CN110648861A - In-situ growth of braided porous channel NiCo2O4Method of nanosheet - Google Patents
In-situ growth of braided porous channel NiCo2O4Method of nanosheet Download PDFInfo
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- 239000002135 nanosheet Substances 0.000 title claims abstract description 24
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 95
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 43
- 239000000758 substrate Substances 0.000 claims abstract description 29
- 229910003266 NiCo Inorganic materials 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- 229910005949 NiCo2O4 Inorganic materials 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 239000006260 foam Substances 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 238000004140 cleaning Methods 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 7
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000002064 nanoplatelet Substances 0.000 claims description 6
- 238000000137 annealing Methods 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 5
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 4
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 239000007772 electrode material Substances 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 8
- 239000002070 nanowire Substances 0.000 abstract description 6
- 238000004146 energy storage Methods 0.000 abstract description 4
- 239000011148 porous material Substances 0.000 abstract description 4
- 239000003990 capacitor Substances 0.000 abstract description 3
- 239000011149 active material Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000000151 deposition Methods 0.000 abstract 1
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 238000005406 washing Methods 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- -1 nano needles Substances 0.000 description 3
- YTBWYQYUOZHUKJ-UHFFFAOYSA-N oxocobalt;oxonickel Chemical compound [Co]=O.[Ni]=O YTBWYQYUOZHUKJ-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000002057 nanoflower Substances 0.000 description 2
- 239000002073 nanorod Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- OVARTBFNCCXQKS-UHFFFAOYSA-N propan-2-one;hydrate Chemical compound O.CC(C)=O OVARTBFNCCXQKS-UHFFFAOYSA-N 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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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- H—ELECTRICITY
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/13—Energy storage using capacitors
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Abstract
The invention discloses an in-situ growth braided porous channel NiCo2O4The method of the nano-sheet comprises the steps of firstly, uniformly growing a layer of villiform pore canals with anisotropic structures on a foam nickel substrate through low-temperature oil bath, and then depositing and growing anisotropic NiCo in the pore canals by combining a high-temperature hydrothermal method2O4And finally, the nanowires are interwoven to form an in-situ grown self-woven structure in a high-temperature and high-pressure environment. The self-woven mat-shaped structure not only has the characteristics of the nano-sheets and provides a large number of active sites for the growth of active materials, but also has a mat-shaped structure formed by mutually interweaving the nano-sheets,the stability of the electrode material structure can be obviously improved, the service life of the material can be prolonged, and the application of the electrode material in the field of energy storage is widened. The method has the advantages of simple process, short production period and easy control, and provides a new idea for the research in the field of pseudo-capacitor material structure design.
Description
Technical Field
The invention belongs to the technical field of super capacitors, and particularly relates to an in-situ grown braided porous NiCo2O4A method of nanoplatelets.
Background
In recent years, transition metal oxides have been widely studied as electrode materials for the preparation of high energy density pseudocapacitive supercapacitors. This is because the transition metal oxide has multiple valence states of the element, which can provide a higher specific capacitance (Csp) than the conductive polymer. Wherein, NiCo is used2O4Is most commonly used because of spinel nickel cobalt ore (NiCo)2O4) Has high theoretical capacitance (1370F g 1), environment-friendly property, better electronic conductivity and high electrochemical activity (Ni)2+/Ni3+And Co2+/Co3+Redox couple), etc.
As part of a full supercapacitor device, the electrode material is considered to be a key component affecting the electrochemical performance of the supercapacitor. Therefore, in terms of improving the performance of the pseudo capacitor, the structural design of the electrode material is an effective means for improving the capacitive performance of the device. With respect to the structural morphology of the material, the electrode material having a hierarchical/porous structure can increase the specific surface area, improve the contact area between the electrode and the electrolyte, shorten the diffusion path of electrolyte ions, and enhance the structural stability. Three-dimensional (3D) structures may exhibit better cycling performance compared to one-dimensional (1D) and two-dimensional (2D) structures, as 3D features are advantageous to accommodate structural changes and efficient ion and electron diffusion.
NiCo with the shapes of nano thin slices, nano particles, nano needles, nano flowers, nano wires, nano rods and the like prepared by the predecessors before research2O4There are no 3D structures, but they are fundamentally assembled into 3D nanoflowers by 2D nanosheets only, or into 3D echinoid structures by 1D nanowires. No studies have been reported on a binder-free electrode material having characteristics such as an excellent conductivity of a 1D structure, a growth site having a rich 2D structure, and a spatial structure having an excellent 3D structure.
