CN112661203B - Nano rod-like NiCo 2 O 4 Preparation method and application of material - Google Patents
Nano rod-like NiCo 2 O 4 Preparation method and application of material Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 43
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- 238000000034 method Methods 0.000 claims abstract description 19
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- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 5
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 5
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Images
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a nanorod NiCo 2 O 4 The preparation method of the material and the application thereof are that cobalt salt and 2-methylimidazole are subjected to hydrothermal reaction to obtain Co-ZIF, then the Co-ZIF is added into cobalt salt and nickel salt aqueous solution again to carry out hydrothermal reaction, then the mixture is calcined for 1 to 4 hours in air atmosphere at 300 to 550 ℃ to remove templates, then the mixture is washed by ethanol and deionized water, and finally the mixture is dried at 60 ℃ to obtain the rod-shaped NiCo 2 O 4 A material. The nano rod-shaped NiCo 2 O 4 The preparation process of the material is simple, the equipment investment is small, the preparation period is short, the cost is low, and the material is similar to NiCo prepared by other methods 2 O 4 The electrochemical performance of the material is more remarkable.
Description
Technical Field
The invention belongs to the technical field of nano materials, and in particular relates to a nano rod-shaped NiCo 2 O 4 A preparation method of the material.
Background
MOF structures composed of metal cation polymers linked by metal cations and organic ligand molecules have become research hotspots in energy storage, catalysis, chemical sensors, and drug delivery, due to their unique nanostructures. The Zeolite Imidazole Framework (ZIF) is one of MOFs, which has a large surface area, abundant micropores and redox reaction sites, and has attracted great attention in the field of electrochemical energy storage. However, MOF materials have the problem of poor conductivity, which not only hinders electron transfer between MOF particles, but also hinders the electron transfer level between the MOF-based active material and the electrode. So many researchers now combine MOF structures with conductive materials to improve their performance. In addition, the MOF material with the hollow structure has a unique hollow structure, and can greatly improve the migration and diffusion of electrons, thereby improving the catalytic performance of the carbon material. Therefore, the preparation of the metal ion doped hollow carbon material has important research significance.
There are many methods for preparing hollow nanostructures, such as template method, vapor deposition method, arc discharge method, etc., among which template method is more common. The method mainly uses certain polymer materials as a framework, grows a compound on the polymer materials through hydrothermal, solvothermal and other methods, and removes a framework template through a carbonization process so as to form a hollow structure.
Disclosure of Invention
The invention aims to provide a method with simple process, short production period,Excellent performance nano rod NiCo 2 O 4 Is prepared by the preparation method of (1).
The invention is realized in the following way: nano rod-like NiCo 2 O 4 The preparation method of the material comprises the following specific preparation processes:
1) Preparation of Co source framework: dissolving cobalt salt and 2-methylimidazole in a methanol solution, mixing, placing into an autoclave for hydrothermal reaction, washing and drying to obtain Co-ZIF for later use;
2) Preparing a precursor: placing Co-ZIF, cobalt salt, nickel salt and urea into deionized water, placing into an autoclave for hydrothermal reaction, washing and drying to obtain a precursor;
3) Preparing a finished product: placing the precursor in a porcelain boat for high-temperature calcination, and naturally cooling to room temperature to obtain rod-shaped NiCo 2 O 4 A material.
Further, the cobalt salt used was cobalt nitrate and the nickel salt used was nickel nitrate.
Further, in the step 1), when the Co source framework is prepared, the mass ratio of the cobalt salt to the 2-methylimidazole is 1:1-2.
Further, in the step 2), the molar ratio of cobalt salt to nickel salt is 1:0.5-2.
Further, in the step 1), the hydrothermal reaction temperature for preparing the cobalt source framework is 60-120 ℃, and the hydrothermal time is 6-12h.
Further, in the step 2), the temperature of the precursor prepared by the hydrothermal reaction is 60-120 ℃, and the hydrothermal time is 12-24 hours.
Further, in the step 3), the calcination temperature is 300-550 ℃, the calcination time is 1-4h, and the calcination atmosphere is air.
The beneficial effects of the invention are as follows:
the invention prepares Co-ZIF by hydrothermal method, then adds metal salt and charres to prepare rod-shaped NiCo 2 O 4 Nano material, niCo prepared by the method 2 O 4 When the nano material is applied to the anode material of the super capacitor, the electrode material with large specific capacitance and low pollution can be effectively generated, because the Co-ZIF has large specific surface area, enough redox sites can be provided and ion expansion can be acceleratedRate of dispersion, with NiCo 2 O 4 To a certain extent, contributes to improving the conductivity of the electrode, improving the coulombic efficiency and finally improving the electrochemical performance; in addition, the invention optimizes the reaction condition of the process, greatly simplifies the synthesis process and reduces the cost.
