CN109461591B - Manganese dioxide nanotube @ Ni-Co LDH/cobalt disulfide nanocage composite material and preparation method and application thereof - Google Patents
Manganese dioxide nanotube @ Ni-Co LDH/cobalt disulfide nanocage composite material and preparation method and application thereof Download PDFInfo
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- 239000002091 nanocage Substances 0.000 title claims abstract description 106
- 239000002131 composite material Substances 0.000 title claims abstract description 101
- 229910017709 Ni Co Inorganic materials 0.000 title claims abstract description 99
- 229910003267 Ni-Co Inorganic materials 0.000 title claims abstract description 99
- 229910003262 Ni‐Co Inorganic materials 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title claims abstract description 49
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims description 71
- 229910017052 cobalt Inorganic materials 0.000 title description 6
- 239000010941 cobalt Substances 0.000 title description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title description 6
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 title description 2
- 239000011258 core-shell material Substances 0.000 claims abstract description 38
- 239000003960 organic solvent Substances 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011593 sulfur Substances 0.000 claims abstract description 12
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 12
- 239000007772 electrode material Substances 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 239000002071 nanotube Substances 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 8
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 7
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 4
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 4
- 238000004729 solvothermal method Methods 0.000 claims description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000011259 mixed solution Substances 0.000 description 30
- 239000000243 solution Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 8
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 6
- 238000002484 cyclic voltammetry Methods 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
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- 239000002244 precipitate Substances 0.000 description 5
- 239000003990 capacitor Substances 0.000 description 4
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
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- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 4
- 239000012621 metal-organic framework Substances 0.000 description 4
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- 238000003756 stirring Methods 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
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- 239000013078 crystal Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 3
- 238000004626 scanning electron microscopy Methods 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000004697 Polyetherimide Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
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- 239000002086 nanomaterial Substances 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 description 2
- 229920001601 polyetherimide Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GFLJTEHFZZNCTR-UHFFFAOYSA-N 3-prop-2-enoyloxypropyl prop-2-enoate Chemical compound C=CC(=O)OCCCOC(=O)C=C GFLJTEHFZZNCTR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000011796 hollow space material Substances 0.000 description 1
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- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
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- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
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- H—ELECTRICITY
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- 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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- B82Y40/00—Manufacture or treatment of nanostructures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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Abstract
The invention discloses MnO with a one-dimensional axial hierarchical structure2Nanotube @ Ni-Co LDH/CoS2The nanometer cage composite material and its preparation process and application includes the following steps: MnO of2The nano tube @ Ni-Co LDH nano cage core-shell composite material and a sulfur source are subjected to contact reaction in an organic solvent, and then post-treatment is carried out to prepare MnO with a one-dimensional axial hierarchical structure2Nanotube @ Ni-Co LDH/CoS2A nanocage composite. MnO of the one-dimensional axial grading structure2Nanotube @ Ni-Co LDH/CoS2The nanocage composite material has excellent electrochemical performance, so that the nanocage composite material can be applied to a supercapacitor electrode material, and meanwhile, the preparation method has the advantages of simplicity in operation, low cost, mild conditions, environmental friendliness and the like.
Description
Technical Field
The invention relates to a core-shell heterostructure composite material, in particular to MnO with a one-dimensional axial hierarchical structure2Nanotube @ Ni-Co LDH/CoS2A nano cage composite material and a preparation method and application thereof.
Background
The electrochemical super capacitor as an energy storage device has the excellent characteristics of rapid charge and discharge, high power density, good cycle stability and the like, and attracts people to pay attention. Therefore, under the condition of high power output and rapid energy storage, the electrochemical super capacitor can effectively make up the defects of the lithium ion battery, so that the electrochemical super capacitor can be widely applied to electronic equipment, an energy storage power supply and a hybrid electric vehicle. However, the energy density and rate capability of electrochemical supercapacitors are low relative to lithium ion batteries, so research on supercapacitors today is mainly focused on achieving high energy density while maintaining high power density.
The metal-organic framework Materials (MOFs) are crystalline porous materials with periodic network structures formed by self-assembly of transition metal ions and organic ligands, and have the advantages of high porosity, low density, large specific surface area and the like. MOFs, which have a porous structure with a high surface area, are considered to be bifunctional materials combining a sacrificial template and a metal precursor for constructing a high-efficiency electrochemical supercapacitor electrode material with internal voids and a functional shell. However, MOF-derived hollow porous materials suffer from low conductivity and instability due to their independent particle structure and excess space within the particles, which leads to capacitance decay and rate capability degradation. For example, Yusuke Yamauchi et al reported that ZIF-67 combined with hollow ppy nanotubes as a supercapacitor electrode material in the journal of Appl. Mater. interfaces of ACS database only obtained a specific capacitance of 597.67F/g at a current density of 1A/g. In the Nanoscale journal of the RSC database, Dairong Chen et al reported that hollow nano-polyhedral layered double hydroxide derived from a ZIF-67 template is used as an electrode material of a super capacitor, and the specific capacitance and the cycle stability of the double hydroxide are poor.
