CN111276338B - Preparation method and application of CoO/NiOOH composite material - Google Patents
Preparation method and application of CoO/NiOOH composite material Download PDFInfo
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- 229910002640 NiOOH Inorganic materials 0.000 title claims abstract description 65
- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 87
- 239000002244 precipitate Substances 0.000 claims abstract description 56
- 238000003756 stirring Methods 0.000 claims abstract description 43
- 238000002156 mixing Methods 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- 238000001354 calcination Methods 0.000 claims abstract description 20
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 18
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 14
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000001868 cobalt Chemical class 0.000 claims abstract description 13
- 239000000725 suspension Substances 0.000 claims abstract description 8
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims abstract description 7
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims abstract description 7
- 230000001681 protective effect Effects 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 41
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(II) oxide Inorganic materials [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 88
- 239000000243 solution Substances 0.000 description 80
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 44
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 30
- 239000000463 material Substances 0.000 description 24
- 238000002484 cyclic voltammetry Methods 0.000 description 23
- 239000011149 active material Substances 0.000 description 22
- 239000007772 electrode material Substances 0.000 description 15
- 229910052759 nickel Inorganic materials 0.000 description 13
- 229910002567 K2S2O8 Inorganic materials 0.000 description 12
- -1 compounds nickel hydroxide Chemical class 0.000 description 12
- 241000080590 Niso Species 0.000 description 11
- 229910021607 Silver chloride Inorganic materials 0.000 description 11
- 239000006229 carbon black Substances 0.000 description 11
- 238000010277 constant-current charging Methods 0.000 description 11
- 125000004122 cyclic group Chemical group 0.000 description 11
- 238000007599 discharging Methods 0.000 description 11
- 239000008151 electrolyte solution Substances 0.000 description 11
- 239000006260 foam Substances 0.000 description 11
- 238000000227 grinding Methods 0.000 description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 description 11
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 239000011259 mixed solution Substances 0.000 description 9
- 239000002086 nanomaterial Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000000137 annealing Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007600 charging Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000012921 cobalt-based metal-organic framework Substances 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000877463 Lanio Species 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000009510 drug design Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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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
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
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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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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Abstract
The invention relates to a preparation method of a CoO/NiOOH composite material, which comprises the following steps: s1: dissolving soluble cobalt salt in methanol to obtain a methanol solution of the cobalt salt; dissolving 2-methylimidazole in methanol to obtain a methanol solution of 2-methylimidazole; mixing the methanol solution of the cobalt salt and the methanol solution of the 2-methylimidazole under the condition of stirring to obtain a uniform solution; s2: placing the uniform solution in a reaction kettle for hydrothermal reaction, and calcining precipitates obtained by the hydrothermal reaction under the conditions of washing, drying and protective atmosphere to obtain CoO; s3: adding the CoO obtained in the step S2 into water, and adding nickel sulfate and K under the stirring condition2S2O8And (3) forming a uniform suspension, then dropwise adding ammonia water into the uniform suspension to adjust the pH value of the solution to 9.5-10.5, reacting under the conditions of heating and stirring, and washing and drying the precipitate after reaction to obtain the CoO/NiOOH composite material. Compared with the prior art, the invention has the advantages of environmental protection, simple preparation method, convenience for large-scale production and the like.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a preparation method and application of a CoO/NiOOH composite material.
Background
The increasing shortage of fossil fuels has driven the development of sustainable and renewable energy sources, the environmental-friendly energy convention and storage systems that effectively utilize energy sources. Supercapacitors are considered as energy storage devices with great promise for high power density, fast charge and discharge, and long cycle life, especially in terms of specific energy and power. Cobalt-based materials such as cobalt oxides and hydroxides are considered ideal electrodes for supercapacitors due to their high electrochemical activity and theoretical capacitance. However, charge transport between the electrolyte and the electroactive cobalt species is limited by slow ion diffusion and insulating properties in conventional dense electrodes.
