CN115497745A - Flower-like multi-level structured core-shell nickel cobaltate-manganese cobaltate electrode material and preparation method thereof - Google Patents
Flower-like multi-level structured core-shell nickel cobaltate-manganese cobaltate electrode material and preparation method thereof Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 239000011258 core-shell material Substances 0.000 title claims abstract description 65
- 239000007772 electrode material Substances 0.000 title claims abstract description 57
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 50
- 239000011572 manganese Substances 0.000 title claims abstract description 50
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 46
- 239000002243 precursor Substances 0.000 claims abstract description 43
- 239000002131 composite material Substances 0.000 claims abstract description 41
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000007787 solid Substances 0.000 claims abstract description 21
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 50
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 239000012046 mixed solvent Substances 0.000 claims description 10
- 150000001868 cobalt Chemical class 0.000 claims description 9
- 150000002696 manganese Chemical class 0.000 claims description 9
- 150000002815 nickel Chemical class 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical group O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 6
- ALIMWUQMDCBYFM-UHFFFAOYSA-N manganese(2+);dinitrate;tetrahydrate Chemical group O.O.O.O.[Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ALIMWUQMDCBYFM-UHFFFAOYSA-N 0.000 claims description 6
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical group O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 claims 1
- 238000004729 solvothermal method Methods 0.000 abstract description 11
- 239000003990 capacitor Substances 0.000 abstract description 5
- 238000005530 etching Methods 0.000 abstract description 5
- 238000012983 electrochemical energy storage Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 2
- 239000002041 carbon nanotube Substances 0.000 abstract 2
- 229910021393 carbon nanotube Inorganic materials 0.000 abstract 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 abstract 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 abstract 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 abstract 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 229910003266 NiCo Inorganic materials 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 239000013078 crystal Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 229910052596 spinel Inorganic materials 0.000 description 5
- 239000011029 spinel Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 4
- 238000003384 imaging method Methods 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
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- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000002524 electron diffraction data Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000011112 process operation Methods 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
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- 230000002195 synergetic effect Effects 0.000 description 2
- 229910016507 CuCo Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 239000002803 fossil fuel Substances 0.000 description 1
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- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
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- 229910001416 lithium ion Inorganic materials 0.000 description 1
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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
- H01G11/24—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
-
- 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
-
- 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
- H01G11/46—Metal oxides
-
- 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
- H01G11/84—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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- Y—GENERAL 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
- 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
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a core-shell nickel cobaltate-manganese cobaltate composite electrode material with a flower-shaped multi-stage structure and a preparation method thereof, and belongs to the technical field of functional material preparation. The method comprises the steps of taking isopropanol and polyhydroxy alcohol as solvents, taking nickel nitrate, manganese nitrate and cobalt nitrate as raw materials, preparing a solid spherical nickel-manganese-cobalt precursor compound by a solvothermal method, etching the precursor compound by water and an alkaline organic solvent to obtain a flower-shaped multi-level structural core-shell precursor compound, and calcining the compound at high temperature to prepare the flower-shaped multi-level structural core-shell nickel cobaltate-manganese cobaltate composite electrode material. The core-shell nickel cobaltate-manganese cobaltate with the flower-shaped multi-stage structure has the diameter of about 1.0 mu m and the specific surfaceThe product is as high as 120.6m 2 •g ‑1 . When the carbon nano-tube is used as an electrode material in a super capacitor, the carbon nano-tube has better electrochemical energy storage performance. At current densities of 4.0, 6.0, 10, 15 and 20 A.g ‑1 Then, the capacitances are 1636, 1494, 1310, 1100 and 940 F.g ‑1 . At 15 A.g ‑1 After 5000 times of charge-discharge cycles, the capacitance can still reach 984.5 F.g ‑1 . The preparation method is easy to operate and implement, low in cost, high in yield and good in reproducibility.
Description
Technical Field
The invention relates to a core-shell nickel cobaltate-manganese cobaltate electrode material with a flower-shaped multi-stage structure and a preparation method thereof, belonging to the technical field of functional material preparation.
Background
The rapid development of energy storage technology is promoted by the increasingly prominent problems of fossil fuel consumption, energy exhaustion, environmental pollution and the like. Among various energy storage devices (such as lithium ion batteries, solar cells, fuel cells, and supercapacitors), supercapacitors have drawn much attention due to their advantages of long cycle life, high power density, and the like. Electrode materials are key factors influencing the performance of super capacitor devices, so that the search for developing high-performance electrode materials is urgent.
