CN109616331B - Core-shell type nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material and preparation method thereof - Google Patents
Core-shell type nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material and preparation method thereof Download PDFInfo
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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Abstract
The invention discloses a nanoflower core-shell nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material and a preparation method thereof. The nano flower core-shell type nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material is MnCo2O4.5The nanometer flower is taken as the core, and the nickel hydroxide nanometer sheet grows uniformly on the surface of the nanometer flower, so that the nanometer flower core-shell type nickel hydroxide nanometer sheet/manganese cobalt oxide composite electrode material which has high specific capacity and charging and discharging stability and does not need a binder and a conductive agent is prepared, the nanometer flower core-shell type nickel hydroxide nanometer sheet/manganese cobalt oxide composite electrode material can be used in the field of supercapacitors, and the preparation process is simple, the operation is convenient, and the repeatability is high.
Description
Technical Field
The invention belongs to the technical field of supercapacitor material synthesis, and relates to a core-shell nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material and a preparation method thereof.
Background
In recent years, supercapacitors have been widely studied for their advantages of high specific capacity, high power density, long cycle life, portability, compactness, high safety, and the like. However, certain achievements are achieved on improving the energy storage performance such as specific capacity, power density, stability and energy density of the super capacitor. However, due to the rapid development and the progress of demand in society, people now have higher and higher requirements on the aspects of high efficiency, safety, intelligence and the like of the operation of electronic devices, and supercapacitors are one of the main energy devices, and the supercapacitors are generally divided into three types based on energy storage mechanisms and electrode material properties: (1) electrochemical double layer capacitors, in which the electron adsorption desorption (purely electrostatic process) is stored; (2) oxidation-reduction reactions occurring at the electrode surface based on different faraday capacitor charge storage mechanisms; (3) a hybrid capacitor combining two mechanisms. However, the capacitor energy density of the electric double layer is low, in contrast to faraday capacitor material due to the electric double layer material.
Key factors affecting capacitor performance are: electrode material, electrolyte and current collector matched with the electrode material, diaphragm, packaging preparation process and the like. Among them, the electrode material is the key of the super capacitor and is also the focus of the research of the super capacitor at present. Carbon-based materials, metal oxide materials and conductive polymer materials are the most widely studied of the three types of electrode materials. Among them, metal oxides can undergo rapid and reversible oxidation/reduction reactions, intercalation/deintercalation reactions or adsorption/desorption reactions in an electrochemical environment, and such reactions are the main forms of pseudocapacitance energy storage/release, so that the pseudocapacitor can store more than ten times of energy theoretically as much as an electric double layer capacitor, and thus, the pseudocapacitor is a hotspot for research in the field of capacitors nowadays. The study of transition metal oxides and their hydroxides (nickel manganese cobalt) is more important from the viewpoint of the active material as a main component of the electrode material.
Compared with carbon-based materials, nickel hydroxide is concerned because of higher specific capacitance, but the ion diffusion and the resistance of the nickel hydroxide hinder the use of the nickel hydroxide as an electrode material, and the problem still needs to be solved, and the reduction of the thickness dimension effectively reduces the ion diffusion resistance to improve the capacitance performance.
The prior art cn201810345079.x provides a preparation method of a composite electrode material, which comprises the following preparation steps: mixing soluble divalent nickel salt, soluble divalent cobalt salt, hexamethylenetetramine, lanthanum manganate and a solvent to obtain a mixed solution; adding foamed nickel into the mixed solution for hydrothermal reaction to obtain a precursor; and drying and annealing the precursor in sequence to obtain the composite electrode material. The core-shell nanoflower structure grows on the conductive substrate foamed nickel and is directly used as an electrode, the use of a conductive agent and a bonding agent in the traditional coating method is avoided, the extra contact resistance is reduced, and NiCo is used2O4And LaMnO3The synergistic effect of the two components widens the potential window and improves the energy density of the super capacitor.
The prior art CN201711481492.0 discloses a preparation method of a polyacrylonitrile/molybdenum disulfide composite material for a super capacitor. Will twoSodium molybdate hydrate (Na)2MoO4·2H2O), thiourea (CH)4N2S) and a polymethyl methacrylate/polyacrylonitrile (PMMA/PAN) core-shell structure are uniformly mixed, and the mixture is carbonized at high temperature after hydrothermal reaction to obtain the MoS2/PAN composite material. The preparation method disclosed by the invention adopts PMMA as a template to form a PAN hollow spherical structure with uniform large pores, and MoS2 nanoflower grows on the surface of the PAN, so that the electrolyte ions are conveniently transported, the specific surface area is higher, and a double electric layer is favorably formed.
