CN105439143B - A kind of classifying porous activated carbon and preparation method for ultracapacitor - Google Patents
A kind of classifying porous activated carbon and preparation method for ultracapacitor Download PDFInfo
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- CN105439143B CN105439143B CN201410413010.8A CN201410413010A CN105439143B CN 105439143 B CN105439143 B CN 105439143B CN 201410413010 A CN201410413010 A CN 201410413010A CN 105439143 B CN105439143 B CN 105439143B
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Abstract
A kind of classifying porous activated carbon for ultracapacitor, it is characterised in that：The described classifying porous absorbent charcoal material for ultracapacitor, it using disodium ethylene diamine tetraacetate is chemical activating agent, organic matter for carbon source to be, is obtained through chemical activation under high temperature, carbon source includes sucrose.A kind of preparation method of classifying porous activated carbon for ultracapacitor, it is characterised in that：Take a certain amount of carbon matrix precursor stirring and dissolving in water；A certain amount of disodium ethylene diamine tetraacetate is added in the solution of carbon matrix precursor, will be placed in baking oven and dry under this mixture certain temperature；By the product being dried to obtain, high-temperature process, product are cleaned with acid solution under an inert atmosphere, are then washed with deionized to neutrality, are dried can obtain activated carbon in an oven.Advantages of the present invention：More excellent high rate performance is shown, the characteristics of working condition is gentle, and step is simple, and energy expenditure is low.It is simple with excellent capacitive property, preparation technology.
Description
Technical field
The present invention relates to electrode material for super capacitor technical field, a kind of more particularly to point for ultracapacitor
Level porous activated carbon and preparation method.
Background technology
Ultracapacitor is called electrochemical capacitor, is a kind of novel energy-storing element made using electric double layer principle.It is super
Level capacitor has the advantages that power density is high relative to secondary cell, had extended cycle life, charge/discharge rates are fast, in electronic vapour
The fields such as car, wind-power electricity generation, mobile device have a wide range of applications.
Activated carbon has the characteristics that specific surface area height, good conductivity, chemical stability are high and cost is cheap, is at present only
The electrode material for super capacitor of one commercialization.The method that active carbon with high specific surface area mainly uses chemical activation is prepared at present,
Conventional chemical activating agent has：Potassium hydroxide, sodium hydroxide, zinc chloride etc..In addition, prepared at present using above chemical activating agent
Activated carbon based on micropore, there is larger charge-transfer resistance when as electrode material for super capacitor, be unfavorable for
Used under high current.
Yupeng Guo et al. do carbon source using rice husk, and potassium hydroxide does chemical activating agent, and chemistry is living after being first pyrolyzed
The method of change is prepared for active carbon with high specific surface area.This activated carbon activates the carbon material obtained for one hour at 750 DEG C and compares table
Area reaches 1930m2g-1, specific capacitance value is 125F g-1(Materials Chemistry and Physics 80(2003)
704–709).Rufford et al. uses ZnCl2The specific surface area for activating the obtained activated carbon of method of coffee grounds is 1019m2g-1,
Specific capacitance value in sulfuric acid electrolyte can reach 368F g-1(Electrochemistry Communications 10
(2008)1594–1597).And carbon source is done using bagasse, the activated carbon being prepared in the twice carbon source of zinc chloride compares table
Area reaches 1373m2g-1, specific capacitance reaches 300F g-1(Journal of Power Sources 195(2010)912–
918)。
Activated carbon prepared by above method is both needed to as microporous activated carbon, and electric charge is in electrode hole during fast charging and discharging
Interior transmission resistance is larger, relatively low in high current bottom electrode capacity retention, causes the decline of capacitor power performance.
For the present invention using disodium ethylene diamine tetraacetate as chemical activating agent, the organic matter such as sucrose does carbon source, chemical at high temperature
Activation can prepare the classifying porous activated carbon of high mesoporous ratio.Activated carbon prepared by this method is suitable as ultracapacitor
Electrode material uses.
