CN113745010A - Ternary composite material and preparation method and application thereof - Google Patents

Ternary composite material and preparation method and application thereof Download PDF

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CN113745010A
CN113745010A CN202110918398.7A CN202110918398A CN113745010A CN 113745010 A CN113745010 A CN 113745010A CN 202110918398 A CN202110918398 A CN 202110918398A CN 113745010 A CN113745010 A CN 113745010A
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composite material
mos
cnb
graphene
ternary composite
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CN113745010B (en
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赵斌元
王礼建
宁月生
赖奕坚
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Shanghai Jiaotong University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • 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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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
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    • 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
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    • H—ELECTRICITY
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    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H—ELECTRICITY
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    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—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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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Abstract

The invention discloses a ternary composite material and a preparation method and application thereof. A ternary composite material comprises a hollow carbon nano material and MoS2The hollow carbon nano material is of a concave bowl-shaped structure, and the bowl is made of a graphene nano sheetMoS is loaded on the outer surface of the bowl wall in the shape structure2Nanosheets and forming a binary composite material, wherein the graphene nanosheets coat the binary composite material to obtain the ternary composite material; the bowl wall of bowl form structure is hierarchical porous structure, hierarchical porous structure includes macropore, micropore and mesopore, the aperture of macropore is for being > 50nm, the aperture of micropore is for being < 2nm, the aperture of mesopore is 2 ~ 50 nm. According to the application, a hydrothermal method is adopted to coat graphene nanosheets on a binary composite material CNB @ MoS2To form a sandwich-like multi-level structure of the ternary composite material CNB @ MoS2the/Graphene is beneficial to the transmission of electrons in the charge and discharge process.

Description

Ternary composite material and preparation method and application thereof
Technical Field
The invention relates to the field of nano material technology and energy science, in particular to a ternary composite material and a preparation method and application thereof.
Background
Two-dimensional layered transition metal oxy/sulfides, e.g. molybdenum disulfide (MoS)2) Tin disulfide (SnS)2) And tungsten disulfide (WS)2) The material has unique electronic structure and physical properties, and is widely applied to the fields of photoelectronic equipment, solar cells, lithium ion secondary battery anode materials, super capacitor electrode materials and the like. Compared with the electrode material which only carries out charge adsorption or oxidation-reduction reaction on the surface or the near surface of the material, the two-dimensional layered material has high active reaction sites, so that the two-dimensional layered material has larger effective utilization rate of the active material. Of these two-dimensional layered materials, MoS2Not only is environment-friendly, but also has a unique graphite-like layered structure, thereby causing extensive attention of researchers. MoS2Formed of an S-Mo-S layered structure stacked by Van der Waals forces, the interlayer spacing between two adjacent layers is 0.615nm, which is greater than that of graphite (0.335 nm). As supercapacitor electrode materials, MoS2The charge storage mechanism includes: (1) MoS2An electric double layer capacitance formed at an interface between the sheet and the electrolyte; (2) MoS2The larger interlayer spacing of (1) accelerates the rapid and reversible insertion and extraction of electrolyte ions between layers, contributing a portion of the intercalation pseudocapacitance, and (3) the pseudocapacitance contributed by the redox reaction generated by the Mo atoms. The valence state of the oxidation state of the Mo atom is +2 to +6The specific capacitance is up to 1200F g-1. However, the effective utilization of this extremely high theoretical specific capacitance is severely limited by two problems: (1) during charging and discharging, electrolyte diffuses into the MoS2The depth of the electrode is limited, and only the electrode material on the surface or near the surface can generate oxidation-reduction reaction, so that the effective utilization rate of the electrode material is low; (2) single layer MoS2The conductivity on the sheet layer is excellent and is similar to that of metal, but the conductivity between the adjacent sheet layers is very poor, the charge transfer is not rapid enough, the embedded capacitance reaction of embedding and releasing electrolyte ions is easy to be controlled by diffusion, and MoS is reduced2The ability to store charge at high current densities hinders the exploitation of its capacitive capabilities.
In response to these two problems, researchers have proposed different strategies to improve electrochemical performance. The most effective solution is to mix the MoS2And is compounded with carbon material (such as porous carbon, carbon fiber, carbon nanotube, graphene, carbon ball, etc.). Among them, hollow carbon nanomaterials having high specific surface area, large volume ratio, low density, stable physicochemical properties and unique hollow structure have been widely used in the fields of supercapacitors, lithium ion batteries, drug and catalyst carriers, gas adsorption and separation, and the like. Mixing MoS2The composite material is compounded with the hollow carbon nano material, not only can enhance the conductivity of the material, but also the hollow carbon capsule with larger specific surface area is MoS2The nanoplatelets provide numerous reaction sites to better disperse MoS2Nanosheets. The composite material of the two can combine the advantages of the two, including MoS2High capacitance performance and high conductivity and double layer capacitance characteristics of the hollow carbon spheres. However, MoS grown on the surface of carbon spheres2The nanoplatelets are poorly conductive, inhibiting electron transfer, especially at high current densities. On the other hand, MoS grown on the surface of the carbon shell2The nanoplatelets are still typically thick (mostly above 20 nm) preventing fast transfer of electrons and ions, which is detrimental to the development of electrochemical performance.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, it is an object of the present invention to provide a ternary composite material, a method for preparing the same, and a use thereof, which solve the problems of the prior art.