Prior art CN201310443177.4 discloses a composition containing MnCo2O4.5The preparation method of the electrode material of the super capacitor. MnCo obtained by the method of the invention2O4.5As an electrode material of the super capacitor, the material reserves are abundant and easy to obtain, the price is low, and the super capacitor has high performance, large multiplying power performance and stable cycle performance.
In addition, at present, no report is provided about a nanoflower core-shell nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material.
Disclosure of Invention
One of the objects of the present invention is to provide a nanoflower core-shell nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material for solving the problems of low capacitance, poor cycle stability, etc. of manganese cobalt oxide. The nanometer flower core-shell type nickel hydroxide nanosheet/manganese cobalt oxide composite material has higher specific surface area and conductivity, has higher capacitance and charge-discharge stability when being used as a capacitor electrode material, and can be applied to the field of super capacitor electrodes.
The second purpose of the present invention is to provide a preparation method of the core-shell nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material, wherein the preparation method comprises the steps of preparing a nano flower core-shell nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material by using manganese cobalt oxide as a precursor, ammonium fluoride as a structure directing agent, nickel chloride as a nickel source, and urea as an external alkali under the promotion effect of the external alkali, wherein a hydrothermal-calcination-hydrothermal method is adopted to uniformly grow the nickel hydroxide nanosheet on the manganese cobalt oxideOn the cobalt oxide core, thereby solving MnCo2O4.5Poor conductivity and easy agglomeration; on the other hand, the nickel hydroxide is uniformly grown on MnCo2O4.5In the above, the problem of charge and discharge stability generated when the super capacitor is used is solved.
The invention relates to a nanometer flower core-shell type nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material, which is prepared from MnCo2O4.5As a nucleus, nickel hydroxide nanosheets were uniformly grown on the surface thereof.
The invention also provides the nano flower core-shell type nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material, which is characterized in that; the nano flower core-shell type nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material is MnCo2O4.5The nanometer flower is a core, nickel hydroxide nanometer sheets uniformly grow on the surface of the nanometer flower, and the nanometer flower core-shell type nickel hydroxide nanometer sheet/manganese cobalt oxide composite electrode material is prepared by the following steps:
(1) carrying out ultrasonic dispersion on cobalt chloride hexahydrate, manganese chloride tetrahydrate, ammonium fluoride and urea in deionized water uniformly (the power is 500-;
in the mixed solution, the components and the content are as follows according to the calculation of each liter:
(2) transferring the mixed solution obtained in the step (1) into a hydrothermal kettle, then adding foamed nickel with the length of 10mm multiplied by 50mm, carrying out hydrothermal reaction for 6 hours at the temperature of 100-140 ℃, washing the obtained foamed nickel with absolute ethyl alcohol and deionized water for several times, blowing the washed foamed nickel with nitrogen flow, and carrying out vacuum drying at the temperature of 70 ℃ for 12 hours;
(3) putting the foamed nickel prepared in the step (2) into a muffle furnace, and calcining for 1-3h at the temperature of 300-350 ℃ to obtain the loaded MnCo2O4.5The nickel foam of (4);
(4) adding the foamed nickel obtained in the step (3) into a mixed solution of nickel chloride hexahydrate, ammonium fluoride and urea, and then carrying out hydrothermal reaction at 160-; then washing the composite electrode material with absolute ethyl alcohol and ionized water for several times, drying the composite electrode material with nitrogen airflow, and performing vacuum drying at 70 ℃ for 12 hours to prepare the nanoflower core-shell nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material;
in the mixed solution, the components and the content are as follows according to the calculation of each liter:
as a preferred technical scheme of the invention, the mixed solution obtained in the steps (1) and (4) of the preparation process comprises the following components by weight per liter:
in the mixed solution in the step (1), the content of the components is as follows according to per liter:
in the mixed solution in the step (4), the content of the components is as follows according to per liter:
as a preferred technical scheme of the invention, the mixed solution obtained in the steps (1) and (4) of the preparation process comprises the following components by weight per liter:
in the mixed solution in the step (1), the content of the components is as follows according to per liter:
