CN111573746B - Porous nickel-cobalt oxide and two-step synthesis method thereof - Google Patents
Porous nickel-cobalt oxide and two-step synthesis method thereof Download PDFInfo
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- YTBWYQYUOZHUKJ-UHFFFAOYSA-N oxocobalt;oxonickel Chemical compound [Co]=O.[Ni]=O YTBWYQYUOZHUKJ-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 238000001308 synthesis method Methods 0.000 title claims abstract description 19
- 239000002135 nanosheet Substances 0.000 claims abstract description 51
- 239000004005 microsphere Substances 0.000 claims abstract description 27
- CZAYMIVAIKGLOR-UHFFFAOYSA-N [Ni].[Co]=O Chemical class [Ni].[Co]=O CZAYMIVAIKGLOR-UHFFFAOYSA-N 0.000 claims abstract description 22
- DZMKCIZPYSTJLZ-UHFFFAOYSA-L cobalt(2+);2,3-dihydroxypropanoate Chemical compound [Co+2].OCC(O)C([O-])=O.OCC(O)C([O-])=O DZMKCIZPYSTJLZ-UHFFFAOYSA-L 0.000 claims abstract description 21
- 239000000758 substrate Substances 0.000 claims abstract description 17
- 238000011065 in-situ storage Methods 0.000 claims abstract description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 48
- 239000002244 precipitate Substances 0.000 claims description 48
- 239000000243 solution Substances 0.000 claims description 44
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 24
- 239000011259 mixed solution Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 16
- -1 polytetrafluoroethylene Polymers 0.000 claims description 16
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 16
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- 238000005303 weighing Methods 0.000 claims description 11
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- 238000010304 firing Methods 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims 2
- 238000003786 synthesis reaction Methods 0.000 claims 2
- 239000002055 nanoplate Substances 0.000 claims 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims 1
- 238000005054 agglomeration Methods 0.000 abstract description 5
- 230000002776 aggregation Effects 0.000 abstract description 5
- 229910017052 cobalt Inorganic materials 0.000 abstract description 3
- 239000010941 cobalt Substances 0.000 abstract description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 3
- 230000008093 supporting effect Effects 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 10
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 239000003990 capacitor Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 239000002131 composite material Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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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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- C01G53/04—Oxides; Hydroxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01G11/24—Electrodes 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
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
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Abstract
The invention discloses a porous nickel-cobalt oxide and a two-step synthesis method thereof, comprising a cobalt-glycerate ball substrate, wherein a nickel-cobalt oxide nanosheet grows and is combined with the cobalt-glycerate ball substrate in situ; the nickel cobalt oxide nanosheets are stacked to form three-dimensional porous microspheres, and a plurality of columnar nickel cobalt oxides vertically grow on the surfaces of the nickel cobalt oxide nanosheets; the diameter of the three-dimensional porous microsphere is 6-12 μm; the height of the columnar nickel-cobalt oxide is 10-30 nm; also disclosed is a two-step synthesis method for making porous nickel cobalt oxides; the nickel-cobalt oxide nanosheets grow out by taking the template as the center, so that the uniformity of the appearance is ensured, the agglomeration phenomenon is avoided, the columnar nickel-cobalt oxide vertically grown on the nickel-cobalt oxide nanosheets by taking cobalt in the template as the original point forms a supporting effect among the nanosheets, and the specific surface area and the structural stability are further increased.
Description
Technical Field
The invention belongs to the field of nano composite material preparation, and particularly relates to a porous nickel-cobalt oxide and a two-step synthesis method thereof.
Background
The super capacitor has the advantages of higher power density, longer service life, environmental protection and the like, and has wide application prospect in various fields such as military, hybrid electric vehicles, intelligent instruments and the like. At present, the performance and cycle life of super capacitors are still important issues, and the electrode material of the capacitor is a core factor determining the performance of the capacitor, so it is important to develop efficient and stable electrode materials. The nickel-cobalt oxide can generate Ni2+/Ni3+ and Co2+/Co3+ redox reaction pairs in the electrochemical reaction process, so that the nickel-cobalt oxide has higher conductivity and electrochemical activity than single nickel and cobalt oxide, and has lower hydrogen evolution potential and better stability in alkaline electrolyte. The nickel-cobalt oxide has the characteristics of high electrochemical activity, excellent conductivity, high stability, environmental friendliness and the like, so that the nickel-cobalt oxide becomes a hot spot for research on electrode materials of super capacitors.
