CN114044912A - A kind of Ni-Co-ZIF composite material and its preparation method and application - Google Patents

A kind of Ni-Co-ZIF composite material and its preparation method and application Download PDF

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CN114044912A
CN114044912A CN202111214903.6A CN202111214903A CN114044912A CN 114044912 A CN114044912 A CN 114044912A CN 202111214903 A CN202111214903 A CN 202111214903A CN 114044912 A CN114044912 A CN 114044912A
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zif
composite material
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nickel
deionized water
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蔺华林
赵玉壮
李梦琰
杨洋
孙彬
任飞鹤
陈亚莉
卢义麟
穆晓银
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Shanghai Institute of Technology
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    • 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
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Abstract

本发明涉及一种Ni‑Co‑ZIF复合材料及其制备方法与应用，其中制备方法包括：泡沫镍预处理；将可溶性镍盐、二甲基咪唑溶于去离子水中，充分溶解并获得溶液A；将可溶性钴盐、二甲基咪唑溶于去离子水中，充分溶解并获得溶液B；将溶液A和溶液B进行混合，搅拌均匀后得到Ni‑Co‑ZIF溶液；将泡沫镍浸泡在Ni‑Co‑ZIF溶液中，在室温下进行搅拌、浸泡，以此将Ni‑Co‑ZIF负载于处理后的泡沫镍之上；清洗，干燥，得到Ni‑Co‑ZIF复合材料产品。与现有技术相比，本发明通过一步浸泡法合成了Ni‑Co‑ZIF复合材料，利用一步浸泡法将Ni‑Co‑ZIF复合材料负载于泡沫镍之上，大大缩短了合成与电极制作时间，Ni‑Co‑ZIF复合材料具有良好的电化学性能，且Ni‑Co‑ZIF复合材料制备方法简单，对环境友好。

Figure 202111214903

The invention relates to a Ni-Co-ZIF composite material and a preparation method and application thereof, wherein the preparation method comprises: foam nickel pretreatment; dissolving soluble nickel salt and dimethylimidazole in deionized water, fully dissolving and obtaining solution A ; Dissolve soluble cobalt salt and dimethylimidazole in deionized water, fully dissolve and obtain solution B; mix solution A and solution B, and stir to obtain Ni-Co-ZIF solution; soak nickel foam in Ni- In the Co-ZIF solution, the Ni-Co-ZIF is loaded on the treated nickel foam by stirring and soaking at room temperature; cleaning and drying to obtain a Ni-Co-ZIF composite product. Compared with the prior art, the Ni-Co-ZIF composite material is synthesized by a one-step soaking method, and the Ni-Co-ZIF composite material is loaded on the nickel foam by a one-step soaking method, which greatly shortens the synthesis and electrode fabrication time. , Ni‑Co‑ZIF composite material has good electrochemical performance, and the preparation method of Ni‑Co‑ZIF composite material is simple and environmentally friendly.

Figure 202111214903

Description

Ni-Co-ZIF composite material and preparation method and application thereof
Technical Field
The invention relates to a Ni-Co-ZIF composite material and a preparation method and application thereof, in particular to a Ni-Co-ZIF composite material and a preparation method and application thereof.
Background
With the development of science and technology, electronic equipment is more and more popular, and therefore, the requirements of people on energy storage devices are further improved. The problem of the need of people for energy demand and technical development can be solved under ideal conditions by developing more excellent energy storage equipment. Currently, the main energy storage devices in the market are batteries (lead batteries, lithium batteries, metal air batteries, fuel batteries, sodium batteries, magnesium batteries, etc.) and capacitors as auxiliary devices. The main difference between the super capacitor and the battery and the fuel cell is that the super capacitor has the advantages of long cycle life, high power density, large charging and discharging current and the like, the cycle life and the stability of the super capacitor easily exceed 100 ten thousand cycles, and the battery electrode can reach the level only when the battery is charged and discharged at low depth of discharge, and the super capacitor is pollution-free and environment-friendly, and the super capacitor is used as the supplement or even the replacement of the battery at present, so the super capacitor has great potential to become a mainstream energy storage device in the future.
As a constituent of the supercapacitor, an electrode material having a specific structure determines the performance of the supercapacitor. In summary, for the last decade, transition metals, especially nickel, cobalt, copper and zinc elements, have been widely used in research and development of energy storage electrode materials due to their excellent electrochemical properties and abundant natural resources. Nickel cobalt compounds have received increasing attention in recent years as a new type of multifunctional material. However, the electrochemical performance of the existing nickel-cobalt compounds is not particularly ideal, and the synthesis efficiency is low.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a Ni-Co-ZIF composite material and a preparation method and application thereof.
