CN112110489A - Micro-spherical CuS-MoS2Method for preparing composite material - Google Patents
Micro-spherical CuS-MoS2Method for preparing composite material Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 101
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 48
- 229910052961 molybdenite Inorganic materials 0.000 claims abstract description 47
- 239000010949 copper Substances 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 26
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000005406 washing Methods 0.000 claims abstract description 20
- 239000004005 microsphere Substances 0.000 claims abstract description 17
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000007864 aqueous solution Substances 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 13
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000011684 sodium molybdate Substances 0.000 claims abstract description 11
- 235000015393 sodium molybdate Nutrition 0.000 claims abstract description 11
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 239000002244 precipitate Substances 0.000 claims abstract description 8
- 239000003990 capacitor Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 229910001868 water Inorganic materials 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- 238000000197 pyrolysis Methods 0.000 claims abstract description 5
- 239000008367 deionised water Substances 0.000 claims description 27
- 229910021641 deionized water Inorganic materials 0.000 claims description 27
- 238000001291 vacuum drying Methods 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 11
- 239000007772 electrode material Substances 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 239000000243 solution Substances 0.000 abstract description 19
- 239000000463 material Substances 0.000 description 13
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 10
- 229910001220 stainless steel Inorganic materials 0.000 description 10
- 239000010935 stainless steel Substances 0.000 description 10
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 8
- 229910015667 MoO4 Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000000840 electrochemical analysis Methods 0.000 description 3
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 2
- 229940112669 cuprous oxide Drugs 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 102000036675 Myoglobin Human genes 0.000 description 1
- 108010062374 Myoglobin Proteins 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- -1 transition metal sulfides Chemical class 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000007704 wet chemistry method Methods 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/06—Sulfides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/12—Sulfides
-
- 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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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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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- 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
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- C01P2004/32—Spheres
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- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
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Abstract
The invention belongs to the technical field of super capacitors, and particularly discloses a microspherical CuS-MoS2The preparation method of the composite material comprises the following steps: mixing the aqueous solution of copper nitrate trihydrate and the aqueous solution of ethanolamine, and carrying out pyrolysis reaction to obtain CuO-Cu2An O composite material; mixing CuO-Cu2Dissolving the O composite material in water; dissolving sodium molybdate and thiourea in water to obtain a mixed solution; mixing CuO-Cu2Adding the water solution of the O composite material into the mixed solution, carrying out hydrothermal reaction, and sequentially washing and drying the obtained precipitate to obtain the CuS-MoS2A composite material. The invention provides a microspheric CuS-MoS2The preparation method of the composite material adopts a simple hydrothermal method and adopts CuO-Cu2Taking the O composite microspheres as a sacrificial template, and preparing MoS while vulcanizing the microspheres by utilizing a sacrificial template method2Obtaining CuS-MoS2The method has low cost and simple process.
Description
Technical Field
The invention belongs to the technical field of super capacitors, and particularly discloses a microspherical CuS-MoS2A method for preparing a composite material.
Background
Among transition metal sulfides, molybdenum disulfide (MoS)2) Is a typical two-dimensional nano material, has excellent mechanical properties, large specific surface area and higher theoretical specific capacitance, is an ideal electrode material of a super capacitor, but MoS2Further development is limited by poor conductivity. Copper sulfide (CuS) is one of the candidates of electrode material with application prospect, and not only has low price and rich material source, but also has higher theoretical specific capacity (560 mAh.g)-1) And excellent conductivity (10)-3S·cm-1) It is widely used in chemical sensors, solar cells, lithium ion batteries, etc. Thus, the CuS and MoS are combined2The composite material can obtain electrochemical performance superior to that of single material by utilizing the synergistic effect of the two materials.
