CN113593931B - Preparation method of supercapacitor electrode material NiCoMn-LDH/functionalized graphene - Google Patents
Preparation method of supercapacitor electrode material NiCoMn-LDH/functionalized graphene Download PDFInfo
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
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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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Abstract
The invention relates to a preparation method of a supercapacitor electrode material NiCoMn-LDH/functionalized graphene, which belongs to the technical field of electrochemical materials and comprises the following three steps: (1) preparing functionalized graphene, (2) preparing NiCoMn-LDH, and (3) preparing a supercapacitor electrode material NiCoMn-LDH/Functionalized Graphene (FGN). The electrode material NiCoMn-LDH/functionalized graphene of the super capacitor synthesized by the invention has higher capacity and excellent cycling stability performance, and the assembled asymmetric super capacitor has higher energy density, power density and better cycling stability; meanwhile, the synthesis method is simple and easy to operate, has relatively low cost, needs few types of reagents and is environment-friendly, and solves the problem of large-scale application of the LDH material in the super capacitor.
Description
Technical Field
The invention relates to a preparation method of a supercapacitor electrode material NiCoMn-LDH/functionalized graphene, and belongs to the technical field of electrochemical materials.
Background
With the increasing consumption of fossil energy such as petroleum and coal and the obvious pollution and greenhouse effect caused by the use of the fossil energy, it is important to find a novel energy source with low consumption, high energy storage, cleanness and no pollution. The super capacitor has the advantages of high specific capacity, high power density, high rate performance, long cycle life and the like, has very wide application prospect in energy storage, and mainly comprises three parts of an electrode, electrolyte and a diaphragm. The electrode material plays a decisive influence on the performance of the super capacitor, and the research and preparation of the high-performance electrode material plays a crucial role in the development of the super capacitor.
The graphene material is a two-dimensional film material with wide application, and has the advantages of high conductivity, high specific surface area, good stability, good mechanical properties and the like, so that the graphene material has a large application space. The layered double hydroxides are also called LDHs for short, are layered crystal hydroxides with special structures consisting of two or more than two metal elements, and have special and regular two-dimensional layered structures, so that interlayer ions can be replaced and even can be stripped into single-layer structures, and simultaneously have higher theoretical capacity, and the LDHs are considered as battery type electrode materials with great research significance. Common electrode materials mainly comprise NiAl-LDH, NiMn-LDH, NiCo-LDH and the like. But the application of the conductive material as an electrode material is greatly limited due to the poor conductivity and easy agglomeration and stacking to influence the specific surface area active sites of the conductive material.
Disclosure of Invention
The invention aims to provide a preparation method of a supercapacitor electrode material NiCoMn-LDH/functionalized graphene, which combines LDHs and a graphene material with high conductivity and large specific surface area to form a two-dimensional nanostructure electrode material with higher capacity and excellent cycling stability.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a supercapacitor electrode material NiCoMn-LDH/functionalized graphene comprises the following steps:
(1) preparing functionalized graphene: preparing thermal reduction graphene oxide (rGO) by using graphene oxide as a raw material through a thermal reduction method, combining the rGO with para aminobenzoic acid in a diazotization mode to obtain diazotized graphene (CG), and combining aniline-2, 5-disulfonic acid monosodium salt with the CG through an EDCI condensation reaction at a certain temperature to obtain Functionalized Graphene (FGN);
(2) preparation of NiCoMn-LDH: anhydrous ethanol is used as a solvent, and metal salt hydrates of three elements of nickel, cobalt and manganese are mixed to form NiCoMn-LDH dispersion liquid by a simple coprecipitation method under the action of a precipitator;
(3) preparing a supercapacitor electrode material NiCoMn-LDH/Functionalized Graphene (FGN): and preparing an FGN dispersion liquid, dropwise adding the FGN dispersion liquid into the NiCoMn-LDH dispersion liquid, mechanically stirring for 10-14 h at normal temperature, centrifuging, washing and drying to obtain the electrode material NiCoMn-LDH/Functionalized Graphene (FGN) of the super capacitor.
The technical scheme of the invention is further improved as follows: the reaction temperature of the EDCL condensation reaction in the step (1) is 30-90 ℃, and the reaction time is 12-72 h.