The traditional energy storage mechanism of the double electric layer super capacitor is that the principle of physical adsorption of charges is utilized to store energy, a larger specific surface area is needed, the Ni-Co-ZIF composite material belongs to one metal organic framework, the larger specific surface area exists naturally, more active sites can be provided, however, the conductivity of the metal organic framework is poorer, so that the Ni-Co-ZIF composite material is synthesized by a one-step soaking method through soluble nickel salt, soluble cobalt salt and dimethyl imidazole, and the conductivity of the Ni-Co-ZIF composite material is greatly improved. Meanwhile, the Ni-Co-ZIF composite material can store and release more charges through oxidation-reduction reaction so as to achieve high energy density and high power density. The behavior of pseudocapacitive materials is determined by charge transport, since they depend on surface or near-surface redox reactions. Therefore, their theoretically predicted high capacitance is rarely obtained in practical experiments.
The purpose of the invention can be realized by the following technical scheme:
the first purpose of the technical scheme is to protect a preparation method of a Ni-Co-ZIF composite material, which comprises the following steps:
(1) pretreating foamed nickel for later use;
(2) dissolving soluble nickel salt and dimethyl imidazole in deionized water, and performing ultrasonic dispersion to fully dissolve the soluble nickel salt and the dimethyl imidazole to obtain a solution A;
(3) dissolving soluble cobalt salt and dimethyl imidazole in deionized water, and performing ultrasonic dispersion to fully dissolve the soluble cobalt salt and the dimethyl imidazole to obtain a solution B;
(4) mixing the solution A and the solution B, and uniformly stirring to obtain a Ni-Co-ZIF solution;
(5) soaking the foamed nickel treated in the step (1) in a Ni-Co-ZIF solution, stirring and soaking at room temperature, and loading the Ni-Co-ZIF on the treated foamed nickel;
(6) and respectively cleaning the foamed nickel loaded with the Ni-Co-ZIF composite material by using deionized water and absolute ethyl alcohol, and drying to obtain a Ni-Co-ZIF composite material product.
Further, in the step (1), the foamed nickel with the size of 1 cm x 4 cm is soaked in acetone, water and absolute ethyl alcohol for 30 minutes respectively, then ultrasonic treatment is carried out for 15 minutes respectively, and drying is carried out for standby after repeating the steps for three times.
Further, in the steps (2) to (3), the soluble nickel salt is nickel nitrate hexahydrate, and the soluble cobalt salt is cobalt nitrate hexahydrate.
Furthermore, in the step (4), the mass/volume ratio of the soluble nickel salt, the soluble cobalt salt, the dimethyl imidazole and the deionized water is 1 (0.8-1.2) to 1.5-2 to 60-100 ml.
Further, in the step (4), the mol/volume ratio of the soluble nickel salt to the soluble cobalt salt to the dimethyl imidazole to the deionized water is 1 mmol: 1 mmol: 5 mmol: (30-55) mL.
Further, in the step (4), in the step (5), the reaction temperature is 5-40 ℃ and the reaction time is 6-24 hours.
Further, in the step (1) and the step (6), the drying mode is vacuum drying, and the temperature is 55-65 ℃ in the drying process, and the time is 10-14 h.
The second purpose of the technical scheme is to protect the Ni-Co-ZIF composite material prepared by the method.
The third purpose of the technical scheme is to protect the application of the Ni-Co-ZIF composite material in the super capacitor.
Further, stirring and soaking at room temperature for 12 hours, loading Ni-Co-ZIF on the processed foamed nickel, respectively cleaning the foamed nickel loaded with the Ni-Co-ZIF composite material for 3 times by using deionized water and absolute ethyl alcohol, placing the cleaned foamed nickel in a vacuum drying oven at 60 ℃ for vacuum drying for 12 hours, and directly using the cleaned foamed nickel as a working electrode after drying in the vacuum drying oven without further manufacturing electrodes.
Compared with the prior art, the invention has the following technical advantages:
1) the Ni-Co-ZIF composite material is synthesized by a one-step soaking method, and is formed by mutually connecting nano structures with rich pore structures, and the material has a large specific surface area, can provide more active sites, can promote the flow diffusion of electrolyte and further improves the electrochemical performance of the material.
2) The specific surface area of the ZIF compound is superior to that of other active carbon compounds, so that the prepared working electrode has high energy density and power density and can be applied to a super capacitor.
Drawings
FIG. 1 is a CV diagram of the Ni-Co-ZIF composite material prepared in example 1 at various sweep rates.
FIG. 2 is a GCD plot of the Ni-Co-ZIF composite prepared in example 1 at a current density of 1A/g.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. In the technical scheme, characteristics such as preparation means, materials, structures or composition ratios and the like which are not explicitly described are all regarded as common technical characteristics disclosed in the prior art. If the starting products or processing techniques are not specifically indicated, they are all conventional commercial products or conventional processing techniques in the art.
