CN107492655B - molybdenum disulfide/carbon composite material and preparation method and application thereof - Google Patents
molybdenum disulfide/carbon composite material and preparation method and application thereof Download PDFInfo
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- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 57
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 50
- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 98
- 229920000128 polypyrrole Polymers 0.000 claims abstract description 28
- 239000002127 nanobelt Substances 0.000 claims abstract description 24
- 239000011218 binary composite Substances 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 24
- 239000006185 dispersion Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 17
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
- 238000000967 suction filtration Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000011684 sodium molybdate Substances 0.000 claims description 10
- 235000015393 sodium molybdate Nutrition 0.000 claims description 10
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 9
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 239000011780 sodium chloride Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 28
- 238000011065 in-situ storage Methods 0.000 abstract description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 5
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 5
- 238000004073 vulcanization Methods 0.000 abstract description 5
- 239000003990 capacitor Substances 0.000 abstract description 3
- 239000007772 electrode material Substances 0.000 abstract description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract 1
- 239000011258 core-shell material Substances 0.000 abstract 1
- 229910052750 molybdenum Inorganic materials 0.000 abstract 1
- 239000011733 molybdenum Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- 239000000463 material Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 230000001681 protective effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 229910052573 porcelain Inorganic materials 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002074 nanoribbon Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- -1 transition metal sulfide Chemical class 0.000 description 1
Classifications
-
- 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
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- 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
-
- 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
-
- 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
-
- 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
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
-
- 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
-
- 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
- Y02E60/13—Energy storage using capacitors
Abstract
The invention relates to a molybdenum disulfide/carbon composite material and a preparation method and application thereof. The preparation method of the molybdenum disulfide/carbon composite material comprises the following steps: preparing a molybdenum trioxide nanobelt by a hydrothermal method, carrying out low-temperature reaction to grow polypyrrole on the surface of the molybdenum trioxide nanobelt in situ to obtain a molybdenum trioxide-polypyrrole binary composite material with a core-shell structure, and then carrying out high-temperature vulcanization to prepare a molybdenum disulfide/carbon composite material. The molybdenum disulfide/carbon composite material prepared by the invention can be used as an ideal electrode material of novel energy sources such as a high-performance super capacitor, a lithium ion battery, a solar battery and the like. The molybdenum disulfide/carbon composite material prepared by the invention has the advantages of stable chemical property, good conductivity, high capacity and the like.
Description
Technical Field
The invention belongs to the technical field of carbon composite materials, and particularly relates to a molybdenum disulfide/carbon composite material as well as a preparation method and application thereof.
Background
As a typical transition metal sulfide, molybdenum disulfide has a special layered structure, the intercalation and de-intercalation of Li < + > are facilitated by weak van der Waals force between layers, and meanwhile, molybdenum disulfide also has good double-electric-layer charge storage capacity, so that molybdenum disulfide has high theoretical lithium storage capacity and has good application prospect as a lithium ion battery cathode material. Meanwhile, due to the preferentially exposed active sites and the long-range/short-range ordered atomic arrangement, the nano-structure molybdenum disulfide electrocatalyst is expected to replace noble metal Pt to realize the electrochemical hydrogen evolution reaction. However, practical applications of molybdenum disulfide materials are greatly limited due to their poor electrical conductivity, large volume expansion during lithium storage, and inadequate electrochemically active sites in the hydrogen evolution reaction. The structure of the molybdenum disulfide material is optimally designed on the nanoscale, so that an effective way for improving the electrochemical performance of the molybdenum disulfide material is provided. Among the nanometer materials with various structures, the molybdenum disulfide with the nanometer belt structure has the advantages of high length-diameter ratio, large specific surface area, high electrical conductivity and certain mechanical strength. In addition, in order to further improve the structural stability and the electrical conductivity of the composite material, the molybdenum disulfide and the carbon material are compounded to have important significance.