Disclosure of Invention
The invention aims to provide an in-situ grown braided porous channel NiCo2O4A method of nanoplatelets.
Aiming at the purposes, the technical scheme adopted by the invention comprises the following steps:
1. at normal temperature, ultrasonically dipping a foamed nickel substrate in 1-3 mol/L acetone aqueous solution for 20-40 minutes, and then ultrasonically dipping in 5-10% hydrochloric acid for 20-40 minutes; and after soaking, repeatedly cleaning the foamed nickel substrate to be neutral by using absolute ethyl alcohol and deionized water, and drying the cleaned foamed nickel substrate in vacuum at the temperature of 80-100 ℃.
2. Soaking the foamed nickel substrate subjected to vacuum drying in the step 1 in a pretreatment solution, and heating and reacting for 30-120 minutes at 80-110 ℃, wherein the pretreatment solution contains 0.3-0.5 mmol/L of Ni (NO)3)2、0.5～1mmol/L Co(NO3)2、1.0～1.5mmol/L NH4NO3And a 1-5% volume concentration aqueous solution of dimethyl sulfoxide; and after the reaction is finished, repeatedly ultrasonically cleaning the foamed nickel substrate by using deionized water and absolute ethyl alcohol, and drying to obtain the pretreated foamed nickel substrate.
3. Dipping the foamed nickel substrate pretreated in the step 2 into a solution containing 0.5-1 mmol/L Co (NO)3)2、0.3～0.5mmol/L NiCl20.2-0.4 mmol/L hexadecyl trimethyl ammonium bromide and 1-1.5 mmol/L urea, carrying out hydrothermal reaction at 80-110 ℃ for 5-8 hours, and ultrasonically cleaning with absolute ethyl alcohol and deionized water after the reaction is finished, and drying.
4. Annealing the foamed nickel substrate obtained in the step 3 at 250-400 ℃ for 1-4 hours in an air atmosphere to obtain braided porous NiCo2O4Nanosheets.
In the step 1, at normal temperature, preferably, the foamed nickel substrate is ultrasonically immersed in 2mol/L acetone aqueous solution for 30 minutes, and then ultrasonically immersed in hydrochloric acid with the mass concentration of 7-8% for 30 minutes, wherein the ultrasonic power is 100W.
In the step 2, preferably, the foamed nickel substrate dried in vacuum in the step 1 is soaked in the pretreatment solution, and is heated and reacted for 60 to 90 minutes at 90 to 100 ℃.
In the step 2, the pretreatment solution preferably contains 0.35 to 0.40mmol/L of Ni (NO)3)2、0.7～0.8mmol/L Co(NO3)2、1.12～1.13mmol/L NH4NO3And 2-3% volume concentration dimethyl sulfoxide aqueous solution.
In the step 3, preferably, the foamed nickel substrate pretreated in the step 2 is immersed in a solution containing 0.7 to 0.8mmol/L Co (NO)3)2、0.35～0.40mmol/L NiCl20.3 to 0.4mmol/L hexadecyl trimethyl ammonium bromide and 1.3 to 1.5mol/L urea, and carrying out hydrothermal reaction at 90 to 100 ℃ for 6 to 7 hours.
In the step 4, the acicular nickel-cobalt bimetal hydroxide foamed nickel substrate grown in the step 3 is preferably annealed for 2-3 hours at 300-320 ℃ in an air atmosphere, and the temperature rise rate of the annealing is 1-5 ℃/min.
The invention has the following beneficial effects:
1. NiCo grown in situ according to the invention2O4The use of no adhesive is beneficial to improving the conductivity of the electrode material, and meanwhile, the generation of 'dead volume' capacitance is reduced, and the energy storage device is easy to process.
2. The invention relates to a self-woven mat-shaped structure NiCo through in-situ growth2O4The nano-sheets not only have the characteristics of nano-wires, but also have the characteristics of nano-sheets, provide a large number of active sites for the growth of active materials, and simultaneously, the nano-sheets are made of NiCo2O4The nanowires are formed in a linear arrangement, and a large number of gaps exist between the wires, so that a transmission path is shortened for the transmission of ions in the electrolyte. Moreover, the mat-shaped structure formed by interweaving the nano sheets can effectively relieve the volume expansion problem of the electrode material in the charging and discharging process, remarkably improve the structural stability of the electrode material, prolong the service life of the material and widen the application of the electrode material in the field of energy storage.
