CN114804219A - Flower-shaped transition metal oxide assembled by two-dimensional porous nanosheets and preparation method and application thereof - Google Patents
Flower-shaped transition metal oxide assembled by two-dimensional porous nanosheets and preparation method and application thereof Download PDFInfo
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- 239000002135 nanosheet Substances 0.000 title claims abstract description 61
- 229910000314 transition metal oxide Inorganic materials 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 17
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004202 carbamide Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- -1 transition metal salt Chemical class 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 239000012467 final product Substances 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 53
- 238000001354 calcination Methods 0.000 claims description 35
- 150000003624 transition metals Chemical class 0.000 claims description 28
- 229910052759 nickel Inorganic materials 0.000 claims description 27
- 229910017052 cobalt Inorganic materials 0.000 claims description 25
- 239000010941 cobalt Substances 0.000 claims description 25
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 25
- 239000011572 manganese Substances 0.000 claims description 25
- 229910052748 manganese Inorganic materials 0.000 claims description 25
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000004108 freeze drying Methods 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- 150000002823 nitrates Chemical class 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- 239000003990 capacitor Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 239000007772 electrode material Substances 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 8
- 239000000047 product Substances 0.000 abstract description 4
- 238000012983 electrochemical energy storage Methods 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 239000011148 porous material Substances 0.000 description 19
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 18
- 229910000480 nickel oxide Inorganic materials 0.000 description 11
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 11
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 5
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 102000020897 Formins Human genes 0.000 description 3
- 108091022623 Formins Proteins 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000007605 air drying Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- LQKOJSSIKZIEJC-UHFFFAOYSA-N manganese(2+) oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Mn+2].[Mn+2].[Mn+2].[Mn+2] LQKOJSSIKZIEJC-UHFFFAOYSA-N 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C01G53/00—Compounds of nickel
- C01G53/04—Oxides; Hydroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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Abstract
The invention discloses a flower-shaped transition metal oxide assembled by two-dimensional porous nanosheets, and a preparation method and application thereof; the preparation method of the metal oxidation comprises the following steps: firstly, ethanol is used as a solvent, transition metal salt and urea are used as solutes to prepare a precursor in a solvothermal system, and finally the precursor is calcined in a muffle furnace to prepare a final product. The preparation method provided by the invention has the advantages of low material price, high product purity, good dispersibility, controllable aperture, simple process steps, easiness in operation and certain universality. The flower-shaped transition metal oxide assembled by the two-dimensional porous nanosheets can be directly used as an electrode material of a supercapacitor, has excellent electrochemical behavior, and can be applied to occasions such as high stability and electrochemical energy storage devices.
Description
Technical Field
The invention relates to the technical field of preparation of electrode materials, in particular to a flower-shaped transition metal oxide assembled by two-dimensional porous nanosheets, and a preparation method and application thereof.
Background
Super capacitors have ultrahigh power density, excellent cycle performance and fast charging capability, and have received wide attention in many fields. The electrode material is one of the components of the super capacitor and plays a crucial role in the development of the super capacitor. In the electrode material, the porous metal oxide-based nano material has greater advantages in nano materials with different shapes and sizes, and the porous metal oxide-based nano material has the advantages of high theoretical capacitance, good redox reversibility, environmental friendliness and the like and is widely applied to the super capacitor. The low efficiency of the transport between the electrolyte and the electrode material limits the electrochemical performance of the metal oxide during the electrochemical reaction. Therefore, the research on the porous nano material is increasingly intensive, which utilizes the open space, high specific surface area and structural variability of the electrode material to improve the electrochemical performance of the electrode material. However, there is little concern about the effect of pore distribution in porous materials on improving electrochemical performance.
It is therefore an urgent problem to provide a porous material having an excellent pore distribution.
Disclosure of Invention
In view of the above, the invention discloses a flower-like transition metal oxide assembled by two-dimensional porous nanosheets, and a preparation method and application thereof. The problem that the transmission efficiency between the existing transition metal oxide and electrolyte is low is solved.