To achieve the above objects and other related objects, the present invention is achieved by the following technical solutions.
One of the purposes of the invention is to provide a ternary composite material, which comprises a hollow carbon nano material and MoS2The hollow carbon nanomaterial is of a concave bowl-shaped structure, and MoS is loaded on the outer surface of a bowl wall of the bowl-shaped structure2Nanosheets and forming a binary composite material, wherein the graphene nanosheets coat the binary composite material to obtain the ternary composite material;
the bowl wall of bowl form structure is hierarchical porous structure, hierarchical porous structure includes macropore, micropore and mesopore, the aperture of macropore is for being > 50nm, the aperture of micropore is for being < 2nm, the aperture of mesopore is 2 ~ 50 nm.
Preferably, the MoS2The transverse size of the nano sheet is 20-80 nm.
Preferably, the average particle size of the hollow carbon nanomaterial is 100 to 200 nm.
Preferably, the transverse dimension of the graphene nano sheet is 0.5-10 μm.
Preferably, the specific surface area of the composite material is 400-800 m2 g-1。
Preferably, the nitrogen content of the composite material is 2-12 at%.
Preferably, the oxygen content of the composite material is 3-12 at%.
Preferably, the MoS in the composite material is based on the total mass of the composite material2The content of (A) is 10 wt% -60 wt%.
The second purpose of the invention is to provide a preparation method of the ternary composite material, which comprises the following steps:
carrying out first hydrothermal reaction on the hollow carbon nano material and a sulfur source to obtain the binary composite material;
and carrying out a second hydrothermal reaction on the binary composite material, the graphene and the hydrazine hydrate, and calcining to obtain the ternary composite material.
Preferably, the sulphur source is selected from one or both of ammonium thiomolybdate and thiourea.
Preferably, the temperature of the first hydrothermal reaction is 100-200 ℃.
Preferably, the time of the first hydrothermal reaction is 8-24 h.
Preferably, the mass ratio of the hollow carbon nanomaterial to the sulfur source is 30: (0.5 to 8).
Preferably, the medium of the first hydrothermal reaction is ethanol. Specifically, the mass ratio of the sulfur source to the ethanol is (0.1-4) g:20 ml.
Preferably, the proportion of the binary composite material, graphene and hydrazine hydrate is 45 mg: (5-100) mg: (2-5) ml.
Preferably, the temperature of the second hydrothermal reaction is 100-200 ℃.
Preferably, the time of the second hydrothermal reaction is 8-24 h.
Preferably, the medium of the second hydrothermal reaction is water.
Preferably, the temperature of the calcination is 300 ℃ to 500 ℃.
Preferably, the calcination is carried out in a protective atmosphere. Specifically, the protective atmosphere is an inert gas or nitrogen.
Preferably, the calcination time is 1h to 3 h.
Preferably, the preparation method of the hollow carbon nanomaterial comprises the following steps:
SiO2polymerizing the nanospheres, resorcinol, ethylenediamine and formaldehyde, and then dropwise adding a pore-foaming agent for hydrolysis reaction to obtain a precipitate;
carbonizing and calcining the precipitate;
and etching the calcined product by hydrofluoric acid to obtain the hollow carbon nano material.
More preferably, the SiO2The particle size of the nanospheres is 200-300 nm.
More preferably, said SiO2The particle size of the nanosphere can be 200 nm-260 nm, and can also be 240 nm-300 nm.
More preferably, the SiO2Nanospheres include pretreatment. Specifically, the pretreatment is to treat SiO2The nanospheres are dispersed in the medium. Specifically, the medium is a mixed solvent formed of water and ethanol. More specifically, the concentration of ethanol in the mixed solvent is 10-90 v/v%. Preferably, the SiO is2The mass-volume ratio of the nanospheres to the medium is (0.3-0.6) g:100 ml.
More preferably, the temperature of the polymerization reaction is from 25 ℃ to 45 ℃.
More preferably, the temperature of the polymerization reaction may be 25 to 28 ℃, or 28 to 32 ℃, or 32 to 35 ℃, or 35 to 38 ℃, or 38 to 45 ℃.
More preferably, the SiO2The mass ratio of the nanospheres to the resorcinol is (0.1-0.2): (0.3-0.6).
More preferably, the ratio of the resorcinol, the ethylenediamine and the formaldehyde is (0.1-0.2) g, 0.32ml and (0.15-0.3) ml.
More preferably, the porogen is selected from one or both of tetraethyl orthosilicate and cetyltrimethylammonium bromide.
Further preferably, the porogen comprises a pretreatment. Specifically, the pretreatment is to disperse a pore-foaming agent in a medium. The medium is ethanol. More specifically, the volume ratio of the pore-foaming agent to the medium is 1 (34-133).
More preferably, the porogen is reacted with SiO2The volume mass ratio of the nanospheres is (0.1-0.6) ml and (0.3-0.6) g.
More preferably, the concentration of the hydrofluoric acid is 5 wt% to 15 wt%.
