CN110047658B - Carbon and sulfur double-doped electrode material and preparation method thereof - Google Patents
Carbon and sulfur double-doped electrode material and preparation method thereof Download PDFInfo
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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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
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Abstract
The invention provides a carbon and sulfur double-doped nickel-cobalt double hydroxide electrode material, a preparation method thereof and a super capacitor prepared from the material. The electrode material comprises a carbon and sulfur double-doped nickel-cobalt double hydroxide electrode material. The preparation method is that nickel salt and cobalt salt are deposited on a conductive substrate by a constant voltage cathode electrochemical deposition method; the electrode material and the conductive substrate are directly connected without adding an adhesive, so that the resistance is effectively reduced, the high-performance double-doped nickel-cobalt double hydroxide electrode material is obtained, and the defect of poor multiplying power performance of the traditional double hydroxide electrode material is overcome. The preparation method disclosed by the invention is simple in preparation process, low in cost, short in period and suitable for commercial application. The super capacitor prepared by taking the electrode material as a positive electrode and the active carbon as a negative electrode has good charge-discharge performance, high power density and energy density; the method conforms to the development trend of both high energy density and high power density of the super capacitor.
Description
Technical Field
The invention relates to an electrode material of a super capacitor, in particular to a carbon and sulfur double-doped nickel-cobalt double hydroxide electrode material, a preparation method thereof and a super capacitor made of the electrode material.
Background
The super capacitor is also called as farad capacitor and gold capacitor, and is a novel electric energy storage component; supercapacitors are generally classified into electric double layer supercapacitors and pseudocapacitive supercapacitors. The super capacitor is a novel component which can provide super power while providing high energy density and has the characteristics of capacitance and battery. The super capacitor has the four remarkable characteristics of long service life, strong environmental adaptability, high charge-discharge efficiency and high energy density; thus making it one of the hot topics of current research. The super capacitor is composed of electrodes, electrolyte and a diaphragm, and the structure and the performance of an electrode material play a decisive influence on the performance of the super capacitor. Transition metal oxides and hydroxides are used as electrode materials of pseudo-capacitor super capacitors, wherein the contained elements such as Ru, Mn, Zn, Ni and Co have different valence, and the change between different valence states can be generated in the electrochemical process to realize the Faraday pseudo-capacitance reaction. Therefore, the compound formed by coordination of the metal elements and the nonmetal elements has higher theoretical specific capacity. However, the transition metal oxide and hydroxide have poor conductivity, and thus have problems of poor magnification and short lifetime. Therefore, it is necessary to develop a supercapacitor electrode material having a low internal resistance and high rate characteristics.
Disclosure of Invention
The invention aims to solve the problems of large internal resistance, poor multiplying power, short service life, high cost, complex preparation process and difficult large-scale production of the electrode material of the conventional super capacitor, particularly the pseudo-capacitor super capacitor, and provides a novel nickel-cobalt double hydroxide electrode material doped with carbon and sulfur and a preparation method thereof, wherein the preparation method comprises the following steps: and provides a super capacitor with high energy density and high power density made of carbon and sulfur double-doped nickel-cobalt double hydroxide electrode material.
The nickel-cobalt double hydroxide electrode material prepared by carbon and sulfur double doping is used for increasing the reaction activity and the reaction sites, so that the electrode material has higher stability; and the electrode material of the pseudo-capacitor super capacitor and the super capacitor manufactured by the electrode material have the advantages of high specific capacity, high rate characteristic, low resistance, high charging and discharging coulombic efficiency and the like.
In order to achieve the above object, the present invention is achieved by the following technical means.