Disclosure of Invention
The invention aims to provide MnO with a one-dimensional axial hierarchical structure2Nanotube @ Ni-Co LDH/CoS2Nano cage composite material, preparation method and application thereof, MnO of one-dimensional axial hierarchical structure2Nanotube @ Ni-Co LDH/CoS2The nanocage composite material has excellent electrochemical performance, so that the nanocage composite material can be applied to a supercapacitor electrode material, and meanwhile, the preparation method has the advantages of simplicity in operation, low cost, mild conditions, environmental friendliness and the like.
In order to achieve the above object, the present invention provides MnO of one-dimensional axial hierarchical structure2Nanotube @ Ni-CoLDH/CoS2The nanocage composite material comprises a core and a shell coated outside the core, wherein the core is MnO2The shell of the nanotube is Ni-CoLDH/CoS2Hollow nanocages in which Ni-Co LDH/CoS2The hollow nano cage is a hollow nano cage consisting of layered Ni-Co double hydroxide Ni-CoLDH, and CoS is formed between the Ni-Co LDH lamellae2。
The invention also provides a preparation methodMnO of one-dimensional axial grading structure2Nanotube @ Ni-Co LDH/CoS2The preparation method of the nanocage composite material comprises the following steps: MnO of2The nano tube @ Ni-Co LDH nano cage core-shell composite material and a sulfur source are subjected to contact reaction in an organic solvent, and then post-treatment is carried out to prepare MnO with a one-dimensional axial hierarchical structure2Nanotube @ Ni-Co LDH/CoS2A nanocage composite.
The invention further provides MnO of the one-dimensional axial hierarchical structure2Nanotube @ Ni-CoLDH/CoS2The application of the nanocage composite material in the electrode material of the supercapacitor.
By the technical scheme, the invention passes through MnO2MnO with one-dimensional axial hierarchical structure formed by contact reaction of nanotube @ Ni-Co LDH nano cage core-shell composite material and sulfur source2Nanotube @ Ni-Co LDH/CoS2A nanocage composite; MnO of the one-dimensional axial hierarchical structure relative to a single material2Nanotube @ Ni-Co LDH/CoS2The nano cage composite material combines a hollow material with a good conductive nano material, so that a continuous conductive network is obtained, the transmission of charges is promoted, the internal resistance of the material is reduced, the performance and the stability of the material are improved, the specific capacitance and the cycling stability of the material are greatly improved, and the excellent electrochemical performance is realized. Under the current density of 1A/g, the specific capacitance of the core-shell heterostructure composite material can reach 1547F/g. Meanwhile, the preparation method has the characteristics of simple operation, low cost, mild conditions, environmental protection and the like, and the synthesis period is short, so that the method can meet the requirement of commercial large-scale industrial preparation.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a one-dimensional axially graded MnO prepared in example 12Nanotube @ Ni-Co LDH/CoS2High power electron microscope (SEM) images of nanocage composites;
FIG. 2 shows MnO of one-dimensional axial hierarchical structure prepared in example 12Nanotube @ Ni-Co LDH/CoS2A low power electron microscope (SEM) image of the nanocage composite;
FIG. 3 shows MnO of one-dimensional axial hierarchical structure prepared in example 12Nanotube @ Ni-Co LDH/CoS2A Transmission Electron Microscope (TEM) image of the nanocage composite;
FIG. 4 shows MnO of one-dimensional axial hierarchical structure prepared in example 12Nanotube @ Ni-Co LDH/CoS2An X-ray diffraction (XRD) pattern of the nanocage composite;
FIG. 5 shows MnO of one-dimensional axial hierarchical structure prepared in example 12Nanotube @ Ni-Co LDH/CoS2High Resolution Transmission Electron Microscopy (HRTEM) images of nanocage composites;
FIG. 6 is a one-dimensional axially graded MnO prepared in example 12Nanotube @ Ni-Co LDH/CoS2Cyclic Voltammogram (CV) of the nanocage composite;
FIG. 7 shows MnO of one-dimensional axial hierarchical structure prepared in example 12Nanotube @ Ni-Co LDH/CoS2A constant current charge and discharge curve diagram (CP) of the nano cage composite material under different current densities;
FIG. 8 is a one-dimensional axially graded MnO prepared in example 12Nanotube @ Ni-Co LDH/CoS2Nanocage composite at a current density of 10A g-1Cyclic-specific capacitance plots of time.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides MnO with a one-dimensional axial hierarchical structure2Nanotube @ Ni-Co LDH/CoS2The nanocage composite material comprises a core and a shell coated outside the core, wherein the core is MnO2The shell of the nanotube is Ni-Co LDH/CoS2Hollow nanocages in which Ni-Co LDH/CoS2The hollow nano cage is a hollow nano cage consisting of layered Ni-Co double hydroxide Ni-Co LDH, and CoS is formed between the Ni-Co LDH lamellae2。
The invention also provides MnO with the one-dimensional axial hierarchical structure2Nanotube @ Ni-Co LDH/CoS2The preparation method of the nanocage composite material comprises the following steps: MnO of2The nano tube @ Ni-Co LDH nano cage core-shell composite material and a sulfur source are subjected to contact reaction in an organic solvent, and then post-treatment is carried out to prepare MnO with a one-dimensional axial hierarchical structure2Nanotube @ Ni-Co LDH/CoS2A nanocage composite.
