CN113066674B - Nickel-cobalt-zinc ternary transition metal hydroxide electrode material with multistage nanostructure and preparation method and application thereof - Google Patents

Nickel-cobalt-zinc ternary transition metal hydroxide electrode material with multistage nanostructure and preparation method and application thereof Download PDF

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CN113066674B
CN113066674B CN202110314878.2A CN202110314878A CN113066674B CN 113066674 B CN113066674 B CN 113066674B CN 202110314878 A CN202110314878 A CN 202110314878A CN 113066674 B CN113066674 B CN 113066674B
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cobalt
nickel
zinc
transition metal
metal hydroxide
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CN113066674A (en
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黄子航
马天翼
李慧
孙放放
孟凡瑾
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Liaoning University
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Abstract

The invention relates to a nickel-cobalt-zinc ternary transition metal hydroxide electrode material with a multilevel structure for a super capacitor, and a preparation method and application thereof, and belongs to the technical field of energy storage. The invention adopts a method of combining hydrothermal and electrochemical steps to construct a hierarchical nano structure of combining nano sheets and nano wires, namely, a nickel-cobalt-zinc nano wire grows on a carbon cloth substrate through nitrate of hydrothermal nickel-cobalt-zinc, and then a crystal structure is recast in strong alkaline electrolyte by using an electrochemical method on the basis of the nickel-cobalt-zinc nano wire, so that a structure of combining two-dimensional ultrathin nano sheets and one-dimensional nano wires is obtained. When the material is applied to the positive electrode of the super capacitor, the integral capacitance is improved by more than five times, and the practicability of the material in the aspect of the super capacitor is greatly improved.

Description

Nickel-cobalt-zinc ternary transition metal hydroxide electrode material with multistage nanostructure and preparation method and application thereof
Technical Field
The invention belongs to the technical field of new energy, and particularly relates to a nickel-cobalt-zinc ternary transition metal hydroxide electrode material with a multistage nanostructure, and a preparation method and application thereof.
Background
The gradual depletion of conventional fossil fuels has made energy and environmental problems more and more prominent, and researchers have been focused on developing various new clean energy sources, such as solar energy, wind energy, tidal energy, etc., which have intermittent nature and cannot continuously and stably output energy required for production and life, and thus convert it into electric energy for more convenient storage and output. Batteries and supercapacitors are widely studied and used as mainstream energy storage devices. The super capacitor has the advantages of high power density, high charging and discharging speed, long service life, environmental friendliness and the like, and is widely applied to the fields of smart power grids, hybrid vehicles, portable electronic equipment and the like.
However, compared with batteries, supercapacitors have severely restricted development and application thereof due to low energy density, and improving the specific capacitance of materials is considered as one of the solutions for increasing energy density. Among them, nickel cobalt, a transition metal, has a very high theoretical capacitance, and zinc, as a semiconductor, has a good conductivity, and the organic combination of the three is deeply studied as an electrode material. However, the capacitance of the materials is far from reaching a satisfactory degree, so that the specific capacitance of the nickel-cobalt-zinc material is continuously improved by reasonably constructing the microscopic nanostructure of the materials in a simpler and more efficient manner, which is very necessary to solve the problem of low energy density of the super capacitor.
Disclosure of Invention
The invention aims to construct nickel-cobalt-zinc ternary transition metal hydroxide combining nanosheets and nanowires on carbon cloth by a hydrothermal and electrochemical combined method, increase active sites of a nickel-cobalt-zinc electrode material and achieve the purpose of improving the specific capacitance of the electrode material.
