CN116216780A - Broken shell-shaped MoS 2 Nanosphere material and preparation method and application thereof - Google Patents
Broken shell-shaped MoS 2 Nanosphere material and preparation method and application thereof Download PDFInfo
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- CN116216780A CN116216780A CN202310184777.7A CN202310184777A CN116216780A CN 116216780 A CN116216780 A CN 116216780A CN 202310184777 A CN202310184777 A CN 202310184777A CN 116216780 A CN116216780 A CN 116216780A
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- 239000002077 nanosphere Substances 0.000 title claims abstract description 54
- 239000000463 material Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 101100069231 Caenorhabditis elegans gkow-1 gene Proteins 0.000 title description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 38
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 33
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims abstract description 21
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 19
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 14
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 239000003125 aqueous solvent Substances 0.000 claims abstract description 5
- 239000007772 electrode material Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000002002 slurry Substances 0.000 claims description 6
- 239000003990 capacitor Substances 0.000 claims description 5
- 235000015393 sodium molybdate Nutrition 0.000 claims description 5
- 239000011684 sodium molybdate Substances 0.000 claims description 5
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 5
- 239000011149 active material Substances 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000006258 conductive agent Substances 0.000 claims description 4
- MODMKKOKHKJFHJ-UHFFFAOYSA-N magnesium;dioxido(dioxo)molybdenum Chemical compound [Mg+2].[O-][Mo]([O-])(=O)=O MODMKKOKHKJFHJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004513 sizing Methods 0.000 claims description 2
- 238000012983 electrochemical energy storage Methods 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000011232 storage material Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000012360 testing method Methods 0.000 description 8
- 239000011229 interlayer Substances 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 239000002057 nanoflower Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 5
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 5
- 238000010899 nucleation Methods 0.000 description 5
- 230000006911 nucleation Effects 0.000 description 5
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- -1 transition metal sulfide Chemical class 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 description 3
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000012010 growth Effects 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
- 238000012795 verification Methods 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
- 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
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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- C01P2004/32—Spheres
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- 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
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Abstract
The invention belongs to the technical field of electrochemical energy storage materials, and discloses a shell-broken MoS 2 The preparation method comprises the following steps: step 1, uniformly dispersing long-chain quaternary ammonium salt, molybdate and thiourea in an aqueous solvent to obtain a mixed solution; wherein the long-chain quaternary ammonium salt is one or two of hexadecyl trimethyl ammonium bromide and dodecyl trimethyl ammonium bromide; step 2, carrying out hydrothermal reaction on the mixed solution at 190-240 ℃, and cooling to room temperature to obtain the shell-broken MoS 2 Nanosphere material. The invention has the advantages of easily obtained raw materials, low reaction temperature, no environmental pollution, easy separation of products and pure productsHigh degree, good and uniform appearance, simple preparation process and suitability for industrialized popularization and application.
Description
Technical Field
The invention relates to the technical field of electrochemical energy storage materials, in particular to a shell-broken MoS 2 Nanosphere material and a preparation method and application thereof.
Background
MoS 2 As a representative member of the transition metal sulfide, the material is an ideal material for the supercapacitor electrode due to the characteristics of high conductivity, good hydrophilicity, multiple active sites, simple preparation and the like.
And in the prior art, the prepared MoS 2 Is a complete nanosphere, resulting in MoS 2 The active site at the center of the nanosphere is not fully utilized. Meanwhile, the crystallinity is poor, the interlayer spacing is small, and the MoS is comprehensively caused 2 The nanometer flower ball has poor charge storage capability and limits MoS 2 As an electrode for supercapacitors.
MoS 2 Can be classified into 2H-MoS according to the difference of crystal structures 2 、1T-MoS 2 、3R-MoS 2 Wherein the 3R phase and the 1T phase are metastable phases, and the metastable phases can be converted into stable 2H phases under the influence of pressure, irradiation and heat. And 2H-MoS 2 Smaller interlayer spacing
Leading to slow intercalation and deintercalation of electrolyte ions between layers thereof, limiting 2H-MoS 2 Is used for the electrochemical performance of the battery.
To this end, the invention provides a shell-broken MoS 2 Nanosphere material and a preparation method and application thereof.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a shell-broken MoS 2 Nanosphere material and a preparation method and application thereof.