The technical scheme of the invention is further improved as follows: the metal salt of the nickel element in the step (2) is any one of nickel chloride, nickel acetate and nickel sulfate; the metal salt of the cobalt element is any one of cobalt chloride, cobalt acetate and cobalt sulfate; the metal salt of manganese element is any one of manganese chloride, manganese acetate and manganese sulfate.
The technical scheme of the invention is further improved as follows: the precipitant in the step (2) is one of ammonium carbamate, ammonium carbonate and ammonium bicarbonate.
The technical scheme of the invention is further improved as follows: the reaction temperature of the simple coprecipitation method in the step (2) is 60 ℃, and the stirring reaction time is 8-12 h.
The technical scheme of the invention is further improved as follows: the molar ratio of nickel, cobalt and manganese elements in the step (2) is 8:4: 1-4.
The technical scheme of the invention is further improved as follows: the molar ratio of nickel, cobalt and manganese elements in the step (2) is 8:4: 3.
The technical scheme of the invention is further improved as follows: the simple coprecipitation method in step (2) also requires the addition of an aqueous sodium chloride solution.
The technical scheme of the invention is further improved as follows: the mass ratio of the NiCoMn-LDH to the Functionalized Graphene (FGN) in the step (3) is 10: 1-1: 10.
Due to the adoption of the technical scheme, the invention has the following technical effects:
the electrode material NiCoMn-LDH/functionalized graphene of the super capacitor synthesized by the invention has higher capacity and excellent cycling stability performance, and the assembled asymmetric super capacitor has higher energy density, power density and better cycling stability; meanwhile, the synthesis method is simple and easy to operate, has relatively low cost, needs few types of reagents and is environment-friendly, and solves the problem of large-scale application of the LDH material in the super capacitor.
According to the invention, the functionalized graphene and NiCoMn-LDH are prepared into the composite electrode material, the surface electronic structure of the LDHs nanosheet is further regulated and controlled, the interface charge transport is improved, and the electron and ion transport capacity is improved.
Drawings
FIG. 1 is an XRD pattern of NiCoMn-LDH/FGN prepared by example 1 of the present invention;
FIG. 2 is a thermogravimetric comparison of samples prepared in example 1 of the present invention with comparative examples 2 and 3;
FIG. 3 is an SEM picture of NiCoMn-LDH/FGN prepared by example 2 of the present invention;
FIG. 4 is a TEM image of NiCoMn-LDH/FGN prepared by example 2 of the present invention;
FIG. 5 is a cyclic voltammogram of NiCoMn-LDH/FGN prepared in example 3 of the present invention;
FIG. 6 is a graph showing the charge and discharge curves of NiCoMn-LDH/FGN prepared in example 4 of the present invention;
FIG. 7 is a graph showing the charge and discharge curves of NiCoMn-LDH/FGN prepared in comparative example 1 of the present invention;
FIG. 8 is a graph comparing the cycling stability of samples prepared according to example 1 of the present invention with comparative examples 2 and 3;
FIG. 9 is a TEM image of NiCoMn-LDH/CG prepared in comparative example 3 of the present invention.
Detailed Description
The invention is described in further detail below with reference to the following figures and specific embodiments:
a preparation method of a supercapacitor electrode material NiCoMn-LDH/functionalized graphene comprises the following steps:
(1) preparation of functionalized graphene
The graphene oxide is prepared by using a modified Hummers method. And (3) heating the tubular furnace to 800 ℃, taking about 0.1g of ground graphene oxide into a crucible each time, placing the crucible into the tubular furnace, and taking out after about 120 seconds to obtain the thermal reduction graphene oxide (rGO).
Putting p-aminobenzoic acid into a beaker filled with a certain amount of concentrated hydrochloric acid and deionized water, cooling to 0 ℃, and dropwise adding NaNO2Cooling the solution to 0 ℃, stirring for 10 minutes, adding rGO into a beaker, stirring for 10-14 hours, stopping the reaction, centrifuging, washing with absolute ethyl alcohol, hydrochloric acid and deionized water respectively, and washingAfter the washing is completed, the obtained product is dried in an oven at 60 ℃ for 12 hours to obtain diazotized graphene (CG).