in the mixed solution in the step (4), the content of the components is as follows according to per liter:
as a preferred technical scheme of the invention, the mixed solution obtained in the steps (1) and (4) of the preparation process comprises the following components by weight per liter:
in the mixed solution in the step (1), the content of the components is as follows according to per liter:
in the mixed solution in the step (4), the content of the components is as follows according to per liter:
as a preferred technical scheme of the invention, the mixed solution obtained in the steps (1) and (4) of the preparation process comprises the following components by weight per liter:
in the mixed solution in the step (1), the content of the components is as follows according to per liter:
in the mixed solution in the step (4), the content of the components is as follows according to per liter:
as a preferred technical scheme of the invention, the preparation method comprises the following steps:
(1) mixing cobalt chloride hexahydrate, manganese chloride, ammonium fluoride and urea, and performing ultrasonic dispersion uniformly in deionized water to obtain a uniformly mixed solution;
(2) transferring the mixed solution obtained in the step (1) into a hydrothermal kettle, then adding 10mm multiplied by 50mm foamed nickel, carrying out hydrothermal reaction for 6h at the temperature of 100 ℃ and 140 ℃, washing the mixture for several times by using absolute ethyl alcohol and deionized water, blowing the mixture by using nitrogen airflow for drying, and carrying out vacuum drying;
(3) placing the foamed nickel prepared in the step (2) into a muffle furnace, controlling the temperature to be 300-350 ℃ under the condition of air, and calcining for 1-3h to prepare the supported MnCo2O4.5The nickel foam of (4);
(4) and (3) adding the foamed nickel obtained in the step (3) into a mixed solution of nickel chloride, ammonium fluoride and urea, carrying out hydrothermal reaction for 10-16 h at the temperature of 160-200 ℃, washing with absolute ethanol and ionized water for several times, blowing by using nitrogen gas flow, and finally carrying out vacuum drying for 12h at the temperature of 70 ℃, thereby preparing the nano flower core-shell type nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material.
The beneficial effects of the invention compared with the prior art comprise:
the obtained nano flower core-shell type nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material has high specific capacity and high charging and discharging stability, does not need a binder or a conductive agent, and can be used as a supercapacitor electrode material.
The preparation process of the nanometer flower core-shell type nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material is simple, convenient to operate and high in repeatability.
The nano flower core-shell type nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material is MnCo2O4.5The structure is a nanoflower structure, and the nickel hydroxide nanosheets uniformly grow on the core, so that the nickel hydroxide nanosheets are free of serious agglomeration, uniform in size and good in overall conductivity.
Furthermore, the nanometer flower core-shell type nickel hydroxide nanometer sheet/manganese cobalt oxide composite electrode material is characterized in that the nickel hydroxide nanometer sheet is uniformly attached to MnCo2O4.5The nanometer flower structure greatly weakens the MnCo2O4.5The agglomeration phenomenon appears, the nanoflower has no obvious agglomeration phenomenon, and the nanoflower presents a uniform nanoflower shapeThe composite electrode material has good conductivity, and gaps among the nanosheets greatly promote the transmission rate and the electron transfer rate of the electrolyte, so that the nanoflower core-shell nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material has high specific capacitance and charge-discharge stability.
Furthermore, according to the preparation method of the nano flower core-shell type nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material, the nano flower core-shell type nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material is prepared by a hydrothermal and calcining method, so that the preparation process is simple to operate, has low requirements on equipment, is easy to control the reaction process, has no pollution to the environment, has high repeatability, and is suitable for industrial production.
Drawings
FIG. 1 shows a nanoflower core-shell nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material, MnCo, obtained in example 12O4.5Nanoflower and comparative XRD patterns of nickel hydroxide alone.
FIG. 2 is a scanning electron micrograph of a polar material, wherein FIG. 2a shows the nanoflower MnCo obtained in example 12O4.5Scanning electron microscope images of the pole material; fig. 2b is a scanning electron microscope image of the nano flower core-shell type nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material obtained in example 1.
