CN105439143A - Hierarchical porous activated carbon used for a super capacitor and preparation method thereof - Google Patents
Hierarchical porous activated carbon used for a super capacitor and preparation method thereof Download PDFInfo
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- CN105439143A CN105439143A CN201410413010.8A CN201410413010A CN105439143A CN 105439143 A CN105439143 A CN 105439143A CN 201410413010 A CN201410413010 A CN 201410413010A CN 105439143 A CN105439143 A CN 105439143A
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- gac
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- ultracapacitor
- activated carbon
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Abstract
Hierarchical porous activated carbon used for a super capacitor is characterized in that: the hierarchical porous activated carbon material used for the super capacitor is prepared by high temperature chemical activation, wherein ethylenediamine tetraacetic acid disodium salt is used as a chemical activating agent, and an organic matter is used as a carbon source. A preparation method of the hierarchical porous activated carbon used for the super capacitor is characterized in that: a certain amount of a carbon precursor is dissolved in water with stirring; a certain amount of the ethylenediamine tetraacetic acid disodium salt is added into the carbon precursor solution, and at a constant temperature the mixture is put into an oven for drying; high-temperature treatment of the dried product is performed in an inert atmosphere, the product is washed with an acid solution, then washed with deionized water until being neutral, and dried in the oven to obtain the activated carbon. Advantages are that the hierarchical porous activated carbon exhibits more excellent rate performance, has mild producing conditions, simple steps, low energy consumption and other characteristics, and has excellent capacitance performance and simple preparation process.
Description
Technical field
The present invention relates to electrode material for super capacitor technical field, particularly a kind of classifying porous gac for ultracapacitor and preparation method.
Background technology
Ultracapacitor is electrochemical capacitor again, is a kind of novel energy-storing element adopting electrostatic double layer principle to make.Ultracapacitor relative to secondary cell have power density high, have extended cycle life, the advantage such as charge/discharge rates is fast, have a wide range of applications in fields such as electromobile, wind-power electricity generation, mobile equipments.
Gac has the features such as specific surface area is high, good conductivity, chemical stability are high and with low cost, is the electrode material for super capacitor of current Unique Product.Prepare the method that active carbon with high specific surface area mainly adopts chemical activation at present, conventional chemical activating agent has: potassium hydroxide, sodium hydroxide, zinc chloride etc.In addition, the current gac adopting above chemical activating agent to prepare, based on micropore, having larger charge-transfer resistance when being used as electrode material for super capacitor, being unfavorable for using under big current.
The people such as YupengGuo adopt rice husk to do carbon source, and potassium hydroxide does chemical activating agent, and after first pyrolysis, the method for chemical activation has prepared active carbon with high specific surface area.This gac activates the carbon material specific surface area obtained for a hour and reaches 1930m at 750 DEG C
2g
-1, ratio capacitance value is 125Fg
-1(MaterialsChemistryandPhysics80 (2003) 704 – 709).The people such as Rufford adopt ZnCl
2the specific surface area that the method for activation coffee grounds obtains gac is 1019m
2g
-1, the ratio capacitance value in sulfuric acid electrolyte can reach 368Fg
-1(ElectrochemistryCommunications10 (2008) 1594 – 1597).And adopting bagasse to do carbon source, the gac specific surface area prepared when zinc chloride doubles carbon source reaches 1373m
2g
-1, ratio capacitance reaches 300Fg
-1(JournalofPowerSources195 (2010) 912 – 918).
Gac prepared by above method is all required to be microporous activated carbon, and in the process of fast charging and discharging, the transmission resistance of electric charge in electrode hole is comparatively large, lower at big current lower electrode capacity retention, causes the decline of capacitor power performance.
The present invention is chemical activating agent with disodium ethylene diamine tetraacetate, and the organism such as sucrose do carbon source, and at high temperature chemical activation can prepare the classifying porous gac of high mesoporous ratio.Gac prepared by present method is suitable as electrode material for super capacitor and uses.