The cobalt monoxide (CoO) has high electrochemical activity and theoretical capacitance of more than 4000F g-1. CoO electrodes of different morphologies were developed to increase the surface area and ion diffusion rate to enhance the performance of supercapacitors. In recent years, in order to improve the electrochemical performance of supercapacitor electrodes, rational design of nanostructure morphology has been explored. Interconnected rough nanostructures can provide good charge transfer paths and provide large contact specific areas and electrolyte/electrode interfaces. Furthermore, the controlled generation of pores on the nanostructures leads to the formation of porous membrane morphology, and the adjustment of pore size and distribution has a significant impact on the performance of the supercapacitor. To achieve a porous membrane structure, various methods have been developed, including spray pyrolysis, electroless plating solution deposition, anodic electrodeposition, and cathodic electrodeposition. For example, NiO nanowires were obtained by hydrothermal combined annealing processes and showed improved electrochemical performance. Also, we have recently demonstrated that a subsequent annealing process after sol-thermal synthesis is applied to the LaNiO of supercapacitors3The microstructure of the electrode can be significantly influenced. Therefore, the electrochemical activity of the CoO electrode can be optimized by adjusting the annealing process to finely adjust the CoO structure, so that the performance of the supercapacitor is improved. Further improving the electrochemical performance of the CoO electrode is a research hotspot of those skilled in the art.
Disclosure of Invention
The invention aims to overcome the defect that the electrochemical performance of a CoO electrode in the prior art needs to be improved, and provides a preparation method and application of a CoO/NiOOH composite material.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of a CoO/NiOOH composite material comprises the following steps:
s1: dissolving soluble cobalt salt in methanol to obtain a methanol solution of the cobalt salt; dissolving 2-methylimidazole in methanol to obtain a methanol solution of 2-methylimidazole; mixing the methanol solution of the cobalt salt and the methanol solution of the 2-methylimidazole under the condition of stirring to obtain a uniform solution;
s2: placing the uniform solution in a reaction kettle for hydrothermal reaction, and calcining precipitates obtained by the hydrothermal reaction under the conditions of washing, drying and protective atmosphere to obtain CoO;
s3: adding the CoO obtained in the step S2 into water, and adding nickel sulfate and K under the stirring condition2S2O8And (3) forming a uniform suspension, then dropwise adding ammonia water into the uniform suspension to adjust the pH value of the solution to 9.5-10.5, reacting under the conditions of heating and stirring, and washing and drying the precipitate after reaction to obtain the CoO/NiOOH composite material.
In the step S1, the soluble cobalt salt is cobalt nitrate.
In the step S1, the molar ratio of the soluble cobalt salt to the 2-methylimidazole is 1-2.
In the step S2, the reaction kettle is an autoclave, the temperature of the hydrothermal reaction is 80-120 ℃, and the reaction time is 6-10 h.
In the step S2, the protective atmosphere in the calcination process is nitrogen, the calcination temperature is 350-450 ℃, and the calcination time is 2-4 h.
During step S3, nickel sulfate and K2S2O8The molar ratio of (A) to (B) is 1 to 2.
In the process of step S3, the charging ratio of nickel sulfate to CoO is (1-2) mmol, (10-20) mg.
In the step S3 process, the reaction temperature is 80-100 ℃, and the reaction time is 1-2 h.
In the processes of the step S2 and the step S3, the drying process is vacuum drying, the drying temperature is 50-70 ℃, and the drying time is 11-13 hours.
The invention also provides an application of the CoO/NiOOH composite material obtained by the preparation method, and the CoO/NiOOH composite material is prepared into a working electrode.
The invention compounds nickel hydroxide and CoO, because the actual capacity is very close to the theoretical capacity, and the invention has good cycle stability; in addition, nickel is widely used in rechargeable alkaline batteries and supercapacitors because of Ni (OH)2The reduction potential of the half-cell reaction of NiOOH is 0.49V; therefore, proper control of the charging overvoltage can oxidize the Ni (II) (OH) on the surface of the metallic nickel2The conversion of the thin film into hydroxide (ni (iii) OOH) with in situ growth of the corresponding (hydro) oxide is the simplest and most efficient method, while nickel has low cost, high conductivity and electrochemical stability, making it also applicable for supercapacitor electrode materials.
In the process of preparing the CoO/NiOOH composite material, an intermediate product CoO is an MOF material, and Co-MOF is a crystalline porous material assembled by metal Co ions and organic ligands with ordered open pore channels. The special structure makes Co-MOFs an ideal template for preparing good nano-structures. The organic ligand can be pyrolyzed and converted into a carbon framework, so that the advantages of large specific surface area, large porosity, large pore volume, ordered tunnels and the like of the MOF precursor structure are inherited, and the prepared electrode material has better electrochemical performance
Compared with the prior art, the invention has the following advantages:
1. the CoO/NiOOH composite material prepared by the invention has the advantages of large specific surface area, large porosity, large pore volume, ordered tunnels and the like, and can achieve good electrochemical performance, and the CoO/NiOOH composite material obtained by the technical scheme can be 1800F/g as high as an electrode material;
2. the CoO/NiOOH composite material prepared by the invention has a hierarchical structure and has a synergistic effect in the aspect of improving the electrochemical performance of the CoO/NiOOH composite material. Meanwhile, enough electroactive sites and abundant electrolyte diffusion channels can be provided, and higher energy density can be obtained from the electrode material;
3. the raw materials adopted by the preparation method are pollution-free, and the solvent generated in the preparation process is non-toxic.