The invention provides a preparation method of a carbon and sulfur double-doped nickel-cobalt double hydroxide electrode material, according to the invention, nickel salt and cobalt salt are mixed into a uniform solution according to a designed molar ratio, thiourea and glucose are added into the uniform solution, and a constant voltage cathode electrochemical deposition method is adopted to prepare the nickel-cobalt double hydroxide electrode material, which specifically comprises the following process steps:
(1) raw material preparation
The method comprises the following steps of (1) mixing nickel salt and cobalt salt in a mass ratio of (10): 1-1: 1; then dissolving them in deionized water, stirring them until they are completely dissolved to obtain uniform solution;
(2) addition of a Sulfur and carbon Source
Adding thiourea as a sulfur source into the uniform solution, wherein the content of the thiourea is 0.1M; the content of glucose as a carbon source is 0-10 mM;
(3) conductive substrate treatment
Cutting the conductive substrate according to the design size, and respectively carrying out ultrasonic cleaning on the conductive substrate by using hydrochloric acid, acetone, deionized water and alcohol;
(4) cathodic electrochemical deposition using constant voltage
Depositing nickel salt and cobalt salt on a cleaned conductive substrate by adopting a constant-voltage cathode electrochemical deposition method, wherein the constant-voltage cathode electrochemical deposition voltage is-2V to-0.7V; the deposition time is 0-3600 seconds; the deposition temperature is 0-100 ℃; thus obtaining the electrode material;
(5) heat treatment of the deposited electrode material
And taking out the electrode material obtained by deposition, washing with deionized water for three to five times, then placing the electrode material in a 60 ℃ oven for drying for 2 hours, and then carrying out annealing heat treatment under the atmosphere condition to obtain the carbon and sulfur double-doped nickel-cobalt double hydroxide electrode material.
Further, the conductive substrate is selected from any one of carbon paper, carbon cloth, carbon fiber, or foamed nickel.
Further, the conductive substrate is cut into a rectangular shape according to a design size.
Further, the mass ratio of the nickel salt to the cobalt salt is 3: 1-1: 1.
further, the nickel salt is nickel nitrate or nickel chloride, and the cobalt salt is cobalt nitrate or cobalt chloride.
Further, the voltage of the constant voltage cathode electrochemical deposition is-1.5V to-1V; the deposition time is 1200-1800 seconds; the deposition temperature is 20-35 ℃.
Further, the electrode material electrochemically deposited by the constant voltage cathode is annealed and heat-treated under the atmosphere of argon, nitrogen or air.
Furthermore, the annealing treatment temperature under the atmosphere condition is 50-350 ℃, and the treatment time is 1-300 minutes; the temperature rising speed is 1-5 ℃/min.
Still further, the annealing heat treatment temperature is 200 ℃ and the heat treatment time is 120 minutes.
The electrode material prepared by the preparation method of the invention is a nickel-cobalt double hydroxide electrode material containing carbon and sulfur double doping.
The invention also provides application of the carbon and sulfur double-doped nickel-cobalt double hydroxide electrode material prepared by the method in preparation of a super capacitor.
In the application, the positive electrode of the super capacitor is made of the carbon and sulfur double-doped nickel-cobalt double hydroxide electrode material.
The electrode material provided by the invention comprises two transition group metals of nickel ions and cobalt ions, wherein the nickel ions have higher electrochemical activity, the cobalt ions have higher conductivity and stability, and the nickel ions and the cobalt ions are compounded to form a bimetallic compound, so that the conductivity and the electrochemical activity of the compound can be effectively improved. The carbon is doped, so that the conductivity of the material can be obviously improved, and the internal resistance of the electrode material is effectively reduced; the electronegativity of sulfur is lower than that of oxygen, so that the structure of the electrode material can be more flexible due to the doping of sulfur, and a rapid and reversible Faraday reaction can be generated on the surface of the electrode material, so that the electrochemical performance of the electrode material is improved; the co-doping of sulfur and carbon not only ensures the high electrochemical performance of the electrode material, but also effectively reduces the resistance, and obtains the electrode material with excellent performance. In addition, the content of the added glucose is controlled within the range, so that the conductivity of the electrode material can be improved, and the improvement of the specific capacity of the electrode material is not influenced, and therefore, the optimization of various performances of the electrode material can be realized to the greatest extent.
The nickel-cobalt double hydroxide electrode material with excellent performance prepared by the method is applied to a super capacitor, so that the energy density and the power density of the super capacitor are improved. Meanwhile, compared with noble metal ruthenium, the nickel salt and cobalt salt are easily obtained and have low price; the preparation process is simple by adopting the electrochemical deposition method, and the preparation process can be accurately controlled; the method is suitable for large-scale batch production, thereby realizing the possibility of commercialization. In conclusion, the electrode material of the super capacitor and the preparation method thereof provided by the invention have great advantages in performance, cost and commercial production.
