CN110060876B - NGA @ PEDOT material and preparation method of super capacitor for dragonfly-shaped micro unmanned aerial vehicle - Google Patents

NGA @ PEDOT material and preparation method of super capacitor for dragonfly-shaped micro unmanned aerial vehicle Download PDF

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CN110060876B
CN110060876B CN201910324290.8A CN201910324290A CN110060876B CN 110060876 B CN110060876 B CN 110060876B CN 201910324290 A CN201910324290 A CN 201910324290A CN 110060876 B CN110060876 B CN 110060876B
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nga
capacitor
capacitors
pedot
unmanned aerial
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CN110060876A (en
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辛青
郭志成
臧月
林君
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Hangzhou Dianzi University
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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
    • H01G11/10—Multiple hybrid or EDL capacitors, e.g. arrays or modules
    • 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
    • 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
    • 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
    • H01G11/48—Conductive polymers
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Abstract

The invention discloses a preparation method of an NGA @ PEDOT material and a super capacitor for a dragonfly-shaped micro unmanned aerial vehicle, the NGA @ PEDOT material is prepared firstly, then a nickel sheet, the NGA @ PEDOT material, PVA/KOH gel solid electrolyte, the NGA @ PEDOT material and the nickel sheet are sequentially pressed, and then the nickel sheet, the NGA @ PEDOT material and the nickel sheet are stacked in sequence and then pressed into a manufactured capacitor; 4 flexible capacitors are bent and assembled into a hollow oval shape and are connected in series to form a group of series capacitors; the 3-8 hollow elliptic capacitors connected in series are overlapped and connected in parallel, and the method has the advantages of simplicity, high efficiency, good reproducibility, large-scale preparation and the like. The method improves the specific capacitance of the whole material, and has the characteristics of large power density, wide working voltage window, rapid charge and discharge and the like.