Drawings
FIG. 1 is a comparative view of the preparation process of examples and comparative examples;
FIG. 2 is an electron micrograph of a plurality of materials, wherein a is NiCo obtained in example 1 2 O 4 SEM electron micrograph of-1 (300 nm scale), b being NiCo 2 O 4 SEM electron micrograph of-1 (100 nm Scale), c is NiCo obtained in comparative example 1 2 O 4 SEM electron micrograph of-2, d is NiCo obtained in comparative example 2 2 O 4 SEM electron micrograph of-3, e is NiCo obtained in comparative example 3 2 O 4 -4 SEM electron micrograph, f is the SEM electron micrograph of Co-ZIF obtained in comparative example 4;
FIG. 3 is a TEM transmission diagram of various materials, where a is NiCo obtained in example 1 2 O 4 TEM transmission diagram of-1, b is NiCo obtained in comparative example 1 2 O 4 TEM transmission diagram of-2, c is NiCo obtained in comparative example 2 2 O 4 TEM transmission diagram of-3, d is NiCo obtained in comparative example 3 2 O 4 -4, e is a TEM transmission of the Co-ZIF prepared in comparative example 4;
FIG. 4 is an XRD pattern for various materials, where a is NiCo prepared in comparative example 1 2 O 4 XRD pattern of-2, b being NiCo prepared in comparative example 2 2 O 4 XRD pattern of-3, c is NiCo obtained in comparative example 3 2 O 4 -4, d is the XRD pattern of the Co-ZIF prepared in comparative example 4;
FIG. 5 is a NiCo obtained in example 1 2 O 4 -XRD pattern of 1;
FIG. 6 is a NiCo obtained in example 1 2 O 4 -XPS map of 1;
FIG. 7 shows charge and discharge patterns of various materials at different current densities, where a is NiCo prepared in example 1 2 O 4 Charging and discharging map of-1, b is NiCo prepared in comparative example 1 2 O 4 Charging and discharging electrogram of-2, c is NiCo prepared in comparative example 2 2 O 4 Charging and discharging map of-3, d is NiCo prepared in comparative example 3 2 O 4 Charging and discharging electrogram of-4, e is the charging and discharging electrogram of Co-ZIF prepared in comparative example 4;
FIG. 8 is a NiCo obtained in example 1 2 O 4 -1 NiCo prepared in comparative example 2 O 4 -2、NiCo 2 O 4 -3、NiCo 2 O 4 -4 and Co-ZIF made electrode materials applied to chemical capacitors.
Detailed Description
The following detailed description of the preferred embodiments of the invention is provided to enable those skilled in the art to more readily understand the advantages and features of the invention and to make a clear and concise definition of the scope of the invention.
Example 1
Nanorod-shaped material NiCo 2 O 4 -1, comprising the steps of:
(1) Preparation of Co-ZIF: weighing 2.9g of cobalt nitrate and 3.3g of 2-methylimidazole respectively dissolved in 20mL of methanol solution, mixing, placing into a 50mL autoclave, maintaining at 100 ℃ for 12 hours, washing with deionized water and ethanol, and drying at 60 ℃ for 12 hours;
(2) Preparing a precursor: weighing 0.2g of Co-ZIF,0.2908g of nickel nitrate, 0.5821g of cobalt nitrate and 0.3003g of urea, adding into 35mL of deionized water, placing into a 50mL autoclave, maintaining at 120 ℃ for 12h, centrifugally collecting, washing with water and ethanol, and drying at 60 ℃ for 12h;
(3) Preparation of the samples: and (3) placing the precursor in a porcelain boat, heating to 350 ℃ from room temperature at a speed of 1 ℃/min under an air atmosphere, calcining for 2 hours, and naturally cooling to the room temperature to obtain the sample.
FIG. 2 (a) shows NiCo obtained in this example 2 O 4 SEM electron micrograph of-1 (300 nm scale), FIG. 2 (b) is NiCo 2 O 4 SEM electron micrograph of-1 (100 nm scale), it can be seen from the two figures that the material has a rod-like structure.