More preferably, the temperature of the hydrolysis reaction is 25 ℃ to 45 ℃.
More preferably, the temperature of the carbonization is 300 ℃ to 400 ℃.
More preferably, the carbonization time is 1-3 h.
More preferably, the calcining temperature is 600-900 ℃.
More preferably, the calcining time is 1-3 h.
More preferably, the etching time is 8-48 h.
More preferably, the carbonization or calcination is carried out in a protective atmosphere.
The invention also aims to provide the application of the ternary composite material as a drug carrier, an electrode material or an adsorption material.
The fourth object of the present invention is to provide an electrode having a current collector coated with the ternary composite material.
It is a fifth object of the present invention to provide a capacitor comprising the above-mentioned electrode.
Two-dimensional MoS in ternary composites in the present application2The nano-sheets are uniformly dispersed on the outer surface of the hollow carbon nano-material CNB. Two-dimensional MoS2The size of the nano sheet can be controllably adjusted between 20nm and 80nm according to the concentration of a precursor sulfur source. With the introduction of the graphene nanosheets, MoS is loaded2The hollow carbon nano material is wrapped to form a sandwich-shaped structure.
According to the application, a hydrothermal method is adopted to coat graphene nanosheets on a binary composite material CNB @ MoS2To form a sandwich-like multi-level structure of the ternary composite material CNB @ MoS2(ii)/Graphene. The hollow carbon nanomaterial CNB has a bowl-shaped structure, and the high specific surface area and the hierarchical porous structure of the CNB can be MoS2The nanosheets uniformly grow on the surfaces of the nanosheets to provide multiple active sites, the unique bowl-shaped structure is beneficial to improving the contact area between adjacent particles, meanwhile, the transmission distance of electrolyte ions is shortened, and the rapid charge and discharge performance of the material is improved. As a two-dimensional carbon nanostructure, graphene has a high specific surface area, an ultrahigh length-diameter ratio, and excellent conductivity; the graphene serves as a 'conductive bridge' in the ternary composite material, and is beneficial to the transmission of electrons in the charge and discharge process. Binary composite CNB @ MoS2Can be used as a 'separant', thereby relieving the agglomeration effect of the graphene nano-sheets and providing partial double electric layersCapacitance (EDLC). When used as an electrode material of a supercapacitor, the 0D +2D +2D ternary composite material CNB @ MoS2the/Graphene can obtain the ratios 0D CNB and 0D +2D CNB @ MoS2Better electrochemical performance. In addition, the graphene nanosheet can improve the conductivity of the ternary composite material, can also serve as a protective layer to improve structural change in the long-term charge and discharge process, and improves the cycling stability of the electrode material. The ternary composite material CNB @ MoS of the present application2the/Graphene provides a new approach for potential electrochemical energy storage and conversion.
Compared with the prior art, the invention has the following beneficial effects:
1) the preparation process is simple, and the CNB @ MoS can be coated with the graphene by a simple hydrothermal method and a simple heat treatment method2And forming a 0D +2D +2D multidimensional architecture on the surface of the material.
2) The ternary composite material CNB @ MoS prepared by the invention2the/Graphene has a high specific surface area, a hierarchical porosity with micropores, mesopores and macropores and a high nitrogen and oxygen loading.
3) The invention has the advantages of wide raw material source, low synthesis cost, simple equipment and mild reaction condition, and is suitable for large-scale industrial production.
4) The ternary composite material CNB @ MoS prepared by the invention2the/Graphene combines the unique advantages of the hollow carbon nano material, such as good conductivity, higher specific surface area and pore volume, multi-level pore distribution and high nitrogen content, and MoS2The unique structural advantages of the material. The graphene can be used as a conductive bridge and wrapped in a binary composite material CNB @ MoS2Outer, forming CNB @ MoS2The hierarchical multidimensional structure of/Graphene is beneficial to the transmission of electrons in the charging and discharging processes. Binary composite material CNB @ MoS2Can be used as a "release agent" to mitigate the agglomeration effect of graphene nanoplatelets and provide partial Electric Double Layer Capacitance (EDLC). Therefore, the supercapacitor electrode and the supercapacitor prepared from the ternary composite material have excellent specific capacitance performance, and also have good rate performance and cycling stability.
Drawings
Fig. 1 shows an SEM image of a hollow carbon nanomaterial CNB of example 1 in the present application.
Fig. 4 shows a TEM image of the hollow carbon nanomaterial CNB of example 1 in the present application.
FIG. 2 shows the binary composite CNB @ MoS of example 1 of the present application2SEM image of (d).
FIG. 5 shows the binary composite CNB @ MoS of example 1 of the present application2A TEM image of (a).
FIG. 3 shows the ternary composite CNB @ MoS of example 1 of the present application2SEM image of/Graphene.
FIG. 6 shows the ternary composite CNB @ MoS of example 1 of the present application2TEM image of/Graphene.
FIG. 7 shows the ternary composite CNB @ MoS of example 2 of the present application2SEM image of/Graphene.
FIG. 8 shows the ternary composite CNB @ MoS of example 3 of the present application2SEM image of/Graphene.
FIG. 9 shows the ternary composite CNB @ MoS of example 1 of the present application2XRD pattern of/Graphene.