Example 1:
a preparation method of a Ni-Co-ZIF composite material electrode comprises the following steps:
soaking foamed nickel with the size of 1 cm by 4 cm in acetone, water and absolute ethyl alcohol for 30 minutes respectively, then performing ultrasonic treatment for 15 minutes respectively, repeating the steps for three times, and drying for later use; 1mmol of Ni (NO)3)2·6H2Dissolving O and 5mmol 2-MI in 20mL deionized water, and performing ultrasonic treatment in an ultrasonic instrument for 5 minutes to fully dissolve the O and 5mmol 2-MI to obtain a solution A; 1mmol of Co (NO)3)2·6H2Dissolving O and 5mmol 2-MI in 20mL deionized water, and performing ultrasonic treatment in an ultrasonic instrument for 5 minutes to fully dissolve the O and 5mmol 2-MI to obtain a solution B; mixing the solution A and the solution B, stirring the mixed solution for 12 hours under magnetic stirring, and uniformly stirring to obtain a Ni-Co-ZIF solution; soaking one quarter of the processed foamed nickel in a Ni-Co-ZIF solution, stirring and soaking for 12 hours at room temperature, and loading the Ni-Co-ZIF on the processed foamed nickel; and (3) respectively cleaning the nickel foam loaded with the Ni-Co-ZIF composite material by using deionized water and absolute ethyl alcohol for 3 times, and placing the cleaned nickel foam in a vacuum drying oven at 60 ℃ for vacuum drying for 12 hours to obtain the Ni-Co-ZIF working electrode (noted as NCZ-1).
Three-electrode tests (cyclic voltammetry and constant current charging and discharging methods) were performed using an electrochemical workstation (chenhua CHI760e) for the electrochemical performance of the working electrode: the reference electrode of the three-electrode system test is a standard Ag/AgCl electrode, the counter electrode is a Pt electrode, the working electrode consists of NCZ-1 loaded on foamed nickel and the foamed nickel, and the electrolyte solution used by the three-electrode system test is a prepared 6M KOH solution. The specific capacitance and the cyclic stability of the composite material are detected by using cyclic voltammetry test, and the composite material has excellent oxidation-reduction capability.
FIG. 1 is a CV diagram of the prepared Ni-Co-ZIF composite material at different sweep rates, wherein the sweep rates are respectively 10mV/s, 20mV/s and 40 mV/s. As can be seen from FIG. 1, in the voltage range of-0.2 to 0.2V, 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 Ni-Co-ZIF composite material has good reversibility and stability.
FIG. 2 is a GCD curve of the prepared Ni-Co-ZIF composite material at a current density of 1A/g, and good symmetry of the curve can be seen from FIG. 2 to confirm that the redox reaction has good reversibility.
Example 2:
a preparation method of a Ni-Co-ZIF composite material electrode comprises the following steps:
soaking foamed nickel with the size of 1 cm by 4 cm in acetone, water and absolute ethyl alcohol for 30 minutes respectively, then performing ultrasonic treatment for 15 minutes respectively, repeating the steps for three times, and drying for later use; 1mmol of Ni (NO)3)2·6H2Dissolving O and 4mmol 2-MI in 20mL deionized water, and performing ultrasonic treatment in an ultrasonic instrument for 5 minutes to fully dissolve the O and 4mmol 2-MI to obtain a solution A; 1mmol of Co (NO)3)2·6H2Dissolving O and 4mmol 2-MI in 20mL deionized water, and performing ultrasonic treatment in an ultrasonic instrument for 5 minutes to fully dissolve the O and 4mmol 2-MI to obtain a solution B; mixing the solution A and the solution B, stirring the mixed solution for 12 hours under magnetic stirring, and uniformly stirring to obtain a Ni-Co-ZIF solution; soaking one quarter of the processed foamed nickel in a Ni-Co-ZIF solution, stirring and soaking for 12 hours at room temperature, and loading the Ni-Co-ZIF on the processed foamed nickel; and (3) respectively cleaning the nickel foam loaded with the Ni-Co-ZIF composite material by using deionized water and absolute ethyl alcohol for 3 times, and placing the cleaned nickel foam in a vacuum drying oven at 60 ℃ for vacuum drying for 12 hours to obtain the Ni-Co-ZIF working electrode (noted as NCZ-2).
Three-electrode tests (cyclic voltammetry and constant current charging and discharging methods) were performed using an electrochemical workstation (chenhua CHI760e) for the electrochemical performance of the working electrode: the reference electrode of the three-electrode system test is a standard Ag/AgCl electrode, the counter electrode is a Pt electrode, the working electrode consists of NCZ-2 loaded on foamed nickel and the foamed nickel, and the electrolyte solution used by the three-electrode system test is a prepared 6M KOH solution. The specific capacitance and the cyclic stability of the composite material are detected by using cyclic voltammetry test, and the composite material has excellent oxidation-reduction capability.