Example 2
Nanorod-shaped material NiCo 2 O 4 The preparation method of (2) comprises the following steps:
(1) Preparation of Co-ZIF: weighing 2.9g of cobalt nitrate, respectively dissolving 3.3g of 2-methylimidazole in 20mL of methanol solution, putting into a 50mL autoclave, maintaining at 100 ℃ for 12 hours, washing with deionized water and ethanol, and drying at 60 ℃ for 12 hours;
(2) Preparing a precursor: weighing 0.2g of Co-ZIF, 0.1454g of nickel nitrate, 0.5821g of cobalt nitrate and 0.3003g of urea, adding into 35mL of deionized water, placing into a 50mL autoclave, maintaining at 120 ℃ for 6 hours, centrifugally collecting, washing with water and ethanol, drying at 60 ℃ for 12 hours, centrifugally collecting, washing with water and ethanol, and drying at 60 ℃ for 12 hours;
(3) Preparation of the samples: and (3) placing the precursor in a porcelain boat, heating to 300 ℃ from room temperature at a speed of 1 ℃/min under an air atmosphere, calcining for 4 hours, and naturally cooling to the room temperature to obtain the sample.
Example 3
Nanorod-shaped material NiCo 2 O 4 The preparation method of (2) comprises the following steps:
(1) Preparation of Co-ZIF: weighing 2.9g of cobalt nitrate, respectively dissolving 3.3g of 2-methylimidazole in 20mL of methanol solution, putting into a 50mL autoclave, maintaining at 120 ℃ for 6 hours, washing with deionized water and ethanol, and drying at 60 ℃ for 12 hours;
(2) Preparing a precursor: 0.2g of Co-ZIF,0.2908g of nickel nitrate, 0.2908g of cobalt nitrate and 0.3003g of urea were weighed into 35mL of deionized water, placed into a 50mL autoclave, kept at 60℃for 24 hours, centrifugally collected, washed with water and ethanol, and dried at 60℃for 12 hours. Washing with water and ethanol after centrifugal collection, and drying at 60 ℃ for 12 hours;
(3) Preparation of the samples: and placing the precursor in a porcelain boat, heating to 400 ℃ from room temperature at a speed of 1 ℃/min under the air, calcining for 2 hours, and naturally cooling to the room temperature to obtain the sample.
Example 4
Nanorod-shaped material NiCo 2 O 4 The preparation method of (2) comprises the following steps:
(1) Preparation of Co-ZIF: weighing 2.9g of cobalt nitrate, respectively dissolving 3.3g of 2-methylimidazole in 20mL of methanol solution, putting into a 50mL autoclave, maintaining at 100 ℃ for 12 hours, washing with deionized water and ethanol, and drying at 60 ℃ for 12 hours;
(2) Preparing a precursor: weighing 0.2g of Co-ZIF, 0.5821g of nickel nitrate, 0.5821g of cobalt nitrate and 0.3003g of urea, adding into 35mL of deionized water, placing into a 50mL autoclave, maintaining at 60 ℃ for 24 hours, centrifugally collecting, washing with water and ethanol, drying at 60 ℃ for 12 hours, centrifugally collecting, washing with water and ethanol, and drying at 60 ℃ for 12 hours;
(3)NiCo 2 O 4 preparation of Co-ZIF: and placing the precursor in a porcelain boat, heating to 500 ℃ from room temperature at a speed of 1 ℃/min under the air, calcining for 1h, and naturally cooling to room temperature to obtain the sample.
Comparative example 1
NiCo 2 O 4 -2 a process for the preparation of a material comprising the steps of:
(1) Preparation of Co-ZIF: weighing 2.9g of cobalt nitrate, respectively dissolving 3.3g of 2-methylimidazole in 20mL of methanol solution, putting into a 50mL autoclave, maintaining at 100 ℃ for 12 hours, washing with deionized water and ethanol, and drying at 60 ℃ for 12 hours;
(2) Preparing a precursor: weighing 0.2g of Co-ZIF,0.2908g of nickel nitrate and 0.3003g of urea, adding into 35mL of deionized water, placing into a 50mL autoclave, maintaining at 120 ℃ for 12 hours, centrifugally collecting, washing with water and ethanol, drying at 60 ℃ for 12 hours, centrifugally collecting, washing with water and ethanol, and drying at 60 ℃ for 12 hours;
(3) Preparation of the samples: and placing the precursor in a porcelain boat, heating to 350 ℃ from room temperature at a speed of 1 ℃/min under the air, calcining for 2 hours, and naturally cooling to the room temperature to obtain the sample.
Comparative example 2
NiCo 2 O 4 -3 a process for the preparation of a material comprising the steps of:
(1) Preparation of Co-ZIF: weighing 2.0g of cobalt nitrate, respectively dissolving 3.9g of 2-methylimidazole in 200mL of methanol solution, aging at room temperature for 24h, centrifugally collecting, and drying at 60 ℃ for 12h;
(2) Preparing a precursor: weighing 0.2g of Co-ZIF, dissolving 0.3g of nickel nitrate in 100mL of ethanol, stirring for 1h, centrifugally collecting, and drying at 60 ℃ for 12h;
(3) Preparation of the samples: and placing the precursor in a porcelain boat, heating to 350 ℃ from room temperature at a speed of 1 ℃/min under the air, calcining for 2 hours, and naturally cooling to the room temperature to obtain the sample.
