CN113363080B - NF @ Co-MOF @ NiMoO 4 Composite material and preparation method and application thereof - Google Patents

NF @ Co-MOF @ NiMoO 4 Composite material and preparation method and application thereof Download PDF

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CN113363080B
CN113363080B CN202110594114.3A CN202110594114A CN113363080B CN 113363080 B CN113363080 B CN 113363080B CN 202110594114 A CN202110594114 A CN 202110594114A CN 113363080 B CN113363080 B CN 113363080B
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nimoo
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CN113363080A (en
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蒋继波
黄星
孙冉
丛海山
王云云
李雨露
李明晶
许文秀
陈晓敏
周少博
唐佳斌
韩生
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Shanghai Institute of Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Abstract

The invention relates to NF @ Co-MOF @ NiMoO 4 The preparation method of the composite material comprises the following steps: (1) Dissolving dimethyl imidazole and cobalt nitrate hexahydrate in water respectively, stirring and dispersing uniformly to completely dissolve the dimethyl imidazole and the cobalt nitrate hexahydrate, and mixing the dimethyl imidazole and the cobalt nitrate hexahydrate together to obtain a mixed solution I; (2) Placing foam nickel serving as a carrier into the mixed solution I, and standing to grow to obtain NF @ Co-MOF; (3) Na is mixed with 2 MoO 4 ·2H 2 O、Ni(NO 3 ) 2 ·6H 2 And O is dispersed in water to obtain a second mixed solution, and the target product is prepared by taking the second mixed solution as an electrodeposition solution and NF @ Co-MOF as a carrier and adopting a one-step cyclic voltammetry electrodeposition method. Compared with the prior art, the composite material prepared by the invention has a unique nano honeycomb structure, co-MOF is used as an organic metal framework structure, the structure is highly porous and well arranged, rich active sites can be provided to reduce diffusion length, and NiMoO is fully exerted 4 The advantage of high specific capacitance; in addition, the preparation method is environment-friendly, simple and easy to operate, and convenient for large-scale industrial production.

Description

NF @ Co-MOF @ NiMoO 4 Composite material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of electrochemical nano materials, and relates to NF @ Co-MOF @ NiMoO 4 A composite material and a preparation method and application thereof.
Background
To meet the increasing demand for clean energy technology, many energy storage and conversion devices, such as fuel cells, batteries and supercapacitors, have been developed. Supercapacitors (SCs) stand out in many energy storage devices due to their high power delivery, fast charge and discharge performance and excellent cycling stability. The super capacitor is classified into a double electric layer capacitance super capacitor and a pseudo capacitance/battery type super capacitor. The former attracts charged particles in the electrolyte through the surface or pore structure of the electrode material to form an electric double layer structure, and has good cycle performance and a high voltage window. The latter is through a fast reversible redox faraday reaction, involving the action of the electrode material during energy storage.
Transition metal oxides are a hot point for research as electrode materials of pseudo-capacitance supercapacitors. Representative of these is ruthenium oxide (RuO) 2 ). But it is expensive, toxic and not suitable for wide application. Therefore, it is necessary to search for inexpensive, environmentally friendly and harmless transition metal oxides for intensive research. Due to the above advantages, nickel oxide and molybdenum trioxide are widely used in supercapacitors. Currently, several studies have demonstrated that synthesizing nanostructured nickel molybdenum binary oxide arrays on conductive substrates such as NF can effectively increase conductivity and reduce ion diffusion paths compared to single mono-oxides.
Reasonable morphology is also one of the important factors for improving electrochemical kinetics. In recent years, the hot Metal Organic Frameworks (MOFs) have been studied, which are compounds composed of metal ions and organic ligands and having a porous crystal structure, the structure of which is highly porous and well-arranged, and MOF materials have diversity, large pore volume and abundant organic substances, so that they can be used as templates/precursors and provide abundant active sites to reduce diffusion length.
For example, chinese patent CN112670093A discloses a porous Co 3 O 4 The @ Ni-MOF core-shell structure nanosheet array material and the preparation method thereof comprise the following steps: uniformly mixing cobalt nitrate hexahydrate, 2-methylimidazole and deionized water, adding a foamed nickel substrate, reacting at room temperature to obtain a Co-MOF precursor, and calcining to obtain porous Co 3 O 4 Nanosheet array, and finally, mixing porous Co 3 O 4 Mixing the nano-sheet array, nickel salt and amino terephthalic acid in DMF (dimethyl formamide), and carrying out hydrothermal reaction to obtain porous Co 3 O 4 Is a core, and the ultrathin Ni-MOF nanosheet is a core-shell array material of a shell. However, in the three-electrode test of the nanomaterial in the patent, the rate performance is only about 54%, which is relatively lower than the constant current charge-discharge rate performance of other materials.
Disclosure of Invention
The invention aims to provide NF @ Co-MOF @ NiMoO 4 A composite material is prepared from Co-MOF and NiMoO through mixing 4 The nickel is compounded on highly porous foam nickel to achieve the effect of enhancing the electrochemical performance, thereby overcoming the defects of Co-MOF and NiMoO 4 The application of the electrode material of the super capacitor is limited, and the like.
The purpose of the invention can be realized by the following technical scheme:
one of the technical schemes of the invention provides NF @ Co-MOF @ NiMoO 4 The preparation method of the composite material comprises the following steps:
(1) Dissolving dimethyl imidazole and cobalt nitrate hexahydrate in water respectively, stirring and dispersing uniformly to completely dissolve the dimethyl imidazole and the cobalt nitrate hexahydrate, and mixing the mixture together to obtain a mixed solution I;
(2) Putting foam nickel serving as a carrier into the mixed solution I, and standing and growing to obtain NF @ Co-MOF;
(3) Mixing Na 2 MoO 4 ·2H 2 O、Ni(NO 3 ) 2 ·6H 2 Dispersing O in water to obtain a second mixed solution, taking the second mixed solution as electrodeposition liquid, taking NF @ Co-MOF as a carrier, and preparing the NF @ Co-MOF @ NiMoO by adopting a one-step cyclic voltammetry electrodeposition method 4 The composite material is the target product.