3. The invention prepares NiCo with common characteristics of one-dimensional nano-wire, two-dimensional nano-sheet and three-dimensional self-weaving structure for the first time2O4The method has the advantages of simple process, short production period and easy control, and provides a new idea for the research in the field of pseudocapacitance material structure design.
Drawings
FIG. 1 is a scanning electron micrograph of a foamed nickel substrate after pretreatment in example 1 (wherein (b) is a partial enlarged view of (a)).
FIG. 2 shows a woven porous NiCo channel obtained in example 12O4Scanning electron micrographs of the nanoplatelets (where (b) is a partial magnified view of (a)).
FIG. 3 shows a woven porous NiCo channel obtained in example 12O4X-ray diffraction pattern of the nanoplatelets.
FIG. 4 shows a braided porous channel NiCo obtained in example 12O4Cycling stability curve of the nanoplatelets.
Detailed Description
The present invention will be described in further detail with reference to the following drawings and examples, but the scope of the present invention is not limited to the following examples.
Example 1
1. Cutting the foamed nickel into square sheets with the specification of 1cm multiplied by 0.25cm, then placing the cut foamed nickel in 2mol/L acetone water solution for ultrasonic immersion for 30min at normal temperature, and then placing the foamed nickel in hydrochloric acid with the mass concentration of 7% for immersion for 30min, wherein the ultrasonic power is 100W; after the impregnation, the foam nickel is repeatedly cleaned to be neutral by using absolute ethyl alcohol and deionized water, and the cleaned foam nickel is dried for 1 hour in a vacuum drying oven at the temperature of 90 ℃.
2. Soaking the foamed nickel dried in the step 1 in 20mL of pretreatment solution containing 0.375mmol/L Ni (NO)3)2、0.75mmol/L Co(NO3)2、1.125mmol/L NH4NO3And heating the aqueous solution of dimethyl sulfoxide with the volume concentration of 2.5% in an oil bath at 90 ℃ for reaction for 60min, repeatedly ultrasonically cleaning the sample for several times by using deionized water and absolute ethyl alcohol after the reaction is finished, and drying the sample in an oven at 60 ℃ for 2h to obtain the pretreated foamed nickel.
3. Immersing the foamed nickel substrate pretreated in the step 2 in 20mL of solution containing 0.75mmol/L Co (NO)3)2、0.375mol/L NiCl20.3mol/L hexadecyl trimethyl ammonium bromide and 1.35mol/L urea in polytetrafluoroethyleneAnd (3) in a lined reaction kettle, standing at 100 ℃ under a sealed condition for hydrothermal reaction for 6 hours, after the reaction is finished, cleaning with absolute ethyl alcohol and deionized water in a 40W ultrasonic cleaning instrument for 5 minutes each time, repeatedly cleaning for 3 times, and drying in an oven at 80 ℃ for 3 hours at constant temperature.
4. Putting the sample obtained in the step 3 into a tube furnace, heating to 300 ℃ at the speed of 1 ℃/min in the air atmosphere, preserving heat for 2h, carrying out high-temperature annealing treatment on the sample, taking out the sample, cleaning the sample for 5min each time in a 40W ultrasonic cleaning instrument by using deionized water and absolute ethyl alcohol after the sample is recovered to the room temperature, repeatedly cleaning the sample for 3 times, then putting the cleaned sample into an oven at the temperature of 80 ℃ and drying the cleaned sample for 3h to obtain the braided porous NiCo with porous channels2O4Nanosheets.
