CN110379647B - Preparation method of nano-porous nickel/nickel oxide loaded ultrathin cobalt hydroxide nanosheet flexible electrode material - Google Patents

Preparation method of nano-porous nickel/nickel oxide loaded ultrathin cobalt hydroxide nanosheet flexible electrode material Download PDF

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CN110379647B
CN110379647B CN201910746630.6A CN201910746630A CN110379647B CN 110379647 B CN110379647 B CN 110379647B CN 201910746630 A CN201910746630 A CN 201910746630A CN 110379647 B CN110379647 B CN 110379647B
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nickel
nickel oxide
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cobalt hydroxide
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CN110379647A (en
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秦春玲
赵峰
张岩
刘杨
王志峰
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Hebei University of Technology
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    • H—ELECTRICITY
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    • 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
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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
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    • H—ELECTRICITY
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    • 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
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    • H—ELECTRICITY
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    • 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
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    • 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
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    • H01G11/68—Current collectors characterised by their material
    • H—ELECTRICITY
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    • 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
    • H01G11/66—Current collectors
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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
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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    • Y02E60/13—Energy storage using capacitors

Abstract

A preparation method of a nano-porous nickel/nickel oxide loaded ultrathin cobalt hydroxide nanosheet flexible electrode material. According to the method, Ni-Zr-Ti alloy is used as a precursor, a layer of ultrathin cobalt hydroxide nanosheet is electrodeposited on the surface of the strip by using a three-electrode system through soaking in HF solution and heat treatment, and the nano porous nickel/nickel oxide supported ultrathin cobalt hydroxide nanosheet flexible electrode material is obtained. The method has the advantages of simplicity, safety and low cost, and the prepared electrode material of the super capacitor has no adhesive and current collector, has large specific surface area and good electrochemical performance, and overcomes the defects of complex process flow, long time consumption, high cost and the like of the current preparation of the nano porous nickel and cobalt electrode material.

Description

Preparation method of nano-porous nickel/nickel oxide loaded ultrathin cobalt hydroxide nanosheet flexible electrode material
The technical field is as follows:
the invention belongs to the field of preparation of electrode materials of supercapacitors, and mainly relates to preparation of an ultrathin cobalt hydroxide nanosheet electrode material loaded on the surface of nano-porous nickel/nickel oxide.
Background art:
global warming and depletion of fossil fuels have become environmental issues that humans have to face in the 21 st century. With the improvement of living standard of people, mobile phones, mobile computers and new energy automobiles become an indispensable part in daily life. The normal use of the products can not leave the energy storage equipment, but the daily use experience of the products is seriously influenced by the defects of small specific capacitance, low charging and discharging speed, small energy density and the like of the existing energy storage device. Compared with the traditional capacitor, the super capacitor has received attention from many researchers due to its excellent characteristics of safety, environmental protection, fast charging and discharging speed, high power density and high energy density.
An important factor affecting the electrochemical performance of supercapacitors is the electrode material. The electrode materials of the super capacitor are mainly divided into three types, namely metal oxides, conductive polymers and various active carbon materials. The high specific surface area of the activated carbon material is a great feature compared with other materials, but the excessive specific surface area means the increase of micropores, and the increase of the micropores hinders the electron conduction of the carbon material itself. Therefore, although the specific surface area of the carbon material is high, the utilization rate thereof is not high. Compared with carbon materials, the conductive polymer material has lower cost and can reduce the equivalent resistance of the electrode. However, due to the lack of efficient N doping, the cell voltage of conductive polymers cannot be as high as that of carbon-based cells, and the polymers degrade due to volume expansion and contraction during long-term cycling, resulting in poor cycling stability. Ni and Co as transition metals have abundant oxide and hydroxide reserves, low price, higher theoretical specific capacitance and better cycling stability, and are considered as novel energy storage electrode materials with the most application prospect.
