CN107492655A - A kind of molybdenum disulfide/carbon composite and its preparation method and application - Google Patents
A kind of molybdenum disulfide/carbon composite and its preparation method and application Download PDFInfo
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- CN107492655A CN107492655A CN201710550112.8A CN201710550112A CN107492655A CN 107492655 A CN107492655 A CN 107492655A CN 201710550112 A CN201710550112 A CN 201710550112A CN 107492655 A CN107492655 A CN 107492655A
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- molybdenum disulfide
- carbon composite
- molybdenum
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- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 66
- 239000002131 composite material Substances 0.000 title claims abstract description 60
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 96
- 229920000128 polypyrrole Polymers 0.000 claims abstract description 29
- 239000011218 binary composite Substances 0.000 claims abstract description 14
- 239000011248 coating agent Substances 0.000 claims abstract description 13
- 238000000576 coating method Methods 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003990 capacitor Substances 0.000 claims abstract description 3
- 239000007772 electrode material Substances 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000006185 dispersion Substances 0.000 claims description 20
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- 150000003233 pyrroles Chemical class 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- 235000015393 sodium molybdate Nutrition 0.000 claims description 12
- 239000003999 initiator Substances 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- 239000005864 Sulphur Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 239000011780 sodium chloride Substances 0.000 claims description 8
- 239000011684 sodium molybdate Substances 0.000 claims description 8
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- 238000010828 elution Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 238000004073 vulcanization Methods 0.000 claims description 3
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- 230000002045 lasting effect Effects 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 abstract description 21
- 239000002127 nanobelt Substances 0.000 abstract description 8
- 238000011065 in-situ storage Methods 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000011258 core-shell material Substances 0.000 abstract 1
- 230000006641 stabilisation Effects 0.000 abstract 1
- 238000011105 stabilization Methods 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 11
- 239000010410 layer Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000003643 water by type Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 229910052573 porcelain Inorganic materials 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000007710 freezing Methods 0.000 description 3
- 230000008014 freezing Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 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
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001052 transient effect Effects 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 present invention relates to a kind of molybdenum disulfide/carbon composite and its preparation method and application, for the molybdenum disulfide confinement in the composite in the carbon-coating of hollow nanometer band structure, composite outer layer is the carbon-coating of N doping.Molybdenum disulfide of the present invention/carbon composite preparation method includes：Molybdenum trioxide nano band is prepared by hydro-thermal method, low-temp reaction obtains the molybdenum trioxide polypyrrole binary composite of core shell structure in molybdenum trioxide nano belt surface growth in situ polypyrrole, then prepares molybdenum disulfide/carbon composite by high temperature vulcanized.Molybdenum disulfide/carbon composite prepared by the present invention can be used as the ideal electrode material of the novel energy such as high-performance super capacitor and lithium ion battery, solar cell.Molybdenum disulfide/carbon composite prepared by the present invention has the advantages that chemical property stabilization, good conductivity, capacity are high.
Description
Technical field
The invention belongs to carbon composite technical field, more particularly to a kind of molybdenum disulfide/carbon composite and its preparation
Methods and applications.
Background technology
As a kind of typical transient metal sulfide, molybdenum disulfide has special layer structure, and its interlayer is weaker
Van der Waals force is advantageous to Li+ insertion and deintercalation, while molybdenum disulfide also has good electric double layer charge storage, thus
It has higher theoretical lithium storage content, is had a good application prospect as lithium ion battery negative material.Simultaneously as its
Preferentially the atomic arrangement of exposed avtive spot and long-range/shortrange order, nanostructured molybdenum disulfide elctro-catalyst are expected to substitute
Precious metals pt realizes electrochemistry evolving hydrogen reaction.However, due to the larger volume during its own poor electric conductivity, storage lithium
Insufficient electro-chemical activity site, greatly limit the practical application of molybdenum disulfide material in expansion and evolving hydrogen reaction.