The invention relates to a shell-broken MoS 2 The nanosphere material and the preparation method and application thereof are realized by the following technical scheme:
a first object of the present invention is to provide a shell-broken MoS 2 The preparation method of the nanosphere material comprises the following steps:
wherein the long-chain quaternary ammonium salt is one or two of hexadecyl trimethyl ammonium bromide and dodecyl trimethyl ammonium bromide;
Further, the molybdate is any one of ammonium molybdate, magnesium molybdate, zinc molybdate and sodium molybdate.
Further, the molar ratio of the long-chain quaternary ammonium salt, the molybdate and the thiourea is (1-2) 1 (25-35).
Further, the time of the hydrothermal reaction is 15-24 hours.
Further, the dosage ratio of the long-chain quaternary ammonium salt to the water solvent is (1.2-1.5) g (40-50) mL.
A second object of the present invention is to provide a shell-broken MoS prepared by the above-mentioned preparation method 2 Nanosphere material.
A third object of the present invention is to provide a shell-broken MoS as described above 2 The application of nanosphere materials in supercapacitors.
Further, the shell-broken MoS 2 The nanosphere material is used in the super capacitor after being made into an electrode material.
Further, the shelled MoS is prepared by the steps of 2 The nanosphere material is made into an electrode material:
s1, using the shell-broken MoS 2 The nanosphere material is an active material, and the nanosphere material, a binder and a conductive agent are dispersed in an organic solvent to obtain slurry;
s2, coating the slurry on a current collector, and drying to obtain the electrode material.
Further, the binder is PVDF, the conductive agent is acetylene black, and the organic solvent is NMP solution.
Further, the current collector is carbon paper;
the coating area of the current collector sizing agent is 1cm multiplied by 1cm, and the coating quality is controlled to be 1.4-1.6 mg.
Compared with the prior art, the invention has the following beneficial effects:
the invention makes MoS through uniformly dispersing long-chain quaternary ammonium salt, molybdate and thiourea in water solvent and then carrying out hydrothermal reaction treatment 2 During the nucleation and crystallization process, long-chain quaternary ammonium salt (CTAB and/or DTAB) is used for nucleation and growth, and the long-chain quaternary ammonium salt is long-chain organic macromolecules between the nano flower sheets so as to reduce the interaction force between two layers of nano sheets, thereby causing the nano flower balls to be broken to form a shell-broken structure, and further preparing the shell-broken MoS with large interlayer spacing, high crystallinity and excellent charge storage performance 2 A nanomaterial.
The method has the advantages of easily obtained raw materials, low reaction temperature, no environmental pollution, easy separation of products, high purity of the obtained products, good and uniform appearance, simple preparation process and suitability for industrial popularization and application.
MoS prepared by the invention 2 The nanosphere material has a shell-broken structure such that MoS 2 The reactive sites inside the nanoflower are exposed, so that the contribution of the pseudo-capacitor is greatly improved, and the charge storage capacity of the material is improved; and long-chain quaternary ammonium salt is in MoS 2 Is of the MoS is expanded by intercalation in the matrix 2 The large interlayer spacing is more favorable for intercalation of ions so as to improve the ion transmission speed, and the material has excellent electrochemical performance. Thus, the shell-broken MoS prepared by the invention 2 The nanosphere material can be used as a supercapacitor electrode material, and has the performances of high specific capacitance, high cycling stability and the like when being used as the supercapacitor electrode material.
Drawings
FIG. 1 is a broken shell MoS prepared in example 1 2 Scanning Electron Microscope (SEM) photographs of nanosphere supercapacitor electrode materials;
FIG. 2 is a broken shell MoS prepared in example 2 2 Scanning Electron Microscope (SEM) photographs of nanosphere supercapacitor electrode materials;
FIG. 3 is a broken shell MoS prepared in example 1 2 X-ray diffraction (XRD) patterns of nanosphere supercapacitor electrode materials;
FIG. 4 is an enlarged view of a portion of FIG. 3;
FIG. 5 is a cyclic voltammogram of the electrode prepared in example 10 at different scan rates;
FIG. 6 is a cyclic voltammogram of the electrode prepared in example 11 at different scan rates;
FIG. 7 is a constant current charge and discharge curve of the electrode prepared in example 10 at different current densities;
fig. 8 is a constant current charge-discharge curve of the electrode prepared in example 11 at different current densities.