The invention has the advantages and beneficial technical effects as follows:
the nickel-cobalt double hydroxide electrode material prepared by carbon and sulfur double doping is used for increasing the reaction activity and the reaction sites, so that the electrode material has higher stability; the pseudo-capacitor super capacitor electrode material with the advantages of high specific capacity, high rate characteristic, low resistance, high charging and discharging coulombic efficiency and the like is obtained; the electrode material prepared by the invention solves the problems of large internal resistance, short service life, high cost, complex preparation process and difficult large-scale production of the electrode material of the conventional super capacitor, particularly the pseudo-capacitor super capacitor; the invention is deposited on a conductive substrate by a constant voltage cathode electrochemical deposition method; the electrode material is directly connected with the conductive substrate without adding an adhesive, so that the resistance is effectively reduced, the high-performance double-doped nickel-cobalt double hydroxide electrode material is obtained, and the defect of poor multiplying power performance of the traditional double hydroxide electrode material is overcome; and the preparation process is simple, the cost is low, the period is short, and the method is suitable for commercial application. The super capacitor prepared by taking the electrode material as a positive electrode and the active carbon as a negative electrode has good charge-discharge performance, high power density and energy density; the method conforms to the development trend of both high energy density and high power density of the super capacitor.
Drawings
FIG. 1 shows the AC impedance test results of the Ni-Co double hydroxide electrode material prepared in example 1 of the present invention;
fig. 2 is a result of a rate characteristic test of the nickel-cobalt double hydroxide electrode material prepared in example 1 of the present invention;
FIG. 3 shows the AC impedance test results of the Ni-Co double hydroxide electrode material prepared in example 2 of the present invention;
fig. 4 is a result of a rate characteristic test of the nickel-cobalt double hydroxide electrode material prepared in example 2 of the present invention;
FIG. 5 shows the AC impedance test results of the Ni-Co double hydroxide electrode material prepared in example 3 of the present invention;
fig. 6 is a result of a rate characteristic test of the nickel-cobalt double hydroxide electrode material prepared in example 3 of the present invention;
FIG. 7 shows the AC impedance test results of the Ni-Co double hydroxide electrode material prepared in example 4 of the present invention;
fig. 8 is a result of a rate characteristic test of the nickel-cobalt double hydroxide electrode material prepared in example 4 of the present invention;
FIG. 9 shows the AC impedance test results of the Ni-Co double hydroxide electrode material prepared in example 5 of the present invention;
fig. 10 is a result of rate characteristic test of the nickel-cobalt double hydroxide electrode material prepared in example 5 of the present invention;
fig. 11 shows the result of cyclic voltammetry test of a supercapacitor made of the nickel-cobalt double hydroxide electrode material prepared in example 5 of the present invention;
fig. 12 is a graph showing the relationship between the energy density and the power density of a supercapacitor made of the nickel-cobalt double hydroxide electrode material prepared in example 5 of the present invention.
Detailed Description
The technical solutions of the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The materials used in the following examples were purchased from Kyushu Chang glass transform Inc.
Example 1
0.1127g of nickel nitrate and 0.0371g of cobalt nitrate are weighed and added into 50ml of deionized water to be stirred until the nickel nitrate and the cobalt nitrate are completely dissolved to form a uniform solution; weighing 0.3825g of thiourea and 0.0198g of glucose, adding the thiourea and the glucose into the solution, and stirring until the thiourea and the glucose are completely dissolved to obtain a uniform solution; cutting the carbon cloth into a rectangle of 1cm × 1.5cm, and ultrasonically cleaning with hydrochloric acid, acetone, deionized water and alcohol for 10min respectively.
Adopting constant voltage cathode electrochemical deposition, taking cut clean carbon cloth as a conductive substrate, wherein the deposition voltage is-1.5V, Ag/AgCl is used as a reference electrode, a Pt electrode is used as a counter electrode, the deposition temperature is 20 ℃, and the deposition time is 1200 seconds; obtaining the carbon and sulfur double-doped nickel-cobalt double hydroxide electrode material.
And taking out the nickel-cobalt double hydroxide electrode material obtained by deposition, washing the nickel-cobalt double hydroxide electrode material with deionized water for three to five times, then placing the electrode material in a 60 ℃ oven for drying for 2 hours, and carrying out annealing heat treatment under the argon atmosphere condition, wherein the treatment temperature is 200 ℃, the heating rate is 1 ℃/min, and the treatment time is 120 minutes, so as to obtain the carbon-sulfur double-doped nickel-cobalt double hydroxide electrode material.
The prepared electrode material is placed in 2M KOH electrolyte, Ag/AgCl is used as a reference electrode, a Pt electrode is used as a counter electrode to carry out electrochemical test, and the test result shows that the current density is 0.5Ag-1When the specific capacity reaches 1255F g-1(ii) a As shown in fig. 1 and 2.
