CN111199835A - Preparation method of nickel cobalt selenium/nickel cobalt double hydroxide composite electrode material with hierarchical structure - Google Patents
Preparation method of nickel cobalt selenium/nickel cobalt double hydroxide composite electrode material with hierarchical structure Download PDFInfo
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- CN111199835A CN111199835A CN202010077591.8A CN202010077591A CN111199835A CN 111199835 A CN111199835 A CN 111199835A CN 202010077591 A CN202010077591 A CN 202010077591A CN 111199835 A CN111199835 A CN 111199835A
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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
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
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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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
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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
Abstract
The invention relates to an electrode material technology, and aims to provide a preparation method of a nickel cobalt selenium/nickel cobalt double hydroxide composite electrode material with a hierarchical structure. The method comprises the following steps: immersing carbon cloth in a mixed solution of nickel nitrate hexahydrate, cobalt nitrate hexahydrate, urea, water and ethanol, carrying out heat preservation reaction, ultrasonically cleaning, placing the obtained product and selenium powder in a tubular furnace, and carrying out high-temperature treatment in an argon atmosphere; and taking the treated carbon cloth as a working electrode, and electrochemically depositing nickel-cobalt double hydroxide on the surface of the carbon cloth by adopting a chronopotentiometric method to finally obtain the electrode material. The invention avoids the limitation of coating electrodes and is beneficial to the application of electrode materials in flexible devices. The composite material has the advantages of large specific surface area, high stacking density and ordered network structure favorable for charge transmission, improves the conductivity of the composite material, and provides considerable specific capacitance for the composite material. Greatly reduces the electron transfer impedance, improves the utilization rate of the active substance and further improves the capacitance performance of the electrode.
Description
Technical Field
The invention relates to a preparation method of a coralline nickel-cobalt-selenium/nickel-cobalt-double hydroxide composite electrode material with a hierarchical structure for a super capacitor, belonging to the technical field of material science.
Background
Electrochemical energy storage is an important way for solving the problems of fossil fuel exhaustion and environmental pollution, and the super capacitor has wide application prospect in the fields of modern electric equipment, flexible wearable power supplies and the like by virtue of the advantages of high rate performance, rapid charge and discharge, high cycle performance, wide working temperature range, environmental friendliness and the like. The electrode material is a key factor determining the performance of the energy device, the energy density and the cycle life of the electrode material are further improved while the high power density is maintained, and the main challenge for solving the practical application problem of the super capacitor is still achieved.
The reasonable design and regulation of the structure and components of the electrode material are effective ways for improving the electrochemical performance of the electrode material. The transition metal-based Layered Double Hydroxide (LDH) meets the basic requirements for preparing an ideal electrode material due to the characteristics of adjustable chemical composition, excellent oxidation-reduction performance, easy intercalation and the like. In addition, due to the unique two-dimensional structure, the material has higher specific surface area and enough interlayer spacing, not only is the electrochemical active site increased, but also the ion transmission distance is shortened, and the electrochemical performance of the material is greatly improved.
However, due to the semiconductor characteristics of the double hydroxide, the conductivity of the material is poor, which affects the further improvement of the electrochemical performance. And the problem of stacking of sheets caused by the interaction of hydrogen bonds in the layered structure destroys the structural stability of the electrode material, thereby reducing the cycle performance of the electrode and limiting the application of the transition metal-based layered double hydroxide in the electrochemical field.
Disclosure of Invention
The invention aims to solve the problem of overcoming the defects in the prior art and provides a preparation method of a nickel-cobalt-selenium/nickel-cobalt-double-hydroxide composite electrode material with a hierarchical structure. The coralline NiCoSe @ NiCoLDH nano array with the core-shell structure can be synthesized on the carbon cloth substrate by the method, and the prepared electrode material can be directly used for a super capacitor.
In order to solve the technical problem, the technical scheme adopted by the invention is as follows:
the preparation method of the nickel-cobalt-selenium/nickel-cobalt-double hydroxide composite electrode material with the hierarchical structure comprises the following steps:
(1) taking carbon cloth with proper size, cleaning and drying for later use;
(2) taking nickel nitrate hexahydrate, cobalt nitrate hexahydrate and urea according to the mol ratio of 1: 2: 4, adding a proper amount of water and ethanol, and magnetically stirring until a uniform purple red transparent solution is formed; transferring the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene inner container, immersing the carbon cloth obtained in the step (1) in the mixed solution, sealing the reaction kettle, and then preserving heat at 120 ℃ for reaction for 3-12 hours;
(3) cooling to room temperature, taking out the carbon cloth from the reaction kettle, and ultrasonically cleaning the carbon cloth with deionized water and absolute ethyl alcohol for several times; vacuum drying at 60 ℃ for 12h to obtain carbon cloth with a nickel-cobalt precursor nanorod array growing on the surface (the product is purple on the surface of the carbon cloth);
(4) placing a proper amount of selenium powder in the middle of the tube furnace, placing the carbon cloth in the step (3) in a lower air inlet of the selenium powder in the tube furnace, and continuously introducing argon; heating to 450 ℃, keeping the temperature for 2h, continuously introducing argon after the heat treatment is finished until the temperature is reduced to room temperature, and obtaining the carbon cloth with the nickel-cobalt-selenium nanorod array matrix growing on the surface (the product is black on the surface of the carbon cloth);
(5) and (3) taking the carbon cloth obtained in the step (4) as a working electrode, and electrochemically depositing nickel-cobalt double hydroxide on the surface of the carbon cloth by adopting a time potential method, wherein the finally obtained carbon cloth is the NiCoSe @ NiCoLDH integral electrode material with the coral-shaped hierarchical structure on the surface (the product is dark purple on the surface of the carbon cloth).
