CN107910512B - Preparation method of multilayer core-shell structure composite electrode material - Google Patents
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- 239000007772 electrode material Substances 0.000 title claims abstract description 37
- 239000011258 core-shell material Substances 0.000 title claims abstract description 32
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 47
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000003756 stirring Methods 0.000 claims abstract description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 30
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 27
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 27
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 27
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 27
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 24
- 238000001354 calcination Methods 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000007983 Tris buffer Substances 0.000 claims abstract description 14
- 239000012298 atmosphere Substances 0.000 claims abstract description 14
- 239000004005 microsphere Substances 0.000 claims abstract description 14
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims abstract description 14
- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000005530 etching Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000001291 vacuum drying Methods 0.000 claims description 17
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims 4
- 229960001149 dopamine hydrochloride Drugs 0.000 claims 4
- 230000000694 effects Effects 0.000 abstract description 5
- 239000011259 mixed solution Substances 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 229960003638 dopamine Drugs 0.000 description 8
- 238000009210 therapy by ultrasound Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 229920001021 polysulfide Polymers 0.000 description 2
- 239000005077 polysulfide Substances 0.000 description 2
- 150000008117 polysulfides Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- SNNYSJNYZJXIFE-UHFFFAOYSA-L 2-(benzenesulfinyl)ethylsulfinylbenzene;palladium(2+);diacetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O.C=1C=CC=CC=1S(=O)CCS(=O)C1=CC=CC=C1 SNNYSJNYZJXIFE-UHFFFAOYSA-L 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000011998 white catalyst Substances 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- 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
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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
- H01M4/48—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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention relates to a preparation method of a composite electrode material with a multilayer core-shell structure, which comprises the following steps: mixing SiO2Dispersing the microspheres in Tris buffer solution, adding DA, stirring and reacting to obtain SiO2@ PDA; dispersing in the mixed solution, stirring for reaction, adding TBOT for continuous reaction to obtain SiO2@PDA@TiO2(ii) a Dispersing in Tris buffer solution, adding DA, stirring and reacting to obtain SiO2@PDA@TiO2@ PDA; calcining in inert atmosphere, and etching with NaOH to obtain hollow-C @ TiO2@ C; mixed with sublimed sulphur in N2Calcining in the atmosphere to obtain the multilayer core-shell structure composite electrode material. The method is simple, the raw material source is convenient, the method is safe and environment-friendly, the cost is low, the method is suitable for large-scale production, and the prepared multilayer structure can effectively improve the conductivity of the electrode material and inhibit the shuttle effect, so that the electrochemical performance of the lithium-sulfur battery is enhanced.
Description
Technical Field
The invention belongs to the technical field of electrode materials of lithium-sulfur batteries, and particularly relates to a preparation method of a composite electrode material with a multilayer core-shell structure.
Background
In recent years, with the rapid development of the fields of mobile electronic devices, electric automobiles and renewable energy sources, people have made higher demands on energy storage devices. Because the traditional lithium ion battery cannot meet the development requirement more and more due to the limit of the energy density, the development of a new generation of energy storage system is necessary. Lithium-sulfur batteries using elemental sulfur as the positive electrode and metal lithium as the negative electrode are increasingly receiving wide attention due to their advantages of high energy density, overcharge resistance, rich sulfur resources, low cost, and the like. However, the current lithium-sulfur battery has the problems of poor conductivity, poor stability due to shuttle effect, low coulombic efficiency and the like, which prevent the commercial application of the lithium-sulfur battery. Therefore, how to further improve the performance of the lithium-sulfur battery has attracted research interest.
The carbon material has excellent conductivity, large specific surface area and rich pore channels. The internal pore canal is beneficial to the entering of sulfur, provides electronic and ionic conductivity, and can be used as a tiny electrochemical reaction generator to effectively inhibit the dissolution of polysulfide. The oxide has good adsorption performance on polysulfide, and can effectively inhibit shuttle effect.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a multilayer core-shell structure composite electrode material, the method is simple, the raw material source is convenient, the method is safe and environment-friendly, the cost is low, and the method is suitable for large-scale production.