In the present invention, the amount of each material to be used may be selected within a wide range, but in order to further increase the MnO to be obtained2Nanotube @ Ni-Co LDH/CoS2Electrochemical Properties of nanocage composite, preferably MnO2The weight ratio of the nanotube @ Ni-CoLDH nanocage core-shell composite material to the sulfur source is 0.03: 0.015-0.12.
In the present invention, the amount of the organic solvent to be used may be selected within a wide range, but in order to further increase the MnO to be obtained2Nanotube @ Ni-Co LDH/CoS2Electrochemical Properties of nanocage composite, preferably MnO2The dosage ratio of the nanotube @ Ni-CoLDH nanocage core-shell composite material to the organic solvent is 0.03 g: 30-40 mL.
In the present invention, the conditions for the contact reaction can be selected within a wide range, but in order to further improve the MnO to be obtained2Nanotube @ Ni-Co LDH/CoS2Electrochemical Properties of nanocage composite, optimizationThe contact reaction satisfies the following conditions: the reaction temperature is 85-95 ℃ and the reaction time is 2-5 h.
In the present invention, the mode of the contact reaction can be selected within a wide range, but in order to further improve the MnO to be obtained2Nanotube @ Ni-Co LDH/CoS2Electrochemical performance of the nanocage composite material, preferably, the contact reaction is performed by a solvothermal method.
In the present invention, the kind of the sulfur source can be selected within a wide range, but in order to further improve the MnO to be obtained2Nanotube @ Ni-Co LDH/CoS2Electrochemical performance of the nanocage composite, preferably, the sulfur source is selected from at least one of thioacetamide, sodium sulfide, and sulfur powder;
in the present invention, the kind of the organic solvent can be selected within a wide range, but in order to further improve the MnO to be obtained2Nanotube @ Ni-Co LDH/CoS2Electrochemical performance of the nanocage composite, preferably, the organic solvent is selected from at least one of ethanol, methanol, and N, N-dimethylformamide.
In the present invention, MnO2The average diameter of the nanotube @ Ni-Co LDH nanocage core-shell composite material can be selected within a wide range, but in order to further improve the MnO prepared2Nanotube @ Ni-Co LDH/CoS2Electrochemical Properties of nanocage composite, preferably MnO2The average diameter of the nanotube @ Ni-Co LDH nanocage core-shell composite material is 300-400 nm.
In the present invention, the order of addition of the materials can be selected within a wide range, but in order to further improve the MnO to be obtained2Nanotube @ Ni-Co LDH/CoS2The electrochemical performance of the nanocage composite material is preferably, the feeding sequence of the preparation method is as follows: MnO is firstly added2Dispersing the nanotube @ Ni-Co LDH nano cage core-shell composite material in an organic solvent to form a solution A, and dispersing a sulfur source in the organic solvent to form a solution B; then, the solution A and the solution B are mixed.
In the present invention, the step of post-treatment may be selected within a wide range, but in order to further improve the electrochemical properties of the prepared nanocage core-shell composite material, preferably, in step 3), the post-treatment comprises: the reaction system was centrifuged, and then the centrifuged precipitate was washed and then dried.