In order to achieve the purpose, the invention adopts the technical scheme that: a nickel-cobalt-zinc ternary transition metal hydroxide electrode material with a multilevel nanostructure is prepared by the following steps:
1) dissolving cobalt nitrate, nickel nitrate, zinc nitrate, urea and ammonium acetate in deionized water to form a precursor solution, and immersing the cleaned carbon cloth in the precursor solution for hydrothermal treatment to form a nickel-cobalt-zinc nanowire, namely CC @ NCZ-wires;
2) placing the nickel-cobalt-zinc nano wire in a three-electrode system, carrying out cyclic voltammetry treatment under strong base electrolyte, soaking a treated sample in deionized water to remove redundant electrolyte, and then drying in a vacuum drying oven at 60 ℃ for 12 hours to obtain a structure combining the nickel-cobalt-zinc nano sheet and the nano wire, namely CC @ NCZ-wires @ NC-sheets.
Further, the nickel-cobalt-zinc ternary transition metal hydroxide electrode material with the multilevel nanostructure is characterized in that the molar ratio of cobalt nitrate: nickel nitrate: zinc nitrate: urea: ammonium acetate 3:1.5:0.5-2.5:6: 5.
Further, the nickel-cobalt-zinc ternary transition metal hydroxide electrode material with the multistage nanostructure is characterized in that the hydrothermal treatment is carried out at 130 ℃ for 5 hours.
Further, the nickel-cobalt-zinc ternary transition metal hydroxide electrode material with the multilevel nanostructure is characterized in that in the step 1), the carbon cloth cleaning method specifically comprises the following steps: the carbon cloth was rinsed with absolute ethanol, followed by sonication with deionized water.
Further, the nickel-cobalt-zinc ternary transition metal hydroxide electrode material with a multilevel nanostructure is characterized in that, in the step 2), the ternary system is as follows: the CC @ NCZ-wires obtained in the step 1) are used as working electrodes, the Hg/HgO electrode is used as a reference electrode, and the carbon paper is used as a counter electrode.
Further, the nickel-cobalt-zinc ternary transition metal hydroxide electrode material with the multilevel nanostructure is characterized in that in the step 2), the strong base electrolyte is: 1-6M potassium hydroxide solution.
Further, the nickel-cobalt-zinc ternary transition metal hydroxide electrode material with the multilevel nanostructure is characterized in that in the step 2), specific parameters of the cyclic voltammetry treatment are as follows: sweeping speed of 50mV/s, and circulating for 1000 circles.
The nickel-cobalt-zinc ternary transition metal hydroxide electrode material with the multilevel nanostructure is applied to a super capacitor.
Further, the application refers to the application of any one of the nickel-cobalt-zinc ternary transition metal hydroxide electrode materials with the multilevel nanostructure as a positive electrode material in a super capacitor.
The invention has the following advantages:
(1) the invention prepares the porous rod-shaped nickel-cobalt-zinc ternary metal hydroxide electrode material with a multistage nano structure by combining a simple hydrothermal method and a strong base intervention electrochemical method, namely, on the basis of a nickel-cobalt-zinc nanowire synthesized by the hydrothermal method, the nickel-cobalt-zinc particularly zinc is not strong base resistant, the nickel-cobalt-zinc nanowire surface and near-surface crystal is reconstructed by using a strong base electrolyte and an electrochemical cyclic voltammetry method, and a special structure combining an outer nickel-cobalt nanosheet and an inner nickel-cobalt-zinc nanowire is prepared by using a single nickel-cobalt-zinc nanowire structure, compared with a single nanowire, the multistage structure has more exposed active sites, the specific capacitance of the material is greatly improved, meanwhile, the expansion behavior caused by excessive ion embedding materials can be relieved by combining the multistage structure, and the electrode material still maintains the structure of the nanowire as a whole, this vertically distributed structure in turn facilitates rapid diffusion of the electrolyte.
(2) Compared with other methods for secondarily depositing the nanosheets on the surfaces of the nanowires, the method for directly converting the nickel-cobalt-zinc nanowires into the nanosheets in situ saves more raw materials.
Drawings
FIG. 1 is a scanning electron microscope image of Ni-Co-Zn ternary transition metal hydroxide with low magnification (a) and high magnification (b) in step (1) of example 1.
