CN112479258A - Molybdenum disulfide-carbon hollow sphere and preparation method and application thereof - Google Patents
Molybdenum disulfide-carbon hollow sphere and preparation method and application thereof Download PDFInfo
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- CN112479258A CN112479258A CN202011501382.8A CN202011501382A CN112479258A CN 112479258 A CN112479258 A CN 112479258A CN 202011501382 A CN202011501382 A CN 202011501382A CN 112479258 A CN112479258 A CN 112479258A
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- molybdenum disulfide
- hollow sphere
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- molybdenum
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- QXDDUAGHAWNZHJ-UHFFFAOYSA-N [C].[Mo](=S)=S Chemical compound [C].[Mo](=S)=S QXDDUAGHAWNZHJ-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 57
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 43
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 29
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 25
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 24
- 239000011733 molybdenum Substances 0.000 claims abstract description 24
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000001291 vacuum drying Methods 0.000 claims abstract description 23
- 238000005406 washing Methods 0.000 claims abstract description 17
- 239000002135 nanosheet Substances 0.000 claims abstract description 16
- 238000001354 calcination Methods 0.000 claims abstract description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 239000000047 product Substances 0.000 claims abstract description 10
- 150000003839 salts Chemical group 0.000 claims abstract description 10
- 239000013067 intermediate product Substances 0.000 claims abstract description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 28
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 27
- 229910052717 sulfur Inorganic materials 0.000 claims description 27
- 239000011593 sulfur Substances 0.000 claims description 27
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000011780 sodium chloride Substances 0.000 claims description 14
- 239000001103 potassium chloride Substances 0.000 claims description 13
- 235000011164 potassium chloride Nutrition 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical group [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 11
- 239000011609 ammonium molybdate Substances 0.000 claims description 11
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 11
- 229940010552 ammonium molybdate Drugs 0.000 claims description 11
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 7
- 229930006000 Sucrose Natural products 0.000 claims description 7
- 239000008103 glucose Substances 0.000 claims description 7
- 239000005720 sucrose Substances 0.000 claims description 7
- 239000011258 core-shell material Substances 0.000 claims description 6
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- 229960003638 dopamine Drugs 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- WFLYOQCSIHENTM-UHFFFAOYSA-N molybdenum(4+) tetranitrate Chemical compound [N+](=O)([O-])[O-].[Mo+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] WFLYOQCSIHENTM-UHFFFAOYSA-N 0.000 claims description 3
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 claims description 3
- 239000011684 sodium molybdate Substances 0.000 claims description 3
- 235000015393 sodium molybdate Nutrition 0.000 claims description 3
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 3
- 125000000185 sucrose group Chemical group 0.000 claims description 3
- 239000007773 negative electrode material Substances 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 229910052593 corundum Inorganic materials 0.000 description 23
- 239000010431 corundum Substances 0.000 description 23
- 229910052573 porcelain Inorganic materials 0.000 description 23
- 238000004321 preservation Methods 0.000 description 21
- 239000012153 distilled water Substances 0.000 description 18
- 238000012360 testing method Methods 0.000 description 17
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 239000002077 nanosphere Substances 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 11
- 238000001035 drying Methods 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 238000003917 TEM image Methods 0.000 description 8
- 239000012300 argon atmosphere Substances 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 230000010287 polarization Effects 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- -1 transition metal sulfide Chemical class 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241000257465 Echinoidea Species 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- XMYKNCNAZKMVQN-NYYWCZLTSA-N [(e)-(3-aminopyridin-2-yl)methylideneamino]thiourea Chemical compound NC(=S)N\N=C\C1=NC=CC=C1N XMYKNCNAZKMVQN-NYYWCZLTSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZKKLPDLKUGTPME-UHFFFAOYSA-N diazanium;bis(sulfanylidene)molybdenum;sulfanide Chemical compound [NH4+].[NH4+].[SH-].[SH-].S=[Mo]=S ZKKLPDLKUGTPME-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000010325 electrochemical charging Methods 0.000 description 1
- 238000010326 electrochemical discharging Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/06—Sulfides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
-
- B01J35/33—
-
- B01J35/51—
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- 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 molybdenum disulfide-carbon hollow sphere and a preparation method and application thereof, and belongs to the field of preparation of nano materials. The preparation method comprises the steps of preparing a precursor solution by taking a molybdenum source, thiourea, a carbon source and an inorganic salt template as raw materials, then carrying out vacuum drying treatment on the obtained precursor solution to obtain a core/shell intermediate product with an inorganic salt core, carrying out calcination treatment to obtain a core/shell structure product with a molybdenum disulfide outer layer, and washing to remove the inorganic salt core to obtain the molybdenum disulfide-carbon hollow sphere. The preparation method has the advantages of simple process flow, low production cost and energy consumption and easy large-scale production. The nanoscale molybdenum disulfide-carbon hollow sphere prepared by the invention is hollow, takes the carbon hollow sphere as a core and takes the molybdenum disulfide nanosheet as a shell, and has a large specific surface area, so that the nanoscale molybdenum disulfide-carbon hollow sphere has more reactive active sites, has excellent electrocatalytic performance and battery performance, and can be applied to the fields of energy, catalysis and the like.
