CN110844899A - Carbon nano tube composite cobalt sulfide nano material and preparation method and application thereof - Google Patents

Carbon nano tube composite cobalt sulfide nano material and preparation method and application thereof Download PDF

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CN110844899A
CN110844899A CN201911029079.XA CN201911029079A CN110844899A CN 110844899 A CN110844899 A CN 110844899A CN 201911029079 A CN201911029079 A CN 201911029079A CN 110844899 A CN110844899 A CN 110844899A
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cobalt
nano tube
carbon nano
tube composite
carbon
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杨伟
薛召
孙瑞瑞
李林林
孙辉文
雷康州
陈胜洲
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Guangzhou University
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Guangzhou University
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    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/15Nano-sized carbon materials
    • C01B32/158Carbon nanotubes
    • C01B32/16Preparation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00Compounds of cobalt
    • C01G51/30Sulfides
    • HELECTRICITY
    • H01BASIC ELECTRIC 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 [EDLCs]; Processes specially adapted for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their materials
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581Chalcogenides or intercalation compounds thereof
    • H01M4/5815Sulfides
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • H01M4/625Carbon or graphite
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00Structure or properties of carbon nanotubes
    • C01B2202/20Nanotubes characterized by their properties
    • C01B2202/22Electronic properties
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00Crystal-structural characteristics
    • C01P2002/70Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
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    • C01P2004/03Particle morphology depicted by an image obtained by SEM
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/40Electric properties
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13Energy storage using capacitors

Abstract

The invention provides a carbon nanotube composite cobalt sulfide nano material and a preparation method and application thereof, wherein the preparation method comprises the steps of firstly, uniformly mixing a cobalt salt solution, a zinc salt solution and a 2-methylimidazole solution, reacting to obtain a precipitate, washing and drying to obtain a zeolite imidazole ester framework structure material; then roasting the zeolite imidazole ester framework structure material in an inert atmosphere to obtain a carbon nano tube composite metal cobalt nano material; and finally, uniformly mixing the carbon nano tube composite metal cobalt nano material with sulfur, and carrying out a vulcanization reaction in an inert atmosphere to obtain the carbon nano tube composite cobalt sulfide nano material. The material is useful as an active material for electrodes. According to the invention, the zeolite imidazole ester framework structure material is subjected to high-temperature roasting to form the carbon nano tube in situ, so that the expansion of the material is inhibited, the expansion amplitude is reduced, the structural stability is improved, and the super capacitor and the lithium-sulfur battery still have high capacity retention rate after hundreds of cycles.

Description

Carbon nano tube composite cobalt sulfide nano material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of electrode materials, and particularly relates to a carbon nano tube composite cobalt sulfide nano material, and a preparation method and application thereof.
Background
The super capacitor is a novel energy storage device, has the advantages of long cycle service life, rapid charge and discharge, high power density and the like, and is widely applied to various fields, such as military industry, electronic products, civil use and industrial fields. The main electrode material of the super capacitor is a carbon material, and the advantages of the carbon material, such as high specific surface area and abundant pore structure, are mainly utilized. However, the carbon material has the defect of low wettability, so that electrolyte ions are prevented from completely entering micropores, the specific surface utilization rate of the carbon material is greatly reduced, and the capacity of the super capacitor is severely limited.
The transition metal sulfide electrode material (such as CoS, NiS, ZnS, MoS and the like) has a unique nano structure, good electrochemical activity and low electronegativity and is another electrode material applicable to a super capacitor. However, when the transition metal sulfide is applied to a supercapacitor, the volume expansion of the material is severe in the charging and discharging processes, and meanwhile, the sulfide intermediate is dissolved in the electrolyte, so that the rate capability and the cycle performance of the capacitor are reduced.
The lithium-sulfur battery is a novel battery which takes metal lithium as a negative electrode material and elemental sulfur as a positive electrode active substance, wherein sulfur in a positive electrode is generally loaded into various carriers for fixation, but the carriers expand in volume in the charging and discharging process, so that the capacity is reduced, the cycle life of the battery is poor, and the popularization and the application of the lithium-sulfur battery are hindered.