The invention relates to a preparation method of a multilayer core-shell structure composite electrode material, which comprises the following steps:
(1) mixing SiO2Dispersing the microspheres in a Tris buffer solution, adding dopamine DA hydrochloride, stirring for reaction, centrifugally washing, and drying in vacuum to obtain SiO2@ PDA; wherein SiO is2The dosage ratio of the microspheres to the DA is 0.1-0.2 g: 0.2-0.3 g;
(2) will be provided withSiO obtained in step (1)2Dispersing @ PDA in the mixture of absolute ethyl alcohol and ammonia water, stirring for reaction, adding tetrabutyl titanate TBOT, continuing stirring for reaction, centrifugally washing, and vacuum drying to obtain SiO2@PDA@TiO2(ii) a Wherein SiO is2The dosage ratio of @ PDA, absolute ethyl alcohol, ammonia water and TBOT is 0.1-0.3 g: 100mL of: 0.3 mL: 0.5-1.5 mL;
(3) SiO obtained in the step (2)2@PDA@TiO2Dispersing in Tris buffer solution, adding dopamine DA hydrochloride, stirring for reaction, centrifugally washing, and vacuum drying to obtain SiO2@PDA@TiO2@ PDA; wherein SiO is2@PDA@TiO2And the dosage ratio of DA is 0.1-0.15 g: 0.1-0.2 g;
(4) SiO obtained in the step (3)2@PDA@TiO2Calcining @ PDA in inert atmosphere to obtain SiO2@C@TiO2Etching @ C with NaOH solution, centrifugally washing, and vacuum drying to obtain hollow-C @ TiO2@C；
(5) The hollow-C @ TiO obtained in the step (4)2@ C and sublimed sulfur according to the mass ratio of 1: 0.1-10 parts by weight of the mixture is uniformly mixed and ground, and then N is added2Calcining in the atmosphere to obtain the multilayer core-shell structure composite electrode material S @ C @ TiO2@C。
SiO in the step (1)2The microspheres are prepared from
The method takes 2.5mL of tetraethoxysilane TEOS, 27.5mL of absolute ethyl alcohol, 22.5mL of deionized water and 7.5mL of ammonia water with the mass fraction of 28% as raw materials, and the raw materials are stirred for 4-6 hours at normal temperature, centrifugally washed and dried in vacuum to prepare the white catalyst with the diameter of 145-155 nm.
The technological parameters of the stirring reaction in the step (2) are as follows: the reaction temperature is 40-50 ℃, and the reaction time is 10-40 min.
The TBOT is added in the step (2) and the technological parameters of the stirring reaction are as follows: the reaction temperature is 40-50 ℃, and the reaction time is 20-24 h.
And (3) the pH value of the Tris buffer solution in the steps (1) and (3) is 8-9.
And (3) stirring and reacting for 9-12 h.
The dispersion in the steps (1), (2) and (3) is ultrasonic dispersion, and the ultrasonic dispersion time is 10-40 min.
The process conditions of the centrifugal washing in the steps (1), (2), (3) and (4) are that deionized water and absolute ethyl alcohol are respectively used for washing for 3 times.
And (4) the inert atmosphere in the step (4) is nitrogen atmosphere or argon atmosphere.
The calcination process parameters in the step (4) are as follows: the calcination temperature is 400-900 ℃, the heating rate is 2 ℃/min, and the calcination time is 2-4 h.
The process conditions of NaOH etching in the step (4) are as follows: and etching the substrate for 4-20 hours at 40-100 ℃ by using 50-100 mL of 2-6 mol/L NaOH solution.
And (5) grinding for 10-40 min.
The calcination process parameters in the step (5) are as follows: the calcination temperature is 150-160 ℃, and the calcination time is 22-26 h.
And (4) applying the multilayer core-shell structure composite electrode material in the step (5) as a sulfur S-loaded conductive framework to an electrode material of a lithium sulfur battery.
Advantageous effects
(1) The invention has the advantages of convenient raw material source, low cost, simple preparation method, environmental protection and safety, and is suitable for large-scale production.
(2) The multilayer core-shell structure lithium-sulfur battery electrode material prepared by the preparation method has an internal cavity with the diameter of about 150nm and enough space for allowing volume expansion of sulfur generated in the charging and discharging processes; the multi-layer structure of the porous carbon material @ oxide @ carbon material can effectively improve the conductivity of the electrode material, can inhibit the shuttle effect, and has a stable structure, so that the electrochemical performance of the lithium-sulfur battery is enhanced.
