CN110060876A - A kind of preparation method of NGA@PEDOT material and the super capacitor for dragonfly shape miniature drone - Google Patents
A kind of preparation method of NGA@PEDOT material and the super capacitor for dragonfly shape miniature drone Download PDFInfo
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- CN110060876A CN110060876A CN201910324290.8A CN201910324290A CN110060876A CN 110060876 A CN110060876 A CN 110060876A CN 201910324290 A CN201910324290 A CN 201910324290A CN 110060876 A CN110060876 A CN 110060876A
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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
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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
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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
- H01G11/48—Conductive polymers
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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
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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
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- 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
A kind of preparation method of super capacitor the invention discloses NGA@PEDOT material and for dragonfly shape miniature drone, the present invention first prepares NGA@PEDOT material, then nickel thin slice, NGA@PEDOT material, PVA/KOH gel solid state electrolyte, NGA@PEDOT material, nickel thin slice are successively pressurizeed, it is stacked according still further to sequence described above, re-compacted manufactured capacitor；4 above-mentioned flexible capacitor bendings are assembled into hollow ellipse shape and are connected into one group of series capacitor；The concatenated hollow ellipse capacitor stack adductions connection of above-mentioned 3-8, method has many advantages, such as to be simple and efficient, favorable reproducibility, can prepare with scale.The features such as this method improves the specific capacitance of material entirety, possesses biggish power density, wider operating voltage window, fast charging and discharging.
Description
Technical field
The invention belongs to super capacitor new material energy storage field more particularly to a kind of NGA@PEDOT material and it is used for
The preparation method of the super capacitor of dragonfly shape miniature drone.
Background technique
The major advantage of unmanned plane is that buying expenses are low and dangerous without pilot injures and deaths, its main feature is that small in size, light weight,
Mobility is good, good concealment, cruise duration are long, particularly suitable for executing dangerous big task, is mainly used as target drone and scouting.In nothing
In man-machine, miniature drone expense is low, without injures and deaths, light, small, flexible, motor-driven more prominent, particularly suitable for Small Unit Action and street fighting
It scouts.Dynamical problem is the critical issue of miniature drone operation, since miniature drone only has about 15cm long, so capacitor is big
Small meeting is strictly limited, and needs the material of high specific capacitance and light weight.
According to charge-storage mechanism, supercapacitor can simply be divided into electrochemical double layer capacitor, fake capacitance and mix
Close capacitor.Double layer capacitor is by storing electrostatic charge in surface of active material reversible adsorption desorption electrolyte ion
, carbon based material is usually the material of preferable double layer capacitor.Fake capacitance is the oxygen that Rapid reversible occurs on the surface of the material
Change reduction reaction to store charge, transition metal oxide and conducting polymer are usually the electrode material of fake capacitance.Mixing electricity
Container is then related to two kinds of mechanism storage charges of electric double layer and fake capacitance, insertion abjection and electric double layer in conjunction with Faraday pseudo-capacitance
The reaction of surface adsorption desorption can improve the energy density of super capacitor not wasted power density again.
NGA@PEDOT is a kind of novel poly- 3,4- ethene dioxythiophene (PEDOT) cladding nitrogen-doped graphene gel
(NGA) material.For conducting polymer due to its excellent electric conductivity, specific capacitance is big, and preparation process is simple, as fake capacitance
Material causes the extensive concern of researchers, and PEDOT is a kind of organic high molecular polymer of high conductivity.Three-dimensional grapheme
In the structure of gel, the formation of hole is stacked by the curling of construction unit-graphene nanometer sheet, solidifying compared to traditional charcoal
Glue, Graphene gel has nano pore structure abundant, and the flexibility of graphene sheet layer makes it have preferable mechanical property,
N doping further improves the conductivity of material.The composite material can be mentioned as the electrode material of all solid state super capacitor
The specific capacitance of high capacitance.
Summary of the invention
The present invention prepares the NGA PEDOT material with high conductivity aiming at the problem that the unmanned maneuver energy storage of dragonfly shape,
As the electrode material of electrochemical capacitor, and the design feature of dragonfly shape unmanned plane is combined, prepares the complete solid of high specific capacitance
State supercapacitor is powered to dragonfly shape unmanned plane.