Further, in the step (1), the molar ratio of the dimethyl imidazole to the cobalt nitrate hexahydrate is (10-6): 1.
Further, in the step (1), the ratio of the addition amount of the cobalt nitrate hexahydrate to the water is 1mmol: (15-25) mL.
Further, in the step (2), standing growth is carried out at room temperature for 4-6 h.
Further, in the step (2), the used nickel foam is sequentially treated with acetone, ethanol and water for several times in advance.
Further, in the step (3), na 2 MoO 4 ·2H 2 O、Ni(NO 3 ) 2 ·6H 2 The molar ratio of O is (1-3) to 1. Meanwhile, ni (NO) 3 ) 2 ·6H 2 The ratio of the addition of O to water may be 1mmol:45-55ml.
Further, in the step (3), the one-step cyclic voltammetry electrodeposition process is carried out at room temperature, the voltage range used for CV electrodeposition is-1.2-0.2V, the scanning rate is 5-25mV/s, and the scanning period is 15-35.
When mixing dimethylimidazole and cobalt nitrate hexahydrate solution, double bonds in dimethylimidazole are broken to react with cobalt ions in cobalt nitrate to generate Co-MOF; during the reaction, the foam nickel is left to suspend in the mixed solution, and the generated Co-MOF is partially deposited on the foam nickel. The obtained NF @ Co-MOF is electrodeposited in a sodium molybdate and nickel nitrate solution, so that the final reaction product NF @ Co-MOF @ NiMoO can be generated 4 . During the reaction, the foam nickel is used as a substrate for natural deposition and electrodeposition for NiMoO due to the highly porous structure of the foam nickel 4 Depositing on the precursor of NF @ Co-MOF by a simple method to obtain the final product.
At high temperatures, the structure of Co-MOF tends to collapse. Therefore, the temperature for standing growth is not too high, and room temperature is often adopted to ensure that the production of the skeleton structure with multiple active sites is ensured; when the temperature is too low, the growth activity is lowered, and the formation of the metal-organic framework is not facilitated. In addition, when the solvent used for the ratio of dimethylimidazole to cobalt nitrate is ethanol at 4.
The second technical scheme of the invention provides NF @ Co-MOF @ NiMoO 4 A composite material prepared by the preparation method.
The third technical proposal of the invention provides NF @ Co-MOF @ NiMoO 4 The application of the composite material, and the composite material is made into a working electrode and is used in a super capacitor.
Further, when specifically applied, NF @ Co-MOF @ NiMoO 4 Grinding the composite material, uniformly mixing the ground composite material with carbon black and polytetrafluoroethylene, and then pressing the mixture on a foam nickel sheet to obtain a working electrode, wherein the working electrode is NF @ Co-MOF @ NiMoO 4 The mass ratio of the composite material, the carbon black and the polytetrafluoroethylene is 8 (0.8-1.2) to (0.8-1.2).
Compared with the prior art, the invention has the following advantages:
(1) NF @ Co-MOF @ NiMoO prepared by the invention 4 The composite material has unique nano-layered structure, high porous structure of NF and Co-MOF, obviously increased active sites, shortened ion diffusion length, and binary metal oxide NiMoO 4 The composite material can fully exert the advantage of high theoretical specific capacitance, thereby improving the electrochemical performance of the composite material.
(2) NF @ Co-MOF @ NiMoO prepared by the invention 4 The composite material is used as a working electrode in a super capacitor, and the specific capacitance of the composite material can reach 1719.3F/g at most.
(3) The preparation method has the advantages of low cost of raw materials, no pollution, no toxicity of solvents generated in the preparation process, good electrochemical performance of the composite material in the super capacitor and realization of large-scale industrial popularization.
Detailed Description
The present invention will be described in detail with reference to specific examples. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
In the following examples, cobalt nitrate hexahydrate, dimethylimidazole and Na as raw materials 2 MoO 4 ·2H 2 O、 Ni(NO 3 ) 2 ·6H 2 O was analytically pure and purchased from national reagents, inc. The remainder, unless otherwise stated, is intended to indicate that the starting materials or processing techniques are conventional and commercially available in the art.
Example 1:
NF @ Co-MOF @ NiMoO 4 The preparation method and the application of the composite material comprise the following steps:
step one, respectively dissolving 8mmol of dimethylimidazole and 1mmol of cobalt nitrate hexahydrate in 20mL of water, and stirring and dispersing uniformly to completely dissolve the dimethylimidazole and the cobalt nitrate hexahydrate to obtain a solution A and a solution B;
mixing the solution A and the solution B together to obtain a mixed solution, putting 1cm multiplied by 8mm foamed nickel which is sequentially treated by acetone, ethanol and water for 3 times into the mixed solution as a carrier, adopting a solution standing growth method, and standing and reacting for 4 hours at room temperature to prepare NF @ Co-MOF;
thirdly, adding 1mmol of Na 2 MoO 4 ·2H 2 O、1mmol Ni(NO 3 ) 2 ·6H 2 Dissolving O in 50mL of water, stirring and uniformly dispersing by ultrasound to completely dissolve the O to obtain a mixed solution, taking the mixed solution as an electrodeposition solution, taking 1cm multiplied by 1cm NF @ Co-MOF as a working electrode, a platinum wire as a counter electrode and Ag/AgCl as a reference electrode, maintaining the electrodeposition solution at room temperature, and carrying out scanning at a scanning rate of 20mV/s for 30 scanning periods. Taking out the sample after the electrodeposition is finished, washing the sample for three times by deionized water, putting the sample into a vacuum oven, and drying the sample for 12 hours at the temperature of 60 ℃ to obtain NF @ Co-MOF @ NiMoO 4 A composite material. The foam nickel loaded with the composite material is used as a working electrode, namely Co-MOF @ NiMoO 4 Working electrode (note CNMO-1).