FIG. 10 shows the ternary composite CNB @ MoS of example 1 of the present application2TGA profile of/Graphene.
Fig. 11 is a graph showing constant current charge and discharge curves of the electrodes obtained in examples 7, 8 and 9 of the present application.
Fig. 12 shows the cycling stability profiles of the electrodes obtained for examples 7, 8 and 9 of the present application.
FIG. 13 shows the ternary composite CNB @ MoS of example 1 in the present application2XPS plot of/Graphene.
Detailed Description
The following description of the embodiments of the present invention is provided for illustrative purposes, and other advantages and effects of the present invention will become apparent to those skilled in the art from the present disclosure.
Before the present embodiments are further described, it is to be understood that the scope of the invention is not limited to the particular embodiments described below; it is also to be understood that the terminology used in the examples is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the present invention. Test methods in which specific conditions are not specified in the following examples are generally carried out under conventional conditions or under conditions recommended by the respective manufacturers.
When numerical ranges are given in the examples, it is understood that both endpoints of each of the numerical ranges and any value therebetween can be selected unless the invention otherwise indicated. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In addition to the specific methods, devices, and materials used in the examples, any methods, devices, and materials similar or equivalent to those described in the examples may be used in the practice of the invention in addition to the specific methods, devices, and materials used in the examples, in keeping with the knowledge of one skilled in the art and with the description of the invention.
In the examples of the present application, SiO2The particle size of the nanospheres is 250 nm.
Example 1
In this embodiment, the preparation method of the ternary composite material includes the following steps:
1)0.5g of SiO2Dispersing the nanospheres in 100mL of 10 v/v% ethanol aqueous solution, dropwise adding 0.15g of resorcinol, 0.32mL of ethylenediamine and 0.4mL of formaldehyde in sequence, heating and stirring at 25 ℃ for polymerization reaction, then dropwise adding 0.4mL of tetraethyl orthosilicate, hydrolyzing at 35 ℃ for 24h, separating precipitates and drying;
carbonizing the precipitate at 300 ℃ for 1h under an inert atmosphere, and then heating to 900 ℃ at a heating rate of 5 ℃/min and calcining for 2 h;
and soaking the calcined product in a hydrofluoric acid aqueous solution with the concentration of 10 wt% for etching for 12 hours to obtain a hollow carbon nano material marked as CNB.
2) Dissolving 1g ammonium thiomolybdate in 20ml deionized water, ultrasonic dispersing for 30min, mixing with 30mg CNB, and continuing ultrasonic treatment1 h; then transferring the mixture to a hydrothermal reaction kettle, carrying out hydrothermal reaction for 12h at 150 ℃, centrifugally cleaning the mixture for a plurality of times by using deionized water and ethanol, and drying the mixture at 80 ℃ to obtain a binary composite material marked as CNB @ MoS2。
3) 45mg of the above binary composite and 45mg of graphene were added to 15ml of deionized water. After ultrasonic dispersion at room temperature for 2 hours, 2ml of hydrazine hydrate was added, and then the mixture was transferred to a hydrothermal reaction kettle lined with teflon and subjected to hydrothermal reaction at 180 ℃ for 12 hours. Centrifugally cleaning with deionized water and absolute ethyl alcohol, and vacuum drying at 80 ℃ for 12 h; then calcining the mixture for 2 hours at 300 ℃ under the protection of argon gas to obtain a ternary composite material marked as CNB @ MoS2/Graphene。
Fig. 1 is an SEM image of the hollow carbon nanomaterial CNB in example 1. Fig. 4 is a TEM image of the hollow carbon nanomaterial CNB in example 1. As can be seen from fig. 1 and 4, the hollow carbon nanomaterial CNB has a bowl-shaped structure, a particle size of about 200nm, a bowl wall thickness of 5 to 20nm, the bowl wall of the bowl-shaped structure has a hierarchical porous structure, the hierarchical porous structure includes macropores, micropores, and mesopores, a pore diameter of the macropores is greater than 50nm, a pore diameter of the micropores is less than 2nm, and a pore diameter of the mesopores is 2 to 50 nm.
FIG. 2 shows the binary composite CNB @ MoS of example 12SEM image of (d). FIG. 5 shows the binary composite CNB @ MoS of example 12A TEM image of (a). As can be seen from FIGS. 2 and 5, CNB @ MoS2Is in a bowl-shaped structure, the grain diameter is about 200nm, the thickness of the bowl wall is 5-20 nm, and MoS2The nano-sheet grows on the outer surface of the bowl wall in the bowl-shaped structure of the hollow carbon nano-material, MoS2The nanoplatelet has a transverse dimension of 20 nm.
FIG. 3 is the ternary composite CNB @ MoS of example 12SEM image of/Graphene. FIG. 6 shows the ternary composite CNB @ MoS of example 12TEM image of/Graphene. As can be seen from FIGS. 3 and 6, the ternary composite CNB @ MoS2The Graphene is of a bowl-shaped structure, the particle size is about 200nm, and the transverse size of the Graphene nanosheet is 1 micrometer. MoS2The nano-sheet grows on the outer surface of the bowl wall in the bowl-shaped structure of the hollow carbon nano-material and forms CNB @ MoS2. Graphene nanosheets uniformly wrapped in binary composite material CNB @ MoS2Forming a sandwich-like multilevel structure.