Description
Technical Field
The invention belongs to the field of nano material preparation, and particularly relates to a molybdenum disulfide-carbon hollow sphere and a preparation method and application thereof.
Background
Molybdenum disulfide is a typical two-dimensional transition metal sulfide, and is widely used in the fields of solid lubricants, catalysis, supercapacitors and battery energy storage due to the graphene-like layered structure. Molybdenum disulfide has a composition of almost 670mA · h · g as a battery material-1Due to its structural characteristics, the lithium ion is easy to insert and extract. In addition, the layered structure of molybdenum disulfide also endows the molybdenum disulfide with more active sites, so that the molybdenum disulfide is widely used as a catalyst for hydrogen evolution reaction. However, pure molybdenum disulfide is not ideal in both applications, and as a battery material, the pure molybdenum disulfide has poor stability and fast capacity fading; as an electrocatalyst, pure molybdenum disulfide is more prone to aggregation, which greatly reduces its own active sites. Therefore, the preparation of the molybdenum disulfide composite material to improve the electrochemical performance of the molybdenum disulfide composite material becomes a hot topic.
Among the numerous composite candidate materials, carbon materials, particularly nano hollow carbon spheres, are particularly desirable to researchers. The nano hollow carbon sphere has a unique hollow structure and excellent physical and chemical properties, and shows a huge application prospect in the fields of energy conversion, adsorption, biomedicine and catalysis. However, in order to obtain hollow carbon spheres with excellent performance, the morphology and structure of the hollow carbon spheres are generally optimized and controlled. The problems faced at present are that the process is complicated, difficult to control, needs to sacrifice the template and cannot be recycled. Therefore, the development of a preparation method which is efficient, pollution-free and low in cost has very important significance.
The invention patent CN 105098151A discloses a molybdenum disulfide-carbon hollow sphere hybrid material and a preparation method thereof. According to the method, amino modified silicon dioxide particles are used as a template, then an organic pyrolytic carbon raw material and ammonium tetrathiomolybdate are subjected to solvothermal reaction to coat the template, high-temperature treatment is carried out under an inert atmosphere, and finally the silicon dioxide template is removed to obtain the molybdenum disulfide-carbon hollow sphere. The method has the advantages of complex process and complex preparation process, hydrofluoric acid is required to be used when the silicon dioxide is removed, the production cost is further increased, and the silicon dioxide cannot be recycled. The invention patent CN 108091837A discloses a molybdenum disulfide/carbon composite material, a preparation method and application thereof. The method comprises the steps of preparing hollow carbon spheres with different layers by adjusting the amounts of 3-AP, formaldehyde and ammonia water, filtering, washing, drying, grinding and calcining after preparing the hollow spheres, adding the hollow spheres into ammonium molybdate and thiourea solution for heating reaction, and finally filtering, washing and drying. The prepared product is applied to the field of lithium ion batteries. Although the number of carbon layers is effectively controlled, the process is complicated, particularly reagents used in the preparation process and acetone used for washing belong to organic substances, except environmental pollution, more harmful factors are difficult to control, and the wide application of the waste liquor after treatment is further limited.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a molybdenum disulfide-carbon hollow sphere, and a preparation method and application thereof. The invention provides a preparation method of a molybdenum disulfide-carbon hollow sphere, which is pollution-free, green and environment-friendly and has a simple process.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the invention discloses a preparation method of molybdenum disulfide-carbon hollow spheres, which comprises the following steps: uniformly dispersing a molybdenum source, a sulfur source, a carbon source and an inorganic salt template in water to obtain a precursor solution; and carrying out vacuum drying treatment on the obtained precursor solution to obtain a core/shell intermediate product with an inorganic salt core, calcining the obtained core/shell intermediate product to obtain a core/shell structure product with a molybdenum disulfide outer layer, and washing the obtained core/shell structure product with the molybdenum disulfide outer layer to remove the inorganic salt core to obtain the molybdenum disulfide-carbon hollow sphere.
Preferably, the molybdenum source is ammonium molybdate, sodium molybdate, molybdenum chloride or molybdenum nitrate, and the sulfur source is thiourea.