There are many preparation methods of nickel-cobalt oxide, such as that in chinese patent (CN 102656650A), porous nickel cobaltate nanosheets are prepared by using hollow carbon spheres as templates, and the nickel cobaltate nanosheets are stacked to form a porous structure. The hollow carbon spheres and the nickel cobaltate nanosheets are combined to form a three-dimensional porous structure, so that the conductivity of the three-dimensional porous structure can be improved, the specific surface area and the reaction active sites of the three-dimensional porous structure are increased, and higher specific capacitance is realized. For example, a Chinese patent (CN 110342589A) prepares a loose nickel cobaltate composite material with a flower-like structure of a loose nickel cobaltate nanosheet with uniform surface distribution by a one-step hydrothermal method, and the huge specific surface area and the loose structure of the material enhance the capability of the material serving as an active electrode of a super capacitor for storing electrons, so that the high specific capacitance of 817.5F g < -1 > is obtained. For example, in chinese patent (CN 104291385B), a hydrothermal synthesis method in which isopropanol is added as a solvent is used to prepare the nickel cobaltate mesoporous microsphere with an opening, thereby greatly increasing the specific surface area of the material. At present, nickel-cobalt oxide materials with high specific surface areas prepared by various methods show good electrochemical energy storage performance. However, the methods are difficult to control the accumulation mode and growth direction of the nickel cobalt oxide, so that the obtained nickel cobalt oxide material has non-uniform morphology and agglomeration phenomenon.
Disclosure of Invention
The invention aims to: the cobalt-glycerate spheres are used as a self-sacrifice template to form the three-dimensional porous nickel-cobalt oxide microspheres, wherein the nickel-cobalt oxide nanosheets can grow out by taking the template as the center, the uniformity of the appearance can be ensured, the agglomeration phenomenon can be avoided, the columnar nickel-cobalt oxide vertically grown on the nickel-cobalt oxide nanosheets by taking cobalt in the template as the origin forms a supporting effect among the nanosheets, and the specific surface area and the structural stability are further increased.
The technical scheme adopted by the invention is as follows:
a porous nickel cobalt oxide comprises a cobalt-glycerate ball substrate, and nickel cobalt oxide nanosheets are grown in situ on the cobalt-glycerate ball substrate.
Furthermore, nickel cobalt oxide nanosheets are stacked to form three-dimensional porous microspheres, and a plurality of columnar nickel cobalt oxides vertically grow on the surfaces of the nickel cobalt oxide nanosheets.
Furthermore, the diameter of the three-dimensional porous microsphere is 6-12 μm.
Further, the height of the columnar nickel cobalt oxide is 10-30 nm.
The two-step synthesis method of the porous nickel cobalt oxide comprises the following steps:
1) adding Co (NO) 50-500mg per 30-80ml isopropanol solution3)2Stirring for 5-60 min;
2) weighing 2-20ml of glycerol solution, adding the glycerol solution into the mixed solution subjected to ultrasonic treatment, and stirring for 5-60 minutes;
3) transferring the mixture to a polytetrafluoroethylene reaction kettle to react at the temperature of 100 ℃ and 200 ℃ for 6 to 36 hours; (ii) a
4) After the reaction is finished, taking the precipitate, and centrifugally washing the precipitate by using water and ethanol;
5) drying the washed precipitate in an oven at the temperature of 30-150 ℃ for 5-20 hours;
6) adding 50-150mg of dried powder into 20-60ml of deionized water, and stirring for 5-60 minutes;
7) measuring 0.1-2M Co (NO)3)2Solution, 0.1-2M Ni (NO)3)2Solutions ofAdding the mixture into the mixed solution, wherein the molar ratio of Co to Ni is 1-2, and stirring for 5-60 minutes;
8) weighing 50-200mg of urea and 50-200mg of ammonium fluoride, adding into the mixed solution, and stirring for 5-60 minutes;
9) transferring the mixture into a polytetrafluoroethylene reaction kettle to react at 90-200 ℃ for 5-30 hours;
10) after the reaction is finished, taking the precipitate, and centrifugally washing the precipitate by using water and ethanol;
11) drying the washed precipitate in an oven at the temperature of 30-100 ℃ for 5-20 hours;
12) and putting the dried powder into a tubular furnace, and air-firing at 200-400 ℃ for 1-5 hours to obtain the porous nickel-cobalt oxide.