However, the currently prepared nano nickel and cobalt electrode material still can not meet the daily use requirement. On one hand, powdery oxides or hydroxides of Ni and Co are easy to agglomerate to hinder the transmission of ions, and need to be mixed with a binder and loaded on a current collector to exert the capacitance characteristic of the current collector, and the introduction of the binder and the current collector inevitably causes the increase of the internal resistance of electron transmission, so that the utilization rate of an active material is reduced; on the other hand, the flexibility of the electrode and its stability of electrochemical performance under different bending angles are also an important factor affecting its application. Therefore, the development of a flexible wearable electrode material with high active material utilization rate and free-standing is an important research field of current researchers.
In the prior art, the publication No. CN109686581A 'cobalt hydroxide/rGO/nickel hydroxide sandwich-shaped flexible electrode material and a preparation method thereof', carbon fiber cloth subjected to ultrasonic treatment is used as a substrate, the carbon fiber cloth is dried for 12-48 hours and then subjected to hydrothermal treatment for 3-9 hours, a layer of nickel hydroxide is deposited on the carbon cloth, a layer of rGO is deposited on the surface of the carbon cloth by using an electrodeposition method after the carbon cloth is dried, and then a layer of cobalt hydroxide is deposited on the carbon cloth subjected to hydrothermal treatment for 6-15 hours by using the carbon cloth on which the rGO/nickel hydroxide is deposited, so that the cobalt hydroxide/rGO/nickel hydroxide sandwich-shaped flexible electrode material is obtained. The preparation process has the advantages of complex flow, long total period, extremely low efficiency, strict requirements on equipment and experimental environment, and difficulty in realizing controllable preparation and large-scale preparation of the electrode material.
In the prior art, publication No. CN 106710889A' discloses a multi-level structure cobalt hydroxide electrode material and a preparation method thereof, in the patent, cobalt nitrate, aluminum nitrate, urea and deionized water are mixed for hydrothermal reaction for 12-24 h, after the reaction is finished, the cobalt aluminum hydroxide is obtained by centrifuging, washing and freeze-drying for 24-48 h, and the multi-level cobalt hydroxide electrode material is obtained by dissolving the prepared cobalt aluminum hydroxide in the deionized water and adding sodium hydroxide or potassium hydroxide solution to etch the aluminum hydroxide. First, the extent of the reaction of etching aluminum hydroxide using an alkaline solution is difficult to control. Secondly, the active substance prepared by the method can exert the capacitance characteristic of the active substance only by being loaded on a Pt net, on one hand, the introduction of current collectors such as the Pt net and the like inevitably causes the increase of the internal resistance of electron transmission, and the utilization rate of the active substance is reduced; on the other hand, the electrode is easily broken under a large angle bending and the electrochemical performance is easily affected.
The invention content is as follows:
the invention aims to provide a preparation method of a nano-porous nickel/nickel oxide loaded ultrathin cobalt hydroxide nanosheet flexible electrode material, aiming at the defects in the prior art. According to the method, Ni-Zr-Ti alloy is used as a precursor, a layer of ultrathin cobalt hydroxide nanosheet is electrodeposited on the surface of the strip by using a three-electrode system through soaking in HF solution and heat treatment, and the nano porous nickel/nickel oxide supported ultrathin cobalt hydroxide nanosheet flexible electrode material is obtained. The method has the advantages of simplicity, safety and low cost, and the prepared electrode material of the super capacitor has no adhesive and current collector, has large specific surface area and good electrochemical performance, and overcomes the defects of complex process flow, long time consumption, high cost and the like of the current preparation of the nano porous nickel and cobalt electrode material.
The technical scheme of the invention is as follows:
a preparation method of a nano-porous nickel/nickel oxide loaded ultrathin cobalt hydroxide nanosheet flexible electrode material comprises the following steps:
first, preparing a nano porous nickel/nickel oxide template
Soaking and corroding Ni-Zr-Ti alloy amorphous strips serving as precursors in 0.03-0.08M HF solution for 2-6 h by adopting a natural dealloying process to prepare nano porous nickel; after the corrosion is finished, washing the surface of the strip, then placing the strip into a tubular furnace, carrying out heat treatment at 250-450 ℃ for 2-4 h, and continuously introducing oxygen at the speed of 200-400 mL/min in the period to prepare a nano porous nickel/nickel oxide template;
second, preparation of cobalt hydroxide nanosheet
In a three-electrode system, a working electrode is the nano-porous nickel/nickel oxide template prepared in the first step, a counter electrode is a metal platinum sheet, and a reference electrode is an Ag/AgCl electrode; placing the nano-porous nickel/nickel oxide template prepared in the first step into a cobalt source solution, and electrodepositing a layer of ultrathin cobalt hydroxide nanosheets, namely the nano-porous nickel/nickel oxide supported ultrathin cobalt hydroxide nanosheet flexible electrode material;
wherein the deposition potential is-1.5 to-1.0V, and the deposition time is 10 to 60 min; the cobalt source solution is a mixed solution containing cobalt nitrate hexahydrate and urea, and the molar ratio is that the cobalt nitrate hexahydrate: urea is 5: 1-10: 1; the molar concentration of the cobalt nitrate hexahydrate in the cobalt source solution is 3-8 mM.