The invention further provides MnO of the one-dimensional axial hierarchical structure2Nanotube @ Ni-CoLDH/CoS2The application of the nanocage composite material in the electrode material of the supercapacitor.
The invention also provides a manganese dioxide nanotube @ Ni-Co LDH nanocage core-shell composite material with a one-dimensional structure, which comprises a core and a shell coated outside the core, wherein the core is MnO2The shell of the nanotube is a Ni-Co LDH hollow nano cage, wherein the Ni-Co LDH hollow nano cage is a hollow nano cage consisting of hollow nano polyhedral layered Ni-Co double hydroxide.
The invention also provides a preparation method of the manganese dioxide nanotube @ Ni-Co LDH nanocage core-shell composite material with the one-dimensional structure, which comprises the following steps:
1) MnO of2Dispersing the nanotube @ ZIF-67 in an organic solvent to form a mixed solution A;
2) dispersing a nickel source in an organic solvent to form a mixed solution B;
3) mixing the mixed solution A and the mixed solution B, then carrying out contact reaction, and then carrying out post-treatment to prepare a manganese dioxide nanotube @ Ni-Co LDH nanocage core-shell composite material with a one-dimensional structure;
wherein, MnO2The nano tube @ ZIF-67 consists of a core and a shell coated outside the core, wherein the core is MnO2The shell of the nanotube is a ZIF-67 polyhedron.
In the above preparation method of manganese dioxide nanotube @ Ni-Co LDH nanocage core-shell composite material, the amount of each material may be selected within a wide range, but in order to further improve the electrochemical properties of the prepared nanocage core-shell composite material, preferably, MnO is used2The weight ratio of the nanotube @ ZIF-67 to the nickel source is 0.05 g: 0.05-0.1 g.
In the preparation method of the manganese dioxide nanotube @ Ni-Co LDH nanocage core-shell composite material, the dosage of the organic solvent can be in a wide rangeSelected in the enclosure, but in order to further improve the electrochemical properties of the prepared nanocage core-shell composite, preferably, in step 1), MnO2The using amount ratio of the nanotube @ ZIF-67 to the organic solvent is 0.05 g: 5-10 mL; in the step 2), the dosage ratio of the nickel source to the organic solvent is 0.05-0.1 g: 10-20 mL.
In the above preparation method of the manganese dioxide nanotube @ Ni-Co LDH nanocage core-shell composite material, the kind of the nickel source may be selected within a wide range, but in order to further improve the electrochemical properties of the prepared nanocage core-shell composite material, preferably, the nickel source is selected from at least one of cobalt nitrate hexahydrate, sodium sulfide, and sulfur powder.
In the above preparation method of the manganese dioxide nanotube @ Ni-Co LDH nanocage core-shell composite material, the kind of the organic solvent may be selected within a wide range, but in order to further improve the electrochemical properties of the prepared nanocage core-shell composite material, preferably, the organic solvent is at least one selected from ethanol, methanol, and N, N-dimethylformamide.
In the above preparation method of manganese dioxide nanotube @ Ni-Co LDH nanocage core-shell composite material, the size of the shell and the nanocage core-shell composite material may be selected within a wide range, but in order to further improve the electrochemical properties of the prepared nanocage core-shell composite material, preferably, MnO is used2The average diameter of the nanotube @ ZIF-67 is 300-400nm, and the average diameter of the Ni-CoLDH nanocage is 80-150 nm.
In the preparation method of the manganese dioxide nanotube @ Ni-Co LDH nanocage core-shell composite material, the dispersion mode can be selected within a wide range, but in order to further improve the electrochemical properties of the prepared nanocage core-shell composite material, in steps 1) and 2), the dispersion mode is preferably ultrasonic oscillation, and the ultrasonic time is 3-15 min.
In step 3) of the preparation method of the manganese dioxide nanotube @ Ni-Co LDH nanocage core-shell composite material, the conditions of the contact reaction can be selected within a wide range, but in order to further improve the electrochemical properties of the prepared nanocage core-shell composite material, preferably, in step 3), the contact reaction satisfies the following conditions: the method is carried out by a reflux method or a solvothermal method, the reaction time is 2.5-5h, and the reaction temperature is 70-90 ℃.
In step 3) of the above preparation method of manganese dioxide nanotube @ Ni-Co LDH nanocage core-shell composite material, the post-treatment step may be selected within a wide range, but in order to further improve the electrochemical properties of the prepared nanocage core-shell composite material, preferably, in step 3), the post-treatment comprises: the reaction system was centrifuged, and then the centrifuged precipitate was washed and then dried.