For the braided porous NiCo channel obtained above2O4SEM representation is carried out on the nanosheets, and the results are shown in the figures 1-2. As can be seen from fig. 1, a layer of Ni — Co precursor with a villiated three-dimensional porous structure is uniformly grown on the surface of the nickel foam, fig. 2 compares with the sample surface of fig. 1, nickel cobalt oxide with a sheet structure is uniformly distributed, and it is further clearly observed from the enlargement of fig. 2(b), the nanosheets are formed by orderly arranged nanorods (needles), and due to the three-dimensional porous channel structure grown on the surface of the pretreated nickel foam, under the reaction conditions of high pressure and high temperature, the nucleation and growth angles of the combination products have anisotropic characteristics, so that the generation of the nano needle-like nickel cobalt oxide is caused, and the nano needle-like nickel cobalt oxide is interwoven to form a porous channel structure similar to a woven mat shape. The pore size of 50-200 nm can be estimated from the partial enlarged view and belongs to the ultra-large pore. In order to confirm the phase of the sample, XRD characterization was performed, and the results are shown in fig. 3. As can be seen from FIG. 3, four characteristic diffraction peaks, with NiCo, appear at 31 °, 36.5 °, 59.3 ° and 65.1 ° 2 θ2O4The characteristic peaks of (JCPDS: 87-0712) are consistent, and the rest three characteristic diffraction peaks of 44.5 degrees, 51.8 degrees and 76.4 degrees are consistent with the foam nickel. The electrochemical cycling stability was further tested and the results are shown in figure 4. As shown in fig. 4, at 3A g-1At a current density of < 1 >, 5000 cycles of charge-discharge test was carried out on the sample, which had an initial capacity retention of 85%, as compared with the literature (Electrochimica Acta,2013,106: 2)26-234; rsc Advances,2015,5:33146-33154), the braided porous channel NiCo2O4The chemical structure is stable. The research shows that the structure can obviously improve the stability of the material and the service life of the material, and broadens the application of the material in the field of energy storage.
Example 2
1. This step is the same as step 1 of example 1.
2. Soaking the foamed nickel dried in the step 1 in 20mL of pretreatment solution containing 0.375mmol/L Ni (NO)3)2、0.75mmol/L Co(NO3)2、1.125mmol/L NH4NO3And heating the aqueous solution of dimethyl sulfoxide with the volume concentration of 2.5% in an oil bath at 100 ℃ for 30min for reaction, repeatedly ultrasonically cleaning the sample for several times by using deionized water and absolute ethyl alcohol after the reaction is finished, and drying the sample in an oven at 60 ℃ for 2h to obtain the pretreated foamed nickel.
3. Immersing the foamed nickel substrate pretreated in the step 2 in 20mL of solution containing 0.75mmol/L Co (NO)3)2、0.375mol/L NiCl2The preparation method comprises the following steps of standing in a reaction kettle with a polytetrafluoroethylene lining and an aqueous solution of 0.3mol/L hexadecyl trimethyl ammonium bromide and 1.35mol/L urea under a closed condition at 100 ℃ for hydrothermal reaction for 8 hours, washing the reaction product with absolute ethyl alcohol and deionized water in a 40W ultrasonic cleaner for 5min each time after the reaction is finished, repeatedly washing the reaction product for 3 times, and drying the reaction product in an oven at 80 ℃ for 3 hours at constant temperature.
4. The procedure was the same as that of example 1, step 4, to obtain a braided porous NiCo channel2O4Nanosheets.
Example 3
1. This step is the same as step 1 of example 1.
2. Soaking the foamed nickel dried in the step 1 in 20mL of pretreatment solution containing 0.375mmol/L Ni (NO)3)2、0.75mmol/L Co(NO3)2、1.125mmol/L NH4NO3Heating the aqueous solution of dimethyl sulfoxide with the volume concentration of 2.5 percent in an oil bath at 100 ℃ for 90min for reaction, and after the reaction is finished, using deionized water and anhydrousAnd (3) repeatedly ultrasonically cleaning the sample by using ethanol for several times, and then drying the sample in an oven at 60 ℃ for 2h to obtain the pretreated foamed nickel.
3. Immersing the foamed nickel substrate pretreated in the step 2 in 20mL of solution containing 0.75mmol/L Co (NO)3)2、0.375mol/L NiCl2The preparation method comprises the following steps of standing in a reaction kettle with a polytetrafluoroethylene lining and an aqueous solution of 0.3mol/L hexadecyl trimethyl ammonium bromide and 1.35mol/L urea under a closed condition at 100 ℃ for hydrothermal reaction for 5 hours, washing with absolute ethyl alcohol and deionized water in a 40W ultrasonic cleaning instrument for 5 minutes each time after the reaction is finished, repeatedly washing for 3 times, and drying in an oven at 80 ℃ for 3 hours at constant temperature.