Dissolving aniline-2, 5-disulfonic acid monosodium salt in deionized water, adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride EDCl and N-hydroxysuccinimide NHS, stirring at normal temperature for 2h, adding a CG sample, stirring at 30-90 ℃ for 12-72 h, centrifugally washing, drying at 20-200 ℃ for 8-36 h or freeze-drying at-40-20 ℃ for 8-36 h to obtain Functionalized Graphene (FGN).
(2) Preparation of NiCoMn-LDH
Adding a precipitant which is one of ammonium carbamate, ammonium carbonate and ammonium bicarbonate into a flask filled with the absolute ethanol solution at 60 ℃ to obtain a solution I.
Dissolving metal salts of nickel, cobalt and manganese elements in a molar ratio of 8:4: 1-4 in absolute ethyl alcohol, wherein the metal salts of the nickel elements are any one of nickel chloride, nickel acetate and nickel sulfate; the metal salt of the cobalt element is any one of cobalt chloride, cobalt acetate and cobalt sulfate; the metal salt of the manganese element is any one of manganese chloride, manganese acetate and manganese sulfate, and is added into the solution I, and the solution II is obtained by stirring at 60 ℃.
And dissolving NaCl in boiled deionized water, adding the NaCl into the solution II, and continuously stirring for 8-12 h at the temperature of 60 ℃ to obtain the NiCoMn-LDH dispersion liquid.
(3) Preparation of electrode material NiCoMn-LDH/Functionalized Graphene (FGN) of super capacitor
Dissolving FGN in deionized water for ultrasonic dispersion to obtain FGN dispersion liquid.
Dropwise adding the FGN dispersion liquid into the NiCoMn-LDH dispersion liquid, wherein the mass ratio of the NiCoMn-LDH to the Functionalized Graphene (FGN) is 10: 1-1: 10, mechanically stirring at normal temperature for 10-14 h, standing, centrifuging, washing, drying at 20-200 ℃ for 8-36 h or freeze-drying at-40-20 ℃ for 8-36 h, and obtaining the NiCoMn-LDH/functionalized graphene composite electrode material.
Example 1
A preparation method of a supercapacitor electrode material NiCoMn-LDH/functionalized graphene comprises the following steps:
(1) preparation of functionalized graphene
The graphene oxide is prepared by using a modified Hummers method. And (3) heating the tubular furnace to 800 ℃, taking about 0.1g of ground graphene oxide into a crucible each time, placing the crucible into the tubular furnace, and taking out after about 120 seconds to obtain the thermal reduction graphene oxide (rGO).
1.7g of p-aminobenzoic acid is put into a 100mL beaker filled with 5mL of concentrated hydrochloric acid and 10mL of deionized water to be cooled to 0 ℃, and 3 mL of NaNO with the concentration of 0.3g/mL is dropwise added2And (3) cooling the solution to 0 ℃, stirring for 10 minutes, adding 60mg of rGO into a beaker, stirring for 10 hours, stopping the reaction, centrifuging, washing with absolute ethyl alcohol, hydrochloric acid and deionized water respectively, and after washing is finished, drying in a 60 ℃ oven for 12 hours to obtain the diazotized graphene (CG).
0.1346g of aniline-2, 5-disulfonic acid monosodium salt is dissolved in deionized water, 0.231g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride EDCl and 0.21g of N-hydroxysuccinimide NHS are added, the mixture is stirred at normal temperature for 2 hours, 50mg of CG sample is added, the mixture is stirred at 70 ℃ for 36 hours, and the mixture is centrifugally washed and dried at 60 ℃ for 12 hours to obtain the Functionalized Graphene (FGN).
(2) Preparation of NiCoMn-LDH
0.3g of ammonium bicarbonate was added to a flask containing 30mL of absolute ethanol solution at 60 ℃ to give solution I.
Dissolving nickel chloride, cobalt chloride and manganese chloride with the total molar weight of 0.0042mol and the molar ratio of nickel, cobalt and manganese elements of 8:4:1 in 20mL of absolute ethyl alcohol, adding the solution into the solution I, and stirring at 60 ℃ to obtain a solution II.
And (3) dissolving 0.1-5.0 g of NaCl in 40mL of boiled deionized water, adding the solution into the solution II, and continuously stirring for 8 hours at the temperature of 60 ℃ to obtain the NiCoMn-LDH dispersion liquid.