Disclosure of Invention
The invention aims to solve the technical problem of providing a molybdenum disulfide/carbon composite material and a preparation method and application thereof.
According to the molybdenum disulfide/carbon composite material, molybdenum disulfide confinement in the composite material is in the carbon layer with the hollow nano-belt structure, and the outer layer of the composite material is a nitrogen-doped carbon layer.
The preparation method of the molybdenum disulfide/carbon composite material comprises the following steps:
(1) Dissolving sodium molybdate and sodium chloride in a mass ratio of 10:1-1:20 in water, continuously stirring, adjusting the pH value to 0-2, carrying out hydrothermal reaction at the temperature of 160-220 ℃ for 10-48h, carrying out suction filtration on the obtained solution, washing, and then drying to obtain a molybdenum trioxide nanobelt; wherein the concentration of the sodium molybdate dissolved in the water is 0.01-0.1 g/mL;
(2) Stirring and dispersing the molybdenum trioxide nanobelts in water, adding pyrrole and an initiator, reacting for 6-48h at 0 +/-10 ℃, centrifuging, washing and drying the obtained dispersion liquid to obtain a molybdenum trioxide/polypyrrole binary composite material; wherein the mass ratio of the molybdenum trioxide to the pyrrole is 1:1-20, and the molar ratio of the initiator to the pyrrole is 1:8-4: 1;
(3) mixing the molybdenum trioxide/polypyrrole binary composite material with sulfur powder according to the mass ratio of 1:2-10, grinding, vulcanizing under protective gas at the vulcanization temperature of 600-.
The mass ratio of the sodium molybdate to the sodium chloride in the step (1) is 2:1-1: 2; the concentration of the sodium molybdate dissolved in the water is 0.02-0.05 g/mL.
In the step (1), the pH value is adjusted to be 0.5-1.5, and the pH value is adjusted by hydrochloric acid solution.
In the step (1), hydrothermal reaction is carried out at 180-200 ℃ for 18-30 h.
The initiator in the step (2) is ammonium persulfate, potassium persulfate or ferric chloride; the mass ratio of the molybdenum trioxide to the pyrrole is 1: 10; the molar ratio of the initiator to the pyrrole is 1: 1-4.
The reaction in the step (2) is carried out for 12-24h at 0 +/-2 ℃.
the mass ratio of the molybdenum trioxide/polypyrrole binary composite material to the sulfur powder in the step (3) is 1: 4-5; the protective gas is nitrogen or argon, the vulcanization process parameter is 800 ℃, the heat preservation time is 4h, and the heating rate is 2-5 ℃/min.
The washing in the step (3) is washing with hydrochloric acid and then washing with water.
The molybdenum disulfide/carbon composite material is applied to electrode materials of super capacitors, lithium ion batteries and solar batteries.
According to the invention, through simple process design, molybdenum trioxide is used as a precursor, polypyrrole is coated outside the molybdenum trioxide, and the binary composite material is vulcanized at high temperature to prepare the novel molybdenum disulfide/carbon composite material. The composite material structurally shows that molybdenum disulfide is confined in a carbon layer of a hollow nanobelt structure, and redundant space is still left in the carbon layer of the hollow nanobelt. The composite material has the following advantages: the composite material with the nanostructure has a large length-diameter ratio, a large specific surface area and certain mechanical strength, and is endowed with certain stability; the molybdenum disulfide grown in the carbon layer in a limited area has high specific surface area, so that the high contact area of an electrode/electrolyte and sufficient electrochemical active sites are ensured; the excellent conductivity of the outer carbon is beneficial to the transmission of electrons, and the overall conductivity of the composite material is improved; the internal cavity structure can effectively relieve structural deformation caused by long-time electrochemical reaction. Therefore, the molybdenum disulfide and the carbon material are effectively compounded, so that a good synergistic enhancement effect can be achieved, and the composite material with excellent performance is prepared.