Drawings
FIG. 1 is a scanning electron microscope image of low power field emission of the multilayer core-shell structure composite electrode material prepared in example 1 of the present invention;
FIG. 2 is a high-power field emission transmission electron microscope picture of the multilayer core-shell structure composite electrode material prepared in example 1 of the present invention;
fig. 3 is an electrical property test result of the multilayer core-shell structure composite electrode material prepared in example 1 of the present invention.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
(1) Weighing 27.5mL of absolute ethyl alcohol, 22.5mL of deionized water and 7.5mL of ammonia water with the mass fraction of 28%, pouring the mixture into a flask, uniformly stirring, dropwise adding 2.5mL of tetraethoxysilane TEOS, stirring at normal temperature for 4 hours, respectively centrifugally washing 3 times by using the absolute ethyl alcohol and the deionized water, and drying in vacuum to obtain white SiO2The diameter of the microsphere is 145-155 nm.
(2) 0.2g of SiO obtained in step (1)2Adding the microspheres into 100mL of Tris buffer solution (pH 8.5), performing ultrasonic treatment for 30min to uniformly disperse the microspheres, adding 0.2g of dopamine DA hydrochloride, stirring to react for 9h, performing centrifugal washing for 3 times by using absolute ethyl alcohol and deionized water respectively, and performing vacuum drying to obtain brownish black SiO2@PDA。
(3) 0.14g of SiO obtained in step (2)2Adding @ PDA into a mixed solution of 100mL of absolute ethyl alcohol and 0.3mL of ammonia water, performing ultrasonic treatment for 30min to uniformly disperse, stirring and reacting for 30min at 45 ℃, adding 0.75mL of tetrabutyl titanate TBOT, continuing stirring and reacting for 20h, respectively performing centrifugal washing for 3 times by using absolute ethyl alcohol and deionized water, and performing vacuum drying to obtain brown SiO2@PDA@TiO2。
(4) 0.1g of SiO obtained in step (3)2@PDA@TiO2Adding into 100mL Tris buffer solution (pH 8.5), ultrasonically dispersing for 30min, adding 0.1g dopamine DA hydrochloride, stirring for reaction for 9h, centrifuging and washing with anhydrous ethanol and deionized water for 3 times, and vacuum drying to obtain brownish black SiO2@PDA@TiO2@PDA。
(5) SiO obtained in the step (4)2@PDA@TiO2@ PDA was placed in a tube furnace under an inert atmosphere (N)2Or Ar) calcining at 750 ℃ for 2h, and heating rate is 2 ℃/min to obtain black SiO2@C@TiO2@ C, etching with 4mol/L NaOH, stirring at 60 deg.C for 6h, centrifuging and washing with anhydrous ethanol and deionized water for 3 times, and vacuum drying to obtain black hollow-C @ TiO2@C。
(6) The hollow-C @ TiO obtained in the step (5)2@ C, and sublimed sulfur in a mass ratio of 1: 4 grinding for 30min, mixing uniformly, and adding into N2Calcining for 24 hours at the temperature of 155 ℃ in the atmosphere to obtain the black multilayer core-shell structure composite electrode material S @ C @ TiO2@C。
The multilayer core-shell structure composite electrode material S @ C @ TiO obtained in the embodiment2The low power field emission scanning electron microscope picture of @ C is shown in FIG. 1, and the high power field emission transmission electron microscope picture is shown in FIG. 2, which shows that the sulfur-containing material has an internal cavity with a diameter of about 150nm and sufficient space to allow volume expansion of sulfur generated during charging and discharging.
For the multilayer core-shell structure composite electrode material S @ C @ TiO obtained in the embodiment2The results of testing the electrical properties at @ C are shown in FIG. 3, which indicates that the specific discharge capacity at 0.1C is 1184mAh g-1The specific discharge capacities at 0.2C, 0.5C, 1C, 2C and 5C multiplying powers are 801mAh g respectively-1，614mAh g-1，503mAh g-1，397mAh g-1，336mAh g-1。
Example 2
(1) 0.2g of SiO obtained in step (1) of example 12Adding the microspheres into 100mL of Tris buffer solution (pH 8.5), performing ultrasonic treatment for 30min to uniformly disperse the microspheres, adding 0.2g of dopamine DA hydrochloride, stirring to react for 9h, performing centrifugal washing for 3 times by using absolute ethyl alcohol and deionized water respectively, and performing vacuum drying to obtain brownish black SiO2@PDA。