Therefore, the performance of the super capacitor or the lithium-sulfur battery is limited by the performance of the electrode material, and the cycle performance of the super capacitor or the lithium-sulfur battery is seriously reduced by the volume expansion phenomenon of the electrode material in the charging and discharging processes.
Disclosure of Invention
The invention aims to solve the problem of cycle performance reduction caused by volume expansion of an electrode material in the prior art, and provides a carbon nano tube composite cobalt sulfide nano material and a preparation method and application thereof.
The invention provides a preparation method of a carbon nano tube composite cobalt sulfide nano material, which comprises the following steps:
(1) uniformly mixing a cobalt salt solution, a zinc salt solution and a 2-methylimidazole solution, reacting to obtain a precipitate, washing and drying to obtain a zeolite imidazole ester framework structure material;
(2) roasting the zeolite imidazole ester framework structure material in the step (1) in an inert atmosphere to obtain a carbon nano tube composite metal cobalt nano material;
(3) and (3) uniformly mixing the carbon nano tube composite metal cobalt nano material with sulfur, and carrying out a vulcanization reaction in an inert atmosphere to obtain the carbon nano tube composite cobalt sulfide nano material.
Further, in the step (2), the roasting temperature is 700-900 ℃, and the roasting time is 1-3 h.
Further, the temperature of the vulcanization reaction in the step (3) is 600-700 ℃.
Further, in the step (1), the drying temperature is 80-120 ℃, and the drying time is 12-24 hours.
Further, the cobalt salt and the zinc salt are nitrate, chloride or sulfate of cobalt or zinc respectively; preferably, the cobalt salt and the zinc salt are cobalt nitrate and zinc nitrate, respectively.
Further, the concentration of the cobalt salt solution, the zinc salt solution or the 2-methylimidazole solution is 0.2-0.5 mol/L; preferably, the concentration of the cobalt salt solution and the zinc salt solution is 0.2mol/L, and the concentration of the 2-methylimidazole solution is 0.5 mol/L.
The invention also provides the carbon nano tube composite cobalt sulfide nano material prepared by the preparation method.
Meanwhile, the invention also provides an electrode, and the active material of the electrode is the carbon nano tube composite cobalt sulfide nano material.
The invention also provides a super capacitor, which comprises electrolyte, a diaphragm arranged in the electrolyte, and a positive electrode and a negative electrode which are arranged on two sides of the diaphragm, wherein the active material of the positive electrode is a carbon nano tube composite cobalt sulfide nano material.
The invention also provides a lithium-sulfur battery, which comprises lithium ion electrolyte, a diaphragm arranged in the lithium ion electrolyte, and a positive electrode and a negative electrode which are arranged on two sides of the diaphragm, wherein the negative electrode is a metal lithium sheet, and the active material of the positive electrode is a carbon nano tube composite cobalt sulfide nano material.
Compared with the prior art, the method utilizes the characteristic that the carbon content of the dimethyl imidazole organic ligand in the zeolite imidazole ester framework structure material is rich to calcine the zeolite imidazole ester framework structure material at high temperature, generates the carbon nano tube on the surface of the zeolite imidazole ester framework structure material in situ, modifies the surface structure of the material, inhibits the expansion of the material, reduces the expansion amplitude, improves the structural stability, and prevents the reduction of the cycle performance caused by the structural collapse; and the specific surface area of the material can be increased, and the pore size distribution can be improved. Meanwhile, the material with the structure of the di-zeolite imidazole ester skeleton contains rich cobalt ions, and can form cobalt sulfide after vulcanization, thereby improving the electrochemical activity of the material and being capable of being well used as an electrode material of a super capacitor and a lithium-sulfur battery.
Drawings
FIG. 1 is a scanning electron microscope image of a carbon nanotube composite metal cobalt nanomaterial and a carbon nanotube composite cobalt sulfide nanomaterial;
FIG. 2 is an XRD pattern of a carbon nanotube composite metal cobalt nanomaterial;
FIG. 3 is an XRD pattern of a carbon nanotube composite cobalt sulfide nanomaterial;
FIG. 4 is a cyclic voltammogram of the electrode of example 2;
FIG. 5 is a constant current charge and discharge curve at a current density of 1A/g for the positive electrode of the asymmetric supercapacitor of example 2;
FIG. 6 is a constant current charge/discharge curve at a current density of 100mA/g for the positive electrode of the lithium sulfur battery of example 2;
FIG. 7 is a graph of the discharge performance of the positive electrode of the lithium sulfur battery of example 2 at different current densities;
FIG. 8 is a graph of the cycling performance of the positive electrode of the lithium sulfur battery of example 2 at a current density of 1000 mA/g.
