CN104795248B - A kind of catkin electrode material for super capacitor and preparation method and ultracapacitor - Google Patents
A kind of catkin electrode material for super capacitor and preparation method and ultracapacitor Download PDFInfo
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- CN104795248B CN104795248B CN201510224032.4A CN201510224032A CN104795248B CN 104795248 B CN104795248 B CN 104795248B CN 201510224032 A CN201510224032 A CN 201510224032A CN 104795248 B CN104795248 B CN 104795248B
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- 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 present invention is to provide a kind of catkin electrode material for super capacitor and preparation method and ultracapacitor.Catkin and potassium hydroxide are mixed and is first raised to 400 DEG C with the heating rate of 5 DEG C/min and continues 1 2h, then is raised to 850 DEG C with the heating rate of 10 DEG C/min and continues 1 2h, then natural cooling, obtained porous silicon carbide catkin electrode material.Porous silicon carbide catkin is added in thiourea solution, after 0.5 1h of strong stirring, is heated at 80 90 DEG C and is evaporated moisture；By obtained material under argon gas protection, 800 DEG C are raised to the programming rate of 10 DEG C/min, natural cooling after 2 3h of continuous heating, obtained nitrogen sulfur doping carbonization catkin electrode material.The present invention is prepared for New Type of Carbon nanometer sheet material that is a kind of while having the features such as specific surface area is big, and adsorption activity point is more, porous with two dimension, and preparation process is simple.The electrode prepared by this carbon nanosheet material shows splendid capacitive property.
Description
Technical field
The present invention relates to a kind of electrode material for super capacitor.The present invention also relates to be a kind of super capacitor electrode
The preparation method of pole material.
Background technology
Ultracapacitor is that one kind can not only be using double layer capacitor come energy storage, and can utilize electrode/solution
The redox reaction on surface stores the energy accumulating device of energy, while it is also electrochemical capacitor or fake capacitance electricity
Container.Ultracapacitor have can high current fast charging and discharging, cycle-index is more, can low-temperature operation, maintenance frequency it is considerably less
And the advantages that possessing certain memory effect.According to energy storage mechnism difference ultracapacitor can be divided into double layer capacitor,
Faradic pseudo-capacitor and mixed capacitor.Ultracapacitor forward direction high-specific-power and high-energy-density development, with oxo transition metal
Compound and porous charcoal are respectively that the hybrid super capacitor of positive and negative anodes is important development direction from now on.Electrochemistry is anti-during discharge and recharge
Energy conversion process and electric double layer energy storage process is answered to be carried out respectively in the two poles of the earth simultaneous equal.Electric double layer capacitance allows high current
Fast charging and discharging, and pseudo capacitance can realize big energy stores by the faraday's reaction of Rapid reversible, both combine
Get up, combine two kinds of energy storage mechnisms of ultracapacitor and battery, be expected to realize two kinds of energy storage mode performance complements, obtain high energy
The performances such as metric density, high power density, long circulation life, high working voltage.
Influence the key factor of ultracapacitor development have electrode material, with the matched electrolyte of electrode material and electrode
Technology of preparing etc., wherein electrode material are to restrict the key of ultracapacitor.Research of the people to electrode material is concentrated mainly on
Porous carbon materials, conducting polymer materials and metal oxide materials three major types.For the first kind Carbon materials as super
The material of capacitor, main advantage is that specific surface area is high, electronic impedance is small and cycle performance is high, and current research is mainly
The carbon material of the zero dimension degree such as activated carbon, mesoporous carbon and carbosphere；The one-dimensional carbon material such as carbon nano-fiber, carbon nanotubes；Graphite
The carbon material of the two dimension such as alkene, graphene oxide and redox graphene.The performance for improving capacitor mainly improves its specific capacity,
Power density and energy density.This requires electrode material needs the conductive ion in sufficiently large specific surface area and electrolyte
Can quickly it be transmitted in electrode material.For zero dimension carbon materials such as current activated carbons and mesoporous carbon, although its have compared with
Big specific surface area, but since pore size distribution$ is unreasonable and duct occlusion, cause high rate performance poor.And carbon nanotubes and
The one-dimensional carbon material such as carbon fiber, although smaller with higher electric conductivity, specific surface area, it is possible to provide ion inhale deactivation
Point is few, therefore its specific capacitance is restricted.And for studying more fiery graphene and derivative carbon material at present, due to
Planar structure with larger specific surface area and higher electric conductivity, particularly two dimension, helps to shorten the transmission way of ion
Footpath, is quite favored in capacitor research field.But the preparation process of graphene is complicated, and required experimental facilities will
Ask high, be unfavorable for mass producing.
The content of the invention
It is an object of the present invention to provide a kind of cheap, high catkin electrode of super capacitor material of energy density
Material.The second object of the present invention be to provide a kind of preparation method purpose of the present invention of catkin electrode material for super capacitor it
Three are to provide a kind of ultracapacitor containing catkin electrode.