Preferably, the carbon source is sucrose, glucose or dopamine.
Preferably, the inorganic salt template is sodium chloride or potassium chloride.
Preferably, the mass ratio of the inorganic salt template to the carbon source is 10 (1-5).
Preferably, the usage ratio of the molybdenum source and the sulfur source is as follows: the molar ratio of the molybdenum element to the sulfur element is 1: 2.
Preferably, the total mass of the molybdenum source and the sulfur source is 10-100% of the total mass of the carbon source.
Preferably, the vacuum drying conditions are as follows: the vacuum drying temperature is 40-80 ℃, and the vacuum drying time is 12-24 h.
Further preferably, the temperature of the vacuum drying is 70 ℃ and the time is 18 h.
Preferably, the conditions of the calcination are: in an inert atmosphere, the heating rate is 1-5 ℃/min, the heat preservation temperature is 400-800 ℃, and the heat preservation time is 2-6 h.
The invention also discloses a molybdenum disulfide-carbon hollow sphere prepared by the preparation method, which comprises the following steps: forming the molybdenum disulfide-carbon hollow sphere with a hollow core-shell structure by taking the carbon hollow sphere as a core and taking a molybdenum disulfide nanosheet as a shell, wherein the molybdenum disulfide-carbon hollow sphere is in a monodispersed state;
the diameter of the molybdenum disulfide-carbon hollow sphere is 100-1000 nm, and the diameter of the carbon hollow sphere is 10-900 nm.
Preferably, the diameter of the molybdenum disulfide-carbon hollow sphere is 260-930 nm, and the diameter of the carbon hollow sphere is 220-900 nm.
Further preferably, the thickness of the shell layer of the molybdenum disulfide nanosheet is 10-70 nm.
Preferably, the molybdenum disulfide-carbon hollow sphere is 10 mA-cm-1The polarization voltage corresponding to the current is 150-220 mV.
Preferably, the molybdenum disulfide-carbon hollow sphere takes 0.01-3.0V as a charging and discharging voltage range, and the specific capacity after electrochemical charging and discharging circulation for 40 circles is 620-713 mA-h/g.
The invention also discloses application of the molybdenum disulfide-carbon hollow sphere as a hydrogen evolution catalyst.
The invention also discloses an application of the molybdenum disulfide-carbon hollow sphere in preparation of a lithium battery anode material.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a preparation method of molybdenum disulfide-carbon hollow spheres, which is based on the principle that a sol-gel method is adopted: during vacuum drying, because the inorganic salt template in the precursor solution is separated out along with the reduction of moisture, an inorganic salt core is formed at first, and along with the continuous reduction of moisture, a molybdenum source, a sulfur source and a carbon source are gathered on the surface of the inorganic salt core to form a shell, so that a core/shell intermediate product with the inorganic salt core is formed; after high-temperature calcination treatment, the molybdenum element and the sulfur element in the molybdenum source and the sulfur source continue to form a molybdenum disulfide outer layer, and a core/shell structure product with the molybdenum disulfide outer layer is formed; and finally, washing to remove inorganic salt cores contained in the hollow molybdenum disulfide-carbon hollow spheres. In addition, the inorganic salt template is used as a template sacrificial agent, and can be dried and separated out for continuous recycling after being washed and removed, so that the waste of production resources is avoided, and the environment is friendly and pollution-free; compared with the existing method, the selection of the inorganic salt template is more green and convenient to process. Therefore, the preparation method has the characteristics of simple process flow, convenient operation, no need of using an organic solvent, low production cost and energy consumption, easy large-scale production and wide universality.
Further, sodium chloride or potassium chloride is used as a template sacrificial agent, and after being washed by distilled water, the sodium chloride or potassium chloride can be continuously recycled and reutilized after being dried, so that the sodium chloride or potassium chloride can be continuously utilized; secondly, the sodium chloride or potassium chloride selected is readily soluble in water, ensuring that they are completely removed during the washing process.
The method comprises the steps of adding molybdenum and sulfur elements into sodium chloride or potassium chloride serving as a template and sucrose or organic matters serving as a carbon source according to a molar ratio of 1:2, and then calcining at high temperature and washing with distilled water to obtain the molybdenum disulfide-carbon hollow sphere.
Furthermore, the thickness of the outer shell layer of the molybdenum disulfide can be controlled by controlling the dosage ratio of the carbon source and the inorganic salt template, so that the shape of the product molybdenum disulfide-carbon hollow sphere can be controllably adjusted by the preparation method.