Description

NGA @ PEDOT material and preparation method of super capacitor for dragonfly-shaped micro unmanned aerial vehicle
Technical Field
The invention belongs to the field of super-capacitor new material energy storage, and particularly relates to an NGA @ PEDOT material and a preparation method of a super-capacitor for a dragonfly-shaped micro unmanned aerial vehicle.
Background
The unmanned aerial vehicle has the main advantages of low purchasing cost and no danger of pilot casualties, is characterized by small volume, light weight, good maneuverability, good concealment and long endurance time, is particularly suitable for executing tasks with large danger, and is mainly used as a target drone and reconnaissance. Among the unmanned aerial vehicles, the micro unmanned aerial vehicle has the advantages of low cost, no casualties, lightness, smallness, flexibility and more outstanding maneuvering, and is particularly suitable for small troops to act and street fighting reconnaissance. The power problem is the key problem of the operation of the micro unmanned aerial vehicle, and because the micro unmanned aerial vehicle is only about 15cm long, the size of the capacitor is strictly limited, and a material with high specific capacitance and light weight is required.
Supercapacitors can be simply classified into electrochemical double layer capacitors, pseudocapacitors and hybrid capacitors according to the charge storage mechanism. Electric double layer capacitors store electrostatic charge by reversibly absorbing and desorbing electrolyte ions at the surface of the active material, and carbon-based materials are generally preferred materials for electric double layer capacitors. The pseudocapacitance is a charge stored by a rapid and reversible oxidation-reduction reaction on the surface of a material, and the transition metal oxide and the conductive polymer are generally electrode materials of the pseudocapacitance. The hybrid capacitor relates to two mechanisms of an electric double layer and a pseudo capacitor to store charges, and the energy density of the super capacitor can be improved without losing the power density by combining the embedding and releasing of the Faraday pseudo capacitor and the surface adsorption and desorption reaction of the electric double layer.
NGA @ PEDOT is a novel material in which poly 3, 4-ethylenedioxythiophene (PEDOT) is used to coat nitrogen-doped graphene gel (NGA). The conductive polymer has excellent conductivity, large specific capacitance and simple preparation process, so that the conductive polymer is widely concerned by researchers as a material of pseudocapacitance, and PEDOT is an organic high-molecular polymer with high conductivity. In the structure of the three-dimensional graphene gel, pores are formed by curling and stacking a construction unit, namely graphene nano sheets, compared with the traditional carbon gel, the graphene gel has a rich nano-pore structure, the flexibility of graphene sheet layers enables the graphene gel to have better mechanical properties, and the conductivity of the material is further improved by nitrogen doping. The composite material can be used as an electrode material of an all-solid-state super capacitor to improve the specific capacitance of the capacitor.
Disclosure of Invention
Aiming at the problem of dragonfly-shaped unmanned aerial vehicle kinetic energy storage, the NGA @ PEDOT material with high conductivity is prepared and used as an electrode material of an electrochemical capacitor, and the structural characteristics of the dragonfly-shaped unmanned aerial vehicle are combined to prepare the all-solid-state supercapacitor with high specific capacitance to supply power to the dragonfly-shaped unmanned aerial vehicle.
The preparation method of the NGA @ PEDOT super capacitor electrode is characterized by comprising the following steps:
(1) dissolving melamine in a graphene oxide solution, sequentially adding VC and ammonia water, performing ultrasonic treatment at 1-4 ℃ to completely dissolve the melamine, then forming organogel in the mixed solution at 80 ℃ by using a water bath method, and firing the organogel at 900 ℃ for 2h in an inert atmosphere to obtain NGA, wherein the concentration of the graphene oxide solution is 0.5-5mg/ml, the mass ratio of graphene oxide to VC is 1:1, and the mass ratio of graphene oxide to ammonia water is 4: 1; the mass ratio of the melamine to the graphene oxide is 1:100-3: 100; NGA is nitrogen-doped graphene gel; VC is vitamin C;
(2) adding NGA into butyl acetate, wherein the content of NGA is 15 wt.%, adding EDOT according to the proportion of 50 μ l/ml, and performing ultrasonic treatment for 1 h; EDOT is 3, 4-ethylenedioxythiophene;
(3) dissolving iron p-toluenesulfonate in a mixed solution of ethanol and water, wherein the volume ratio of ethanol to water is 3:1, the content of iron p-toluenesulfonate is 0.6 wt.%, dripping the solution on the material obtained in the step (2), performing ultrasonic mixing, standing at room temperature for 6 hours, polymerizing, and drying at room temperature for 1 hour to obtain the NGA @ PEDOT material.
A dragonfly-shaped micro unmanned aerial vehicle super capacitor preparation method; the method specifically comprises the following steps: sequentially pressurizing the nickel sheet, the NGA @ PEDOT material, the PVA/KOH gel solid electrolyte, the NGA @ PEDOT material and the nickel sheet, stacking the materials in sequence, and pressing to prepare a capacitor with the thickness of 4 x 5 x 4 mm; 4 flexible capacitors are bent and assembled into a hollow oval shape and are connected in series to form a group of series capacitors; the 3-8 hollow elliptical capacitors connected in series are overlapped and connected in parallel, and the dragonfly-shaped micro unmanned aerial vehicle power supply capacitor can be obtained.
The invention has the beneficial effects that: the method has the advantages of simplicity, high efficiency, good reproducibility, large-scale preparation and the like. The method improves the specific capacitance of the whole material, has the characteristics of large power density, wide working voltage window, quick charge and discharge and the like, wherein a capacitor bank adopts a series-parallel combination mode of a plurality of capacitors, can bear high voltage, and can well solve the problem of sudden short circuit of a certain capacitor. In addition, the advantages of stable performance, good low-temperature performance and long service life make the application range of the composite material extremely wide.
Drawings
FIG. 1: a cross-sectional view of a 4 x 5 x 4mm capacitor structure;
FIG. 2: series cross-sectional view of 4 capacitors.
Detailed Description
For a better understanding of the present invention, reference will now be made to the following examples which are set forth to illustrate, but are not to be construed to limit the present invention.
The first embodiment is as follows: dissolving melamine in a graphene oxide solution, performing ultrasonic treatment at 4 ℃ to completely dissolve the melamine, sequentially adding VC and ammonia water, sealing a membrane, performing ultrasonic treatment at low temperature for 2 hours, then forming organogel in the mixed solution at 80 ℃ by using a water bath method, and firing the organogel at 900 ℃ for 2 hours under an inert atmosphere to obtain NGA; wherein the concentration of the graphene oxide solution is 0.5mg/ml, the mass ratio of the graphene oxide to VC is 1:1, the mass ratio of the graphene oxide to ammonia water is 4:1, and the mass ratio of melamine to the graphene oxide is 1: 100; putting 1mg of NGA into butyl acetate, wherein the content of the NGA is 15 wt.%, adding EDOT according to the proportion of 50 mul/ml, and carrying out ultrasonic treatment for 1h to obtain a mixed solution; 0.25g of iron p-toluenesulfonate is dissolved in a mixed solution of 3ml of ethanol and 1ml of water, and then dropped into the mixed solution, and after ultrasonic mixing, the mixed solution is stood at room temperature for 6 hours and then polymerized. And cleaning with ethanol, and drying at room temperature for 1h to obtain the NGA @ PEDOT material.