Further, the molar ratio of Co to Ni in step 7) was 1.
Further, the molar ratio of Co to Ni in step 7) was 1.5.
Further, the molar ratio of Co to Ni in step 7) was 2.
Further, the isopropanol solution in the step 1) is 30-50 ml.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. according to the invention, the cobalt-glycerate spheres are used as a self-sacrifice template to form the three-dimensional porous nickel cobalt oxide microspheres, wherein the nickel cobalt oxide nanosheets can develop and grow by taking the template as the center, so that the uniformity of the appearance can be ensured and the agglomeration phenomenon can be avoided, and the columnar nickel cobalt oxide vertically grown on the nickel cobalt oxide nanosheets by taking cobalt in the template as the origin forms a supporting effect among the nanosheets, so that the specific surface area and the structural stability are further increased.
2. The nickel-cobalt oxide nanosheet increases the specific surface area of the material along with the columnar convex structure on the sheet, and increases the utilization rate of the active material
3. The three-dimensional porous microspheres avoid the agglomeration phenomenon of the material, further increase the reactive sites of the material and the electrolyte, improve the specific capacitance of the material, and are mainly used as the anode material of the super capacitor.
4. The invention provides a novel technical approach for preparing a porous nickel cobalt oxide composite material by a self-template method, wherein cobalt-glycerate spheres are used as templates, a nickel cobalt nanosheet precursor is hydrothermally synthesized, and the porous nickel cobalt oxide nanosheet composite material rich in oxygen vacancies is prepared through subsequent heat treatment, so that the specific surface area is increased, and the controllability of the particle uniformity is good.
According to the invention, cobalt-glycerate spheres are used as a template, and in the process of hydro-thermal synthesis of the nickel-cobalt nanosheet, cobalt ions in the template are combined with redundant nickel ions to form the columnar nickel-cobalt oxide, so that a plurality of columnar nickel-cobalt oxides vertically growing are distributed on the surface of the prepared nickel-cobalt oxide nanosheet, more active sites are provided, and the prepared nickel-cobalt oxide nanosheet has better electrochemical performance and higher cycling stability when used as a supercapacitor electrode, and has a good application prospect.
Drawings
FIG. 1 is a schematic diagram of the morphology and structure of porous nickel cobalt oxide with a molar ratio of Ni to Co of 1;
FIG. 2 is an enlarged schematic structural view of a porous nickel cobalt oxide having a molar ratio of Ni to Co of 1;
FIG. 3 is a schematic diagram of the morphology of nickel cobalt oxide with a molar ratio of Ni to Co of 1.5;
FIG. 4 is a schematic diagram of the morphology of nickel cobalt oxide with a molar ratio of Ni to Co of 2.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
A porous nickel cobalt oxide comprises a cobalt-glycerate ball substrate, and nickel cobalt oxide nanosheets are grown in situ on the cobalt-glycerate ball substrate.
Furthermore, nickel cobalt oxide nanosheets are stacked to form three-dimensional porous microspheres, and a plurality of columnar nickel cobalt oxides vertically grow on the surfaces of the nickel cobalt oxide nanosheets.
Furthermore, the diameter of the three-dimensional porous microsphere is 6-12 μm.
Further, the height of the columnar nickel cobalt oxide is 10-30 nm.