FIG. 9 shows the ternary composite CNB @ MoS of example 12XRD pattern of/Graphene. As can be seen from FIG. 9, MoS2The crystallization peaks appeared at 13.1 °, 32.9 °, 39.1 ° and 58.6 °, which can be well indexed to 2H-MoS2The (002), (100), (103) and (110) hkl crystal plane diffraction (JCPDS No. 37-1492) of (A) shows that the ternary composite material of the embodiment has better crystallinity and hexagonal MoS with high purity2。
FIG. 10 shows the ternary composite CNB @ MoS of example 12TGA profile of/Graphene. From FIG. 10, TGA can deduce binary composite CNB @ MoS from the residual amount2And ternary composite CNB @ MoS2MoS in Graphene2The contents are 50.3% and 26.4%, respectively.
FIG. 13 is the ternary composite CNB @ MoS of example 12XPS plot of/Graphene. As can be seen from fig. 13, the content of N in the ternary composite material was 8 at%, and the content of O was 9 at%.
Example 2
In this embodiment, the preparation method of the ternary composite material includes the following steps:
1)0.5g of SiO2Dispersing the nanospheres in 100mL of 10 v/v% ethanol aqueous solution, sequentially dropwise adding 0.15g of resorcinol, 0.32mL of ethylenediamine and 0.4mL of formaldehyde into the solution at 35 ℃, heating and stirring for polymerization reaction, then dropwise adding 0.4mL of tetraethyl orthosilicate, hydrolyzing the mixture at 35 ℃ for 24 hours, separating precipitates and drying;
carbonizing the precipitate at 300 ℃ for 1h under an inert atmosphere, and then heating to 900 ℃ at a heating rate of 5 ℃/min and calcining for 2 h;
and soaking the calcined product in a hydrofluoric acid aqueous solution with the concentration of 10 wt% for etching for 12 hours to obtain the hollow carbon nano material marked as CNB.
2) Dissolving 2g of ammonium thiomolybdate in 20ml of deionized water, carrying out ultrasonic dispersion for 30min, mixing with 30mg of CNB, and continuing ultrasonic treatment for 1 h; then transferring the mixture into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 8 hours at 180 ℃, and centrifugally cleaning the mixture by using deionized water and ethanolThen drying at 80 ℃ to obtain a binary composite material marked as CNB @ MoS2。
3) 45mg of the above binary composite and 60mg of graphene were added to 15ml of deionized water. After ultrasonic dispersion at room temperature for 2 hours, 2.5ml of hydrazine hydrate was added, and then the mixture was transferred to a hydrothermal reaction kettle lined with teflon and subjected to hydrothermal reaction at 200 ℃ for 12 hours. Centrifugally cleaning with deionized water and absolute ethyl alcohol, and vacuum drying at 80 ℃ for 12 h; then calcining the mixture for 1 hour at 500 ℃ under the protection of argon gas to obtain a ternary composite material marked as CNB @ MoS2/Graphene。
FIG. 7 shows the ternary composite CNB @ MoS of example 22SEM image of/Graphene. As can be seen from FIG. 7, the ternary composite material has a bowl-shaped structure and a particle size of about 200 nm; MoS260nm in lateral dimension; specific surface area of the ternary composite material is 600m2 g-1(ii) a The nitrogen content and the oxygen content were 8% and 12%, respectively. MoS2The nano-sheet grows on the outer surface of the bowl wall in the bowl-shaped structure of the hollow carbon nano-material and forms a binary composite material CNB @ MoS2The graphene nanosheets are uniformly wrapped in the binary composite material CNB @ MoS2The surface of the composite material is formed into a sandwich-shaped multi-level structure of the ternary composite material CNB @ MoS2/Graphene。
Example 3
In this embodiment, the preparation method of the ternary composite material includes the following steps:
1)0.5g of SiO2Dispersing the nanospheres in 100mL of 10 v/v% ethanol aqueous solution, sequentially dropwise adding 0.15g of resorcinol, 0.32mL of ethylenediamine and 0.2mL of formaldehyde into the solution at 35 ℃, heating and stirring for polymerization reaction, then dropwise adding 0.4mL of tetraethyl orthosilicate, hydrolyzing the mixture at 35 ℃ for 24 hours, separating precipitates and drying;
carbonizing the precipitate at 300 ℃ for 1h under an inert atmosphere, and then heating to 900 ℃ at a heating rate of 5 ℃/min and calcining for 2 h;
and soaking the calcined product in a hydrofluoric acid aqueous solution with the concentration of 10 wt% for etching for 12 hours to obtain a hollow carbon nano material marked as CNB.
