CN109273274B - NiMnO3 electrode material with high specific surface area and preparation method and application thereof - Google Patents

NiMnO3 electrode material with high specific surface area and preparation method and application thereof Download PDF

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CN109273274B
CN109273274B CN201811109904.2A CN201811109904A CN109273274B CN 109273274 B CN109273274 B CN 109273274B CN 201811109904 A CN201811109904 A CN 201811109904A CN 109273274 B CN109273274 B CN 109273274B
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mixed solution
nimno
electrode material
specific surface
surface area
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CN109273274A (en
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黄乃宝
乔少明
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Dalian Maritime University
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their material
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/24Electrodes 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their material
    • H01G11/46Metal oxides
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13Energy storage using capacitors

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  • Power Engineering (AREA)
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  • Chemical & Material Sciences (AREA)
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Abstract

The invention relates to NiMnO with a high specific surface area3An electrode material and a preparation method and application thereof, belonging to the field of electrode materials. NiMnO with high specific surface area3The preparation method of the electrode material comprises the steps of dissolving potassium permanganate, nickel nitrate, urea and ammonium fluoride in water to form a mixed solution; placing the mixed solution in a microwave hydrothermal reaction kettle, and reacting for 2-5 h at 120-200 ℃ to obtain powder; and (3) carrying out heat treatment on the powder under the air condition to obtain the powder. NiMnO prepared using the method of the present invention3The electrode material is a flower-shaped nanosheet, has a high specific surface area, contains more crystal defects, increases effective active sites of the material, provides more sites for the material to undergo redox, and improves the capacitance characteristic of the material essentially.