The invention further provides application of the manganese dioxide nanotube @ Ni-Co LDH nanocage core-shell composite material with the one-dimensional structure in a supercapacitor electrode material.
The invention also provides MnO2A method of making nanotube @ ZIF-67, comprising:
1) MnO of monomer2Dispersing the nano tube and the cobalt source in an organic solvent to form a mixed solution A;
2) dispersing 2-methylimidazole and a surfactant in an organic solvent to form a mixed solution B;
3) mixing the mixed solution A and the mixed solution B, carrying out contact reaction, and then carrying out post-treatment to prepare MnO2Nanotube @ ZIF-67.
In MnO2Preparation method of nano tube @ ZIF-67, dosage of each material is selected in a wide range, but MnO is further improved2Electrochemical Properties of nanotubes @ ZIF-67, preferably monomeric MnO2The weight ratio of the nano tube, the cobalt source, the 2-methylimidazole and the surfactant is 0.02-0.06 g: 0.29-0.32 g: 0.65-0.7 g: 0.35-0.4 g.
In MnO2In step 1) of the method for producing nanotubes @ ZIF-67, the amount of the organic solvent is selected within a wide range, but in order to further increase MnO2Electrochemical Properties of nanotubes @ ZIF-67, preferably, in step 1), monomeric MnO2The dosage ratio of the nanotube and the organic solvent is 0.02-0.06 g: 20-30 mL.
In MnO2In step 2) of the preparation method of nanotube @ ZIF-67, the amount of the organic solvent is selected within a wide range, but in order to further increase MnO2The electrochemical property of the nanotube @ ZIF-67 is that in the step 2), the dosage ratio of 2-methylimidazole to the organic solvent is 0.65-0.7 g: 8-15 mL.
In MnO2Preparation method of nanotube @ ZIF-67, the kind of cobalt source is selected in a wide range, but MnO is further increased2Electrochemical properties of the nanotubes @ ZIF-67, preferably, the cobalt source is selected from at least one of cobalt nitrate, cobalt chloride, and cobalt sulfate.
In MnO2Preparation of nanotubes @ ZIF-67 the surfactant type was selected within a wide range, but to further increase the MnO2Electrochemical properties of the nanotubes @ ZIF-67, preferably, the surfactant is selected from at least one of polyvinylpyrrolidone, PVP, polydiallyldimethylammonium chloride, PDDA, and polyetherimide, PEI.
In MnO2Preparation method of nanotube @ ZIF-67, the kind of organic solvent is selected from a wide range, but MnO is further increased2Electrochemical properties of the nanotubes @ ZIF-67, preferably, the organic solvent is selected from at least one of methanol, ethanol, and N, N-dimethylformamide.
In MnO2Preparation method of nanotube @ ZIF-67, the way of dispersion is selected within a wide range, but MnO is further increased2The electrochemical property of the nanotube @ ZIF-67 is preferably that in the steps 1) and 2), the dispersion is carried out by ultrasonic oscillation, and the ultrasonic time is 3-15 min.
In MnO2Method for producing nanotube @ ZIF-67, conditions for the contact reaction are selected from a wide range, but MnO is further increased2Electrochemical properties of the nanotubes @ ZIF-67, preferably, in step 3), the contact reaction satisfies the following conditions: under the condition of stirring, the reaction time is 0.5-3h, and the reaction temperature is 15-35 ℃.
In MnO2In the preparation method of the nanotube @ ZIF-67, the post-treatment process is wideIs selected within the range of (1), but in order to further increase MnO2Electrochemical properties of nanotubes @ ZIF-67, preferably, in step 3), the post-processing comprises: the reaction system was centrifuged, and then the centrifuged precipitate was washed and then dried. Among them, the conditions for drying may be selected within a wide range, but in order to further improve the drying effect, it is preferable that the drying temperature is 75 to 80 ℃ and the drying time is 24 to 30 hours.
The present invention will be described in detail below by way of examples.
Preparation example 1
Monomer MnO2Preparing the nanotube:
first, 0.304g of KMnO was added under stirring4And 0.6ml of HCl (37 vol%) was added to 35ml of distilled water to form a homogeneous solution; then, transferring the solution into a polytetrafluoroethylene-lined stainless steel autoclave with the capacity of 50ml, placing the autoclave in an oven at 140 ℃ for 12 hours, and cooling to room temperature; the resulting brown precipitate was then filtered, washed several times with deionized water and dried under vacuum at 80 ℃ for 12 h.
Preparation example 2
1) 0.04g of monomer MnO2The nanotubes and 0.29g of cobalt nitrate hexahydrate were dispersed in 20ml of methanol, and ultrasonically dispersed for 10 minutes to obtain a uniform mixed solution a.