The technical scheme provided by the invention is specifically that, in a first aspect, the invention provides a preparation method of flower-shaped transition metal oxide assembled by two-dimensional porous nanosheets, which comprises the following steps:
1) preparing a precursor in a solvothermal system by taking transition metal salt and urea as solutes;
2) and calcining the precursor to obtain the final product flower-shaped transition metal oxide assembled by the two-dimensional porous nanosheets.
Preferably, in the step 1), the transition metal salt is one of nitrates of transition metals cobalt, manganese and nickel, the solvent used for the nitrates of the transition metals cobalt and manganese is methanol, and the solvent used for the nitrates of the transition metal nickel is ethanol.
Preferably, the method of preparing the precursor is: adding nitrates of transition metals cobalt and manganese and urea into a methanol solution, adding nitrates of transition metals nickel and urea into an ethanol solution, stirring for 1 hour to obtain a uniform mixed solution, transferring the mixed solution into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, sealing, putting into a forced air drying box, heating to 100 ℃ and 150 ℃, reacting for 5-15 hours, slowly cooling to room temperature, standing for at least 1 day, filtering, washing, and drying to obtain a precursor.
Wherein the drying after washing is freeze-drying.
Preferably, the calcining in step 2) is performed by: transferring the precursor obtained in the step 1) into a muffle furnace, heating to 300-500 ℃, calcining in air for 1-2h, washing, and freeze-drying.
In a second aspect, the invention provides a flower-like transition metal oxide assembled by two-dimensional porous nanosheets, and the flower-like transition metal oxide is prepared by the method.
In a third aspect, the invention provides application of a flower-shaped transition metal oxide assembled by two-dimensional porous nanosheets, wherein the metal oxide is applied to a supercapacitor.
The invention provides a preparation method of flower-shaped transition metal oxide assembled by two-dimensional porous nanosheets, which is low in material price, high in product purity, good in dispersity, controllable in pore size, simple in process steps, easy to operate and certain in universality. The flower-shaped transition metal oxide assembled by the two-dimensional porous nanosheets can be directly used as an electrode material of a supercapacitor, has excellent electrochemical behavior, and can be applied to occasions such as high stability and electrochemical energy storage devices.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the disclosure.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the invention and together with the description, serve to explain the principles of the invention.
In order to more clearly illustrate the embodiments or technical solutions in the prior art of the present invention, the drawings used in the description of the embodiments or prior art will be briefly described below, and it is obvious for those skilled in the art that other drawings can be obtained based on these drawings without creative efforts.
Fig. 1 is an XRD test pattern of flower-like transition metal (cobalt, manganese and nickel) oxides assembled from two-dimensional porous nanosheets provided by the present disclosure;
wherein, a is Co 3 O 4 ；b:MnO 2 ；c:NiO；
FIG. 2 is an SEM image of flower-like transition metal (cobalt, manganese and nickel) oxides assembled from two-dimensional porous nanosheets provided by the present disclosure;
wherein a, b is Co 3 O 4 ；c,d:MnO 2 ；e,f:NiO。
FIG. 3 is an XPS Survey spectrum of flower-like transition metal (cobalt, manganese and nickel) oxides assembled from two-dimensional porous nanosheets provided by the present disclosure;
wherein, a is Co 3 O 4 ；b:MnO 2 ；c:NiO；
FIG. 4 is a cyclic voltammetry curve of flower-like cobaltosic oxide assembled by two-dimensional porous nano-sheets provided by the present disclosure;
FIG. 5 is a constant current charge-discharge curve of flower-like cobaltosic oxide assembled by two-dimensional porous nano-sheets, provided by the present disclosure;
FIG. 6 is a diagram of a calcination mechanism of flower-like transition metal (cobalt, manganese and nickel) oxide assembled by two-dimensional porous nanosheets provided by the present disclosure;