The content of the invention
It is an object of the invention to prepare a kind of activated carbon of high mesopore proportion, specific method is by with ethylenediamine tetrem
Acid disodium is that the organic matters such as chemical activating agent, sucrose do carbon source, through high temperature pyrolysis (charing) and chemical activation, obtains Gao Bibiao
Area is classified porous activated carbon.The mesoporous ratio of activated carbon prepared by this method is high, as electrode material for super capacitor, shows
Excellent high rate performance.
The invention provides a kind of classifying porous activated carbon for ultracapacitor, it is characterised in that：Described is used for
The classifying porous absorbent charcoal material of ultracapacitor, it using disodium ethylene diamine tetraacetate is chemical activating agent, organic matter for carbon source to be,
Obtained through chemical activation under high temperature, carbon source includes sucrose.
A kind of preparation method of classifying porous activated carbon for ultracapacitor, it is characterised in that：Comprise the following steps：
(1) a certain amount of carbon matrix precursor stirring and dissolving in water is taken；
(2) a certain amount of disodium ethylene diamine tetraacetate is added in the solution of carbon matrix precursor, by this mixture certain temperature
Under be placed in baking oven dry；
(3) by the product being dried to obtain high-temperature process under an inert atmosphere；
(4) product is cleaned with acid solution, is then washed with deionized to neutrality, is dried can obtain activity in an oven
Charcoal.
In step (1), carbon matrix precursor includes：One or more in sucrose, glucose, furfuryl alcohol, phenolic resin etc..
In step (2), the mass ratio of disodium ethylene diamine tetraacetate and carbon matrix precursor is 20:1 to 1:20, described inertia
Atmosphere is nitrogen or argon gas.
Drying temperature is 10-250 DEG C in an oven in step (2).
Treatment temperature is 400-2000 DEG C in step (3).
Drying temperature is 10-250 DEG C in an oven in step (4).
Advantages of the present invention：
Activated carbon prepared by the present invention has higher specific surface area and mesoporous ratio.The work prepared with traditional chemical activation
Property charcoal compare, using the inventive method prepare activated carbon show more excellent high rate performance.Due to using organic salt second
Edetate disodium makees activator instead of highly basic, carbonizes progress synchronous with activation, activated carbon preparation side provided by the present invention
Method has the characteristics of working condition is gentle, and step is simple, and energy expenditure is low.High mesoporous rate activated carbon prepared by the present invention is as super
Level capacitor electrode material, has an excellent capacitive property, and the electrode material has that preparation technology is simple, electric capacity high rate performance height
The advantages that.There is higher specific capacity with the electrode of super capacitor that the activated carbon makees active material preparation, show excellent
High rate performance.It is 4 by activator and carbon source mass ratio:The 1 activated carbon specific surface area prepared reaches 1342m2g-1, in 1000mV
s-1Specific capacitance value reaches 145F g under sweep speed-1。
Brief description of the drawings
Fig. 1 is the nitrogen Adsorption and desorption isotherms of activated carbon prepared by the embodiment of the present invention 1；
Fig. 2 is the cyclic voltammetry curve of activated carbon electrodes prepared by the embodiment of the present invention 1；
Fig. 3 is the nitrogen Adsorption and desorption isotherms of activated carbon prepared by the embodiment of the present invention 2；
Fig. 4 is the cyclic voltammetry curve of activated carbon electrodes prepared by the embodiment of the present invention 2；
Fig. 5 is the nitrogen Adsorption and desorption isotherms of activated carbon prepared by the embodiment of the present invention 3；
Fig. 6 is the cyclic voltammetry curve of activated carbon electrodes prepared by the embodiment of the present invention 3.
Embodiment
The following examples will be further described to the present invention, but not thereby limiting the invention.