Advantageous effects
(1) The molybdenum disulfide/carbon composite material with a hollow structure is simply and effectively prepared by hydrothermal reaction, in-situ polymerization and high-temperature vulcanization technology. The material is of a hollow structure, can relieve the capacity rapid attenuation caused by the volume change of molybdenum sulfide in the charging and discharging processes, simultaneously increases the contact area of the molybdenum sulfide and electrolyte, improves the electrochemical active area, and is beneficial to the capacity improvement.
(2) The carbon layer of the outer layer of the invention is derived from polypyrrole, so that the carbon layer is nitrogen-doped carbon, and the conductivity of the composite material is further improved.
(3) The preparation method is simple in preparation process and easy to operate, is an effective and rapid preparation method, and realizes the conversion of the outer polypyrrole layer into nitrogen-doped carbon and the conversion of the inner molybdenum trioxide layer into molybdenum disulfide through the high-temperature vulcanization step.
(4) The molybdenum disulfide/carbon composite material prepared by the invention has a hollow structure and a carbon-based composite structure, and can effectively relieve structural stress generated by intercalation/deintercalation of lithium ions or surface Faraday reaction in the process of repeated charge and discharge, thereby improving the cycling stability of the electrode, and being used as an ideal electrode material of a high-performance super capacitor, a lithium ion battery and a solar battery.
Drawings
Figure 1 is an SEM image of the molybdenum disulfide/carbon composite prepared in example 1.
Figure 2 is a TEM image of a molybdenum disulfide/carbon composite prepared in example 1.
Figure 3 is an XRD pattern of the molybdenum disulfide/carbon composite prepared in example 1 and the molybdenum disulfide prepared in comparative example 1.
Figure 4 is a graph of the cycling performance of the molybdenum disulfide/carbon composite prepared in example 1 and the molybdenum disulfide prepared in comparative example 1 at a current density of 0.1Ag -1.
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. preparing a molybdenum trioxide nanobelt by a hydrothermal method:
Adding 1.21g of sodium molybdate and 0.6g of sodium chloride into 60mL of deionized water to obtain a solution, continuously stirring for 10 minutes to obtain a uniform dispersion solution, adding 3mol/L of hydrochloric acid solution to adjust the pH value to 1, transferring the solution to a hydrothermal kettle, carrying out hydrothermal reaction in an oven at the reaction temperature of 180 ℃ for 24 hours, carrying out suction filtration on the obtained dispersion solution to separate light blue precipitate when the reaction kettle is cooled to room temperature, washing the obtained solid with deionized water, and drying the solid in the oven at 60 ℃ for 24 hours to obtain the molybdenum trioxide nanobelt.
2. growing polypyrrole on a molybdenum trioxide nano-belt in situ to obtain a molybdenum trioxide/polypyrrole binary composite material:
Adding 40mg of the obtained molybdenum trioxide nanobelt into a 250mL flask, adding 80mL of deionized water, stirring to uniformly disperse molybdenum trioxide in water to obtain a dispersion solution, measuring 200 mu L of pyrrole (0.00288mol) by using a pipette, adding into the flask, stirring for 10 minutes, dropwise adding 20mL of initiator ammonium persulfate solution (16.5mg/mL), controlling the molar ratio of pyrrole to ammonium persulfate to be 2:1, putting the flask into a low-temperature freezing and circulating pump, setting the reaction temperature to be 0 +/-2 ℃, stirring for reaction for 12 hours, growing polypyrrole on molybdenum trioxide through in-situ polymerization reaction, after the reaction is finished, carrying out suction filtration on the dispersion solution, washing the obtained solid with deionized water for several times, and drying at 60 ℃ for 24 hours under a vacuum condition to obtain the molybdenum trioxide/polypyrrole binary composite material.