The Chenhua CHI760e electrochemical workstation adopts a cyclic voltammetry and constant current charging and discharging method, and adopts a three-electrode system to perform electrochemical test: the foam nickel sheet of CNMO-1 is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a 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 composite material are detected, and cyclic voltammetry tests show that the composite material has excellent redox capability. The specific capacitance of the composite material reaches 1719.3F/g in 2mol/L KOH solution and at a current density of 0.5A/g.
Example 2:
NF @ Co-MOF @ NiMoO 4 The preparation method and the application of the composite material comprise the following steps:
firstly, respectively dissolving 6mmol of dimethyl imidazole and 1mmol of cobalt nitrate hexahydrate in 20mL of water, and stirring and dispersing uniformly to completely dissolve the dimethyl imidazole and the cobalt nitrate hexahydrate to obtain a solution A and a solution B;
mixing the solution A and the solution B together to obtain a mixed solution, putting 1cm multiplied by 8mm foamed nickel which is sequentially treated by acetone, ethanol and water for 3 times into the mixed solution as a carrier, adopting a solution standing growth method, and standing and reacting for 4 hours at room temperature to prepare NF @ Co-MOF;
thirdly, adding 1mmol of Na 2 MoO 4 ·2H 2 O、1mmol Ni(NO 3 ) 2 ·6H 2 Dissolving O in 50mL of water, stirring and uniformly dispersing by ultrasound to completely dissolve the O to obtain a mixed solution, taking the mixed solution as an electrodeposition solution, taking 1cm multiplied by 1cm NF @ Co-MOF as a working electrode, a platinum wire as a counter electrode, ag/AgCl as a reference electrode, maintaining the electrodeposition solution at room temperature, wherein the scanning rate is 20mV/s, and the scanning period is 30. Taking out the sample after the electrodeposition is finished, washing the sample for three times by deionized water, putting the sample into a vacuum oven, and drying the sample for 12 hours at the temperature of 60 ℃ to obtain NF @ Co-MOF @ NiMoO 4 A composite material. The foam nickel loaded with the composite material is used as a working electrode, namely Co-MOF @ NiMoO 4 Working electrode (note CNMO-2).
The Chenhua CHI760e electrochemical workstation adopts a cyclic voltammetry and constant current charging and discharging method, and adopts a three-electrode system to perform electrochemical test: the foam nickel sheet of CNMO-2 is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a 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 composite material are detected, and cyclic voltammetry tests show that the composite material has excellent redox capability. The specific capacitance of the composite material reaches 1634.1F/g under the condition of 2mol/L KOH solution and 1A/g current density.
Example 3:
NF @ Co-MOF @ NiMoO 4 The preparation method and the application of the composite material comprise the following steps:
step one, respectively dissolving 10mmol of dimethyl imidazole and 1mmol of cobalt nitrate hexahydrate in 20mL of water, and stirring and dispersing uniformly to completely dissolve the dimethyl imidazole and the cobalt nitrate hexahydrate to obtain a solution A and a solution B;
mixing the solution A and the solution B together to obtain a mixed solution, putting 1cm multiplied by 8mm foamed nickel which is sequentially treated by acetone, ethanol and water for 3 times into the mixed solution as a carrier, adopting a solution standing growth method, and standing and reacting for 4 hours at room temperature to prepare NF @ Co-MOF;
thirdly, adding 1mmol of Na 2 MoO 4 ·2H 2 O、1mmol Ni(NO 3 ) 2 ·6H 2 Dissolving O in 50mL of water, stirring and uniformly dispersing by ultrasound to completely dissolve the O to obtain a mixed solution, taking the mixed solution as an electrodeposition solution, taking 1cm multiplied by 1cm NF @ Co-MOF as a working electrode, a platinum wire as a counter electrode, ag/AgCl as a reference electrode, maintaining the electrodeposition solution at room temperature, wherein the scanning rate is 20mV/s, and the scanning period is 30. Taking out the sample after the electro-deposition is finished, washing the sample with deionized water for three times, putting the sample into a vacuum oven, and drying the sample for 12 hours at the temperature of 60 ℃ to obtain NF @ Co-MOF @ NiMoO 4 A composite material. The foam nickel loaded with the composite material is used as a working electrode, namely Co-MOF @ NiMoO 4 Working electrode (note CNMO-3).
The Chenhua CHI760e electrochemical workstation adopts a cyclic voltammetry and constant current charging and discharging method, and adopts a three-electrode system to perform electrochemical test: the foam nickel sheet of CNMO-3 is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a 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 composite material are detected, and cyclic voltammetry tests show that the composite material has excellent redox capability. The specific capacitance of the composite material reaches 1656.6F/g in 2mol/L KOH solution and at a current density of 0.5A/g.
Example 4:
NF @ Co-MOF @ NiMoO 4 The preparation method and the application of the composite material comprise the following steps:
step one, respectively dissolving 8mmol of dimethyl imidazole and 1mmol of cobalt nitrate hexahydrate in 20mL of water, and stirring and dispersing uniformly to completely dissolve the dimethyl imidazole and the cobalt nitrate hexahydrate to obtain a solution A and a solution B;
mixing the solution A and the solution B together to obtain a mixed solution, putting 1cm multiplied by 8mm foamed nickel which is treated by acetone, ethanol and water for 3 times in sequence into the mixed solution as a carrier, adopting a solution standing growth method, and standing and reacting for 5 hours at room temperature to obtain NF @ Co-MOF;
thirdly, adding 1mmol of Na 2 MoO 4 ·2H 2 O、1mmol Ni(NO 3 ) 2 ·6H 2 Dissolving O in 50mL of water, stirring and uniformly dispersing by ultrasound to completely dissolve the O to obtain a mixed solution, taking the mixed solution as an electrodeposition solution, taking 1cm multiplied by 1cm NF @ Co-MOF as a working electrode, a platinum wire as a counter electrode, ag/AgCl as a reference electrode, maintaining the electrodeposition solution at room temperature, wherein the scanning rate is 20mV/s, and the scanning period is 30. Taking out the sample after the electrodeposition is finished, washing the sample for three times by deionized water, putting the sample into a vacuum oven, and drying the sample for 12 hours at the temperature of 60 ℃ to obtain NF @ Co-MOF @ NiMoO 4 A composite material. The foam nickel loaded with the composite material is used as a working electrode, namely Co-MOF @ NiMoO 4 Working electrode (CNMO-4).
