass of the acid solution can be controlled, so that the treatment of K in the glass hollow microsphere can be promoted 2 O、Al 2 O 3 And part B 2 O 3 The impurities are removed by acid etching, thereby obtaining porous SiO 2 Particles and residual boron oxide, thereby facilitating subsequent rapid temperature rise to sublimate the residual boron oxide and further obtaining pure porous amorphous SiO 2 And (3) particles.
In the practical use process, the mass concentration of the hydrochloric acid used for acid etching is generally 1M, and the dosage of the hydrochloric acid used for acid etching satisfies the following conditions: 1g of glass hollow microsphere is at least 100ml of 1M hydrochloric acid.
Based on one general inventive concept, the application provides an application of a method for preparing porous hollow silicon spheres by using glass hollow microspheres, wherein the porous hollow silicon spheres obtained by the method are used for preparing a battery anode material.
In the embodiment of the application, the obtained porous hollow silicon spheres are used as anode materials of lithium ion batteries to be assembled into CR2025 button batteries after being coated by carbon, and the specific steps are as follows:
adding pure porous hollow silicon spheres and 1 mol.L of water into the mixture -1 Ultrasonic at room temperature for 30min in HCl according to wSi: wC (what is C) 6 H 7 Aniline (C) was added n=1:6 6 H 7 N, analytically pure), magnetically stirring at room temperature for 10min;
ammonium persulfate ((NH) was weighed out in an amount equivalent to that of aniline 4 ) 2 S 2 O 8 Dissolved in 1 mol.L -1 Is prepared into 0.5 mol.L in HCl solution -1 And slowly dripping all ammonium persulfate solution into the pure porous hollow silicon sphere suspension under room temperature magnetic stirring, and continuing room temperature magnetic stirring for 12 hours to obtain a dark green suspension.
Through 9600 r.min -1 Centrifugal separation and vacuum drying at 60 ℃ for 12hAnd (3) placing the mixture into a tubular furnace, and treating the mixture for 2 hours at 1000 ℃ under Ar gas flow to obtain the Si and C coated Si@C anode material. The voltage range between the charge and discharge of the battery tester is set to be 0.01V-2.0V (vs Li/Li) + ) All the above tests were carried out at 25 ℃.
The application is realized based on the above method, and specific steps of the method can refer to the above embodiment, and because the application adopts some or all of the technical solutions of the above embodiment, at least the application has all the beneficial effects brought by the technical solutions of the above embodiment, and will not be described in detail herein.
The application will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. The experimental procedures, which are not specified in the following examples, are generally determined according to national standards. If the corresponding national standard does not exist, the method is carried out according to the general international standard, the conventional condition or the condition recommended by the manufacturer.
Example 1
As shown in fig. 1, a method for preparing porous hollow silicon spheres by using glass hollow microspheres comprises the following steps:
s1, heating and preserving heat of the hollow glass microspheres to generate amplitude modulation decomposition reaction to obtain SiO 2 The treated glass hollow microspheres are alternately distributed with other oxide micro-areas;
s2, carrying out acid etching on the treated glass hollow microspheres, filtering, and then quickly heating to 1500 ℃ to obtain porous amorphous SiO shown in figure 2 2 Particles;
s3, porous amorphous SiO 2 Adding magnesium powder into the particles, performing ball milling, and performing a magnesian reduction reaction under an argon gas strip to obtain a mixture containing nano silicon and magnesium oxide;
s4, adding the mixture into hydrochloric acid, rinsing, filtering, and drying to obtain the porous hollow silicon spheres.
As can be seen from FIG. 2, the amorphous SiO of the glass hollow microsphere component can be judged to remain after filtration by the steamed bread peak around 22 DEG 2 And (3) particles.
The end temperature T of the heating was 360 ℃.
The time for heat preservation is 5 hours.
The end temperature of the rapid warming was 1500 ℃.
Porous amorphous SiO 2 The mass ratio of the particles to the magnesium powder is 1:1.
The magnesian reduction reaction comprises a heating stage and a heat preservation stage, wherein the end temperature of the heating stage is 550 ℃, and the time of the heat preservation stage is 6h.
The acid solution used for acid etching is hydrochloric acid, and the ratio of the mass of the hollow glass bead to the mass of the acid solution used for acid etching is more than or equal to 1g/mol.
Example 2
Example 2 and example 1 were compared, and the difference between example 2 and example 1 is that:
the end temperature T of the heating was 360 ℃.