3. Preparing a molybdenum disulfide/carbon composite material by vulcanizing a molybdenum trioxide/polypyrrole precursor at a high temperature:
20mg of the molybdenum trioxide/polypyrrole obtained above and 100mg of sulfur powder were weighed, ground in agate, mixed uniformly, and added to a porcelain ark 6cm in length and 3cm in width. And (4) vulcanizing at high temperature in a tube furnace. The protective gas is nitrogen, the heating rate is 5 ℃/min, the termination temperature is 800 ℃, and the heat preservation time is 4 h. And after the reaction is finished, washing the obtained solid with hydrochloric acid for several times, then washing the dispersion with water, carrying out suction filtration, and drying the obtained product at 60 ℃ for 24 hours under a vacuum condition to obtain the molybdenum disulfide/carbon composite material.
fig. 1 is an SEM image of the molybdenum disulfide/carbon composite material of this embodiment, and it can be observed from the figure that the prepared molybdenum disulfide/carbon composite material has a nanoribbon structure, the length is about 3-6 μm, the width is about 100-200nm, the good aspect ratio thereof is favorable for the transmission of electrons, and the nanoribbon should form a three-dimensional interpenetrating structure, so as to reduce the transmission path of ions and electrons, and further improve the conductivity of the material.
Fig. 2 is a TEM image of the molybdenum disulfide/carbon composite material of the present example, from which it can be observed that the prepared molybdenum disulfide/carbon composite material has a unique hollow structure. The carbon layer with the thickness of 20nm is arranged outside, and the conductivity of the whole material is improved by the carbon layer; the molybdenum sulfide inside is of a lamellar structure, agglomeration of the molybdenum sulfide is inhibited, full exposure of molybdenum sulfide active sites is facilitated, and improvement of the circulation stability is facilitated.
example 2
1. Preparing a molybdenum trioxide nanobelt by a hydrothermal method:
Adding 1.21g of sodium molybdate and 0.6g of sodium chloride into 60mL of deionized water to obtain a solution, continuously stirring for 10 minutes to obtain a uniform dispersion solution, adding 3mol/L of hydrochloric acid solution to adjust the pH value to 1, transferring the solution to a hydrothermal kettle, carrying out hydrothermal reaction in an oven at the reaction temperature of 180 ℃ for 24 hours, carrying out suction filtration on the obtained dispersion solution to separate light blue precipitate when the reaction kettle is cooled to room temperature, washing the obtained solid with deionized water, and drying the solid in the oven at 60 ℃ for 24 hours to obtain the molybdenum trioxide nanobelt.
2. Growing polypyrrole on a molybdenum trioxide nano-belt in situ to obtain a molybdenum trioxide/polypyrrole binary composite material:
Adding 40mg of the obtained molybdenum trioxide nanobelt into a 250mL flask, adding 80mL of deionized water, stirring to uniformly disperse molybdenum trioxide in water to obtain a dispersion, measuring 100 mu L of pyrrole (0.00144mol) by using a pipette, adding into the flask, stirring for 10 minutes, dropwise adding 10mL of initiator ammonium persulfate solution (16.5mg/mL), controlling the molar ratio of pyrrole to ammonium persulfate to be 2:1, putting the flask into a low-temperature freezing and circulating pump, setting the reaction temperature to be 0 +/-2 ℃, stirring for reaction for 12 hours, growing polypyrrole on molybdenum trioxide through in-situ polymerization reaction, after the reaction is finished, carrying out suction filtration on the dispersion, washing the obtained solid with deionized water for several times, and drying at 60 ℃ for 24 hours under a vacuum condition to obtain the molybdenum trioxide/polypyrrole binary composite material.
3. Preparing a molybdenum disulfide/carbon composite material by vulcanizing a molybdenum trioxide/polypyrrole precursor at a high temperature:
20mg of the molybdenum trioxide/polypyrrole obtained above and 100mg of sulfur powder were weighed, ground in agate, mixed uniformly, and added to a porcelain ark 6cm in length and 3cm in width. And (4) vulcanizing at high temperature in a tube furnace. The protective gas is nitrogen, the heating rate is 5 ℃/min, the termination temperature is 800 ℃, and the heat preservation time is 4 h. And after the reaction is finished, washing the obtained solid with hydrochloric acid for several times, then washing the dispersion with water, carrying out suction filtration, and drying the obtained product at 60 ℃ for 24 hours under a vacuum condition to obtain the molybdenum disulfide/carbon composite material.