The Chenhua CHI760e electrochemical workstation adopts a cyclic voltammetry and constant current charging and discharging method, and adopts a three-electrode system to perform electrochemical test: the CMNO-4 foam nickel sheet is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a 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 composite material are detected, and cyclic voltammetry tests show that the composite material has excellent redox capability. The specific capacitance of the composite material reaches 1592.8F/g in 2mol/L KOH solution and at a current density of 1A/g.
Example 5:
NF @ Co-MOF @ NiMoO 4 The preparation method and the application of the composite material comprise the following steps:
step one, respectively dissolving 8mmol of dimethylimidazole and 1mmol of cobalt nitrate hexahydrate in 20mL of water, and stirring and dispersing uniformly to completely dissolve the dimethylimidazole and the cobalt nitrate hexahydrate to obtain a solution A and a solution B;
mixing the solution A and the solution B together to obtain a mixed solution, putting 1cm multiplied by 8mm foamed nickel which is treated by acetone, ethanol and water for 3 times in sequence into the mixed solution as a carrier, adopting a solution standing growth method, and standing and reacting for 6 hours at room temperature to obtain NF @ Co-MOF;
thirdly, adding 1mmol of Na 2 MoO 4 ·2H 2 O、1mmol Ni(NO 3 ) 2 ·6H 2 Dissolving O in 50mL of water, stirring and uniformly dispersing by ultrasound to completely dissolve the O to obtain a mixed solution, taking the mixed solution as an electrodeposition solution, taking 1cm multiplied by 1cm NF @ Co-MOF as a working electrode, a platinum wire as a counter electrode, ag/AgCl as a reference electrode, maintaining the electrodeposition solution at room temperature, wherein the scanning rate is 20mV/s, and the scanning period is 30. Taking out the sample after the electro-deposition is finished, washing the sample with deionized water for three times, putting the sample into a vacuum oven, and drying the sample for 12 hours at the temperature of 60 ℃ to obtain NF @ Co-MOF @ NiMoO 4 A composite material. The foam nickel loaded with the composite material is used as a working electrode, namely Co-MOF @ NiMoO 4 Working electrode (CNMO-5).
The Chenghua CHI760e electrochemical workstation adopts a cyclic voltammetry and constant current charging and discharging method and adopts a three-electrode system for electrochemical test: the CMNO-5 foam nickel sheet is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a 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 composite material are detected, and cyclic voltammetry tests show that the composite material has excellent redox capability. The specific capacitance of the composite material reaches 1537.14F/g in 2mol/L KOH solution and at a current density of 0.5A/g.
Example 6:
NF @ Co-MOF @ NiMoO 4 Composite materialThe preparation method and the application thereof comprise the following steps:
step one, respectively dissolving 8mmol of dimethyl imidazole and 1mmol of cobalt nitrate hexahydrate in 20mL of water, and stirring and dispersing uniformly to completely dissolve the dimethyl imidazole and the cobalt nitrate hexahydrate to obtain a solution A and a solution B;
mixing the solution A and the solution B together to obtain a mixed solution, putting 1cm multiplied by 8mm foamed nickel which is treated by acetone, ethanol and water for 3 times in sequence into the mixed solution as a carrier, adopting a solution standing growth method, and standing and reacting for 4 hours at room temperature to obtain NF @ Co-MOF;
thirdly, adding 1mmol of Na 2 MoO 4 ·2H 2 O、1mmol Ni(NO 3 ) 2 ·6H 2 Dissolving O in 50mL of water, stirring and uniformly dispersing by ultrasound to completely dissolve the O to obtain a mixed solution, taking the mixed solution as an electrodeposition solution, taking 1cm multiplied by 1cm NF @ Co-MOF as a working electrode, a platinum wire as a counter electrode, ag/AgCl as a reference electrode, maintaining the electrodeposition solution at room temperature, wherein the scanning rate is 5mV/s, and the scanning period is 30. Taking out the sample after the electrodeposition is finished, washing the sample for three times by deionized water, putting the sample into a vacuum oven, and drying the sample for 12 hours at the temperature of 60 ℃ to obtain NF @ Co-MOF @ NiMoO 4 A composite material. The foam nickel loaded with the composite material is used as a working electrode, namely Co-MOF @ NiMoO 4 Working electrode (CNMO-6).
The Chenhua CHI760e electrochemical workstation adopts a cyclic voltammetry and constant current charging and discharging method, and adopts a three-electrode system to perform electrochemical test: the CMNO-6 foam nickel sheet is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a 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 composite material are detected, and cyclic voltammetry tests show that the composite material has excellent redox capability. The specific capacitance of the composite material reaches 1485F/g in 2mol/L KOH solution and at a current density of 0.5A/g.
Example 7:
NF @ Co-MOF @ NiMoO 4 The preparation method and the application of the composite material comprise the following steps:
step one, respectively dissolving 8mmol of dimethylimidazole and 1mmol of cobalt nitrate hexahydrate in 20mL of water, and stirring and dispersing uniformly to completely dissolve the dimethylimidazole and the cobalt nitrate hexahydrate to obtain a solution A and a solution B;
mixing the solution A and the solution B together to obtain a mixed solution, putting 1cm multiplied by 8mm foamed nickel which is sequentially treated by acetone, ethanol and water for 3 times into the mixed solution as a carrier, adopting a solution standing growth method, and standing and reacting for 4 hours at room temperature to prepare NF @ Co-MOF;
thirdly, adding 1mmol of Na 2 MoO 4 ·2H 2 O、1mmol Ni(NO 3 ) 2 ·6H 2 Dissolving O in 50mL of water, stirring and uniformly dispersing by ultrasound to completely dissolve the O to obtain a mixed solution, taking the mixed solution as an electrodeposition solution, taking 1cm multiplied by 1cm NF @ Co-MOF as a working electrode, a platinum wire as a counter electrode, ag/AgCl as a reference electrode, maintaining the electrodeposition solution at room temperature, wherein the scanning rate is 10mV/s, and the scanning period is 30. Taking out the sample after the electro-deposition is finished, washing the sample with deionized water for three times, putting the sample into a vacuum oven, and drying the sample for 12 hours at the temperature of 60 ℃ to obtain NF @ Co-MOF @ NiMoO 4 A composite material. The foam nickel loaded with the composite material is used as a working electrode, namely Co-MOF @ NiMoO 4 Working electrode (note CNMO-7).