The Ni-Zr-Ti alloy is preferably Ni40Zr20Ti40。
The size of the amorphous strip is preferably 1cm multiplied by 1mm multiplied by 20 μm to 5cm multiplied by 3mm multiplied by 30 μm.
The equipment and raw materials used for preparing the nano porous nickel/nickel oxide loaded ultrathin cobalt hydroxide nanosheet flexible electrode material are obtained by a known way, and the preparation method is simple and easy to master.
Compared with the prior art, the invention has the prominent substantive characteristics as follows:
(1) the nano porous nickel/nickel oxide template prepared by the method is strip-shaped, and the electrodeposition directly on the nano porous nickel/nickel oxide template can not only avoid the introduction of foam nickel or activated carbon cloth to realize self-support, but also endow the electrode material with extra specific capacitance due to the existence of the bottom layer nickel oxide.
(2) The nano porous nickel/nickel oxide template prepared by the method has extremely high porosity, can realize the tight combination of the cobalt hydroxide nanosheet and the matrix, and can effectively avoid the agglomeration of the cobalt hydroxide nanosheet during deposition.
Compared with the prior art, the invention has the following benefits and effects:
(1) at present, no relevant report exists for preparing an electrode material by using nano porous nickel/nickel oxide as a template and electrodepositing cobalt hydroxide on the surface of the nano porous nickel/nickel oxide. With Ni40Zr20Ti40The amorphous strip is a precursor, and the intermediate layer is still in an amorphous state after dealloying, so that excellent flexibility can be provided for the electrode material.
(2) Compared with the traditional nano-porous and nano-sheet metal, the method deposits a layer of ultrathin flake cobalt hydroxide on the surface of the nano-porous nickel/nickel oxide, and leaves a certain gap between sheets, so that certain relation is formed between holes and sheets, the specific surface area of an electrode material is favorably improved, the transmission of ions in electrolyte is favorably realized, and the utilization rate of active substances is greatly improved. Compared with the electrochemical performance of the nano porous nickel/nickel oxide electrode, the electro-precipitationThe electrode of the cobalt hydroxide ultrathin nano-sheet shows extremely high specific capacitance, because the specific capacitance of the nickel/nickel oxide at the bottom layer and the specific capacitance of the cobalt hydroxide at the surface layer are included in the total specific capacitance. By regulating the concentration of Co source and deposition time, the optimal specific capacitance can reach 1243.6F/cm3。
(3) The electrode material prepared by the invention has excellent flexibility and electrochemical stability, the electrochemical performance of the electrode material does not fluctuate greatly under different bending angles, and the electrode material has good application prospect in the field of flexible wearable electrode materials.
Description of the drawings:
FIG. 1: scanning electron microscope photographs of the nanoporous nickel/nickel oxide supported ultrathin cobalt hydroxide nanosheet electrode of example 1.
FIG. 2: elemental spectrum analysis chart of the nanoporous nickel/nickel oxide supported ultrathin cobalt hydroxide nanosheet electrode in example 1.
FIG. 3: the charge-discharge curve of the nano-porous nickel/nickel oxide supported ultrathin cobalt hydroxide nanosheet electrode in example 1.
FIG. 4: a constant current charging and discharging curve diagram of the nano porous nickel/nickel oxide/cobalt hydroxide ultrathin nanosheet electrode in example 2.
FIG. 5: the charge-discharge curve diagram of the nano-porous nickel/nickel oxide/cobalt hydroxide ultrathin nanosheet electrode in example 3.