Drawings
FIG. 1 is an SEM image of a CoO/NiOOH composite material of example 1;
FIG. 2 is a cyclic voltammogram at different sweep rates for the CoO/NiOOH composite of example 1;
FIG. 3 is a graph of GCD of the CoO/NiOOH composite of example 1 at different current densities.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
A preparation method and application of a CoO/NiOOH composite material comprise the following steps:
in the first step, 1mmol of Co (NO)3)2·6H2O, 1mmol of 2-methylimidazole are respectively dissolved in 40mL of methanol, the two solutions are quickly mixed and slowly mixed into a purple uniform solution under vigorous stirring,
secondly, putting the mixed purple solution into a high-pressure kettle for hydrothermal reaction at 80 ℃ for 6 hours, washing the reacted precipitate with ethanol, drying the precipitate in vacuum at 60 ℃ for 12 hours, calcining the precipitate in nitrogen at 350 ℃ for 2 hours at the heating rate of 5 ℃ min-1To obtain CoO
Step three, adding 10mg CoO obtained in the S2 process into 100mL water, stirring uniformly, adding 2mmol NiSO under the condition of vigorous stirring4·6H2O，2mmol K2S2O8To form a uniform suspension, adding ammonia water dropwise into the mixture to adjust the pH of the solution to 10, and heating at 80 deg.CStirring for 1h, washing the precipitate after reaction with ethanol, and vacuum drying at 60 ℃ for 12h to obtain CoO/NiOOH. Grinding the active material, and uniformly mixing the ground active material with carbon black and polytetrafluoroethylene according to the mass ratio of 8:1:1 to obtain a CoO/NiOOH working electrode (CN-1).
The Chenghua CHI760e electrochemical workstation adopts cyclic voltammetry and constant current charging and discharging methods, and adopts a three-electrode system: CN-1 foam nickel sheet is used as a working electrode, Ag/AgCl electrode is used as a reference electrode, Pt electrode is used as a counter electrode, and 2mol/L KOH is used as an electrolyte solution. The specific capacitance and the cyclic stability of the material are detected, and cyclic voltammetry tests, such as fig. 2, show that the material has excellent oxidation-reduction capability.
FIG. 1 is an SEM image of the prepared CoO/NiOOH composite material at 10 μm, and it can be seen that the porous nanostructure is rich in active substances, and can provide sufficient electroactive sites and rich electrolyte diffusion channels.
FIG. 2 is a CV diagram of the resulting CoO/NiOOH composite at different sweep rates, which are 10, 20, 40, 50, 100mV/s, respectively. As can be seen from the figure, at a voltage range of 0-0.6V, there are a pair of symmetrical redox peaks, and as the sweep rate increases, the oxidation peak and the reduction peak move to the right and left, respectively. The phenomenon shows that the prepared CoO/NiOOH composite material has good reversibility and stability.
FIG. 3 is a GCD graph of the prepared CoO/NiOOH composite material under different current densities, wherein the current densities are respectively 0.5, 1, 2, 5 and 10A/g, and the specific capacitance of the electrode material reaches 1582.05F/g in a 2mol/L KOH solution and at a current density of 0.5A/g.
Example 2
A preparation method and application of a CoO/NiOOH composite material comprise the following steps:
in the first step, 1mmol of Co (NO)3)2·6H2Dissolving O, 2mmol 2-methylimidazole in 40mL methanol respectively, rapidly mixing the two solutions, slowly mixing the two solutions under vigorous stirring to obtain uniform solution,
second, the mixed purple solution is put into an autoclave forHydrothermal reaction at 80 deg.C for 6 hr, washing the reacted precipitate with ethanol, vacuum drying at 60 deg.C for 12 hr, calcining under nitrogen at 350 deg.C for 2 hr at a rate of 5 deg.C/min-1To obtain CoO
Step three, adding 10mg CoO obtained in the S2 process into 100mL water, stirring uniformly, adding 2mmol NiSO under the condition of vigorous stirring4·6H2O，2mmol K2S2O8And then ammonia water is added into the mixed solution drop by drop to adjust the pH of the solution to 10, the solution is stirred for 1h under the heating condition of 80 ℃, the precipitate after reaction is washed by ethanol, and the precipitate is dried for 12h under vacuum at 60 ℃ to obtain the CoO/NiOOH. Grinding the active material, and uniformly mixing the ground active material with carbon black and polytetrafluoroethylene according to the mass ratio of 8:1:1 to obtain a CoO/NiOOH working electrode (CN-2).