(3) Preparation of electrode material NiCoMn-LDH/Functionalized Graphene (FGN) of super capacitor
Dissolving 50mg of FGN in 50mL of deionized water for ultrasonic dispersion to obtain FGN dispersion liquid.
Dropwise adding the FGN dispersion liquid into the NiCoMn-LDH dispersion liquid, wherein the mass ratio of NiCoMn-LDH to Functionalized Graphene (FGN) is 10:1, mechanically stirring at normal temperature for 10h, standing, centrifuging, washing, and drying at 60 ℃ for 12h to obtain the NiCoMn-LDH/functionalized graphene composite electrode material.
FIG. 1 demonstrates that the NiCoMn-LDH/FGN80 composite electrode material prepared still exhibits the XRD pattern of a typical LDH.
Example 2
A preparation method of a supercapacitor electrode material NiCoMn-LDH/functionalized graphene comprises the following steps:
(1) preparation of functionalized graphene
The graphene oxide is prepared by using a modified Hummers method. And (3) heating the tubular furnace to 800 ℃, taking about 0.1g of ground graphene oxide into a crucible each time, placing the crucible into the tubular furnace, and taking out after about 120 seconds to obtain the thermal reduction graphene oxide (rGO).
1.7g of p-aminobenzoic acid is put into a 100mL beaker filled with 5mL of concentrated hydrochloric acid and 10mL of deionized water to be cooled to 0 ℃, and 3 mL of NaNO with the concentration of 0.3g/mL is dropwise added2And (3) cooling the solution to 0 ℃, stirring for 10 minutes, adding 60mg of rGO into a beaker, stirring for 14 hours, stopping the reaction, centrifuging, washing with absolute ethyl alcohol, hydrochloric acid and deionized water respectively, and after washing is finished, drying in a 60 ℃ oven for 12 hours to obtain the diazotized graphene (CG).
0.1346g of aniline-2, 5-disulfonic acid monosodium salt is dissolved in deionized water, 0.231g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride EDCl and 0.21g of N-hydroxysuccinimide NHS are added, the mixture is stirred at normal temperature for 2 hours, 50mg of CG sample is added, the mixture is stirred at 90 ℃ for 15 hours, and the mixture is centrifugally washed and dried at 30 ℃ for 36 hours to obtain Functionalized Graphene (FGN).
(2) Preparation of NiCoMn-LDH
0.3g of ammonium carbonate was added to a flask containing 30mL of an absolute ethanol solution at 60 ℃ to obtain a solution I.
Dissolving nickel sulfate, cobalt sulfate and manganese sulfate with the total molar weight of 0.0042mol and the molar ratio of nickel, cobalt and manganese elements of 8:4:3 in 20mL of absolute ethyl alcohol, adding the mixture into the solution I, and stirring at 60 ℃ to obtain a solution II.
And (3) dissolving 0.1-5.0 g of NaCl in 40mL of boiled deionized water, adding the solution into the solution II, and continuously stirring for 12 hours at the temperature of 60 ℃ to obtain the NiCoMn-LDH dispersion liquid.
(3) Preparation of electrode material NiCoMn-LDH/Functionalized Graphene (FGN) of super capacitor
Dissolving 50mg of FGN in 50mL of deionized water for ultrasonic dispersion to obtain FGN dispersion liquid.
Dropwise adding the FGN dispersion liquid into NiCoMn-LDH dispersion liquid, wherein the mass ratio of NiCoMn-LDH to Functionalized Graphene (FGN) is 1:5, mechanically stirring at normal temperature for 12h, standing, centrifuging, washing, and drying at 20 ℃ for 32h to obtain the NiCoMn-LDH/functionalized graphene composite electrode material.
FIGS. 3 and 4 show that graphene and LDH in the prepared NiCoMn-LDH/FGN can be well combined together.
Example 3
A preparation method of a supercapacitor electrode material NiCoMn-LDH/functionalized graphene comprises the following steps:
(1) preparation of functionalized graphene
The graphene oxide is prepared by using a modified Hummers method. And (3) heating the tubular furnace to 800 ℃, taking about 0.1g of ground graphene oxide into a crucible each time, placing the crucible into the tubular furnace, and taking out after about 120 seconds to obtain the thermal reduction graphene oxide (rGO).