FIG. 7 is SEM images of different calcination temperatures of flower-like cobaltosic oxide assembled by two-dimensional porous nano-sheets according to the invention;
wherein, a is 400 ℃; b, 450 ℃; c, 500 ℃;
FIG. 8 is SEM images of different calcination temperatures of flower-like manganese tetraoxide assembled by two-dimensional porous nano-sheets of the invention;
wherein, a is 300 ℃; b is 350 ℃; c, 400 ℃; b, 450 ℃; c, 500 ℃;
FIG. 9 is SEM images of different calcination temperatures of flower-like nickel tetroxide assembled by two-dimensional porous nano-sheets of the present invention;
wherein a and e are 400 ℃; b. f is 450 ℃; c. g, 500 ℃; d. h is 600 ℃;
11) fig. 10 is a graph of specific surface area and pore size analysis of flower-like nickel oxide assembled by two-dimensional porous nanosheets of the present invention at different calcination temperatures. Fig. 8 shows that the flaky surface area and pore size distribution of the flower-like nickel oxide assembled by the two-dimensional porous nanosheets obtained by the present invention are greatly different at different calcination temperatures, which indicates that the calcination temperature has a large influence on the surface area and the pore size distribution, and the surface area of the material is the largest when the calcination temperature is 450 ℃;
wherein, a is 400 ℃; b, 450 ℃; c, 500 ℃; d, 600 ℃.
Detailed Description
Reference will now be made in detail to the exemplary embodiments, examples of which are illustrated in the accompanying drawings. When the following description refers to the accompanying drawings, like numbers in different drawings represent the same or similar elements unless otherwise indicated. The embodiments described in the following exemplary embodiments do not represent all embodiments consistent with the present invention. Rather, they are merely examples of systems consistent with certain aspects of the invention, as detailed in the appended claims.
In order to solve a series of defects such as low transmission efficiency between a transition metal oxide and an electrolyte in the prior art, the embodiment provides a preparation method of a flower-shaped transition metal oxide assembled by two-dimensional porous nanosheets, which comprises the following steps:
1) sequentially adding transition metal salt and urea as solutes to prepare a precursor in a solvothermal system;
2) and calcining the precursor to obtain the final product flower-shaped transition metal oxide assembled by the two-dimensional porous nanosheets.
The method for preparing the precursor comprises the following steps: respectively adding transition metals of cobalt, manganese and urea into a methanol solution, adding nitrate of transition metal of nickel and urea into an ethanol solution, stirring for 1 hour to obtain a uniform mixed solution, transferring the mixed solution into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, sealing, putting into a forced air drying box, heating to 100 ℃ and 150 ℃, and reacting for 5-15 hours; preferably, the temperature is raised to 120 ℃, and the reaction is carried out for 12 hours; slowly cooling to room temperature, standing for at least 1 day, filtering, washing, and drying to obtain a precursor, wherein the washing and drying are freeze drying.
Because the cobalt oxide, the manganese oxide and the nickel oxide are adopted, the material has higher theoretical specific capacitance, and the material has excellent micropore and mesopore distribution, thereby being beneficial to charge accumulation and electrolyte ion transmission and improving the specific capacitance.
The concentrations of the cobalt nitrate, the manganese nitrate and the nickel nitrate are all 0.011 mol/L; after the urea is added into the absolute ethyl alcohol solution, the concentration is 0.03 mol/L.
The freeze drying specifically comprises: the resulting product was transferred to a lyophilizer for a period of 2 d.
The calcining method in the step 2) comprises the following steps: transferring the precursor obtained in the step 1) into a porcelain boat, placing the porcelain boat in a muffle furnace, heating to 300-500 ℃, calcining for 1-2h, and cooling to room temperature to obtain the flower-like transition metal (cobalt, manganese and nickel) oxide assembled by the two-dimensional porous nanosheets. Wherein the preferred calcining temperature of the cobalt oxide in the muffle furnace is 450 ℃ and the calcining time is 2 h.