2) 4g of ammonium thiomolybdate are dissolvedUltrasonically dispersing in 20ml of deionized water for 30min, mixing with 30mg of CNB, and continuously ultrasonically treating for 1 h; then transferring the mixture to a hydrothermal reaction kettle, carrying out hydrothermal reaction for 8h at 200 ℃, centrifugally cleaning the mixture for a plurality of times by using deionized water and ethanol, and drying the cleaned mixture at 80 ℃ to obtain a binary composite material marked as CNB @ MoS2。
3) 45mg of the above binary composite and 100mg of graphene were added to 15ml of deionized water. After ultrasonic dispersion at room temperature for 2 hours, 2.5ml of hydrazine hydrate was added, and then the mixture was transferred to a hydrothermal reaction kettle lined with teflon and subjected to hydrothermal reaction at 150 ℃ for 24 hours. Centrifugally cleaning with deionized water and absolute ethyl alcohol, and vacuum drying at 80 ℃ for 12 h; then calcining the mixture for 3 hours at 300 ℃ under the protection of argon gas to obtain a ternary composite material marked as CNB @ MoS2/Graphene。
FIG. 8 is the ternary composite CNB @ MoS of example 32SEM image of/Graphene. As can be seen from FIG. 8, the ternary composite material has a bowl-shaped structure, a particle size of about 200nm and MoS2The nano-sheet grows on the outer surface of the bowl wall in the bowl-shaped structure of the hollow carbon nano-material CNB and forms a binary composite material CNB @ MoS2The graphene nanosheets are uniformly wrapped in the binary composite material CNB @ MoS2The surface of the composite material is formed into a sandwich-shaped multi-level structure of the ternary composite material CNB @ MoS2/Graphene。
Example 4
In this embodiment, the preparation method of the ternary composite material includes the following steps:
1)0.5g of SiO2Dispersing the nanospheres in 100mL of 10 v/v% ethanol aqueous solution, sequentially dropwise adding 0.2g of resorcinol, 0.32mL of ethylenediamine and 0.3mL of formaldehyde into the solution to perform polymerization reaction at 45 ℃ under stirring, then dropwise adding 0.6mL of tetraethyl orthosilicate, hydrolyzing the tetraethyl orthosilicate at 45 ℃ for 24 hours, separating precipitates and drying;
carbonizing the precipitate at 400 ℃ for 3h under an inert atmosphere, and then heating to 600 ℃ at a heating rate of 5 ℃/min and calcining for 3 h;
and soaking the calcined product in a hydrofluoric acid aqueous solution with the concentration of 5 wt% for etching for 48 hours to obtain a hollow carbon nano material marked as CNB.
2) Dissolving 0.5g of ammonium thiomolybdate in 20ml of deionized water, carrying out ultrasonic dispersion for 30min, mixing with 30mg of CNB, and continuing ultrasonic treatment for 1 h; then transferring the mixture to a hydrothermal reaction kettle, carrying out hydrothermal reaction for 24h at 100 ℃, centrifugally cleaning the mixture for a plurality of times by using deionized water and ethanol, and drying the cleaned mixture at 80 ℃ to obtain a binary composite material marked as CNB @ MoS2。
3) 45mg of the above binary composite and 5mg of graphene were added to 15ml of deionized water. After ultrasonic dispersion at room temperature for 2h, 2.5ml of hydrazine hydrate was added, and then the mixture was transferred to a hydrothermal reaction kettle lined with teflon and subjected to hydrothermal reaction at 100 ℃ for 24 h. Centrifugally cleaning with deionized water and absolute ethyl alcohol, and vacuum drying at 80 ℃ for 12 h; then calcining the mixture for 3 hours at 500 ℃ under the protection of argon gas to obtain a ternary composite material marked as CNB @ MoS2/Graphene。
The ternary composite material of the embodiment has a bowl-shaped structure and the particle size of about 200 nm. MoS2The nano-sheet grows on the outer surface of the bowl wall in the bowl-shaped structure of the hollow carbon nano-material CNB and forms a binary composite material CNB @ MoS2The graphene nanosheets are uniformly wrapped in CNB @ MoS2The surface of the composite material forms a sandwich-shaped ternary composite material CNB @ MoS with a multilevel structure2/Graphene。
Example 5
In this embodiment, the preparation method of the ternary composite material includes the following steps:
1)0.5g of SiO2Adding the nanospheres into 100mL of 10 v/v% ethanol aqueous solution, dropwise adding 0.1g of resorcinol, 0.32mL of ethylenediamine and 0.15mL of formaldehyde in sequence, stirring at 45 ℃ for polymerization reaction, then dropwise adding 0.1mL of tetraethyl orthosilicate, hydrolyzing at 45 ℃ for 24h, separating precipitates and drying;
carbonizing the precipitate at 400 ℃ for 3h under an inert atmosphere, and then heating to 900 ℃ at a heating rate of 5 ℃/min and calcining for 1 h;
and soaking the calcined product in a hydrofluoric acid aqueous solution with the concentration of 15 wt% for etching for 8 hours to obtain a hollow carbon nano material, wherein the mark is CNB.