Example 2
0.1127g of nickel nitrate and 0.0371g of cobalt nitrate are weighed and added into 50ml of deionized water to be stirred until the nickel nitrate and the cobalt nitrate are completely dissolved to form a uniform solution; weighing 0.3825g of thiourea and 0.0991g of glucose, adding the thiourea and the glucose into the solution, and stirring until the thiourea and the glucose are completely dissolved to obtain a uniform solution; cutting the foamed nickel into a rectangle of 2cm multiplied by 1cm, and respectively ultrasonically cleaning for 10min by hydrochloric acid, acetone, deionized water and alcohol.
Adopting constant voltage cathode electrochemical deposition, taking the cut clean foamed nickel as a conductive substrate, wherein the deposition voltage is-1.5V, Ag/AgCl is used as a reference electrode, a Pt electrode is used as a counter electrode, the deposition temperature is 35 ℃, and the deposition time is 1800 seconds; obtaining the carbon and sulfur double-doped nickel-cobalt double hydroxide electrode material.
And taking out the nickel-cobalt double hydroxide electrode material obtained by deposition, washing the nickel-cobalt double hydroxide electrode material with deionized water for three to five times, then drying the electrode material in a 60 ℃ drying oven for 2 hours, and carrying out annealing heat treatment under the condition of nitrogen atmosphere at the treatment temperature of 150 ℃, at the heating rate of 2 ℃/min and for 150 minutes to obtain the carbon-sulfur double-doped nickel-cobalt double hydroxide electrode material.
Placing the obtained electrode material in 2M KOH electrolyte, using Ag/AgCl as a reference electrode and a Pt electrode as a counter electrode to carry out electrochemical test, wherein the test result shows that the current density is 0.5A g-1The specific capacity reaches 1245F g-1(ii) a As shown in fig. 3 and 4.
Example 3
0.0905g of nickel chloride and 0.0301g of cobalt chloride are weighed and added into 50ml of deionized water to be stirred until the nickel chloride and the cobalt chloride are completely dissolved to form a uniform solution; weighing 0.3825g of thiourea and 0.0049g of glucose, adding the thiourea and the glucose into the solution, and stirring until the thiourea and the glucose are completely dissolved to form a uniform solution; cutting the carbon paper into 2cm × 1cm rectangles, and respectively ultrasonically cleaning for 10min by using hydrochloric acid, acetone, deionized water and alcohol.
And (2) performing electrochemical deposition on the cut clean carbon paper serving as a conductive substrate by adopting a constant-voltage cathode, wherein the deposition voltage is-1V, Ag/AgCl is used as a reference electrode, a Pt electrode is used as a counter electrode, the deposition temperature is 50 ℃, and the deposition time is 1800 seconds, so that the carbon and sulfur double-doped nickel-cobalt double hydroxide electrode material is obtained.
Taking out the nickel-cobalt double hydroxide electrode material obtained by deposition, and washing with deionized water for three to five times; and then drying the electrode material in a 60 ℃ oven for 2 hours, and carrying out annealing heat treatment at the air atmosphere condition for 120 minutes at the treatment temperature of 200 ℃, wherein the heating rate is 3 ℃/min, so as to obtain the carbon and sulfur double-doped nickel-cobalt double hydroxide electrode material.
Placing the obtained electrode material in 2M KOH electrolyte, using Ag/AgCl as a reference electrode and a Pt electrode as a counter electrode to carry out electrochemical test, wherein the test result shows that the current density is 1A g-1When the specific capacity reaches 2177F g-1When the current density is increased by 50 times, the retention rate of 69.7 percent still exists; as shown in fig. 5 and 6.
Example 4
0.0905g of nickel chloride and 0.0301g of cobalt chloride are weighed and added into 50ml of deionized water to be stirred until the nickel chloride and the cobalt chloride are completely dissolved to form a uniform solution; weighing 0.3825g of thiourea and 0.0065g of glucose, adding the thiourea and the glucose into the solution, and stirring until the thiourea and the glucose are completely dissolved to form a uniform solution; cutting carbon fiber into 2cm × 1cm rectangle, and ultrasonic cleaning with hydrochloric acid, acetone, deionized water, and alcohol for 10min respectively.
And (2) performing electrochemical deposition on the cut clean carbon fiber serving as a conductive substrate by adopting a constant-voltage cathode, wherein the deposition voltage is-2V, Ag/AgCl is used as a reference electrode, a Pt electrode is used as a counter electrode, the deposition time is 1800 seconds, and the deposition temperature is 100 ℃, so that the carbon and sulfur double-doped nickel-cobalt double hydroxide electrode material is obtained.