The manganese oxide is calcined in a muffle furnace at the temperature of 400 ℃ for 2 h. The calcination temperature of the nickel oxide in a muffle furnace is 450 ℃, and the nickel oxide is calcined for 2 hours. The temperature rise speed of the muffle furnace is 5 ℃ for min -1 Rate of temperature decreaseAt 5 deg.C for min -1 。
The flower-shaped transition metal oxide assembled by the two-dimensional porous nanosheets prepared by the method is proved to be beneficial to the transmission of electrons due to the structural characteristics of the flower-shaped transition metal oxide;
the flower-shaped transition metal (cobalt, manganese and nickel) oxide assembled by the two-dimensional porous nanosheets is applied to a supercapacitor as an electrode material.
The invention selects transition metal (cobalt, manganese and nickel) nitrate, urea, absolute methanol and ethanol as raw materials, and adopts a solvothermal method to prepare the core-shell structure composite material. The method has the advantages of easy operation, low cost of raw materials, simple equipment and no pollution in the preparation process.
The invention will now be further illustrated with reference to specific examples, which are not intended to limit the scope of the invention.
Example 1
Preparation of flower-like transition metal (cobalt, manganese and nickel) oxide assembled by two-dimensional porous nanosheets:
respectively adding 0.011mol of transition metal (cobalt and manganese) nitrate and 0.03mol of urea into 1L of anhydrous methanol solution, adding 0.011mol of transition metal nickel nitrate and 0.03mol of urea into 1L of anhydrous ethanol solution, and stirring and mixing uniformly to obtain a mixed solution: cobalt nitrate-urea-methanol solution, manganese nitrate-urea-methanol solution, nickel nitrate-urea-ethanol solution; then the homogeneous mixed solutions were transferred to a polytetrafluoroethylene autoclave having a volume of 50mL, respectively. And sealing the reaction kettle and putting the reaction kettle into a blast drying box. Heating to make the temperature of the air-blast drying oven reach 120 ℃ from room temperature, raising the temperature at the rate of 2 ℃ for min-1, and keeping the temperature for 12 hours under the condition. Slowly cooling to room temperature, standing for at least 1 day to obtain precipitate; filtering, sequentially washing with water and ethanol for three times, drying in a freeze dryer for 2d, transferring the obtained product into a muffle furnace, heating to 400-450 deg.C in air atmosphere, and heating at 5 deg.C for 5 min -1 Calcining for 2h, cooling to room temperature, and finally obtaining three oxides of flower-shaped transition metals cobalt, manganese and nickel assembled by the two-dimensional porous nanosheets respectively.
(II) detection
1) The performance indexes are shown in Table 1
TABLE 1
| Material | Specific surface area (m) 2 g -1 ) | Pore volume (cm) 3 g -1 ) |
| Co 3 O 4 | 52.3 | 0.06 |
| MnO 2 | 56.9 | 0.102 |
| NiO | 117.96 | 0.43 |
As can be seen from table 1, the flower-like transition metal oxides (cobalt, manganese and nickel) assembled by the two-dimensional porous nanosheets all have large specific surface areas and pore volumes, which indicates that the flower-like transition metal oxides cobalt, manganese and nickel assembled by the two-dimensional porous nanosheets prepared by the universal method may have excellent performance as supercapacitor electrode materials.
2) Fig. 1 is an XRD pattern of flower-like transition metal (cobalt, manganese and nickel) oxides assembled from two-dimensional porous nanosheets. As can be seen from fig. 1, flower-like transition metal (cobalt, manganese and nickel) oxides assembled by two-dimensional porous nanosheets in the present invention were successfully prepared.