The invention also discloses the molybdenum disulfide-carbon hollow sphere prepared by the preparation method, the molybdenum disulfide nanosheet is taken as the shell, the nanoscale particle size can be effectively achieved, and the two-dimensional layered structure of molybdenum disulfide and the hollow core-shell structure of the molybdenum disulfide-carbon hollow sphere are combined to enable the molybdenum disulfide-carbon hollow sphere to have a higher specific surface area, so that the active sites of molybdenum disulfide are greatly enriched. In addition, the molybdenum disulfide-carbon hollow spheres prepared by the preparation method are similar to sea urchins, the core-shell structure of each molybdenum disulfide-carbon hollow sphere is obvious, aggregation does not occur, a monodispersed state is presented, and the electrochemical performance of the material can be effectively enhanced.
The invention also discloses application of the molybdenum disulfide-carbon hollow sphere as a hydrogen evolution catalyst and application of the molybdenum disulfide-carbon hollow sphere in preparation of a lithium battery cathode material. The molybdenum disulfide-carbon hollow sphere has good battery performance, and the electrocatalytic hydrogen evolution performance is not negligible. The related tests prove that the sample is 10mA cm-1The polarization voltage corresponding to the current is 150-220 mV, so that the electrocatalytic hydrogen evolution performance is excellent; the specific capacity is 620-713 mA.h/g after electrochemical charge-discharge circulation for 40 circles by taking 0.01-3.0V as the charge-discharge voltage range; therefore, the molybdenum disulfide-carbon hollow sphere has excellent electrocatalytic performance and battery performance.
Drawings
FIG. 1 is an XRD pattern of a sample of a hollow molybdenum disulfide-carbon sphere prepared in example 1;
FIG. 2 is a TEM image of a hollow sphere of molybdenum disulfide-carbon prepared in example 2;
FIG. 3 is a TEM image of a hollow sphere of molybdenum disulfide-carbon prepared in example 3;
FIG. 4 is a TEM image of a hollow sphere of molybdenum disulfide-carbon prepared in example 4;
FIG. 5 is the LSV curve of the catalytic hydrogen evolution of the hollow molybdenum disulfide-carbon spheres prepared in example 4;
figure 6 is a graph of the cell cycling performance of the molybdenum disulfide-carbon hollow spheres prepared in example 4;
FIG. 7 is a TEM image of a hollow molybdenum disulfide-carbon sphere prepared in example 5;
FIG. 8 is the LSV curve of the catalytic hydrogen evolution of the hollow molybdenum disulfide-carbon spheres prepared in example 5;
figure 9 is the cell cycling performance of the molybdenum disulfide-carbon hollow spheres prepared in example 5.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention discloses a molybdenum disulfide-carbon hollow sphere which is prepared by preparing a precursor solution from a molybdenum source, a sulfur source, a carbon source and an inorganic salt template through a sol-gel method, vacuum drying and high-temperature calcination; wherein the molar ratio of the molybdenum element to the sulfur element is 1: 2;
the molybdenum disulfide-carbon hollow sphere takes the carbon hollow sphere as a core and the molybdenum disulfide as a shell, and presents a hollow molybdenum disulfide-carbon hollow sphere with a core-shell structure.
Specifically, the molybdenum source is ammonium molybdate, sodium molybdate, molybdenum chloride or molybdenum nitrate; the sulfur source is thiourea; the carbon source is sucrose, glucose and dopamine; the inorganic salt template is sodium chloride or potassium chloride.
The invention also discloses a preparation method of the molybdenum disulfide-carbon hollow sphere, which comprises the following steps:
1) weighing an inorganic salt template (sodium chloride or potassium chloride) and a carbon source, a molybdenum source and a sulfur source, dissolving the inorganic salt template and the carbon source, the molybdenum source and the sulfur source in distilled water, and stirring to form a colorless and transparent precursor solution; weighing a molybdenum source and a sulfur source according to the molar ratio of the molybdenum element to the sulfur element of 1: 2;
2) pouring the prepared precursor solution into a corundum porcelain boat, and placing the corundum porcelain boat in a vacuum drying oven for vacuum drying for 12-24 hours at the temperature of 40-80 ℃; (formation of inorganic salt core)
3) Calcining the product obtained by vacuum drying at 400-800 ℃ under inert gas; (formation of molybdenum disulfide outer layer)
4) And washing the calcined product with distilled water (removing the inorganic salt core) to obtain the molybdenum disulfide-carbon hollow sphere.
And 4) forming the molybdenum disulfide-carbon hollow sphere with a hollow core-shell structure by taking the carbon hollow sphere as a core and taking a molybdenum disulfide nanosheet as a shell.
