CN112110489B - Micro-spherical CuS-MoS2Method for preparing composite material - Google Patents

Micro-spherical CuS-MoS2Method for preparing composite material Download PDF

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CN112110489B
CN112110489B CN202011017959.8A CN202011017959A CN112110489B CN 112110489 B CN112110489 B CN 112110489B CN 202011017959 A CN202011017959 A CN 202011017959A CN 112110489 B CN112110489 B CN 112110489B
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cuo
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CN112110489A (en
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朱秀红
琚鑫
郭立松
邢宏娜
冯伟
冯娟
宗妍
李兴华
郑新亮
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Northwestern University
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    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G39/00Compounds of molybdenum
    • C01G39/06Sulfides
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    • C01G3/00Compounds of copper
    • C01G3/12Sulfides
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/24Electrodes 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their material
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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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

Micro-spherical CuS-MoS2Of composite materialsPreparation method
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 alparation of CuS@MoS2Heterogeneous 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 (0.3 g) 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 Cu2Surface of O template, and finally, hollow CuS @ MoS is promoted by heat treatment2Generation 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 O microspheres are used as sacrificial templates and are simple and greenSynthesizing porous CuS-MoS by 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-MoS2Linear plot between logarithm of peak current and logarithm of scan 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 stirring was carried outAfter stirring for 15min, 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; ultrasonically water-soluble CuO-Cu2O 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 presents petal microspheric shapeThe diameter is 5-8um, the size is uniform, small particles scattered after vulcanization appear on the surfaces of petals, and the petal-shaped microspherical material can effectively improve the specific surface area of the material and increase the transmission channel of electrons, so that the electrode material with a porous microspherical structure and the morphology plays a positive role in 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) 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 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 (3)

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 copper nitrate trihydrate aqueous solution and ethanolamine aqueous solution, fully stirring, keeping at 180 ℃ for 12h, and performing pyrolysisReacting, 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, keeping the mixed solution at 200 ℃ for 24 hours 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 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.
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