FIG. 3 is a cyclic voltammetry curve of the nanoflower core-shell nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material obtained in example 1, which is 5mV.s from inside to outside in sequence-1-50mV.s-1。
FIG. 4 shows the charging and discharging curves of the nano flower core-shell nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material obtained in example 1 under different currents, which are 20A g in sequence from left to right-1-3A g-1。
Fig. 5 is a cycle stability curve of the nanoflower core-shell nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material obtained in example 1.
FIG. 6 shows the nanoflower core-shell nickel hydroxide nanosheet/manganese cobalt oxide composite obtained in example 2The cyclic voltammetry curve of the electrode material is 5mV.s from inside to outside in sequence-1-50mV.s-1。
FIG. 7 is a cycle stability curve of the nano flower core-shell type nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material obtained in example 3, which is 5mV.s from inside to outside in sequence-1-60mV.s-1。
FIG. 8 is a charging and discharging curve of the nano flower core-shell nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material obtained in example 4 under different currents, which is 8A g from left to right in sequence-1-1A g-1。
Detailed Description
The invention will be further elucidated, without being limited, by the following specific embodiments, in conjunction with the accompanying drawings.
Example 1
The invention relates to a nanometer flower core-shell type nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material, which is prepared from MnCo2O4.5And (3) uniformly growing nickel hydroxide nanosheets on the surface of the core.
The invention also provides a preparation method of the nano flower core-shell type nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material, which comprises the following steps:
(1) carrying out ultrasonic dispersion on cobalt chloride hexahydrate, manganese chloride tetrahydrate, ammonium fluoride and urea in deionized water uniformly (the power is 500- & gt 600W) to obtain a uniformly mixed solution;
in the mixed solution, the components and the content are as follows according to the calculation of each liter:
(2) transferring the mixed solution obtained in the step (1) into a hydrothermal kettle, then adding 10mm multiplied by 50mm foamed nickel, carrying out hydrothermal reaction for 6 hours at 120 ℃, washing the mixture for several times by using absolute ethyl alcohol and deionized water, blowing the mixture by using nitrogen flow, and carrying out vacuum drying for 12 hours at 70 ℃;
(3) putting the foamed nickel prepared in the step (2) into a muffle furnace, and calcining at 350 DEG C2h, namely preparing the supported MnCo2O4.5The nickel foam of (4);
(4) adding the foamed nickel obtained in the step (3) into a mixed solution of nickel chloride hexahydrate, ammonium fluoride and urea, carrying out hydrothermal reaction for 12 hours at 180 ℃, washing with absolute ethanol and ionized water of the absolute ethanol for several times, blow-drying with nitrogen airflow, and finally carrying out vacuum drying for 12 hours at 70 ℃, thereby obtaining the nanoflower core-shell nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material;
in the mixed solution, the components and the content are as follows according to the calculation of each liter:
the resulting XRD pattern is shown in FIG. 1. As can be seen from FIG. 1, the above preparation method produces pure nickel hydroxide and MnCo2O4.5The composite material of (3) has no obvious impurity peak.
The scanning electron micrographs obtained are shown in FIGS. 2a and 2b, respectively. As can be seen from FIGS. 2a and 2b, the nickel hydroxide nanosheets uniformly grow on MnCo2O4.5Nano flowers; the prepared nanometer flower core-shell type nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material has good conductivity and is uniform in core-shell structure, so that the nanometer flower core-shell type nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material has a large specific surface area.
The prepared nano flower core-shell type nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material is used as a working electrode, a binder and a conductive agent are not needed, a three-electrode system (a platinum sheet electrode is used as a reference electrode, and silver chloride is used as a reference electrode) is selected for capacitance test, and the capacitance test is carried out in 2M KOH solution.
And (3) performing a cyclic stability performance test on the prepared nano flower core-shell type nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material at a scanning rate of 5-50 mV/s by adopting an electrochemical workstation, wherein the obtained cyclic voltammetry curve graph is shown in FIG. 3. As can be seen from FIG. 3, the obtained nanoflower core-shell nickel hydroxide nanosheet/manganese cobalt oxide composite material has good cycle performance and can be applied to the field of supercapacitor electrodes.
And (3) measuring the charge and discharge performance of the obtained nano flower core-shell type nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material at a current density of 3-20A/g by using an electrochemical workstation, wherein the obtained charge and discharge curve is shown in fig. 4. As can be seen from fig. 4, the nanoflower core-shell nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material has good charge and discharge properties when used as a supercapacitor electrode material.