FIG. 2 is a scanning electron microscope image of the Ni-Co-Zn ternary transition metal hydroxide of example 2, step (1), at a low magnification (a) and at a high magnification (b).
FIG. 3 is a scanning electron microscope image of the Ni-Co-Zn ternary transition metal hydroxide of example 3 step (1) with a low magnification (a) and a high magnification (b).
FIG. 4 is a scanning electron microscope image of the Ni-Co-Zn ternary transition metal hydroxide with a multi-stage structure in step (2) of example 4 with a low magnification (a) and a high magnification (b).
Fig. 5(a) is a transmission electron microscope picture of the nickel cobalt zinc ternary transition metal hydroxide in step (1) of example 4, and fig. 5(b) is a transmission electron microscope picture of the nickel cobalt zinc ternary transition metal hydroxide having a multilevel structure in step (2).
Fig. 6 is XRD charts of the nickel cobalt zinc ternary transition metal hydroxide of step (1) and the nickel cobalt zinc ternary transition metal hydroxide having a multilevel structure of step (2) in example 4.
FIG. 7 is the cyclic voltammogram (a) and charging/discharging curve (b) of the nickel-cobalt-zinc ternary transition metal hydroxide of example 5 at different sweep rates and different current densities.
Fig. 8 is a cyclic voltammetry curve (a) and a charge-discharge curve (b) at different scan rates and different current densities of the nickel-cobalt-zinc ternary transition metal hydroxide having a multilevel structure of example 6.
Fig. 9 is a comparison graph (a) of cyclic voltammograms, a comparison graph (b) of charge and discharge curves, and a comparison graph (c) of area capacitances of the nickel cobalt zinc ternary transition metal hydroxide of example 5 and the nickel cobalt zinc ternary transition metal hydroxide of example 6 having a multi-stage structure.
Detailed Description
Example 1
A preparation method of a nickel-cobalt-zinc ternary transition metal hydroxide electrode material with a multilevel nanostructure comprises the following steps:
(1) dissolving 3mM cobalt nitrate, 1.5mM nickel nitrate, 0.5mM zinc nitrate, 6mM urea and 5mM ammonium acetate in 35ml deionized water to form a precursor solution, cutting a carbon cloth into 3cm multiplied by 4cm, washing with absolute ethyl alcohol, then performing ultrasonic treatment for 5min by using the deionized water, immersing the cleaned carbon cloth in the precursor solution, performing hydrothermal treatment at 130 ℃ for 5h, and forming a nickel-cobalt-zinc nanowire, namely CC @ NCZ-wire;
(2) in a three-electrode system, CC @ NCZ-wires is used as a working electrode, carbon paper is used as a counter electrode, Hg/HgO electrode is used as a reference electrode, cyclic voltammetry treatment is carried out in 6M potassium hydroxide electrolyte, sweep speed of 50mV/s is carried out for 1000 circles, a sample obtained after treatment is soaked in deionized water to remove redundant electrolyte, and then the sample is dried in a vacuum drying oven for 12 hours at 60 ℃ to obtain a structure combining nickel-cobalt-zinc nanosheets and nanowires, namely CC @ NCZ-wires @ NC-sheets.
FIG. 1 is a scanning electron microscope image of the product obtained in step (1) of example 1, in lower magnification FIG. 1(a) and in higher magnification FIG. 1 (b). As can be seen from fig. 1, when the content of zinc nitrate is 0.5mM, the synthesized nanowires are mostly stuck together, the bent fuzz-like, undesired upright and clear nanowire structure is not favorable for the subsequent steps, and therefore the content of zinc nitrate should be adjusted to obtain a suitable nanowire structure.