Detailed Description
As described in the background, the present invention contemplates 2H-MoS 2 Consists of three atomic layers (three covalently bonded S-Mo-S layers) stacked and held together by weak van der waals interactions. The 2H-MoS can be regulated and controlled by weak Van der Waals force between layers 2 Is a layer spacing of (c). Thus, the present invention has been made in an effort to produce 2H-MoS with large interlayer spacing and high specific volume 2 Has potential to be an electrode material of super capacitor with excellent performance. And the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.
The invention provides a shell-broken MoS 2 The preparation method of the nanosphere material comprises the following steps:
in the invention, thiourea is preferably used as the sole sulfur source, and the thiourea can be decomposed to generate carbon dioxide and ammonium ions at the high temperature of the subsequent hydrothermal reaction, so that high air pressure and alkaline environment are provided for the hydrothermal reaction, and the hydrothermal reaction is promoted.
The invention is not limited to the specific type of molybdate, so long as the molybdate can be used for obtaining the shell-broken MoS with large interlayer spacing under the induction action of long-chain quaternary ammonium salt in the subsequent hydrothermal process with thiourea 2 The nanospheres may be, for example, any one selected from sodium molybdate, magnesium molybdate, zinc molybdate and sodium molybdate.
In order to ensure that the long-chain quaternary ammonium salt can play the role of induction, the long-chain quaternary ammonium salt is preferably selected from one or two of Cetyl Trimethyl Ammonium Bromide (CTAB) and Dodecyl Trimethyl Ammonium Bromide (DTAB). And the molar ratio of the long-chain quaternary ammonium salt, the molybdate and the thiourea is 1-2:1:25-35.
The invention is not limited to a specific mode of dispersing the long-chain quaternary ammonium salt, the molybdate and the thiourea in the water solvent, and only needs to be capable of uniformly dispersing the long-chain quaternary ammonium salt, the molybdate and the thiourea to obtain a mixed solution with uniform components. For example, dispersion may be performed by ultrasonic or agitation.
in order to ensure the obtained MoS 2 On the basis that the nanosphere material has a shell-broken structure with uniform morphology, moS is improved 2 The yield of the nanosphere material is preferably 180-240 ℃ in the hydrothermal reaction, and the reaction time is 15-24 hours.
The invention aims to obtain pure shell-broken MoS 2 The nanosphere material is prepared by cooling a product obtained after hydrothermal reaction to room temperature, filtering to obtain a solid product, washing and drying the solid product in sequence, and obtaining a solid component which is pure shell-broken MoS after drying 2 Nanosphere material. Preferably, the washing method is to adopt deionized water and absolute ethyl alcohol to wash for several times respectively; the drying is carried out in a vacuum drying oven, the drying temperature is 45-70 ℃, and the drying time is 36-60 h.
Example 1
The present embodiment provides a shell-broken MoS 2 The preparation method of the nanosphere material comprises the following steps:
(1) Accurately weighing 1.4484g of ammonium molybdate tetrahydrate, 2.8418g of thiourea and 0.7g of CTAB, dispersing the ammonium molybdate tetrahydrate, 2.8418g of thiourea and 0.7g of CTAB in a beaker filled with 45mL of deionized water, and fully dissolving the ammonium molybdate tetrahydrate and the CTAB under the action of magnetic stirring to form a uniform solution to obtain a reaction solution;
(2) Transferring the reaction solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining of which the capacity is 100mL, heating the reaction solution in an oven at the constant temperature of 190 ℃ for 15 hours, and naturally cooling the reaction solution to room temperature after the reaction is finished.
(3) Taking out black solid precipitate at the bottom of the polytetrafluoroethylene lining, washing for 3 times by deionized water and absolute ethyl alcohol respectively, and then placing in a vacuum drying oven to be dried at 60 ℃ to constant weight to obtain solid powder, namely shell-broken MoS 2 The electrode material of the nanosphere super capacitor.
Example 2
The present embodiment provides a shell-broken MoS 2 Nanosphere materials and methods of preparation differ from example 1 only in:
in this example, the long chain quaternary ammonium salt is DTAB.
Example 3
The present embodiment provides a shell-broken MoS 2 Nanosphere materials and methods of preparation differ from example 1 only in:
in this embodiment, the molar ratio of the long-chain quaternary ammonium salt, the molybdate and the thiourea is 1:1:30;
the temperature of the hydrothermal reaction is 180 ℃ and the time is 15 hours;
the dosage ratio of the long-chain quaternary ammonium salt to the water solvent is 1.2g:45mL.