CuS-MoS in the prior art2The preparation method of the composite material mainly comprises the following steps: (1) 0.5g of MoS2The nanocrystals were dispersed in 2.0mL of 1.0 wt% chitosan acetic acid solution, sonicated, and centrifuged at room temperature for 10 min.The precipitate was then dispersed into 5.0mL of 2M Cu (NO)3)2In the aqueous solution, the pH was adjusted to 9.0. Degassing with high purity nitrogen for 30 min, and adding 5.0M Na2S aqueous solution, reacting for 12 hours at room temperature, and finally centrifuging, washing and drying (Zhang B., Zhang Y., Liang W.B., et al. coater Sulfide-Functionalized Molybdenum nanoparticles as nanoenzzyme semiconductors for Electrochemical analysis of Myoglobin in Cardiovascular disease. RSC adv.,2017, 2486-containing 2493), wherein the scheme is prepared by a wet chemistry method, the steps are complicated, and the cost is high; (2) liu f.g. et al prepared by a one pot solvothermal method using copper nanowires as templates, in which MoS occurred2Precipitation and simultaneous conversion of Cu to CuS (Liu F.G., Xu R.Z., Hong L., et al. simple Morphology-Tunable Preparation of CuS @ MoS)2Heterogeneous Based on Template method. chemistry Select 2020,5, 360-; (3) 5mL of polyvinylpyrrolidone, and adding CuCl under stirring2Aqueous solution (0.2M) and 5mL NiCl2The solution (0.2M) was taken in 60mL of H2O, after 10 minutes, 5mL of an aqueous glucose solution (1M) including sodium citrate (0.6M) and K2 CO3A10 mL solution of (1.1M) was placed in the above reaction system and stirred for 30 minutes until a blue solution was obtained. The bottle was then placed in an autoclave lined with teflon and left at 80 ℃ for 2 h. By using H2O and C2H5OH rinsing and centrifuging for several times to collect red sample, namely Cu2And (4) O particles. Taking 10mg of Cu2O into distilled water (15mL), Na was added under vigorous stirring2MoO4(50mg), ethanol (25mL), urea (0.3g) and thioacetamide (35mg) were dispersed in the solution, the solution was placed in a Teflon lined autoclave at 160 ℃ for 24 hours, then dried by centrifugal washing, and the product was taken up in H2Calcining the mixture in S for 5 hours at the temperature of 400 ℃ to obtain CuS @ MoS2And (3) sampling. Hollow cube CuS @ MoS2Is through Cu2O and MoS2Precipitation of, two-dimensional MoS2Nanosheet aggregated in Cu2The surface of the O-die plate, finally, is promoted by heat treatmentHollow CuS @ MoS2Generation of microcubes (Zhou H., Lv Z.L., Liu H., et al2microcubes with super lithium storage. Electrochimica Acta 250(2017) 376-383), which is complicated in experiment and expensive in cost.
Disclosure of Invention
Aiming at the technical problems, the invention provides a microspherical CuS-MoS2The preparation method of the composite material adopts a simpler hydrothermal method and adopts CuO-Cu2Taking the O composite microspheres as a sacrificial template, and preparing MoS while vulcanizing the microspheres by utilizing a sacrificial template method2Obtaining CuS-MoS2The method has low cost and simple process.
The invention provides a microspheric CuS-MoS2The preparation method of the composite material comprises the following steps:
S1、CuO-Cu2preparing an O composite material:
mixing the copper nitrate trihydrate aqueous solution with the ethanolamine aqueous solution, fully stirring, carrying out pyrolysis reaction, and sequentially washing and drying the obtained precipitate to obtain the CuO-Cu2An O composite material;
S2、CuS-MoS2preparing a composite material:
dissolving sodium molybdate and thiourea in water to obtain a mixed solution;
the CuO-Cu is added2Adding an aqueous solution of an O composite material into the mixed solution, fully stirring for hydrothermal reaction, and sequentially washing and drying the obtained precipitate to obtain the CuS-MoS2A composite material;
wherein the molar ratio of the copper nitrate trihydrate to the copper and sulfur in the thiourea is 1: 1-1.5, wherein the molar ratio of the sodium molybdate to the molybdenum and the sulfur in the thiourea is 1: 2 to 3.
Preferably, the concentration of the copper nitrate trihydrate aqueous solution is 0.17mol/L, and the concentration of the ethanolamine aqueous solution is 2 mol/L.
Preferably, the pyrolysis reaction in S1 is maintained at 180 ℃ for 12 h.
Preferably, the hydrothermal reaction in S2 is maintained at 200 ℃ for 24 h.
Preferably, the washing in S1 and S2 is with deionized water and the drying is vacuum drying at 80 ℃ for 12 h.
The invention also provides the CuS-MoS prepared by the preparation method2And (3) microspheres.
The invention also provides the CuS-MoS2The application of the microspheres in the electrode material of the super capacitor.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a microspheric CuS-MoS2Preparation method of composite material, porous CuO-Cu2The porous CuS-MoS is synthesized by taking the O microspheres as a sacrificial template and adopting a simple green sacrificial template method2The microsphere composite material has petal-shaped microspherical morphology, can effectively improve the electrochemical performance of the material, and the core-shell structure of the microsphere composite material enables CuS and MoS2The two materials are mutually promoted, the defects of the two materials are improved, the performance of the two materials is improved, the prepared electrode material is used as an electrode of a super capacitor, and the detection proves that the material has good electrochemical performance, so that the electrode material has good application value and research significance in the fields of super capacitors and photoelectric cell devices.