The two-step synthesis method of the porous nickel cobalt oxide comprises the following steps:
1) adding Co (NO) 50-500mg per 30-80ml isopropanol solution3)2Stirring for 5-60 min;
2) weighing 2-20ml of glycerol solution, adding the glycerol solution into the mixed solution subjected to ultrasonic treatment, and stirring for 5-60 minutes;
3) transferring the mixture to a polytetrafluoroethylene reaction kettle to react at the temperature of 100 ℃ and 200 ℃ for 6 to 36 hours;
4) after the reaction is finished, taking the precipitate, and centrifugally washing the precipitate by using water and ethanol;
5) drying the washed precipitate in an oven at the temperature of 30-150 ℃ for 5-20 hours;
6) adding 50-150mg of dried powder into 20-60ml of deionized water, and stirring for 5-60 minutes;
7) measuring 0.1-2M Co (NO)3)2Solution, 0.1-2M Ni (NO)3)2Adding the solution into the mixed solution, wherein the molar ratio of Co to Ni is 1-2, and stirring for 5-60 minutes;
8) weighing 50-200mg of urea and 50-200mg of ammonium fluoride, adding into the mixed solution, and stirring for 5-60 minutes;
9) transferring the mixture into a polytetrafluoroethylene reaction kettle to react at 90-200 ℃ for 5-30 hours;
10) after the reaction is finished, taking the precipitate, and centrifugally washing the precipitate by using water and ethanol;
11) drying the washed precipitate in an oven at the temperature of 30-100 ℃ for 5-20 hours;
12) and putting the dried powder into a tubular furnace, and air-firing at 200-400 ℃ for 1-5 hours to obtain the porous nickel-cobalt oxide.
Further, the ratio of Co to Ni in step 7) is 1.
Further, the ratio of Co to Ni in step 7) was 1.5.
Further, the ratio of Co to Ni in step 7) is 2.
Further, the isopropanol solution in the step 1) is 30-50 ml.
Example 1
A porous nickel cobalt oxide comprises a cobalt-glycerate ball substrate, and nickel cobalt oxide nanosheets are grown in situ on the cobalt-glycerate ball substrate.
Furthermore, nickel cobalt oxide nanosheets are stacked to form three-dimensional porous microspheres, and a plurality of columnar nickel cobalt oxides vertically grow on the surfaces of the nickel cobalt oxide nanosheets.
Furthermore, the diameter of the three-dimensional porous microsphere is 6-12 μm.
Further, the height of the columnar nickel cobalt oxide is 10-30 nm.
The two-step synthesis method of the porous nickel cobalt oxide comprises the following steps:
1) 200mg of Co (NO) per 50ml of isopropanol solution3)2Stirring for 10 minutes;
2) measuring 15ml of glycerol solution, adding the glycerol solution into the mixed solution subjected to ultrasonic treatment, and stirring for 10 minutes;
3) transferring the mixture into a polytetrafluoroethylene reaction kettle to react at 160 ℃ for 16 hours; (ii) a
4) After the reaction is finished, taking the precipitate, and centrifugally washing the precipitate by using water and ethanol;
5) drying the washed precipitate in an oven at the temperature of 60 ℃ for 12 hours;
6) adding 100mg of dried powder into each 20ml of deionized water, and stirring for 20 minutes;
7) 0.5M Co (NO) was measured out3)2Solution, 0.5M Ni (NO)3)2Adding the solution into the mixed solution, wherein the molar ratio of Co to Ni is 1, and stirring for 20 minutes;
8) weighing 150mg of urea and 100mg of ammonium fluoride, adding into the mixed solution, and stirring for 20 minutes;
9) transferring the mixture into a polytetrafluoroethylene reaction kettle to react at 120 ℃ for 12 hours;
10) after the reaction is finished, taking the precipitate, and centrifugally washing the precipitate by using water and ethanol;
11) drying the washed precipitate in an oven at the temperature of 60 ℃ for 12 hours;
12) and putting the dried powder into a tubular furnace, and burning the powder in the air at 350 ℃ for 2 hours to obtain the porous nickel-cobalt oxide.
The porous nickel cobalt oxide is three-dimensional porous particles, and a plurality of columnar nickel cobalt oxides vertically grown are arranged on the nickel cobalt oxide nano-chip, so that the space is utilized to the maximum extent, the specific surface area is greatly increased, the structure is unique and stable, and the transportation and the exchange of ions in electrolyte are facilitated.
Example 2
A porous nickel cobalt oxide comprises a cobalt-glycerate ball substrate, and nickel cobalt oxide nanosheets are grown in situ on the cobalt-glycerate ball substrate.
Furthermore, nickel cobalt oxide nanosheets are stacked to form three-dimensional porous microspheres, and a plurality of columnar nickel cobalt oxides vertically grow on the surfaces of the nickel cobalt oxide nanosheets.
Furthermore, the diameter of the three-dimensional porous microsphere is 6-12 μm.
Further, the height of the columnar nickel cobalt oxide is 10-30 nm.