Example 4
The present embodiment provides a shell-broken MoS 2 Nanosphere materials and methods of preparation differ from example 1 only in:
in this embodiment, the molar ratio of the long-chain quaternary ammonium salt, the molybdate and the thiourea is 1.5:1:35;
the temperature of the hydrothermal reaction is 240 ℃ and the time is 24 hours;
the dosage ratio of the long-chain quaternary ammonium salt to the water solvent is 1.5g:45mL.
Example 5
The present embodiment provides a shell-broken MoS 2 Nanosphere materials and methods of preparation differ from example 1 only in:
in this embodiment, the molar ratio of the long-chain quaternary ammonium salt, the molybdate and the thiourea is 1.3:1:25;
the temperature of the hydrothermal reaction is 220 ℃ and the time is 20 hours;
the dosage ratio of the long-chain quaternary ammonium salt to the water solvent is 1.3g:45mL.
Example 6
The present embodiment provides a shell-broken MoS 2 Nanosphere materials and methods of preparation differ from example 1 only in:
in this embodiment, the molar ratio of the long-chain quaternary ammonium salt, the molybdate and the thiourea is 1.4:1:15;
the temperature of the hydrothermal reaction is 200 ℃ and the time is 18 hours;
the dosage ratio of the long-chain quaternary ammonium salt to the water solvent is 1.4g:45mL.
Example 7
The present embodiment provides a shell-broken MoS 2 Nanosphere materials and methods of preparation differ from example 1 only in:
in this embodiment, the molybdate is sodium molybdate.
Example 8
The present embodiment provides a shell-broken MoS 2 Nanosphere materials and methods of preparation differ from example 1 only in:
in this example, the molybdate is magnesium molybdate.
Example 9
The present embodiment provides a shell-broken MoS 2 Nanosphere materials and methods of preparation differ from example 1 only in:
in this example, the molybdate is zinc molybdate.
Example 10
The embodiment provides an electrode material for a supercapacitor, and the preparation method of the electrode material comprises the following steps:
s1, weighing 0.005g PVDF, 0.005g acetylene black and 0.04g of the shell-broken MoS prepared in example 1 2 The nanosphere electrode material is put into an agate mortar, and 0.6ml of NMP solution is added dropwise, and the mixture is sufficiently ground for 5min to obtain slurry;
s2, uniformly coating the slurry on the carbon paper, controlling the coating area to be 1cm multiplied by 1cm, controlling the coating quality to be 1.4-1.6 mg, putting the uniformly coated carbon paper in a vacuum drying oven, and drying at 60 ℃ to constant weight to obtain the corresponding electrode.
Example 11
The present embodiment provides an electrode material for a supercapacitor, and the preparation method is different from embodiment 10 in that:
broken shell MoS prepared in example 2 2 The nanosphere electrode material is an active material.
Example 12
The present embodiment provides an electrode material for a supercapacitor, and the preparation method is different from embodiment 10 in that:
the shelled MoS prepared in any one of examples 3-9 2 The nanosphere electrode material is an active material.
Comparative example 1
The present embodiment provides a MoS 2 Nanomaterial and its preparation method differs from example 1 only in that:
no long-chain quaternary ammonium salt is added.
Test section
Scanning Electron Microscope (SEM) testing
The invention relates to the shell-broken MoS prepared in the example 1 and the example 2 2 The nanosphere material was subjected to SEM testing, the test results of which are shown in fig. 1 and 2.
FIG. 1 is a broken shell MoS prepared in example 1 2 SEM spectra of nanosphere materials, wherein the left figure is SEM spectra at 5 μm scale and the right figure is SEM spectra at 1 μm scale.
FIG. 2 is a broken shell MoS prepared in example 2 2 SEM spectra of nanosphere materials, wherein the left figure is SEM spectra at 5 μm scale and the right figure is SEM spectra at 700nm scale.
As can be seen from FIGS. 1 and 2, the microscopic morphologies of the products prepared in example 1 and example 2 were both represented as shell-broken MoS 2 A nanosphere.
(II) X-ray diffraction (XRD) test
The invention relates to the shell-broken MoS prepared in the example 1 2 XRD testing of nanosphere materials, testing thereofThe results are shown in fig. 3 and 4, where fig. 4 is an enlarged view of a portion of fig. 3 in the 2θ angle range of 5 to 15.