Description

NiMnO with high specific surface area3Electrode material and preparation method and application thereof
Technical Field
The invention relates to NiMnO with a high specific surface area3An electrode material and a preparation method and application thereof, belonging to the field of electrode materials.
Background
With the continuous deterioration of climate and the use of a large amount of energy, the search for an efficient energy storage technology has been highly valued by researchers in various countries. Super capacitor is a new type of energy storage device, and has higher energy density than traditional capacitor, higher power density and cycle life than battery. As one of the main devices of the super capacitor, the electrode material is currently researched mainly in three aspects: transition metal oxides, carbon materials, and conductive polymers. The transition metal oxide belongs to a pseudo-capacitance electrode material, and has higher specific volume compared with a carbon material because the stored energy generates redox reaction through the surface of the material; the transition metal oxide is less prone to change in shape during continuous charge/discharge, and therefore has a better cycle life than conductive polymers. The most studied are the transition metal oxide electrode materials.
However NiMnO3As one of the materials of the super capacitor, the related research is less, and the method for improving the material mainly aims to improve the conductivity of the material and increase the specific surface area of the material. Currently, the main research in the two aspects is NiMnO3The material is compounded with a high-conductivity material, so that the electrochemical performance of the material is improved; on the other hand, the research on NiMnO3The specific surface area of the material is increased by adjusting the shape of the materialThe effective active sites are increased, the oxidation-reduction reaction is increased, the charge storage capacity is increased, and the performance of the material is improved.
Disclosure of Invention
To improve NiMnO3The electrochemical performance of the material is substantially improved, and the capacitive characteristic of the material is essentially improved3A preparation method of the electrode material. The invention aims to provide the flower-shaped NiMnO with simple and convenient operation, high yield and high specific surface area for preparing the super capacitor3A preparation method of the electrode material.
NiMnO with high specific surface area3The preparation method of the electrode material comprises the steps of dissolving potassium permanganate, nickel nitrate, urea and ammonium fluoride in water to form a mixed solution; placing the mixed solution in a microwave hydrothermal reaction kettle, reacting for 2-5 h at 120-200 ℃, cooling at room temperature after the reaction is finished, standing, centrifugally cleaning, and drying to obtain powder; carrying out heat treatment on the powder under the air condition to obtain the powder, wherein the heat treatment condition is as follows: heating to 350-650 ℃ from room temperature at the heating rate of 2-5 ℃/min, keeping the temperature for 1-2 h, and cooling to room temperature along with the furnace.
The urea concentration in the mixed solution is 0.4 mol/L-1.0 mol/L, the ammonium fluoride concentration is 0.1 mol/L-0.8 mol/L, the potassium permanganate concentration is 2.0 g/L-8.5 g/L, and the molar ratio of the potassium permanganate to the nickel nitrate is 1: 1-3: 1.
In the above technical solution, preferably, the potassium permanganate and the nickel nitrate in the mixed solution are disposed in an atomic ratio of Ni/Mn to 1: 1.
In the technical scheme, potassium permanganate, nickel nitrate, urea and ammonium fluoride are dissolved in water to form a mixed solution; and placing the mixed solution into a microwave hydrothermal reaction kettle, and reacting for 2-5 h in the microwave hydrothermal reactor at the temperature of 120-200 ℃.
Preferably, after dissolving potassium permanganate, nickel nitrate, urea and ammonium fluoride in water at room temperature, continuously stirring for 30-60 min at the rotating speed of 500-700 rpm to obtain a fully dissolved mixed solution.
Preferably, the volume ratio of the mixed solution to the reaction kettle is 30:100, the mixed solution is placed in a 100ml microwave reaction kettle, the microwave heating is carried out in a microwave hydrothermal reactor at the temperature of 120-200 ℃ for 1-5 h, the reactor is cooled to room temperature, and the mixed solution is taken out.
Preferably, deionized water and ethanol solution are respectively used for centrifugal cleaning for 3 times under the conditions that the rotating speed is 3500 rpm and the time is 4 min; the powder was dried at 60 ℃ for 12h and ground to the desired particle size.
Preferably, the mixed solution is placed in a microwave hydrothermal reaction kettle and reacted for 3 hours at 160 ℃.
Preferably, the temperature is raised to 450 ℃ from the room temperature at the heating rate of 2 ℃/min, and the temperature is kept for 2h and then cooled to the room temperature along with the furnace.
Preferably, the concentration of urea in the mixed solution is 0.4 mol/L, the concentration of ammonium fluoride is 0.2 mol/L, the concentration of potassium permanganate is 5.3 g/L, and the concentration of nickel nitrate is 9.7 g/L.
Another object of the present invention is to provide NiMnO of high specific surface area prepared by the above method3An electrode material.
The NiMnO of the invention3The electrode material is a flower-shaped nano sheet.
The NiMnO of the invention3The electrode material is a porous material, and the aperture is 2-35 nm.
The NiMnO of the invention3The specific surface area of the electrode material was 74.9m2/g,
It is still another object of the present invention to provide NiMnO prepared by the above method3The electrode material is applied as the electrode material of the super capacitor.
The invention has the beneficial effects that: NiMnO prepared using the method of the present invention3The electrode material is a flower-shaped nanosheet, has a high specific surface area, contains more crystal defects, increases effective active sites of the material, provides more sites for the material to undergo redox, and improves the capacitance characteristic of the material essentially. Meanwhile, the material has good conductivity and cycling stability, and is an ideal electrode material of the super capacitor. The NiMnO3 electrode material prepared by the method is simple to operate, time and energy consumption are greatly saved, and the flow is lessThe method has the advantages of low equipment investment and good repeatability, and is convenient for solving the problem of difficult large-scale production.
Drawings
FIGS. 1(a) and (b) are high specific surface area NiMnO prepared in example 1 of the present invention3SEM photograph of the electrode material; as can be seen from FIG. 1(a) under a low power mirror, NiMnO was prepared3The appearance of the electrode material is composed of a single flower-shaped appearance, and other appearances are not included; as can be seen from the high power lens in FIG. 1(b), the flower-like structure is composed of a plurality of nanosheets, and the specific surface area of the material is greatly increased by the structure.