1.7g of p-aminobenzoic acid is put into a 100mL beaker filled with 5mL of concentrated hydrochloric acid and 10mL of deionized water to be cooled to 0 ℃, and 3 mL of NaNO with the concentration of 0.3g/mL is dropwise added2And (3) cooling the solution to 0 ℃, stirring for 10 minutes, adding 60mg of rGO into a beaker, stirring for 12 hours, stopping the reaction, centrifuging, washing with absolute ethyl alcohol, hydrochloric acid and deionized water respectively, and after washing is finished, drying in a 60 ℃ oven for 12 hours to obtain the diazotized graphene (CG).
0.1346g of aniline-2, 5-disulfonic acid monosodium salt is dissolved in deionized water, 0.231g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride EDCl and 0.21g of N-hydroxysuccinimide NHS are added, the mixture is stirred at normal temperature for 2 hours, 50mg of CG sample is added, the mixture is stirred at 90 ℃ for 15 hours, and the mixture is centrifugally washed and dried at 30 ℃ for 36 hours to obtain Functionalized Graphene (FGN).
(2) Preparation of NiCoMn-LDH
0.3g of ammonium carbamate was added to a flask containing 30mL of absolute ethanol solution at 60 ℃ to obtain solution I.
Dissolving nickel sulfate, cobalt sulfate and manganese sulfate with the total molar weight of 0.0042mol and the molar ratio of nickel, cobalt and manganese elements of 8:4:2 in 20mL of absolute ethyl alcohol, adding the mixture into the solution I, and stirring at 60 ℃ to obtain a solution II.
And (3) dissolving 0.1-5.0 g of NaCl in 40mL of boiled deionized water, adding the solution into the solution II, and continuously stirring for 8 hours at the temperature of 60 ℃ to obtain the NiCoMn-LDH dispersion liquid.
(3) Preparation of electrode material NiCoMn-LDH/Functionalized Graphene (FGN) of super capacitor
Dissolving 50mg of FGN in 50mL of deionized water for ultrasonic dispersion to obtain FGN dispersion liquid.
Dropwise adding the FGN dispersion liquid into the NiCoMn-LDH dispersion liquid, wherein the mass ratio of NiCoMn-LDH to Functionalized Graphene (FGN) is 1:10, mechanically stirring at normal temperature for 10 hours, standing, centrifuging, washing, and drying at 180 ℃ for 8 hours to obtain the NiCoMn-LDH/functionalized graphene composite material.
FIG. 5 demonstrates that the electrode material NiCoMn-LDH/FGN of the supercapacitor has a significant redox curve.
Example 4
A preparation method of a supercapacitor electrode material NiCoMn-LDH/functionalized graphene comprises the following steps:
(1) preparation of functionalized graphene
The graphene oxide is prepared by using a modified Hummers method. And (3) heating the tubular furnace to 800 ℃, taking about 0.1g of ground graphene oxide into a crucible each time, placing the crucible into the tubular furnace, and taking out after about 120 seconds to obtain the thermal reduction graphene oxide (rGO).
1.7g of p-aminobenzoic acid is put into a 100mL beaker filled with 5mL of concentrated hydrochloric acid and 10mL of deionized water to be cooled to 0 ℃, and 3 mL of NaNO with the concentration of 0.3g/mL is dropwise added2And (3) cooling the solution to 0 ℃, stirring for 10 minutes, adding 60mg of rGO into a beaker, stirring for 12 hours, stopping the reaction, centrifuging, washing with absolute ethyl alcohol, hydrochloric acid and deionized water respectively, and after washing is finished, drying in a 60 ℃ oven for 12 hours to obtain the diazotized graphene (CG).
0.1346g of aniline-2, 5-disulfonic acid monosodium salt is dissolved in deionized water, 0.231g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride EDCl and 0.21g of N-hydroxysuccinimide NHS are added, the mixture is stirred at normal temperature for 2 hours, 50mg of CG sample is added, the mixture is stirred at 60 ℃ for 50 hours, and the mixture is centrifugally washed and freeze-dried at-40 ℃ for 12 hours to obtain Functionalized Graphene (FGN).
(2) Preparation of NiCoMn-LDH
0.3g of ammonium bicarbonate was added to a flask containing 30mL of absolute ethanol solution at 60 ℃ to give solution I.