The preparation method of the capacitor structure comprises the following steps:
(101) forming the foamed nickel 1,5 into flexible nickel sheets under a pressure of 0.8 tons, and cutting and preparing into squares of 4 x 5 x 1 mm; pressing NGA @ PEDOT material 2,4 with a pressure of 0.1 tonne to a size of 4 x 5 x 1 mm; preparing PVA/KOH solid electrolyte 3 into 4 x 5 x 1 mm; and (3) sequentially assembling and pressing into a cuboid with the size of 4 x 5 x 4mm according to the figure 1, wherein a tab 6 is used as a positive electrode of the capacitor in the figure 1, and a tab 7 is used as a negative electrode of the capacitor.
(102) The series connection is carried out by 4 capacitors (101), and as shown in fig. 2, 14, 15, 16 and 17 are 4 capacitors (101), wherein the tabs 6, 8, 10 and 12 are respectively the positive electrodes of the electric appliance, and the tabs 7, 9, 11 and 13 are respectively the negative electrodes of the capacitors. The 4 capacitors are connected in series to form a series capacitor, the positive electrode of the series capacitor is a tab 12, and the negative electrode of the series capacitor is a tab 7. 18 are hollow for housing the aircraft body and serve to support the capacitor bank.
(103) The power supply capacitor of the dragonfly-shaped micro unmanned aerial vehicle can be obtained by superposing and connecting 2 (102) prepared series-connected hollow elliptical capacitors in parallel, and the specific capacitance of the capacitor is 200F/g at the moment.
The second embodiment is as follows: dissolving melamine in a graphene oxide solution, performing ultrasonic treatment at 1 ℃ to completely dissolve the melamine, adding VC and ammonia water, sealing a membrane, performing ultrasonic treatment at low temperature for 2 hours, then forming organogel in the mixed solution at 80 ℃ by using a water bath method, and firing the organogel at 800 ℃ for 2 hours under an inert atmosphere to obtain NGA; the graphene oxide solution is 2mg/ml in concentration, the mass ratio of graphene oxide to VC is 1:1, the mass ratio of graphene oxide to ammonia water is 4:1, and the mass ratio of melamine to graphene oxide is 1: 50; putting 1mg of NGA into butyl acetate, wherein the content of the NGA is 15 wt.%, adding EDOT according to the proportion of 50 mul/ml, and carrying out ultrasonic treatment for 1h to obtain a mixed solution; 0.25g of iron p-toluenesulfonate is dissolved in a mixed solution of 3ml of ethanol and 1ml of water, and then dropped into the mixed solution, and after ultrasonic mixing, the mixed solution is stood at room temperature for 6 hours and then polymerized. And cleaning with ethanol, and drying at room temperature for 1h to obtain the NGA @ PEDOT material.
The preparation method of the capacitor structure comprises the following steps:
(201) forming the foamed nickel 1,5 into flexible nickel sheets under a pressure of 0.8 tons, and cutting and preparing into squares of 4 x 5 x 1 mm; pressing NGA @ PEDOT material 2,4 with a pressure of 0.1 tonne to a size of 4 x 5 x 1 mm; preparing PVA/KOH solid electrolyte 3 into 4 x 5 x 1 mm; and (3) sequentially assembling and pressing into a cuboid with the size of 4 x 5 x 4mm according to the figure 1, wherein a tab 6 is used as a positive electrode of the capacitor in the figure 1, and a tab 7 is used as a negative electrode of the capacitor.
(202) The series connection is carried out by 4 capacitors (201), such as 4 capacitors (201) shown in 14, 15, 16 and 17 in figure 2, wherein the tabs 6, 8, 10 and 12 are respectively the positive electrodes of the electric appliance, and the tabs 7, 9, 11 and 13 are respectively the negative electrodes of the capacitors. The 4 capacitors are connected in series to form a series capacitor, the positive electrode of the series capacitor is a tab 12, and the negative electrode of the series capacitor is a tab 7. 18 are hollow for housing the aircraft body and serve to support the capacitor bank.
(203) The dragonfly-shaped micro unmanned aerial vehicle power supply capacitor can be obtained by superposing and connecting 4 (202) prepared series-connected hollow elliptical capacitors in parallel, and the specific capacitance of the capacitor is 430F/g at the moment.
The third concrete implementation mode: dissolving melamine in a graphene oxide solution, performing ultrasonic treatment at 2 ℃ to completely dissolve the melamine, adding VC and ammonia water, performing film sealing and low-temperature ultrasonic treatment for 2 hours, then forming organogel in the mixed solution at 80 ℃ by using a water bath method, and firing the organogel for 2 hours at 850 ℃ under an inert atmosphere to obtain NGA; the graphene oxide solution is 5mg/ml in concentration, the mass ratio of graphene oxide to VC is 1:1, the mass ratio of graphene oxide to ammonia water is 4:1, and the mass ratio of melamine to graphene oxide is 3: 100; putting 1mg of NGA into butyl acetate, wherein the content of the NGA is 15 wt.%, adding EDOT according to the proportion of 50 mul/ml, and carrying out ultrasonic treatment for 1h to obtain a mixed solution; 0.25g of iron p-toluenesulfonate is dissolved in a mixed solution of 3ml of ethanol and 1ml of water, and then dropped again into the mixed solution, and after ultrasonic mixing, the mixed solution is stood at room temperature for 6 hours and then polymerized. And cleaning with ethanol, and drying at room temperature for 1h to obtain the NGA @ PEDOT material.
The preparation method of the capacitor structure comprises the following steps:
(301) forming the foamed nickel 1,5 into flexible nickel sheets under a pressure of 0.8 tons, and cutting and preparing into squares of 4 x 5 x 1 mm; pressing NGA @ PEDOT material 2,4 to a size of 4 x 5 x 1mm with a pressure of 0.05-0.1 tonne; preparing PVA/KOH solid electrolyte 3 into 4 x 5 x 1 mm; and (3) sequentially assembling and pressing into a cuboid with the size of 4 x 5 x 4mm according to the figure 1, wherein a tab 6 is used as a positive electrode of the capacitor in the figure 1, and a tab 7 is used as a negative electrode of the capacitor.
(302) The series connection is carried out by 4 capacitors (401), and as shown in figure 2, 14, 15, 16 and 17 are 4 capacitors (301), wherein the tabs 6, 8, 10 and 12 are respectively the positive electrodes of the electric appliance, and the tabs 7, 9, 11 and 13 are respectively the negative electrodes of the capacitors. The 4 capacitors are connected in series to form a series capacitor, the positive electrode of the series capacitor is a tab 12, and the negative electrode of the series capacitor is a tab 7. 18 are hollow for housing the aircraft body and serve to support the capacitor bank.
(303) 6 (302) prepared hollow elliptical capacitors connected in series are superposed and connected in parallel, so that the dragonfly-shaped micro unmanned aerial vehicle power supply capacitor can be obtained, and the specific capacitance of the capacitor is 560F/g.