The structure of optimization design molybdenum disulfide material is to improve a kind of effective way of its chemical property on nanoscale.In numerous knots
In the nano material of structure, the molybdenum disulfide of nanometer band structure has draw ratio high, and specific surface area is big, and electrical conductivity is high, has certain
Mechanical strength.In addition, in order to further improve its structural stability and electric conductivity, by molybdenum disulfide with carbon material is compound has
Significance.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of molybdenum disulfide/carbon composite and preparation method thereof and should
With preparation process of the present invention is environmentally friendly, preparation cost is cheap, molybdenum disulfide/carbon composite electrochemical performance.
A kind of molybdenum disulfide/carbon composite of the present invention, the molybdenum disulfide confinement in the composite are received hollow
In the carbon-coating of rice band structure, composite outer layer is the carbon-coating of N doping.
A kind of preparation method of molybdenum disulfide/carbon composite of the present invention, comprises the following steps：
(1) it is 10 by mass ratio:1-1:20 sodium molybdate is dissolved in water with sodium chloride, lasting stirring, and regulation pH value is
0-2, hydro-thermal reaction 10-48h is carried out at 160-220 DEG C, resulting solution is filtered, washed, then dry, obtain molybdenum trioxide
Nanobelt；The concentration that wherein sodium molybdate is dissolved in water is 0.01-0.1g/mL；
(2) molybdenum trioxide nano band is dispersed with stirring in water, adds pyrroles and initiator, react 6- at 0 ± 10 DEG C
48h, by the centrifugation of gained dispersion liquid, washing and dry, obtain molybdenum trioxide/polypyrrole binary composite；Wherein molybdenum trioxide
Mass ratio with pyrroles is 1:The mol ratio of 1-20, initiator and pyrroles are 1:8-4:1；
(3) by molybdenum trioxide/polypyrrole binary composite and sulphur powder according to mass ratio 1:2-10 is mixed, and grinding, is being protected
Vulcanize under shield gas, curing temperature is 600-1000 DEG C, is washed, and dries, obtains molybdenum disulfide/carbon composite.
The mass ratio of sodium molybdate and sodium chloride is 2 in the step (1):1-1:2；The concentration that sodium molybdate is dissolved in water is
0.02-0.05g/mL。
Regulation pH value is 0.5-1.5 in the step (1), is adjusted with hydrochloric acid solution.
In the step (1) hydro-thermal reaction 18-30h is carried out at 180-200 DEG C.
Initiator is ammonium persulfate, potassium peroxydisulfate or iron chloride in the step (2)；Molybdenum trioxide and the mass ratio of pyrroles
For 1:10；The mol ratio of initiator and pyrroles are 1:1-4.
In the step (2) 12-24h is reacted at 0 ± 2 DEG C.
Molybdenum trioxide/polypyrrole binary composite and sulphur powder mass ratio are 1 in the step (3):4-5；Protection gas be
Nitrogen or argon gas, vulcanization parameters are 800 DEG C, soaking time 4h of temperature, and the speed of heating is 2-5 DEG C/min.
Washing is first to be washed with water with salt acid elution in the step (3).
A kind of application of molybdenum disulfide/carbon composite of the present invention, as ultracapacitor and lithium ion battery, too
The electrode material of positive energy battery.
The present invention passes through simple technological design, using molybdenum trioxide as presoma, its outside cladding polypyrrole, to its binary
Composite progress is high temperature vulcanized, and a kind of new molybdenum disulfide/carbon composite is prepared.The composite is in structure
Molybdenum disulfide confinement is shown as in the carbon-coating of hollow nanometer band structure, and still has unnecessary sky in hollow nanobelt carbon-coating
Between.The composite has following advantage：The composite of nanometer band structure has larger draw ratio, specific surface area in itself
Greatly, there is certain mechanical strength, impart the certain stability of composite；Confinement is grown in the molybdenum disulfide tool in carbon-coating
There is high-specific surface area to ensure the high contact area of electrode/electrolyte and sufficient electro-chemical activity site；Outer layer carbon is excellent
Electric conductivity is advantageous to the transmission of electronics, improves the overall electric conductivity of composite；Internal cavity structure can effectively delay
Solve the structural deformation that prolonged electrochemical reaction triggers.Therefore, molybdenum disulfide and carbon material are carried out it is effective compound, can be with
Reach good chemiluminescence, to prepare the composite of excellent performance.