Comparative example 3
NiCo 2 O 4 -3 a process for the preparation of a material comprising the steps of:
(1) Preparation of Co-ZIF: weighing 2.0g of cobalt nitrate, respectively dissolving 3.9g of 2-methylimidazole in 200mL of methanol solution, aging at room temperature for 24h, centrifugally collecting, and drying at 60 ℃ for 12h;
(2) Preparing a precursor: weighing 0.2g of Co-ZIF, dissolving 0.3g of nickel nitrate and 0.6004g of cobalt nitrate in 100mL of ethanol, stirring for 1h, centrifugally collecting, and drying at 60 ℃ for 12h;
(3) Preparation of the samples: and placing the precursor in a porcelain boat, heating to 350 ℃ from room temperature at a speed of 1 ℃/min under the air, calcining for 2 hours, and naturally cooling to the room temperature to obtain the sample.
Comparative example 4
The preparation method of the Co-ZIF comprises the following steps:
(1) Preparing a precursor: weighing 2.0g of cobalt nitrate, respectively dissolving 3.9g of 2-methylimidazole in 200mL of methanol solution, aging at room temperature for 24h, centrifugally collecting, and drying at 60 ℃ for 12h;
(2) Preparation of the samples: and placing the precursor in a porcelain boat, heating to 350 ℃ from room temperature at a speed of 1 ℃/min under the air, calcining for 2 hours, and naturally cooling to the room temperature to obtain the sample.
Correlation performance test
1. FIG. 2 a shows NiCo obtained in example 1 2 O 4 SEM electron micrograph of-1 (300 nm scale), the whole structure is bar-shaped, b is NiCo 2 O 4 SEM electron micrograph of-1 (100 nm Scale), c is NiCo obtained in comparative example 1 2 O 4 SEM electron micrograph of-2, the structure being a mixture of plate and rod-like structures, d being NiCo obtained in comparative example 2 2 O 4 SEM electron micrograph of-3, the structure being hollow, e being NiCo obtained in comparative example 3 2 O 4 -4, the structure is sheet-like, f is SEM electron micrograph of Co-ZIF (i.e. precursor of example 1) prepared in comparative example 4, the structure is polyhedral.
The rod-shaped NiCo obtained in example 1 2 O 4 The materials prepared in the other comparative examples have uniform morphology and small particles on the surface can increase the redox active sites, and such a structure helps to improve the electrochemical performance of the electrode material.
2. FIGS. 4 (a-d) are NiCo prepared in comparative examples 2 O 4 -2、NiCo 2 O 4 -3、NiCo 2 O 4 -XRD pattern of 4, ZIF-67. FIG. 5 is a NiCo obtained in example 1 2 O 4 -XRD pattern of 1, diffraction peak positions of about 2θ=19 °, 31 °, 37 °, 45 °, 55 °, 59 °, 65 °, corresponding crystals (111), (220), (311), (400), (422), (511), and (440), respectively.
As can be seen from the figure, XRD of the several materials obtained showed NiCo 2 O 4 Diffraction peaks of (JCPCDS: 73-1702). The diffraction peak of example 1 was clear and there was no impurity peak, indicating that the product prepared in example 1 was of higher purity and no impurity.
3. FIG. 6 is a NiCo obtained in example 1 2 O 4 The XPS pattern of-1 further illustrates the presence of Ni, co, O in the material, consistent with the XRD results.
4. The electrochemical performance test is completed on the Shanghai Chenhua CHI660 electrochemical workstation. A three-electrode system is adopted: the foam nickel uniformly coated with the prepared material is used as a working electrode, a platinum sheet electrode is used as a counter electrode, and a saturated calomel electrode is used as a reference electrode. In the experiments, all potentials were relative to the saturated calomel electrode, and all experiments were performed at room temperature. The working electrode is prepared by using Al before using 2 O 3 Powder
Repeatedly polishing on chamois leather, and sequentially using absolute ethanolAnd ultrasonically cleaning with distilled water, and airing for later use.
Electrode preparation: the resulting sample, acetylene black and PVDF were mixed at 8:1: mixing 1 by mass ratio with 2mL of isopropanol, performing ultrasonic treatment for 20min to fully dissolve the sample, drying overnight at a constant temperature of 60 ℃ in a vacuum drying oven, and performing electrochemical performance test of cyclic voltammetry and constant current charge and discharge in 6M KOH electrolyte.