Dissolving nickel chloride, cobalt chloride and manganese chloride with the total molar weight of 0.0042mol and the molar ratio of nickel, cobalt and manganese elements of 8:4:4 in 20mL of absolute ethyl alcohol, adding the solution into the solution I, and stirring at 60 ℃ to obtain a solution II.
And (3) dissolving 0.1-5.0 g of NaCl in 40mL of boiled deionized water, adding the solution into the solution II, and continuously stirring for 8 hours at the temperature of 60 ℃ to obtain the NiCoMn-LDH dispersion liquid.
(3) Preparation of electrode material NiCoMn-LDH/Functionalized Graphene (FGN) of super capacitor
Dissolving 50mg of FGN in 50mL of deionized water for ultrasonic dispersion to obtain FGN dispersion liquid.
Dropwise adding the FGN dispersion liquid into NiCoMn-LDH dispersion liquid, wherein the mass ratio of NiCoMn-LDH to Functionalized Graphene (FGN) is 5:1, mechanically stirring at normal temperature for 12h, standing, centrifuging, washing, and freeze-drying at-20 ℃ for 32h to obtain the NiCoMn-LDH/functionalized graphene composite electrode material.
FIG. 6 shows that NiCoMn-LDH/FGN has excellent electrochemical reversibility and high coulombic efficiency.
Comparative example 1
A preparation method of a supercapacitor electrode material NiCoMn-LDH/functionalized graphene comprises the following steps:
(1) preparation of functionalized graphene
The graphene oxide is prepared by using a modified Hummers method. And (3) heating the tubular furnace to 800 ℃, taking about 0.1g of ground graphene oxide into a crucible each time, placing the crucible into the tubular furnace, and taking out after about 120 seconds to obtain the thermal reduction graphene oxide (rGO).
1.7g of p-aminobenzoic acid is put into a 100mL beaker filled with 5mL of concentrated hydrochloric acid and 10mL of deionized water to be cooled to 0 ℃, and 3 mL of NaNO with the concentration of 0.3g/mL is dropwise added2And (3) cooling the solution to 0 ℃, stirring for 10 minutes, adding 60mg of rGO into a beaker, stirring for 10 hours, stopping the reaction, centrifuging, washing with absolute ethyl alcohol, hydrochloric acid and deionized water respectively, and after washing is finished, drying in a 60 ℃ oven for 12 hours to obtain the diazotized graphene (CG).
0.1346g of aniline-2, 5-disulfonic acid monosodium salt is dissolved in deionized water, 0.231g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride EDCl and 0.21g of N-hydroxysuccinimide NHS are added, the mixture is stirred at normal temperature for 2 hours, 50mg of CG sample is added, the mixture is stirred at 70 ℃ for 36 hours, and the mixture is centrifugally washed and dried at 60 ℃ for 12 hours to obtain the Functionalized Graphene (FGN).
(2) Preparation of NiCoMn-LDH
0.3g of urea was added to a flask containing 30mL of absolute ethanol solution at 60 ℃ to obtain solution I.
Dissolving nickel chloride, cobalt chloride and manganese chloride with the total molar weight of 0.0042mol and the molar ratio of nickel, cobalt and manganese elements of 8:4:1 in 20mL of absolute ethyl alcohol, adding the solution into the solution I, and stirring at 60 ℃ to obtain a solution II.
And (3) dissolving 0.1-5.0 g of NaCl in 40mL of boiled deionized water, adding the solution into the solution II, and continuously stirring for 8 hours at the temperature of 60 ℃ to obtain the NiCoMn-LDH dispersion liquid.
(3) Preparation of electrode material NiCoMn-LDH/Functionalized Graphene (FGN) of super capacitor
Dissolving 50mg of FGN in 50mL of deionized water for ultrasonic dispersion to obtain FGN dispersion liquid.
Dropwise adding the FGN dispersion liquid into the NiCoMn-LDH dispersion liquid, wherein the mass ratio of NiCoMn-LDH to Functionalized Graphene (FGN) is 10:1, mechanically stirring at normal temperature for 10h, standing, centrifuging, washing, and drying at 60 ℃ for 12h to obtain the NiCoMn-LDH/functionalized graphene composite material.