Example 2
A preparation method of a nickel-cobalt-zinc ternary transition metal hydroxide electrode material with a multilevel nanostructure comprises the following steps:
(1) dissolving 3mM cobalt nitrate, 1.5mM nickel nitrate, 2.5mM zinc nitrate, 6mM urea and 5mM ammonium acetate in 35ml deionized water to form a precursor solution, and immersing the cleaned carbon cloth in the precursor solution for hydrothermal treatment at 130 ℃ for 5 hours to form a nickel-cobalt-zinc nanowire, namely CC @ NCZ-wire;
(2) in a three-electrode system, CC @ NCZ-wires is used as a working electrode, carbon paper is used as a counter electrode, Hg/HgO electrode is used as a reference electrode, cyclic voltammetry treatment is carried out in 6M potassium hydroxide electrolyte, sweep speed of 50mV/s is carried out for 1000 circles, a sample obtained after treatment is soaked in deionized water to remove redundant electrolyte, and then the sample is dried in a vacuum drying oven for 12 hours at 60 ℃ to obtain a structure combining nickel-cobalt-zinc nanosheets and nanowires, namely CC @ NCZ-wires @ NC-sheets.
FIG. 2 shows scanning electron micrographs of the product obtained in step (1) of example 2, at low magnification (FIG. 2a) and at high magnification (FIG. 2b), respectively. As can be seen from fig. 2, when the content of zinc nitrate is increased from 0.5mM to 2.5mM, the material turns into a nanosheet structure, which is undesirable, and therefore the content of zinc nitrate should be continuously adjusted to obtain a suitable nanowire structure.
Example 3
A preparation method of a nickel-cobalt-zinc ternary transition metal hydroxide electrode material with a multilevel nanostructure comprises the following steps:
(1) dissolving 3mM cobalt nitrate, 1.5mM nickel nitrate, 1.5mM zinc nitrate, 6mM urea and 5mM ammonium acetate in 35ml deionized water to form a precursor solution, and immersing the cleaned carbon cloth in the precursor solution for hydrothermal treatment at 130 ℃ for 5 hours to form a nickel-cobalt-zinc nanowire, namely CC @ NCZ-wire;
(2) in a three-electrode system, CC @ NCZ-wires is used as a working electrode, carbon paper is used as a counter electrode, Hg/HgO electrode is used as a reference electrode, cyclic voltammetry treatment is carried out in 6M potassium hydroxide electrolyte, sweep speed of 50mV/s is carried out for 1000 circles, a sample obtained after treatment is soaked in deionized water to remove redundant electrolyte, and then the sample is dried in a vacuum drying oven for 12 hours at 60 ℃ to obtain a structure combining nickel-cobalt-zinc nanosheets and nanowires, namely CC @ NCZ-wires @ NC-sheets.
FIG. 3 shows scanning electron micrographs of the product obtained in step (1) of example 3, at low magnification (FIG. 3a) and at high magnification (FIG. 3b), respectively. As can be seen from FIG. 3, when the content of zinc nitrate is reduced from 2.5mM to 1.5mM, the obtained nickel-cobalt-zinc nanowires are clearly identified and uniformly distributed, so that the nickel-cobalt-zinc nanowires synthesized by 1.5mM of zinc nitrate are selected as the optimal conditions.
Example 4
A preparation method of a nickel-cobalt-zinc ternary transition metal hydroxide electrode material with a multilevel nanostructure comprises the following steps:
(1) dissolving 3mM cobalt nitrate, 1.5mM nickel nitrate, 1.5mM zinc nitrate, 6mM urea and 5mM ammonium acetate in 35ml deionized water to form a precursor solution, and immersing the cleaned carbon cloth in the precursor solution for hydrothermal treatment at 130 ℃ for 5 hours to form a nickel-cobalt-zinc nanowire, namely CC @ NCZ-wire;
(2) in a three-electrode system, CC @ NCZ-wires is used as a working electrode, carbon paper is used as a counter electrode, Hg/HgO electrode is used as a reference electrode, cyclic voltammetry treatment is carried out in 6M potassium hydroxide electrolyte, sweep speed of 50mV/s is carried out for 1000 circles, a sample obtained after treatment is soaked in deionized water to remove redundant electrolyte, and then the sample is dried in a vacuum drying oven for 12 hours at 60 ℃ to obtain a structure combining nickel-cobalt-zinc nanosheets and nanowires, namely CC @ NCZ-wires @ NC-sheets.
