CN108735517B

CN108735517B - Basic zinc carbonate supercapacitor electrode material and preparation method thereof

Info

Publication number: CN108735517B
Application number: CN201810534409.XA
Authority: CN
Inventors: 朱少敏; 徐冰; 李准; 赵宇; 王建海; 邓晗; 杨玉彬
Original assignee: Dalian Jiaotong University
Current assignee: Dalian Jiaotong University
Priority date: 2018-05-30
Filing date: 2018-05-30
Publication date: 2020-09-25
Anticipated expiration: 2038-05-30
Also published as: CN108735517A

Abstract

The invention discloses a basic zinc carbonate supercapacitor electrode material and a preparation method thereof, wherein the method comprises the following steps: (1) removing the surface oxide film of the foamed nickel by acid washing; washing with deionized water to neutrality and drying; (2) preparing zinc nitrate, aluminum nitrate and urea to obtain a mixed solution. The molar concentration of urea in the solution is 0.05-0.15mol/L, the molar ratio of zinc nitrate to aluminum nitrate is 5-1: 1, and the molar ratio of urea to the total amount of zinc nitrate and aluminum nitrate is 5-2: 1; (3) putting the processed foamed nickel into the mixed solution in the step (2) for ultrasonic treatment; (4) putting the mixed solution and the foamed nickel into a reaction kettle for hydrothermal treatment; the hydrothermal temperature is 100-140 ℃, and the hydrothermal time is 1-20 hours. (5) And cooling after the hydrothermal reaction is finished, taking out the foamed nickel, washing and drying. The preparation method is simple, environment-friendly, low in cost and easy for large-scale production.

Description

Basic zinc carbonate supercapacitor electrode material and preparation method thereof

Technical Field

The invention relates to an electrode material of a basic zinc carbonate super capacitor and a preparation method thereof.

Background

The energy storage system is an important link of power grid peak regulation and new energy power generation, and the continuous exhaustion of fossil fuels further stimulates the effective storage research of solar energy and wind energy. Super capacitors have high specific power, fast charge/discharge, and long cycle life characteristics, and are receiving wide attention.

The electrode material of the super capacitor comprises a carbon-based material, metal oxides and a composite material thereof. The carbon material electrode has a relatively small specific capacitance although it has a high charge/discharge rate, and the metal oxide electrode has a high specific capacitance but a poor conductivity. On the other hand, a typical supercapacitor electrode is composed of an active material, a conductive material, and a binder, and the internal resistance of the supercapacitor comes from the electron resistance of the electrode material, the contact resistance of the electrode and a current collector, the diffusion resistance and electrolyte resistance of ions moving in micropores, and the like. The presence of the binder increases the electrode resistance, prevents the effective contact of the electrolyte with the active material, and has a certain weight to form a certain dead volume.

Disclosure of Invention

In order to solve the above problems, the invention provides a preparation method of an electrode material of a basic zinc carbonate supercapacitor, which comprises the following steps:

(1) removing the surface oxide film of the foamed nickel by acid washing; washing with deionized water to neutrality and drying;

(2) preparing zinc nitrate, aluminum nitrate and urea to obtain a mixed solution. The molar concentration of urea in the solution is 0.05-0.15mol/L, the molar ratio of zinc nitrate to aluminum nitrate is 5-1: 1, and the molar ratio of urea to the total amount of zinc nitrate and aluminum nitrate is 5-2: 1;

(3) putting the processed foamed nickel into the mixed solution in the step (2) for ultrasonic treatment;

(4) putting the mixed solution and the foamed nickel into a reaction kettle for hydrothermal treatment; the hydrothermal temperature is 100-140 ℃, and the hydrothermal time is 1-20 hours.

(5) And cooling after the hydrothermal reaction is finished, taking out the foamed nickel, washing and drying to obtain the basic zinc carbonate composite electrode material with the foamed nickel surface growing in situ.

Further, in the technical scheme, in the step (1), the foamed nickel is placed into hydrochloric acid for soaking and ultrasonic treatment to remove the surface oxide film, wherein the molar concentration of the hydrochloric acid is 0.5-2mol/L, and the ultrasonic treatment time is 10-30 minutes.

Further, in the technical scheme, in the step (3), the ultrasonic time is 10-30 minutes, and the volume ratio of the foamed nickel to the mixed solution is 1: 2-5.

Further, in the technical scheme, in the step (4), the volume ratio of the foamed nickel to the mixed solution is 1: 2-5.

The invention provides the basic zinc carbonate supercapacitor electrode material prepared by the preparation method.

The preparation method is simple, the zinc nitrate, the aluminum nitrate and the precipitator urea are all industrial conventional reagents, the environment is friendly, the cost is low, and the large-scale production is easy to realize. The basic zinc carbonate growing in situ on the surface of the foamed nickel is in a two-dimensional sawtooth sheet shape to an ordered regular hexagon nanometer sheet shape, and the composite electrode material shows higher specific capacitance and cycling stability in an electrochemical test.