FIG. 7 shows that the supercapacitor electrode material NiCoMn-LDH/Functionalized Graphene (FGN) of comparative example 1 has a lower capacitance compared to example 4.
Comparative example 2
A preparation method of a supercapacitor electrode material NiCoMn-LDH/thermal reduction graphene oxide comprises the following steps:
(1) preparation of thermally reduced graphene oxide
The graphene oxide is prepared by using a modified Hummers method. And (3) heating the tubular furnace to 800 ℃, taking about 0.1g of ground graphene oxide into a crucible each time, placing the crucible into the tubular furnace, and taking out after about 120 seconds to obtain the thermal reduction graphene oxide (rGO).
(2) Preparation of NiCoMn-LDH
0.3g of ammonium bicarbonate was added to a flask containing 30mL of absolute ethanol solution at 60 ℃ to give solution I.
Dissolving nickel chloride, cobalt chloride and manganese chloride with the total molar weight of 0.0042mol and the molar ratio of nickel, cobalt and manganese elements of 8:4:1 in 20mL of absolute ethyl alcohol, adding the solution into the solution I, and stirring at 60 ℃ to obtain a solution II.
And (3) dissolving 0.1-5.0 g of NaCl in 40mL of boiled deionized water, adding the solution into the solution II, and continuously stirring for 8 hours at the temperature of 60 ℃ to obtain the NiCoMn-LDH dispersion liquid.
(3) Preparation of electrode material NiCoMn-LDH/thermal reduction graphene oxide (rGO) of super capacitor
Dissolving 50mg of rGO in 50mL of deionized water for ultrasonic dispersion to obtain an rGO dispersion liquid.
Dropwise adding the rGO dispersion liquid into NiCoMn-LDH dispersion liquid, wherein the mass ratio of NiCoMn-LDH to thermal reduction graphene oxide (rGO) is 10:1, mechanically stirring at normal temperature for 10h, standing, centrifuging, washing, and drying at 60 ℃ for 12h to obtain the NiCoMn-LDH/thermal reduction graphene oxide composite electrode material.
Comparative example 3
A preparation method of a supercapacitor electrode material NiCoMn-LDH/diazotized graphene comprises the following steps:
(1) preparation of diazotized graphene
The graphene oxide is prepared by using a modified Hummers method. And (3) heating the tubular furnace to 800 ℃, taking about 0.1g of ground graphene oxide into a crucible each time, placing the crucible into the tubular furnace, and taking out after about 120 seconds to obtain the thermal reduction graphene oxide (rGO).
1.7g of p-aminobenzoic acid is put into a 100mL beaker filled with 5mL of concentrated hydrochloric acid and 10mL of deionized water to be cooled to 0 ℃, and 3 mL of NaNO with the concentration of 0.3g/mL is dropwise added2And (3) cooling the solution to 0 ℃, stirring for 10 minutes, adding 60mg of rGO into a beaker, stirring for 10 hours, stopping the reaction, centrifuging, washing with absolute ethyl alcohol, hydrochloric acid and deionized water respectively, and after washing is finished, drying in a 60 ℃ oven for 12 hours to obtain the diazotized graphene (CG).
(2) Preparation of NiCoMn-LDH
0.3g of ammonium bicarbonate was added to a flask containing 30mL of absolute ethanol solution at 60 ℃ to give solution I.
Dissolving nickel chloride, cobalt chloride and manganese chloride with the total molar weight of 0.0042mol and the molar ratio of nickel, cobalt and manganese elements of 8:4:1 in 20mL of absolute ethyl alcohol, adding the solution into the solution I, and stirring at 60 ℃ to obtain a solution II.
And (3) dissolving 0.1-5.0 g of NaCl in 40mL of boiled deionized water, adding the solution into the solution II, and continuously stirring for 8 hours at the temperature of 60 ℃ to obtain the NiCoMn-LDH dispersion liquid.
(3) Preparation of electrode material NiCoMn-LDH/diazotized graphene (CG) of supercapacitor
50mg of CG was dissolved in 50mL of deionized water for ultrasonic dispersion to obtain a CG dispersion.