FIG. 4 is a high-magnification and low-magnification scanning electron microscope image of CC @ NCZ-windows @ NC-sheets obtained in step (2) of example 4. FIG. 5 is a transmission electron micrograph of CC @ NCZ-wines obtained in step (1) of example 4 (FIG. 5a) and CC @ NCZ-wines @ NC-sheets obtained in step (2). As can be seen from fig. 4 and 5, the nickel-cobalt-zinc nanowire undergoes a significant change in surface structure after the electrochemical treatment in the second step, and as the nickel-cobalt-zinc crystals on the surface and near the surface undergo crystal reconstruction under the action of strong alkali disintegration and charge promotion, a layer of ultrathin nanosheet is formed on the surface of the nickel-cobalt-zinc nanowire, and the hierarchical porous structure has more exposed active sites, so that the expansion behavior of the material in the charging and discharging processes can be relieved, and the nickel-cobalt-zinc nanowire is very suitable for being used as an electrode material of a supercapacitor
FIG. 6 is an XRD spectrum of CC @ NCZ-wines and CC @ NCZ-wines @ NC-sheets prepared in example 4. The figure shows that the material is of a polycrystalline structure, the characteristic peak of zinc is suddenly reduced or even disappears through comparison of front and back spectrograms, and the characteristic peak of nickel and cobalt still exists, so that the disintegration of nickel-cobalt-zinc crystals on the surface and near-surface of a nanowire is accelerated by using the corrosion of strong base on nickel-cobalt-zinc, particularly zinc, so that the reconstruction of the nickel-cobalt crystals is promoted to be correct, and the reduction of the spectrogram intensity after electrochemical reconstruction shows that the crystallinity of the nickel-cobalt crystals on the surface is reduced, the crystal defect degree is increased, and the charge storage is more facilitated.
Example 5
The nickel-cobalt-zinc ternary transition metal hydroxide electrode material is applied to a super capacitor.
The method comprises the following steps: the nickel-cobalt-zinc ternary transition metal hydroxide electrode material is used as a working electrode, a mercury oxide electrode is used as a reference electrode, carbon paper is used as a counter electrode, 1M KOH is used as electrolyte, and the electrode material is respectively subjected to cyclic voltammetry scanning test and constant current charge and discharge test in the potential ranges of-0.1-0.8V and 0-0.5V.
FIG. 7a is the cyclic voltammetry curves of the nickel-cobalt-zinc ternary transition metal hydroxide electrode material of example 5 at different sweep rates, from which it can be seen that a pair of redox peaks appear in the potential range of-0.1-0.8V, and belong to the pseudocapacitance material; FIG. 7b is the constant current charging and discharging curve of the Ni-Co-Zn ternary transition metal hydroxide electrode of example 5, and the current density is 1mA cm-2When it is in area ratioCapacity 1913.48mF cm-2。
Example 6
The nickel-cobalt-zinc ternary transition metal hydroxide electrode material with the multilevel nanostructure is applied to a super capacitor.
The method comprises the following steps: the method comprises the steps of taking a nickel-cobalt-zinc ternary transition metal hydroxide electrode material with a multistage nanostructure as a working electrode, a mercury oxide electrode as a reference electrode, carbon paper as a counter electrode, and 1M KOH as an electrolyte, and respectively carrying out cyclic voltammetry scanning test and constant current charge and discharge test on the electrode material within the potential ranges of-0.3-0.8V and 0-0.5V.