3) Fig. 2 is a Scanning Electron Microscope (SEM) photograph of flower-like transition metal (cobalt, manganese, and nickel) oxides assembled from two-dimensional porous nanosheets. As can be seen from FIG. 2, the metal oxides prepared by the present invention all exhibit a flower-like structure assembled in a sheet shape, and have a uniformly distributed pore structure on the sheet-like structure. As can be seen from FIG. 2a, the obtained cobaltosic oxide has a lamellar flower-like structure, the thickness of the nanosheet is about 10nm, and the diameter of the hole is about 7 nm. As can be seen from FIG. 2c, the resulting manganese dioxide exhibits a lamellar flower-like structure with a thickness of the nanosheets of about 8nm and pores of about 6nm in diameter. As can be seen from FIG. 2e, the obtained nickel oxide exhibits a lamellar flower-like structure, the thickness of the nanosheet is about 5nm, and the diameter of the hole is about 10 nm.
4) FIG. 3 is an XPS Survey spectrum of flower-like transition metal (cobalt, manganese and nickel) oxides assembled from two-dimensional porous nanosheets of the present invention. From the analysis of fig. 3, the flower-like transition metal (cobalt, manganese and nickel) oxide material assembled by the two-dimensional porous nanosheets obtained by the method is composed of two elements of Co and O, Mn and O, Ni and O respectively.
5) Fig. 4 is a cyclic voltammetry curve of flower-like cobaltosic oxide assembled by two-dimensional porous nanosheets of the present invention. Fig. 4 shows that the flower-like cobaltosic oxide assembled by the two-dimensional porous nanosheets exhibits mirror current response at different scanning speeds, and has an oxidation reduction peak, which indicates that the flower-like cobaltosic oxide has both double-layer capacitance characteristics and pseudo-capacitance characteristics. And shows good cycle performance under different sweeping speeds.
6) FIG. 5 is a constant current charge-discharge curve of flower-like cobaltosic oxide assembled by two-dimensional porous nano-sheets according to the invention. From FIG. 5, it can be seen that the composite electrode material obtained in the present invention is shown at 1A g -1 The longer discharge time at current density indicates that it has excellent charge storage characteristics.
7) FIG. 6 is a preparation mechanism diagram of flower-like transition metal (cobalt, manganese and nickel) oxide assembled by two-dimensional porous nano sheets. The pore size distribution of the nanosheet surface can be adjusted by the calcination temperature.
8) Fig. 7 is SEM images of different calcination temperatures of flower-like cobaltosic oxide assembled by two-dimensional porous nanosheets of the present invention. Fig. 7 shows that the pore size distribution of the flaky surface of the flower-like nickel oxide assembled by the two-dimensional porous nanosheets obtained by the present invention has a large difference at different calcination temperatures, which indicates that the calcination temperature has a large influence on the micro-morphology.
9) Fig. 8 is SEM images of different calcination temperatures of flower-like manganese tetraoxide assembled by two-dimensional porous nanosheets of the present invention. Fig. 8 shows that the pore size distribution of the flaky surface of the flower-like nickel oxide assembled by the two-dimensional porous nanosheets obtained by the present invention has a large difference at different calcination temperatures, which indicates that the calcination temperature has a large influence on the micro-morphology.
10) Fig. 9 is SEM images of different calcination temperatures of flower-like nickel tetroxide assembled by two-dimensional porous nanosheets of the present invention. Fig. 9 shows that the pore size distribution of the flaky surface of the flower-like nickel oxide assembled by the two-dimensional porous nanosheets obtained by the present invention has a large difference at different calcination temperatures, which indicates that the calcination temperature has a large influence on the micro-morphology.
11) Fig. 10 is a graph of specific surface area and pore size analysis of flower-like nickel oxide assembled by two-dimensional porous nanosheets of the present invention at different calcination temperatures. Fig. 10 shows that the flaky surface area and pore size distribution of the flower-like nickel oxide assembled by the two-dimensional porous nanosheets obtained by the present invention have large differences at different calcination temperatures, which indicates that the calcination temperature has a large influence on the surface area and pore size distribution differences, and the surface area of the material is the largest when the calcination temperature is 450 ℃.
Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. This application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claims.