The Chenghua CHI760e electrochemical workstation adopts a cyclic voltammetry and constant current charging and discharging method and adopts a three-electrode system for electrochemical test: the CMNO-7 foam nickel sheet is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a 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 composite material are detected, and cyclic voltammetry tests show that the composite material has excellent redox capability. The specific capacitance of the composite material reaches 1497.17F/g in 2mol/L KOH solution and at a current density of 1A/g.
Example 8:
NF @ Co-MOF @ NiMoO 4 The preparation method and the application of the composite material comprise the following steps:
step one, respectively dissolving 8mmol of dimethyl imidazole and 1mmol of cobalt nitrate hexahydrate in 20mL of water, and stirring and dispersing uniformly to completely dissolve the dimethyl imidazole and the cobalt nitrate hexahydrate to obtain a solution A and a solution B;
mixing the solution A and the solution B together to obtain a mixed solution, putting 1cm multiplied by 8mm foamed nickel which is treated by acetone, ethanol and water for 3 times in sequence into the mixed solution as a carrier, adopting a solution standing growth method, and standing and reacting for 4 hours at room temperature to obtain NF @ Co-MOF;
thirdly, adding 1mmol of Na 2 MoO 4 ·2H 2 O、1mmol Ni(NO 3 ) 2 ·6H 2 Dissolving O in 50mL of water, stirring and uniformly dispersing by ultrasound to completely dissolve the O to obtain a mixed solution, taking the mixed solution as an electrodeposition solution, taking 1cm multiplied by 1cm NF @ Co-MOF as a working electrode, a platinum wire as a counter electrode and Ag/AgCl as a reference electrode, maintaining the electrodeposition solution at room temperature, and carrying out scanning at a scanning rate of 15mV/s for 30 scanning periods. Taking out the sample after the electrodeposition is finished, washing the sample for three times by deionized water, putting the sample into a vacuum oven, and drying the sample for 12 hours at the temperature of 60 ℃ to obtain NF @ Co-MOF @ NiMoO 4 A composite material. The foam nickel loaded with the composite material is used as a working electrode, namely Co-MOF @ NiMoO 4 Working electrode (note CNMO-8).
The Chenghua CHI760e electrochemical workstation adopts a cyclic voltammetry and constant current charging and discharging method and adopts a three-electrode system for electrochemical test: the CMNO-8 foam nickel sheet is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a 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 composite material are detected, and cyclic voltammetry tests show that the composite material has excellent redox capability. The specific capacitance of the composite material reaches 1560.1F/g in 2mol/L KOH solution and at a current density of 2A/g.
Example 9:
NF @ Co-MOF @ NiMoO 4 The preparation method and the application of the composite material comprise the following steps:
step one, respectively dissolving 8mmol of dimethylimidazole and 1mmol of cobalt nitrate hexahydrate in 20mL of water, and stirring and dispersing uniformly to completely dissolve the dimethylimidazole and the cobalt nitrate hexahydrate to obtain a solution A and a solution B;
mixing the solution A and the solution B together to obtain a mixed solution, putting 1cm multiplied by 8mm foamed nickel which is treated by acetone, ethanol and water for 3 times in sequence into the mixed solution as a carrier, adopting a solution standing growth method, and standing and reacting for 4 hours at room temperature to obtain NF @ Co-MOF;
thirdly, 1mmol of Na 2 MoO 4 ·2H 2 O、1mmol Ni(NO 3 ) 2 ·6H 2 Dissolving O in 50mL of water, stirring and uniformly dispersing by ultrasound to completely dissolve the O to obtain a mixed solution, taking the mixed solution as an electrodeposition solution, taking 1cm multiplied by 1cm NF @ Co-MOF as a working electrode, a platinum wire as a counter electrode, ag/AgCl as a reference electrode, maintaining the electrodeposition solution at room temperature, wherein the scanning rate is 25mV/s, and the scanning period is 30. Taking out the sample after the electrodeposition is finished, washing the sample for three times by deionized water, putting the sample into a vacuum oven, and drying the sample for 12 hours at the temperature of 60 ℃ to obtain NF @ Co-MOF @ NiMoO 4 A composite material. The foam nickel loaded with the composite material is used as a working electrode, namely Co-MOF @ NiMoO 4 Working electrode (note CNMO-9).
The Chenhua CHI760e electrochemical workstation adopts a cyclic voltammetry and constant current charging and discharging method, and adopts a three-electrode system to perform electrochemical test: the CMNO-9 foam nickel sheet is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a 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 composite material are detected, and cyclic voltammetry tests show that the composite material has excellent redox capability. The specific capacitance of the composite material reaches 1701.69F/g in 2mol/L KOH solution and at a current density of 1A/g.
Example 10:
NF @ Co-MOF @ NiMoO 4 The preparation method and the application of the composite material comprise the following steps:
step one, respectively dissolving 8mmol of dimethyl imidazole and 1mmol of cobalt nitrate hexahydrate in 20mL of water, and stirring and dispersing uniformly to completely dissolve the dimethyl imidazole and the cobalt nitrate hexahydrate to obtain a solution A and a solution B;
mixing the solution A and the solution B together to obtain a mixed solution, putting 1cm multiplied by 8mm foamed nickel which is treated by acetone, ethanol and water for 3 times in sequence into the mixed solution as a carrier, adopting a solution standing growth method, and standing and reacting for 4 hours at room temperature to obtain NF @ Co-MOF;
thirdly, adding 1mmol of Na 2 MoO 4 ·2H 2 O、1mmol Ni(NO 3 ) 2 ·6H 2 Dissolving O in 50mL of water, stirring and uniformly dispersing by ultrasound to completely dissolve the O to obtain a mixed solution, taking the mixed solution as an electrodeposition solution, taking 1cm multiplied by 1cm NF @ Co-MOF as a working electrode, a platinum wire as a counter electrode, ag/AgCl as a reference electrode, maintaining the electrodeposition solution at room temperature, wherein the scanning rate is 20mV/s, and the scanning period is 15. Taking out the sample after the electrodeposition is finished, washing the sample for three times by deionized water, putting the sample into a vacuum oven, and drying the sample for 12 hours at the temperature of 60 ℃ to obtain NF @ Co-MOF @ NiMoO 4 A composite material. The foam nickel loaded with the composite material is used as a working electrode, namely Co-MOF @ NiMoO 4 Working electrode (CNMO-10).