Detailed Description
According to the invention, the zeolite imidazole ester framework structure material is subjected to high-temperature roasting to form the carbon nano tube in situ, and is vulcanized, and meanwhile, the structural stability and the electrochemical activity of the material are improved.
Example 1
The embodiment provides a carbon nanotube composite cobalt sulfide nano material, and a preparation method thereof comprises the following steps:
(1) 1.0g of Co (NO)3)2·6H2O and 1.0g Zn (NO)3)2·6H2O is dissolved in 15ml of methanol solution respectively to obtain 0.2mol/L of Co (NO)3)2Solution and Zn (NO)3)2Further, 1.2g of 2-methylimidazole was dissolved in 30ml of a methanol solution sufficiently to obtain a 0.5 mol/L2-methylimidazole solution.
Mixing Co (NO)3)2The solution is slowly dripped into 2-methylimidazole solution, and the mixed solution is slowly dripped into Zn (NO)3)2And stirring the solution for 30min and standing the solution for 24h to form precipitates. And collecting the precipitate, dispersing the precipitate into a methanol solution, centrifuging for many times, washing for at least 3 times by using deionized water, and drying at 80-120 ℃ for 12-24 hours to obtain blue powder, namely the zeolite imidazole ester framework structure material.
(2) And (2) taking 1.0g of the blue powder obtained in the step (1), and roasting at a high temperature of 700 ℃ (or 800 ℃, 900 ℃) for 1-3 h, preferably 2h, in a nitrogen atmosphere to obtain black powder, namely the carbon nano tube composite metal cobalt nano material.
(3) And (3) putting 0.1g of black powder and 1.0g of sulfur powder into a quartz boat, uniformly mixing, and vulcanizing at 600 ℃ for 2h in a nitrogen atmosphere to obtain the carbon nano tube composite cobalt sulfide nano material.
The materials obtained in the above steps are characterized, and the results are shown in fig. 1-3.
Fig. 1 is a scanning electron microscope image of a carbon nanotube composite metal cobalt nanomaterial and a carbon nanotube composite cobalt sulfide nanomaterial at different baking temperatures in the steps, wherein a, c, and e respectively represent carbon nanotube composite cobalt sulfide nanomaterials obtained by baking at 700 ℃, 800 ℃, and 900 ℃, and b, d, and e respectively correspond to the carbon nanotube composite cobalt sulfide nanomaterials obtained by vulcanizing the carbon nanotube composite cobalt sulfide nanomaterials of a, c, and e.
From fig. 1a, c and e, it can be seen that the carbon nanotube composite metal cobalt nanomaterial has carbon nanotubes distributed on the surface, the carbon nanotubes on the surface are less at the baking temperature of 700 ℃, and the carbon nanotubes on the surface are the largest at the baking temperature of 900 ℃. With the rise of the roasting temperature of the zeolite imidazole ester framework structure material, the surface roughness of the carbon nano tube composite metal cobalt nano material is gradually increased, but the dodecahedron structure can still be maintained at different roasting temperatures.
As shown in fig. 1b, d, and e, after the carbon nanotube composite metal cobalt nanomaterial with the baking temperature of 700 ℃ is vulcanized, the dodecahedral structure of the material is not significantly changed, but the amount of the carbon nanotubes on the surface of the material is reduced; the carbon nano tube composite metal cobalt nano material with the roasting temperature of 800 ℃ still keeps a dodecahedron structure after vulcanization, but the surface carbon nano tube is more remained and is rougher than that before vulcanization. The carbon nano tube composite metal cobalt nano material with the roasting temperature of 900 ℃ is obviously reduced after being vulcanized. The carbon nano tube has high conductivity, and the materials show that the abundant carbon nano tubes are distributed, so that the carbon nano tube composite cobalt sulfide nano material with the structure has high conductivity; meanwhile, the carbon nano tube contains rich pore channels, and can provide more reaction active sites and contact area for the carbon nano tube composite cobalt sulfide nano material.