Beneficial effect
(1) present invention is simply and effectively prepared in having by hydro-thermal reaction, in-situ polymerization and high temperature vulcanized technology
Molybdenum disulfide/carbon composite of hollow structure.Material is hollow structure, can alleviate volume of the molybdenum sulfide in charge and discharge process
Capacity rapid decay caused by change, while the contact area of molybdenum sulfide and electrolyte is added, improve electro-chemical activity
Area, be advantageous to the raising of capacity.
(2) carbon-coating of outer layer of the present invention is derived from polypyrrole, therefore carbon-coating is the carbon of N doping, is further increased compound
The electric conductivity of material.
(3) preparation process of the present invention is simple, easily operated, is a kind of effectively efficiently preparation method, high temperature vulcanized step
Realize that outer layer polypyrrole layer is converted into the vulcanization of the carbon and internal layer molybdenum trioxide of N doping and is changed into molybdenum disulfide.
(4) molybdenum disulfide/carbon composite prepared by the present invention, hollow structure and carbon-based composite construction can effectively be alleviated
Due to structural stress caused by the intercalation/deintercalation or surface faraday's reaction of lithium ion during repeated charge, so as to carry
The high cyclical stability of electrode, can be used as high-performance super capacitor and lithium ion battery, the desired electrical of solar cell
Pole material.
Brief description of the drawings
Fig. 1 is the SEM figures of molybdenum disulfide/carbon composite prepared by embodiment 1.
Fig. 2 is the TEM figures of molybdenum disulfide/carbon composite prepared by embodiment 1.
The molybdenum disulfide XRD that Fig. 3 is molybdenum disulfide/carbon composite prepared by embodiment 1 and prepared by comparative example 1.
Fig. 4 is that molybdenum disulfide/carbon composite prepared by embodiment 1 and molybdenum disulfide prepared by comparative example 1 are close in electric current
Spend for 0.1Ag-1Under cycle performance figure.
Embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limitation the scope of the present invention.In addition, it is to be understood that after the content of the invention lectured has been read, people in the art
Member can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited
Scope.
Embodiment 1
1st, molybdenum trioxide nano band is prepared by hydro-thermal method：
1.21g sodium molybdates and 0.6g sodium chloride are added in 60mL deionized waters and obtain solution, is persistently stirred 10 minutes,
Uniform dispersion is obtained, adds 3mol/L hydrochloric acid solutions regulation pH to 1, is transferred in water heating kettle anti-in carrying out hydro-thermal in baking oven
Should, reaction temperature is 180 DEG C, reaction time 24h, and gained dispersion liquid filter and divided by the cooling of question response kettle up to room temperature
From light blue precipitation therein, gained solid is cleaned with deionized water, 60 DEG C of dry 24h, obtain molybdenum trioxide in baking oven
Nanobelt.
2nd, growth in situ polypyrrole obtains molybdenum trioxide/polypyrrole binary composite on molybdenum trioxide nano band：
The above-mentioned gained molybdenum trioxide nano bands of 40mg are added in 250mL flasks, adding the stirring of 80ml deionized waters makes three
Molybdenum oxide, which is dispersed in water, obtains dispersion liquid, and measuring 200 μ L pyrroles (0.00288mol) with pipette adds above-mentioned flask
In, after stirring 10 minutes, 20ml initiator ammonium persulfate solution (16.5mg/ml) is added dropwise, controls pyrroles and persulfuric acid
The mol ratio of ammonium is 2:1, flask is put into cryogenic freezing circulating pump, it is 0 ± 2 DEG C, stirring reaction 12h to set reaction temperature,
Polypyrrole is grown by home position polymerization reaction on molybdenum trioxide, after reaction terminates, dispersion liquid is filtered, gained solid is spent
Several times, 60 DEG C of dry 24h, obtain molybdenum trioxide/polypyrrole binary composite to ion water washing under vacuum.
3rd, high temperature vulcanized molybdenum trioxide/polypyrrole presoma prepares molybdenum disulfide/carbon composite：
The above-mentioned gained molybdenum trioxide/polypyrroles of 20mg and 100mg sulphur powders are weighed, is ground in agate, is well mixed, is added
To long 6cm, in wide 3cm porcelain Noah's ark.Tube furnace is high temperature vulcanized.Protective gas is nitrogen, and heating rate is 5 DEG C/min, is terminated
Temperature is 800 DEG C, soaking time 4h.After reaction terminates, by gained solid with salt acid elution several times, then by dispersion liquid water
Wash, filter, products therefrom 60 DEG C of dry 24h under vacuum, obtain molybdenum disulfide/carbon composite.