The Chenghua CHI760e electrochemical workstation adopts cyclic voltammetry and constant current charging and discharging methods, and adopts a three-electrode system: CN-2 foam nickel sheet is used as a working electrode, Ag/AgCl electrode is used as a reference electrode, Pt electrode is used as a counter electrode, and 2mol/L KOH is used as an electrolyte solution. The specific capacitance and the cyclic stability of the material are detected, and cyclic voltammetry tests show that the material has excellent redox capability. The specific capacitance of the electrode material of the invention reaches 1448.26F/g in 2mol/L KOH solution and at a current density of 0.5A/g.
Example 3
A preparation method and application of a CoO/NiOOH composite material comprise the following steps:
in the first step, 1mmol of Co (NO)3)2·6H2Dissolving O, 1mmol 2-methylimidazole in 40mL methanol respectively, rapidly mixing the two solutions, slowly mixing the two solutions under vigorous stirring to obtain uniform solution,
secondly, putting the mixed purple solution into a high-pressure kettle for hydrothermal reaction at 100 ℃ for 6 hours, washing the reacted precipitate with ethanol, drying the precipitate in vacuum at 60 ℃ for 12 hours, calcining the dried precipitate in nitrogen at 350 ℃ for 2 hours, and raising the temperatureRate 5 ℃ min-1To obtain CoO
Thirdly, adding 15mg CoO obtained in the S2 process into 100mL water, stirring uniformly, adding 2mmol NiSO under the condition of vigorous stirring4·6H2O，2mmol K2S2O8And then ammonia water is added into the mixed solution drop by drop to adjust the pH of the solution to 10, the solution is stirred for 1h under the heating condition of 80 ℃, the precipitate after reaction is washed by ethanol, and the precipitate is dried for 12h under vacuum at 60 ℃ to obtain the CoO/NiOOH. Grinding the active material, and uniformly mixing the ground active material with carbon black and polytetrafluoroethylene according to the mass ratio of 8:1:1 to obtain a CoO/NiOOH working electrode (CN-3).
The Chenghua CHI760e electrochemical workstation adopts cyclic voltammetry and constant current charging and discharging methods, and adopts a three-electrode system: CN-3 foam nickel sheet is used as a working electrode, Ag/AgCl electrode is used as a reference electrode, Pt electrode is used as a counter electrode, and 2mol/L KOH is used as an electrolyte solution. The specific capacitance and the cyclic stability of the material are detected, and cyclic voltammetry tests show that the material has excellent redox capability. The specific capacitance of the electrode material of the invention reaches 1528.13F/g in 2mol/L KOH solution and at a current density of 0.5A/g.
Example 4
A preparation method and application of a CoO/NiOOH composite material comprise the following steps:
in the first step, 1mmol of Co (NO)3)2·6H2Dissolving O, 1mmol 2-methylimidazole in 40mL methanol respectively, rapidly mixing the two solutions, slowly mixing the two solutions under vigorous stirring to obtain uniform solution,
secondly, putting the mixed purple solution into a high-pressure kettle for hydrothermal reaction at 100 ℃ for 8h, washing the reacted precipitate with ethanol, drying the precipitate in vacuum at 60 ℃ for 12h, calcining the precipitate in nitrogen at 350 ℃ for 2h at the heating rate of 5 ℃ min-1To obtain CoO
Thirdly, adding 15mg CoO obtained in the S2 process into 100mL water, stirring uniformly, adding 2mmol NiSO under the condition of vigorous stirring4·6H2O，2mmol K2S2O8And then ammonia water is added into the mixed solution drop by drop to adjust the pH of the solution to 10, the solution is stirred for 1h under the heating condition of 80 ℃, the precipitate after reaction is washed by ethanol, and the precipitate is dried for 12h under vacuum at 60 ℃ to obtain the CoO/NiOOH. Grinding the active material, and uniformly mixing the ground active material with carbon black and polytetrafluoroethylene according to the mass ratio of 8:1:1 to obtain a CoO/NiOOH working electrode (CN-4).
