CN106847537A - A kind of preparation method of composite electrode material for super capacitor - Google Patents
A kind of preparation method of composite electrode material for super capacitor Download PDFInfo
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- CN106847537A CN106847537A CN201710025776.2A CN201710025776A CN106847537A CN 106847537 A CN106847537 A CN 106847537A CN 201710025776 A CN201710025776 A CN 201710025776A CN 106847537 A CN106847537 A CN 106847537A
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- flower
- shape
- porous
- carbon ball
- metal oxide
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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
-
- 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
-
- 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
-
- 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
The invention discloses a kind of preparation method and application of the combination electrode for ultracapacitor, the preparation method of described combination electrode is to prepare " flower-shape " basic zinc carbonate template using hydro-thermal reaction, then last layer phenolic resin is applied in above-mentioned " flower-shape " template, porous " flower-shape " carbon ball is obtained through carbonization, finally grown in above-mentioned porous " flower-shape " carbon ball using hydro-thermal reaction/metal oxide-loaded, by coated porous " flower-shape " carbon ball of the metal oxide prepared by the present invention or porous " flower-shape " carbon ball is metal oxide-loaded can be as the electrode material of ultracapacitor, this porous " flower-shape " structure improves the utilization rate of specific surface area, and metal oxide improves specific capacitance, can be widely used in the middle of the field of ultracapacitor equal energy source device.
Description
Technical field
The present invention relates to a kind of new energy field, more particularly to a kind of preparation method of composite electrode material for super capacitor
Background technology
Fossil energy is largely used in the middle of energy device, because fossil energy is a kind of non-renewable energy resources, while compared with
Low energy conversion efficiency limits its application and development in electronic device.And ultracapacitor is due to higher capacitance
Amount, energy density are big, the advantages of have extended cycle life fast with charge/discharge rates, as a kind of new energy for substituting traditional fossil energy
Source.Specifically, ultracapacitor is a kind of new energy-storage travelling wave tube, because its capacity is big, can high current fast charging and discharging, circulation
The advantages of life-span is lasting, is widely used in startup power supply, the pulse power, military affairs, device for mobile communication, computer and electricity
In the research fields such as electrical automobile.According to the difference of energy storage mechnism, ultracapacitor can be divided into following three kinds：Double layer capacitor,
Faraday pseudo-capacitance and hybrid super capacitor.Double layer capacitor is mainly by the interface between electrode/electrolyte
The electric double layer for being formed carrys out energy storage, and such capacitor has power density and fabulous cycle performance very high.The counterfeit electricity of faraday
, mainly there is the chemisorbed/desorption or oxygen of Rapid reversible by the two-dimensional space in the surface of electrode or body phase in container
Change reduction reaction and carry out energy storage, be there are faradic currents to produce the characteristics of the reaction, its theoretical specific capacitance and energy density are than double electricity
Layer capacitor is higher by 10~100 times.
Commercialization electrode material for super capacitor typically uses activated carbon at present, because activated carbon has light weight, specific surface
The advantages of product height, good conductivity, but the specific capacitance of the ultracapacitor with activated carbon as electrode material is low, and specific surface area is utilized
The low shortcoming of rate, it is difficult to the equipment for meeting big energy system, in order to overcome the deficiency, commercial sources typically use activated carbon/metal
The combination electrode material of oxide, but because specific surface area loss is serious, the low shortcoming of load factor limits the property of combination electrode
Can, therefore the suitable load matrix material of research is come to improve the performance of combination electrode be active demand.
The content of the invention
Shortcoming and deficiency it is an object of the invention to overcome prior art, the invention provides a kind of metal oxide bag
Cover the combination electrode material of porous " flower-shape " carbon ball (or porous " flower-shape " carbon ball is metal oxide-loaded) and applied
In the middle of ultracapacitor.Porous " flower-shape " carbon ball prepared by the present invention has the specific surface area and multi-stage pore structure of superelevation,
The utilization rate that this multistage empty structure improves specific surface turns into the excellent carrier of metal oxide, while utilizing " flower-shape " carbon
The excellent electric conductivity of ball, can improve the electric conductivity of metal oxide semiconductor, and the fake capacitance of metal oxide can be carried
The specific capacity and energy density of ultracapacitor high.