Specifically, the molybdenum disulfide-carbon hollow spheres are in a monodisperse state.
Wherein the mass ratio of the sodium chloride or the potassium chloride to the carbon source is (0.1-5) to (0.01-0.5).
Wherein the total mass of the molybdenum source and the sulfur source is 10-100% of the total mass of the carbon source.
Preferably, the vacuum drying temperature is 70 ℃ and the drying time is 18 h.
Wherein, the calcining conditions are as follows: in an inert atmosphere, the heating rate is 1-5 ℃/min, the heat preservation temperature is 400-800 ℃, and the heat preservation time is 2-6 h; preferably, the conditions of calcination are: in an argon atmosphere, the heating rate is 1-5 ℃/min, the heat preservation temperature is 600-800 ℃, and the heat preservation time is 2-4 h.
Specifically, in the embodiment of the invention, the diameter of the obtained molybdenum disulfide-carbon hollow sphere is 100-1000 nm, and the diameter of the carbon hollow sphere is 10-500 nm; preferably, the diameter of the molybdenum disulfide-carbon hollow sphere is 260-930 nm, the diameter of the carbon hollow sphere is 220-900 nm, and the thickness of the shell layer of the molybdenum disulfide nanosheet is 10-70 nm.
As the reaction conditions in the preparation method are simple and easy to control, the reactants are common and mild in performance, and toxic substances such as hydrofluoric acid, organic reagents and the like are not needed in the treatment process, the used template has recoverability, which is incomparable with a silicon dioxide template. Therefore, the preparation method has popularization applicability: the method can be used for preparing the molybdenum disulfide-carbon hollow sphere and provides possibility for the design of hollow structures of other metals or transition metals. The invention is described in further detail below with reference to the following figures and specific examples:
example 1
(1) 0.1104g of ammonium molybdate, 0.0952g of thiourea, 2g of sucrose and 4g of sodium chloride were weighed respectively, added to 20mL of distilled water, and stirred to form a colorless transparent solution.
Wherein the total mass of the molybdenum source and the sulfur source is 100 percent of the total mass of the carbon source.
(2) Pouring the colorless solution into a corundum porcelain boat, placing the corundum porcelain boat into a vacuum drying oven, and drying the corundum porcelain boat for 18 hours at 70 ℃.
(3) And (3) putting the dried sample into a tubular furnace, wherein the heating rate is 2 ℃/min, the heat preservation temperature is 800 ℃, and the heat preservation time is 4h under the argon atmosphere.
(4) And after the temperature of the furnace is reduced, centrifugally washing the obtained sample for 5 times by using distilled water to obtain the molybdenum disulfide-carbon hollow sphere sample.
And (3) carrying out X-ray analysis diffraction on the prepared sample to obtain an XRD (X-ray diffraction) pattern as shown in figure 1, wherein the position of an XRD peak of the prepared sample conforms to the standard peak types of molybdenum disulfide and carbon, and the prepared sample is proved to be pure molybdenum disulfide-carbon.
Example 2
(1) 0.0736g of ammonium molybdate, 0.0634g of thiourea, 0.2g of sucrose and 2g of sodium chloride were weighed out separately and added to 20mL of distilled water, followed by stirring to obtain a colorless transparent solution.
Wherein the total mass of the molybdenum source and the sulfur source is 68.5 percent of the total mass of the carbon source.
(2) Pouring the colorless solution into a corundum porcelain boat, placing the corundum porcelain boat into a vacuum drying oven, and drying the corundum porcelain boat for 18 hours at 70 ℃.
(3) And (3) putting the dried sample into a tubular furnace, wherein the heating rate is 2 ℃/min, the heat preservation temperature is 600 ℃, and the heat preservation time is 2h under the argon atmosphere.
(4) And after the temperature of the furnace is reduced, centrifugally washing the obtained sample for 5 times by using distilled water to obtain the molybdenum disulfide-carbon hollow sphere sample.
A TEM image of the prepared molybdenum disulfide-carbon hollow sphere sample is shown in fig. 2, and it can be seen that after calcining at 600 ℃ and keeping the temperature for 2 hours, the prepared molybdenum disulfide-carbon hollow sphere sample presents a hollow nanosphere shape, the hollow nanosphere is composed of a carbon hollow sphere and molybdenum disulfide nanosheets on the outer layer, the average diameter is 418nm, the average size of the carbon hollow sphere inside is 323nm, and the average thickness of the molybdenum disulfide nanosheets is about 48 nm.
Example 3
(1) 0.1104g of ammonium molybdate, 0.0952g of thiourea, 0.4g of glucose and 2g of sodium chloride were weighed respectively, added to 15mL of distilled water, and stirred to form a colorless transparent solution.