And as can be seen from FIGS. 3 and 4, it was confirmed that the products prepared in examples 1 and 2 of the present invention were each lamellar MoS by comparison with the JCPDS No.37-1492 card 2 。
(III) electrochemical Performance test
The electrode materials prepared in examples 10 and 11 were electrochemically tested in a three-electrode test system under the following conditions: the working electrode was the electrode prepared in comparative example 10, the reference electrode was an Ag/AgCl electrode, the counter electrode was a platinum sheet electrode, and the electrolyte was a 1M sodium sulfate solution.
Electrochemical test data are shown in fig. 5-8, wherein fig. 5 is cyclic voltammograms of the electrode prepared in example 10 at different scan rates; FIG. 6 is a cyclic voltammogram of the electrode prepared in example 11 at different scan rates; FIG. 7 is a constant current charge and discharge curve of the electrode prepared in example 10 at different current densities; fig. 8 is a constant current charge-discharge curve of the electrode prepared in example 11 at different current densities.
And according to the rectangular-like shapes of fig. 5 and 6, it is shown that the materials prepared in example 1 and example 2 are capacitive electrode materials, the voltage window of which is-0.7 to 0.1V, and are supercapacitor electrode materials.
The linear curve characteristics of FIGS. 7 and 8 further demonstrate the MoS of the materials obtained in example 1 and example 2 2 Is described.
By verifying the products obtained in the above examples and comparative examples, moS was obtained during the preparation without the addition of long chain quaternary ammonium salts (CTAB and/or DTAB) 2 The surface energy to be the lowest in the nucleation crystallization process is usually present in the form of nanoflower spheres and is (2H-MoS) 2 ) The interlayer spacing is
The invention adds long-chain quaternary ammonium salt (CTAB/DTAB) to make MoS 2 Nucleation growth around CTAB/DTAB, CTAB/DTAB longThe chain organic macromolecule reduces the interaction force between two layers of nano sheets among the nano flower sheets, so that the nano flower ball is broken to form a shell-broken structure, and the CTAB/DTAB induction preparation method of the invention prepares 2H-MoS 2 Is>
When the water consumption is changed, the volume of the air column in the reaction kettle is changed, which affects the pressure in the reaction kettle in the hydrothermal reaction, thereby affecting the structure of the final product; in addition, when the temperature of the hydrothermal reaction is changed, the reaction temperature is changed to 2H-MoS 2 The nucleation, crystallization and growth rate are obviously affected, the optimal technological conditions are obtained through experimental verification, and the prepared product has good specific capacitance and uniform morphology.
It should be apparent that the embodiments described above are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Claims (10)
1. Broken shell-shaped MoS 2 The preparation method of the nanosphere material is characterized by comprising the following steps:
step 1, uniformly dispersing long-chain quaternary ammonium salt, molybdate and thiourea in an aqueous solvent to obtain a mixed solution;
wherein the long-chain quaternary ammonium salt is one or two of hexadecyl trimethyl ammonium bromide and dodecyl trimethyl ammonium bromide;
step 2, carrying out hydrothermal reaction on the mixed solution at 190-240 ℃, and cooling to room temperature to obtain the shell-broken MoS 2 Nanosphere material.
2. The method of claim 1, wherein the molybdate is any of ammonium molybdate, magnesium molybdate, zinc molybdate, and sodium molybdate.
3. The method according to claim 1, wherein the molar ratio of the long-chain quaternary ammonium salt, the molybdate to the thiourea is 1 to 2:1 (25 to 35).
4. The method of claim 1, wherein the hydrothermal reaction time is 15 to 24 hours.
5. The method according to claim 1, wherein the ratio of the long-chain quaternary ammonium salt to the aqueous solvent is (1.2-1.5) g (40-50) mL.
6. A shell-broken MoS prepared by the method of any one of claims 1 to 5 2 Nanosphere material.
7. A shell-broken MoS as set forth in claim 6 2 The application of the nanosphere material in the electrode material of the super capacitor.
8. The use according to claim 7, wherein the shell-broken MoS is obtained by 2 The nanosphere material is made into an electrode material:
s1, using the shell-broken MoS 2 The nanosphere material is an active material, and the nanosphere material, a binder and a conductive agent are dispersed in an organic solvent to obtain slurry;
s2, coating the slurry on a current collector, and drying to obtain the electrode material.
9. The use according to claim 8, wherein the binder is PVDF, the conductive agent is acetylene black, and the organic solvent is an NMP solution.
10. The use of claim 8, wherein the current collector is carbon paper;
the coating area of the current collector sizing agent is 1cm multiplied by 1cm, and the coating quality is controlled to be 1.4-1.6 mg.
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