The Chenghua CHI760e electrochemical workstation adopts a cyclic voltammetry and constant current charging and discharging method and adopts a three-electrode system for electrochemical test: the method comprises the following steps of taking a CMNO-10 foam nickel sheet as a working electrode, an Ag/AgCl electrode as a reference electrode, a Pt electrode as a counter electrode and 2mol/L KOH as an electrolyte solution. The specific capacitance and the cyclic stability of the composite material are detected, and cyclic voltammetry tests show that the composite material has excellent redox capability. The specific capacitance of the composite material reaches 1634.61F/g under the condition of 2mol/L KOH solution and the current density of 0.5A/g.
Example 11:
NF @ Co-MOF @ NiMoO 4 The preparation method and the application of the composite material comprise the following steps:
step one, respectively dissolving 8mmol of dimethylimidazole and 1mmol of cobalt nitrate hexahydrate in 20mL of water, and stirring and dispersing uniformly to completely dissolve the dimethylimidazole and the cobalt nitrate hexahydrate to obtain a solution A and a solution B;
mixing the solution A and the solution B together to obtain a mixed solution, putting 1cm multiplied by 8mm foamed nickel which is treated by acetone, ethanol and water for 3 times in sequence into the mixed solution as a carrier, adopting a solution standing growth method, and standing and reacting for 4 hours at room temperature to obtain NF @ Co-MOF;
thirdly, adding 1mmol of Na 2 MoO 4 ·2H 2 O、1mmol Ni(NO 3 ) 2 ·6H 2 Dissolving O in 50mL of water, stirring and uniformly dispersing by ultrasound to completely dissolve the O to obtain a mixed solution, taking the mixed solution as an electrodeposition solution, taking 1cm multiplied by 1cm NF @ Co-MOF as a working electrode, a platinum wire as a counter electrode, ag/AgCl as a reference electrode, maintaining the electrodeposition solution at room temperature, wherein the scanning rate is 20mV/s, and the scanning period is 20. Taking out the sample after the electro-deposition is finished, washing the sample with deionized water for three times, putting the sample into a vacuum oven, and drying the sample for 12 hours at the temperature of 60 ℃ to obtain NF @ Co-MOF @ NiMoO 4 A composite material. The foam nickel loaded with the composite material is used as a working electrode, namely Co-MOF @ NiMoO 4 Working electrode (note CNMO-11).
The Chenghua CHI760e electrochemical workstation adopts a cyclic voltammetry and constant current charging and discharging method and adopts a three-electrode system for electrochemical test: the CMNO-11 foam nickel sheet is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a 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 composite material are detected, and cyclic voltammetry tests show that the composite material has excellent redox capability. The specific capacitance of the composite material reaches 1660.36F/g in 2mol/L KOH solution and at a current density of 0.5A/g.
Example 12:
NF @ Co-MOF @ NiMoO 4 The preparation method and the application of the composite material comprise the following steps:
step one, respectively dissolving 8mmol of dimethyl imidazole and 1mmol of cobalt nitrate hexahydrate in 20mL of water, and stirring and dispersing uniformly to completely dissolve the dimethyl imidazole and the cobalt nitrate hexahydrate to obtain a solution A and a solution B;
mixing the solution A and the solution B together to obtain a mixed solution, putting 1cm multiplied by 8mm foamed nickel which is treated by acetone, ethanol and water for 3 times in sequence into the mixed solution as a carrier, adopting a solution standing growth method, and standing and reacting for 4 hours at room temperature to obtain NF @ Co-MOF;
in the third step, the first step is to use,1mmol of Na 2 MoO 4 ·2H 2 O、1mmol Ni(NO 3 ) 2 ·6H 2 Dissolving O in 50mL of water, stirring and uniformly dispersing by ultrasound to completely dissolve the O to obtain a mixed solution, taking the mixed solution as an electrodeposition solution, taking 1cm multiplied by 1cm NF @ Co-MOF as a working electrode, a platinum wire as a counter electrode, ag/AgCl as a reference electrode, maintaining the electrodeposition solution at room temperature, wherein the scanning rate is 20mV/s, and the scanning period is 35. Taking out the sample after the electrodeposition is finished, washing the sample for three times by deionized water, putting the sample into a vacuum oven, and drying the sample for 12 hours at the temperature of 60 ℃ to obtain NF @ Co-MOF @ NiMoO 4 A composite material. The foam nickel loaded with the composite material is used as a working electrode, namely Co-MOF @ NiMoO 4 Working electrode (note CNMO-12).
The Chenghua CHI760e electrochemical workstation adopts a cyclic voltammetry and constant current charging and discharging method and adopts a three-electrode system for electrochemical test: the CMNO-12 foam nickel sheet is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a 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 composite material are detected, and cyclic voltammetry tests show that the composite material has excellent redox capability. The specific capacitance of the composite material reaches 1631.94F/g under 2mol/L KOH solution and 2A/g current density.
Comparative example 1:
compared with example 1, most of them are the same, except that the introduction of nickel foam is omitted.
The Chenghua CHI760e electrochemical workstation adopts a cyclic voltammetry and constant current charging and discharging method and adopts a three-electrode system for electrochemical test: the CNMO foam nickel sheet is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a 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 composite material are detected, and cyclic voltammetry tests show that the composite material has excellent redox capability. The specific capacitance of the composite material reaches 952.7F/g in 2mol/L KOH solution and at a current density of 0.5A/g.