Drawings
FIG. 1 shows CuO-Cu prepared in example 12SEM image of O composite; wherein a is CuO-Cu2An image of the micro-morphology of the O composite material under 1 um; b is CuO-Cu2A micro-topography image of the O composite material under 500 nm;
FIG. 2 is the CuS-MoS prepared in example 12SEM images of the composite; wherein a, b, c and d are respectively CuS-MoS2Microscopic morphology images of the composite material under 50um, 20um, 8um and 5 um;
FIG. 3 is the CuS-MoS prepared in example 12Electrochemical test results of the composite; wherein a and b are CV and GCD curves of CuS, respectively, and c and d are CuS-MoS curves2Is the CV and GCD plot of (e) is CuS-MoS2Logarithm of peak current and scan rateLinear plot between logarithm of rate, f is CuS and CuS-MoS at different current densities2Comparison of specific capacitance of composite materials.
Detailed Description
The present invention is described in further detail below with reference to specific examples, which are intended to be illustrative and not limiting of the scope of the invention.
Example 1
Micro-spherical CuS-MoS2The preparation method of the composite material comprises the following steps:
S1、CuO-Cu2preparing an O composite material:
1.930g of copper nitrate trihydrate was added to 48mL of deionized water, 16mL of 2M ethanolamine was added and stirred for 15min, after which the stirred solution was transferred to a 50mL stainless steel autoclave and heated to 180 ℃ for 12 h. Then, centrifugally washing the prepared composite material for 5 times by using deionized water, and placing the composite material in a vacuum drying oven for vacuum drying for 12 hours at the temperature of 80 ℃ to prepare the CuO-Cu2O, sacrificing the template;
S2、CuS-MoS2preparing a composite material:
prepared CuO-Cu2And dissolving the O composite material in 55mL of deionized water, and ultrasonically cleaning for 5 min. 77.5mg of sodium molybdate (Na) are taken2MoO4) And 121.5mg of thiourea (H)2NCSNH2) Dissolving in 50mL deionized water, placing in a magnetic stirrer, stirring for 10min, and then adding the well-sonicated CuO-Cu2The O composite was poured into a mixing vessel and stirred, after which the well stirred solution was transferred to a 50mL stainless steel autoclave and heated to 200 ℃ for 24 h. Then centrifugally washing the prepared composite material with deionized water for 5 times, placing the washed composite material in a vacuum drying oven at 80 ℃ for 12h, and drying the composite material in vacuum to obtain CuS-MoS2A composite material.
In the embodiment of the invention, copper nitrate is pyrolyzed in an autoclave to form CuO-Cu2The black precipitate of O and ethanolamine have catalytic effect, and the black precipitate contains partial impurity, and is washed centrifugally and dried to obtain sacrificial template CuO-Cu2O powder; ultrasoundCuO-Cu dissolved in water2O is sulfurized by the added thiourea to obtain CuS, and simultaneously, the added sodium molybdate is sulfurized to obtain MoS2(ii) a The sulfurization reaction is more thorough and the CuS and MoS are more thoroughly carried out by the hydrothermal reaction2Compounded into CuS-MoS2And (3) microspheres.
The CuO-Cu prepared in step S1 and step S22O material and CuS-MoS2The composite material was examined by scanning electron microscopy, and the results are shown in fig. 1 and 2.
As can be seen from FIG. 1, CuO-Cu2The surface of the O composite material is uniform and porous microspheres formed by gathering a plurality of small particles, and the diameter of the microspheres is 2-3 um;
as can be seen from FIG. 2, CuS-MoS2The shape of the composite material is petal microspherical, the diameter is 5-8um, the size is uniform, small particles scattered after vulcanization appear on the surface of the petals, the petal microspherical material can effectively improve the specific surface area of the material and can increase the transmission channel of electrons, so that the electrode material with the porous microspherical structure and the shape has positive effects on the aspects of stable structure, rapid ion transmission and the like.