The time for heat preservation is 12 hours.
The end temperature of the rapid warming was 1500 ℃.
Porous amorphous SiO 2 The mass ratio of the particles to the magnesium powder is 1:0.8.
The magnesian reduction reaction comprises a heating stage and a heat preservation stage, wherein the end temperature of the heating stage is 660 ℃, and the time of the heat preservation stage is 4 hours.
Example 3
Example 3 was compared with example 1, and the difference between example 3 and example 1 was:
the end temperature T of the heating was 360 ℃.
The time for heat preservation is 24 hours.
The end temperature of the rapid warming was 1500 ℃.
Porous amorphous SiO 2 The mass ratio of the particles to the magnesium powder is 1:0.9.
The magnesian reduction reaction comprises a heating stage and a heat preservation stage, wherein the end temperature of the heating stage is 720 ℃, and the time of the heat preservation stage is 2h.
Example 4
Example 4 and example 1 were compared, and example 4 and example 1 differ in that:
the end temperature T of the heating was 300 ℃.
The time for heat preservation is 24 hours.
The end temperature of the rapid warming was 1500 ℃.
Porous amorphous SiO 2 The mass ratio of the particles to the magnesium powder is 1:1.
The magnesian reduction reaction comprises a heating stage and a heat preservation stage, wherein the end temperature of the heating stage is 660 ℃, and the time of the heat preservation stage is 4 hours.
Example 5
Example 5 was compared with example 1, and the difference between example 5 and example 1 was:
the end temperature T of the heating was 400 ℃.
The time for heat preservation is 5 hours.
The end temperature of the rapid warming was 1500 ℃.
Porous amorphous SiO 2 The mass ratio of the particles to the magnesium powder is 1:1.
The magnesian reduction reaction comprises a heating stage and a heat preservation stage, wherein the end temperature of the heating stage is 660 ℃, and the time of the heat preservation stage is 4 hours.
Comparative example 1
Comparative example 1 was compared with example 1, and the difference between comparative example 1 and example 1 was that:
only the commercial porous hollow silicon spheres are used as cathode materials of lithium ion batteries after being coated by carbon to assemble the CR2025 button battery.
Related experiment and effect data:
the assembled batteries obtained in each example and comparative example were subjected to constant current charge and discharge test using a battery tester to characterize the performance, and the results are shown in table 1.
Table 1 table of performance of assembled batteries of examples and comparative examples for constant current charge and discharge
The electrochemical curves of the assembled batteries obtained in comparative example 1 and example 1 after 400 cycles are shown in fig. 3.
As can be seen from FIG. 3, the electrochemical cycle curve of the Si@C anode prepared in comparative example 1 has a discharge capacity of 880.3 mAh.g after 400 cycles -1 The capacity retention rate is 36.5%, and the electrochemical cycle curve of the Si@C anode prepared by the pure porous hollow silicon spheres has a discharge capacity of 1117.7 mAh.g after 400 cycles -1 The capacity retention rate was 55.5%, showing excellent cycle stability and better electrochemical performance.
XRD and N of the porous hollow silicon spheres obtained in example 1 were examined 2 The desorption-adsorption conditions and the results are shown in fig. 4 and 5.
As can be seen from fig. 4, the identified peak positions are significant peak positions of crystalline Si, which indicates that the porous hollow silicon spheres after acid etching treatment only remain crystalline Si particles, and fig. 5 has obvious hysteresis loops, indicating that the porous hollow silicon spheres have a porous structure.
The electrochemical properties of the assembled batteries obtained in each example were measured and are shown in table 1.
As can be seen from table 1, each example exhibited superior electrochemical performance in that the discharge capacity after 400 charge and discharge cycles was superior to that of the comparative example after 4000 charge and discharge cycles, and the capacity retention rate was also superior to that of the comparative example.
One or more technical solutions in the embodiments of the present application at least have the following technical effects or advantages:
(1) According to the method for preparing the porous hollow silicon spheres by using the glass hollow microspheres, provided by the embodiment of the application, the glass hollow microspheres which are the existing industrial chemical mature products are used as precursors, and then the porous hollow silicon spheres for the negative electrode of the lithium ion battery are obtained by copying through a simple magnesian reduction process flow, and the structure of the Si precursor hollow spheres which are expensive, exquisite and complex in manufacturing cost is not required to be designed independently, so that the whole production equipment is simple, the process is simple, and the production efficiency is high.