A kind of preparation method of composite electrode material for super capacitor of the present invention, comprises the following steps：
Step (1)：Prepare 15mg/ml containing 6 zinc nitrate solutions of the crystallization water, it is then certain to being added in the solution
The urea and altheine of amount are up to dissolving, thirdly the mass ratio of material is zinc nitrate:Urea:Altheine=1:0.5:
1, above-mentioned solution is fitted into the hydrothermal reaction kettle of polytetrafluoroethylliner liner, 100-130 DEG C of reaction 3-12h.To react what is obtained
The scrubbed dried for standby of basic zinc carbonate；
Step (2)：The basic carbonate zinc solution that 8mg/ml is obtained through step (1) is prepared, is then sequentially added a certain amount of
The ethanol and ammoniacal liquor of octadecyl bromination ammonium and resorcinol and certain volume, wherein basic zinc carbonate:Cetyl front three
Base ammonium bromide:The mass ratio of resorcinol is 1:4:0.7, add formalin, wherein ethanol after stirring half an hour at 35 DEG C:
The volume ratio of formaldehyde is 60:1,6-12h is then reacted at 35 DEG C, take out and stand 12h, centrifugation product is dried, will be above-mentioned
Dried material is placed in tubular type carbide furnace under the protection of nitrogen to be protected at 150 DEG C successively with the heating rate of 5 DEG C/min
Warm 1h, is incubated 30min at 300 DEG C, 2h is incubated at 800 DEG C, and the black powder of gained is washed for several times with 1M HCl solutions, dries
Can obtain porous " flower-shape " carbon ball afterwards；
Step (3)：Porous " flower-shape " carbon ball in step (2) is added in the metal salt solution of 0.02M, wherein porous
" flower-shape " carbon ball:The concentration of metal salt solution is 1mg/ml, and above-mentioned solution is placed in hydrothermal reaction kettle, 160 DEG C of reaction 12h,
Product is washed into drying, you can obtain coated porous " flower-shape " carbon ball of metal oxide or porous " flower-shape " carbon ball carried metal
Oxide；
Step (4)：Coated porous " flower-shape " carbon ball of the metal oxide of step (3) or porous " flower-shape " carbon ball are loaded
Metal oxide is assembled into ultracapacitor, and its electrolyte used is 1MNa2SO4 solution, is filled in electrochemical workstation and constant current
Electrochemical property test is carried out respectively on electric discharge instrument.
Slaine is potassium permanganate in the step (3), any one in cobalt nitrate.
Brief description of the drawings
Fig. 1 is using the SEM figures of porous " flower-shape " carbon ball prepared by the embodiment of the present invention 1
Specific embodiment
Below by way of specific embodiment, the invention will be further described, and these embodiments should not be understood paired this hair
Bright claims are construed as limiting.
Embodiment 1
Step (1)：Contain 6 nitric acid of the crystallization water to sequentially add 1.2g in the beaker equipped with 80ml deionized waters
The altheine of zinc, the urea of 0.6g and 1.2g, stirring makes it fully dissolve, and above-mentioned solution is loaded the water of 100ml
In hot kettle, 130 DEG C of reaction 3h will react the product for obtaining and wash drying, that is, obtain white basic carbonate zinc powder；
Step (2)：To the basic zinc carbonate added in the reaction vessel equipped with 100ml water in 0.8g steps (1), 3.45g
Cetyl trimethylammonium bromide, the resorcinol of 0.525g, then to the ethanol and the ammonia of 0.2ml that 45ml is poured into container
Water, instills the formalin of 0.75ml after said mixture is sufficiently stirred for into 0.5h at 35 DEG C, 35 DEG C of reaction 6h are kept, by institute
Reactant centrifugation, washing, dry after be placed in tubular type carbide furnace 1h, 300 be incubated at 150 DEG C with 5 DEG C/min heating rates
0.5h is incubated at DEG C, 2h is incubated at 800 DEG C, the black powder of gained wash for several times with 1M HCl solutions, can after drying
To porous " flower-shape " carbon ball；
Step (3)：Take porous " flower-shape " carbon ball in 0.35g steps (2) and be added to the permanganic acid that 35ml concentration is 0.02M
In potassium solution, above-mentioned solution is placed in hydrothermal reaction kettle, product is washed drying, you can aoxidized by 160 DEG C of reaction 12h
Coated porous " flower-shape " carbon ball of manganese；
Step (4)：Coated porous " flower-shape " carbon ball of the manganese oxide of step (3) is assembled into ultracapacitor, its electricity consumption
Solution liquid is 1MNa2SO4Solution, electrochemical property test is carried out on electrochemical workstation and constant current charge-discharge instrument respectively, through surveying
Test result shows that electrode specific capacitance of the ultracapacitor when charging and discharging currents density is 1A/g is up to 550F/g, in scanning speed
When rate is 10mV/s, specific capacitance is up to 525F/g.
Embodiment 2
With the difference of embodiment 1 be reaction condition described in its step (1) to react 5h at 100 DEG C, result table after tested
Bright, electrode specific capacitance of the ultracapacitor when charging and discharging currents density is 1A/g is up to 456F/g, is 10mV/ in sweep speed
During s, specific capacitance is up to 423F/g.
Embodiment 3
It is the reaction time 8h described in step (2) with the difference of embodiment 1, result shows that ultracapacitor exists after tested
Electrode specific capacitance when charging and discharging currents density is 1A/g is up to 451F/g, and when sweep speed is 10mV/s, specific capacitance is up to
420F/g。
Embodiment 4
It is the reaction time 10h described in its step (2) with the difference of embodiment 1, result shows after tested, ultracapacitor
Electrode specific capacitance when charging and discharging currents density is 1A/g is up to 328F/g, and when sweep speed is 10mV/s, specific capacitance is high
Up to 300F/g.