Detailed Description
Example 1:
the invention provides a preparation method of an active nano porous nickel/nickel oxide loaded ultrathin cobalt hydroxide nanosheet flexible electrode material, which mainly comprises the following steps:
s1: selecting the alloy component as Ni40Zr20Ti40Immersing the precursor into an etching solution to etch for 6h by using an amorphous strip with the size of 2cm multiplied by 1.5mm multiplied by 20 mu M as a precursor and 0.03M HF solution as the etching solution, washing residual HF solution on the surface of the strip by deionized water after the etching is finished, then placing the strip into a tubular furnace to carry out heat treatment for 2h at 250 ℃, and continuously introducing oxygen at the speed of 200mL/min during the heat treatment for 2hSo as to prepare a nano porous nickel/nickel oxide template;
s2: and (3) after the template prepared in the S1 is cooled to room temperature, washing the template for 3-4 times by using deionized water and alcohol, then immersing the template into a mixed solution of cobalt nitrate hexahydrate and urea with a molar concentration ratio of 10:1 by adopting a three-electrode system, wherein the molar concentration of the cobalt nitrate hexahydrate is 8mM, and depositing a layer of cobalt hydroxide on the nano porous nickel/nickel oxide template.
Wherein the system used for deposition is a three-electrode system, the template made by S1 is used as a working electrode, a metal platinum sheet is used as a counter electrode, an Ag/AgCl electrode is used as a reference electrode, the deposition potential is-1.0V, and the time is 10 min.
In order to test the electrochemical performance of the prepared electrode material, a constant current charge-discharge curve of the prepared electrode material is tested under a three-electrode system by using an electrochemical workstation. The electrode material prepared in S2 is a working electrode, a metal platinum sheet is a counter electrode, an Ag/AgCl electrode is a reference electrode, an electrolyte is a 1mol/L KOH solution, and the constant current charging and discharging current density is 1A/cm3The voltage window is 0.45V.
Fig. 1 is a scanning electron microscope image of the nano-porous nickel/nickel oxide supported ultrathin cobalt hydroxide nanosheet electrode in the present embodiment, which can clearly see that uniform flaky cobalt hydroxide grows on the surface of the nano-porous nickel/nickel oxide, the thickness of the cobalt hydroxide nanosheet is only 9.63nm as measured by using nano measure measurement software, and the cobalt hydroxide nanosheet is uniformly distributed on a bottom layer nickel/nickel oxide template, so that a larger specific surface area is provided for the attachment of an active substance; moreover, a certain distance is kept between the sheets, and the transmission of ions in holes at the bottom layer in the electrode reaction process is not influenced, so that the specific capacitance of the prepared composite electrode has the specific capacitance of nickel/nickel oxide and the specific capacitance of cobalt hydroxide at the surface layer.
Fig. 2 is an energy spectrum analysis diagram of the nano-porous nickel/nickel oxide supported ultrathin cobalt hydroxide nanosheet electrode in the present embodiment, peaks of metallic nickel and cobalt appear in the diagram, which indicates that cobalt and nickel coexist, and the coexistence of nickel/nickel oxide/cobalt hydroxide is further determined by combining X-ray diffraction detection.
FIG. 3 shows the preparation of Nanopolymer in this embodimentThe constant-current charge-discharge curve diagram of the porous nickel/nickel oxide/cobalt hydroxide nanosheet clearly shows obvious charge and discharge platforms from the curve, which correspond to the oxidation reaction and the reduction reaction respectively, and shows the pseudocapacitance characteristics of the nanosheet. Calculated at 1A/cm3The specific capacitance under the current density is as high as 1243.6F/cm3。
Example 2:
s1: selecting the alloy component as Ni40Zr20Ti40Taking an amorphous strip with the size of 1cm multiplied by 1mm multiplied by 20 mu M as a precursor, using 0.05M HF solution as corrosive liquid, corroding for 4h, washing residual HF solution on the surface of the strip with deionized water after the corrosion is finished, then placing the strip in a tubular furnace, and carrying out heat treatment for 3h at 350 ℃, wherein oxygen is continuously introduced at the speed of 300mL/min in the period of time, so that the nano porous nickel/nickel oxide template can be prepared;
s2: and (3) after the template prepared in the S1 is cooled to room temperature, washing the template for 3-4 times by using deionized water and alcohol, then immersing the template into a solution in which cobalt nitrate hexahydrate and urea are mixed according to a molar concentration ratio of 8:1, wherein the molar concentration of the cobalt nitrate hexahydrate is 6mM, and depositing a layer of cobalt hydroxide on the nano-porous nickel/nickel oxide template.