2) 0.65g of 2-methylimidazole and 0.37g of polyvinylpyrrolidone (PVP) were dispersed in 10ml of methanol, and ultrasonic dispersion was carried out for 5 minutes to obtain a uniform mixed solution B.
3) Rapidly pouring the mixed solution B into the mixed solution A under stirring, reacting for 1h under stirring at room temperature (25 ℃), centrifuging the reaction system, washing the centrifuged precipitate with methanol for 5 times, centrifuging at 5000rpm, and vacuum drying at 75 ℃ for 24 h to obtain MnO2Nanotube @ ZIF-67;
4) adding 0.05g MnO2@ ZIF-67 is dispersed into 20ml ethanol and uniformly dispersed by ultrasonic for 5min to obtain a mixed solution A; dispersing 0.1g of nickel nitrate hexahydrate in 5ml of ethanol, and uniformly dispersing by ultrasonic for 5min to obtain a mixed solution B; mixing the mixed solution A with the mixture under magnetic stirringMixing the mixed solution B, and transferring the solution into a stainless steel autoclave with a polytetrafluoroethylene lining; placing the autoclave in an oven at 80 deg.C for 4h, cooling to room temperature (25 deg.C), washing with ethanol for 3 times, centrifuging, and vacuum drying at 70 deg.C for 12h to obtain MnO2The nanotube @ Ni-Co LDH nanocage composite material.
Preparation example 3
MnO was obtained according to preparation example 22A nanotube @ Ni-Co LDH nanocage composite material, except that the monomer MnO2The amount of nanotubes was 0.02g, cobalt nitrate hexahydrate 0.29g, 2-methylimidazole 0.65g, polyvinylpyrrolidone (PVP) 0.35g and nickel nitrate hexahydrate 0.08 g.
Preparation example 4
MnO was obtained according to preparation example 22A nanotube @ Ni-Co LDH nanocage composite material, except that the monomer MnO2The amount of nanotubes used was 0.06g, the amount of cobalt nitrate hexahydrate in step 1) was 0.32g, the amount of 2-methylimidazole was 0.7g, the amount of polyvinylpyrrolidone (PVP) was 0.4g, and the amount of nickel nitrate hexahydrate was 0.1 g.
Preparation example 5
MnO was obtained according to preparation example 22The difference of the nanotube @ Ni-Co LDH nanocage composite material is that the mixed solution A and the mixed solution B are mixed, then the solution is transferred into a round-bottom flask, and the round-bottom flask is placed in an oil bath kettle at the temperature of 70 ℃, stirred, heated and refluxed for 5 hours and then cooled to room temperature.
Preparation example 6
MnO was obtained according to preparation example 22The difference of the nanotube @ Ni-Co LDH nanocage composite material is that the mixed solution A and the mixed solution B are mixed, then the solution is transferred into a round-bottom flask, and the round-bottom flask is placed in an oil bath kettle at the temperature of 90 ℃, stirred, heated and refluxed for 2.5 hours and then cooled to room temperature.
Preparation example 7
MnO was obtained according to preparation example 22The difference of the nanotube @ Ni-Co LDH nanocage composite material is that the mixed solution A and the mixed solution B are mixed and then transferred toIn a stainless steel autoclave lined with polytetrafluoroethylene; the autoclave was placed in an oven at 80 ℃ for 4h and then cooled to room temperature.
Preparation example 8
MnO was obtained according to preparation example 22The nanotube @ Ni-Co LDH nanocage composite material is characterized in that the mixed solution A and the mixed solution B are mixed, and then the mixed solution A and the mixed solution B are transferred into a stainless steel autoclave with a polytetrafluoroethylene lining; the autoclave was placed in an oven at 70 ℃ for 5h and then cooled to room temperature.
Preparation example 9
MnO was obtained according to preparation example 22The nanotube @ Ni-Co LDH nanocage composite material is characterized in that the mixed solution A and the mixed solution B are mixed, and then the mixed solution A and the mixed solution B are transferred into a stainless steel autoclave with a polytetrafluoroethylene lining; the autoclave was placed in an oven at 90 ℃ for 2.5h and then cooled to room temperature.
Example 1
0.03g of MnO in preparation example 12Dissolving the nanotube @ Ni-Co LDH nanocage composite material in 15mL of ethanol to prepare a solution A, and dissolving 0.09g of thioacetamide in 15mL of ethanol to prepare a solution B; then mixing the solution A and the solution B under magnetic stirring, and transferring the solution into a polytetrafluoroethylene-lined stainless steel autoclave with the capacity of 50 ml; finally, the autoclave was placed in an oven at 90 ℃ for 2h and then cooled to room temperature, washed 6 times with ethanol and dried under vacuum at 70 ℃ for 18 h.