Taking out the nickel-cobalt double hydroxide electrode material obtained by deposition, and washing with deionized water for three to five times; and then, drying the electrode in a 60 ℃ oven for 2 hours, and carrying out heat treatment for 0 minute at 350 ℃ under the argon atmosphere, wherein the heating rate is 4 ℃/min, so as to obtain the carbon and sulfur double-doped nickel-cobalt double hydroxide electrode material.
Placing the obtained electrode material in 2M KOH electrolyte, using Ag/AgCl as a reference electrode and a Pt electrode as a counter electrode to carry out electrochemical test, wherein the test result shows that the current density is 1A g-1When the specific capacity reaches 2106F g-1When the current density is increased by 50 times, the retention rate is 58 percent; as shown in fig. 7 and 8.
Example 5
0.0905g of nickel chloride and 0.0301g of cobalt chloride are weighed and added into 50ml of deionized water to be stirred until the nickel chloride and the cobalt chloride are completely dissolved to form a uniform solution; weighing 0.3825g of thiourea and 0.0049g of glucose, adding the thiourea and the glucose into the solution, and stirring until the thiourea and the glucose are completely dissolved to form a uniform solution; cutting foamed nickel into 2cm × 1cm rectangles, and respectively ultrasonically cleaning with hydrochloric acid, acetone, deionized water and alcohol for 10 min.
And (2) performing electrochemical deposition on the cathode by adopting a constant voltage, taking the cut clean foamed nickel as a conductive substrate, wherein the deposition voltage is-0.7V, using Ag/AgCl as a reference electrode, a Pt electrode as a counter electrode, performing bubble deposition for 3600 seconds, and performing deposition at 0 ℃ to obtain the carbon and sulfur double-doped nickel-cobalt double hydroxide electrode material.
Taking out the nickel-cobalt double hydroxide electrode material obtained by deposition, and washing with deionized water for three to five times; then, drying the electrode material in a 60 ℃ oven for 2 hours, and carrying out heat treatment under the nitrogen atmosphere condition, wherein the treatment temperature is 50 ℃ and the treatment time is 300 minutes; obtaining the carbon and sulfur double-doped nickel-cobalt double hydroxide electrode material.
Placing the obtained electrode material in 2M KOH electrolyte, using Ag/AgCl as a reference electrode and a Pt electrode as a counter electrode to carry out electrochemical test, wherein the test result shows that the current density is 0.5A g-1When the specific capacity reaches 2083.3F g-1When the current density is increased by 100 times, the retention rate is 69.9 percent; as shown in fig. 9 and 10.
In addition, the invention also provides application of the carbon and sulfur double-doped nickel-cobalt double hydroxide electrode material in preparation of a super capacitor.
The supercapacitor comprises positive and negative electrodes, wherein the positive electrode is made of the electrode material prepared in the embodiment 5. The specific manufacturing method comprises the following steps: the electrode material prepared in the above example 5 was used as a positive electrode, commercial activated carbon was used as a negative electrode, and the separator used was a polyimide separator; then the positive and negative electrodes are mutually faced, the two electrodes are separated by a diaphragm, 6M KOH electrolyte is added, a conductive steel sheet and a gasket are added, and a certain pressure is applied to seal the super capacitor battery case, thus the super capacitor battery is prepared. The super capacitor made of the electrode material has extremely high energy density of 0.2A g-1When the energy density reaches 64Wh Kg-1(ii) a At the same time, the power density is high, and the power density is 14.5Kw Kg-1When the current is over; the energy density can reach 20.6Wh Kg-1. As shown in fig. 11 and 12.
TABLE 1 Current Density 0.5A g-1And 1A g-1Specific capacity test result and partial performance index of electrode material of time-sharing super capacitor
Note: the specific capacitance measuring voltage is 0-0.45V, and the electrolyte is 2mol/L KOH solution.
The electrode material provided by the invention contains two transition metals, nickel ions have higher electrochemical activity, cobalt ions have higher conductivity and stability, and the compound formed by nickel and cobalt can effectively improve the conductivity and electrochemical activity of the nickel-cobalt bimetallic compound.