Comparative example 2:
compared to example 1, most of them are the same except that the foamed nickel is changed to a carbon cloth.
The Chenghua CHI760e electrochemical workstation adopts a cyclic voltammetry and constant current charging and discharging method and adopts a three-electrode system for electrochemical test: the CNMO foam nickel sheet is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a 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 composite material are detected, and cyclic voltammetry tests show that the composite material has excellent redox capability. The specific capacitance of the composite material reaches 853.1F/g in 2mol/L KOH solution and at a current density of 0.5A/g.
Comparative example 3:
compared with example 1, most of them are the same except that Na is added 2 MoO 4 ·2H 2 O、Ni(NO 3 ) 2 ·6H 2 The molar ratio of O is 0.5.
The Chenghua CHI760e electrochemical workstation adopts a cyclic voltammetry and constant current charging and discharging method and adopts a three-electrode system for electrochemical test: the CNMO foam nickel sheet is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a 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 composite material are detected, and cyclic voltammetry tests show that the composite material has excellent redox capability. The specific capacitance of the composite material reaches 1013.9F/g in 2mol/L KOH solution and at a current density of 0.5A/g.
Example 13:
NF @ Co-MOF @ NiMoO 4 The preparation method and the application of the composite material comprise the following steps:
step one, respectively dissolving 8mmol of dimethylimidazole and 1mmol of cobalt nitrate hexahydrate in 20mL of water, and stirring and dispersing uniformly to completely dissolve the dimethylimidazole and the cobalt nitrate hexahydrate to obtain a solution A and a solution B;
mixing the solution A and the solution B together to obtain a mixed solution, putting 1cm multiplied by 8mm foamed nickel which is treated by acetone, ethanol and water for 3 times in sequence into the mixed solution as a carrier, adopting a solution standing growth method, and standing and reacting for 4 hours at room temperature to obtain NF @ Co-MOF;
thirdly, adding 3mmol of Na 2 MoO 4 ·2H 2 O、1mmol Ni(NO 3 ) 2 ·6H 2 Dissolving O in 50mL of water, stirring and uniformly dispersing by ultrasound to completely dissolve the O to obtain a mixed solution, taking the mixed solution as an electrodeposition solution, taking 1cm multiplied by 1cm NF @ Co-MOF as a working electrode, a platinum wire as a counter electrode, ag/AgCl as a reference electrode, maintaining the electrodeposition solution at room temperature, wherein the scanning rate is 20mV/s, and the scanning period is 30. Taking out the sample after the electro-deposition is finished, washing the sample with deionized water for three times, putting the sample into a vacuum oven, and drying the sample for 12 hours at the temperature of 60 ℃ to obtain NF @ Co-MOF @ NiMoO 4 A composite material. The foam nickel loaded with the composite material is used as a working electrode, namely Co-MOF @ NiMoO 4 Working electrode (CNMO-13).
The Chenghua CHI760e electrochemical workstation adopts a cyclic voltammetry and constant current charging and discharging method and adopts a three-electrode system for electrochemical test: the foam nickel sheet of CNMO-13 is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a 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 composite material are detected, and cyclic voltammetry tests show that the composite material has excellent redox capability.
Example 14:
NF @ Co-MOF @ NiMoO 4 The preparation method and the application of the composite material comprise the following steps:
step one, respectively dissolving 8mmol of dimethyl imidazole and 1mmol of cobalt nitrate hexahydrate in 20mL of water, and stirring and dispersing uniformly to completely dissolve the dimethyl imidazole and the cobalt nitrate hexahydrate to obtain a solution A and a solution B;
mixing the solution A and the solution B together to obtain a mixed solution, putting 1cm multiplied by 8mm foamed nickel which is treated by acetone, ethanol and water for 3 times in sequence into the mixed solution as a carrier, adopting a solution standing growth method, and standing and reacting for 4 hours at room temperature to obtain NF @ Co-MOF;
thirdly, adding 2mmol of Na 2 MoO 4 ·2H 2 O、1mmol Ni(NO 3 ) 2 ·6H 2 Dissolution of OStirring and uniformly dispersing by ultrasound in 50mL of water to completely dissolve the mixture to obtain a mixed solution, taking the mixed solution as an electrodeposition solution, taking 1cm multiplied by 1cm NF @ Co-MOF as a working electrode, a platinum wire as a counter electrode, ag/AgCl as a reference electrode, maintaining the electrodeposition solution at room temperature, wherein the scanning rate is 20mV/s, and the scanning period is 30. Taking out the sample after the electro-deposition is finished, washing the sample with deionized water for three times, putting the sample into a vacuum oven, and drying the sample for 12 hours at the temperature of 60 ℃ to obtain NF @ Co-MOF @ NiMoO 4 A composite material. The foam nickel loaded with the composite material is used as a working electrode, namely Co-MOF @ NiMoO 4 Working electrode (note CNMO-14).
The Chenghua CHI760e electrochemical workstation adopts a cyclic voltammetry and constant current charging and discharging method and adopts a three-electrode system for electrochemical test: the foam nickel sheet of CNMO-14 is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a 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 composite material are detected, and cyclic voltammetry tests show that the composite material has excellent redox capability.