Among the electrode materials, spinel type (AB) 2 O 4 ) The redox reaction initiated by the material is jointly participated by two different transition metal ions, and can provide higher conductivity and electrochemical activity than single metal ions under the synergistic action. Thus, spinel type materials are widely developed for use in supercapacitors. The electrode material can be endowed with excellent physicochemical properties by component optimization and construction of a novel micro-nano structure, so that the electrochemical performance of the electrode material is improved. Among a plurality of micro-nano structures, the hollow micro-nano structure/material has the characteristics of low density, high specific surface area, favorability for electron and ion diffusion and the like, and has wide application in the field of energy storage and conversion. Can be seen through component optimization and hollow constructionThe micro-nano electrode material is an effective strategy for improving the performance of the super capacitor device. Currently, single spinel type (NiCo) 2 O 4 、MnCo 2 O 4 、CuCo 2 O 4 、ZnCo 2 O 4 ) Hollow electrode materials are reported, but two-component spinel type hollow composite electrode materials are rarely involved. Therefore, the research and development of the two-component spinel type hollow composite electrode material with simple process operation, high yield and good reproducibility has very important significance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of a flower-shaped multi-level structured core-shell nickel cobaltate-manganese cobaltate composite electrode material, which has simple process operation and low production cost; the other purpose is to provide the core-shell nickel cobaltate-manganese cobaltate composite electrode material with the flower-shaped multi-level structure and good electrochemical energy storage performance.
In order to achieve the purpose of the invention, in the technical scheme of the invention, nickel salt, manganese salt and cobalt salt are added into a mixed solvent of isopropanol and polyhydroxy alcohol, stirred, dissolved and uniformly mixed, the solution is transferred into a reaction kettle, and a solid spherical nickel-manganese-cobalt precursor compound is obtained through solvothermal reaction. The precursor compound is etched by water and an alkaline organic solvent to obtain a core-shell precursor compound with a flower-like multilevel structure, and the core-shell nickel cobaltate-manganese cobaltate composite electrode material with the flower-like multilevel structure can be prepared by calcining the core-shell precursor compound at high temperature.
The method comprises the following specific steps:
1) Preparing a solid spherical nickel-manganese-cobalt precursor compound: adding nickel salt, manganese salt and cobalt salt into a mixed solvent of isopropanol and polyhydroxy alcohol, stirring, dissolving and uniformly mixing to prepare a reaction solution; transferring the reaction solution into a reaction kettle, heating for reaction (180-220 ℃), and naturally cooling to room temperature after the reaction is finished; and centrifugally separating, washing and drying the product to obtain the solid spherical nickel-manganese-cobalt precursor compound. The concentration of nickel salt in the reaction solution is 0.0013-0.0052 mol.L -1 The concentration of manganese salt is 0.0013-0.0052 mol.L -1 The concentration of cobalt salt is 0.0026-0.0104 mol.L -1 The molar ratio of nickel salt, manganese salt and cobalt salt is 1:1:2, the volume ratio of the isopropanol to the polyhydroxy alcohol is 1-5: 1.
2) Preparing a core-shell precursor compound with a flower-shaped multilevel structure: dispersing the solid spherical nickel-manganese-cobalt precursor compound prepared in the step (1) into water and an alkaline organic solvent, uniformly stirring, transferring the mixture into a reaction kettle, heating for reaction (120-160 ℃), and naturally cooling to room temperature after the reaction is finished; and centrifugally separating, washing and drying the product to obtain the flower-like multi-stage structure core-shell precursor compound. The volume ratio of water to the alkaline organic solvent is 1:4 to 4:1.
3) Preparing a core-shell nickel cobaltate-manganese cobaltate composite electrode material with a flower-like multilevel structure: the prepared core-shell precursor compound with the flower-like multilevel structure is calcined at high temperature (450-550 ℃) in the air atmosphere to obtain the core-shell nickel cobaltate-manganese cobaltate composite electrode material with the flower-like multilevel structure.