In the invention, in the step (1), the size of the carbon cloth is 1cm × 2 cm; the cleaning is as follows: placing the carbon cloth in a cleaning solution for ultrasonic cleaning, and sequentially using 3M dilute hydrochloric acid, acetone, deionized water and absolute ethyl alcohol as the cleaning solution, wherein the cleaning time is 20 minutes each time; the drying is that: drying in a vacuum oven at 60 deg.C for 12 h.
In the invention, in the step (2), the volume ratio of the water to the ethanol is 14: 1.
In the invention, in the step (4), the dosage of the selenium powder is 0.6g relative to the carbon cloth with the size of 1cm multiplied by 2 cm; the carbon cloth is placed 10cm away from the selenium powder; the heating rate is controlled to be 10 ℃/min in the heating process, and the cooling mode after the heat treatment is furnace cooling.
In the invention, in the step (5), during electrochemical deposition, a counter electrode is a platinum sheet electrode of 1cm × 1cm, and a reference electrode is a silver/silver chloride electrode; the electrolyte is a mixed solution containing nickel nitrate hexahydrate and cobalt nitrate hexahydrate, and the respective concentrations are 0.0334mol/L and 0.0666mol/L respectively; the initial potential of the electrodeposition is-1.0V, and the duration is 100-500 s.
Compared with the prior art, the invention has the beneficial effects that:
1. the nickel-cobalt precursor nanorod array directly prepared on the surface of the carbon cloth by using a hydrothermal method avoids the limitation of coating an electrode, and is beneficial to the application of an electrode material in a flexible device.
2. The nickel-cobalt-selenium nanorod array obtained by selenizing in the argon atmosphere has a large specific surface area, high stacking density and an ordered network structure beneficial to charge transmission, provides a self-supporting framework for improving the circulation stability of nickel-cobalt double hydroxide, improves the conductivity of the composite material, and provides a considerable specific capacitance for the composite material.
3. The nickel-cobalt double hydroxide is deposited on the surface of the nickel-cobalt-selenium nanorod array by an electrochemical method to form a NiCoSe @ NiCoLDH coral-shaped core-shell structure, so that the electron transfer impedance is greatly reduced, the utilization rate of active substances is improved, and the capacitance performance of the electrode is further improved by combining the ultra-large specific surface area of the two-dimensional layered double hydroxide. And the hierarchical structure has an internal space and a porous structure, so that the volume change of the active material in the charging and discharging process can be buffered, the stability of the structure is improved, and the cycling stability of the electrode is improved.
4. The NiCoSe @ NiCoLDH integral electrode material with the coral-shaped hierarchical structure prepared by the invention can be directly used as an electrode of a supercapacitor. The electrode material is firmly loaded on the surface of the carbon cloth, the growth is uniform, the specific surface area is large, and the contact interface of the electrode and the electrolyte is effectively improved. When used as an electrode, the current density is 2mA cm-2The specific capacitance of the area reaches 10.6F cm-1When the current density is increased to 30mA cm-2In the case of (2), a specific capacitance of 82.5% is still maintained; at a current density of 30mA cm-2The retention rate of the specific capacitance is up to 84.7 percent when the charge and the discharge are cycled for 5000 times under the condition of (1).
Drawings
FIG. 1 is an SEM morphology of the NiCoSe @ NiCoLDH composite electrode prepared in example 2;
FIG. 2 is a CV diagram of the NiCoSe @ NiCoLDH composite electrode prepared in example 2.
Detailed Description
The present invention is further described below with reference to examples and comparative examples, which allow a person skilled in the art to more fully understand the present invention, but do not limit the present invention in any way.
The present invention will be further described with reference to examples and comparative examples.
Example 1
(1) Sequentially placing a carbon cloth with the size of 1cm multiplied by 2cm in 3M dilute hydrochloric acid, acetone, deionized water and absolute ethyl alcohol for ultrasonic cleaning, wherein the cleaning time is 20 minutes each time; and finally drying in a vacuum oven at 60 ℃ for 12h for later use.
(2) Taking 1 millimole of nickel nitrate hexahydrate, 2 millimole of cobalt nitrate hexahydrate and 4 millimole of urea, adding 70mL of water and 5mL of ethanol, and magnetically stirring until a uniform mauve transparent solution is formed; transferring the obtained solution into a stainless steel reaction kettle with a polytetrafluoroethylene inner container, immersing the carbon cloth obtained in the step (1) in the solution, sealing, and then preserving heat for 3 hours at 120 ℃.