And dropwise adding the CG dispersion liquid into the NiCoMn-LDH dispersion liquid, wherein the mass ratio of the NiCoMn-LDH to the diazotized graphene (CG) is 10:1, mechanically stirring at normal temperature for 10 hours, standing, centrifuging, washing, and drying at 60 ℃ for 12 hours to obtain the NiCoMn-LDH/diazotized graphene composite electrode material.
FIG. 9 shows that the degree of binding of graphene and LDH samples of the supercapacitor electrode material NiCoMn-LDH/diazotized graphene (CG) prepared in comparative example 3 is low; FIG. 8 shows that NiCoMn-LDH/functionalized graphene composite electrode material has high capacitance and good electrical stability; FIG. 2 shows that the binding of FGN to NiCoMn-LDH is significantly higher than in control examples 2 and 3.
Claims (9)
1. A preparation method of a supercapacitor electrode material NiCoMn-LDH/functionalized graphene is characterized by comprising the following steps:
(1) preparing functionalized graphene: preparing thermal reduction graphene oxide (rGO) by using graphene oxide as a raw material through a thermal reduction method, combining the rGO with para aminobenzoic acid in a diazotization mode to obtain diazotized graphene (CG), and combining aniline-2, 5-disulfonic acid monosodium salt with the CG through an EDCI condensation reaction at a certain temperature to obtain Functionalized Graphene (FGN);
(2) preparation of NiCoMn-LDH: anhydrous ethanol is used as a solvent, and metal salt hydrates of three elements of nickel, cobalt and manganese are mixed to form NiCoMn-LDH dispersion liquid by a simple coprecipitation method under the action of a precipitator;
(3) preparing a supercapacitor electrode material NiCoMn-LDH/Functionalized Graphene (FGN): and preparing an FGN dispersion liquid, dropwise adding the FGN dispersion liquid into the NiCoMn-LDH dispersion liquid, mechanically stirring for 10-14 h at normal temperature, centrifuging, washing and drying to obtain the electrode material NiCoMn-LDH/Functionalized Graphene (FGN) of the super capacitor.
2. The preparation method of the electrode material NiCoMn-LDH/functionalized graphene for the supercapacitor according to claim 1, wherein the preparation method comprises the following steps: the reaction temperature of the EDCL condensation reaction in the step (1) is 30-90 ℃, and the reaction time is 12-72 h.
3. The preparation method of the electrode material NiCoMn-LDH/functionalized graphene for the supercapacitor according to claim 1, wherein the preparation method comprises the following steps: the metal salt of the nickel element in the step (2) is any one of nickel chloride, nickel acetate and nickel sulfate; the metal salt of the cobalt element is any one of cobalt chloride, cobalt acetate and cobalt sulfate; the metal salt of manganese element is any one of manganese chloride, manganese acetate and manganese sulfate.
4. The preparation method of the electrode material NiCoMn-LDH/functionalized graphene for the supercapacitor according to claim 1, wherein the preparation method comprises the following steps: the precipitant in the step (2) is one of ammonium carbamate, ammonium carbonate and ammonium bicarbonate.
5. The preparation method of the electrode material NiCoMn-LDH/functionalized graphene for the supercapacitor according to claim 1, wherein the preparation method comprises the following steps: the reaction temperature of the simple coprecipitation method in the step (2) is 60 ℃, and the stirring reaction time is 8-12 h.
6. The preparation method of the electrode material NiCoMn-LDH/functionalized graphene for the supercapacitor according to claim 1, wherein the preparation method comprises the following steps: the molar ratio of nickel, cobalt and manganese elements in the step (2) is 8:4: 1-4.
7. The preparation method of the electrode material NiCoMn-LDH/functionalized graphene for the supercapacitor according to claim 1, wherein the preparation method comprises the following steps: the molar ratio of nickel, cobalt and manganese elements in the step (2) is 8:4: 3.
8. The preparation method of the electrode material NiCoMn-LDH/functionalized graphene for the supercapacitor according to claim 1, wherein the preparation method comprises the following steps: the simple coprecipitation method in step (2) also requires the addition of an aqueous sodium chloride solution.
9. The preparation method of the electrode material NiCoMn-LDH/functionalized graphene for the supercapacitor according to claim 1, wherein the preparation method comprises the following steps: the mass ratio of the NiCoMn-LDH to the Functionalized Graphene (FGN) in the step (3) is 10: 1-1: 10.
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