Example 15:
NF @ Co-MOF @ NiMoO 4 The preparation method and the application of the composite material comprise the following steps:
step one, respectively dissolving 8mmol of dimethyl imidazole and 1mmol of cobalt nitrate hexahydrate in 20mL of water, and stirring and dispersing uniformly to completely dissolve the dimethyl imidazole and the cobalt nitrate hexahydrate to obtain a solution A and a solution B;
mixing the solution A and the solution B together to obtain a mixed solution, putting 1cm multiplied by 8mm foamed nickel which is sequentially treated by acetone, ethanol and water for 3 times into the mixed solution as a carrier, adopting a solution standing growth method, and standing and reacting for 4 hours at room temperature to prepare NF @ Co-MOF;
thirdly, 2mmol of Na 2 MoO 4 ·2H 2 O、1mmol Ni(NO 3 ) 2 ·6H 2 Dissolving O in 50mL water, stirring and uniformly dispersing with ultrasound to completely dissolve to obtain mixed solution, using the mixed solution as electrodeposition solution, using 1cm × 1cm NF @ Co-MOF as working electrode, and using platinum wire as counter electrodeAg/AgCl is used as a reference electrode, the electro-deposition solution is maintained at room temperature, the scanning speed is 25mV/s, and the scanning period is 30. Taking out the sample after the electro-deposition is finished, washing the sample with deionized water for three times, putting the sample into a vacuum oven, and drying the sample for 12 hours at the temperature of 60 ℃ to obtain NF @ Co-MOF @ NiMoO 4 A composite material. The foam nickel loaded with the composite material is used as a working electrode, namely Co-MOF @ NiMoO 4 Working electrode (CNMO-15).
The Chenghua CHI760e electrochemical workstation adopts a cyclic voltammetry and constant current charging and discharging method and adopts a three-electrode system for electrochemical test: the foam nickel sheet of CNMO-15 is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a 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 composite material are detected, and cyclic voltammetry tests show that the composite material has excellent redox capability.
Example 16:
NF @ Co-MOF @ NiMoO 4 The preparation method and the application of the composite material comprise the following steps:
step one, respectively dissolving 8mmol of dimethyl imidazole and 1mmol of cobalt nitrate hexahydrate in 20mL of water, and stirring and dispersing uniformly to completely dissolve the dimethyl imidazole and the cobalt nitrate hexahydrate to obtain a solution A and a solution B;
mixing the solution A and the solution B together to obtain a mixed solution, putting 1cm multiplied by 8mm foamed nickel which is sequentially treated by acetone, ethanol and water for 3 times into the mixed solution as a carrier, adopting a solution standing growth method, and standing and reacting for 4 hours at room temperature to prepare NF @ Co-MOF;
thirdly, adding 2mmol of Na 2 MoO 4 ·2H 2 O、1mmol Ni(NO 3 ) 2 ·6H 2 Dissolving O in 50mL of water, stirring and uniformly dispersing by ultrasound to completely dissolve the O to obtain a mixed solution, taking the mixed solution as an electrodeposition solution, taking 1cm multiplied by 1cm NF @ Co-MOF as a working electrode, a platinum wire as a counter electrode, ag/AgCl as a reference electrode, maintaining the electrodeposition solution at room temperature, wherein the scanning rate is 5mV/s, and the scanning period is 30. Taking out the sample after the electrodeposition is finished, washing the sample for three times by deionized water, and putting the sample into a vacuum ovenDrying at 60 deg.C for 12h to obtain NF @ Co-MOF @ NiMoO 4 A composite material. The foam nickel loaded with the composite material is used as a working electrode, namely Co-MOF @ NiMoO 4 Working electrode (CNMO-16).
The Chenhua CHI760e electrochemical workstation adopts a cyclic voltammetry and constant current charging and discharging method, and adopts a three-electrode system to perform electrochemical test: the foam nickel sheet of CNMO-16 is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a 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 composite material are detected, and cyclic voltammetry tests show that the composite material has excellent redox capability.
In the above examples, the water added in the first step can be arbitrarily adjusted within a range of 15 to 25mL, and similarly, the water added in the third step can be arbitrarily adjusted within a range of 45 to 55mL, according to actual needs.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims (4)

1. NF @ Co-MOF @ NiMoO 4 The preparation method of the composite material is characterized by comprising the following steps:
(1) Dissolving dimethyl imidazole and cobalt nitrate hexahydrate in water respectively, stirring and dispersing uniformly to completely dissolve the dimethyl imidazole and the cobalt nitrate hexahydrate, and mixing the dimethyl imidazole and the cobalt nitrate hexahydrate together to obtain a mixed solution I;
(2) Putting foam nickel serving as a carrier into the mixed solution I, and standing and growing to obtain NF @ Co-MOF;
(3) Na is mixed with 2 MoO 4 ·2H 2 O、Ni(NO 3 ) 2 ·6H 2 Dispersing O in water to obtain a mixed solution IIAnd the mixed solution II is used as electrodeposition liquid, NF @ Co-MOF is used as a carrier, and a one-step cyclic voltammetry electrodeposition method is adopted to prepare the NF @ Co-MOF @ NiMoO 4 The composite material is a target product;
in the step (1), the molar ratio of the dimethyl imidazole to the cobalt nitrate hexahydrate is (10-6) to 1;
in the step (2), standing and growing are carried out at room temperature for 4-6 h;
in the step (3), na 2 MoO 4 ·2H 2 O、Ni(NO 3 ) 2 ·6H 2 The molar ratio of O is (1-3) to 1;
in the step (1), the addition amount ratio of the cobalt nitrate hexahydrate to the water is 1mmol: (15-25) mL;
in the step (2), the used foamed nickel is sequentially treated for a plurality of times by acetone, ethanol and water in advance;
in the step (3), the one-step cyclic voltammetry electrodeposition process is carried out at room temperature, the voltage range used for electrodeposition is-1.2-0.2V, the scanning rate is 5-25mV/s, and the scanning period is 15-35.
2. NF @ Co-MOF @ NiMoO 4 A composite material produced by the production method according to claim 1.
3. An NF @ Co-MOF @ NiMoO as claimed in claim 2 4 Use of a composite material, characterized in that the composite material is made into a working electrode and used in a supercapacitor.
4. An NF @ Co-MOF @ NiMoO according to claim 3 4 The application of the composite material is characterized in that when in specific application, NF @ Co-MOF @ NiMoO is used 4 Grinding the composite material, uniformly mixing the ground composite material with carbon black and polytetrafluoroethylene, and then pressing the mixture on a foam nickel sheet to obtain the working electrode, wherein the working electrode comprises NF @ Co-MOF @ NiMoO 4 The mass ratio of the composite material to the carbon black to the polytetrafluoroethylene is 8 (0.8-1.2) to 0.8-1.2.
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