CN111086990A - Preparation method of silicon-carbon microspheres - Google Patents
Preparation method of silicon-carbon microspheres Download PDFInfo
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- CN111086990A CN111086990A CN201911406643.5A CN201911406643A CN111086990A CN 111086990 A CN111086990 A CN 111086990A CN 201911406643 A CN201911406643 A CN 201911406643A CN 111086990 A CN111086990 A CN 111086990A
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- 239000004005 microsphere Substances 0.000 title claims abstract description 37
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 46
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 16
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 16
- 235000019441 ethanol Nutrition 0.000 claims abstract description 15
- 239000000243 solution Substances 0.000 claims abstract description 15
- 239000005457 ice water Substances 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- 229920000767 polyaniline Polymers 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 239000012298 atmosphere Substances 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 17
- 229910052799 carbon Inorganic materials 0.000 description 15
- 239000002131 composite material Substances 0.000 description 10
- 238000003917 TEM image Methods 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- 239000005543 nano-size silicon particle Substances 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 238000001354 calcination Methods 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 229910021389 graphene Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000002134 carbon nanofiber Substances 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 238000010041 electrostatic spinning Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N hydrochloric acid Substances Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 239000011856 silicon-based particle Substances 0.000 description 2
- 239000002153 silicon-carbon composite material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000007833 carbon precursor Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920001690 polydopamine Polymers 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
Abstract
The invention discloses a preparation method of silicon carbon microspheres, which belongs to the technical field of synthesis of inorganic chemical materials and specifically comprises the following steps: dissolving anilineIn absolute ethyl alcohol to obtain 0.1-1 mol.L‑1Adding silicon powder into the solution, and stirring for 30-90 minutes; dissolving ammonium persulfate in water with the same volume, slowly and dropwise adding the prepared ammonium persulfate solution into the mixed solution under the condition of ice-water bath, reacting for 6-12h in the ice-water bath, washing with water for several times, washing with ethanol for several times, and drying in an oven to obtain a dark green product, namely silicon @ polyaniline which is used as a precursor of the silicon-carbon microsphere; and (III) taking the precursor, keeping the temperature of 900 ℃ for 1-6h in the inert gas atmosphere, and then cooling to room temperature to obtain the silicon-carbon microspheres.
Description
Technical Field
The invention relates to synthesis of inorganic chemical materials, in particular to a preparation method of silicon-carbon microspheres.
Background
The silicon carbon microsphere has the characteristics of good chemical stability, thermal stability, excellent conductivity and the like, and is a silicon carbon material with wide application prospect.
With the development of the times, high-performance chemical power sources have become hot research in order to meet the increasing energy demand. Lithium ion batteries are considered to be novel power supplies meeting energy requirements due to high capacity and stable cycle life, and in the lithium ion batteries, the cathode material is traditionally carbon material, and the theoretical specific capacity is only 372 mAh & g-1The demand for high capacity cannot be satisfied. On the other hand, the theoretical specific capacity of silicon can reach 4200 mAh g-1And the silicon has lower lithium extraction potential (< 0.5V vs. Li/Li)+) So that the silicon material becomes the most hot novel lithium ion negative electrode material. However, since the silicon material itself has low conductivity and severe volume expansion during charge and discharge, the silicon particles are crushed, the cycle life is low, and commercial application thereof is seriously hindered. The structure and electrical performance structure can be improved by methods such as encapsulating silicon particles with carbon materials. Through silicon-carbon compounding, the lithium ion battery can obtain higher specific capacity, longer cycling stability and better conductivity.