Example 3
1. preparing a molybdenum trioxide nanobelt by a hydrothermal method:
Adding 1.21g of sodium molybdate and 0.6g of sodium chloride into 60mL of deionized water to obtain a solution, continuously stirring for 10 minutes to obtain a uniform dispersion solution, adding 3mol/L of hydrochloric acid solution to adjust the pH value to 1, transferring the solution to a hydrothermal kettle, carrying out hydrothermal reaction in an oven at the reaction temperature of 180 ℃ for 24 hours, carrying out suction filtration on the obtained dispersion solution to separate light blue precipitate when the reaction kettle is cooled to room temperature, washing the obtained solid with deionized water, and drying the solid in the oven at 60 ℃ for 24 hours to obtain the molybdenum trioxide nanobelt.
2. Growing polypyrrole on a molybdenum trioxide nano-belt in situ to obtain a molybdenum trioxide/polypyrrole binary composite material:
Adding 40mg of the obtained molybdenum trioxide nanobelt into a 250mL flask, adding 80mL of deionized water, stirring to uniformly disperse molybdenum trioxide in water to obtain a dispersion, measuring 50 mu L of pyrrole (0.00072mol) by using a pipette, adding into the flask, stirring for 10 minutes, dropwise adding 5mL of initiator ammonium persulfate solution (16.5mg/mL), controlling the molar ratio of pyrrole to ammonium persulfate to be 2:1, putting the flask into a low-temperature refrigeration circulating pump, setting the reaction temperature to be 0 +/-2 ℃, stirring for reaction for 12 hours, growing polypyrrole on molybdenum trioxide through in-situ polymerization reaction, after the reaction is finished, carrying out suction filtration on the dispersion, washing the obtained solid with deionized water for several times, and drying at 60 ℃ for 24 hours under a vacuum condition to obtain the molybdenum trioxide/polypyrrole binary composite material.
3. Preparing a molybdenum disulfide/carbon composite material by vulcanizing a molybdenum trioxide/polypyrrole precursor at a high temperature:
20mg of the molybdenum trioxide/polypyrrole obtained above and 100mg of sulfur powder were weighed, ground in agate, mixed uniformly, and added to a porcelain ark 6cm in length and 3cm in width. And (4) vulcanizing at high temperature in a tube furnace. The protective gas is nitrogen, the heating rate is 5 ℃/min, the termination temperature is 800 ℃, and the heat preservation time is 4 h. And after the reaction is finished, washing the obtained solid with hydrochloric acid for several times, then washing the dispersion with water, carrying out suction filtration, and drying the obtained product at 60 ℃ for 24 hours under a vacuum condition to obtain the molybdenum disulfide/carbon composite material.
Comparative example 1
Adding 1.21g of sodium molybdate and 0.6g of sodium chloride into 60mL of deionized water to obtain a solution, continuously stirring for 10 minutes to obtain a uniform dispersion solution, adding 3mol/L of hydrochloric acid solution to adjust the pH value to 1, transferring the solution to a hydrothermal kettle, carrying out hydrothermal reaction in an oven at the reaction temperature of 180 ℃ for 24 hours, carrying out suction filtration on the obtained dispersion solution to separate light blue precipitate when the reaction kettle is cooled to room temperature, washing the obtained solid with deionized water, and drying the solid in the oven at 60 ℃ for 24 hours to obtain the molybdenum trioxide nanobelt.