It is 1 in mass ratio that the catkin electrode material for super capacitor of the present invention, which is,:1~2, catkin and potassium hydroxide are mixed
, grind into powder, under argon gas protection, is first raised to 400 DEG C of lasting 1-2h with the heating rate of 5 DEG C/min, then with 10 DEG C/
The heating rate of min is raised to 850 DEG C of lasting 1-2h, then natural cooling, obtained porous silicon carbide catkin electrode material.
The catkin electrode material for super capacitor of the present invention can also be according to the porous quality by carbonization catkin and thiocarbamide
Than for 1:3~4 ratio, porous silicon carbide catkin is added in thiourea solution, after strong stirring 0.5-1h, is added at 80-90 DEG C
Moisture is evaporated by heat；By obtained material under argon gas protection, 800 DEG C are raised to the programming rate of 10 DEG C/min, continuous heating
Natural cooling after 2-3h, obtained nitrogen sulfur doping carbonization catkin electrode material.
The preparation method of catkin electrode material for super capacitor of the present invention is：It is 1 in mass ratio:1~2, by catkin with
Potassium hydroxide is mixed, grind into powder, under argon gas protection, is first raised to 400 DEG C of lasting 1-2h with the heating rate of 5 DEG C/min,
850 DEG C of lasting 1-2h are raised to the heating rate of 10 DEG C/min again, then natural cooling, obtains porous silicon carbide catkin electrode material
Material.
The catkin electrode material for super capacitor of the present invention, which obtains preparation method, to be included：According to porous by carbonization catkin
Mass ratio with thiocarbamide is 1:3~4 ratio, porous silicon carbide catkin is added in thiourea solution, after strong stirring 0.5-1h,
Moisture is evaporated by heating at 80-90 DEG C；By obtained material under argon gas protection, 800 are raised to the programming rate of 10 DEG C/min
DEG C, natural cooling after continuous heating 2-3h, obtains nitrogen sulfur doping carbonization catkin electrode material.
The present invention the ultracapacitor containing catkin electrode be：It is to electricity to be carbonized catkin as working electrode, platinum electrode
Pole, saturated calomel electrode are as reference electrode, with 6mol L-1KOH, 1molL-1Na2SO4Or their mixture is electricity
Liquid is solved, forms ultracapacitor.
The present invention the ultracapacitor containing catkin electrode be：Catkin is carbonized as working electrode, platinum electricity using nitrogen sulfur doping
Extremely to electrode, saturated calomel electrode as reference electrode, with 6mol L-1KOH, 1molL-1Na2SO4Or theirs is mixed
Compound is electrolyte, forms ultracapacitor.
The present invention is prepared for a kind of same by being simply carbonized to biomass catkin and carrying out effectively nitrogen sulfur doping
When have that specific surface area is big, and adsorption activity point is more, have that two dimension is porous, and New Type of Carbon nanometer the features such as preparation process is simple
Sheet material.The electrode prepared by this carbon nanosheet material shows splendid capacitive property.
The essence of the present invention is the electrode structure using ultracapacitor, with nitrogen sulfur doping carbonization catkin substitution charcoal and RuO2
Deng the electrode material as ultracapacitor, discharge and recharge is carried out in neutral electrolyte, forms the electrode of ultracapacitor, is obtained
Super electrochemical capacitance.
The advantage of the invention is that natural catkin is hollow tube, activates, be carbonized and nitrogen sulfur doping by KOH
Afterwards, become, pore size distribution$ bigger than surface rationally, activation point it is more, there is the nitrogen sulfur doping carbonization catkin electricity of two-dimentional loose structure
Pole material.Overcome other materials poorly conductive, the shortcomings that capacity is low.Nitrogen sulfur doping carbonization catkin electrode material, both maintained
The cyclical stability of carbon, and have the height ratio capacity characteristic of fake capacitance concurrently.Super electricity is used as by the use of nitrogen sulfur doping carbonization catkin electrode
The electrode material of container, not only raw material rich reserves be easy to get, it is cheap, and super capacitor performance is high, big high rate performance number,
Stable cycle performance.
Embodiment
Illustrate below and the present invention is described in more detail.
It is 1 in mass ratio:1~2,5g catkins are mixed with potassium hydroxide, grind into powder is put into tube furnace, is protected in argon gas
Under shield, 400 DEG C of lasting 1-2h are first raised under 5 DEG C/min heating rates, 10 DEG C/min is warming up to 850 DEG C afterwards, continues 1-2h,
Then natural cooling, obtains porous silicon carbide catkin.
It is 1 by carbonization catkin and thiocarbamide:3~4 mass ratio, 0.1g porous silicon carbides catkin is added in thiourea solution, by force
After strong stirring 0.5-1h, then moisture is evaporated by heating at 80-90 DEG C；Obtained material is sent into tube furnace, is protected in argon gas
Under, it is raised to 800 DEG C with the programming rate of 10 DEG C/min, natural cooling after continuous heating 2-3h, obtains nitrogen sulfur doping carbonization catkin
Electrode material.