The preparation method of NGA@PEDOT super capacitor electrode, it is characterised in that method includes the following steps:
(1), melamine is dissolved in graphene oxide solution, sequentially adds VC and ammonium hydroxide, 1-4 DEG C of ultrasound makes it completely
Dissolution, then makes mixed liquor form organogel in 80 DEG C of water temperatures with immersion method, by organogel 800- under an inert atmosphere
900 DEG C of firing 2h obtain NGA, and wherein graphene oxide solution concentration is 0.5-5mg/ml, and graphene oxide is with VC mass ratio
The mass ratio of 1:1, graphene oxide and ammonium hydroxide is 4:1；The mass ratio of melamine and graphene oxide is 1:100-3:100；
NGA is nitrogen-doped graphene gel；VC is vitamin C；
(2), NGA being put into butyl acetate, the content of NGA is 15wt.%, and EDOT is added in the ratio of 50 μ l/ml,
Ultrasonic 1h；EDOT is 3,4- ethene dioxythiophene；
(3), p-methyl benzenesulfonic acid iron is dissolved in the mixed liquor of ethyl alcohol and water, wherein the volume ratio of ethyl alcohol and water is 3:1, to first
The content of benzene sulfonic acid iron is stored at room temperature 6h by solution drips on step (2) resulting material for 0.6wt.% after ultrasonic mixing
It is polymerizable afterwards, 1h is dried at room temperature, can obtain NGA@PEDOT material.
The preparation method of the super capacitor of dragonfly shape miniature drone；Specifically: by nickel thin slice, NGA@PEDOT material,
PVA/KOH gel solid state electrolyte, NGA@PEDOT material, nickel thin slice successively pressurize, and stack according still further to sequence described above, re-compacted
The capacitor of 4*5*4mm is made；4 above-mentioned flexible capacitor bendings are assembled into hollow ellipse shape and are connected into one group of string
Join capacitor；Above-mentioned 3-8 concatenated hollow ellipse capacitor stack adduction connection, can obtain dragonfly shape miniature drone power supply electricity
Hold.
Have many advantages, such as to be simple and efficient the beneficial effects of the present invention are: this method, favorable reproducibility, can prepare with scale.
This method improves the specific capacitance of material entirety, possesses biggish power density, wider operating voltage window, fast charging and discharging etc.
Feature, wherein capacitance group uses the series-parallel combination of multiple capacitors, can bear high voltage, and can be good at handling
The problem of a certain capacitor suddenly-applied short circuit.In addition to this, performance is stablized, and low temperature performance well, the advantage of service life length make its application
Range is extremely wide.
Detailed description of the invention
The sectional view of Fig. 1: 4*5*4mm capacitor arrangement；
Fig. 2: 4 capacitors series connection sectional views.
Specific embodiment
In order to better understand the present invention, the present invention is further explained in the light of specific embodiments.
Specific embodiment 1: melamine is dissolved in graphene oxide solution, ultrasound keeps it completely molten at 4 DEG C
Solution, sequentially adds VC and ammonium hydroxide, and sealer low temperature ultrasonic handles 2h, is then formed with mixed liquor in 80 DEG C of water temperatures with immersion method
Machine gel, by organogel, 900 DEG C of firing 2h obtain NGA under an inert atmosphere；Wherein graphene oxide solution concentration is
0.5mg/ml, graphene oxide and VC mass ratio are 1:1, and the mass ratio with ammonium hydroxide is 4:1, melamine and graphene oxide
Mass ratio is 1:100；1mg NGA is put into butyl acetate, the content of NGA is 15wt.%, and according to the ratio of 50 μ l/ml
EDOT is added, ultrasonic 1h obtains mixed liquor；The p-methyl benzenesulfonic acid iron of 0.25g is dissolved into the mixed liquor of 3ml ethyl alcohol and 1ml water,
It drips in above-mentioned mixed liquor, is stored at room temperature after ultrasonic mixing polymerizable after 6h again.After ethyl alcohol cleans drying at room temperature 1h, it can obtain
NGA@PEDOT material.
Capacitor arrangement preparation method:
(101) nickel foam 1,5 is formed into nickel thin slice flexible under 0.8 ton of pressure, cutting is prepared into the side of 4*5*1mm
Shape；By NGA@PEDOT material 2,4, is suppressed with 0.1 ton of pressure, 4*5*1mm size is made；By PVA/KOH solid electrolyte 3,
4*5*1mm size is made；The cuboid for being pressed into 4*5*4mm is successively assembled by Fig. 1, tab 6 is used as capacitor anode in Fig. 1,
Tab 7 is used as capacitor anode.
(102) it is connected with the capacitor in 4 (101), as 14,15,16,17 be 4 (101) made electricity in Fig. 2
Container, wherein tab 6,8,10,12 is the anode of electric appliance respectively, and tab 7,9,11,13 is the cathode of capacitor respectively.4 electricity
Container, which is together in series, forms a series connection group capacitor, and the anode of series connection group capacitor is tab 12, and cathode is tab 7.18 is hollow,
For placing aircraft body, and play the role of Support Capacitor group.