The Chenghua CHI760e electrochemical workstation adopts cyclic voltammetry and constant current charging and discharging methods, and adopts a three-electrode system: CN-4 foam nickel sheet is used as a working electrode, Ag/AgCl electrode is used as a reference electrode, Pt electrode is used as a counter electrode, and 2mol/L KOH is used as an electrolyte solution. The specific capacitance and the cyclic stability of the material are detected, and cyclic voltammetry tests show that the material has excellent redox capability. The specific capacitance of the electrode material of the invention reaches 1082.5F/g in 2mol/L KOH solution and at a current density of 0.5A/g.
Example 5
A preparation method and application of a CoO/NiOOH composite material comprise the following steps:
in the first step, 1mmol of Co (NO)3)2·6H2Dissolving O, 1mmol 2-methylimidazole in 40mL methanol respectively, rapidly mixing the two solutions, slowly mixing the two solutions under vigorous stirring to obtain uniform solution,
secondly, putting the mixed purple solution into a high-pressure kettle for hydrothermal reaction at 100 ℃ for 6 hours, washing the reacted precipitate with ethanol, drying the precipitate in vacuum at 60 ℃ for 12 hours, calcining the precipitate under the condition of nitrogen at 400 ℃ for 2 hours at the heating rate of 5 ℃ min-1To obtain CoO
Step three, adding 10mg CoO obtained in the S2 process into 100mL water, stirring uniformly, adding 2mmol NiSO under the condition of vigorous stirring4·6H2O，2mmol K2S2O8To form a uniform suspension, adding ammonia water dropwise into the mixture to adjust the pH of the solution to 10, stirring at 80 deg.C for 1h, and precipitatingThe product is washed by ethanol and dried in vacuum at 60 ℃ for 12h to obtain CoO/NiOOH. Grinding the active material, and uniformly mixing the ground active material with carbon black and polytetrafluoroethylene according to the mass ratio of 8:1:1 to obtain a CoO/NiOOH working electrode (CN-5).
The Chenghua CHI760e electrochemical workstation adopts cyclic voltammetry and constant current charging and discharging methods, and adopts a three-electrode system: CN-5 foam nickel sheet is used as a working electrode, Ag/AgCl electrode is used as a reference electrode, Pt electrode is used as a counter electrode, and 2mol/L KOH is used as an electrolyte solution. The specific capacitance and the cyclic stability of the material are detected, and cyclic voltammetry tests show that the material has excellent redox capability. The specific capacitance of the electrode material of the invention reaches 1132.17F/g in 2mol/L KOH solution and at a current density of 0.5A/g.
Example 6
A preparation method and application of a CoO/NiOOH composite material comprise the following steps:
in the first step, 1mmol of Co (NO)3)2·6H2Dissolving O, 1mmol 2-methylimidazole in 40mL methanol respectively, rapidly mixing the two solutions, slowly mixing the two solutions under vigorous stirring to obtain uniform solution,
secondly, putting the mixed purple solution into a high-pressure kettle for hydrothermal reaction at 100 ℃ for 6 hours, washing the reacted precipitate with ethanol, drying the precipitate in vacuum at 60 ℃ for 12 hours, calcining the precipitate in nitrogen at 350 ℃ for 4 hours at the heating rate of 5 ℃ min-1To obtain CoO
Step three, adding 20mg CoO obtained in the S2 process into 100mL water, stirring uniformly, adding 2mmol NiSO under the condition of vigorous stirring4·6H2O，2mmol K2S2O8And then ammonia water is added into the mixed solution drop by drop to adjust the pH of the solution to 10, the solution is stirred for 1h under the heating condition of 80 ℃, the precipitate after reaction is washed by ethanol, and the precipitate is dried for 12h under vacuum at 60 ℃ to obtain the CoO/NiOOH. Grinding the active material, and uniformly mixing the ground active material with carbon black and polytetrafluoroethylene according to the mass ratio of 8:1:1 to obtain a CoO/NiOOH working electrode (CN-6).
The Chenghua CHI760e electrochemical workstation adopts cyclic voltammetry and constant current charging and discharging methods, and adopts a three-electrode system: CN-6 foam nickel sheet is used as a working electrode, Ag/AgCl electrode is used as a reference electrode, Pt electrode is used as a counter electrode, and 2mol/L KOH is used as an electrolyte solution. The specific capacitance and the cyclic stability of the material are detected, and cyclic voltammetry tests show that the material has excellent redox capability. The specific capacitance of the electrode material of the invention reaches 1365.82F/g in 2mol/L KOH solution and at a current density of 0.5A/g.