In the method of the present invention, the nickel salt is preferably nickel nitrate hexahydrate, the manganese salt is preferably manganese nitrate tetrahydrate, the cobalt salt is preferably cobalt nitrate hexahydrate, the polyhydric alcohol is preferably glycerol or ethylene glycol, and the basic organic solvent is preferably N-methylpyrrolidone or N, N-dimethylformamide.
The invention has the following advantages and innovation points:
1. synthesizing a solid spherical nickel-manganese-cobalt precursor compound by a solvothermal method, deriving a flower-shaped multi-level structural core-shell precursor compound by using the compound as a template under the etching of water and an alkaline organic solvent, and calcining the compound at high temperature to prepare the flower-shaped multi-level structural core-shell nickel cobaltate-manganese cobaltate composite electrode material.
2. The electrochemical performance of the core-shell nickel cobaltate-manganese cobaltate composite electrode material with the flower-shaped multi-level structure is improved by utilizing the synergistic effect of three metal ions of nickel-manganese-cobalt, and when the core-shell nickel cobaltate-manganese cobaltate composite electrode material is applied to a super capacitor device, the current density is 4.0, 6.0, 10, 15 and 20 A.g -1 Then, the capacitance is 1636, 1494, 1310, 1100 and 940 F.g -1 At 15A · g -1 After 5000 times of charge-discharge cycles, the capacitance can still reach 984.5 F.g -1 . The result shows that the core-shell nickel cobaltate-manganese cobaltate composite electrode material with the flower-like multilevel structure has good application prospect in electrochemical energy storage.
Drawings
FIG. 1 is a schematic diagram of the synthesis of a flower-like multi-stage structured core-shell nickel cobaltate-manganese cobaltate electrode material.
FIG. 2 is the scanning electron micrographs (a, b) and the transmission electron micrograph (c) of the solid spherical nickel-manganese-cobalt precursor compound obtained in example 1 of the present invention,
scanning electron micrographs (d, e) and transmission electron micrographs (f) of the core-shell precursor compound with the flower-like multilevel structure obtained after etching.
FIG. 3 is an X-ray powder diffraction pattern of the flower-like multi-level structured core-shell nickel cobaltate-manganese cobaltate composite electrode material obtained in example 1 of the present invention.
Fig. 4 is scanning electron micrographs (a, b) and transmission electron micrographs (c, d) of the core-shell nickel cobaltate-manganese cobaltate composite electrode material with the flower-like multilevel structure obtained in example 1 of the present invention, a high-resolution transmission electron micrograph (e) of the core-shell nickel cobaltate-manganese cobaltate composite electrode material with the flower-like multilevel structure, a selected-region electron diffraction pattern (f) of the core-shell nickel cobaltate-manganese cobaltate composite electrode material with the flower-like multilevel structure, a dark-field scanning transmission electron micrograph (g) of the core-shell nickel cobaltate-manganese cobaltate composite electrode material with the flower-like multilevel structure, a composition imaging diagram of Ni, co, and Mn elements, and a composition overlapping imaging diagram of the Ni, co, and Mn elements.
Fig. 5 is a nitrogen adsorption-desorption graph of the flower-like multi-stage core-shell nickel cobaltate-manganese cobaltate composite electrode material obtained in example 1 of the present invention.
Fig. 6 shows the electrochemical properties of the flower-like multi-stage structured core-shell nickel cobaltate-manganese cobaltate composite electrode material obtained in example 1 of the present invention: (a) cyclic voltammetry curves at different sweep rates, (b) charging and discharging curves at different current densities, (c) corresponding capacitances at different current densities, and (d) corresponding to different sweep rates
15Ag -1 Stability curve after 5000 times of lower cycle charge and discharge.
Detailed Description
To better illustrate the invention, the following examples are given to further illustrate the invention without limiting its scope.
Example 1
(1) Adding 0.35mmol of nickel nitrate hexahydrate, 0.35mmol of manganese nitrate tetrahydrate and 0.70mmol of cobalt nitrate hexahydrate into a mixed solvent of 80mL of isopropanol and 16mL of glycerol, stirring, dissolving, uniformly mixing, transferring the reaction solution into a reaction kettle, carrying out solvothermal reaction for 6h at 180 ℃, naturally cooling to room temperature after the reaction is finished, carrying out centrifugal separation on the product, washing with absolute ethyl alcohol for several times, and drying to obtain the solid spherical nickel-manganese-cobalt precursor compound.