For the preparation of carbon microsphere, hydrothermal method, electrostatic spinning, CVD method and the like are mainly adopted at present, and preparation tools of the methodsThe process is complex, the influence factors are more, and the difficulty of condition control is also higher. For this reason, many new simple and practical methods are being developed. Document [1 ]]Sucrose, oxalic acid and the like are used as raw materials, and a one-step hydrothermal method is adopted to prepare the composite material with silicon nanoparticles embedded in porous carbon microspheres. Document [2 ]]The carbon coating is produced by a Chemical Vapor Deposition (CVD) process, in which acetylene is selected as the carbon precursor. The material being CaCO3As template, CVD on silicon @ CaCO3Depositing a layer of amorphous carbon on the microspheres and then etching off the CaCO with dilute hydrochloric acid3And (5) template to obtain the silicon-carbon composite material with a hollow structure. Document [3]Uniformly dissolving the nano silicon particles in an ethanol solution of citric acid, and preparing the amorphous carbon coated silicon core-shell composite structure by a spray drying method at 400 ℃. Document [4 ]]The silicon/carbon nanofiber composite electrode material with the core-shell structure is prepared by taking polyacrylonitrile as a carbon source and adopting an electrostatic spinning process, and silicon nanoparticles are wrapped in a core by a carbon shell formed by carbon nanofibers. Document [5 ]]And (3) taking polyvinyl alcohol (PVA) as a carbon source, and carrying out carbon coating on the silicon nanoparticles by adopting a high-temperature pyrolysis method under an inert atmosphere to obtain the silicon-carbon composite material with the thickness of the carbon shell layer being 5-10 nm. Document [6]And mixing graphite and silicon powder by adopting a high-energy ball milling method to prepare the silicon/graphite composite material. Document [7 ]]Coating a layer of SiO on the surface of the silicon nano-particles by adopting a sol-gel method2A shell layer which is coated with pyrolytic carbon by taking sucrose as a carbon source and SiO2And etching by using HF to obtain the yolk-shell structure composite material. Document [8]The phenolic polymer-silicon composite material is obtained by a chemical synthesis method and then is carbonized under inert atmosphere to obtain Si/SiOxA carbon fiber composite material. Document [9 ]]The yolk-shell composite material is synthesized by taking polydopamine as a carbon source. Document [10 ]]After the mixture of silicon nano-particles and graphene oxide is freeze-dried, the mixture contains 10% (volume fraction) of H2And performing thermal reduction under Ar atmosphere to prepare the silicon/graphene composite material. Document [11]Firstly, polyaniline is grafted to the surface of silicon nanoparticles, then, the graphene is coated on the surface of the particles in a self-assembly manner by utilizing the pi-pi action and the electrostatic attraction between the polyaniline and the graphene, and then, the Si @ C/G composite material is obtained through high-temperature carbonization.
So far, the literature and patent of the method for synthesizing the silicon carbon microspheres by using aniline as a raw material and using an alcohol solvent method are not published and reported.
Reference documents:
[1]Jeong M G, Du H L, Islam M, et al. Self-Rearrangement of SiliconNanoparticles Embedded in Micro-Carbon Sphere Framework for High-Energy andLong-Life Lithium-Ion Batteries[J]. Nano Letters, 2017, 17(9):5600-5606.
[2]ZHANG L, RANJUSHA R, GUO H P, et al.A green and facile way to preparegranadilla-like silicon-based anode materials for Li-ion batteries[J].Advanced Functional Materials, 2016, 26 (3) :440-446.
[3]NG S H, WANG J, WEXLER D, et al.Highly reversible lithium storage inspheroidal carbon-coated silicon nanocomposites as anodes for lithium-ionbatteries[J].Angewandte Chemie, 2006, 45 (41) :6896-6899.
[4]HWANG T H, LEE Y M, KONG B S, et a1.Electrospun core shell fibers forrobust silicon nanoparticle based lithium ion battery anodes[J].Nano Lett,2012, 12:802.
[5]HWA Y, KIM W S, HONG S H, et al.High capacity and rate capability ofcore–shell structured nano-Si/C anode for Li-ion batteries[J].ElectrochimActa, 2012, 71 (3) :201–205.
[6]ZUO P J, WANG Z B, YIN G P, et al.Electrochemical investigation ofsilicon/carbon composite as anode material for lithium ion batteries[J].JMater Sci, 2008, 43 (9) :3149–3152.
[7]ZHOU X Y, TANG J J, YANG J, et al.Silicon@carbon hollow core–shellheterostructures novel anode materials for lithium ion batteries[J].Electrochim Acta, 2013, 87 (1) :663–668.
[8]GOMEZ-CAMER J L, MORALES J, SANCHEZ L.Anchoring Si nanoparticles tocarbon nanofibers:an efficient procedure for improving Si performance in Libatteries[J].J Mater Chem, 2011, 21 (3) :811–818.