Example 7
A preparation method and application of a CoO/NiOOH composite material comprise the following steps:
in the first step, 1mmol of Co (NO)3)2·6H2Dissolving O, 1mmol 2-methylimidazole in 40mL methanol respectively, rapidly mixing the two solutions, slowly mixing the two solutions under vigorous stirring to obtain uniform solution,
secondly, putting the mixed purple solution into a high-pressure kettle for hydrothermal reaction at 100 ℃ for 6 hours, washing the reacted precipitate with ethanol, drying the precipitate in vacuum at 60 ℃ for 12 hours, calcining the precipitate in nitrogen at 350 ℃ for 2 hours at the heating rate of 5 ℃ min-1To obtain CoO
Step three, adding 20mg CoO obtained in the S2 process into 100mL water, stirring uniformly, adding 2mmol NiSO under the condition of vigorous stirring4·6H2O，4mmol K2S2O8And then ammonia water is added into the mixed solution drop by drop to adjust the pH of the solution to 10, the solution is stirred for 1h under the heating condition of 80 ℃, the precipitate after reaction is washed by ethanol, and the precipitate is dried for 12h under vacuum at 60 ℃ to obtain the CoO/NiOOH. Grinding the active material, and uniformly mixing the ground active material with carbon black and polytetrafluoroethylene according to the mass ratio of 8:1:1 to obtain a CoO/NiOOH working electrode (CN-7).
The Chenghua CHI760e electrochemical workstation adopts cyclic voltammetry and constant current charging and discharging methods, and adopts a three-electrode system: CN-7 foam nickel sheet is used as a working electrode, Ag/AgCl electrode is used as a reference electrode, Pt electrode is used as a counter electrode, and 2mol/L KOH is used as an electrolyte solution. The specific capacitance and the cyclic stability of the material are detected, and cyclic voltammetry tests show that the material has excellent redox capability. The specific capacitance of the electrode material of the invention reaches 1028.29F/g in 2mol/L KOH solution and at a current density of 0.5A/g.
Example 8
A preparation method and application of a CoO/NiOOH composite material comprise the following steps:
in the first step, 1mmol of Co (NO)3)2·6H2Dissolving O, 1mmol 2-methylimidazole in 40mL methanol respectively, rapidly mixing the two solutions, slowly mixing the two solutions under vigorous stirring to obtain uniform solution,
secondly, putting the mixed purple solution into a high-pressure kettle for hydrothermal reaction at 100 ℃ for 6 hours, washing the reacted precipitate with ethanol, drying the precipitate in vacuum at 60 ℃ for 12 hours, calcining the precipitate in nitrogen at 350 ℃ for 2 hours at the heating rate of 5 ℃ min-1To obtain CoO
Step three, adding 10mg CoO obtained in the S2 process into 100mL water, stirring uniformly, adding 2mmol NiSO under the condition of vigorous stirring4·6H2O，2mmol K2S2O8And then ammonia water is added into the mixed solution drop by drop to adjust the pH of the solution to 10, the solution is stirred for 1h under the heating condition of 90 ℃, the precipitate after reaction is washed by ethanol, and the precipitate is dried for 12h under vacuum at 60 ℃ to obtain the CoO/NiOOH. Grinding the active material, and uniformly mixing the ground active material with carbon black and polytetrafluoroethylene according to the mass ratio of 8:1:1 to obtain the CoO/NiOOH working electrode (CN-8).
The Chenghua CHI760e electrochemical workstation adopts cyclic voltammetry and constant current charging and discharging methods, and adopts a three-electrode system: CN-8 foam nickel sheet is used as a working electrode, Ag/AgCl electrode is used as a reference electrode, Pt electrode is used as a counter electrode, and 2mol/L KOH is used as an electrolyte solution. The specific capacitance and the cyclic stability of the material are detected, and cyclic voltammetry tests show that the material has excellent redox capability. The specific capacitance of the electrode material of the invention reaches 1127.5F/g in 2mol/L KOH solution and at a current density of 0.5A/g.