The two-step synthesis method of the porous nickel cobalt oxide comprises the following steps:
1) 200mg of Co (NO) per 50ml of isopropanol solution3)2Stirring for 10 minutes;
2) measuring 15ml of glycerol solution, adding the glycerol solution into the mixed solution subjected to ultrasonic treatment, and stirring for 10 minutes;
3) transferring the mixture into a polytetrafluoroethylene reaction kettle to react at 160 ℃ for 16 hours; (ii) a
4) After the reaction is finished, taking the precipitate, and centrifugally washing the precipitate by using water and ethanol;
5) drying the washed precipitate in an oven at the temperature of 60 ℃ for 12 hours;
6) adding 100mg of dried powder into each 20ml of deionized water, and stirring for 20 minutes;
7) 0.5M Co (NO) was measured out3)2Solution, 0.5M Ni (NO)3)2Adding the solution into the mixed solution, wherein the molar ratio of Co to Ni is 1.5, and stirring for 20 minutes;
8) weighing 150mg of urea and 100mg of ammonium fluoride, adding into the mixed solution, and stirring for 20 minutes;
9) transferring the mixture into a polytetrafluoroethylene reaction kettle to react at 120 ℃ for 12 hours;
10) after the reaction is finished, taking the precipitate, and centrifugally washing the precipitate by using water and ethanol;
11) drying the washed precipitate in an oven at the temperature of 60 ℃ for 12 hours;
12) and putting the dried powder into a tubular furnace, and burning the powder in the air at 350 ℃ for 2 hours to obtain the porous nickel-cobalt oxide.
The porous nickel-cobalt oxide consists of a plurality of needle-shaped nickel-cobalt oxides, wherein a small amount of needle-shaped nickel-cobalt oxides form nickel-cobalt needle-punched microspheres, most of the needle-shaped nickel-cobalt oxides are amorphous and connected into a net shape, and few porous spherical particles of the nickel-cobalt oxides vertically grow on nickel-cobalt nano-chips.
Example 3
A porous nickel cobalt oxide comprises a cobalt-glycerate ball substrate, and nickel cobalt oxide nanosheets are grown in situ on the cobalt-glycerate ball substrate.
Furthermore, nickel cobalt oxide nanosheets are stacked to form three-dimensional porous microspheres, and a plurality of columnar nickel cobalt oxides vertically grow on the surfaces of the nickel cobalt oxide nanosheets.
Furthermore, the diameter of the three-dimensional porous microsphere is 6-12 μm.
Further, the height of the columnar nickel cobalt oxide is 10-30 nm.
The two-step synthesis method of the porous nickel cobalt oxide comprises the following steps:
1) 200mg of Co (NO) per 50ml of isopropanol solution3)2Stirring for 10 minutes;
2) measuring 15ml of glycerol solution, adding the glycerol solution into the mixed solution subjected to ultrasonic treatment, and stirring for 10 minutes;
3) transferring the mixture into a polytetrafluoroethylene reaction kettle to react at 160 ℃ for 16 hours; (ii) a
4) After the reaction is finished, taking the precipitate, and centrifugally washing the precipitate by using water and ethanol;
5) drying the washed precipitate in an oven at the temperature of 60 ℃ for 12 hours;
6) adding 100mg of dried powder into each 20ml of deionized water, and stirring for 20 minutes;
7) 0.5M Co (NO) was measured out3)2Solution, 0.5M Ni (NO)3)2Adding the solution into the mixed solution, wherein the molar ratio of Co to Ni is 2, and stirring for 20 minutes;
8) weighing 150mg of urea and 100mg of ammonium fluoride, adding into the mixed solution, and stirring for 20 minutes;
9) transferring the mixture into a polytetrafluoroethylene reaction kettle to react at 120 ℃ for 12 hours;
10) after the reaction is finished, taking the precipitate, and centrifugally washing the precipitate by using water and ethanol;
11) drying the washed precipitate in an oven at the temperature of 60 ℃ for 12 hours;
12) and putting the dried powder into a tubular furnace, and burning the powder in the air at 350 ℃ for 2 hours to obtain the porous nickel-cobalt oxide.