Embodiment 5
It is that metal salt solution described in its step (3) is cobalt nitrate solution with the difference of embodiment 1, products therefrom is porous
" flower-shape " carbon ball loads cobalt oxide, and result shows after tested, electrode of the ultracapacitor when charging and discharging currents density is 1A/g
Specific capacitance is up to 540F/g, and when sweep speed is 10mV/s, specific capacitance is up to 501F/g.
Above-described embodiment is the present invention preferably implementation method, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from Spirit Essence of the invention and the change, modification, replacement made under principle, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (3)
1. a kind of preparation method of composite electrode material for super capacitor, it is characterised in that：Comprise the following steps：
Step (1)：Prepare 15mg/ml containing 6 zinc nitrate solutions of the crystallization water, it is then a certain amount of to being added in the solution
Urea and altheine are up to dissolving, thirdly the mass ratio of material is zinc nitrate:Urea:Altheine=1:0.5:1, will
Above-mentioned solution is fitted into the hydrothermal reaction kettle of polytetrafluoroethylliner liner, 100-130 DEG C of reaction 3-12h.The alkali formula for obtaining will be reacted
The scrubbed dried for standby of zinc carbonate；
Step (2)：The basic carbonate zinc solution that 8mg/ml is obtained through step (1) is prepared, a certain amount of 18 are then sequentially added
The ethanol and ammoniacal liquor of alkyl bromination ammonium and resorcinol and certain volume, wherein basic zinc carbonate:Cetyl trimethyl bromine
Change ammonium:The mass ratio of resorcinol is 1:4:0.7, add formalin, ethanol after stirring half an hour at 35 DEG C:The body of formaldehyde
Product is than being 60:1,6-12h is then reacted at 35 DEG C, take out and stand 12h, centrifugation product is dried, will be above-mentioned dried
Material is placed in tubular type carbide furnace and is incubated 1h, 300 at 150 DEG C successively with the heating rate of 5 DEG C/min under the protection of nitrogen
30min is incubated at DEG C, 2h is incubated at 800 DEG C, the black powder of gained is washed for several times with 1M HCl solutions, can obtained after drying
To porous " flower-shape " carbon ball；
Step (3)：Porous " flower-shape " carbon ball in step (2) is added in the metal salt solution of 0.02M, wherein porous " flower
Shape " carbon ball:The concentration of metal salt solution is 1mg/ml, and above-mentioned solution is placed in hydrothermal reaction kettle, 160 DEG C of reaction 12h, will be produced
Thing washs drying, you can obtain coated porous " flower-shape " carbon ball of metal oxide or the oxidation of porous " flower-shape " carbon ball carried metal
Thing；
Step (4)：By coated porous " flower-shape " carbon ball of the metal oxide of step (3) or porous " flower-shape " carbon ball carried metal
Oxide is assembled into ultracapacitor, and its electrolyte used is 1MNa2SO4 solution.
2. preparation method according to claim 1, it is characterised in that：Slaine is potassium permanganate, nitre in the step (3)
Any one in sour cobalt.
3. application of the combination electrode material that the preparation method according to claims 1 or 2 is obtained in ultracapacitor.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110323431A (en) * | 2019-07-10 | 2019-10-11 | 中国人民解放军国防科技大学 | Preparation of porous carbon microspheres and application of porous carbon microspheres in lithium-sulfur battery |
| CN111029167A (en) * | 2019-12-30 | 2020-04-17 | 辽宁科技大学 | Method for preparing supercapacitor electrode material by using needle-shaped coke-based carbon material |
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| CN101774646B (en) * | 2009-01-12 | 2011-11-09 | 中国科学院过程工程研究所 | Preparation method of spinel ferrite hollow sphere with core-shell structure |
| CN102059082B (en) * | 2010-11-30 | 2012-06-27 | 重庆大学 | Method for preparing nano manganese dioxide/carbon composite microsphere |
| CN102352003B (en) * | 2011-07-19 | 2013-01-02 | 黑龙江大学 | Preparation method of phenolic resin microballoons and method for preparing phenolic resin-based carbon spheres by use of preparation method |
| CN103041758B (en) * | 2013-01-17 | 2015-01-07 | 复旦大学 | Magnetic hollow multihole carbon ball with core-shell structure and preparation method of magnetic hollow multihole carbon ball |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110323431A (en) * | 2019-07-10 | 2019-10-11 | 中国人民解放军国防科技大学 | Preparation of porous carbon microspheres and application of porous carbon microspheres in lithium-sulfur battery |
| CN110323431B (en) * | 2019-07-10 | 2021-01-01 | 中国人民解放军国防科技大学 | Preparation of porous carbon microspheres and application of porous carbon microspheres in lithium-sulfur battery |
| CN111029167A (en) * | 2019-12-30 | 2020-04-17 | 辽宁科技大学 | Method for preparing supercapacitor electrode material by using needle-shaped coke-based carbon material |
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