Example 9
A preparation method and application of a CoO/NiOOH composite material comprise the following steps:
in the first step, 1mmol of Co (NO)3)2·6H2Dissolving O, 1mmol 2-methylimidazole in 40mL methanol respectively, rapidly mixing the two solutions, slowly mixing the two solutions under vigorous stirring to obtain uniform solution,
secondly, putting the mixed purple solution into a high-pressure kettle for hydrothermal reaction at 100 ℃ for 6 hours, washing the reacted precipitate with ethanol, drying the precipitate in vacuum at 60 ℃ for 12 hours, calcining the precipitate in nitrogen at 350 ℃ for 2 hours at the heating rate of 5 ℃ min-1To obtain CoO
Step three, adding 10mg CoO obtained in the S2 process into 100mL water, stirring uniformly, adding 2mmol NiSO under the condition of vigorous stirring4·6H2O，2mmol K2S2O8And then ammonia water is added into the mixed solution drop by drop to adjust the pH of the solution to 10, the solution is stirred for 2 hours under the heating condition of 80 ℃, the precipitate after reaction is washed by ethanol, and the precipitate is dried for 12 hours under vacuum at 60 ℃ to obtain the CoO/NiOOH. Grinding the active material, and uniformly mixing the ground active material with carbon black and polytetrafluoroethylene according to the mass ratio of 8:1:1 to obtain the CoO/NiOOH working electrode (CN-9).
The Chenghua CHI760e electrochemical workstation adopts cyclic voltammetry and constant current charging and discharging methods, and adopts a three-electrode system: CN-9 foam nickel sheet is used as a working electrode, Ag/AgCl electrode is used as a reference electrode, Pt electrode is used as a counter electrode, and 2mol/L KOH is used as an electrolyte solution. The specific capacitance and the cyclic stability of the material are detected, and cyclic voltammetry tests show that the material has excellent redox capability. The specific capacitance of the electrode material of the invention reaches 1321.45F/g in 2mol/L KOH solution and at a current density of 0.5A/g.
Example 10
A preparation method and application of a CoO/NiOOH composite material comprise the following steps:
in the first step, 1mmol of Co (NO)3)2·6H2Dissolving O, 1mmol 2-methylimidazole in 40mL methanol respectively, rapidly mixing the two solutions, slowly mixing the two solutions under vigorous stirring to obtain uniform solution,
secondly, putting the mixed purple solution into a high-pressure kettle for hydrothermal reaction at 100 ℃ for 6 hours, washing the reacted precipitate with ethanol, drying the precipitate in vacuum at 60 ℃ for 12 hours, calcining the precipitate in nitrogen at 350 ℃ for 2 hours at the heating rate of 5 ℃ min-1To obtain CoO
Step three, adding 20mg CoO obtained in the S2 process into 100mL water, stirring uniformly, adding 1mmol NiSO under the condition of vigorous stirring4·6H2O，2mmol K2S2O8And then ammonia water is added into the mixed solution drop by drop to adjust the pH of the solution to 9.5, the solution is stirred for 2 hours under the heating condition of 80 ℃, the precipitate after reaction is washed by ethanol, and the precipitate is dried for 13 hours under vacuum at 50 ℃ to obtain the CoO/NiOOH. Grinding the active material, and uniformly mixing the ground active material with carbon black and polytetrafluoroethylene according to the mass ratio of 8:1:1 to obtain the CoO/NiOOH working electrode (CN-9).
The Chenghua CHI760e electrochemical workstation adopts cyclic voltammetry and constant current charging and discharging methods, and adopts a three-electrode system: CN-9 foam nickel sheet is used as a working electrode, Ag/AgCl electrode is used as a reference electrode, Pt electrode is used as a counter electrode, and 2mol/L KOH is used as an electrolyte solution. The specific capacitance and the cyclic stability of the material are detected, and cyclic voltammetry tests show that the material has excellent redox capability. The specific capacitance of the electrode material of the invention reaches 1021.40F/g in 2mol/L KOH solution and at a current density of 0.5A/g.