The nickel-cobalt nanosheets of the porous nickel-cobalt oxide are interpenetrated with a plurality of needle-shaped nickel-cobalt oxides, and also have partial needle-shaped nickel-cobalt oxides which are connected in a staggered manner to form a net shape, and columnar nickel-cobalt oxides vertically grown on the nickel-cobalt nanosheets are closely arranged, so that the thickness of the nickel-cobalt nanosheets is obviously increased, and partial nickel-cobalt nanosheets are relatively dispersed and cannot form three-dimensional porous spherical particles.
Example 4
A porous nickel cobalt oxide comprises a cobalt-glycerate ball substrate, and nickel cobalt oxide nanosheets are grown in situ on the cobalt-glycerate ball substrate.
Furthermore, nickel cobalt oxide nanosheets are stacked to form three-dimensional porous microspheres, and a plurality of columnar nickel cobalt oxides vertically grow on the surfaces of the nickel cobalt oxide nanosheets.
Furthermore, the diameter of the three-dimensional porous microsphere is 6-12 μm.
Further, the height of the columnar nickel cobalt oxide is 10-30 nm.
The two-step synthesis method of the porous nickel cobalt oxide comprises the following steps:
1) 200mg of Co (NO) per 40ml of isopropanol solution3)2Stirring for 10 minutes;
2) measuring 15ml of glycerol solution, adding the glycerol solution into the mixed solution subjected to ultrasonic treatment, and stirring for 10 minutes;
3) transferring the mixture into a polytetrafluoroethylene reaction kettle to react at 160 ℃ for 16 hours; (ii) a
4) After the reaction is finished, taking the precipitate, and centrifugally washing the precipitate by using water and ethanol;
5) drying the washed precipitate in an oven at the temperature of 60 ℃ for 12 hours;
6) adding 100mg of dried powder into each 20ml of deionized water, and stirring for 20 minutes;
7) 0.5M Co (NO) was measured out3)2Solution, 0.5M Ni (NO)3)2Adding the solution into the mixed solution, wherein the molar ratio of Co to Ni is 1, and stirring for 20 minutes;
8) weighing 150mg of urea and 100mg of ammonium fluoride, adding into the mixed solution, and stirring for 20 minutes;
9) transferring the mixture into a polytetrafluoroethylene reaction kettle to react at 120 ℃ for 12 hours;
10) after the reaction is finished, taking the precipitate, and centrifugally washing the precipitate by using water and ethanol;
11) drying the washed precipitate in an oven at the temperature of 60 ℃ for 12 hours;
12) and putting the dried powder into a tubular furnace, and burning the powder in the air at 350 ℃ for 2 hours to obtain the porous nickel-cobalt oxide.
In the embodiment, the particle size of the porous nickel cobalt oxide is 8-10 μm, the particle size is obviously reduced, and a plurality of columnar nickel cobalt oxides vertically grown are arranged on the oxide nano-sheets, so that the columnar nickel cobalt oxides are stacked to form three-dimensional porous nickel cobalt oxide microspheres; specifically, the particle size of the porous nickel-cobalt oxide is the size of a three-dimensional porous microsphere.
Example 5
A porous nickel cobalt oxide comprises a cobalt-glycerate ball substrate, and nickel cobalt oxide nanosheets are grown in situ on the cobalt-glycerate ball substrate.
Furthermore, nickel cobalt oxide nanosheets are stacked to form three-dimensional porous microspheres, and a plurality of columnar nickel cobalt oxides vertically grow on the surfaces of the nickel cobalt oxide nanosheets.
Furthermore, the diameter of the three-dimensional porous microsphere is 6-12 μm.
Further, the height of the columnar nickel cobalt oxide is 10-30 nm.