In the electrode material provided by the invention, the doping of the sulfur element can enable the organization structure of the material to be more flexible, so that a rapid and reversible Faraday reaction can be generated on the surface of the material, and the electrochemical performance of the material is improved. The doping of the carbon element can obviously improve the conductivity of the material and reduce the internal resistance of the electrode material.
As can be seen from the above data, the above embodiments of the present invention achieve the following technical effects: the super capacitor prepared by the electrode material provided by the invention has higher electrical property, and especially compared with the super capacitor without any element, the electrochemical property, especially the specific capacity of the electrode material can be obviously improved by doping sulfur; the doping of the carbon element can obviously improve the conductivity of the material; the carbon and the sulfur are simultaneously doped, so that the maximization of electrochemical performance is realized, high specific capacity can be obtained, and the conductivity and the rate characteristic are good.
In addition, the super capacitor provided by the invention has the advantages of simple manufacturing process, low cost, excellent performance, higher energy density and power density, and great marketization application potential.
The electrode material provided by the present invention is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and those skilled in the art can make various modifications and variations. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A preparation method of a carbon and sulfur double-doped nickel-cobalt double hydroxide electrode material is characterized in that nickel salt and cobalt salt are mixed into a uniform solution according to a designed mass ratio, thiourea and glucose are added into the uniform solution, and a constant-voltage cathode electrochemical deposition method is adopted to prepare the nickel-cobalt double hydroxide electrode material, and the preparation method specifically comprises the following process steps:
(1) raw material preparation
The method comprises the following steps of (1) mixing nickel salt and cobalt salt in a mass ratio of (10): 1-1: 1; then dissolving them in deionized water, stirring them until they are completely dissolved to obtain uniform solution;
(2) addition of a Sulfur and carbon Source
Adding thiourea as a sulfur source into the uniform solution, wherein the content of the thiourea is 0.1M; the content of glucose as a carbon source is 0-10 mM;
(3) conductive substrate treatment
Cutting the conductive substrate according to the design size, and respectively carrying out ultrasonic cleaning on the conductive substrate by using hydrochloric acid, acetone, deionized water and alcohol;
(4) cathodic electrochemical deposition using constant voltage
Depositing nickel salt and cobalt salt on a cleaned conductive substrate by adopting a constant-voltage cathode electrochemical deposition method, wherein the constant-voltage cathode electrochemical deposition voltage is-2 to-1.5V; the deposition time is 0-3600 seconds; the deposition temperature is 0-100 ℃; thus obtaining the electrode material;
(5) heat treatment of the deposited electrode material
Taking out the electrode material obtained by deposition, washing the electrode material with deionized water for three to five times, then placing the electrode material in a 60 ℃ drying oven for drying for 2 hours, and then carrying out annealing heat treatment under the atmosphere condition to obtain the carbon and sulfur double-doped nickel-cobalt double hydroxide electrode material;
the nickel salt is nickel chloride, and the cobalt salt is cobalt chloride.
2. The method according to claim 1, wherein the ratio of the nickel salt to the cobalt salt is 3: 1-1: 1.
3. the method according to claim 1, wherein the deposition time is 1200 to 1800 seconds; the deposition temperature is 20-35 ℃.
4. The method according to claim 1, wherein the deposited electrode material is annealed under an atmosphere of argon, nitrogen or air.
5. The method according to claim 1 or 4, wherein the annealing heat treatment temperature under the atmospheric condition is 50 to 350 ℃ and the treatment time is 1 to 300 minutes; the temperature rising speed is 1-5 ℃/min.
6. The method according to claim 5, wherein the annealing heat treatment temperature is 200 ℃ and the treatment time is 120 minutes.
7. Use of the carbon and sulfur double-doped nickel-cobalt double hydroxide electrode material prepared by the preparation method according to any one of claims 1 to 6 in the preparation of a supercapacitor.
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| CN105895383B (en) * | 2016-04-11 | 2018-12-07 | 中国工程物理研究院材料研究所 | A kind of supercapacitor alloy/amorphous nickel cobalt hydroxide combination electrode and preparation method thereof |
| CN105957728B (en) * | 2016-07-21 | 2018-04-13 | 安徽师范大学 | A kind of nickel cobalt double-hydroxide/NiCo2S4Composite nano materials, its preparation method and the application as electrode material for super capacitor |
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| CN109300703A (en) * | 2018-12-04 | 2019-02-01 | 浙江理工大学 | Cobalt nickel bimetal hydroxide nano piece/nitridation carbon coating N doping hollow graphite alkene ball composite material and preparation method and application |
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