Example 11
A preparation method and application of a CoO/NiOOH composite material comprise the following steps:
in the first step, 1mmol of Co (NO)3)2·6H2Dissolving O, 1mmol 2-methylimidazole in 40mL methanol respectively, and dissolving the two solutionsMixing quickly, slowly mixing to obtain uniform solution under vigorous stirring,
secondly, putting the mixed purple solution into a high-pressure kettle for hydrothermal reaction at 100 ℃ for 6 hours, washing the reacted precipitate with ethanol, drying the precipitate in vacuum at 60 ℃ for 12 hours, calcining the precipitate in nitrogen at 350 ℃ for 2 hours at the heating rate of 5 ℃ min-1To obtain CoO
Step three, adding 10mg CoO obtained in the S2 process into 100mL water, stirring uniformly, adding 2mmol NiSO under the condition of vigorous stirring4·6H2O，2mmol K2S2O8And then ammonia water is added into the mixed solution drop by drop to adjust the pH of the solution to 10.5, the solution is stirred for 2 hours under the heating condition of 80 ℃, the precipitate after reaction is washed by ethanol, and the precipitate is dried for 11 hours under vacuum at 70 ℃ to obtain the CoO/NiOOH. Grinding the active material, and uniformly mixing the ground active material with carbon black and polytetrafluoroethylene according to the mass ratio of 8:1:1 to obtain the CoO/NiOOH working electrode (CN-9).
The Chenghua CHI760e electrochemical workstation adopts cyclic voltammetry and constant current charging and discharging methods, and adopts a three-electrode system: CN-9 foam nickel sheet is used as a working electrode, Ag/AgCl electrode is used as a reference electrode, Pt electrode is used as a counter electrode, and 2mol/L KOH is used as an electrolyte solution. The specific capacitance and the cyclic stability of the material are detected, and cyclic voltammetry tests show that the material has excellent redox capability. The specific capacitance of the electrode material of the invention reaches 1021.40F/g in 2mol/L KOH solution and at a current density of 0.5A/g.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (10)
1. A preparation method of a CoO/NiOOH composite material is characterized by comprising the following steps:
s1: dissolving soluble cobalt salt in methanol to obtain a methanol solution of the cobalt salt; dissolving 2-methylimidazole in methanol to obtain a methanol solution of 2-methylimidazole; mixing the methanol solution of the cobalt salt and the methanol solution of the 2-methylimidazole under the condition of stirring to obtain a uniform solution;
s2: placing the uniform solution in a reaction kettle for hydrothermal reaction, and calcining precipitates obtained by the hydrothermal reaction under the conditions of washing, drying and protective atmosphere to obtain CoO;
s3: adding the CoO obtained in the step S2 into water, and adding nickel sulfate and K under the stirring condition2S2O8And (3) forming a uniform suspension, then dropwise adding ammonia water into the uniform suspension to adjust the pH value of the solution to 9.5-10.5, reacting under the conditions of heating and stirring, and washing and drying the precipitate after reaction to obtain the CoO/NiOOH composite material.
2. The method of claim 1, wherein in step S1, the soluble cobalt salt is cobalt nitrate.
3. The method of claim 2, wherein in step S1, the molar ratio of the soluble cobalt salt to 2-methylimidazole is 1-2.
4. The method for preparing a CoO/NiOOH composite material according to claim 1, wherein in the step S2, the reaction kettle is an autoclave, the temperature of the hydrothermal reaction is 80-120 ℃, and the reaction time is 6-10 h.
5. The method for preparing a CoO/NiOOH composite material according to claim 1, wherein in the step S2, the protective atmosphere in the calcination process is nitrogen, the calcination temperature is 350-450 ℃, and the calcination time is 2-4 h.
6. The method of claim 1 for preparing a CoO/NiOOH composite materialCharacterized in that, during step S3, nickel sulfate and K are added2S2O8The molar ratio of (A) to (B) is 1 to 2.
7. The method for preparing a CoO/NiOOH composite material according to claim 1, wherein in the step S3, the input ratio of nickel sulfate to CoO is (1-2) mmol, (10-20) mg.
8. The method for preparing a CoO/NiOOH composite material according to claim 1, wherein in the step S3, the reaction temperature is 80-100 ℃ and the reaction time is 1-2 h.
9. The method of claim 1, wherein in the steps S2 and S3, the drying process is vacuum drying, the drying temperature is 50-70 ℃, and the drying time is 11-13 hours.
10. Application of the CoO/NiOOH composite material obtained by the preparation method according to any one of claims 1 to 9, wherein the CoO/NiOOH composite material is prepared into a working electrode.
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| Ｃｏ添加剂添加方式对 ＮｉＯＯＨ 电极性能的影响;李加勇;《电池工业》;20120831;第17卷(第4期);第213-216页 * |
| Ni/Co-based nanosheet arrays for efficient oxygen evolution reaction;Yong Li等;《Nano Energy》;20180807;第52卷;第360-368页 * |
| Reversible Structural Evolution of NiCoO Evolution Reaction and Identification of the Catalytically Active Phase;Zhu Chen等;《ACS Catal.》;20171208;第8卷;第1238-1247页 * |
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