Fig. 1 is the SEM figures of the molybdenum disulfide/carbon composite of the present embodiment, as can be observed from Figure prepared two
Molybdenum sulfide/carbon composite has nanometer band structure, long about 3-6 μm, and wide about 100-200nm, its preferable draw ratio have
Beneficial to the transmission of electronics, and nanobelt should form the three-dimensional structure run through mutually, reduce ion and electric transmission path, enter
One step improves the electric conductivity of material.
Fig. 2 is the TEM figures of the molybdenum disulfide/carbon composite of the present embodiment, as can be observed from Figure prepared two
Molybdenum sulfide/carbon composite has unique hollow structure.Outside is the carbon-coating that thickness is 20nm, and carbon-coating improves whole material
Electric conductivity；Internal molybdenum sulfide is lamellar structure, it is suppressed that the reunion of molybdenum sulfide itself, is advantageous to filling for molybdenum sulfide avtive spot
Divide exposure, and be advantageous to the raising of cyclical stability.
Embodiment 2
1st, molybdenum trioxide nano band is prepared by hydro-thermal method：
1.21g sodium molybdates and 0.6g sodium chloride are added in 60mL deionized waters and obtain solution, is persistently stirred 10 minutes,
Uniform dispersion is obtained, adds 3mol/L hydrochloric acid solutions regulation pH to 1, is transferred in water heating kettle anti-in carrying out hydro-thermal in baking oven
Should, reaction temperature is 180 DEG C, reaction time 24h, and gained dispersion liquid filter and divided by the cooling of question response kettle up to room temperature
From light blue precipitation therein, gained solid is cleaned with deionized water, 60 DEG C of dry 24h, obtain molybdenum trioxide in baking oven
Nanobelt.
2nd, growth in situ polypyrrole obtains molybdenum trioxide/polypyrrole binary composite on molybdenum trioxide nano band：
The above-mentioned gained molybdenum trioxide nano bands of 40mg are added in 250mL flasks, adding the stirring of 80mL deionized waters makes three
Molybdenum oxide, which is dispersed in water, obtains dispersion liquid, and measuring 100 μ L pyrroles (0.00144mol) with pipette adds above-mentioned flask
In, after stirring 10 minutes, 10mL initiator ammonium persulfate solution (16.5mg/mL) is added dropwise, controls pyrroles and persulfuric acid
The mol ratio of ammonium is 2:1, flask is put into cryogenic freezing circulating pump, it is 0 ± 2 DEG C, stirring reaction 12h to set reaction temperature,
Polypyrrole is grown by home position polymerization reaction on molybdenum trioxide, after reaction terminates, dispersion liquid is filtered, gained solid is spent
Several times, 60 DEG C of dry 24h, obtain molybdenum trioxide/polypyrrole binary composite to ion water washing under vacuum.
3rd, high temperature vulcanized molybdenum trioxide/polypyrrole presoma prepares molybdenum disulfide/carbon composite：
The above-mentioned gained molybdenum trioxide/polypyrroles of 20mg and 100mg sulphur powders are weighed, is ground in agate, is well mixed, is added
To long 6cm, in wide 3cm porcelain Noah's ark.Tube furnace is high temperature vulcanized.Protective gas is nitrogen, and heating rate is 5 DEG C/min, is terminated
Temperature is 800 DEG C, soaking time 4h.After reaction terminates, by gained solid with salt acid elution several times, then by dispersion liquid water
Wash, filter, products therefrom 60 DEG C of dry 24h under vacuum, obtain molybdenum disulfide/carbon composite.