Wherein the total mass of the molybdenum source and the sulfur source is 51.4 percent of the total mass of the carbon source.
(2) Pouring the colorless solution into a corundum porcelain boat, placing the corundum porcelain boat into a vacuum drying oven, and drying the corundum porcelain boat for 18 hours at 70 ℃.
(3) And (3) putting the dried sample into a tubular furnace, wherein the heating rate is 2 ℃/min, the heat preservation temperature is 600 ℃, and the heat preservation time is 4h under the argon atmosphere.
(4) And after the temperature of the furnace is reduced, centrifugally washing the obtained sample for 5 times by using distilled water to obtain the molybdenum disulfide-carbon hollow sphere sample.
A TEM image of the prepared molybdenum disulfide-carbon hollow sphere sample is shown in fig. 3, and it can be seen that after calcining at 600 ℃ and keeping the temperature for 4 hours, the prepared molybdenum disulfide-carbon hollow sphere sample presents a hollow nanosphere shape, the hollow nanosphere is composed of a carbon hollow sphere and molybdenum disulfide nanosheets on the outer layer, the average diameter is 331nm, the average size of the carbon hollow sphere inside is 228nm, and the average thickness of the molybdenum disulfide nanosheets is about 52 nm.
Example 4
(1) 0.1104g of ammonium molybdate, 0.0952g of thiourea, 2g of sucrose and 4g of sodium chloride were weighed respectively, added to 20mL of distilled water, and stirred to form a colorless transparent solution.
Wherein the total mass of the molybdenum source and the sulfur source is 10.3 percent of the total mass of the carbon source.
(2) Pouring the colorless solution into a corundum porcelain boat, placing the corundum porcelain boat into a vacuum drying oven, and drying the corundum porcelain boat for 18 hours at 70 ℃.
(3) And (3) putting the dried sample into a tubular furnace, wherein the heating rate is 2 ℃/min, the heat preservation temperature is 800 ℃, and the heat preservation time is 2h under the argon atmosphere.
(4) And after the temperature of the furnace is reduced, centrifugally washing the obtained sample for 5 times by using distilled water to obtain the molybdenum disulfide-carbon hollow sphere sample.
A TEM image of the prepared molybdenum disulfide-carbon hollow sphere sample is shown in fig. 4, and it can be seen that after calcination at 800 ℃ and heat preservation are carried out for 2 hours, the prepared molybdenum disulfide-carbon hollow sphere sample presents a hollow nanosphere shape, the hollow nanosphere is composed of a carbon hollow sphere and molybdenum disulfide nanosheets on the outer layer, the average diameter is 264nm, the average size of the carbon hollow sphere inside is 235nm, and the average thickness of the molybdenum disulfide nanosheets is about 15 nm.
Using a three-electrode system, silver chlorideThe electrode is a counter electrode, the platinum electrode is a reference electrode, the prepared molybdenum disulfide-carbon hollow sphere is a working electrode, 0.5mol/L potassium hydroxide is electrolyte, an electrochemical workstation is used for carrying out an electrocatalytic hydrogen evolution test, and the obtained polarization curve is shown in fig. 5. 10mA cm-1The corresponding polarization voltage is 156mV, which shows that the sample has better electrocatalytic performance.
The Shenzhen Xinwei battery tester is adopted to test the charge and discharge performance of the battery of the sample in the embodiment, a constant-current charge and discharge specific capacity cycle test experiment is carried out at a current density of 100 mA.h/g, and the charge and discharge voltage range is 0.01-3.0V. The test result is shown in fig. 6, the first charge and discharge capacity of the molybdenum disulfide-carbon hollow sphere is 1060mA · h/g and 750mA · h/g respectively, the first coulombic efficiency is 70.7%, and the specific capacity is maintained at about 703mA · h/g after 40 cycles. The performance of the molybdenum disulfide-carbon hollow sphere is obviously higher than that of the molybdenum disulfide-carbon hollow sphere in the published patent (CN 105098151A), and the molybdenum disulfide-carbon hollow sphere prepared by the method has better battery performance.
Example 5
(1) 0.1104g of ammonium molybdate, 0.0952g of thiourea, 0.4g of glucose and 4g of potassium chloride were weighed respectively, added to 20mL of distilled water, and stirred to form a colorless transparent solution.
Wherein the total mass of the molybdenum source and the sulfur source is 51.4 percent of the total mass of the carbon source.
(2) Pouring the colorless solution into a corundum porcelain boat, placing the corundum porcelain boat into a vacuum drying oven, and drying the corundum porcelain boat for 18 hours at 70 ℃.