Embodiment 1
Take 1g sucrose to be dissolved in 10g water, add 1g disodium ethylene diamine tetraacetates and be well mixed, by mixture in an oven
It is dried at 80 DEG C.Dried mixture is carbonized 2 hours in a nitrogen atmosphere, carbonization temperature is 800 DEG C.Carbonized
Product hydrochloric acid solution pickling afterwards, is then washed with deionized to neutrality, dries 24h at 60 DEG C in baking oven, obtains activity
Charcoal.Physical absorption test shows that the activated carbon specific surface area is 802m2g-1, Adsorption and desorption isotherms are as shown in figure 1, explanation is prepared into
The carbon material arrived is classifying porous activated carbon.Above-mentioned classifying porous activated carbon is pressed into active material:Conductive agent:Binding agent=85:
10:5 ratio carries out being prepared by mixing into electrode slice, the test of three electrode cycle volt-ampere is carried out in 6M KOH electrolyte, as a result such as
Shown in Fig. 2, in 2mV s-1Sweep speed under specific capacitance be 188F g-1。
Embodiment 2
Take 1g sucrose to be dissolved in 10g water, add 2g disodium ethylene diamine tetraacetates and be well mixed, by mixture in an oven
It is dried at 80 DEG C.Dried mixture is carbonized 2 hours in a nitrogen atmosphere, carbonization temperature is 800 DEG C.Carbonized
Product hydrochloric acid solution pickling afterwards, is then washed with deionized to neutrality, dries 24h at 60 DEG C in baking oven, obtains activity
Charcoal.Physical absorption test shows that the activated carbon specific surface area is 1192m2g-1, Adsorption and desorption isotherms are as shown in figure 3, prepared by explanation
Obtained carbon material is classifying porous activated carbon.Above-mentioned classifying porous activated carbon is pressed into active material:Conductive agent:Binding agent=
85:10:5 ratio carries out being prepared by mixing into electrode slice, the test of three electrode cycle volt-ampere is carried out in 6M KOH electrolyte, as a result
As shown in figure 4, in 2mV s-1Sweep speed under specific capacitance be 197F g-1。
Embodiment 3
Take 1g sucrose to be dissolved in 10g water, add 1g disodium ethylene diamine tetraacetates and be well mixed, 80 DEG C are being dried by mixture
Dried in case.Dried mixture is carbonized 2 hours in a nitrogen atmosphere, carbonization temperature is 800 DEG C.Product after being carbonized
With hydrochloric acid solution pickling, then it is washed with deionized to neutrality, dries 24h at 60 DEG C in baking oven, obtain activated carbon.Physics
Absorption test shows that the activated carbon specific surface area is 1342m2g-1, Adsorption and desorption isotherms are as shown in figure 5, the carbon that explanation is prepared
Material is classifying porous activated carbon.Above-mentioned classifying porous activated carbon is pressed into active material:Conductive agent:Binding agent=85:10:5
Ratio carries out being prepared by mixing into electrode slice, the test of three electrode cycle volt-ampere is carried out in 6M KOH electrolyte, as a result such as Fig. 6 institutes
Show, in 2mV s-1Sweep speed under specific capacitance be 221F g-1, in up to 1000mV s-1Specific capacitance value reaches under sweep speed
145F g-1。
Claims (6)
- A kind of 1. classifying porous activated carbon for ultracapacitor, it is characterised in that：Described point for being used for ultracapacitor Level porous active Carbon Materials, it using disodium ethylene diamine tetraacetate is chemical activating agent, organic matter for carbon matrix precursor to be, through changing under high temperature Learn activation to obtain, carbon matrix precursor includes sucrose；(1) a certain amount of carbon matrix precursor stirring and dissolving in water is taken；(2) a certain amount of disodium ethylene diamine tetraacetate is added in the solution of carbon matrix precursor, this mixture certain temperature is underlying Dried in baking oven；(3) by the product being dried to obtain high-temperature process under an inert atmosphere；(4) product is cleaned with acid solution, is then washed with deionized to neutrality, is dried can obtain activated carbon in an oven.