Example 3:
a preparation method of a Ni-Co-ZIF composite material electrode comprises the following steps:
soaking foamed nickel with the size of 1 cm by 4 cm in acetone, water and absolute ethyl alcohol for 30 minutes respectively, then performing ultrasonic treatment for 15 minutes respectively, repeating the steps for three times, and drying for later use; 1mmol of Ni (NO)3)2·6H2Dissolving O and 6mmol 2-MI in 20mL deionized water, and performing ultrasonic treatment in an ultrasonic instrument for 5 minutes to fully dissolve the O and 6mmol 2-MI to obtain a solution A; 1mmol of Co (NO)3)2·6H2Dissolving O and 6mmol 2-MI in 20mL deionized water, and performing ultrasonic treatment in an ultrasonic instrument for 5 minutes to fully dissolve the O and 6mmol 2-MI to obtain a solution B; mixing the solution A and the solution B, stirring the mixed solution for 12 hours under magnetic stirring, and uniformly stirring to obtain a Ni-Co-ZIF solution; soaking one quarter of the processed foamed nickel in a Ni-Co-ZIF solution, stirring and soaking for 12 hours at room temperature, and loading the Ni-Co-ZIF on the processed foamed nickel; and respectively cleaning the nickel foam loaded with the Ni-Co-ZIF composite material for 3 times by using deionized water and absolute ethyl alcohol, and placing the cleaned nickel foam in a vacuum drying oven at 60 ℃ for vacuum drying for 12 hours to obtain the Ni-Co-ZIF working electrode (noted as NCZ-3).
Three-electrode tests (cyclic voltammetry and constant current charging and discharging methods) were performed using an electrochemical workstation (chenhua CHI760e) for the electrochemical performance of the working electrode: the reference electrode of the three-electrode system test is a standard Ag/AgCl electrode, the counter electrode is a Pt electrode, the working electrode consists of NCZ-3 loaded on foamed nickel and the foamed nickel, and the electrolyte solution used by the three-electrode system test is a prepared 6M KOH solution. The specific capacitance and the cyclic stability of the composite material are detected by using cyclic voltammetry test, and the composite material has excellent oxidation-reduction capability.
Example 4:
a preparation method of a Ni-Co-ZIF composite material electrode comprises the following steps:
soaking foamed nickel with the size of 1 cm by 4 cm in acetone, water and absolute ethyl alcohol for 30 minutes respectively, then performing ultrasonic treatment for 15 minutes respectively, repeating the steps for three times, and drying for later use; 1mmol of Ni (NO)3)2·6H2O, 5mmol of 2-MI in 2Carrying out ultrasonic treatment in 0mL of deionized water for 5 minutes in an ultrasonic instrument to fully dissolve the deionized water and obtain a solution A; 1.2mmol of Co (NO)3)2·6H2Dissolving O and 5mmol 2-MI in 20mL deionized water, and performing ultrasonic treatment in an ultrasonic instrument for 5 minutes to fully dissolve the O and 5mmol 2-MI to obtain a solution B; mixing the solution A and the solution B, stirring the mixed solution for 12 hours under magnetic stirring, and uniformly stirring to obtain a Ni-Co-ZIF solution; soaking one quarter of the processed foamed nickel in a Ni-Co-ZIF solution, stirring and soaking for 12 hours at room temperature, and loading the Ni-Co-ZIF on the processed foamed nickel; and (3) respectively cleaning the nickel foam loaded with the Ni-Co-ZIF composite material by using deionized water and absolute ethyl alcohol for 3 times, and placing the cleaned nickel foam in a vacuum drying oven at 60 ℃ for vacuum drying for 12 hours to obtain the Ni-Co-ZIF working electrode (noted as NCZ-4).
Three-electrode tests (cyclic voltammetry and constant current charging and discharging methods) were performed using an electrochemical workstation (chenhua CHI760e) for the electrochemical performance of the working electrode: the reference electrode of the three-electrode system test is a standard Ag/AgCl electrode, the counter electrode is a Pt electrode, the working electrode consists of NCZ-4 loaded on foamed nickel and the foamed nickel, and the electrolyte solution used by the three-electrode system test is a prepared 6M KOH solution. The specific capacitance and the cyclic stability of the composite material are detected by using cyclic voltammetry test, and the composite material has excellent oxidation-reduction capability.
Example 5:
a preparation method of a Ni-Co-ZIF composite material electrode comprises the following steps:
soaking foamed nickel with the size of 1 cm by 4 cm in acetone, water and absolute ethyl alcohol for 30 minutes respectively, then performing ultrasonic treatment for 15 minutes respectively, repeating the steps for three times, and drying for later use; 1mmol of Ni (NO)3)2·6H2Dissolving O and 5mmol 2-MI in 20mL deionized water, and performing ultrasonic treatment in an ultrasonic instrument for 5 minutes to fully dissolve the O and 5mmol 2-MI to obtain a solution A; 0.8mmol of Co (NO)3)2·6H2Dissolving O and 5mmol 2-MI in 20mL deionized water, and performing ultrasonic treatment in an ultrasonic instrument for 5 minutes to fully dissolve the O and 5mmol 2-MI to obtain a solution B; mixing solution A andmixing the solution B, stirring the mixed solution for 12 hours under magnetic stirring, and uniformly stirring to obtain a Ni-Co-ZIF solution; soaking one quarter of the processed foamed nickel in a Ni-Co-ZIF solution, stirring and soaking for 12 hours at room temperature, and loading the Ni-Co-ZIF on the processed foamed nickel; and (3) respectively cleaning the nickel foam loaded with the Ni-Co-ZIF composite material by using deionized water and absolute ethyl alcohol for 3 times, and placing the cleaned nickel foam in a vacuum drying oven at 60 ℃ for vacuum drying for 12 hours to obtain the Ni-Co-ZIF working electrode (noted as NCZ-5).