Summary of the invention
The object of the invention is to the gac preparing a kind of high mesopore proportion, concrete grammar is for by being that the organism such as chemical activating agent, sucrose does carbon source with disodium ethylene diamine tetraacetate, through high temperature pyrolysis (charing) and chemical activation, obtain the classifying porous gac of high-specific surface area.The mesoporous ratio of gac prepared by the method is high, as electrode material for super capacitor, shows excellent high rate performance.
The invention provides a kind of classifying porous gac for ultracapacitor, it is characterized in that: the described classifying porous absorbent charcoal material for ultracapacitor, being take disodium ethylene diamine tetraacetate as chemical activating agent, organism is carbon source, under high temperature, chemical activation obtains, and carbon source comprises sucrose.
For a preparation method for the classifying porous gac of ultracapacitor, it is characterized in that: comprise the steps:
(1) a certain amount of carbon matrix precursor stirring and dissolving in water is got;
(2) in the solution of carbon matrix precursor, a certain amount of disodium ethylene diamine tetraacetate is added, dry by being placed in baking oven under this mixture certain temperature;
(3) product drying obtained pyroprocessing under an inert atmosphere;
(4) product acid solution cleans, and then extremely neutral with deionized water wash, drying can obtain gac in an oven.
In step (1), carbon matrix precursor comprises: one or more in sucrose, glucose, furfuryl alcohol, resol etc.
In step (2), the mass ratio of disodium ethylene diamine tetraacetate and carbon matrix precursor is 20:1 to 1:20, and described inert atmosphere is nitrogen or argon gas.
In step (2), drying temperature is 10-250 DEG C in an oven.
In step (3), treatment temp is 400-2000 DEG C.
In step (4), drying temperature is 10-250 DEG C in an oven.
Advantage of the present invention:
Gac prepared by the present invention has higher specific surface area and mesoporous ratio.Compare with the gac of traditional chemical activation preparation, the gac adopting the inventive method to prepare shows more excellent high rate performance.Owing to adopting organic salt disodium ethylene diamine tetraacetate to replace highly basic to make activator, charing and activation are synchronously carried out, and method for preparation of active carbon provided by the present invention has working condition gentleness, step simply, the feature that energy expenditure is low.The mesoporous rate gac of height prepared by the present invention, as electrode material for super capacitor, has excellent capacitive property, and this electrode materials has that preparation technology is simple, electric capacity high rate performance advantages of higher.As electrode of super capacitor prepared by active substance, there is higher specific storage with this gac, show excellent high rate performance.Be that gac specific surface area prepared by 4:1 reaches 1342m by activator and carbon source mass ratio
2g
-1, at 1000mVs
-1under scanning speed, ratio capacitance value reaches 145Fg
-1.
Accompanying drawing explanation
Fig. 1 is the nitrogen Adsorption and desorption isotherms of gac 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 gac 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 gac 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 the present invention, but not thereby limiting the invention.
Embodiment 1
Get 1g sucrose dissolved in 10g water, add 1g disodium ethylene diamine tetraacetate and mix, carry out drying by mixture in an oven 80 DEG C.Dried mixture is carbonized 2 hours in a nitrogen atmosphere, and carbonization temperature is 800 DEG C.Obtain the pickling of charing after product hydrochloric acid soln, then extremely neutral with deionized water wash, in baking oven, dry 24h at 60 DEG C, obtains gac.Physical adsorption test shows that this gac specific surface area is 802m
2g
-1, Adsorption and desorption isotherms as shown in Figure 1, illustrates that the carbon material prepared is classifying porous gac.By above-mentioned classifying porous gac in active substance: conductive agent: the ratio of binding agent=85:10:5 carries out being mixed with into electrode slice, carry out in 6MKOH electrolytic solution three electrode cycle volt-ampere test, result as shown in Figure 2, at 2mVs
-1scanning speed under ratio capacitance be 188Fg
-1.