(2) 0.14g of SiO obtained in step (1)2Adding @ PDA into a mixed solution of 100mL of absolute ethyl alcohol and 0.3mL of ammonia water, performing ultrasonic treatment for 30min to uniformly disperse, stirring and reacting for 30min at 45 ℃, adding 0.75mL of tetrabutyl titanate TBOT, continuing stirring and reacting for 20h, and performing ultrasonic reaction on the mixture by using absolute ethyl alcohol,Centrifugally washing with deionized water for 3 times, and vacuum drying to obtain brown SiO2@PDA@TiO2。
(3) 0.12g of SiO obtained in step (2)2@PDA@TiO2Adding into 100mL Tris buffer solution (pH 8.5), ultrasonically dispersing for 30min, adding 0.1g dopamine DA hydrochloride, stirring for reaction for 9h, centrifuging and washing with anhydrous ethanol and deionized water for 3 times, and vacuum drying to obtain brownish black SiO2@PDA@TiO2@PDA。
(4) SiO obtained in the step (3)2@PDA@TiO2@ PDA was placed in a tube furnace under an inert atmosphere (N)2Or Ar) calcining at 750 ℃ for 2h, and heating rate is 2 ℃/min to obtain black SiO2@C@TiO2@ C, etching with 4mol/L NaOH, stirring at 60 deg.C for 6h, centrifuging and washing with anhydrous ethanol and deionized water for 3 times, and vacuum drying to obtain black hollow-C @ TiO2@C。
(5) The hollow-C @ TiO obtained in the step (4)2@ C, and sublimed sulfur in a mass ratio of 1: 4 grinding for 30min, mixing uniformly, and adding into N2Calcining for 24 hours at the temperature of 155 ℃ in the atmosphere to obtain the black multilayer core-shell structure composite electrode material S @ C @ TiO2@C。
For the multilayer core-shell structure composite electrode material S @ C @ TiO obtained in the embodiment2Testing the electrical properties of @ C, it can be seen that the specific discharge capacity of the first coil is 1100mAh g at 0.1C-1The specific discharge capacities at 0.2C, 0.5C, 1C, 2C and 5C multiplying powers are respectively 805mAh g-1，632mAh g-1，517mAh g-1，426mAh g-1，325mAh g-1。
Example 3
(1) 0.2g of SiO obtained in step (1) of example 12Adding the microspheres into 100mL of Tris buffer solution (pH 8.5), performing ultrasonic treatment for 30min to uniformly disperse the microspheres, adding 0.2g of dopamine DA hydrochloride, stirring to react for 9h, performing centrifugal washing for 3 times by using absolute ethyl alcohol and deionized water respectively, and performing vacuum drying to obtain brownish black SiO2@PDA。
(2) 0.14g of SiO obtained in step (1)2Adding @ PDA into a mixed solution of 100mL of anhydrous ethanol and 0.3mL of ammonia water, performing ultrasonic treatment for 30min to disperse uniformly, and stirring at 45 DEG CReacting for 30min, adding 0.75mL tetrabutyl titanate TBOT, continuing stirring to react for 20h, respectively centrifugally washing with absolute ethyl alcohol and deionized water for 3 times, and drying in vacuum to obtain brown SiO2@PDA@TiO2。
(3) 0.15g of SiO obtained in step (2)2@PDA@TiO2Adding into 100mL Tris buffer solution (pH 8.5), ultrasonically dispersing for 30min, adding 0.1g dopamine DA hydrochloride, stirring for reaction for 9h, centrifuging and washing with anhydrous ethanol and deionized water for 3 times, and vacuum drying to obtain brownish black SiO2@PDA@TiO2@PDA。
(4) SiO obtained in the step (3)2@PDA@TiO2@ PDA was placed in a tube furnace under an inert atmosphere (N)2Or Ar) calcining at 750 ℃ for 2h, and heating rate is 2 ℃/min to obtain black SiO2@C@TiO2@ C, etching with 4mol/L NaOH, stirring at 60 deg.C for 6h, centrifuging and washing with anhydrous ethanol and deionized water for 3 times, and vacuum drying to obtain black hollow-C @ TiO2@C。
(5) The hollow-C @ TiO obtained in the step (4)2@ C, and sublimed sulfur in a mass ratio of 1: 4 grinding for 30min, mixing uniformly, and adding into N2Calcining for 24 hours at the temperature of 155 ℃ in the atmosphere to obtain the black multilayer core-shell structure composite electrode material S @ C @ TiO2@C。
For the multilayer core-shell structure composite electrode material S @ C @ TiO obtained in the embodiment2Testing the electrical properties of @ C, it can be known that the specific discharge capacity of the first coil is 891mAh g under 0.1C-1The specific discharge capacities at 0.2C, 0.5C, 1C, 2C and 5C multiplying powers are 652mAh g-1，400mAh g-1，298mAh g-1，277mAh g-1，215mAh g-1。
Claims (10)
1. A preparation method of a multilayer core-shell structure composite electrode material comprises the following steps:
(1) mixing SiO2Dispersing the microspheres in a Tris buffer solution, adding dopamine hydrochloride, stirring for reaction, centrifugally washing, and drying in vacuum to obtain SiO2@ PDA; wherein SiO is2The dosage ratio of the microspheres to the dopamine hydrochloride is 0.1-0.2 g: 0.2-0.3 g;