Example 2
Micro-spherical CuS-MoS2The preparation method of the composite material comprises the following steps:
S1、CuO-Cu2preparing an O composite material:
1.930g of copper nitrate trihydrate was added to 48mL of deionized water, 16mL of 2M ethanolamine was added and stirred for 15min, after which the stirred solution was transferred to a 50mL stainless steel autoclave and heated to 180 ℃ for 12 h. Then, centrifugally washing the prepared composite material for 5 times by using deionized water, and placing the composite material in a vacuum drying oven for vacuum drying for 12 hours at the temperature of 80 ℃ to prepare the CuO-Cu2O, sacrificing the template;
S2、CuS-MoS2preparing a composite material:
prepared CuO-Cu2And dissolving the O composite material in 55mL of deionized water, and ultrasonically cleaning for 5 min. 77.5mg of sodium molybdate (Na) are taken2MoO4) And 109.5mg of thiourea (H)2NCSNH2) SolutionDissolving in 50mL deionized water, placing in a magnetic stirrer, stirring for 10min, and then adding the well-sonicated CuO-Cu2The O composite was poured into a mixing vessel and stirred, after which the well stirred solution was transferred to a 50mL stainless steel autoclave and heated to 200 ℃ for 24 h. Then centrifugally washing the prepared composite material with deionized water for 5 times, placing the washed composite material in a vacuum drying oven at 80 ℃ for 12h, and drying the composite material in vacuum to obtain CuS-MoS2A composite material.
Example 3
Micro-spherical CuS-MoS2The preparation method of the composite material comprises the following steps:
S1、CuO-Cu2preparing an O composite material:
1.930g of copper nitrate trihydrate was added to 48mL of deionized water, 16mL of 2M ethanolamine was added and stirred for 15min, after which the stirred solution was transferred to a 50mL stainless steel autoclave and heated to 180 ℃ for 12 h. Then, centrifugally washing the prepared composite material for 5 times by using deionized water, and placing the composite material in a vacuum drying oven for vacuum drying for 12 hours at the temperature of 80 ℃ to prepare a copper oxide-cuprous oxide sacrificial template;
S2、CuS-MoS2preparing a composite material:
prepared CuO-Cu2And dissolving the O composite material in 55mL of deionized water, and ultrasonically cleaning for 5 min. 77.5mg of sodium molybdate (Na) are taken2MoO4) And 134.1mg of thiourea (H)2NCSNH2) Dissolving in 50mL deionized water, placing in a magnetic stirrer, stirring for 10min, and then adding the well-sonicated CuO-Cu2The O composite was poured into a mixing vessel and stirred, after which the well stirred solution was transferred to a 50mL stainless steel autoclave and heated to 200 ℃ for 24 h. Then centrifugally washing the prepared composite material with deionized water for 5 times, placing the washed composite material in a vacuum drying oven at 80 ℃ for 12h, and drying the composite material in vacuum to obtain CuS-MoS2A composite material.
Example 4
Micro-spherical CuS-MoS2The preparation method of the composite material comprises the following steps:
S1、CuO-Cu2preparing an O composite material:
1.930g of copper nitrate trihydrate was added to 48mL of deionized water, 16mL of 2M ethanolamine was added and stirred for 15min, after which the stirred solution was transferred to a 50mL stainless steel autoclave and heated to 180 ℃ for 12 h. Then, centrifugally washing the prepared composite material for 5 times by using deionized water, and placing the composite material in a vacuum drying oven for vacuum drying for 12 hours at the temperature of 80 ℃ to prepare a copper oxide-cuprous oxide sacrificial template;
S2、CuS-MoS2preparing a composite material:
prepared CuO-Cu2And dissolving the O composite material in 55mL of deionized water, and ultrasonically cleaning for 5 min. 77.5mg of sodium molybdate (Na) are taken2MoO4) And 140.0mg of thiourea (H)2NCSNH2) Dissolving in 50mL deionized water, placing in a magnetic stirrer, stirring for 10min, and then adding the well-sonicated CuO-Cu2The O composite was poured into a mixing vessel and stirred, after which the well stirred solution was transferred to a 50mL stainless steel autoclave and heated to 200 ℃ for 24 h. Then centrifugally washing the prepared composite material with deionized water for 5 times, placing the washed composite material in a vacuum drying oven at 80 ℃ for 12h, and drying the composite material in vacuum to obtain CuS-MoS2A composite material.