(3) After the reaction is finished, cooling the reaction kettle to room temperature, taking out the carbon cloth, sequentially placing the carbon cloth in deionized water and absolute ethyl alcohol for ultrasonic cleaning for a plurality of times, and drying the carbon cloth in a vacuum oven at 60 ℃ for 12 hours to obtain the carbon cloth with the nickel-cobalt precursor nanorod array growing on the surface (the product is purple on the surface of the carbon cloth);
(4) placing the carbon cloth obtained in the step (3) and 0.6g of selenium powder in a tube furnace, wherein the distance between the carbon cloth and a lower air inlet of the selenium powder is 10 cm; continuously introducing argon, controlling the heating rate to be 10 ℃/min, heating to 450 ℃, and then preserving heat for 2 h; after the heat treatment is finished, continuously introducing argon, and cooling along with the furnace until the temperature is reduced to room temperature to obtain carbon cloth with the surface growing with the nickel-cobalt-selenium nanorod array matrix (the product is black on the surface of the carbon cloth);
(5) and (4) taking the carbon cloth obtained in the step (4) as a working electrode, and electrochemically depositing the nickel-cobalt double hydroxide by adopting a time potential method. The counter electrode is a platinum sheet electrode of 1cm × 1cm, and the reference electrode is a silver/silver chloride electrode. The electrolyte is a mixed solution containing nickel nitrate hexahydrate and cobalt nitrate hexahydrate, and the respective concentrations are 0.0334mol/L and 0.0666mol/L respectively; electrodeposition was carried out for 300s at an initial potential of-1.0V. The finally obtained carbon cloth is the NiCoSe @ NiCoLDH integral electrode material with the coral-shaped hierarchical structure on the surface (the product is dark purple on the surface of the carbon cloth). The label is NCSe @ NCLDH 1.
(6) And (5) drying the carbon cloth obtained in the step (5) and directly taking the dried carbon cloth as an electrode to perform electrochemical performance test. Wherein, the counter electrode is a platinum sheet electrode, the reference electrode is a mercury/mercury oxide electrode, and the electrolyte is 3M KOH.
Example 2
(1) Sequentially placing a carbon cloth with the size of 1cm multiplied by 2cm in 3M dilute hydrochloric acid, acetone, deionized water and absolute ethyl alcohol for ultrasonic cleaning, wherein the cleaning time is 20 minutes each time; and finally drying in a vacuum oven at 60 ℃ for 12h for later use.
(2) Taking 1 millimole of nickel nitrate hexahydrate, 2 millimole of cobalt nitrate hexahydrate and 4 millimole of urea, adding 70mL of water and 5mL of ethanol, and magnetically stirring until a uniform mauve transparent solution is formed; transferring the obtained solution into a stainless steel reaction kettle with a polytetrafluoroethylene inner container, immersing the carbon cloth obtained in the step (1) in the solution, sealing, and then preserving heat for 6 hours at 120 ℃.
(3) After the reaction is finished, cooling the reaction kettle to room temperature, taking out the carbon cloth, sequentially placing the carbon cloth in deionized water and absolute ethyl alcohol for ultrasonic cleaning for a plurality of times, and drying the carbon cloth in a vacuum oven at 60 ℃ for 12 hours to obtain the carbon cloth with the nickel-cobalt precursor nanorod array growing on the surface (the product is purple on the surface of the carbon cloth);
(4) placing the carbon cloth obtained in the step (3) and 0.6g of selenium powder in a tube furnace, wherein the distance between the carbon cloth and a lower air inlet of the selenium powder is 10 cm; continuously introducing argon, controlling the heating rate to be 10 ℃/min, heating to 450 ℃, and then preserving heat for 2 h; after the heat treatment is finished, continuously introducing argon, and cooling along with the furnace until the temperature is reduced to room temperature to obtain carbon cloth with the surface growing with the nickel-cobalt-selenium nanorod array matrix (the product is black on the surface of the carbon cloth);
(5) and (4) taking the carbon cloth obtained in the step (4) as a working electrode, and electrochemically depositing the nickel-cobalt double hydroxide by adopting a time potential method. The counter electrode is a platinum sheet electrode of 1cm × 1cm, and the reference electrode is a silver/silver chloride electrode. The electrolyte is a mixed solution containing nickel nitrate hexahydrate and cobalt nitrate hexahydrate, and the respective concentrations are 0.0334mol/L and 0.0666mol/L respectively; electrodeposition was carried out for 300s at an initial potential of-1.0V. The finally obtained carbon cloth is the NiCoSe @ NiCoLDH integral electrode material with the coral-shaped hierarchical structure on the surface (the product is dark purple on the surface of the carbon cloth). The label is NCSe @ NCLDH 2.
(6) And (5) drying the carbon cloth obtained in the step (5) and directly taking the dried carbon cloth as an electrode to perform electrochemical performance test. Wherein, the counter electrode is a platinum sheet electrode, the reference electrode is a mercury/mercury oxide electrode, and the electrolyte is 3M KOH.
Example 3
(1) Sequentially placing a carbon cloth with the size of 1cm multiplied by 2cm in 3M dilute hydrochloric acid, acetone, deionized water and absolute ethyl alcohol for ultrasonic cleaning, wherein the cleaning time is 20 minutes each time; and finally drying in a vacuum oven at 60 ℃ for 12h for later use.