(2) SiO obtained in the step (1)2Dispersing @ PDA in the mixture of absolute ethyl alcohol and ammonia water, stirring for reaction, adding tetrabutyl titanate TBOT, continuing stirring for reaction, centrifugally washing, and vacuum drying to obtain SiO2@PDA@TiO2(ii) a Wherein SiO is2The dosage ratio of @ PDA, absolute ethyl alcohol, ammonia water and TBOT is 0.1-0.3 g: 100mL of: 0.3 mL: 0.5-1.5 mL;
(3) SiO obtained in the step (2)2@PDA@TiO2Dispersing in Tris buffer solution, adding dopamine hydrochloride, stirring for reaction, centrifugally washing, and vacuum drying to obtain SiO2@PDA@TiO2@ PDA; wherein SiO is2@PDA@TiO2The dosage ratio of the dopamine hydrochloride is 0.1-0.15 g: 0.1-0.2 g;
(4) SiO obtained in the step (3)2@PDA@TiO2Calcining @ PDA in inert atmosphere to obtain SiO2@C@TiO2Etching @ C with NaOH solution, centrifugally washing, and vacuum drying to obtain hollow-C @ TiO2@C；
(5) The hollow-C @ TiO obtained in the step (4)2@ C and sublimed sulfur according to the mass ratio of 1: 0.1-10 parts by weight of the mixture is uniformly mixed and ground, and then N is added2Calcining in the atmosphere to obtain the multilayer core-shell structure composite electrode material S @ C @ TiO2@C。
2. The preparation method of the multilayer core-shell structure composite electrode material according to claim 1, characterized in that: SiO in the step (1)2The microspheres are prepared from
The method is characterized by taking 2.5mL of tetraethoxysilane TEOS, 27.5mL of absolute ethyl alcohol, 22.5mL of deionized water and 7.5mL of ammonia water with the mass fraction of 26-30% as raw materials, stirring at normal temperature for 4-6 h, centrifuging, washing and drying in vacuum.
3. The preparation method of the multilayer core-shell structure composite electrode material according to claim 1, characterized in that: the technological parameters of the stirring reaction in the step (2) are as follows: the reaction temperature is 40-50 ℃, and the reaction time is 10-40 min; the technological parameters of adding TBOT and continuously stirring for reaction are as follows: the reaction temperature is 40-50 ℃, and the reaction time is 20-24 h.
4. The preparation method of the multilayer core-shell structure composite electrode material according to claim 1, characterized in that: the pH value of the Tris buffer solution in the steps (1) and (3) is 8-9; the stirring reaction time is 9-12 h.
5. The preparation method of the multilayer core-shell structure composite electrode material according to claim 1, characterized in that: the dispersion in the steps (1), (2) and (3) is ultrasonic dispersion, and the ultrasonic dispersion time is 10-40 min.
6. The preparation method of the multilayer core-shell structure composite electrode material according to claim 1, characterized in that: the process conditions of the centrifugal washing in the steps (1), (2), (3) and (4) are that deionized water and absolute ethyl alcohol are respectively used for washing for 3 times.
7. The preparation method of the multilayer core-shell structure composite electrode material according to claim 1, characterized in that: the inert atmosphere in the step (4) is argon atmosphere; the calcination process parameters are as follows: the calcination temperature is 400-900 ℃, the heating rate is 2 ℃/min, and the calcination time is 2-4 h.
8. The preparation method of the multilayer core-shell structure composite electrode material according to claim 1, characterized in that: the process conditions of NaOH etching in the step (4) are as follows: and etching the substrate for 4-20 hours at 40-100 ℃ by using 50-100 mL of 2-6 mol/L NaOH solution.
9. The preparation method of the multilayer core-shell structure composite electrode material according to claim 1, characterized in that: the grinding time in the step (5) is 10-40 min; the calcination process parameters are as follows: the calcination temperature is 150-160 ℃, and the calcination time is 22-26 h.
10. The preparation method of the multilayer core-shell structure composite electrode material according to claim 1, characterized in that: and (4) applying the multilayer core-shell structure composite electrode material in the step (5) as a sulfur S-loaded conductive framework to an electrode material of a lithium sulfur battery.
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