(2) According to the method for preparing the porous hollow silicon spheres by using the glass hollow microspheres, the obtained porous hollow silicon spheres have higher specific capacity and stable spherical structure, and the formed porous hollow structure has the function of buffering the volume expansion of Si on one hand; on the other hand, the depth and the diffusion distance of lithium ion deintercalation are shortened, so that the lithium ion deintercalation electrochemical performance is excellent and stable.
(3) The application of the method for preparing the porous hollow silicon spheres by using the glass hollow microspheres provided by the embodiment of the application applies the obtained porous hollow silicon spheres to the anode material of the lithium ion battery, has stable structure in the battery cycle process, and is beneficial to prolonging the cycle life of the lithium ion battery.
Various embodiments of the application may exist in a range of forms; it should be understood that the description in a range format is merely for convenience and brevity and should not be construed as a rigid limitation on the scope of the application; it is therefore to be understood that the range description has specifically disclosed all possible sub-ranges and individual values within that range. For example, it should be considered that a description of a range from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1, 2, 3, 4, 5, and 6, wherever applicable. In addition, whenever a numerical range is referred to herein, it is meant to include any reference number (fractional or integer) within the indicated range.
In the present application, unless otherwise specified, terms such as "upper" and "lower" are used specifically to refer to the orientation of the drawing in the figures. In addition, in the description of the present specification, the terms "include", "comprising" and the like mean "including but not limited to".
Relational terms such as "first" and "second", and the like may be 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. Herein, "and/or" describing an association relationship of an association object means that there may be three relationships, for example, a and/or B, may mean: a alone, a and B together, and B alone. Wherein A, B may be singular or plural. Herein, "at least one" means one or more, and "a plurality" means two or more. "at least one", "at least one" or the like refer to any combination of these items, including any combination of single item(s) or plural items(s). For example, "at least one (individual) of a, b, or c," or "at least one (individual) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, c may be single or multiple, respectively.
The foregoing is only a specific embodiment of the application to enable those skilled in the art to understand or practice the application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A method for preparing porous hollow silicon spheres by using glass hollow microspheres, which is characterized by comprising the following steps:
heating and preserving heat of the hollow glass beads to generate amplitude modulation decomposition reaction to obtain SiO 2 The treated glass hollow microspheres are alternately distributed with other oxide micro-areas;
acid etching is carried out on the treated glass hollow microspheres, filtering is carried out, and then rapid heating is carried out, thus obtaining porous amorphous SiO 2 Particles;
to said porous amorphous SiO 2 Adding magnesium powder into the particles, performing ball milling, and performing a magnesian reduction reaction in an oxygen-free environment to obtain a mixture containing nano silicon and magnesium oxide;
and adding the mixture into hydrochloric acid, rinsing, filtering, and drying to obtain the porous hollow silicon spheres.
2. The method according to claim 1, characterized in that the end temperature T of the heating satisfies:
0.85Ts≤T≤Ts，
wherein, ts is the stable temperature of the amplitude modulation decomposition reaction.
3. The method according to claim 1, wherein the glass hollow microspheres have a particle size of 10 μm to 30 μm and a wall thickness of 1 μm to 2 μm.
4. The method of claim 1, wherein the incubation time is 1h to 24h.
5. The method of claim 1, wherein the rapid temperature increase is at an endpoint temperature of greater than or equal to 1500 ℃.
6. The method of claim 1, wherein the porous amorphous SiO 2 The mass ratio of the particles to the magnesium powder is more than or equal to 1.
7. The method according to claim 1, wherein the ball milling time is not less than 2 hours; and/or the number of the groups of groups,
the particle size of the magnesium powder is less than or equal to 30 mu m.
8. The method according to claim 1, wherein the magnesium reduction reaction comprises a heating stage and a heat preservation stage, the end temperature of the heating stage is 500-800 ℃, and the time of the heat preservation stage is 2-6 h.
9. The method according to claim 1, wherein the acid solution used for the acid etching is hydrochloric acid, and the ratio of the mass of the hollow glass bead to the mass of the acid solution used for the acid etching is not less than 1g/mol.
10. Use of a method for preparing porous hollow silicon spheres from hollow glass microspheres, wherein the porous hollow silicon spheres obtained by the method according to any one of claims 1-9 are used in the preparation of a battery anode material.
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