As shown in XRD spectrograms before and after vulcanization in figures 2 and 3, the main peaks of the carbon nano tube composite metal cobalt nano material prepared at different roasting temperatures at 44.4 degrees, 51.7 degrees and 76.1 degrees are consistent with the main peak position of Co (JCPDS No. 15-0806); diffraction peak and CoS of carbon nano tube composite cobalt sulfide nano material obtained after vulcanization2The standard peaks of (JCPDS No.89-1492) corresponded, indicating successful CoS formation after sulfurization2. The peak strength of the composite cobalt sulfide nano material of each carbon nano tube in fig. 3 is different, which shows that the influence of the roasting temperature on the crystallinity of the material is large, and the crystallinity of the material prepared at different roasting temperatures is different.
Example 2
The invention also provides an electrode, which takes the carbon nano tube composite cobalt sulfide nano material prepared in the embodiment 1 as an active material, and simultaneously comprises a conductive agent and a binder, wherein the conductive agent can be acetylene black, the binder can be Polytetrafluoroethylene (PTFE) or polyvinylidene fluoride (PVDF), and the preparation method comprises the following steps:
uniformly mixing the carbon nano tube composite cobalt sulfide nano material, the acetylene black conductive agent and the polytetrafluoroethylene binder (or polyvinylidene fluoride binder) according to the mass ratio of 7:2:1, adding a proper amount of ethanol aqueous solution or N-methylpyrrolidone solvent, and ultrasonically oscillating or mechanically stirring to form uniform paste.
And drying the paste at 100 ℃ by blowing air for 12h, taking out, grinding into sheets, placing on foamed nickel, and tabletting to obtain the electrode. Or directly coating the paste on a clean aluminum foil, then drying in vacuum at 120 ℃ for 12h, and cutting into 12 mm-diameter pieces to obtain the electrode, namely the round positive plate.
The asymmetric supercapacitor can be assembled by taking a 6M KOH aqueous solution as an electrolyte, taking a polypropylene porous membrane as a diaphragm arranged in the electrolyte, taking the electrode as a positive electrode and taking an activated carbon electrode as a negative electrode.
In addition, the prepared round positive plate is used as a positive electrode, a metal lithium plate is used as a negative electrode, a polyethylene film with the thickness of 16 microns is used as a diaphragm, 1M bis (trifluoromethyl) sulfonimide lithium is dissolved in a mixed solution of ethylene glycol dimethyl ether/1, 3-dioxolane (the volume ratio is 1:1) to be used as an electrolyte, and a lithium-sulfur battery (the specific model is a CR2032 button cell) is assembled in a glove box.
The cyclic voltammetry curve measured by using the electrode prepared above as a working electrode, mercury/mercury oxide as a reference electrode, and 6M potassium hydroxide aqueous solution as an electrolyte is shown in fig. 4. As can be seen from FIG. 4, the cyclic voltammetry has redox peaks, the positions of the redox peaks are approximately between 0.45V and 0.32V, and the positions of the reduction peaks are between 0.2V and 0.3V, and the electrode material shows obvious pseudocapacitance behavior. The peak area of the electrode made of the carbon nano tube composite cobalt sulfide nano material prepared at the roasting temperature of 800 ℃ is obviously larger than that of the electrode prepared at the roasting temperatures of 700 ℃ and 900 ℃, and the electrode has higher specific capacitance.
The constant current charge-discharge diagram of the assembled asymmetric supercapacitor at a current density of 1A/g is shown in FIG. 5. It can be seen from the figure that the three curves exhibit distinct charge and discharge plateaus, corresponding to the redox peaks of the cyclic voltammograms. The specific capacitance corresponding to the carbon nano tube composite cobalt sulfide nano material prepared at the roasting temperature of 800 ℃ reaches 635.8F/g, and is obviously greater than the specific capacitance corresponding to the roasting temperature of 700 ℃ and 900 ℃.