Example 2
The procedure is as in example 1, except that the oven temperature is 85 ℃ and the reaction is carried out in the oven for 5 hours.
Example 3
The procedure is as in example 1, except that the oven temperature is 95 ℃ and the reaction is carried out in the oven for 2 h.
Example 4
The procedure is as in example 1, except that thioacetamide is used in an amount of 0.12 g.
Example 5
The procedure was as in example 1, except that thioacetamide was used in an amount of 0.015 g.
Example 6
The procedure is as in example 1, except that thioacetamide is used in an amount of 0.06 g.
Example 7
The procedure is as in example 1, except that thioacetamide is replaced by sodium sulfide.
Examples 8 to 15
The procedure is as in example 1, except that MnO is used in examples 8-152The nanotube @ Ni-Co LDH nanocage composite material is sequentially MnO prepared in preparation examples 2-92The nanotube @ Ni-Co LDH nanocage composite material.
Detection example 1
1) The product obtained in example 1 was analyzed for morphology by Scanning Electron Microscopy (SEM), and the results are shown in FIGS. 1 and 2, which indicate that the prepared product is a one-dimensional nanostructure with a diameter of 300-400 nm.
2) The product obtained in example 1 was analyzed by Transmission Electron Microscopy (TEM) and the results are shown in fig. 3; the product is shown to be a one-dimensional axial hierarchical structure, the diameter is 300-400nm, and the Ni-Co LDH/CoS2 nano cage diameter of the shell layer is 80-150 nm.
3) The product obtained in example 1 was examined by X-ray diffraction (XRD) and the result is shown in fig. 4; obtaining MnO corresponding to the map and JCPDS standard card NO.72-19822Diffraction peaks completely matched with those of CoS corresponding to JCPDS standard card No.41-14712The diffraction peaks are completely coincided, the clearly defined diffraction peaks observed at the 2 theta values of 10.9,22.3,34.5 and 60.5 degrees are completely coincided with the hydrotalcite LDH phase, and the XRD pattern can well prove that the substance is MnO2@Ni-Co LDH/CoS2A composite material.
4) The product obtained in example 1 was analyzed by High Resolution Transmission Electron Microscopy (HRTEM) and the results are shown in fig. 5; the lattice spacing near the central region shows 0.32nm, which is comparable to MnO2The (310) crystal face of (A) corresponds to (B); the edge regions show lattice spacings of 0.23 and 0.45nm, which are in good agreement with the (110), (006) crystal plane of ZIF-67 derived Ni-Co LDH. In addition, 0.15nm of lattice spacing is observedIn CoS2The (321) crystal plane of (2). This further indicates that the material is MnO2@Ni-Co LDH/CoS2A composite material.
Similarly, examples 8 to 15 were examined, and the examination results substantially agreed with those of example 1, thereby also indicating that the products of examples 8 to 15 were MnO2@Ni-Co LDH/CoS2A composite material.
Detection example 2
The following tests were carried out using an apparatus of CHI660E electrochemical workstation (manufactured by Shanghai Chenghua apparatus Co., Ltd.). The following tests all used a three-electrode system, in which the MnO of example 1 was used2@Ni-Co LDH/CoS2Composite, acetylene black, Polytetrafluoroethylene (PTFE) according to 7: 2: 1 to make a working electrode; a platinum wire electrode and a Saturated Calomel Electrode (SCE) are respectively used as a counter electrode and a reference electrode; 2mol/L KOH solution was used as an electrolyte.
1) Cyclic Voltammetry (CV) test
Respectively at 5mV s-1、10m V·s-1、20mV·s-1、40mV·s-1、60mV·s-1、80mV·s-1And 100 mV. s-1Scanning at a scanning rate to obtain MnO in example 12@Ni-Co LDH/CoS2The cyclic voltammogram of the composite material is shown in FIG. 6, and the potential of the cyclic voltammogram ranges from 0V to 0.55V. It can be seen from the CV diagram that MnO of one-dimensional axial hierarchical structure is increased along with the increase of scanning speed2Nanotube @ Ni-Co LDH/CoS2The oxidation and reduction peaks of the nano cage composite material are respectively transferred to more negative potentials and positive potentials, thereby showing the quasi-reversible characteristic of the oxidation-reduction reaction and showing the MnO of a one-dimensional axial hierarchical structure2Nanotube @ Ni-Co LDH/CoS2The nanocage composite material has excellent performance of storing electricity.