(2) Taking 1 millimole of nickel nitrate hexahydrate, 2 millimole of cobalt nitrate hexahydrate and 4 millimole of urea, adding 70mL of water and 5mL of ethanol, and magnetically stirring until a uniform mauve transparent solution is formed; transferring the obtained solution into a stainless steel reaction kettle with a polytetrafluoroethylene inner container, immersing the carbon cloth obtained in the step (1) in the solution, sealing, and then preserving heat at 120 ℃ for 12 hours.
(3) After the reaction is finished, cooling the reaction kettle to room temperature, taking out the carbon cloth, sequentially placing the carbon cloth in deionized water and absolute ethyl alcohol for ultrasonic cleaning for a plurality of times, and drying the carbon cloth in a vacuum oven at 60 ℃ for 12 hours to obtain the carbon cloth with the nickel-cobalt precursor nanorod array growing on the surface (the product is purple on the surface of the carbon cloth);
(4) placing the carbon cloth obtained in the step (3) and 0.6g of selenium powder in a tube furnace, wherein the distance between the carbon cloth and a lower air inlet of the selenium powder is 10 cm; continuously introducing argon, controlling the heating rate to be 10 ℃/min, heating to 450 ℃, and then preserving heat for 2 h; after the heat treatment is finished, continuously introducing argon, and cooling along with the furnace until the temperature is reduced to room temperature to obtain carbon cloth with the surface growing with the nickel-cobalt-selenium nanorod array matrix (the product is black on the surface of the carbon cloth);
(5) and (4) taking the carbon cloth obtained in the step (4) as a working electrode, and electrochemically depositing the nickel-cobalt double hydroxide by adopting a time potential method. The counter electrode is a platinum sheet electrode of 1cm × 1cm, and the reference electrode is a silver/silver chloride electrode. The electrolyte is a mixed solution containing nickel nitrate hexahydrate and cobalt nitrate hexahydrate, and the respective concentrations are 0.0334mol/L and 0.0666mol/L respectively; electrodeposition was carried out for 300s at an initial potential of-1.0V. The finally obtained carbon cloth is the NiCoSe @ NiCoLDH integral electrode material with the coral-shaped hierarchical structure on the surface (the product is dark purple on the surface of the carbon cloth). The label is NCSe @ NCLDH 3.
(6) And (5) drying the carbon cloth obtained in the step (5) and directly taking the dried carbon cloth as an electrode to perform electrochemical performance test. Wherein, the counter electrode is a platinum sheet electrode, the reference electrode is a mercury/mercury oxide electrode, and the electrolyte is 3M KOH.
Example 4
(1) Sequentially placing a carbon cloth with the size of 1cm multiplied by 2cm in 3M dilute hydrochloric acid, acetone, deionized water and absolute ethyl alcohol for ultrasonic cleaning, wherein the cleaning time is 20 minutes each time; and finally drying in a vacuum oven at 60 ℃ for 12h for later use.
(2) Taking 1 millimole of nickel nitrate hexahydrate, 2 millimole of cobalt nitrate hexahydrate and 4 millimole of urea, adding 70mL of water and 5mL of ethanol, and magnetically stirring until a uniform mauve transparent solution is formed; transferring the obtained solution into a stainless steel reaction kettle with a polytetrafluoroethylene inner container, immersing the carbon cloth obtained in the step (1) in the solution, sealing, and then preserving heat for 6 hours at 120 ℃.
(3) After the reaction is finished, cooling the reaction kettle to room temperature, taking out the carbon cloth, sequentially placing the carbon cloth in deionized water and absolute ethyl alcohol for ultrasonic cleaning for a plurality of times, and drying the carbon cloth in a vacuum oven at 60 ℃ for 12 hours to obtain the carbon cloth with the nickel-cobalt precursor nanorod array growing on the surface (the product is purple on the surface of the carbon cloth);
(4) placing the carbon cloth obtained in the step (3) and 0.6g of selenium powder in a tube furnace, wherein the distance between the carbon cloth and a lower air inlet of the selenium powder is 10 cm; continuously introducing argon, controlling the heating rate to be 10 ℃/min, heating to 450 ℃, and then preserving heat for 2 h; after the heat treatment is finished, continuously introducing argon, and cooling along with the furnace until the temperature is reduced to room temperature to obtain carbon cloth with the surface growing with the nickel-cobalt-selenium nanorod array matrix (the product is black on the surface of the carbon cloth);
(5) and (4) taking the carbon cloth obtained in the step (4) as a working electrode, and electrochemically depositing the nickel-cobalt double hydroxide by adopting a time potential method. The counter electrode is a platinum sheet electrode of 1cm × 1cm, and the reference electrode is a silver/silver chloride electrode. The electrolyte is a mixed solution containing nickel nitrate hexahydrate and cobalt nitrate hexahydrate, and the respective concentrations are 0.0334mol/L and 0.0666mol/L respectively; at an initial potential of-1.0V, 100s were electrodeposited. The finally obtained carbon cloth is the NiCoSe @ NiCoLDH integral electrode material with the coral-shaped hierarchical structure on the surface (the product is dark purple on the surface of the carbon cloth). The label is NCSe @ NCLDH 4.