2) 0.5g of thioDissolving ammonium molybdate in 20ml deionized water, performing ultrasonic dispersion for 30min, mixing with 30mg of CNB, and continuing ultrasonic treatment for 1 h; then transferring the mixture to a hydrothermal reaction kettle, carrying out hydrothermal reaction for 24h at 100 ℃, centrifugally cleaning the mixture for a plurality of times by using deionized water and ethanol, and drying the mixture at 80 ℃ to obtain a binary composite material marked as CNB @ MoS2。
3) 45mg of the above binary composite and 30mg of graphene were added to 15ml of deionized water. After ultrasonic dispersion at room temperature for 2h, 2.5ml of hydrazine hydrate was added, and then the mixture was transferred to a hydrothermal reaction kettle lined with teflon and subjected to hydrothermal reaction at 100 ℃ for 24 h. Centrifugally cleaning with deionized water and absolute ethyl alcohol, and vacuum drying at 80 ℃ for 12 h; then calcining the mixture for 3 hours at 300 ℃ under the protection of argon gas to obtain a ternary composite material marked as CNB @ MoS2/Graphene。
The ternary composite material of the embodiment has a bowl-shaped structure and the particle size of about 200 nm. MoS2The nano-sheet grows on the outer surface of the bowl wall in the bowl-shaped structure of the hollow carbon nano-material CNB and forms a binary composite material CNB @ MoS2The graphene nanosheets are uniformly wrapped in CNB @ MoS2The surface of the composite material forms a sandwich-shaped ternary composite material CNB @ MoS with a multilevel structure2/Graphene。
Example 6
In this embodiment, the preparation method of the ternary composite material includes the following steps:
1)0.5g of SiO2Dispersing the nanospheres in 100mL of 10 v/v% ethanol aqueous solution, sequentially dropwise adding 0.2g of resorcinol, 0.32mL of ethylenediamine and 0.3mL of formaldehyde into the solution, stirring the solution at 45 ℃ for polymerization reaction, then dropwise adding 0.6mL of tetraethyl orthosilicate, hydrolyzing the mixture at 45 ℃ for 24 hours, separating precipitates and drying the precipitates;
carbonizing the precipitate at 300 ℃ for 1h under an inert atmosphere, and then heating to 900 ℃ at a heating rate of 5 ℃/min and calcining for 3 h;
and soaking the calcined product in a hydrofluoric acid aqueous solution with the concentration of 10 wt% for etching for 24 hours to obtain a hollow carbon nano material marked as CNB.
2) 4g of ammonium thiomolybdate are dissolved in 20ml of deionized water and the solution is homogenizedAfter sound dispersion for 30min, mixing with 30mg of CNB and continuing ultrasonic treatment for 1 h; then transferring the mixture to a hydrothermal reaction kettle, carrying out hydrothermal reaction for 12h at 200 ℃, centrifugally cleaning the mixture for a plurality of times by using deionized water and ethanol, and drying the mixture at 80 ℃ to obtain a binary composite material marked as CNB @ MoS2。
3) 45mg of the above binary composite and 100mg of graphene were added to 15ml of deionized water. After ultrasonic dispersion at room temperature for 2h, 2.5ml of hydrazine hydrate was added, and then the mixture was transferred to a hydrothermal reaction kettle lined with teflon and subjected to hydrothermal reaction at 100 ℃ for 24 h. Centrifugally cleaning with deionized water and absolute ethyl alcohol, and vacuum drying at 80 ℃ for 12 h; then calcining the mixture for 3 hours at 500 ℃ under the protection of argon gas to obtain a ternary composite material marked as CNB @ MoS2/Graphene。
The ternary composite material of the embodiment has a bowl-shaped structure and the particle size of about 200 nm. MoS2The nano-sheet grows on the outer surface of the bowl wall in the bowl-shaped structure of the hollow carbon nano-material CNB and forms a binary composite material CNB @ MoS2The graphene nanosheets are uniformly wrapped in CNB @ MoS2The surface of the composite material forms a sandwich-shaped ternary composite material CNB @ MoS with a multilevel structure2/Graphene。
Example 7
In this embodiment, an electrode and a capacitor are provided, including the following:
the capacitor comprises an electrode and other necessary components, wherein the electrode is prepared according to the following method: the ternary composite material of example 1, acetylene black and polytetrafluoroethylene were mixed in a mass ratio of 8: 1: 1 to prepare a homogeneous slurry, and then coating the slurry on a nickel foam current collector of 1 × 1cm, and drying at 100 ℃ for 12 hours to prepare a working electrode. The loading of the ternary composite material is about 2.0mg cm-2。
The Hg/HgO electrode and Pt were used as reference and counter electrodes, respectively. Electrochemical performance was tested on a CHI 660D electrochemical workstation using a three electrode configuration with 6M KOH as the electrolyte.
Example 8
Except that the ternary composite obtained in example 2 was used to prepare an electrode, the procedure was as in example 7.
Example 9
Except that the ternary composite obtained in example 3 was used to prepare an electrode, the procedure was as in example 7.