Example 5
Micro-spherical CuS-MoS2The preparation method of the composite material comprises the following steps:
S1、CuO-Cu2preparing an O composite material:
1.930g of copper nitrate trihydrate was added to 48mL of deionized water, 16mL of 2M ethanolamine was added and stirred for 15min, after which the stirred solution was transferred to a 50mL stainless steel autoclave and heated to 180 ℃ for 12 h. Then, centrifugally washing the prepared composite material for 5 times by using deionized water, and placing the composite material in a vacuum drying oven for vacuum drying for 12 hours at the temperature of 80 ℃ to prepare the CuO-Cu2O, sacrificing the template;
S2、CuS-MoS2preparing a composite material:
prepared CuO-Cu2And dissolving the O composite material in 55mL of deionized water, and ultrasonically cleaning for 5 min. 77.5mg of sodium molybdate (Na) are taken2MoO4) And 162.9mg of thiourea (H)2NCSNH2) Dissolving in 50mL deionized water, placing in a magnetic stirrer, stirring for 10min, and then adding the well-sonicated CuO-Cu2The O composite was poured into a mixing vessel and stirred, after which the well stirred solution was transferred to a 50mL stainless steel autoclave and heated to 200 ℃ for 24 h. Then centrifugally washing the prepared composite material with deionized water for 5 times, placing the washed composite material in a vacuum drying oven at 80 ℃ for 12h, and drying the composite material in vacuum to obtain CuS-MoS2A composite material.
Example 6
Since the properties of the composites prepared in examples 1-5 were substantially the same, only the CuS-MoS prepared in example 1 was used as follows2The properties of the composite material are illustrated.
The sample prepared in example 1 was used as a working electrode, a platinum sheet electrode as a counter electrode, and a saturated calomel electrode as a reference electrode, and the performance of the sample was measured. All tests were carried out at room temperature, with 3M KOH solution as electrolyte, electrochemical tests were carried out: cyclic voltammetry, constant current charge-discharge and alternating current impedance. The results are shown in FIG. 3.
As can be seen in FIG. 3, CuS-MoS2The electrode materials are respectively 1A g-1,2A·g-1,5A·g-1,8A·g-1And 10A. g-1The specific capacity reaches 320 F.g under the current density-1,406F·g-1,335F·g-1,331F·g-1And 328F g-1The rate capability reaches 102 percent, and is further improved compared with the rate capability of a CuS material, which shows that the CuS-MoS material has the rate capability of CuS-MoS2The composite material has excellent electrochemical performance.
It should be noted that the steps and methods adopted in the claims of the present invention are the same as those of the above-mentioned embodiments, and for the sake of avoiding redundancy, the present invention describes the preferred embodiments, but those skilled in the art can make other changes and modifications to these embodiments once they learn the basic inventive concept. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (7)
1. Micro-spherical CuS-MoS2The preparation method of the composite material is characterized by comprising the following steps:
S1、CuO-Cu2preparing an O composite material:
mixing the copper nitrate trihydrate aqueous solution with the ethanolamine aqueous solution, fully stirring, carrying out pyrolysis reaction, and sequentially washing and drying the obtained precipitate to obtain the CuO-Cu2An O composite material;
S2、CuS-MoS2preparing a composite material:
dissolving sodium molybdate and thiourea in water to obtain a mixed solution;
the CuO-Cu is added2Adding an aqueous solution of an O composite material into the mixed solution, fully stirring for hydrothermal reaction, and sequentially washing and drying the obtained precipitate to obtain the CuS-MoS2A composite material;
wherein the molar ratio of the copper nitrate trihydrate to the copper and sulfur in the thiourea is 1: 1-1.5, wherein the molar ratio of the sodium molybdate to the molybdenum and the sulfur in the thiourea is 1: 2 to 3.
2. The microspheroidal CuS-MoS according to claim 12The preparation method of the composite material is characterized in that the concentration of the copper nitrate trihydrate aqueous solution is 0.17mol/L, and the concentration of the ethanolamine aqueous solution is 2 mol/L.
3. The microspheroidal CuS-MoS according to claim 12A method for preparing a composite material, wherein the pyrolysis reaction in S1 is maintained at 180 ℃ for 12 hours.
4. According to claim 1The micro-spherical CuS-MoS2The preparation method of the composite material is characterized in that the hydrothermal reaction in S2 is kept at 200 ℃ for 24 h.
5. The microspheroidal CuS-MoS according to claim 12The method for preparing the composite material is characterized in that the washing in S1 and S2 is deionized water washing, and the drying is vacuum drying at 80 ℃ for 12 h.
6. CuS-MoS prepared by the preparation method of any one of claims 1 to 52And (3) microspheres.
7. CuS-MoS according to claim 62The application of the microspheres in the electrode material of the super capacitor.
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