(6) And (5) drying the carbon cloth obtained in the step (5) and directly taking the dried carbon cloth as an electrode to perform electrochemical performance test. Wherein, the counter electrode is a platinum sheet electrode, the reference electrode is a mercury/mercury oxide electrode, and the electrolyte is 3M KOH.
Example 5
(1) Sequentially placing a carbon cloth with the size of 1cm multiplied by 2cm in 3M dilute hydrochloric acid, acetone, deionized water and absolute ethyl alcohol for ultrasonic cleaning, wherein the cleaning time is 20 minutes each time; and finally drying in a vacuum oven at 60 ℃ for 12h for later use.
(2) Taking 1 millimole of nickel nitrate hexahydrate, 2 millimole of cobalt nitrate hexahydrate and 4 millimole of urea, adding 70mL of water and 5mL of ethanol, and magnetically stirring until a uniform mauve transparent solution is formed; transferring the obtained solution into a stainless steel reaction kettle with a polytetrafluoroethylene inner container, immersing the carbon cloth obtained in the step (1) in the solution, sealing, and then preserving heat for 6 hours at 120 ℃.
(3) After the reaction is finished, cooling the reaction kettle to room temperature, taking out the carbon cloth, sequentially placing the carbon cloth in deionized water and absolute ethyl alcohol for ultrasonic cleaning for a plurality of times, and drying the carbon cloth in a vacuum oven at 60 ℃ for 12 hours to obtain the carbon cloth with the nickel-cobalt precursor nanorod array growing on the surface (the product is purple on the surface of the carbon cloth);
(4) placing the carbon cloth obtained in the step (3) and 0.6g of selenium powder in a tube furnace, wherein the distance between the carbon cloth and a lower air inlet of the selenium powder is 10 cm; continuously introducing argon, controlling the heating rate to be 10 ℃/min, heating to 450 ℃, and then preserving heat for 2 h; after the heat treatment is finished, continuously introducing argon, and cooling along with the furnace until the temperature is reduced to room temperature to obtain carbon cloth with the surface growing with the nickel-cobalt-selenium nanorod array matrix (the product is black on the surface of the carbon cloth);
(5) and (4) taking the carbon cloth obtained in the step (4) as a working electrode, and electrochemically depositing the nickel-cobalt double hydroxide by adopting a time potential method. The counter electrode is a platinum sheet electrode of 1cm × 1cm, and the reference electrode is a silver/silver chloride electrode. The electrolyte is a mixed solution containing nickel nitrate hexahydrate and cobalt nitrate hexahydrate, and the respective concentrations are 0.0334mol/L and 0.0666mol/L respectively; at an initial potential of-1.0V, 200s were electrodeposited. The finally obtained carbon cloth is the NiCoSe @ NiCoLDH integral electrode material with the coral-shaped hierarchical structure on the surface (the product is dark purple on the surface of the carbon cloth). The label is NCSe @ NCLDH 5.
(6) And (5) drying the carbon cloth obtained in the step (5) and directly taking the dried carbon cloth as an electrode to perform electrochemical performance test. Wherein, the counter electrode is a platinum sheet electrode, the reference electrode is a mercury/mercury oxide electrode, and the electrolyte is 3M KOH.
Example 6
(1) Sequentially placing a carbon cloth with the size of 1cm multiplied by 2cm in 3M dilute hydrochloric acid, acetone, deionized water and absolute ethyl alcohol for ultrasonic cleaning, wherein the cleaning time is 20 minutes each time; and finally drying in a vacuum oven at 60 ℃ for 12h for later use.
(2) Taking 1 millimole of nickel nitrate hexahydrate, 2 millimole of cobalt nitrate hexahydrate and 4 millimole of urea, adding 70mL of water and 5mL of ethanol, and magnetically stirring until a uniform mauve transparent solution is formed; transferring the obtained solution into a stainless steel reaction kettle with a polytetrafluoroethylene inner container, immersing the carbon cloth obtained in the step (1) in the solution, sealing, and then preserving heat for 6 hours at 120 ℃.
(3) After the reaction is finished, cooling the reaction kettle to room temperature, taking out the carbon cloth, sequentially placing the carbon cloth in deionized water and absolute ethyl alcohol for ultrasonic cleaning for a plurality of times, and drying the carbon cloth in a vacuum oven at 60 ℃ for 12 hours to obtain the carbon cloth with the nickel-cobalt precursor nanorod array growing on the surface (the product is purple on the surface of the carbon cloth);
(4) placing the carbon cloth obtained in the step (3) and 0.6g of selenium powder in a tube furnace, wherein the distance between the carbon cloth and a lower air inlet of the selenium powder is 10 cm; continuously introducing argon, controlling the heating rate to be 10 ℃/min, heating to 450 ℃, and then preserving heat for 2 h; after the heat treatment is finished, continuously introducing argon, and cooling along with the furnace until the temperature is reduced to room temperature to obtain carbon cloth with the surface growing with the nickel-cobalt-selenium nanorod array matrix (the product is black on the surface of the carbon cloth);
(5) and (4) taking the carbon cloth obtained in the step (4) as a working electrode, and electrochemically depositing the nickel-cobalt double hydroxide by adopting a time potential method. The counter electrode is a platinum sheet electrode of 1cm × 1cm, and the reference electrode is a silver/silver chloride electrode. The electrolyte is a mixed solution containing nickel nitrate hexahydrate and cobalt nitrate hexahydrate, and the respective concentrations are 0.0334mol/L and 0.0666mol/L respectively; at an initial potential of-1.0V, 400s were electrodeposited. The finally obtained carbon cloth is the NiCoSe @ NiCoLDH integral electrode material with the coral-shaped hierarchical structure on the surface (the product is dark purple on the surface of the carbon cloth). The label is NCSe @ NCLDH 6.