(3) And (3) putting the dried sample into a tubular furnace, wherein the heating rate is 2 ℃/min, the heat preservation temperature is 600 ℃, and the heat preservation time is 4h under the argon atmosphere.
(4) And after the temperature of the furnace is reduced, centrifugally washing the obtained sample for 5 times by using distilled water to obtain the molybdenum disulfide-carbon hollow sphere sample.
A TEM image of the prepared molybdenum disulfide-carbon hollow sphere sample is shown in fig. 7, and it can be seen that after calcining at 600 ℃ and keeping the temperature for 4 hours, the prepared molybdenum disulfide-carbon hollow sphere sample presents a hollow nanosphere shape, the hollow nanosphere is composed of a carbon hollow sphere and molybdenum disulfide nanosheets on the outer layer, the average diameter is 413nm, the average size of the carbon hollow sphere inside is 281nm, and the average thickness of the molybdenum disulfide shell layer is 66 nm.
A three-electrode system is adopted, a silver chloride electrode is used as a counter electrode, a platinum electrode is used as a reference electrode, the prepared molybdenum disulfide-carbon hollow sphere is used as a working electrode, 0.5mol/L potassium hydroxide is used as electrolyte, an electrochemical workstation is used for carrying out an electrocatalytic hydrogen evolution test, and the obtained polarization curve is shown in figure 8. 10mA cm-1The corresponding polarization voltage is 150mV, which shows that the sample has better electrocatalytic performance.
The Shenzhen Xinwei battery tester is adopted to test the charge and discharge performance of the battery of the sample in the embodiment, a constant-current charge and discharge specific capacity cycle test experiment is carried out at a current density of 100 mA.h/g, and the charge and discharge voltage range is 0.01-3.0V. The test result is shown in fig. 9, the first charge and discharge capacity of the molybdenum disulfide-carbon hollow sphere is 1075mA · h/g and 764mA · h/g respectively, the first coulombic efficiency is 71%, and the specific capacity is maintained at about 713mA · h/g after 40 cycles. This is obviously higher than the performance of the hollow molybdenum disulfide-carbon spheres in the published patent (CN 105098151 a), which indicates that the hollow molybdenum disulfide-carbon spheres prepared by the method have better cell performance.
Example 6
(1) 0.1104g of ammonium molybdate, 0.0952g of thiourea, 2g of glucose and 20g of potassium chloride were weighed respectively, added to 50mL of distilled water, and stirred to form a colorless transparent solution.
Wherein the total mass of the molybdenum source and the sulfur source is 10.3 percent of the total mass of the carbon source, and the mass ratio of the carbon source to the inorganic salt template is 0.01: 0.1.
(2) pouring the colorless solution into a corundum porcelain boat, placing the corundum porcelain boat into a vacuum drying oven, and drying the corundum porcelain boat for 24 hours at the temperature of 40 ℃.
(3) And (3) putting the dried sample into a tubular furnace, wherein the heating rate is 1 ℃/min, the heat preservation temperature is 400 ℃, and the heat preservation time is 6h under the argon atmosphere.
(4) And after the temperature of the furnace is reduced, centrifugally washing the obtained sample for 5 times by using distilled water to obtain the molybdenum disulfide-carbon hollow sphere sample.
The prepared molybdenum disulfide-carbon hollow sphere sample presents a hollow nanosphere shape, the hollow nanosphere is composed of a carbon hollow sphere and molybdenum disulfide nanosheets on the outer layer, the average diameter is 926nm, the average size of the carbon hollow sphere inside is 898nm, and the average thickness of a molybdenum disulfide shell layer is 14 nm.
A three-electrode system is adopted, a silver chloride electrode is used as a counter electrode, a platinum electrode is used as a reference electrode, the prepared molybdenum disulfide-carbon hollow sphere is used as a working electrode, 0.5mol/L potassium hydroxide is used as electrolyte, and an electrochemical workstation is used for carrying out electrocatalytic hydrogen evolution test. 10mA cm-1The corresponding polarization voltage is 220mV, which shows that the sample has better electrocatalytic performance.
The Shenzhen Xinwei battery tester is adopted to test the charge and discharge performance of the battery of the sample in the embodiment, a constant-current charge and discharge specific capacity cycle test experiment is carried out at a current density of 100 mA.h/g, and the charge and discharge voltage range is 0.01-3.0V. The specific capacity is kept about 620 mA.h/g after the test cycle is carried out for 40 circles.
Example 7
(1) 0.1104g of ammonium molybdate, 0.0952g of thiourea, 0.2056g of glucose and 2.056g of potassium chloride were weighed respectively, added to 20mL of distilled water, and stirred to form a colorless transparent solution.