Catkin is carbonized as working electrode using nitrogen sulfur doping, is platinum electrode to electrode, using saturated calomel electrode (SCE) conduct
Reference electrode, respectively with 6mol L-1KOH and 1molL-1Na2SO4Deng for electrolyte, its chemical property is tested.This
Outside, by the catkin metal composite oxide that is carbonized, such as MnO2Deng and composite conductive polymer, such as PANI, respectively in different electricity
Cyclic voltammetric is carried out in the range of pressure, discharge and recharge, the test such as AC impedance and cycle life, obtains its chemical property.
1st, catkin electrode material is carbonized as working electrode using nitrogen sulfur doping, is platinum electrode to electrode, using saturation calomel electricity
Pole (SCE) is used as reference electrode, with 6molL-1KOH be electrolyte, in -1~0V voltage ranges, with 1Ag-1Electricity
Current density obtains 357Fg-1Capacity, circulate 10000 capacity and keep 98%.
2nd, catkin electrode material is directly carbonized as working electrode using nitrogen sulfur doping, with 1molL-1Na2SO4For electrolysis
Liquid, is assembled into symmetry capacitor, in 0~1.6V voltage ranges, with 5Ag-1Current density obtain 62Fg-1Appearance
Amount, circulates 10000 capacity and keeps 97%.
3rd, directly with the compound MnO of nitrogen sulfur doping carbonization catkin2Electrode material is working electrode, with 1molL-1Na2SO4
For electrolyte, in 0~1.0V voltage ranges, with 1Ag-1Current density obtain 268Fg-1Capacity, circulate 5000 times
Capacity keeps 93%.
4th, the compound PANI electrode materials of catkin are directly carbonized as working electrode using nitrogen sulfur doping, with 1molL-1H2SO4
For electrolyte, in 0~1.0V voltage ranges, with 0.5Ag-1Current density obtain 357Fg-1Capacity, circulation 2000
Secondary capacity keeps 94%.
Claims (1)
1. a kind of preparation method of catkin electrode material for super capacitor, it is characterized in that：It is 1 in mass ratio:1~2, by catkin with
Potassium hydroxide is mixed, grind into powder, under argon gas protection, is first raised to 400 DEG C of lasting 1-2h with the heating rate of 5 DEG C/min,
850 DEG C of lasting 1-2h are raised to the heating rate of 10 DEG C/min again, then natural cooling, obtains porous silicon carbide catkin；
It is 1 according to the mass ratio of porous silicon carbide catkin and thiocarbamide:3~4 ratio, thiourea solution is added by porous silicon carbide catkin
In, after strong stirring 0.5-1h, heated at 80-90 DEG C and be evaporated moisture；By obtained material under argon gas protection, with 10
DEG C/programming rate of min is raised to 800 DEG C, natural cooling after continuous heating 2-3h, obtains nitrogen sulfur doping carbonization catkin electrode material
Material.
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105140050A (en) * | 2015-08-20 | 2015-12-09 | 西安岳达植物科技有限公司 | Preparation method for nitrogen sulfur doped wormlike graphite supercapacitor electrode material |
| CN105788885B (en) * | 2016-03-09 | 2017-10-31 | 湘潭大学 | A kind of explosion method prepares the preparation method of camellia petal base sulphur, the technique of nitrogen co-doped fold carbon nanosheet and electrode of super capacitor |
| CN107298441A (en) * | 2016-12-21 | 2017-10-27 | 北京化工大学 | A kind of method that use waste biomass material prepares super capacitor material |
| CN106744947A (en) * | 2017-01-16 | 2017-05-31 | 东华大学 | A kind of preparation method of bio-based nitrogen sulfur doping carbon material |
| CN106904606A (en) * | 2017-03-20 | 2017-06-30 | 中国石油大学(北京) | A kind of preparation method and its obtained doping carbon material of the carbon material that adulterates |
| CN109607508A (en) * | 2018-12-29 | 2019-04-12 | 南京工程学院 | A kind of preparation method of electrode material for super capacitor |
| CN109994319B (en) * | 2019-04-11 | 2020-11-27 | 合肥工业大学 | Nitrogen-sulfur co-doped biomass derived carbon material and synthesis method and application thereof |
| CN111115629A (en) * | 2019-12-27 | 2020-05-08 | 暨南大学 | High-specific-surface-area carbon material based on waste tobacco stems and preparation method and application thereof |
| CN111186838A (en) * | 2020-01-07 | 2020-05-22 | 西安理工大学 | Preparation method and application of biomass-based electrode material |
| CN111341567B (en) * | 2020-03-02 | 2021-07-20 | 齐鲁工业大学 | 3D poplar catkin derived carbon-supported NiCo-LDH nanosheet supercapacitor and preparation method thereof |
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| CN104192830A (en) * | 2014-05-20 | 2014-12-10 | 江苏欧力特能源科技有限公司 | Preparing method of nitrogen-sulfur co-doped graphene by hydrothermal method |
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