- A kind of 2. preparation method of the classifying porous activated carbon for ultracapacitor described in claim 1, it is characterised in that： Comprise the following steps：(1) a certain amount of carbon matrix precursor stirring and dissolving in water is taken；(2) a certain amount of disodium ethylene diamine tetraacetate is added in the solution of carbon matrix precursor, this mixture certain temperature is underlying Dried in baking oven；(3) by the product being dried to obtain high-temperature process under an inert atmosphere；(4) product is cleaned with acid solution, is then washed with deionized to neutrality, is dried can obtain activated carbon in an oven.
- 3. according to the preparation method of the classifying porous activated carbon for ultracapacitor described in claim 2, it is characterised in that： In step (2), the mass ratio of disodium ethylene diamine tetraacetate and carbon matrix precursor is 20:1 to 1:20, described inert atmosphere is nitrogen Gas or argon gas.
- 4. according to the preparation method of the classifying porous activated carbon for ultracapacitor described in claim 2, it is characterised in that： In step (2), drying temperature is 10-250 DEG C in an oven.
- 5. according to the preparation method of the classifying porous activated carbon for ultracapacitor described in claim 2, it is characterised in that： In step (3), treatment temperature is 400-2000 DEG C.
- 6. according to the preparation method of the classifying porous activated carbon for ultracapacitor described in claim 2, it is characterised in that： In step (4), drying temperature is 10-250 DEG C in an oven.
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| CN105948018A (en) * | 2016-04-29 | 2016-09-21 | 谢镕安 | Bio-ene charcoal material and preparation method thereof |
| CN106219540A (en) * | 2016-07-25 | 2016-12-14 | 句容市百诚活性炭有限公司 | A kind of preparation method of the activated carbon of multistage open pore structure |
| CN106219539A (en) * | 2016-07-25 | 2016-12-14 | 句容市百诚活性炭有限公司 | A kind of preparation method of high-specific surface area hierarchical porous structure activated carbon |
| CN106861624A (en) * | 2017-04-09 | 2017-06-20 | 中国科学院大学 | A kind of preparation method of the porous carbon of adsorbable organic dyestuff in wastewater |
| CN109133051A (en) * | 2018-09-26 | 2019-01-04 | 桂林电子科技大学 | A kind of HEDTA base porous carbon materials and its preparation method and application |
| CN109731603A (en) * | 2019-01-23 | 2019-05-10 | 河南师范大学 | A kind of universality method and its application of the nitrogen-doped carbon catalyst controllable with single pore-foaming agent preparation pore size |
| CN110028069A (en) * | 2019-04-18 | 2019-07-19 | 河南师范大学 | A kind of preparation method of the advanced carbon electrode material of multi-stage porous for supercapacitor |
| CN110217791A (en) * | 2019-07-15 | 2019-09-10 | 天津工业大学 | A kind of method for preparation of active carbon based on eggshell and saccharide compound |
| CN112250067B (en) * | 2020-09-03 | 2022-05-06 | 方大炭素新材料科技股份有限公司 | Two-step activated high-performance activated carbon, preparation method and lithium ion capacitor electrode |
| CN113044839B (en) * | 2021-04-02 | 2022-09-16 | 清创人和生态工程技术有限公司 | Preparation method and application of hierarchical porous carbon material |
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| CN102757034A (en) * | 2012-08-07 | 2012-10-31 | 中国人民解放军63971部队 | Method for preparing nitrogen-rich porous carbon material |
| CN103272559A (en) * | 2013-05-21 | 2013-09-04 | 北京化工大学 | Application of porous carbon electrode material in electrosorb technology |
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| CN103272559A (en) * | 2013-05-21 | 2013-09-04 | 北京化工大学 | Application of porous carbon electrode material in electrosorb technology |
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