Wherein the system used for deposition is a three-electrode system, the template made by S1 is used as a working electrode, a metal platinum sheet is used as a counter electrode, an Ag/AgCl electrode is used as a reference electrode, the deposition potential is-1.2V, and the time is 30 min.
In order to test the electrochemical performance of the prepared electrode material, a constant current charge-discharge curve of the prepared electrode material is tested under a three-electrode system by using an electrochemical workstation. The electrode material prepared in S2 is a working electrode, a metal platinum sheet is a counter electrode, an Ag/AgCl electrode is a reference electrode, an electrolyte is a 1mol/L KOH solution, and the constant current charging and discharging current density is 1A/cm3The voltage window is 0.45V.
Fig. 4 is a constant current charge and discharge curve diagram of the electrode material prepared in the present embodiment, and it is clear that the charge time and the discharge time are nearly equal, indicating that the electrode material has excellent coulombic efficiency. By calculation, it is at 1A/cm3The specific capacitance at the discharge current density of (2) was 1042.3F/g.
Example 3:
s1: selecting the alloy component as Ni40Zr20Ti40Taking an amorphous strip with the size of 5cm multiplied by 3mm multiplied by 30 mu M as a precursor, using 0.08M HF solution as corrosive liquid, corroding for 2h, washing residual HF solution on the surface of the strip by deionized water after the corrosion is finished, then placing the strip in a tubular furnace, and carrying out heat treatment for 2h at 200 ℃, wherein oxygen is continuously introduced during the heat treatment to obtain the nano porous nickel/nickel oxide template;
s2: and (3) after the template prepared in the S1 is cooled to room temperature, washing the template for 3-4 times by using deionized water and alcohol, and then soaking the template into a solution in which cobalt nitrate hexahydrate and urea are mixed according to the concentration ratio of 5:1, wherein the molar concentration of the cobalt nitrate hexahydrate is 3mM, and a layer of cobalt hydroxide is deposited on the nano porous nickel/nickel oxide template.
Wherein the system used for deposition is a three-electrode system, the template made by S1 is used as a working electrode, a metal platinum sheet is used as a counter electrode, an Ag/AgCl electrode is used as a reference electrode, the deposition potential is-1.5V, and the time is 60 min.
In order to test the electrochemical performance of the prepared electrode material, a constant current charge-discharge curve of the prepared electrode material is tested under a three-electrode system by using an electrochemical workstation. The electrode material prepared in S2 is a working electrode, a metal platinum sheet is a counter electrode, an Ag/AgCl electrode is a reference electrode, an electrolyte is a 1mol/L KOH solution, and the constant current charging and discharging current density is 1A/cm3The voltage window is 0.45V.
Fig. 5 is a graph of the charge and discharge performance of the electrode material prepared in this example, from which the charge and discharge plateaus corresponding to the pseudocapacitance characteristics and nearly equal charge and discharge times can be clearly seen, indicating that the electrode has good reversibility. It was further calculated at 1A/cm3Specific capacitance of 972.5F/cm at discharge current density3。
Comparative example 1:
the strip after dealloying was heat treated at 150 ℃ for 1h and oxygen was introduced at a rate of 80mL/min, with the other steps being the same as in example 1. And performing energy spectrum analysis and X-ray diffraction detection on the prepared electrode material, wherein the ratio of oxygen atoms to cobalt is close to 2:1, and only crystal peaks of cobalt hydroxide and nickel are detected in an X-ray diffraction spectrogram, which shows that only cobalt hydroxide is formed on the surface layer, and the amount of nickel oxide or nickel oxide is not present.