2) Constant current charge-discharge (CP) test
Respectively at 1 A.g-1、2A·g-1、4A·g-1、6A·g-1、8A·g-1And 10A. g-1Constant current charge and discharge detection is carried out to obtain MnO in example 12@Ni-Co LDH/CoS2Composite materialThe constant current charge and discharge curves of the material at different current densities are shown in fig. 7. Wherein the ordinate of the curve, namely the voltage range, is 0-0.55V. The specific capacitance charge and discharge under different current densities are calculated by the following formula. Calculating specific capacitance from charge-discharge diagrams, i.e. MnO of one-dimensional axial hierarchical structure2Nanotube @ Ni-Co LDH/CoS2The specific capacitance of the nano cage composite material is 1547F/g under the current density of 1A/g, which shows MnO of a dimensional axial hierarchical structure2Nanotube @ Ni-Co LDH/CoS2The nanocage composite material has excellent performance of storing electricity.
The capacitance calculation formula is that Cm is (I.t)/(△ V.m), I is the current magnitude, t is the discharge time, △ V is the potential difference, and m is the mass of the sample on the working electrode sheet.
3) Cycle performance detection
At 10A g-1Is cycled 2000 times at a current density of (c) to give the one-dimensional axially graded MnO of example 12Nanotube @ Ni-Co LDH/CoS2The result of the cycle-specific capacitance curve of the nanocage composite material is shown in fig. 8, the final capacity and the initial capacity are compared, the attenuation is less compared with the initial capacity after 2000 cycles, and the MnO with the one-dimensional axial hierarchical structure is illustrated2Nanotube @ Ni-Co LDH/CoS2The nanocage composite has excellent stability.
Similarly, the products of examples 8 to 15 were tested for electrochemical properties according to the above-mentioned method, and the results were substantially identical to those of the product of example 1, thereby also demonstrating that the products of examples 8 to 15 were able to serve as electrode materials for supercapacitors.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (7)
1. MnO with one-dimensional axial hierarchical structure2Nanotube @ Ni-Co LDH/CoS2The preparation method of the nanocage composite material is characterized by comprising the following steps: MnO of2The nano tube @ Ni-Co LDH nano cage core-shell composite material and a sulfur source are subjected to contact reaction in an organic solvent, and then post-treatment is carried out to prepare MnO with a one-dimensional axial hierarchical structure2Nanotube @ Ni-Co LDH/CoS2A nanocage composite;
wherein MnO of the one-dimensional axial hierarchical structure2Nanotube @ Ni-Co LDH/CoS2The nanocage composite material comprises a core and a shell coated outside the core, wherein the core is MnO2Nanotubes, the shell being Ni-Co LDH/CoS2A hollow nanocage, wherein the Ni-Co LDH/CoS2The hollow nano cage is a hollow nano cage consisting of layered Ni-Co double hydroxide Ni-Co LDH, and CoS is formed between the Ni-Co LDH lamellae2(ii) a The contact reaction is carried out by adopting a solvothermal method; the contact reaction satisfies the following conditions: the reaction temperature is 85-95 ℃, and the reaction time is 2-5 h; the preparation method comprises the following steps: MnO is firstly added2Dispersing the nanotube @ Ni-Co LDH nano cage core-shell composite material in an organic solvent to form a solution A, and dispersing a sulfur source in the organic solvent to form a solution B; then, the solution A and the solution B are mixed.
2. The production method according to claim 1, wherein the MnO is2The weight ratio of the nanotube @ Ni-Co LDH nanocage core-shell composite material to the sulfur source is 0.03: 0.015-0.12.
3. The production method according to claim 1, wherein the MnO is2Nanotube @ NThe dosage ratio of the i-Co LDH nano-cage core-shell composite material to the organic solvent is 0.03 g: 30-40 mL.
4. The production method according to claim 1, wherein the sulfur source is selected from at least one of thioacetamide, sodium sulfide, and sulfur powder.
5. The production method according to claim 1, wherein the organic solvent is selected from at least one of ethanol, methanol, and N, N-dimethylformamide.
6. The production method according to claim 1, wherein the MnO is2The average diameter of the nanotube @ Ni-Co LDH nanocage core-shell composite material is 300-400 nm.
7. The MnO of claim 1 with one-dimensional axial hierarchical structure2Nanotube @ Ni-Co LDH/CoS2The application of the nanocage composite material in the electrode material of the supercapacitor.
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