The two-step synthesis method of the porous nickel cobalt oxide comprises the following steps:
1) 200mg of Co (NO) per 30ml of isopropanol solution3)2Stirring for 10 minutes;
2) measuring 15ml of glycerol solution, adding the glycerol solution into the mixed solution subjected to ultrasonic treatment, and stirring for 10 minutes;
3) transferring the mixture into a polytetrafluoroethylene reaction kettle to react at 160 ℃ for 16 hours; (ii) a
4) After the reaction is finished, taking the precipitate, and centrifugally washing the precipitate by using water and ethanol;
5) drying the washed precipitate in an oven at the temperature of 60 ℃ for 12 hours;
6) adding 100mg of dried powder into each 20ml of deionized water, and stirring for 20 minutes;
7) 0.5M Co (NO) was measured out3)2Solution, 0.5M Ni (NO)3)2Adding the solution into the mixed solution, wherein the molar ratio of Co to Ni is 1, and stirring for 20 minutes;
8) weighing 150mg of urea and 100mg of ammonium fluoride, adding into the mixed solution, and stirring for 20 minutes;
9) transferring the mixture into a polytetrafluoroethylene reaction kettle to react at 120 ℃ for 12 hours;
10) after the reaction is finished, taking the precipitate, and centrifugally washing the precipitate by using water and ethanol;
11) drying the washed precipitate in an oven at the temperature of 60 ℃ for 12 hours;
12) and putting the dried powder into a tubular furnace, and burning the powder in the air at 350 ℃ for 2 hours to obtain the porous nickel-cobalt oxide.
In the embodiment, the particle size of the porous nickel cobalt oxide is 6-8 μm, the particle size is reduced, and a plurality of columnar nickel cobalt oxides vertically grown on the nickel cobalt oxide nano-sheets are stacked to form three-dimensional porous nickel cobalt oxide microspheres; specifically, the particle size of the porous nickel-cobalt oxide is the size of a three-dimensional porous microsphere.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (8)
1. A two-step synthesis of porous nickel cobalt oxide comprising a cobalt-glycerate sphere substrate on which bonded nickel cobalt oxide nanoplates are grown in situ, the two-step synthesis of porous nickel cobalt oxide comprising the steps of:
1) adding Co (NO) 50-500mg per 30-80ml isopropanol solution3)2Stirring for 5-60 min;
2) weighing 2-20ml of glycerol solution, adding the glycerol solution into the mixed solution subjected to ultrasonic treatment, and stirring for 5-60 minutes;
3) transferring the mixture to a polytetrafluoroethylene reaction kettle to react at the temperature of 100 ℃ and 200 ℃ for 6 to 36 hours;
4) after the reaction is finished, taking the precipitate, and centrifugally washing the precipitate by using water and ethanol;
5) drying the washed precipitate in an oven at the temperature of 30-150 ℃ for 5-20 hours;
6) adding 50-150mg of dried powder into 20-60ml of deionized water, and stirring for 5-60 minutes;
7) measuring 0.1-2M Co (NO)3)2Solution, 0.1-2M Ni(NO3)2Adding the solution into the mixed solution, wherein the molar ratio of Co to Ni is 1-2, and stirring for 5-60 minutes;
8) weighing 50-200mg of urea and 50-200mg of ammonium fluoride, adding into the mixed solution, and stirring for 5-60 minutes;
9) transferring the mixture into a polytetrafluoroethylene reaction kettle to react at 90-200 ℃ for 5-30 hours;
10) after the reaction is finished, taking the precipitate, and centrifugally washing the precipitate by using water and ethanol;
11) drying the washed precipitate in an oven at the temperature of 30-100 ℃ for 5-20 hours;
12) and putting the dried powder into a tubular furnace, and air-firing at 200-400 ℃ for 1-5 hours to obtain the porous nickel-cobalt oxide.
2. The two-step synthesis method of porous nickel cobalt oxide according to claim 1, characterized in that: the nickel cobalt oxide nanosheets are stacked to form the three-dimensional porous microspheres, and a plurality of columnar nickel cobalt oxides vertically grow on the surfaces of the nickel cobalt oxide nanosheets.
3. The two-step synthesis method of porous nickel cobalt oxide according to claim 2, characterized in that: the diameter of the three-dimensional porous microsphere is 6-12 μm.
4. The two-step synthesis method of porous nickel cobalt oxide according to claim 2, characterized in that: the height of the columnar nickel cobalt oxide is 10-30 nm.
5. The two-step synthesis method of porous nickel cobalt oxide according to claim 1, wherein the molar ratio of Co to Ni in step 7) is 1.
6. The two-step synthesis method of porous nickel cobalt oxide according to claim 1, wherein the molar ratio of Co to Ni in step 7) is 1.5.
7. The two-step synthesis method of porous nickel cobalt oxide according to claim 1, wherein the molar ratio of Co to Ni in step 7) is 2.
8. The two-step synthesis method of porous nickel cobalt oxide according to claim 1, wherein the isopropanol solution in step 1) is 30-50 ml.
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