The constant current charge-discharge curve of the anode of the lithium-sulfur battery under the current density of 100mA/g is shown in fig. 6, and fig. 6 reflects that the battery prepared by using the carbon nano tube composite cobalt sulfide nano material as the electrode material shows two obvious discharge platforms corresponding to the electrochemical process of reducing sulfur into high-valence polysulfide. The discharge platform corresponding to the carbon nano tube composite cobalt sulfide nano material prepared at the roasting temperature of 800 ℃ is obviously higher than that corresponding to other roasting temperatures, and the discharge capacity is highest and reaches 1391 mAh/g.
The discharge performance curves of the positive electrode of the lithium-sulfur battery at different current densities are shown in fig. 7. As can be seen from FIG. 7, the electrode of the present invention can maintain a good capacity under a current density of 100-5000 mA/g, and particularly, the electrode corresponding to the carbon nanotube composite cobalt sulfide nanomaterial prepared at a baking temperature of 800 ℃ has the best performance under different discharge rates.
The cycle performance curve of the positive electrode of the lithium sulfur battery at a current density of 1000mA/g is shown in fig. 8. Fig. 8 shows that after 500 cycles of charge and discharge, the lithium-sulfur battery of the present invention still has a good capacity retention rate, and especially the capacity retention rate of the electrode corresponding to the carbon nanotube composite cobalt sulfide nanomaterial prepared at the baking temperature of 800 ℃ is the best, and is 76.2%.
In conclusion, the zeolite imidazole ester framework material is roasted at high temperature to form the carbon nano tube in situ, so that the expansion of the material is inhibited, the expansion amplitude is reduced, the structural stability is improved, and the super capacitor and the lithium-sulfur battery still have high capacity retention rate after hundreds of cycles. Meanwhile, the high conductivity of the carbon nano tube is utilized to improve the conductivity of the material, more reaction active sites and contact areas are provided for the carbon nano tube composite cobalt sulfide nano material, and the electrochemical activity of the electrode material is improved.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. A preparation method of a carbon nano tube composite cobalt sulfide nano material is characterized by comprising the following steps: the method comprises the following steps:
(1) uniformly mixing a cobalt salt solution, a zinc salt solution and a 2-methylimidazole solution, reacting to obtain a precipitate, washing and drying to obtain a zeolite imidazole ester framework structure material;
(2) roasting the zeolite imidazole ester framework structure material in the step (1) in an inert atmosphere to obtain a carbon nano tube composite metal cobalt nano material;
(3) and (3) uniformly mixing the carbon nano tube composite metal cobalt nano material with sulfur, and carrying out a vulcanization reaction in an inert atmosphere to obtain the carbon nano tube composite cobalt sulfide nano material.
2. The method of claim 1, wherein: in the step (2), the roasting temperature is 700-900 ℃.
3. The method of claim 1, wherein: the temperature of the vulcanization reaction in the step (3) is 600-700 ℃.
4. The method of claim 1, wherein: the cobalt salt and the zinc salt are nitrate, chloride or sulfate of cobalt or zinc respectively.
5. The method of claim 4, wherein: the concentrations of the cobalt salt solution, the zinc salt solution or the 2-methylimidazole solution are 0.2-0.5 mol/L respectively.
6. The method of claim 5, wherein: in the step (1), the drying temperature is 80-120 ℃, and the drying time is 12-24 h.
7. The carbon nanotube composite cobalt sulfide nanomaterial prepared by the preparation method of any one of claims 1 to 6.
8. An electrode, characterized by: the active material of the electrode is the carbon nano tube composite cobalt sulfide nano material prepared by the preparation method of any one of claims 1 to 6.
9. A supercapacitor, characterized by: the positive active material of the super capacitor is the carbon nano tube composite cobalt sulfide nano material prepared by the preparation method of any one of claims 1 to 6.
10. A lithium sulfur battery characterized by: the positive active material of the lithium-sulfur battery is the carbon nano tube composite cobalt sulfide nano material prepared by the preparation method of any one of claims 1 to 6.
CN201911029079.XA 2019-10-28 2019-10-28 Carbon nano tube composite cobalt sulfide nano material and preparation method and application thereof Pending CN110844899A (en)

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