A battery test system is adopted to perform a cycle stability test on the obtained nanoflower core-shell nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material, as shown in fig. 5. As can be seen from FIG. 5, the obtained nanoflower core-shell nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material has good cycling stability.
Example 2
The invention relates to a nanometer flower core-shell type nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material, which is prepared from MnCo2O4.5And (3) uniformly growing nickel hydroxide nanosheets on the surface of the core.
The invention also provides a preparation method of the nano flower core-shell type nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material, which comprises the following steps:
(1) carrying out ultrasonic dispersion on cobalt chloride hexahydrate, manganese chloride tetrahydrate, ammonium fluoride and urea in deionized water uniformly (the power is 500- & gt 600W) to obtain a uniformly mixed solution;
in the mixed solution, the components and the content are as follows according to the calculation of each liter:
(2) transferring the mixed solution obtained in the step (1) into a hydrothermal kettle, then adding 10mm multiplied by 50mm foamed nickel, carrying out hydrothermal reaction for 6 hours at 140 ℃, washing the mixture for several times by using absolute ethyl alcohol and deionized water, blowing the mixture by using nitrogen flow, and carrying out vacuum drying for 12 hours at 70 ℃;
(3) putting the foamed nickel prepared in the step (2) into a muffle furnace, and calcining for 3 hours at 350 ℃ to prepare the supported MnCo2O4.5The nickel foam of (4);
(4) adding the foamed nickel obtained in the step (3) into a mixed solution of nickel chloride hexahydrate, ammonium fluoride and urea, carrying out hydrothermal reaction for 12 hours at 200 ℃, washing with absolute ethanol and ionized water of the absolute ethanol for several times, blow-drying with nitrogen airflow, and finally carrying out vacuum drying for 12 hours at 70 ℃, thereby obtaining the nanoflower core-shell nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material;
in the mixed solution, the components and the content are as follows according to the calculation of each liter:
and (2) performing a cyclic stability performance test on the obtained nanoflower core-shell nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material at scanning rates of 5,10,20,30,40 and 50mV/s by using an electrochemical workstation, wherein an obtained cyclic voltammetry curve graph is shown in fig. 6, and as can be seen from fig. 6, the obtained nanoflower core-shell nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material has good cyclic performance and can be used as a supercapacitor electrode material.
Example 3
The invention relates to a nanometer flower core-shell type nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material, which is prepared from MnCo2O4.5And (3) uniformly growing nickel hydroxide nanosheets on the surface of the core.
The invention also provides a preparation method of the nano flower core-shell type nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material, which comprises the following steps:
(1) uniformly dispersing cobalt chloride hexahydrate, manganese chloride tetrahydrate, ammonium fluoride and urea in deionized water by ultrasonic dispersion under the ultrasonic condition of room temperature and the controlled power of 500-600W to obtain a mixed solution;
in the mixed solution, the components and the content are as follows according to the calculation of each liter:
(2) transferring the mixed solution obtained in the step (1) into a hydrothermal kettle, adding foamed nickel with the length of 1 x 5CM, carrying out hydrothermal reaction at 100 ℃ for 6 hours, washing the obtained foamed nickel with absolute ethyl alcohol and deionized water for several times, blowing the washed foamed nickel with nitrogen airflow, and drying the foamed nickel in vacuum for 12 hours at 70 ℃;
(3) and (3) putting the foamed nickel obtained in the step (2) into a muffle furnace, and calcining for 1h under the condition of air at the temperature of 300 ℃. Obtaining the loaded MnCo2O4.5The nickel foam of (4);
(4) adding the foamed nickel obtained in the step (3) into a mixed solution of nickel chloride hexahydrate, ammonium fluoride and urea, carrying out hydrothermal reaction for 16h at 160 ℃ to obtain foamed nickel, washing the foamed nickel with absolute ethanol and ionized water of the foamed nickel for several times, blowing the foamed nickel with nitrogen airflow for drying, and carrying out vacuum drying for 12h at 70 ℃ to obtain the nanoflower core-shell nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material;
in the mixed solution, the components and the content are as follows according to the calculation of each liter:
and (2) performing a cyclic stability performance test on the obtained nanoflower core-shell nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material at scanning rates of 5,10,20,30,40 and 50mV/s by using an electrochemical workstation, wherein an obtained cyclic voltammetry curve graph is shown in fig. 7, and as can be seen from fig. 7, the obtained nanoflower core-shell nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material has good cyclic performance and can be used as a supercapacitor electrode material.