Drawings

FIG. 1 is an SEM image of an in-situ grown basic zinc carbonate material on the surface of a foamed nickel prepared in example 1 of the present invention;

FIG. 2 is an XRD pattern of a zinc hydroxycarbonate material prepared in example 1;

FIG. 3 is an SEM image of a prepared foamed nickel surface in-situ grown basic zinc carbonate material prepared in example 2;

FIG. 4 is a cyclic voltammogram of the in-situ growth of basic zinc carbonate material on the surface of the foamed nickel prepared in example 1 at different scanning rates;

FIG. 5 is a cyclic voltammogram of the in-situ growth of basic zinc carbonate material on the surface of the foamed nickel prepared in example 2 at different scanning rates;

FIG. 6 is a constant current charge and discharge curve of the basic zinc carbonate material grown in situ on the surface of the foamed nickel prepared in example 1;

FIG. 7 is an SEM image of an in-situ grown basic zinc carbonate material on the surface of foamed nickel prepared in example 3 of the invention;

FIG. 8 is an SEM image of an in-situ grown basic zinc carbonate material on the surface of foamed nickel prepared in example 4 of the present invention;

FIG. 9 is an SEM image of an in-situ grown basic zinc carbonate material on the surface of foamed nickel prepared in example 5 of the invention.

Detailed Description

In the examples, the nickel foam was purchased from Jiangsu Jiayi Sheng foam Metal works and had a thickness of 1.5 mm.

Example 1

An electrode material of a basic zinc carbonate super capacitor and a preparation method thereof are implemented according to the following steps.

(1) Soaking foamed nickel in hydrochloric acid with the concentration of 2mol/L for 10 minutes by ultrasonic treatment, removing a surface oxidation film, washing with deionized water to be neutral, and drying;

(2) preparing zinc nitrate, aluminum nitrate and urea to obtain a mixed solution. The concentration of zinc nitrate in the solution is 0.01mol/L, the concentration of aluminum nitrate is 0.002mol/L, and the molar concentration of urea is 0.06 mol/L.

(3) And (3) putting the treated foamed nickel into the mixed solution in the step (2) for ultrasonic treatment for 10 minutes. The volume ratio of the foamed nickel to the mixed solution is 1: 3.

(4) Putting the mixed solution and the foamed nickel into a reaction kettle for hydrothermal treatment; the volume ratio of the foamed nickel to the etching liquid is 1:3, the hydrothermal temperature is 120 ℃, and the hydrothermal time is 2 hours.

FIG. 4 is a cyclic voltammogram of the prepared foamed nickel surface in-situ growth basic zinc carbonate material at different scanning rates; FIG. 6 is a constant current charge and discharge curve of the prepared foam nickel surface in-situ growth basic zinc carbonate material; the test process is a three-electrode system, a saturated calomel electrode is used as a reference electrode, a platinum electrode is used as a counter electrode, the prepared composite electrode is used as a working electrode, the electrolyte is 6M KOH, constant current charging and discharging are carried out under the current density of 1A/g, and the specific capacitance can reach 1600F/g.

Example 2

The steps of the basic zinc carbonate supercapacitor electrode material are the same as those of example 1, except that in the step (4), the hydrothermal time is 8 hours. Fig. 5 is a cyclic voltammogram of the prepared foamed nickel surface in-situ growth basic zinc carbonate material at different scanning rates. The test process is a three-electrode system, a saturated calomel electrode is used as a reference electrode, a platinum electrode is used as a counter electrode, the prepared composite electrode is used as a working electrode, the electrolyte is 6M KOH, and the specific capacitance can reach 1100F/g when the scanning speed is 50 mV/s.

Example 3

The steps of the basic zinc carbonate supercapacitor electrode material are the same as those of example 1, except that in the step (4), the hydrothermal time is 12 hours.

Example 4

The steps of the basic zinc carbonate supercapacitor electrode material are the same as those of example 1, except that in the step (2), zinc nitrate, aluminum nitrate and urea are prepared into a mixed solution. The concentration of zinc nitrate in the solution is 0.01mol/L, the concentration of aluminum nitrate is 0.005mol/L, and the molar concentration of urea is 0.075 mol/L.

Example 5

The steps of the basic zinc carbonate supercapacitor electrode material are the same as those of example 1, except that in the step (2), zinc nitrate, aluminum nitrate and urea are prepared into a mixed solution. The concentration of zinc nitrate in the solution is 0.01mol/L, the concentration of aluminum nitrate is 0.01mol/L, and the molar concentration of urea is 0.1 mol/L.

Claims

1. A preparation method of an electrode material of a basic zinc carbonate super capacitor is characterized by comprising the following steps:

(2) preparing zinc nitrate, aluminum nitrate and urea to obtain a mixed solution, wherein the molar concentration of the urea in the solution is 0.05-0.15mol/L, the molar ratio of the zinc nitrate to the aluminum nitrate is 5-1: 1, and the molar ratio of the urea to the total amount of the zinc nitrate and the aluminum nitrate is 5-2: 1;

(4) putting the mixed solution and the foamed nickel into a reaction kettle for hydrothermal treatment; the hydrothermal temperature is 100-140 ℃, and the hydrothermal time is 1-20 hours;

(5) cooling after the hydrothermal reaction is finished, taking out the foamed nickel, washing and drying to obtain the basic zinc carbonate composite electrode material with the foamed nickel surface growing in situ;

in the step (1), soaking foamed nickel in hydrochloric acid for ultrasound to remove a surface oxide film, wherein the molar concentration of the hydrochloric acid is 0.5-2.0mol/L, and the ultrasound time is 10-30 minutes;

in the step (3), the ultrasonic time is 10-30 minutes, and the volume ratio of the foamed nickel to the mixed liquid is 1: 2-5.

2. The preparation method of the electrode material of the basic zinc carbonate supercapacitor according to claim 1, wherein the preparation method comprises the following steps: in the step (4), the volume ratio of the foamed nickel to the mixed solution is 1: 2-5.

3. The electrode material of the basic zinc carbonate supercapacitor obtained by the preparation method according to claim 1 or 2.