Three-electrode tests (cyclic voltammetry and constant current charging and discharging methods) were performed using an electrochemical workstation (chenhua CHI760e) for the electrochemical performance of the working electrode: the reference electrode of the three-electrode system test is a standard Ag/AgCl electrode, the counter electrode is a Pt electrode, the working electrode consists of NCZ-5 loaded on foamed nickel and the foamed nickel, and the electrolyte solution used by the three-electrode system test is a prepared 6M KOH solution. The specific capacitance and the cyclic stability of the composite material are detected by using cyclic voltammetry test, and the composite material has excellent oxidation-reduction capability.
Example 6:
a preparation method of a Ni-Co-ZIF composite material electrode comprises the following steps:
soaking foamed nickel with the size of 1 cm by 4 cm in acetone, water and absolute ethyl alcohol for 30 minutes respectively, then performing ultrasonic treatment for 15 minutes respectively, repeating the steps for three times, and drying for later use; 1mmol of Ni (NO)3)2·6H2Dissolving O and 5mmol 2-MI in 20mL deionized water, and performing ultrasonic treatment in an ultrasonic instrument for 5 minutes to fully dissolve the O and 5mmol 2-MI to obtain a solution A; 1mmol of Co (NO)3)2·6H2Dissolving O and 5mmol 2-MI in 20mL deionized water, and performing ultrasonic treatment in an ultrasonic instrument for 5 minutes to fully dissolve the O and 5mmol 2-MI to obtain a solution B; mixing the solution A and the solution B, stirring the mixed solution for 6 hours under magnetic stirring, and uniformly stirring to obtain a Ni-Co-ZIF solution; soaking one quarter of the processed foamed nickel in a Ni-Co-ZIF solution, stirring and soaking for 12 hours at room temperature, and loading the Ni-Co-ZIF on the processed foamed nickel; load NAnd (3) respectively cleaning the foamed nickel of the i-Co-ZIF composite material by using deionized water and absolute ethyl alcohol for 3 times, and placing the cleaned foamed nickel in a vacuum drying oven at 60 ℃ for vacuum drying for 12 hours to obtain the Ni-Co-ZIF working electrode (NCZ-6).
Three-electrode tests (cyclic voltammetry and constant current charging and discharging methods) were performed using an electrochemical workstation (chenhua CHI760e) for the electrochemical performance of the working electrode: the reference electrode of the three-electrode system test is a standard Ag/AgCl electrode, the counter electrode is a Pt electrode, the working electrode consists of NCZ-6 loaded on foamed nickel and the foamed nickel, and the electrolyte solution used by the three-electrode system test is a prepared 6M KOH solution. The specific capacitance and the cyclic stability of the composite material are detected by using cyclic voltammetry test, and the composite material has excellent oxidation-reduction capability.
Example 7:
a preparation method of a Ni-Co-ZIF composite material electrode comprises the following steps:
soaking foamed nickel with the size of 1 cm by 4 cm in acetone, water and absolute ethyl alcohol for 30 minutes respectively, then performing ultrasonic treatment for 15 minutes respectively, repeating the steps for three times, and drying for later use; 1mmol of Ni (NO)3)2·6H2Dissolving O and 6mmol 2-MI in 20mL deionized water, and performing ultrasonic treatment in an ultrasonic instrument for 5 minutes to fully dissolve the O and 6mmol 2-MI to obtain a solution A; 1mmol of Co (NO)3)2·6H2Dissolving O and 6mmol 2-MI in 20mL deionized water, and performing ultrasonic treatment in an ultrasonic instrument for 5 minutes to fully dissolve the O and 6mmol 2-MI to obtain a solution B; mixing the solution A and the solution B, stirring the mixed solution for 24 hours under magnetic stirring, and uniformly stirring to obtain a Ni-Co-ZIF solution; soaking one quarter of the processed foamed nickel in a Ni-Co-ZIF solution, stirring and soaking for 12 hours at room temperature, and loading the Ni-Co-ZIF on the processed foamed nickel; and (3) respectively cleaning the nickel foam loaded with the Ni-Co-ZIF composite material by using deionized water and absolute ethyl alcohol for 3 times, and placing the cleaned nickel foam in a vacuum drying oven at 60 ℃ for vacuum drying for 12 hours to obtain the Ni-Co-ZIF working electrode (noted as NCZ-7).