FIGS. 2(a) - (d) are high specific surface area NiMnO prepared in example 1 of the present invention3TEM photographs of the electrode material; FIGS. 2(a) and (b) further demonstrate NiMnO3The electrode material is in the shape of flower-shaped nanosheets; from the selected area electron diffraction pattern (fig. 2(c)), the material has a good diffraction ring, which proves that the prepared material has good crystallinity; FIG. 2 (d) shows local diffraction fringes after the material morphology is enlarged, and the results are matched with the XRD results by measuring that the lattice spacing is respectively 0.492nm, 0.293nm and 0.208nm corresponding to the crystal planes (111), (121) and (-111).
FIG. 3 is a NiMnO of high specific surface area prepared in example 1 of the present invention3An X-ray diffraction pattern of the electrode material; it can be seen from FIG. 3 that the diffraction peaks mainly at 28.8 °, 39.5 °, 42.8 °, 49.1 °, 59.6 °, 65.0 °, and 78.3 ° correspond to NiMnO3(JCPDS #75-2089) planes (110), (121), (-110), (120), (220), (231), (-211) indicating NiMnO3The material was successfully prepared and had good crystallinity.
FIGS. 4(a) and (b) are high specific surface area NiMnO prepared in example 1 of the present invention3Specific surface area test result pictures of the electrode materials; FIG. 4 shows NiMnO3Specific surface area test results of the electrode material are shown. The left figure is N of the material2The absorption/desorption curve shows that the material is a typical IV type curve, H3 type hysteresis loop, and further proves that the nano flaky structure has the specific surface area of 74.9m2(ii)/g; the right panel is the pore size distribution of the material, it can be seen that the pore size distribution is primarily between 2.0 and 35 nm.
FIG. 5 shows NiMnO of high specific surface area prepared in example 1 of the present invention3The material is used as a cyclic voltammetry curve of an electrode material at different scanning speeds. It can be seen from fig. 5 that, when the material is changed from the low scanning speed to the high scanning speed, the cyclic voltammetry curve shape of the prepared material does not change greatly, which indicates that the material has good rate capability and higher specific volume, and the existence of the redox peak indicates that the material belongs to the pseudocapacitance material.
Detailed Description
The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way.
The test methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1
1) Accurately weighing 1mmol of nickel nitrate, 1mmol of potassium permanganate, 6mmol of ammonium fluoride and 12mmol of urea, pouring into 30ml of deionized water, placing on a magnetic stirrer at room temperature, and stirring at the rotating speed of 700 rpm for 30min to obtain a uniformly mixed solution;
2) pouring the obtained mixed solution into a 100ml microwave hydrothermal reaction kettle, and putting the kettle into a microwave hydrothermal reactor for hydrothermal reaction; the hydrothermal condition is that the reaction is carried out for 3 hours at the temperature of 160 ℃, after the reaction is finished, the reaction kettle is cooled to the room temperature in the reactor and taken out;
3) standing the obtained solution after the hydrothermal reaction for 12h, then carrying out centrifugal cleaning, respectively cleaning with deionized water and ethanol for multiple times under the conditions that the rotating speed is 3500 r/min and the time is 4min, drying the obtained powder at the constant temperature of 60 ℃ for 12h, taking out and grinding the powder until the average particle size is 100-300 nm;
4) and (3) putting the ground powder into a muffle furnace under the air condition for heat treatment, wherein the heat procedure is as follows: heating to 450 ℃ from room temperature at a heating rate of 2 ℃/min, keeping the temperature for 2h, cooling to room temperature along with the furnace, and taking out to obtain black flower-shaped nano-sheet NiMnO with high specific surface area3And (3) powder.
Example 2
1) Accurately weighing 1mmol of nickel nitrate, 2mmol of potassium permanganate, 6mmol of ammonium fluoride and 12mmol of urea, pouring into 30ml of deionized water, placing on a magnetic stirrer at room temperature, and stirring at the rotating speed of 700 rpm for 30min to obtain a uniformly mixed solution;
2) pouring the obtained mixed solution into a 100ml microwave hydrothermal reaction kettle, and putting the kettle into a microwave hydrothermal reactor for hydrothermal reaction; the hydrothermal condition is that the reaction is carried out for 3 hours at the temperature of 160 ℃, after the reaction is finished, the reaction kettle is cooled to the room temperature in the reactor and taken out;
3) standing the obtained solution after the hydrothermal reaction for 12h, then carrying out centrifugal cleaning, respectively cleaning with deionized water and ethanol for multiple times under the conditions that the rotating speed is 3500 r/min and the time is 4min, drying the obtained powder at the constant temperature of 60 ℃ for 12h, taking out and grinding the powder until the average particle size is 100-300 nm;
4) and (3) putting the ground powder into a muffle furnace under the air condition for heat treatment, wherein the heat procedure is as follows: heating to 450 ℃ from room temperature at a heating rate of 2 ℃/min, keeping the temperature for 2h, cooling to room temperature along with the furnace, and taking out to obtain black flower-shaped nano-sheet NiMnO with high specific surface area3And (3) powder.
Example 3
1) Accurately weighing 1mmol of nickel nitrate, 1mmol of potassium permanganate, 6mmol of ammonium fluoride and 12mmol of urea, pouring into 30ml of deionized water, placing on a magnetic stirrer at room temperature, and stirring at the rotating speed of 700 rpm for 30min to obtain a uniformly mixed solution;
2) pouring the obtained mixed solution into a 100ml microwave hydrothermal reaction kettle, and putting the kettle into a microwave hydrothermal reactor for hydrothermal reaction; the hydrothermal condition is that the reaction is carried out for 4 hours at the temperature of 160 ℃, after the reaction is finished, the reaction kettle is cooled to the room temperature in the reactor and taken out;
3) standing the obtained solution after the hydrothermal reaction for 12h, then carrying out centrifugal cleaning, respectively cleaning with deionized water and ethanol for multiple times under the conditions that the rotating speed is 3500 r/min and the time is 4min, drying the obtained powder at the constant temperature of 60 ℃ for 12h, taking out and grinding the powder until the average particle size is 100-300 nm;
4) will be groundPutting the ground powder into a muffle furnace under the air condition for heat treatment, wherein the heat procedure is as follows: heating to 450 ℃ from room temperature at a heating rate of 2 ℃/min, keeping the temperature for 2h, cooling to room temperature along with the furnace, and taking out to obtain black flower-shaped nano-sheet NiMnO with high specific surface area3And (3) powder.
Application example
Porous nano NiMnO prepared in example 13The material, conductive agent active carbon (XC-72), binder (mixed liquid formed by polyvinylidene fluoride (PVDF) and N-methyl pyrrolidone (NMP) in a mass ratio of 1: 4) are mixed into slurry according to a mass ratio of 8: 1:1, the slurry is coated on foamed nickel to prepare an electrode, the electrolyte is 6 mol/L KOH solution, and a three-electrode measurement system is adopted.