It will be understood that the invention is not limited to the precise arrangements described above and shown in the drawings and that various modifications and changes may be made without departing from the scope thereof. The scope of the invention is limited only by the appended claims.
Claims (7)
1. A preparation method of flower-shaped transition metal oxide assembled by two-dimensional porous nanosheets is characterized by comprising the following steps:
1) preparing a precursor in a solvothermal system by taking transition metal salt and urea as solutes;
2) and calcining the precursor to obtain the final product flower-shaped transition metal oxide assembled by the two-dimensional porous nanosheets.
2. The method for preparing a flower-like transition metal oxide assembled by two-dimensional porous nanosheets according to claim 1, wherein the transition metal salt in step 1) is one of nitrates of transition metals cobalt, manganese and nickel, and the solvent used for the transition metals cobalt and manganese in the solvothermal system is methanol and the solvent used for the transition metal nickel is ethanol.
3. The preparation method of the flower-like transition metal oxide assembled by the two-dimensional porous nanosheets according to claim 2, wherein the method for preparing the precursor is: respectively adding nitrate of transition metal cobalt and manganese and urea into a methanol solution, or adding nitrate of transition metal nickel and urea into an ethanol solution, stirring for 1 hour to obtain a uniform mixed solution, transferring the mixed solution into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, sealing, putting into a blast drying box, heating to 100-150 ℃, reacting for 5-15 hours, slowly cooling to room temperature, standing for at least 1 day, filtering, washing, and drying to obtain a precursor.
4. The method for preparing flower-like transition metal oxide assembled by two-dimensional porous nanosheets according to claim 3, wherein the drying after washing is freeze-drying.
5. The preparation method of the flower-like transition metal oxide assembled by the two-dimensional porous nanosheets according to claim 2, wherein the calcination in step 2) is performed by: transferring the precursor obtained in the step 1) into a muffle furnace, heating to 300-500 ℃, calcining in air for 1-2h, washing, and freeze-drying.
6. A flower-like transition metal oxide assembled from two-dimensional porous nanosheets, prepared by the method of claims 1-5.
7. The application of the flower-shaped transition metal oxide assembled by the two-dimensional porous nanosheets is characterized in that the metal oxide is applied to a super capacitor.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103553151A (en) * | 2013-10-12 | 2014-02-05 | 上海工程技术大学 | Preparation method of super capacitor electrode material nickel oxide, |
| CN104701036A (en) * | 2015-03-27 | 2015-06-10 | 吉林化工学院 | Research of super-capacitor electrode material based on graded flowerlike NiCo2O4 |
| WO2015196865A1 (en) * | 2014-06-27 | 2015-12-30 | 江苏华东锂电技术研究院有限公司 | Method for preparing cobaltosic oxide |
| WO2018036001A1 (en) * | 2016-08-24 | 2018-03-01 | 福州大学 | Waxberry-shaped nickel cobalt oxide nanomaterial and preparation method therefor |
| US20210276883A1 (en) * | 2020-03-05 | 2021-09-09 | Northwestern Polytechnical University | Hierarchical porous honeycombed nickel oxide microsphere and preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103553151A (en) * | 2013-10-12 | 2014-02-05 | 上海工程技术大学 | Preparation method of super capacitor electrode material nickel oxide, |
| WO2015196865A1 (en) * | 2014-06-27 | 2015-12-30 | 江苏华东锂电技术研究院有限公司 | Method for preparing cobaltosic oxide |
| CN104701036A (en) * | 2015-03-27 | 2015-06-10 | 吉林化工学院 | Research of super-capacitor electrode material based on graded flowerlike NiCo2O4 |
| WO2018036001A1 (en) * | 2016-08-24 | 2018-03-01 | 福州大学 | Waxberry-shaped nickel cobalt oxide nanomaterial and preparation method therefor |
| US20210276883A1 (en) * | 2020-03-05 | 2021-09-09 | Northwestern Polytechnical University | Hierarchical porous honeycombed nickel oxide microsphere and preparation method thereof |
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