Embodiment 3
1st, molybdenum trioxide nano band is prepared by hydro-thermal method：
1.21g sodium molybdates and 0.6g sodium chloride are added in 60mL deionized waters and obtain solution, is persistently stirred 10 minutes,
Uniform dispersion is obtained, adds 3mol/L hydrochloric acid solutions regulation pH to 1, is transferred in water heating kettle anti-in carrying out hydro-thermal in baking oven
Should, reaction temperature is 180 DEG C, reaction time 24h, and gained dispersion liquid filter and divided by the cooling of question response kettle up to room temperature
From light blue precipitation therein, gained solid is cleaned with deionized water, 60 DEG C of dry 24h, obtain molybdenum trioxide in baking oven
Nanobelt.
2nd, growth in situ polypyrrole obtains molybdenum trioxide/polypyrrole binary composite on molybdenum trioxide nano band：
The above-mentioned gained molybdenum trioxide nano bands of 40mg are added in 250mL flasks, adding the stirring of 80mL deionized waters makes three
Molybdenum oxide, which is dispersed in water, obtains dispersion liquid, and measuring 50 μ L pyrroles (0.00072mol) with pipette adds above-mentioned flask
In, after stirring 10 minutes, 5ml initiator ammonium persulfate solution (16.5mg/mL) is added dropwise, controls pyrroles and ammonium persulfate
Mol ratio be 2:1, flask is put into cryogenic freezing circulating pump, it is 0 ± 2 DEG C, stirring reaction 12h to set reaction temperature,
On molybdenum trioxide by home position polymerization reaction grow polypyrrole, reaction terminate after, dispersion liquid is filtered, by gained solid spend from
Several times, 60 DEG C of dry 24h, obtain molybdenum trioxide/polypyrrole binary composite to sub- water washing under vacuum.
3rd, high temperature vulcanized molybdenum trioxide/polypyrrole presoma prepares molybdenum disulfide/carbon composite：
The above-mentioned gained molybdenum trioxide/polypyrroles of 20mg and 100mg sulphur powders are weighed, is ground in agate, is well mixed, is added
To long 6cm, in wide 3cm porcelain Noah's ark.Tube furnace is high temperature vulcanized.Protective gas is nitrogen, and heating rate is 5 DEG C/min, is terminated
Temperature is 800 DEG C, soaking time 4h.After reaction terminates, by gained solid with salt acid elution several times, then by dispersion liquid water
Wash, filter, products therefrom 60 DEG C of dry 24h under vacuum, obtain molybdenum disulfide/carbon composite.
Comparative example 1
1.21g sodium molybdates and 0.6g sodium chloride are added in 60mL deionized waters and obtain solution, is persistently stirred 10 minutes,
Uniform dispersion is obtained, adds 3mol/L hydrochloric acid solutions regulation pH to 1, is transferred in water heating kettle anti-in carrying out hydro-thermal in baking oven
Should, reaction temperature is 180 DEG C, reaction time 24h, and gained dispersion liquid filter and divided by the cooling of question response kettle up to room temperature
From light blue precipitation therein, gained solid is cleaned with deionized water, 60 DEG C of dry 24h, obtain molybdenum trioxide in baking oven
Nanobelt.
The above-mentioned gained molybdenum trioxide nano bands of 20mg and 100mg sulphur powders are weighed, is ground in agate, is well mixed, is added
To long 6cm, in wide 3cm porcelain Noah's ark.Tube furnace is high temperature vulcanized.Protective gas is nitrogen, and heating rate is 5 DEG C/min, is terminated
Temperature is 800 DEG C, soaking time 4h.After reaction terminates, by gained solid with salt acid elution several times, then by dispersion liquid water
Wash, filter, products therefrom 60 DEG C of dry 24h under vacuum, obtain molybdenum disulfide.
The molybdenum disulfide XRD that Fig. 3 is molybdenum disulfide/carbon composite prepared by embodiment 1 and prepared by comparative example 1, from
It is observed that prepared molybdenum disulfide/carbon composite is in 2 θ=14.3 ° in figure, 32.9 °, 39.5 °, 49.2 °, 58.5 °,
There is the characteristic peak of molybdenum sulfide with 60.3 °, it is brilliant corresponding to (002) of molybdenum disulfide, (100), (103), (110), (008)
Face, the piece layer architecture that further demonstrate inside are the nanometer sheets of molybdenum disulfide.