Claims (10)

1. NiMnO with high specific surface area3The preparation method of the electrode material is characterized by comprising the following steps: dissolving potassium permanganate, nickel nitrate, urea and ammonium fluoride in water to form a mixed solution; placing the mixed solution in a microwave hydrothermal reaction kettle, reacting for 2-5 h at 120-200 ℃, cooling at room temperature after the reaction is finished, standing, centrifugally cleaning, and drying to obtain powder; carrying out heat treatment on the powder under the air condition to obtain the powder, wherein the heat treatment condition is as follows: heating to 350-650 ℃ from room temperature at the heating rate of 2-5 ℃/min, keeping the temperature for 1-2 h, cooling to room temperature along with the furnace,
wherein the concentration of urea in the mixed solution is 0.4 mol/L-1.0 mol/L, the concentration of ammonium fluoride is 0.1 mol/L-0.8 mol/L, the concentration of potassium permanganate is 2.0 g/L-8.5 g/L, the molar ratio of potassium permanganate to nickel nitrate is 1:1,
the NiMnO3The electrode material is a porous material, and the aperture is 2-35 nm; the NiMnO3The specific surface area of the electrode material was 74.9m2/g。
2. The method of claim 1, wherein: at room temperature, dissolving potassium permanganate, nickel nitrate, urea and ammonium fluoride in water, and then continuously stirring for 30-60 min at the rotating speed of 500-700 rpm to obtain a fully dissolved mixed solution.
3. The method of claim 1, wherein: putting the mixed solution into a 100ml microwave reaction kettle according to the volume ratio of the mixed solution to the reaction kettle of 30:100, heating the mixed solution in a microwave hydrothermal reactor at the temperature of 120-200 ℃ for 1-5 h by microwave, cooling the mixed solution in the reactor to room temperature, and taking out the cooled mixed solution.
4. The method of claim 1, wherein: respectively using deionized water and an ethanol solution to centrifugally clean for 3 times under the conditions that the rotating speed is 3500 rpm and the time is 4 min; and drying the powder for 8-24 h at the temperature of 20-100 ℃, and taking out and grinding the powder to the required particle size.
5. The method of claim 1, wherein: and (3) placing the mixed solution in a microwave hydrothermal reaction kettle, and reacting for 3 hours at 160 ℃.
6. The method of claim 1, wherein: the heat treatment conditions are as follows: heating to 450 ℃ from room temperature at the heating rate of 2 ℃/min, preserving heat for 2h, and cooling to room temperature along with the furnace.
7. The method of claim 1, wherein the mixed solution contains urea at a concentration of 0.4 mol/L, ammonium fluoride at a concentration of 0.2 mol/L, potassium permanganate at a concentration of 5.3 g/L, and nickel nitrate at a concentration of 9.7 g/L.
8. NiMnO with high specific surface area prepared by the method of any one of claims 1 to 73An electrode material.
9. The electrode material according to claim 8, wherein: the NiMnO3The electrode material is a porous material, and the aperture is 2-35 nm; the NiMnO3The specific surface area of the electrode material was 74.9m2/g。
10. The NiMnO of claim 83Electrode material as super capacitorApplication of the pole material.
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Inventor after: Yang Guogang

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