Example 4
The invention relates to a nanometer flower core-shell type nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material, which is prepared from MnCo2O4.5And (3) uniformly growing nickel hydroxide nanosheets on the surface of the core.
The invention also provides a preparation method of the nano flower core-shell type nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material, which comprises the following steps:
(1) uniformly dispersing cobalt chloride hexahydrate, manganese chloride tetrahydrate, ammonium fluoride and urea in deionized water by ultrasonic dispersion under the ultrasonic condition of room temperature and the controlled power of 500-600W to obtain a mixed solution;
in the mixed solution, the components and the content are as follows according to the calculation of each liter:
(2) transferring the mixed solution obtained in the step (1) into a hydrothermal kettle, adding foamed nickel with the length of 1 × 5CM, carrying out hydrothermal reaction at 140 ℃ for 6 hours, washing the obtained foamed nickel with absolute ethyl alcohol and deionized water for several times, blowing the washed foamed nickel with nitrogen airflow, and drying the foamed nickel in vacuum for 12 hours at 70 ℃;
(3) and (3) putting the foamed nickel obtained in the step (2) into a muffle furnace, and calcining for 1h under the condition of air at the temperature of 300 ℃. Obtaining the loaded MnCo2O4.5The nickel foam of (4);
(4) adding the foamed nickel obtained in the step (3) into a mixed solution of nickel chloride hexahydrate, ammonium fluoride and urea, carrying out hydrothermal reaction for 16h at 160 ℃ to obtain foamed nickel, washing the foamed nickel with absolute ethanol and ionized water of the foamed nickel for several times, blowing the foamed nickel with nitrogen airflow for drying, and carrying out vacuum drying for 12h at 70 ℃ to obtain the nanoflower core-shell nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material;
in the mixed solution, the components and the content are as follows according to the calculation of each liter:
the charge and discharge performance of the obtained nano flower core-shell type nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material is measured by an electrochemical workstation when the current density is 1,2,3,5 and 8A/g, the obtained charge and discharge curve is shown in figure 4, and as can be seen from figure 4, the nano flower core-shell type nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material has good charge and discharge performance when being used as a supercapacitor electrode material.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple inferences or substitutions may be made without departing from the spirit of the invention and should be considered as falling within the scope of the invention.
Claims (6)
1. A nanometer flower core-shell type nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material is characterized in that; the nano flower core-shell type nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material is MnCo2O4.5The nanometer flower is a core, nickel hydroxide nanometer sheets uniformly grow on the surface of the nanometer flower, and the nanometer flower core-shell type nickel hydroxide nanometer sheet/manganese cobalt oxide composite electrode material is prepared by the following steps:
(1) carrying out ultrasonic dispersion on cobalt chloride hexahydrate, manganese chloride tetrahydrate, ammonium fluoride and urea in deionized water uniformly, wherein the ultrasonic power is 500-600W, so as to obtain a mixed solution;
in the mixed solution, the components and the content are as follows according to the calculation of each liter:
cobalt chloride hexahydrate 0.47g
0.15-0.25g of manganese chloride tetrahydrate
Ammonium fluoride 0.2g
0.6-1g of urea
The balance of deionized water;
(2) transferring the mixed solution obtained in the step (1) into a hydrothermal kettle, then adding foamed nickel with the length of 10mm multiplied by 50mm, carrying out hydrothermal reaction for 6 hours at the temperature of 100-140 ℃, washing the obtained foamed nickel with absolute ethyl alcohol and deionized water for several times, blowing the washed foamed nickel with nitrogen flow, and carrying out vacuum drying at the temperature of 70 ℃ for 12 hours;
(3) putting the foamed nickel prepared in the step (2) into a muffle furnace, and calcining for 1-3h at the temperature of 300-350 ℃ to obtain the loaded MnCo2O4.5The nickel foam of (4);
(4) adding the foamed nickel obtained in the step (3) into a mixed solution of nickel chloride hexahydrate, ammonium fluoride and urea, and then carrying out hydrothermal reaction at 160-; then washing the composite electrode material with absolute ethyl alcohol and ionized water for several times, drying the composite electrode material with nitrogen airflow, and performing vacuum drying at 70 ℃ for 12 hours to prepare the nanoflower core-shell nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material;
in the mixed solution, the components and the content are as follows according to the calculation of each liter:
0.47-0.7g of nickel chloride hexahydrate
Ammonium fluoride 0.2g
0.6-1g of urea
The balance being deionized water.