(2) 0.03g of the prepared solid spherical nickel-manganese-cobalt precursor compound was dispersed in 5.0mL of H 2 And (2) stirring and uniformly mixing the mixed solvent of O and 20mL of N-methylpyrrolidone, transferring the reaction solution into a reaction kettle, carrying out solvothermal reaction for 40min at 160 ℃, naturally cooling to room temperature after the reaction is finished, carrying out centrifugal separation on the product, washing for several times by using absolute ethyl alcohol, and drying to obtain the flower-shaped multi-stage structure core-shell precursor compound.
(3) Calcining the core-shell precursor compound with the flower-like multilevel structure at the high temperature of 500 ℃ for 2.0h in the air atmosphere, and naturally cooling to room temperature after the reaction is finished to obtain the core-shell nickel cobaltate-manganese cobaltate composite electrode material with the flower-like multilevel structure.
In fig. 2, a and b are sem pictures of the obtained nickel-manganese-cobalt precursor compound, and the microstructure thereof is a sphere having a diameter of about 1.0 μm, and c is sem picture thereof in fig. 2, confirming that the sphere has a solid structure and the surface of the sphere is smooth. In the attached drawing 2, d and e are scanning electron micrographs of a solid spherical nickel-manganese-cobalt precursor compound after etching, and it can be seen that the solid sphere is converted into a core-shell spherical structure after etching, and f is a transmission electron micrograph in the attached drawing 2, which shows that the shell in the core-shell structure is composed of nanosheets. After the core-shell precursor compound with the flower-like multilevel structure is calcined at the high temperature of 500 ℃ for 2 hours in the air, the X-ray powder diffraction pattern of the product is shown as the attached figure 3, and the diffraction peak and NiCo in the attached figure 3 2 O 4 (Standard cards JCPDS: 73-1702) and MnCo 2 O 4 (Standard card)JCPDS: 23-1237), indicating that the calcined product is made of NiCo 2 O 4 (Nickel cobaltate) and MnCo 2 O 4 (manganese cobaltate). In the attached figure 4, a and b are scanning electron micrographs of a nickel cobaltate-manganese cobaltate composite electrode material, and it can be found from the figure that the morphology of the obtained nickel cobaltate-manganese cobaltate still maintains a flower-like core-shell structure after the flower-like multi-stage structure core-shell precursor compound is calcined, and c and d in the transmission electron microscope figure 4 further show that the flower-like multi-stage structure nickel cobaltate-manganese cobaltate is a core-shell hollow structure. In FIG. 4, e is a high resolution TEM photograph of the core-shell nickel cobaltate-manganese cobaltate composite electrode material with flower-like multi-stage structure, and it can be seen that the lattice fringe spacing d is 0.285nm (e 1) and 0.456nm (e 2), which correspond to MnCo respectively 2 O 4 Crystal plane (220) of (NiCo) and NiCo 2 O 4 (111) crystal plane of (iii). The inset in FIG. 4f is the selected area electron diffraction pattern with diffraction ring 1 corresponding to MnCo 2 O 4 The (220) plane of (2) and the diffraction ring 2 correspond to MnCo 2 O 4 The (311) crystal face of (1) and the diffraction ring 3 correspond to MnCo 2 O 4 The (400) crystal face of the diffraction ring 4 corresponds to NiCo 2 O 4 The (511) plane of (F) and the diffraction ring 5 correspond to NiCo 2 O 4 The (440) crystal plane of (a) also confirms that the composite electrode material consists of nickel cobaltate-manganese cobaltate through an electron diffraction pattern. Fig. 4g is a dark-field scanning transmission electron micrograph and elemental composition imaging of the flower-like multi-stage structured core-shell nickel cobaltate-manganese cobaltate composite electrode material, and the results show that the Ni, co and Mn elements are uniformly distributed in the flower-like multi-stage structured core-shell nickel cobaltate-manganese cobaltate composite electrode material. It can be further seen from the composition imaging superposition graph of the elements that the three elements of Ni, co and Mn are uniformly distributed in the core-shell space structure of the flower-shaped multilevel structure. FIG. 5 is a nitrogen adsorption-desorption curve of a flower-shaped multi-stage structured core-shell nickel cobaltate-manganese cobaltate composite electrode material, and it can be known from the figure that the specific surface area of the flower-shaped multi-stage structured core-shell nickel cobaltate-manganese