(6) And (5) drying the carbon cloth obtained in the step (5) and directly taking the dried carbon cloth as an electrode to perform electrochemical performance test. Wherein, the counter electrode is a platinum sheet electrode, the reference electrode is a mercury/mercury oxide electrode, and the electrolyte is 3M KOH.
Example 7
(1) Sequentially placing a carbon cloth with the size of 1cm multiplied by 2cm in 3M dilute hydrochloric acid, acetone, deionized water and absolute ethyl alcohol for ultrasonic cleaning, wherein the cleaning time is 20 minutes each time; and finally drying in a vacuum oven at 60 ℃ for 12h for later use.
(2) Taking 1 millimole of nickel nitrate hexahydrate, 2 millimole of cobalt nitrate hexahydrate and 4 millimole of urea, adding 70mL of water and 5mL of ethanol, and magnetically stirring until a uniform mauve transparent solution is formed; transferring the obtained solution into a stainless steel reaction kettle with a polytetrafluoroethylene inner container, immersing the carbon cloth obtained in the step (1) in the solution, sealing, and then preserving heat for 6 hours at 120 ℃.
(3) After the reaction is finished, cooling the reaction kettle to room temperature, taking out the carbon cloth, sequentially placing the carbon cloth in deionized water and absolute ethyl alcohol for ultrasonic cleaning for a plurality of times, and drying the carbon cloth in a vacuum oven at 60 ℃ for 12 hours to obtain the carbon cloth with the nickel-cobalt precursor nanorod array growing on the surface (the product is purple on the surface of the carbon cloth);
(4) placing the carbon cloth obtained in the step (3) and 0.6g of selenium powder in a tube furnace, wherein the distance between the carbon cloth and a lower air inlet of the selenium powder is 10 cm; continuously introducing argon, controlling the heating rate to be 10 ℃/min, heating to 450 ℃, and then preserving heat for 2 h; after the heat treatment is finished, continuously introducing argon, and cooling along with the furnace until the temperature is reduced to room temperature to obtain carbon cloth with the surface growing with the nickel-cobalt-selenium nanorod array matrix (the product is black on the surface of the carbon cloth);
(5) and (4) taking the carbon cloth obtained in the step (4) as a working electrode, and electrochemically depositing the nickel-cobalt double hydroxide by adopting a time potential method. The counter electrode is a platinum sheet electrode of 1cm × 1cm, and the reference electrode is a silver/silver chloride electrode. The electrolyte is a mixed solution containing nickel nitrate hexahydrate and cobalt nitrate hexahydrate, and the respective concentrations are 0.0334mol/L and 0.0666mol/L respectively; at an initial potential of-1.0V, 500s were electrodeposited. The finally obtained carbon cloth is the NiCoSe @ NiCoLDH integral electrode material with the coral-shaped hierarchical structure on the surface (the product is dark purple on the surface of the carbon cloth). The label is NCSe @ NCLDH 7.
(6) And (5) drying the carbon cloth obtained in the step (5) and directly taking the dried carbon cloth as an electrode to perform electrochemical performance test. Wherein, the counter electrode is a platinum sheet electrode, the reference electrode is a mercury/mercury oxide electrode, and the electrolyte is 3M KOH.
Comparative example 1
(1) Sequentially placing a carbon cloth with the size of 1cm multiplied by 2cm in 3M dilute hydrochloric acid, acetone, deionized water and absolute ethyl alcohol for ultrasonic cleaning, wherein the cleaning time is 20 minutes each time; and finally drying in a vacuum oven at 60 ℃ for 12h for later use.
(2) Taking 1 millimole of nickel nitrate hexahydrate, 2 millimole of cobalt nitrate hexahydrate and 4 millimole of urea, adding 70mL of water and 5mL of ethanol, and magnetically stirring until a uniform mauve transparent solution is formed; transferring the obtained solution into a stainless steel reaction kettle with a polytetrafluoroethylene inner container, immersing the carbon cloth obtained in the step (1) in the solution, sealing, and then preserving heat for 6 hours at 120 ℃.
(3) After the reaction is finished, cooling the reaction kettle to room temperature, taking out the carbon cloth, sequentially placing the carbon cloth in deionized water and absolute ethyl alcohol for ultrasonic cleaning for a plurality of times, and drying the carbon cloth in a vacuum oven at 60 ℃ for 12 hours to obtain the carbon cloth with the nickel-cobalt precursor nanorod array growing on the surface (the product is purple on the surface of the carbon cloth);
(4) placing the carbon cloth obtained in the step (3) and 0.6g of selenium powder in a tube furnace, wherein the distance between the carbon cloth and a lower air inlet of the selenium powder is 10 cm; continuously introducing argon, controlling the heating rate to be 10 ℃/min, heating to 450 ℃, and then preserving heat for 2 h; after the heat treatment is finished, continuously introducing argon, and cooling along with the furnace until the temperature is reduced to room temperature to obtain carbon cloth with the surface growing with the nickel-cobalt-selenium nanorod array matrix (the product is black on the surface of the carbon cloth); the marker is NCSe.