Three-electrode tests (cyclic voltammetry and constant current charging and discharging methods) were performed using an electrochemical workstation (chenhua CHI760e) for the electrochemical performance of the working electrode: the reference electrode of the three-electrode system test is a standard Ag/AgCl electrode, the counter electrode is a Pt electrode, the working electrode consists of NCZ-7 loaded on foamed nickel and the foamed nickel, and the electrolyte solution used by the three-electrode system test is a prepared 6M KOH solution. The specific capacitance and the cyclic stability of the composite material are detected by using cyclic voltammetry test, and the composite material has excellent oxidation-reduction capability.
Example 8:
a preparation method of a Ni-Co-ZIF composite material electrode comprises the following steps:
soaking foamed nickel with the size of 1 cm by 4 cm in acetone, water and absolute ethyl alcohol for 30 minutes respectively, then performing ultrasonic treatment for 15 minutes respectively, repeating the steps for three times, and drying for later use; 1mmol of Ni (NO)3)2·6H2Dissolving O and 6mmol 2-MI in 20mL deionized water, and performing ultrasonic treatment in an ultrasonic instrument for 5 minutes to fully dissolve the O and 6mmol 2-MI to obtain a solution A; 1mmol of Co (NO)3)2·6H2Dissolving O and 6mmol 2-MI in 20mL deionized water, and performing ultrasonic treatment in an ultrasonic instrument for 5 minutes to fully dissolve the O and 6mmol 2-MI to obtain a solution B; mixing the solution A and the solution B, stirring the mixed solution for 12 hours under magnetic stirring, and uniformly stirring to obtain a Ni-Co-ZIF solution; soaking one quarter of the processed foamed nickel in a Ni-Co-ZIF solution, stirring and soaking for 6 hours at room temperature, and loading the Ni-Co-ZIF on the processed foamed nickel; and (3) respectively cleaning the nickel foam loaded with the Ni-Co-ZIF composite material by using deionized water and absolute ethyl alcohol for 3 times, and placing the cleaned nickel foam in a vacuum drying oven at 60 ℃ for vacuum drying for 12 hours to obtain the Ni-Co-ZIF working electrode (noted as NCZ-8).
Three-electrode tests (cyclic voltammetry and constant current charging and discharging methods) were performed using an electrochemical workstation (chenhua CHI760e) for the electrochemical performance of the working electrode: the reference electrode of the three-electrode system test is a standard Ag/AgCl electrode, the counter electrode is a Pt electrode, the working electrode consists of NCZ-8 loaded on foamed nickel and the foamed nickel, and the electrolyte solution used by the three-electrode system test is a prepared 6M KOH solution. The specific capacitance and the cyclic stability of the composite material are detected by using cyclic voltammetry test, and the composite material has excellent oxidation-reduction capability.
Example 9:
a preparation method of a Ni-Co-ZIF composite material electrode comprises the following steps:
soaking foamed nickel with the size of 1 cm by 4 cm in acetone, water and absolute ethyl alcohol for 30 minutes respectively, then performing ultrasonic treatment for 15 minutes respectively, repeating the steps for three times, and drying for later use; 1mmol of Ni (NO)3)2·6H2Dissolving O and 6mmol 2-MI in 20mL deionized water, and performing ultrasonic treatment in an ultrasonic instrument for 5 minutes to fully dissolve the O and 6mmol 2-MI to obtain a solution A; 1mmol of Co (NO)3)2·6H2Dissolving O and 6mmol 2-MI in 20mL deionized water, and performing ultrasonic treatment in an ultrasonic instrument for 5 minutes to fully dissolve the O and 6mmol 2-MI to obtain a solution B; mixing the solution A and the solution B, stirring the mixed solution for 12 hours under magnetic stirring, and uniformly stirring to obtain a Ni-Co-ZIF solution; soaking one quarter of the processed foamed nickel in a Ni-Co-ZIF solution, stirring and soaking for 24 hours at room temperature, and loading the Ni-Co-ZIF on the processed foamed nickel; and (3) respectively cleaning the nickel foam loaded with the Ni-Co-ZIF composite material by using deionized water and absolute ethyl alcohol for 3 times, and placing the cleaned nickel foam in a vacuum drying oven at 60 ℃ for vacuum drying for 12 hours to obtain the Ni-Co-ZIF working electrode (NCZ-9).
Three-electrode tests (cyclic voltammetry and constant current charging and discharging methods) were performed using an electrochemical workstation (chenhua CHI760e) for the electrochemical performance of the working electrode: the reference electrode of the three-electrode system test is a standard Ag/AgCl electrode, the counter electrode is a Pt electrode, the working electrode consists of NCZ-9 loaded on foamed nickel and the foamed nickel, and the electrolyte solution used by the three-electrode system test is a prepared 6M KOH solution. The specific capacitance and the cyclic stability of the composite material are detected by using cyclic voltammetry test, and the composite material has excellent oxidation-reduction capability.