cobaltate composite electrode material is as high as 120.6m 2 ·g -1 . The core-shell nickel cobaltate-manganese cobaltate composite electrode material with the flower-like multilevel structure has a large specific surface area, can provide rich ion and electron transmission channels, and can effectively improve the electricity storage characteristics of the electrode material. Therefore, the number of the first and second electrodes is increased,the core-shell nickel cobaltate-manganese cobaltate composite electrode material with the flower-like multi-level structure has potential application prospects in a super capacitor. In the attached figure 6, a is a cyclic voltammetry curve of a flower-shaped multi-stage structured core-shell nickel cobaltate-manganese cobaltate composite electrode material at different sweep rates, and a pair of obvious redox peaks appear in all the curves, which shows that the electrode material is mainly based on a redox reaction mechanism in the storage and conversion of electric energy. B in FIG. 6 is a graph showing charge and discharge curves at different current densities, and c in FIG. 6 shows that the electrode material is at 4.0, 6.0, 10, 15 and 20 A.g -1 Then, the capacitance is 1636, 1494, 1310, 1100 and 940 F.g -1 . In FIG. 6, d is the charge-discharge cycle stability curve of the electrode material at 15A g -1 After 5000 times of charge-discharge cycles, the capacitance can still reach 984.5 F.g -1 This shows that the core-shell nickel cobaltate-manganese cobaltate composite electrode material with the flower-like multilevel structure has good long-cycle stability. In conclusion, the core-shell nickel cobaltate-manganese cobaltate composite electrode material with the flower-shaped multi-level structure has good application value in the aspect of electrochemical energy storage.
Example 2
(1) Adding 0.125mmol of nickel nitrate hexahydrate, 0.125mmol of manganese nitrate tetrahydrate and 0.25mmol of cobalt nitrate hexahydrate into a mixed solvent of 48mL of isopropanol and 48mL of glycerol, stirring, dissolving, uniformly mixing, transferring the reaction solution into a reaction kettle, carrying out solvothermal reaction for 6h at 200 ℃, naturally cooling to room temperature after the reaction is finished, carrying out centrifugal separation on the product, washing with absolute ethyl alcohol for several times, and drying to obtain the solid spherical nickel-manganese-cobalt precursor compound.
(2) 0.08g of the prepared solid spherical nickel-manganese-cobalt precursor compound was dispersed in 5mL of H 2 And (2) stirring and uniformly mixing O and 20mL of a mixed solvent of N, N-dimethylformamide, transferring the reaction solution into a reaction kettle, carrying out solvothermal reaction for 2 hours at the temperature of 160 ℃, naturally cooling to room temperature after the reaction is finished, carrying out centrifugal separation on a product, washing for several times by using absolute ethyl alcohol, and drying to obtain the flower-shaped multi-stage structural core-shell precursor compound.
(3) Calcining the core-shell precursor compound with the flower-like multilevel structure at the high temperature of 450 ℃ for 2.0h in the air atmosphere, and naturally cooling to room temperature after the reaction is finished to obtain the core-shell nickel cobaltate-manganese cobaltate composite electrode material with the flower-like multilevel structure.
Example 3
(1) Adding 0.25mmol of nickel nitrate hexahydrate, 0.25mmol of manganese nitrate tetrahydrate and 0.50mmol of cobalt nitrate hexahydrate into a mixed solvent of 60mL of isopropanol and 36mL of glycerol, stirring, dissolving, uniformly mixing, transferring the reaction solution into a reaction kettle, carrying out solvothermal reaction for 6h at 200 ℃, naturally cooling to room temperature after the reaction is finished, carrying out centrifugal separation on a product, washing with absolute ethyl alcohol for several times, and drying to obtain a solid spherical nickel-manganese-cobalt precursor compound.
(2) 0.03g of the prepared solid spherical nickel-manganese-cobalt precursor compound was dispersed in 5.0mL of H 2 And (2) stirring and uniformly mixing O and 20mL of N-methylpyrrolidone mixed solvent, transferring the reaction solution into a reaction kettle, carrying out solvothermal reaction for 2h at the temperature of 120 ℃, naturally cooling to room temperature after the reaction is finished, carrying out centrifugal separation on a product, washing for several times by using absolute ethyl alcohol, and drying to obtain the flower-shaped multi-stage structure core-shell precursor compound.