[9]LIU N, WU H, MCDOWELL M T, et al.A Yolk-shell design for stabilizedand scalable Li-ion battery alloy anodes[J].Nano Lett, 2012, 12 (6) :3315–3321.
[10]CHABOT V, FENG K, PARK H W, et al.Graphene wrapped siliconnanocomposites for enhanced electrochemical performance in lithium ionbatteries[J].Electrochim Acta, 2014, 130 (4) :127–134.
[11]Li Z F, Zhang H, Liu Q, et al.Novel pyrolyzed polyaniline-graftedsilicon nanoparticles encapsulated in graphene sheets as Li-Ion batteryanodes[J].ACS Appl Mater Interface, 2014, 6 (8) :5996–6002。
disclosure of Invention
The technical problem to be solved by the invention is to provide a method for preparing silicon carbon microspheres by an alcohol solvent method, aiming at the defects in the prior art, the method is simple and easy to implement, and the silicon carbon microspheres with the sphere diameter of 50-200nm can be prepared under mild reaction conditions.
The technical scheme for solving the technical problems is as follows: a preparation method of silicon carbon microspheres specifically comprises the following steps:
the method comprises the following steps: dissolving aniline in anhydrous ethanol with a certain volume to obtain a solution with a concentration of 0.1-1 mol.L-1Adding silicon powder into the solution, and stirring for 30-90 minutes to obtain a mixed solution;
step two: dissolving ammonium persulfate in water with the volume same as that of the absolute ethyl alcohol in the step one, slowly dropwise adding the prepared ammonium persulfate solution into the mixed solution obtained in the step one under the condition of ice-water bath, reacting for 6-12h in the ice-water bath, washing with water for several times and ethanol for several times after the reaction is finished, and drying in a 60 ℃ oven to obtain a dark green product, namely silicon @ polyaniline, which is used as a precursor of the silicon-carbon microsphere;
step three: taking a precursor in N2Or other inert gas atmosphere, at the temperature of 600-900 ℃, and keeping for 1-6h, and then cooling to room temperature to obtain the silicon carbon microspheres.
The mass ratio of the silicon powder in the first step to the monomer aniline is 1: 0.5-10.
The molar ratio of aniline to ammonium persulfate was 1: 1.5.
The invention has the beneficial effects that: according to the invention, aniline is used as a carbon source, and the silicon-carbon microspheres are prepared in an ethanol solution for the first time. The diameter of the prepared silicon-carbon microsphere is 50-200 nm. The silicon carbon microsphere of the invention is used as the electrode material of the lithium ion battery, and has wide application prospect in the aspect of electrode material of the super capacitor.
Drawings
FIG. 1 is a TEM image of silica-carbon microspheres prepared in example 1 of the present invention;
FIG. 2 is a TEM image of silica-carbon microspheres prepared in example 2 of the present invention;
FIG. 3 is a TEM image of silica-carbon microspheres prepared in example 3 of the present invention;
FIG. 4 is a TEM image of silica-carbon microspheres prepared in example 4 of the present invention.
Detailed Description
Example 1
The embodiment provides a preparation method of silicon carbon microspheres, which specifically comprises the following steps:
the method comprises the following steps: dissolving 9.3g of aniline in 100mL of ethanol, adding 0.93g of silicon powder (the mass ratio of the silicon powder to the monomer aniline is 1: 10), and stirring for 60 minutes;
step two: then dissolving 42g of ammonium persulfate in 100mL of water, slowly and dropwise adding the prepared ammonium persulfate solution into the mixed solution under the condition of ice-water bath, reacting for 8 hours in the ice-water bath, washing with water for 3 times and ethanol for 2 times after the reaction is finished, and drying in an oven at 60 ℃. Thus obtaining a dark green product silicon @ polyaniline precursor;
step three: and calcining the precursor at 900 ℃ for 2h in a nitrogen atmosphere to finally obtain the silicon-carbon microsphere, wherein a TEM image of the silicon-carbon microsphere is shown in figure 1.