Fig. 4 is that molybdenum disulfide/carbon composite prepared by embodiment 1 and molybdenum disulfide prepared by comparative example 1 are close in electric current
Spend for 0.1Ag-1Under cycle performance figure, as can be observed from Figure the capability value of pure molybdenum disulfide may be up to 750mAh g-1,
But its cycle performance is poor, the only 180mAh g after the circle of discharge and recharge 300-1.By contrast, prepared molybdenum disulfide/carbon is multiple
Condensation material has higher reversible capacity value and preferable cyclical stability.After 300 circle charge and discharge cycles, its reversible capacity value
It still may be up to 785mAh g-1.This demonstrate raising of the structure of composite to its reversible capacity value and cyclical stability to have
Highly important effect.
Claims (10)
- A kind of 1. molybdenum disulfide/carbon composite, it is characterised in that：Molybdenum disulfide confinement in the composite is received hollow In the carbon-coating of rice band structure, composite outer layer is the carbon-coating of N doping.
- 2. a kind of preparation method of molybdenum disulfide/carbon composite, comprises the following steps：(1) it is 10 by mass ratio:1-1:20 sodium molybdate is dissolved in water with sodium chloride, and lasting stirring, regulation pH value is 0-2, Hydro-thermal reaction 10-48h, resulting solution is filtered at 160-220 DEG C, washing, is then dried, is obtained molybdenum trioxide nano band； The concentration that wherein sodium molybdate is dissolved in water is 0.01-0.1g/mL；(2) molybdenum trioxide nano band is dispersed with stirring in water, adds pyrroles and initiator, react 6-48h at 0 ± 10 DEG C, By the centrifugation of gained dispersion liquid, washing and dry, obtain molybdenum trioxide/polypyrrole binary composite；Wherein molybdenum trioxide and pyrrole The mass ratio coughed up is 1:The mol ratio of 1-20, initiator and pyrroles are 1:8-4:1；(3) by molybdenum trioxide/polypyrrole binary composite and sulphur powder according to mass ratio 1:2-10 is mixed, grinding, in protection gas Lower vulcanization, curing temperature are 600-1000 DEG C, wash, dry, obtain molybdenum disulfide/carbon composite.
- A kind of 3. preparation method of molybdenum disulfide/carbon composite according to claim 2, it is characterised in that：The step Suddenly the mass ratio of sodium molybdate and sodium chloride is 2 in (1):1-1:2；The concentration that sodium molybdate is dissolved in water is 0.02-0.05g/mL.
- A kind of 4. preparation method of molybdenum disulfide/carbon composite according to claim 2, it is characterised in that：The step Suddenly regulation pH value is 0.5-1.5 in (1), is adjusted with hydrochloric acid solution.
- A kind of 5. preparation method of molybdenum disulfide/carbon composite according to claim 2, it is characterised in that：The step Suddenly hydro-thermal reaction 18-30h is carried out at 180-200 DEG C in (1).
- A kind of 6. preparation method of molybdenum disulfide/carbon composite according to claim 2, it is characterised in that：The step Suddenly initiator is ammonium persulfate, potassium peroxydisulfate or iron chloride in (2)；Molybdenum trioxide and the mass ratio of pyrroles are 1:10；Initiator Mol ratio with pyrroles is 1:1-4.
- A kind of 7. preparation method of molybdenum disulfide/carbon composite according to claim 2, it is characterised in that：The step Suddenly 12-24h is reacted at 0 ± 2 DEG C in (2).
- A kind of 8. preparation method of molybdenum disulfide/carbon composite according to claim 2, it is characterised in that：The step Suddenly molybdenum trioxide/polypyrrole binary composite and sulphur powder mass ratio are 1 in (3):4-5；Protection gas is nitrogen or argon gas, is vulcanized Technological parameter is：800 DEG C, soaking time 4h of temperature, the speed of heating is 2-5 DEG C/min.
- A kind of 9. preparation method of molybdenum disulfide/carbon composite according to claim 2, it is characterised in that：The step Suddenly washing is first to be washed with water with salt acid elution in (3).
- A kind of 10. application of molybdenum disulfide/carbon composite as claimed in claim 1, it is characterised in that：As super capacitor Device and lithium ion battery, the electrode material of solar cell.
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