4. The procedure was the same as that of example 1, step 4, to obtain a braided porous NiCo channel2O4Nanosheets.
Claims (7)
1. In-situ growth braided porous channel NiCo2O4A method of nanoplatelets characterized in that the method consists of the steps of:
(1) at normal temperature, ultrasonically dipping a foamed nickel substrate in 1-3 mol/L acetone aqueous solution for 20-40 minutes, and then ultrasonically dipping in 5-10% hydrochloric acid for 20-40 minutes; repeatedly cleaning the foamed nickel substrate to be neutral by using absolute ethyl alcohol and deionized water after soaking, and drying the cleaned foamed nickel substrate in vacuum at 80-100 ℃;
(2) soaking the foamed nickel substrate subjected to vacuum drying in the step (1) in a pretreatment solution, and heating and reacting at 80-110 ℃ for 30-120 minutes, wherein the pretreatment solution contains 0.3-0.5 mmol/L of Ni (NO)3)2、0.5～1mmol/L Co(NO3)2、1.0～1.5mmol/L NH4NO3And a 1-5% volume concentration aqueous solution of dimethyl sulfoxide; after the reaction is finished, repeatedly ultrasonically cleaning the foamed nickel substrate by using deionized water and absolute ethyl alcohol, and drying to obtain a pretreated foamed nickel substrate;
(3) immersing the foamed nickel substrate pretreated in the step (2) in a solution containing 0.5-1 mmol/L Co (NO)3)2、0.3～0.5mmol/L NiCl20.2 to 0.4mmol/L cetyltrimethylammonium bromide,Carrying out hydrothermal reaction for 5-8 hours at 80-110 ℃ in 1-1.5 mmol/L urea aqueous solution, carrying out ultrasonic cleaning by using absolute ethyl alcohol and deionized water after the reaction is finished, and drying;
(4) annealing the foamed nickel substrate obtained in the step (3) for 1-4 hours at 250-400 ℃ in an air atmosphere to obtain braided porous NiCo2O4Nanosheets.
2. The in situ grown braided porous channel NiCo of claim 12O4A method of nanosheet, characterized by: in the step (1), at normal temperature, the foamed nickel substrate is ultrasonically immersed in 2mol/L acetone aqueous solution for 30 minutes, and then ultrasonically immersed in hydrochloric acid with the mass concentration of 7-8% for 30 minutes, wherein the ultrasonic power is 100W.
3. The in situ grown braided porous channel NiCo of claim 12O4A method of nanosheet, characterized by: in the step (2), the foam nickel substrate dried in the step (1) in vacuum is soaked in a pretreatment solution, and is heated and reacted for 60-90 minutes at the temperature of 90-100 ℃.
4. The in situ grown braided porous channel NiCo of claim 1 or 32O4A method of nanosheet, characterized by: in the step (2), the pretreatment solution contains 0.35-0.40 mmol/L Ni (NO)3)2、0.7～0.8mmol/L Co(NO3)2、1.12～1.13mmol/L NH4NO3And 2-3% volume concentration dimethyl sulfoxide aqueous solution.
5. The in situ grown braided porous channel NiCo of claim 12O4A method of nanosheet, characterized by: in the step (3), the foamed nickel substrate pretreated in the step (2) is soaked in a solution containing 0.7-0.8 mmol/L Co (NO)3)2、0.35～0.40mmol/L NiCl20.3 to 0.4mmol/L hexadecyl trimethyl ammonium bromide and 1.3 to 1.5mol/L urea, and carrying out hydrothermal reaction at 90 to 100 ℃ for 6 to 7 hours.
6. The in situ grown braided porous channel NiCo of claim 12O4A method of nanosheet, characterized by: in the step (4), the acicular nickel-cobalt bimetal hydroxide foamed nickel substrate grown in the step (3) is annealed for 2-3 hours at 300-320 ℃ in an air atmosphere.
7. The in situ grown braided porous channel NiCo of claim 1 or 62O4A method of nanosheet, characterized by: the method is characterized in that: in the step (4), the annealing temperature rise rate is 1-5 ℃/min.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910867049.XA CN110648861B (en) | 2019-09-12 | 2019-09-12 | In-situ growth of braided porous channel NiCo2O4Method of nanosheet |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910867049.XA CN110648861B (en) | 2019-09-12 | 2019-09-12 | In-situ growth of braided porous channel NiCo2O4Method of nanosheet |
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| CN110648861A true CN110648861A (en) | 2020-01-03 |
| CN110648861B CN110648861B (en) | 2021-10-15 |
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