(3) Calcining the core-shell precursor compound with the flower-like multilevel structure at the high temperature of 500 ℃ for 2.0h in the air atmosphere, and naturally cooling to room temperature after the reaction is finished to obtain the core-shell nickel cobaltate-manganese cobaltate composite electrode material with the flower-like multilevel structure.
Example 4
(1) Adding 0.50mmol of nickel nitrate hexahydrate, 0.50mmol of manganese nitrate tetrahydrate and 1.0mmol of cobalt nitrate hexahydrate into a mixed solvent of 60mL of isopropanol and 36mL of ethylene glycol, stirring, dissolving, uniformly mixing, transferring the reaction solution into a reaction kettle, carrying out solvothermal reaction for 6h at 220 ℃, naturally cooling to room temperature after the reaction is finished, carrying out centrifugal separation on a product, washing with absolute ethyl alcohol for several times, and drying to obtain a solid spherical nickel-manganese-cobalt precursor compound.
(2) 0.05g of the prepared solid spherical nickel-manganese-cobalt precursor compound was dispersed in 20mL of H 2 Mixing O and 5.0mL of N-methylpyrrolidone, stirring and uniformly mixing, transferring the reaction solution into a reaction kettle, carrying out solvothermal reaction for 2 hours at 140 ℃, and naturally cooling after the reaction is finishedAnd (4) cooling to room temperature, centrifugally separating the product, washing with absolute ethyl alcohol for a plurality of times, and drying to obtain the flower-like multi-level structural core-shell precursor compound.
(3) Calcining the core-shell precursor compound with the flower-shaped multi-stage structure at the high temperature of 550 ℃ for 2.0h in the air atmosphere, and naturally cooling to room temperature after the reaction is finished to obtain the core-shell nickel cobaltate-manganese cobaltate composite electrode material with the flower-shaped multi-stage structure.
Claims (3)
1. The nickel cobaltate-manganese cobaltate composite electrode material is characterized by being of a core-shell structure with a flower-shaped multi-stage structure and prepared through the following steps:
1) Preparing a solid spherical nickel-manganese-cobalt precursor compound: adding nickel salt, manganese salt and cobalt salt into a mixed solvent of isopropanol and polyhydroxy alcohol, stirring, dissolving and uniformly mixing to prepare a reaction solution; transferring the reaction solution into a reaction kettle, heating for reaction, and naturally cooling to room temperature after the reaction is finished; centrifugally separating, washing and drying the product to obtain a solid spherical nickel-manganese-cobalt precursor compound;
2) Preparing a core-shell precursor compound with a flower-shaped multilevel structure: dispersing the solid spherical nickel-manganese-cobalt precursor compound prepared in the step 1) into water and an alkaline organic solvent, transferring the reaction solution into a reaction kettle, heating for reaction, and naturally cooling to room temperature after the reaction is finished; centrifugally separating, washing and drying the product to obtain a flower-like multi-stage structural core-shell precursor compound;
3) Preparing a core-shell nickel cobaltate-manganese cobaltate composite electrode material with a flower-like multilevel structure: calcining the flower-like multi-level structure core-shell precursor compound prepared in the step 2) in an air atmosphere to obtain the nickel cobaltate-manganese cobaltate composite electrode material.
2. The nickel-manganese cobaltate composite electrode material of claim 1, wherein the nickel salt is nickel nitrate hexahydrate, the manganese salt is manganese nitrate tetrahydrate, the cobalt salt is cobalt nitrate hexahydrate, the polyhydric alcohol is glycerol or ethylene glycol, and the alkaline organic solvent is glycerol or ethylene glycolN, N-Dimethylformamide orN-Methyl pyrrolidone.
3. The nickel cobaltate-manganese cobaltate composite electrode material as set forth in claim 1 or 2, wherein the concentration of the nickel salt in the reaction solution in the step (1) is 0.0013-0.0052 mol -1 The concentration of manganese salt is 0.0013-0.0052 mol -1 The concentration of cobalt salt is 0.0026-0.0104 mol -1 The molar ratio of the nickel salt, the manganese salt and the cobalt salt is 1:1:2, the volume ratio of the isopropanol to the polyhydroxy alcohol is 1-5: 1; the volume ratio of the water to the alkaline organic solvent in the step (2) is 1:4 to 4:1.
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