20mg of the molybdenum trioxide nanobelt obtained above and 100mg of sulfur powder were weighed, ground in agate, mixed uniformly, and added to a porcelain ark 6cm long and 3cm wide. And (4) vulcanizing at high temperature in a tube furnace. The protective gas is nitrogen, the heating rate is 5 ℃/min, the termination temperature is 800 ℃, and the heat preservation time is 4 h. And after the reaction is finished, washing the obtained solid with hydrochloric acid for several times, then washing the dispersion with water, carrying out suction filtration, and drying the obtained product at 60 ℃ under a vacuum condition for 24 hours to obtain the molybdenum disulfide.
fig. 3 is XRD patterns of the molybdenum disulfide/carbon composite prepared in example 1 and the molybdenum disulfide prepared in comparative example 1, and it can be observed that the molybdenum disulfide/carbon composite prepared has characteristic peaks of molybdenum sulfide at 2 θ ═ 14.3 °, 32.9 °, 39.5 °, 49.2 °, 58.5 °, and 60.3 °, corresponding to (002), (100), (103), (110), (008) crystal planes of molybdenum disulfide, and further confirms that the internal lamellar structure is a nanosheet of molybdenum disulfide.
FIG. 4 is a graph of the cycling performance of the molybdenum disulfide/carbon composite prepared in example 1 and the molybdenum disulfide prepared in comparative example 1 at a current density of 0.1Ag -1, from which it can be observed that the capacity value of pure molybdenum disulfide can be as high as 750mAh g -1, but the cycling performance is poor, and only 180mAh g -1 is present after 300 cycles of charging and discharging.
Claims (1)
1. A preparation method of a molybdenum disulfide/carbon composite material is characterized by comprising the following steps: the molybdenum disulfide confinement in the composite material is in a carbon layer with a hollow nano-belt structure, and the outer layer of the composite material is a nitrogen-doped carbon layer; the preparation method of the composite material comprises the following steps:
(1) dissolving sodium molybdate and sodium chloride in a mass ratio of 2:1 in water, continuously stirring, adjusting the pH value to 1 by using a hydrochloric acid solution, carrying out hydrothermal reaction for 24 hours at 180 ℃, carrying out suction filtration on the obtained solution, washing, and drying to obtain a molybdenum trioxide nanobelt; wherein the concentration of the sodium molybdate dissolved in the water is 0.02 g/mL;
(2) Stirring and dispersing a molybdenum trioxide nanobelt in water, adding pyrrole and an initiator ammonium persulfate, reacting for 12 hours at 0 +/-2 ℃, centrifuging, washing and drying the obtained dispersion liquid to obtain a molybdenum trioxide/polypyrrole binary composite material; wherein the mass ratio of the molybdenum trioxide to the pyrrole is 1: 1-4.8, and the molar ratio of the initiator to the pyrrole is 1: 2;
(3) Mixing a molybdenum trioxide/polypyrrole binary composite material with sulfur powder according to a mass ratio of 1:5, grinding, and vulcanizing under nitrogen, wherein the vulcanizing process parameters are as follows: the temperature is 800 ℃, the heat preservation time is 4h, the temperature rising rate is 5 ℃/min, the molybdenum disulfide/carbon composite material is obtained by firstly washing with hydrochloric acid, then washing with water and drying.
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| CN109830657B (en) * | 2019-01-14 | 2020-11-03 | 陕西科技大学 | MoS2/MoO2Preparation method of three-dimensional carbon lithium ion battery cathode material |
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| CN111111729B (en) * | 2019-12-18 | 2021-08-13 | 西安交通大学 | Molybdenum disulfide-based nanocomposite material with hollow sandwich laminated structure and preparation method thereof |
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| CN114420459B (en) * | 2022-01-06 | 2023-05-26 | 重庆文理学院 | Carbon/manganese dioxide composite material for super capacitor and preparation method thereof |
| CN115286791B (en) * | 2022-08-16 | 2023-08-18 | 北方民族大学 | Inorganic salt@polypyrrole nano capsule and preparation method and application thereof |
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