Fig. 11 is a constant current charge and discharge graph of the electrodes obtained in examples 7, 8 and 9. As can be seen from fig. 11, the constant current charging and discharging GCD curve of the hollow carbon nanomaterial CNB is shown as an isosceles triangle, which indicates that the behavior is mainly an electric double layer capacitance, and a small portion of pseudocapacitance is generated due to the doping of N and O elements in the hollow carbon nanomaterial CNB. Apparently, MoS2The introduction of (2) generates pseudo capacitance, so that the binary composite material CNB @ MoS2And ternary composite CNB @ MoS2The GCD curve for/Graphene is slightly distorted. Calculating according to the GCD curve to obtain the hollow carbon nano material CNB and the binary composite material CNB @ MoS2And ternary composite CNB @ MoS2Specific capacitance of/Graphene. At 0.2A g-1The specific capacitance of the hollow carbon nano material CNB is 249F g under the current density-1(ii) a Binary composite material CNB @ MoS2To 347F g-1(ii) a Ternary composite material CNB @ MoS2The specific capacitance of/Graphene increased to 588F g-1。
FIG. 12 is a graph showing the cycle stability of the electrodes obtained in examples 7, 8 and 9. As can be seen from fig. 12, after 5000 charge-discharge cycles, the hollow carbon nanomaterial CNB maintained a high capacity retention rate of 91.9%, which is a characteristic of the electric double layer electrode material; binary composite material CNB @ MoS2The retention rate of the capacitance is lower and is only 73.4%, because the volume and the structure of the pseudocapacitance electrode material decay in the oxidation-reduction reaction process, a large amount of attenuation of the capacitance after long-term charge-discharge circulation is inevitably caused; ternary composite material CNB @ MoS2The capacity retention rate of/Graphene is improved to 83.9%.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.

Claims (10)

1. The ternary composite material is characterized by comprising a hollow carbon nano material and MoS2The hollow carbon nanomaterial is of a concave bowl-shaped structure, and MoS is loaded on the outer surface of a bowl wall of the bowl-shaped structure2Nanosheets and forming a binary composite material, wherein the graphene nanosheets coat the binary composite material to obtain the ternary composite material;
the bowl wall of bowl form structure is hierarchical porous structure, hierarchical porous structure includes macropore, micropore and mesopore, the aperture of macropore is for being > 50nm, the aperture of micropore is for being < 2nm, the aperture of mesopore is 2 ~ 50 nm.
2. The ternary composite material of claim 1, wherein said MoS is2The transverse size of the nanosheet is 20-80 nm;
and/or the average particle size of the hollow carbon nano material is 100-200 nm;
and/or the transverse dimension of the graphene nanosheet is 0.5-10 μm;
and/or the specific surface area of the composite material is 400-800 m2 g-1；
And/or the nitrogen content of the composite material is 2-12 at%;
and/or the oxygen content of the composite material is 3-12 at%;
and/or the MoS in the composite material is calculated by taking the total mass of the composite material as a reference2The content of (A) is 10 wt% -60 wt%.
3. A method for preparing the ternary composite material according to any one of claims 1 to 2, comprising the following steps:
carrying out first hydrothermal reaction on the hollow carbon nano material and a sulfur source to obtain the binary composite material;
and carrying out a second hydrothermal reaction on the binary composite material, the graphene and the hydrazine hydrate, and calcining to obtain the ternary composite material.
4. The method according to claim 3, wherein the sulfur source is one or both of ammonium thiomolybdate and thiourea;
and/or the temperature of the first hydrothermal reaction is 100-200 ℃;
and/or the mass ratio of the hollow carbon nano material to the sulfur source is 30: (0.5 to 8).
5. The preparation method according to claim 3, wherein the ratio of the binary composite material, graphene and hydrazine hydrate is 45 mg: (5-100) mg: (2-5) ml;
and/or the temperature of the second hydrothermal reaction is 100-200 ℃;
and/or the calcining temperature is 300-500 ℃;
and/or, the calcining is carried out in a protective atmosphere.
6. The method of claim 3, wherein the hollow carbon nanomaterial is prepared by:
SiO2polymerizing the nanospheres, resorcinol, ethylenediamine and formaldehyde, and then dropwise adding a pore-foaming agent for hydrolysis reaction to obtain a precipitate;
carbonizing and calcining the precipitate;
and etching the calcined product by hydrofluoric acid to obtain the hollow carbon nano material.
7. The method of claim 6, wherein the polymerization reaction temperature is from 25 ℃ to 45 ℃;
and/or, the SiO2The mass ratio of the nanospheres to the resorcinol is (0.1-0.2): (0.3 to 0.6);
and/or the mixture ratio of the resorcinol, the ethylenediamine and the formaldehyde is (0.1-0.2) g, 0.32ml and (0.15-0.3) ml;
and/or the pore-foaming agent is selected from one or two of tetraethyl orthosilicate and hexadecyl trimethylamine bromide;
and/or, the porogenic agent and SiO2The volume mass ratio of the nanospheres is (0.1-0.6) ml and (0.3-0.6) g;
and/or the concentration of the hydrofluoric acid is 5 wt% -15 wt%;
and/or the temperature of the hydrolysis reaction is 25-45 ℃;
and/or the carbonization temperature is 300-400 ℃;
and/or the calcining temperature is 600-900 DEG C
And/or, the carbonization is carried out in a protective atmosphere;
and/or, the calcining is carried out in a protective atmosphere.
8. Use of the ternary composite material according to any one of claims 1 to 2 as a drug carrier, electrode material or adsorbing material.
9. An electrode, characterized in that a current collector of the electrode is coated with the ternary composite material according to any one of claims 1 to 2.
10. A capacitor comprising an electrode according to claim 9.
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