FIG. 8a is the cyclic voltammetry curves of the Ni-Co-Zn ternary transition metal hydroxide electrode with a multi-stage nano-structure of example 5 at different sweep rates, and it can be seen that a pair of redox peaks appear in the potential range of-0.3-0.8V, and belong to the pseudocapacitance material; FIG. 8b is the constant current charging and discharging curve of the Ni-Co-Zn ternary transition metal hydroxide electrode with the multi-level nano-structure in example 5, and it can be seen from the figure that the current density is 1mA cm-2When the specific capacitance of the area is 9809.4mF cm-2。
Fig. 9 is a comparison graph of electrochemical data of a nickel-cobalt-zinc ternary transition metal hydroxide electrode material and a nickel-cobalt-zinc ternary transition metal hydroxide electrode having a multi-level nanostructure, respectively. As can be seen from fig. 9, after the nickel-cobalt-zinc nanowire is reconstructed by a strong base-mediated electrochemical method, the redox peak current of the electrode is increased, the position of the electrode is expanded to two levels, the charging and discharging time is longer than that of the original electrode, the area of the whole electrode is increased by more than five times of the capacitance, and the multiplying power performance is slightly improved compared with that of the original electrode, which indicates that the nickel-cobalt-zinc ternary transition metal hydroxide with a multistage nanostructure prepared by the strong base-mediated electrochemical method has more energy storage sites and a higher material utilization rate.

Claims (7)

1. A nickel-cobalt-zinc ternary transition metal hydroxide electrode material with a multistage nanostructure is characterized in that the preparation method comprises the following steps:
dissolving cobalt nitrate, nickel nitrate, zinc nitrate, urea and ammonium acetate in deionized water to form a precursor solution, and immersing the cleaned carbon cloth in the precursor solution for hydrothermal treatment to form the nickel-cobalt-zinc nanowire;
placing the nickel-cobalt-zinc nanowire in a three-electrode system, carrying out cyclic voltammetry treatment under strong base electrolyte, soaking a sample obtained after treatment in deionized water to remove redundant electrolyte, and then drying in a vacuum drying oven at 60 ℃ for 12 hours to obtain a nickel-cobalt-zinc ternary transition metal hydroxide electrode material;
according to molar ratio, cobalt nitrate: nickel nitrate: zinc nitrate: urea: ammonium acetate =3:1.5:0.5-2.5:6: 5;
the hydrothermal treatment is carried out for 5 hours at the temperature of 130 ℃.
2. The nickel-cobalt-zinc ternary transition metal hydroxide electrode material with the multilevel nanostructure as claimed in claim 1, wherein in the step 1), the carbon cloth is cleaned by a specific method comprising the following steps: the carbon cloth was rinsed with absolute ethanol, followed by sonication with deionized water.
3. The nickel-cobalt-zinc ternary transition metal hydroxide electrode material with a multilevel nanostructure according to claim 1, wherein in the step 2), the ternary system is as follows: the CC @ NCZ-wires obtained in the step 1) are used as working electrodes, the Hg/HgO electrode is used as a reference electrode, and the carbon paper is used as a counter electrode.
4. The nickel-cobalt-zinc ternary transition metal hydroxide electrode material with a multistage nanostructure according to claim 1, wherein in step 2), the strong base electrolyte is: 1-6M potassium hydroxide solution.
5. The nickel-cobalt-zinc ternary transition metal hydroxide electrode material with a multilevel nanostructure according to claim 1, wherein in the step 2), the specific parameters of the cyclic voltammetry treatment are as follows: sweep rate of 50mV/s, cycle 1000 cycles.
6. Use of a nickel cobalt zinc ternary transition metal hydroxide electrode material having a multilevel nanostructure according to any of claims 1 to 5 in a supercapacitor.
7. The use according to claim 6, wherein the nickel-cobalt-zinc ternary transition metal hydroxide electrode material with a multilevel nanostructure is used as a positive electrode material in a super capacitor according to any one of claims 1 to 5.
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