(103) the concatenated hollow ellipse capacitor stack adduction connection prepared by 2 (102), it is miniature can to obtain dragonfly shape
Unmanned plane power supply capacitor, the specific capacitance of capacitor is 200F/g at this time.
Specific embodiment 2: melamine is dissolved in graphene oxide solution, ultrasound keeps it completely molten at 1 DEG C
VC and ammonium hydroxide is added in solution, and sealer low temperature ultrasonic handles 2h, then forms mixed liquor in 80 DEG C of water temperatures with immersion method organic solidifying
Glue, by organogel, 800 DEG C of firing 2h obtain NGA under an inert atmosphere；Wherein graphene oxide solution concentration is 2mg/ml, oxygen
Graphite alkene and VC mass ratio are 1:1, and the mass ratio with ammonium hydroxide is 4:1, and the mass ratio of melamine and graphene oxide is 1:
50；1mg NGA is put into butyl acetate, the content of NGA is 15wt.%, and EDOT is added according to the ratio of 50 μ l/ml, is surpassed
Sound 1h obtains mixed liquor；The p-methyl benzenesulfonic acid iron of 0.25g is dissolved into the mixed liquor of 3ml ethyl alcohol and 1ml water, then drips in upper
It states in mixed liquor, is stored at room temperature after ultrasonic mixing polymerizable after 6h.After ethyl alcohol cleans drying at room temperature 1h, NGA PEDOT can be obtained
Material.
Capacitor arrangement preparation method:
(201) nickel foam 1,5 is formed into nickel thin slice flexible under 0.8 ton of pressure, cutting is prepared into the side of 4*5*1mm
Shape；By NGA@PEDOT material 2,4, is suppressed with 0.1 ton of pressure, 4*5*1mm size is made；By PVA/KOH solid electrolyte 3,
4*5*1mm size is made；The cuboid for being pressed into 4*5*4mm is successively assembled by Fig. 1, tab 6 is used as capacitor anode in Fig. 1,
Tab 7 is used as capacitor anode.
(202) it is connected with the capacitor in 4 (201), as 14,15,16,17 be 4 (201) made electricity in Fig. 2
Container, wherein tab 6,8,10,12 is the anode of electric appliance respectively, and tab 7,9,11,13 is the cathode of capacitor respectively.4 electricity
Container, which is together in series, forms a series connection group capacitor, and the anode of series connection group capacitor is tab 12, and cathode is tab 7.18 is hollow,
For placing aircraft body, and play the role of Support Capacitor group.
(203) the concatenated hollow ellipse capacitor stack adduction connection prepared by 4 (202), it is miniature can to obtain dragonfly shape
Unmanned plane power supply capacitor, the specific capacitance of capacitor is 430F/g at this time.
Specific embodiment 3: melamine is dissolved in graphene oxide solution, ultrasound is made it completely dissolved at 2 DEG C,
VC and ammonium hydroxide is added, sealer low temperature ultrasonic handles 2h, then so that mixed liquor is formed organogel in 80 DEG C of water temperatures with immersion method,
By organogel, 850 DEG C of firing 2h obtain NGA under an inert atmosphere；Wherein graphene oxide solution concentration is 5mg/ml, oxidation
Graphene and VC mass ratio are 1:1, and the mass ratio with ammonium hydroxide is 4:1, and the mass ratio of melamine and graphene oxide is 3:
100；1mg NGA is put into butyl acetate, the content of NGA is 15wt.%, and EDOT is added according to the ratio of 50 μ l/ml, is surpassed
Sound 1h obtains mixed liquor；The p-methyl benzenesulfonic acid iron of 0.25g is dissolved into the mixed liquor of 3ml ethyl alcohol and 1ml water, then drips in again
It drips in above-mentioned mixed liquor, is stored at room temperature after ultrasonic mixing polymerizable after 6h.After ethyl alcohol cleans drying at room temperature 1h, it can obtain
NGA@PEDOT material.
Capacitor arrangement preparation method:
(301) nickel foam 1,5 is formed into nickel thin slice flexible under 0.8 ton of pressure, cutting is prepared into the side of 4*5*1mm
Shape；By NGA@PEDOT material 2,4, is suppressed with 0.05-0.1 tons of pressure, 4*5*1mm size is made；By PVA/KOH solid-state electricity
Matter 3 is solved, 4*5*1mm size is made；The cuboid for being pressed into 4*5*4mm is successively assembled by Fig. 1, tab 6 is used as capacitor in Fig. 1
Anode, tab 7 are used as capacitor anode.