(5) And (4) drying the carbon cloth obtained in the step (4), directly using the dried carbon cloth as an electrode for testing, and testing the electrochemical performance of the material in an electrolytic cell by adopting a Shanghai Chenghua electrochemical workstation E760. Wherein, the counter electrode is a platinum sheet electrode, the reference electrode is a mercury/mercury oxide electrode, and the electrolyte is 3M KOH.
Comparative example 2
(1) Sequentially placing a carbon cloth with the size of 1cm multiplied by 2cm in 3M dilute hydrochloric acid, acetone, deionized water and absolute ethyl alcohol for ultrasonic cleaning, wherein the cleaning time is 20 minutes each time; and finally drying in a vacuum oven at 60 ℃ for 12h for later use.
(2) And (2) taking the carbon cloth obtained in the step (1) as a working electrode, and performing electrochemical deposition in an electrolytic cell by adopting an Shanghai Chenghua electrochemical workstation E760. Electrochemical deposition of Ni-Co double hydroxide by means of time potential method. The counter electrode is a platinum sheet electrode of 1cm × 1cm, and the reference electrode is a silver/silver chloride electrode. The electrolyte is a mixed solution containing nickel nitrate hexahydrate and cobalt nitrate hexahydrate, and the respective concentrations are 0.0334mol/L and 0.0666mol/L respectively; at an initial potential of-1.0V, 300s were electrodeposited, 100s apart. Obtaining carbon cloth with the surface growing nickel-cobalt double hydroxide (the product is purple on the surface of the carbon cloth); the marker was NCLDH.
(3) And (3) drying the carbon cloth obtained in the step (2), directly using the dried carbon cloth as an electrode for testing, and testing the electrochemical performance of the material in an electrolytic cell by adopting a Shanghai Chenghua electrochemical workstation E760. Wherein, the counter electrode is a platinum sheet electrode, the reference electrode is a mercury/mercury oxide electrode, and the electrolyte is 3M KOH.
Effects of the implementation
Fig. 1 is an SEM morphology of the NiCoSe @ NiCoLDH composite electrode prepared in example 2, and it can be seen that the nickel-cobalt layered double hydroxide is uniformly coated on the surface of the NiCoSe nanorod array to form a NiCoSe @ NiCoLDH core-shell structure, which exhibits a coral-like morphology.
Table 1 shows capacitance, rate capability and cycle stability of the products prepared in examples and comparative examples as supercapacitor electrode materials.
As can be seen from Table 1, the NCLDH layered double hydroxide electrode material grown by electrochemical deposition on carbon cloth for use as an electrode at a current density of 2mA cm-2The area specific capacitance of the capacitor is about 1.9F cm-2And the current density was increased to 30mA cm-2The retention rate of the capacitance is reduced to 70.4%; when the NCSe nanorod array grows on carbon cloth through hydrothermal reaction and is used as an electrode, the current density is 2mA cm-2The area specific capacitance of the capacitor is about 2.7F cm-2And the current density is increased to 30mAcm-2The retention rate of the capacitance is reduced to 68.3 percent; compared with the NCSe @ NCLDH2 integral electrode with the coral-shaped hierarchical structure prepared in the embodiment 2 of the invention, the electrode material is firmly loaded on the surface of the carbon cloth and uniformly grows, the contact interface of the electrode/electrolyte is improved, the electron transfer impedance is greatly reduced, the utilization rate of the active material is improved, and the capacitance performance of the electrode is further improved by combining with an ultra-large specific surface area. When used as an electrode, the current density is 2mA cm-2The area specific capacitance of about 10.6Fcm-2And the current density was increased to 30mA cm-2The retention rate of the capacitance is reduced to 84.7 percent, which is far better than NCLDHLayered double hydroxide or NCSe nanorod arrays are electrochemically active when used alone as electrodes. In addition, the core-shell structure of NCSe @ NCLDH2 has an internal space and a porous structure, so that the volume change of an active substance in the charge and discharge process can be buffered, the stability of the structure is improved, and the cycling stability of the electrode is improved. At a current density of 30mA cm-2The retention rate of the specific capacitance is up to 84.7 percent when the charge and the discharge are cycled for 5000 times under the condition of (1).