Example 10:
a preparation method of a Ni-Co-ZIF composite material electrode comprises the following steps:
soaking foamed nickel with the size of 1 cm by 4 cm in acetone, water and absolute ethyl alcohol for 30 minutes respectively, then performing ultrasonic treatment for 15 minutes respectively, repeating the steps for three times, and drying for later use; 1mmol of Ni (NO)3)2·6H2Dissolving O and 6mmol 2-MI in 20mL deionized water, and performing ultrasonic treatment in an ultrasonic instrument for 5 minutes to fully dissolve the O and 6mmol 2-MI to obtain a solution A; 1mmol of Co (NO)3)2·6H2Dissolving O and 6mmol 2-MI in 20mL deionized water, and performing ultrasonic treatment in an ultrasonic instrument for 5 minutes to fully dissolve the O and 6mmol 2-MI to obtain a solution B; mixing the solution A and the solution B, stirring the mixed solution for 12 hours under magnetic stirring, and uniformly stirring to obtain a Ni-Co-ZIF solution; soaking one quarter of the processed foamed nickel in a Ni-Co-ZIF solution, stirring and soaking for 24 hours at room temperature, and loading the Ni-Co-ZIF on the processed foamed nickel; and (3) respectively cleaning the nickel foam loaded with the Ni-Co-ZIF composite material by using deionized water and absolute ethyl alcohol for 3 times, and placing the cleaned nickel foam in a vacuum drying oven at 60 ℃ for vacuum drying for 6 hours to obtain the Ni-Co-ZIF working electrode (noted as NCZ-10).
Three-electrode tests (cyclic voltammetry and constant current charging and discharging methods) were performed using an electrochemical workstation (chenhua CHI760e) for the electrochemical performance of the working electrode: the reference electrode of the three-electrode system test is a standard Ag/AgCl electrode, the counter electrode is a Pt electrode, the working electrode consists of NCZ-10 loaded on foamed nickel and the foamed nickel, and the electrolyte solution used by the three-electrode system test is a prepared 6M KOH solution. The specific capacitance and the cyclic stability of the composite material are detected by using cyclic voltammetry test, and the composite material has excellent oxidation-reduction capability.
Example 11:
a preparation method of a Ni-Co-ZIF composite material electrode comprises the following steps:
soaking foamed nickel with the size of 1 cm by 4 cm in acetone, water and absolute ethyl alcohol for 30 minutes respectively, then performing ultrasonic treatment for 15 minutes respectively, repeating the steps for three times, and drying for later use; 1mmol of Ni (NO)3)2·6H2Dissolving O and 6mmol 2-MI in 20mL deionized water, and performing ultrasonic treatment in an ultrasonic instrument for 5 minutes to fully dissolve the O and 6mmol 2-MI to obtain a solution A; 1mmol of Co (NO)3)2·6H2Dissolving O and 6mmol 2-MI in 20mL deionized water, and performing ultrasonic treatment in an ultrasonic instrument for 5 minutes to fully dissolve the O and 6mmol 2-MI to obtain a solution B; mixing the solution A and the solution B, stirring the mixed solution for 12 hours under magnetic stirring, and uniformly stirring to obtain a Ni-Co-ZIF solution; soaking one quarter of the processed foamed nickel in a Ni-Co-ZIF solution, stirring and soaking for 24 hours at room temperature, and loading the Ni-Co-ZIF on the processed foamed nickel; and (3) respectively cleaning the nickel foam loaded with the Ni-Co-ZIF composite material by using deionized water and absolute ethyl alcohol for 3 times, and placing the cleaned nickel foam in a vacuum drying oven at 60 ℃ for vacuum drying for 24 hours to obtain the Ni-Co-ZIF working electrode (NCZ-11).
Three-electrode tests (cyclic voltammetry and constant current charging and discharging methods) were performed using an electrochemical workstation (chenhua CHI760e) for the electrochemical performance of the working electrode: the reference electrode of the three-electrode system test is a standard Ag/AgCl electrode, the counter electrode is a Pt electrode, the working electrode consists of NCZ-11 loaded on foamed nickel and the foamed nickel, and the electrolyte solution used by the three-electrode system test is a prepared 6M KOH solution. The specific capacitance and the cyclic stability of the composite material are detected by using cyclic voltammetry test, and the composite material has excellent oxidation-reduction capability.
In addition, in the preparation process of the Ni-Co-ZIF composite material, the process conditions can be adjusted randomly within the following process ranges according to requirements (namely, the middle point value or the end value is selected randomly):
dissolving soluble nickel salt and dimethyl imidazole in deionized water, and carrying out ultrasonic treatment in an ultrasonic instrument for 5 minutes to fully dissolve the soluble nickel salt and the dimethyl imidazole to obtain a solution A. Dissolving soluble cobalt salt and dimethyl imidazole in deionized water, and carrying out ultrasonic treatment in an ultrasonic instrument for 5 minutes to fully dissolve the soluble cobalt salt and the dimethyl imidazole to obtain a solution B. And mixing the solution A and the solution B, stirring the mixed solution for 6-24 hours under magnetic stirring, and uniformly stirring to obtain the Ni-Co-ZIF solution.