Comparative example 2:
cobalt nitrate hexahydrate solution is selected as electrodeposition solution, other steps are the same as those in the example 1, the microcosmic appearance of the prepared cobalt hydroxide is hexagonal, the thickness is 3 mu m, and the specific capacitance is only 621.5F/cm3。
Comparative example 3:
the deposition potential is selected to be-0.8V, other steps are the same as those in the embodiment 1, the microscopic morphology of the nano-film is observed after deposition is completed, and the fact that no obvious nano-film is generated on the surface is found. The electrochemical performance of the nano-porous nickel/nickel oxide electrode is measured, the difference between the nano-porous nickel/nickel oxide electrode and the nano-porous nickel/nickel oxide electrode is found to be not much, and a layer of cobalt hydroxide nanosheet is further determined not to be deposited on the surface of the nano-porous nickel/nickel oxide electrode.
Comparative example 4:
the time for depositing cobalt hydroxide on the surface of the nano-pore nickel/nickel oxide is prolonged to 2 hours, and other steps are the same as those in the embodiment 1. After deposition, the strip is bent obviously, which indicates that the internal stress changes. When the flexibility of the belt is tested, the belt is broken by applying a small external force, and self-supporting cannot be realized.
The above comparative examples are cases of experimental failure, and the experimental results can not reach the expectation by randomly changing the preparation process. After experimental parameters are adjusted for many times, the control of process links is strictly determined after practice without restriction, and the temperature and time of heat treatment are strictly controlled and oxygen needs to be continuously introduced when the nano porous nickel/nickel oxide template is prepared. When the cobalt hydroxide ultrathin nanosheet is prepared by electrodeposition, the concentration ratio of a cobalt source to urea is controlled to be 10: 1-5: 1, wherein the concentration of the cobalt nitrate hexahydrate is 3-8 mM; the deposition potential is-1.5 to-1.0V, and the time is 1min to 60 min. When all the parameters are within the range, the nano-porous nickel/nickel oxide supported ultrathin cobalt hydroxide nanosheet flexible electrode material with high electrochemical performance can be prepared.
The invention is not the best known technology.

Claims (3)

1. A preparation method of a nano-porous nickel/nickel oxide loaded ultrathin cobalt hydroxide nanosheet flexible electrode material is characterized by comprising the following steps:
first, preparing a nano porous nickel/nickel oxide template
Soaking and corroding Ni-Zr-Ti alloy amorphous strips serving as precursors in 0.03-0.08M HF solution for 2-6 h by adopting a natural dealloying process to prepare nano porous nickel; after the corrosion is finished, washing the surface of the strip, then placing the strip into a tubular furnace, carrying out heat treatment at 250-450 ℃ for 2-4 h, and continuously introducing oxygen at the speed of 200-400 mL/min in the period to prepare a nano porous nickel/nickel oxide template;
second, preparation of cobalt hydroxide nanosheet
In a three-electrode system, a working electrode is the nano-porous nickel/nickel oxide template prepared in the first step, a counter electrode is a metal platinum sheet, and a reference electrode is an Ag/AgCl electrode; placing the nano-porous nickel/nickel oxide template prepared in the first step into a cobalt source solution, and electrodepositing a layer of ultrathin cobalt hydroxide nanosheets, namely the nano-porous nickel/nickel oxide supported ultrathin cobalt hydroxide nanosheet flexible electrode material;
wherein the deposition potential is-1.5 to-1.0V, and the deposition time is 10 to 60 min; the cobalt source solution is a mixed solution containing cobalt nitrate hexahydrate and urea, and the molar ratio is that the cobalt nitrate hexahydrate: urea is 5: 1-10: 1; the molar concentration of the cobalt nitrate hexahydrate in the cobalt source solution is 3-8 mM.
2. The method for preparing the nano-porous nickel/nickel oxide supported ultrathin cobalt hydroxide nanosheet flexible electrode material of claim 1, wherein the Ni-Zr-Ti alloy is Ni40Zr20Ti40。
3. The method for preparing the nano-porous nickel/nickel oxide supported ultrathin cobalt hydroxide nanosheet flexible electrode material as claimed in claim 1, wherein the amorphous strips have dimensions of 1cm x 1mm x 20 μm to 5cm x 3mm x 30 μm.
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