(302) it is connected with the capacitor in 4 (401), as 14,15,16,17 be 4 (301) made electricity in Fig. 2
Container, wherein tab 6,8,10,12 is the anode of electric appliance respectively, and tab 7,9,11,13 is the cathode of capacitor respectively.4 electricity
Container, which is together in series, forms a series connection group capacitor, and the anode of series connection group capacitor is tab 12, and cathode is tab 7.18 is hollow,
For placing aircraft body, and play the role of Support Capacitor group.
(303) the concatenated hollow ellipse capacitor stack adduction connection prepared by 6 (302), it is miniature can to obtain dragonfly shape
Unmanned plane power supply capacitor, the specific capacitance of capacitor is 560F/g at this time.
Claims (3)
1. a kind of preparation method of NGA@PEDOT material, which is characterized in that this method specifically includes the following steps:
(1), the preparation of NGA
Melamine is dissolved in graphene oxide solution, VC and ammonium hydroxide are sequentially added, ultrasound keeps it completely molten under the conditions of 1-4 DEG C
Solution, then makes mixed liquor form organogel in 80 DEG C of water temperatures with immersion method, by organogel 800-900 under an inert atmosphere
DEG C firing 2h obtains NGA, and wherein graphene oxide solution concentration is 0.5-5mg/ml, and graphene oxide and VC mass ratio are 1:1,
The mass ratio of graphene oxide and ammonium hydroxide is 4:1；The mass ratio of melamine and graphene oxide is 1:100-3:100；NGA is
Nitrogen-doped graphene gel；VC is vitamin C；
(2), NGA is put into butyl acetate, the content of NGA is 15wt.%, and EDOT, ultrasound is added in the ratio of 50 μ l/ml
1h；EDOT is 3,4- ethene dioxythiophene；
(3), p-methyl benzenesulfonic acid iron is dissolved in the mixed liquor of ethyl alcohol and water, wherein the volume ratio of ethyl alcohol and water is 3:1, to toluene sulphur
The content of sour iron is 0.6wt.%, by mixed liquor drippage on step (2) resulting material, after being stored at room temperature 6h after ultrasonic mixing
It is polymerizable, dry 1h at room temperature to get NGA@PEDOT material is arrived, NGA@PEDOT material is i.e. with poly- 3,4-rthylene dioxythiophene packet
Cover the material of nitrogen-doped graphene gel.
2. the preparation method of the super capacitor for dragonfly shape miniature drone, which is characterized in that method includes the following steps:
Nickel thin slice, NGA@PEDOT material, PVA/KOH gel solid state electrolyte, NGA@PEDOT material, nickel thin slice are successively pressurizeed, then
It is stacked according to sequence described above, it is re-compacted that flexible capacitor is made；Four above-mentioned flexible capacitor bendings are assembled into hollow ellipse
Circle is simultaneously connected into a group capacitor；Multiple unit capacitor is superimposed parallel connection, dragonfly shape miniature drone power supply capacitor can be obtained.
3. the preparation method of the super capacitor according to claim 2 for dragonfly shape miniature drone, it is characterised in that:
The capacitor stack adduction connection is 3-8 group.
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| CN201910324290.8A CN110060876B (en) | 2019-04-22 | 2019-04-22 | NGA @ PEDOT material and preparation method of super capacitor for dragonfly-shaped micro unmanned aerial vehicle |
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Citations (4)
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|---|---|---|---|---|
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2019
- 2019-04-22 CN CN201910324290.8A patent/CN110060876B/en active Active
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| CN102558772A (en) * | 2011-12-15 | 2012-07-11 | 河海大学 | Poly(3,4-ethylenedioxythiophene)/sulfonated graphene composite hydrogel and preparation method thereof |
| CN102874796A (en) * | 2012-09-17 | 2013-01-16 | 中国科学院山西煤炭化学研究所 | Nitrogen mixed grapheme hydrogel or aerogel and preparation method thereof |
| CN107958794A (en) * | 2017-10-27 | 2018-04-24 | 东华大学 | All solid state graphene hydrogel ultracapacitor of ultrathin flexible and preparation method thereof |
| CN108525615A (en) * | 2018-03-12 | 2018-09-14 | 东北石油大学 | A kind of preparation and its application of the Ni-based nitrogen-doped graphene aeroge of three-dimensional foam |
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