Example 2
The method comprises the following steps: dissolving 1.86g of aniline in 50mL of ethanol, adding 0.37g of silicon (the mass ratio of the silicon powder to the monomer aniline is 1: 5), and stirring for 30 minutes;
step two: then 8.5g of ammonium persulfate is dissolved in 50mL of water, the prepared ammonium persulfate solution is slowly and dropwise added into the mixed solution under the condition of ice-water bath, the ice-water bath reaction is carried out for 10 hours, after the reaction is finished, the water washing is carried out for 3 times, the ethanol washing is carried out for 2 times, and the mixture is placed into a 60 ℃ oven for drying. Thus obtaining a dark green product silicon @ polyaniline precursor;
step three: and calcining the precursor at 700 ℃ for 2h in a nitrogen atmosphere to finally obtain the silicon-carbon microsphere, wherein a TEM image of the silicon-carbon microsphere is shown in FIG. 2.
Example 3
The method comprises the following steps: dissolving 18g of aniline in 1000mL of ethanol, adding 18g of silicon powder (the mass ratio of the silicon powder to the monomer aniline is 1: 1), and stirring for 30 minutes;
step two: and then dissolving 85g of ammonium persulfate in 1000mL of water, slowly and dropwise adding the prepared ammonium persulfate solution into the mixed solution under the condition of an ice-water bath, reacting for 6 hours in the ice-water bath, washing with water for 3 times and ethanol for 2 times after the reaction is finished, and drying in an oven at 60 ℃. Thus obtaining a dark green product silicon @ polyaniline precursor;
step three: and calcining the precursor at 800 ℃ for 2h in a nitrogen atmosphere to finally obtain the silicon-carbon microsphere, wherein a TEM image of the silicon-carbon microsphere is shown in FIG. 3.
Example 4
The method comprises the following steps: dissolving 1.50g of aniline in 160mL of ethanol, adding 3g of silicon powder (the mass ratio of the silicon powder to the monomer aniline is 1: 0.5), and stirring for 90 minutes;
step two: and then 6.83g of ammonium persulfate is dissolved in 160mL of water, the prepared ammonium persulfate solution is slowly and dropwise added into the mixed solution under the condition of an ice-water bath, the ice-water bath reaction is carried out for 12 hours, after the reaction is finished, the water washing is carried out for 3 times, the ethanol washing is carried out for 2 times, and the mixture is placed into a 60 ℃ oven for drying. Thus obtaining a dark green product silicon @ polyaniline precursor;
step three: and calcining the precursor at 600 ℃ for 1h in an argon atmosphere to finally obtain the silicon-carbon microsphere, wherein a TEM image of the silicon-carbon microsphere is shown in FIG. 4.
In addition to the above embodiments, the present invention may have other embodiments. All technical solutions formed by adopting equivalent substitutions or equivalent transformations fall within the protection scope of the claims of the present invention.
Claims (3)
1. A preparation method of silicon carbon microspheres is characterized by comprising the following steps: the method specifically comprises the following steps:
the method comprises the following steps: dissolving aniline in anhydrous ethanol with a certain volume to obtain a solution with a concentration of 0.1-1 mol.L-1Adding silicon powder into the solution, and stirring for 30-90 minutes to obtain a mixed solution;
step two: dissolving ammonium persulfate in water with the volume same as that of the absolute ethyl alcohol in the step one, slowly dropwise adding the prepared ammonium persulfate solution into the mixed solution obtained in the step one under the condition of ice-water bath, reacting for 6-12h in the ice-water bath, washing with water for several times and ethanol for several times after the reaction is finished, and drying in a 60 ℃ oven to obtain a dark green product, namely silicon @ polyaniline, which is used as a precursor of the silicon-carbon microsphere;
step three: taking a precursor in N2Or other inert gas atmosphere, at the temperature of 600-900 ℃, and keeping for 1-6h, and then cooling to room temperature to obtain the silicon carbon microspheres.
2. The method for preparing silicon-carbon microspheres according to claim 1, wherein the mass ratio of the silicon powder to the monomer aniline in the first step is 1: 0.5-10.
3. The method for preparing silicon-carbon microspheres according to claim 1, wherein the molar ratio of ammonium persulfate to aniline in the second step is 1.5: 1.
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