It should be noted that the above-mentioned embodiments are only for illustrating the present invention and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Claims (5)
1. A preparation method of a nickel cobalt selenium/nickel cobalt double hydroxide composite electrode material with a hierarchical structure is characterized by comprising the following steps:
(1) taking carbon cloth with proper size, cleaning and drying for later use;
(2) taking nickel nitrate hexahydrate, cobalt nitrate hexahydrate and urea according to the mol ratio of 1: 2: 4, adding a proper amount of water and ethanol, and magnetically stirring until a uniform purple red transparent solution is formed; transferring the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene inner container, immersing the carbon cloth obtained in the step (1) in the mixed solution, sealing the reaction kettle, and then preserving heat at 120 ℃ for reaction for 3-12 hours;
(3) cooling to room temperature, taking out the carbon cloth from the reaction kettle, and ultrasonically cleaning the carbon cloth with deionized water and absolute ethyl alcohol for several times; vacuum drying at 60 ℃ for 12h to obtain carbon cloth with a nickel-cobalt precursor nanorod array growing on the surface;
(4) placing a proper amount of selenium powder in the middle of the tube furnace, placing the carbon cloth in the step (3) in a lower air inlet of the selenium powder in the tube furnace, and continuously introducing argon; heating to 450 ℃, then preserving heat for 2h, continuously introducing argon after the heat treatment is finished until the temperature is reduced to room temperature, and obtaining carbon cloth with a nickel-cobalt-selenium nanorod array matrix growing on the surface;
(5) and (4) taking the carbon cloth obtained in the step (4) as a working electrode, and electrochemically depositing nickel-cobalt double hydroxide on the surface of the carbon cloth by adopting a time potential method, wherein the finally obtained carbon cloth is the NiCoSe @ NiCoLDH integral electrode material with the coral-shaped hierarchical structure on the surface.
2. The method according to claim 1, wherein in step (1), the carbon cloth has a size of 1cm x 2 cm; the cleaning is as follows: placing the carbon cloth in a cleaning solution for ultrasonic cleaning, and sequentially using 3M dilute hydrochloric acid, acetone, deionized water and absolute ethyl alcohol as the cleaning solution, wherein the cleaning time is 20 minutes each time; the drying is that: drying in a vacuum oven at 60 deg.C for 12 h.
3. The method according to claim 1, wherein in step (2), the volume ratio of water to ethanol is 14: 1.
4. The method according to claim 1, wherein in the step (4), the selenium powder is used in an amount of 0.6g with respect to a carbon cloth having a size of 1cm x 2 cm; the carbon cloth is placed 10cm away from the selenium powder; the heating rate is controlled to be 10 ℃/min in the heating process, and the cooling mode after the heat treatment is furnace cooling.
5. The method according to claim 1, wherein in step (5), in the electrochemical deposition, a counter electrode is used which is a 1cm x 1cm platinum sheet electrode, and a reference electrode is a silver/silver chloride electrode; the electrolyte is a mixed solution containing nickel nitrate hexahydrate and cobalt nitrate hexahydrate, and the respective concentrations are 0.0334mol/L and 0.0666mol/L respectively; the initial potential of the electrodeposition is-1.0V, and the duration is 100-500 s.
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Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111816453A (en) * | 2020-06-29 | 2020-10-23 | 江苏大学 | Three-dimensional silicon structure/nickel-cobalt hydroxide based composite electrode material and preparation method thereof |
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109585177A (en) * | 2018-11-28 | 2019-04-05 | 浙江大学 | A kind of preparation method of the nickel cobalt phosphorus integral electrodes material of core-shell structure |
CN110465312A (en) * | 2019-05-30 | 2019-11-19 | 华南理工大学 | A kind of self-supporting carbon cloth load cobaltous selenide nickel nanowire preparation method and application |
CN110610816A (en) * | 2019-09-18 | 2019-12-24 | 江苏大学 | Preparation method of carbon cloth-based nickel-cobalt double-metal selenide nano square sheet electrode material |
CN110721711A (en) * | 2019-10-11 | 2020-01-24 | 力行氢能科技股份有限公司 | Phosphide/selenide electrolyzed water hydrogen production catalyst and preparation method thereof |
-
2020
- 2020-01-30 CN CN202010077591.8A patent/CN111199835B/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109585177A (en) * | 2018-11-28 | 2019-04-05 | 浙江大学 | A kind of preparation method of the nickel cobalt phosphorus integral electrodes material of core-shell structure |
CN110465312A (en) * | 2019-05-30 | 2019-11-19 | 华南理工大学 | A kind of self-supporting carbon cloth load cobaltous selenide nickel nanowire preparation method and application |
CN110610816A (en) * | 2019-09-18 | 2019-12-24 | 江苏大学 | Preparation method of carbon cloth-based nickel-cobalt double-metal selenide nano square sheet electrode material |
CN110721711A (en) * | 2019-10-11 | 2020-01-24 | 力行氢能科技股份有限公司 | Phosphide/selenide electrolyzed water hydrogen production catalyst and preparation method thereof |
Non-Patent Citations (3)
Title |
---|
QUAN ZONG: ""Three-dimensional coral-like NiCoP@C@Ni(OH)2 core-shell nanoarrays as battery-type electrodes to enhance cycle stability and energy density for hybrid supercapacitors"", 《CHEMICAL ENGINEERING JOURNAL》 * |
WEIWEI ZHOU: ""Hierarchically constructed NiCo2S4@Ni(1−x)Cox(OH)2 core/shell nanoarrays and their application in energy storage"", 《NANOTECHNOLOGY》 * |
YULU ZHU: ""Three-dimensional core-shell NiCoP@NiCoP array on carbon cloth for high performance flexible asymmetric supercapacitor"", 《ELECTROCHIMICA ACTA》 * |
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CN113707463B (en) * | 2021-07-31 | 2022-12-02 | 洛阳师范学院 | Preparation method of supercapacitor composite electrode material |
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