Claims (3)

1. A preparation method of NGA @ PEDOT material is characterized by comprising the following steps:
(1) preparation of NGA
Dissolving melamine in a graphene oxide solution, sequentially adding VC and ammonia water, performing ultrasonic treatment at 1-4 ℃ to completely dissolve the melamine, then forming organogel in a mixed solution at 80 ℃ by using a water bath method, and firing the organogel at 900 ℃ for 2h in an inert atmosphere to obtain NGA, wherein the concentration of the graphene oxide solution is 0.5-5mg/ml, the mass ratio of graphene oxide to VC is 1:1, and the mass ratio of graphene oxide to ammonia water is 4: 1; the mass ratio of the melamine to the graphene oxide is 1:100-3: 100; NGA is nitrogen-doped graphene gel; VC is vitamin C;
(2) adding NGA into butyl acetate, wherein the content of NGA is 15 wt.%, adding EDOT according to the proportion of 50 μ l/ml, and performing ultrasonic treatment for 1 h; EDOT is 3, 4-ethylenedioxythiophene;
(3) dissolving iron p-toluenesulfonate in a mixed solution of ethanol and water, wherein the volume ratio of ethanol to water is 3:1, the content of iron p-toluenesulfonate is 0.6 wt.%, dripping the mixed solution on the material obtained in the step (2), standing at room temperature for 6 hours after ultrasonic mixing, polymerizing, and drying at room temperature for 1 hour to obtain an NGA @ PEDOT material, namely a material prepared by coating nitrogen-doped graphene gel with poly (3, 4-ethylenedioxythiophene).
2. A preparation method of a super capacitor for a dragonfly-shaped micro unmanned aerial vehicle is characterized by comprising the following steps: preparing NGA @ PEDOT material using the method as recited in claim 1; sequentially pressurizing a nickel sheet, an NGA @ PEDOT material, a PVA/KOH gel solid electrolyte, the NGA @ PEDOT material and the nickel sheet, stacking the materials in sequence, and pressing to prepare a flexible capacitor; bending and assembling four flexible capacitors into a hollow oval shape and connecting the hollow oval shape and the capacitor in series to form a group of capacitors; the multiple groups of capacitors are overlapped and connected in parallel, and the dragonfly-shaped micro unmanned aerial vehicle power supply capacitor can be obtained.
3. The method for preparing the dragonfly-shaped micro unmanned aerial vehicle super capacitor as claimed in claim 2, wherein the capacitors are stacked and connected in parallel into 3-8 groups.
CN201910324290.8A 2019-04-22 2019-04-22 NGA @ PEDOT material and preparation method of super capacitor for dragonfly-shaped micro unmanned aerial vehicle Active CN110060876B (en)

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