And soaking one fourth of the processed foamed nickel in the Ni-Co-ZIF solution, stirring and soaking for 6-24 hours at room temperature, and loading the Ni-Co-ZIF on the processed foamed nickel.
Respectively cleaning the nickel foam loaded with the Ni-Co-ZIF composite material for 3 times by using deionized water and absolute ethyl alcohol, and placing the cleaned nickel foam in a vacuum drying oven at 60 ℃ for vacuum drying for 6-24 hours.
In the preparation method of the Ni-Co-ZIF composite material, the mass ratio of soluble nickel salt, soluble cobalt salt, dimethyl imidazole and deionized water is 1 (0.8-1.2) to 1.5-2 to 60-100 ml.
The preparation method of the Ni-Co-ZIF composite material comprises the steps of soaking, stirring and reacting at room temperature and 5-40 ℃ for 6-24 hours.
In the preparation method of the Ni-Co-ZIF composite material, the adding amount ratio of soluble cobalt salt, soluble nickel salt, dimethyl imidazole and deionized water is 1 mmol: 1 mmol: 5 mmol: (30-55) mL.
In the preparation method of the Ni-Co-ZIF composite material, the drying mode is vacuum drying, and the temperature is 55-65 ℃ in the drying process for 10-14 h.
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 (10)

1. The preparation method of the Ni-Co-ZIF composite material is characterized by comprising the following steps of:
(1) pretreating foamed nickel for later use;
(2) dissolving soluble nickel salt and dimethyl imidazole in deionized water, and performing ultrasonic dispersion to fully dissolve the soluble nickel salt and the dimethyl imidazole to obtain a solution A;
(3) dissolving soluble cobalt salt and dimethyl imidazole in deionized water, and performing ultrasonic dispersion to fully dissolve the soluble cobalt salt and the dimethyl imidazole to obtain a solution B;
(4) mixing the solution A and the solution B, and uniformly stirring to obtain a Ni-Co-ZIF solution;
(5) soaking the foamed nickel treated in the step (1) in a Ni-Co-ZIF solution, stirring and soaking at room temperature, and loading the Ni-Co-ZIF on the treated foamed nickel;
(6) and respectively cleaning the foamed nickel loaded with the Ni-Co-ZIF composite material by using deionized water and absolute ethyl alcohol, and drying to obtain a Ni-Co-ZIF composite material product.
2. The method for preparing a Ni-Co-ZIF composite material according to claim 1, wherein in the step (1), the nickel foam with a size of 1 cm x 4 cm is soaked in acetone, water, and absolute ethanol for 30 minutes, then is subjected to ultrasonic treatment for 15 minutes, and is dried for standby after being repeated three times.
3. The method of claim 1, wherein in steps (2) to (3), the soluble nickel salt is nickel nitrate hexahydrate, and the soluble cobalt salt is cobalt nitrate hexahydrate.
4. The method for preparing a Ni-Co-ZIF composite material as claimed in claim 1, wherein in the step (4), the mass/volume ratio of the soluble nickel salt, the soluble cobalt salt, the dimethyl imidazole and the deionized water is 1 (0.8-1.2) to 1.5-2 to 60-100 ml.
5. The method for preparing the Ni-Co-ZIF composite material according to claim 4, wherein in the step (4), the mol/volume ratio of the soluble nickel salt to the soluble cobalt salt to the dimethyl imidazole to the deionized water is 1 mmol: 1 mmol: 5 mmol: (30-55) mL.
6. The method for preparing a Ni-Co-ZIF composite material according to claim 1, wherein in the step (4), the reaction temperature in the step (5) is 5 to 40 ℃, and the reaction time is 6 to 24 hours.
7. The method for preparing the Ni-Co-ZIF composite material according to claim 1, wherein the drying mode in the step (1) and the drying mode in the step (6) are vacuum drying, and the temperature is 55-65 ℃ and the time is 10-14h in the drying process.
8. A Ni-Co-ZIF composite material prepared by the method as set forth in any one of claims 1 to 7.
9. Use of the Ni-Co-ZIF composite of claim 8 in a supercapacitor.
10. The use of the Ni-Co-ZIF composite material in the supercapacitor according to claim 1, wherein the Ni-Co-ZIF composite material is stirred and soaked at room temperature for 12 hours, Ni-Co-ZIF is loaded on the treated nickel foam, the nickel foam loaded with the Ni-Co-ZIF composite material is washed with deionized water and absolute ethanol for 3 times, respectively, the washed nickel foam is placed in a vacuum drying oven at 60 ℃ for vacuum drying for 12 hours, and the dried nickel foam is directly used as a working electrode after being dried in the vacuum drying oven.
CN202111214903.6A 2021-10-19 2021-10-19 A kind of Ni-Co-ZIF composite material and its preparation method and application Pending CN114044912A (en)

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