Wherein the total mass of the molybdenum source and the sulfur source is 100 percent of the total mass of the carbon source, and the mass ratio of the carbon source to the inorganic salt template is 0.5: 5.
(2) Pouring the colorless solution into a corundum porcelain boat, placing the corundum porcelain boat into a vacuum drying oven, and drying the corundum porcelain boat for 12 hours at the temperature of 80 ℃.
(3) And (3) putting the dried sample into a tubular furnace, wherein the heating rate is 5 ℃/min, the heat preservation temperature is 700 ℃, and the heat preservation time is 3h under the argon atmosphere.
(4) And after the temperature of the furnace is reduced, centrifugally washing the obtained sample for 5 times by using distilled water to obtain the molybdenum disulfide-carbon hollow sphere sample.
The prepared molybdenum disulfide-carbon hollow sphere sample presents a hollow nanosphere shape, the hollow nanosphere is composed of a carbon hollow sphere and molybdenum disulfide nanosheets on the outer layer, the average diameter is 406nm, the average size of the carbon hollow sphere inside is 382nm, and the average thickness of a molybdenum disulfide shell layer is 11 nm. .
A three-electrode system is adopted, a silver chloride electrode is used as a counter electrode, a platinum electrode is used as a reference electrode, the prepared molybdenum disulfide-carbon hollow sphere is used as a working electrode, 0.5mol/L potassium hydroxide is used as electrolyte, and an electrochemical workstation is used for carrying out electrocatalytic hydrogen evolution test. 10mA cm-1The corresponding polarization voltage is 208mV, which shows that the sample has better electrocatalytic performance.
The Shenzhen Xinwei battery tester is adopted to test the charge and discharge performance of the battery of the sample in the embodiment, a constant-current charge and discharge specific capacity cycle test experiment is carried out at a current density of 100 mA.h/g, and the charge and discharge voltage range is 0.01-3.0V. The specific capacity is kept at about 650 mA.h/g after the test is cycled for 40 circles.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (10)
1. A preparation method of a molybdenum disulfide-carbon hollow sphere is characterized by comprising the following steps: uniformly dispersing a molybdenum source, a sulfur source, a carbon source and an inorganic salt template in water to obtain a precursor solution; and carrying out vacuum drying treatment on the obtained precursor solution to obtain a core/shell intermediate product with an inorganic salt core, calcining the obtained core/shell intermediate product to obtain a core/shell structure product with a molybdenum disulfide outer layer, and washing the obtained core/shell structure product with the molybdenum disulfide outer layer to remove the inorganic salt core to obtain the molybdenum disulfide-carbon hollow sphere.
2. The method for preparing the molybdenum disulfide-carbon hollow sphere according to claim 1, wherein the molybdenum source is ammonium molybdate, sodium molybdate, molybdenum chloride or molybdenum nitrate, and the sulfur source is thiourea.
3. The method for preparing the molybdenum disulfide-carbon hollow sphere according to claim 1, wherein the carbon source is sucrose, glucose or dopamine.
4. The method for preparing the molybdenum disulfide-carbon hollow sphere according to claim 1, wherein the inorganic salt template is sodium chloride or potassium chloride.
5. The preparation method of the molybdenum disulfide-carbon hollow sphere according to claim 1, wherein the mass ratio of the inorganic salt template to the carbon source is 10 (1-5).
6. The method for preparing the molybdenum disulfide-carbon hollow sphere according to claim 1, wherein the total mass of the molybdenum source and the sulfur source is 10-100% of the total mass of the carbon source.
7. The method for preparing the molybdenum disulfide-carbon hollow sphere according to claim 1, wherein the vacuum drying conditions are as follows: the vacuum drying temperature is 40-80 ℃, and the vacuum drying time is 12-24 h.
8. The molybdenum disulfide-carbon hollow sphere prepared by the preparation method of any one of claims 1 to 7 is characterized by comprising the following steps: forming the molybdenum disulfide-carbon hollow sphere with a hollow core-shell structure by taking the carbon hollow sphere as a core and taking a molybdenum disulfide nanosheet as a shell, wherein the molybdenum disulfide-carbon hollow sphere is in a monodispersed state;
the diameter of the molybdenum disulfide-carbon hollow sphere is 100-1000 nm, and the diameter of the carbon hollow sphere is 10-900 nm.
9. Use of a molybdenum disulphide-carbon hollow sphere according to claim 8 as a hydrogen evolution catalyst.
10. The use of the molybdenum disulfide-carbon hollow sphere of claim 8 for preparing a negative electrode material for a lithium battery.
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