Embodiment 2
Get 1g sucrose dissolved in 10g water, add 2g disodium ethylene diamine tetraacetate and mix, carry out drying by mixture in an oven 80 DEG C.Dried mixture is carbonized 2 hours in a nitrogen atmosphere, and carbonization temperature is 800 DEG C.Obtain the pickling of charing after product hydrochloric acid soln, then extremely neutral with deionized water wash, in baking oven, dry 24h at 60 DEG C, obtains gac.Physical adsorption test shows that this gac specific surface area is 1192m
2g
-1, Adsorption and desorption isotherms as shown in Figure 3, illustrates that the carbon material prepared is classifying porous gac.By above-mentioned classifying porous gac in active substance: conductive agent: the ratio of binding agent=85:10:5 carries out being mixed with into electrode slice, carry out in 6MKOH electrolytic solution three electrode cycle volt-ampere test, result as shown in Figure 4, at 2mVs
-1scanning speed under ratio capacitance be 197Fg
-1.
Embodiment 3
Get 1g sucrose dissolved in 10g water, add 1g disodium ethylene diamine tetraacetate and mix, 80 DEG C, mixture is dry in an oven.Dried mixture is carbonized 2 hours in a nitrogen atmosphere, and carbonization temperature is 800 DEG C.Obtain the pickling of charing after product hydrochloric acid soln, then extremely neutral with deionized water wash, in baking oven, dry 24h at 60 DEG C, obtains gac.Physical adsorption test shows that this gac specific surface area is 1342m
2g
-1, Adsorption and desorption isotherms as shown in Figure 5, illustrates that the carbon material prepared is classifying porous gac.By above-mentioned classifying porous gac in active substance: conductive agent: the ratio of binding agent=85:10:5 carries out being mixed with into electrode slice, carry out in 6MKOH electrolytic solution three electrode cycle volt-ampere test, result as shown in Figure 6, at 2mVs
-1scanning speed under ratio capacitance be 221Fg
-1, up to 1000mVs
-1under scanning speed, ratio capacitance value reaches 145Fg
-1.
Claims (7)
1. the classifying porous gac for ultracapacitor, it is characterized in that: the described classifying porous absorbent charcoal material for ultracapacitor, being take disodium ethylene diamine tetraacetate as chemical activating agent, organism is carbon source, and under high temperature, chemical activation obtains, and carbon source comprises sucrose.
2. a preparation method for the classifying porous gac for ultracapacitor according to claim 1, is characterized in that: comprise the steps:
(1) a certain amount of carbon matrix precursor stirring and dissolving in water is got;
(2) in the solution of carbon matrix precursor, a certain amount of disodium ethylene diamine tetraacetate is added, dry by being placed in baking oven under this mixture certain temperature;
(3) product drying obtained pyroprocessing under an inert atmosphere;
(4) product acid solution cleans, and then extremely neutral with deionized water wash, drying can obtain gac in an oven.
3. according to the preparation method of the classifying porous gac for ultracapacitor according to claim 2, it is characterized in that: in step (1), carbon matrix precursor comprises: one or more in sucrose, glucose, furfuryl alcohol, resol etc.
4. according to the preparation method of the classifying porous gac for ultracapacitor according to claim 2, it is characterized in that: in step (2), the mass ratio of disodium ethylene diamine tetraacetate and carbon matrix precursor is 20:1 to 1:20, and described inert atmosphere is nitrogen or argon gas.
5. according to the preparation method of the classifying porous gac for ultracapacitor according to claim 2, it is characterized in that: in step (2), drying temperature is 10-250 DEG C in an oven.
6. according to the preparation method of the classifying porous gac for ultracapacitor according to claim 2, it is characterized in that: in step (3), treatment temp is 400-2000 DEG C.
7. according to the preparation method of the classifying porous gac for ultracapacitor according to claim 2, it is characterized in that: in step (4), drying temperature is 10-250 DEG C in an oven.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105948018A (en) * | 2016-04-29 | 2016-09-21 | 谢镕安 | Bio-ene charcoal material and preparation method thereof |
| 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 |
| 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 |
| 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 |
| CN112250067A (en) * | 2020-09-03 | 2021-01-22 | 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 |
| CN113044839A (en) * | 2021-04-02 | 2021-06-29 | 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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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105948018A (en) * | 2016-04-29 | 2016-09-21 | 谢镕安 | Bio-ene charcoal material and preparation method thereof |
| 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 |
| 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 |
| 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 |
| CN112250067A (en) * | 2020-09-03 | 2021-01-22 | 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 |
| 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 |
| CN113044839A (en) * | 2021-04-02 | 2021-06-29 | 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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