The specific capacitances of example 1 and comparative examples 1 to 4 in the present invention were measured as shown in fig. 8, and the specific capacitance was calculated using the formula cs=i·Δt/m·Δv, where Cs is the specific capacitance (F/g), I is the current (a), Δt is the discharge time(s), m is the electrode material mass (g), Δv is the potential difference (V), and the specific capacitance means the amount of electricity that can be discharged per unit weight of the battery or active material.
FIG. 8 is a NiCo obtained in example 1 2 O 4 -1 NiCo prepared in comparative example 2 O 4 -2、NiCo 2 O 4 -3、NiCo 2 O 4 Comparison of specific capacitance data measured for electrode materials made of-4 and Co-ZIF for chemical capacitors, as seen in FIG. 8, the specific capacitance of the electrode of example 1 at a current density of 1A/g was 1376F/g; comparative example 1 electrode has a specific capacitance of 872F/g at a current density of 1A/g; comparative example 2 electrode has a specific capacitance of 416F/g at a current density of 1A/g; comparative example 3 electrode has a specific capacitance of 760F/g at a current density of 1A/g; comparative example 4 the electrode had a specific capacitance of 280F/g at a current density of 1A/g. To sum up rod-like NiCo 2 O 4 The specific capacitance of the electrode made of the material is larger than that of other materials.
The greatest difference of example 1 over the rest of the comparative examples is: the Co-ZIF is taken as a cobalt source framework, two different transition metal salts are added on the framework, and the Co-ZIF can combine different metal centers in the same framework and then is converted into uniform bimetallic organic framework crystals. The bi-metallic organic framework derived from Co-ZIF is not only structurally more complex than a single Co-ZIF structure, but also provides new functionality because the second metal ion replaces the original metal ion. The combination of Co-ZIF and transition metal not only solves the defect of poor conductivity of single MOF (Co-ZIF), but also solves the problem of poor electrochemical performance caused by easy volume expansion of transition metal oxide as electrode material in the charge and discharge process.
The foregoing description is only illustrative of the present invention and is not intended to limit the scope of the invention, and all equivalent structures or equivalent processes or direct or indirect application in other related technical fields are included in the scope of the present invention.
Claims (7)
1. Nano rod-like NiCo 2 O 4 The preparation method of the material is characterized by comprising the following specific preparation processes:
1) Preparation of Co source framework: dissolving cobalt salt and 2-methylimidazole in a methanol solution, mixing, placing into an autoclave for hydrothermal reaction, washing and drying to obtain Co-ZIF for later use;
2) Preparing a precursor: placing Co-ZIF, cobalt salt, nickel salt and urea into deionized water, placing into an autoclave for hydrothermal reaction, washing and drying to obtain a precursor;
3) Preparing a finished product: placing the precursor in a porcelain boat for high-temperature calcination, and naturally cooling to room temperature to obtain rod-shaped NiCo 2 O 4 A material.
2. The nanorod-like NiCo according to claim 1 2 O 4 The preparation method of the material is characterized in that cobalt nitrate is used as cobalt salt, and nickel nitrate is used as nickel salt.
3. The nanorod-like NiCo according to claim 1 2 O 4 The preparation method of the material is characterized in that in the step 1), when the Co source framework is prepared, the mass ratio of cobalt salt to 2-methylimidazole is 1:1-2.
4. The nanorod-like NiCo according to claim 1 2 O 4 The preparation method of the material is characterized in that in the step 2), the molar ratio of cobalt salt to nickel salt is 1:0.5-2.
5. The method for preparing Co-ZIF according to claim 1, wherein in the step 1), the hydrothermal reaction temperature for preparing the cobalt source skeleton is 60-120 ℃ and the hydrothermal time is 6-12h.
6. The nanorod-like NiCo according to claim 1 2 O 4 The preparation method of the material is characterized in that in the step 2), the temperature of the precursor prepared by the hydrothermal reaction is 60-120 ℃, and the hydrothermal time is 12-24 hours.
7. The nanorod-like NiCo according to claim 1 2 O 4 The preparation method of the material is characterized in that in the step 3), the calcination temperature is 300-550 ℃, the calcination time is 1-4h, and the calcination atmosphere is air.
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Application publication date: 20210416 Assignee: Jiangsu Ningda environmental protection Co.,Ltd. Assignor: JIANGSU University OF TECHNOLOGY Contract record no.: X2023980054656 Denomination of invention: Preparation method and application of a nano rod-shaped NiCo2O4material Granted publication date: 20230509 License type: Common License Record date: 20240103 |