2. The nanoflower core-shell nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material of claim 1, wherein: in the mixed solution obtained in the step (1) and the step (4) in the preparation process, the content of the components is as follows in terms of per liter:
in the mixed solution in the step (1), the content of the components is as follows according to per liter:
cobalt chloride hexahydrate 0.47g
Manganese chloride tetrahydrate 0.15g
Ammonium fluoride 0.2g
0.6g of urea
The balance of deionized water;
in the mixed solution in the step (4), the content of the components is as follows according to per liter:
nickel chloride hexahydrate 0.47g
Ammonium fluoride 0.2g
0.6g of urea
The balance being deionized water.
3. The nanoflower core-shell nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material of claim 1, wherein: in the mixed solution obtained in the step (1) and the step (4) in the preparation process, the content of the components is as follows in terms of per liter:
in the mixed solution in the step (1), the content of the components is as follows according to per liter:
cobalt chloride hexahydrate 0.47g
Manganese chloride tetrahydrate 0.25g
Ammonium fluoride 0.2g
Urea 1g
The balance of deionized water;
in the mixed solution in the step (4), the content of the components is as follows according to per liter:
nickel chloride hexahydrate 0.7g
Ammonium fluoride 0.2g
Urea 1g
The balance being deionized water.
4. The nanoflower core-shell nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material of claim 1, wherein: in the mixed solution obtained in the step (1) and the step (4) in the preparation process, the content of the components is as follows in terms of per liter:
in the mixed solution in the step (1), the content of the components is as follows according to per liter:
cobalt chloride hexahydrate 0.47g
Manganese chloride tetrahydrate 0.2g
Ammonium fluoride 0.2g
0.8g of urea
The balance of deionized water;
in the mixed solution in the step (4), the content of the components is as follows according to per liter:
nickel chloride hexahydrate 0.58g
Ammonium fluoride 0.2g
0.8g of urea
The balance being deionized water.
5. The nanoflower core-shell nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material of claim 1, wherein: in the mixed solution obtained in the step (1) and the step (4) in the preparation process, the content of the components is as follows in terms of per liter:
in the mixed solution in the step (1), the content of the components is as follows according to per liter:
cobalt chloride hexahydrate 0.47g
Manganese chloride tetrahydrate 0.2g
Ammonium fluoride 0.2g
Urea 1g
The balance of deionized water;
in the mixed solution in the step (4), the content of the components is as follows according to per liter:
nickel chloride hexahydrate 0.58g
Ammonium fluoride 0.2g
Urea 1g
The balance being deionized water.
6. The nanoflower core-shell nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material of any one of claims 1 to 5, wherein the preparation method comprises the following steps:
(1) mixing cobalt chloride hexahydrate, manganese chloride, ammonium fluoride and urea, and performing ultrasonic dispersion uniformly in deionized water to obtain a uniformly mixed solution;
(2) transferring the mixed solution obtained in the step (1) into a hydrothermal kettle, then adding 10mm multiplied by 50mm foamed nickel, carrying out hydrothermal reaction for 6h at the temperature of 100 ℃ and 140 ℃, washing the mixture for several times by using absolute ethyl alcohol and deionized water, blowing the mixture by using nitrogen airflow for drying, and carrying out vacuum drying;
(3) placing the foamed nickel prepared in the step (2) into a muffle furnace, controlling the temperature to be 300-350 ℃ under the condition of air, and calcining for 1-3h to prepare the supported MnCo2O4.5The nickel foam of (4);
(4) and (3) adding the foamed nickel obtained in the step (3) into a mixed solution of nickel chloride, ammonium fluoride and urea, carrying out hydrothermal reaction for 10-16 h at the temperature of 160-200 ℃, washing with absolute ethanol and ionized water for several times, blowing by using nitrogen gas flow, and finally carrying out vacuum drying for 12h at the temperature of 70 ℃, thereby preparing the nano flower core-shell type nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material.
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