CN101295587A - Production method of high specific energy super capacitor carbonaceous electrode material - Google Patents
Production method of high specific energy super capacitor carbonaceous electrode material Download PDFInfo
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- CN101295587A CN101295587A CNA2008100385352A CN200810038535A CN101295587A CN 101295587 A CN101295587 A CN 101295587A CN A2008100385352 A CNA2008100385352 A CN A2008100385352A CN 200810038535 A CN200810038535 A CN 200810038535A CN 101295587 A CN101295587 A CN 101295587A
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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 preparation method for the carbon electrode material of a high-energy-density super capacitor which is characterized by pre-carbonizing a refinery coke or other form bodies rich in carbon for 0.5 to 5 hours under the temperature of 400 to 900 DEG C; then carrying out ball milling on the refinery coke or other form bodies rich in carbon to 4 to 30 Mum; then carrying out dipping and mixing with KOH at a weight percentage ratio of 1: 3 to 1: 6 (or simultaneously adding the metal salt of 5 to 20wt percent); after physical dehydration, chemical dehydration and activating hole making by being cooperated with catalyzing are carried out on the matters respectively under the temperatures of 100 to 250 DEG C, 300 to 500 DEG C and 700 to 1000 DEG C, then surface chemical treatment in an H2 atmosphere is carried out on the matters under the temperature of 500 to 900 DEG C to manufacture the carbon electrode material. The invention adopts the pre-carbonizing or the combining technology of catalyzing chemical cooperated with activation to manufacture the carbon electrode material; the invention has higher energy density and power density compared with the existing carbon electrode material as the power storage principle of the invention is different from a double electric layer power storage principle.
Description
Technical field:
The present invention relates to a kind of preparation method of new carbon.The preparation method who belongs to a kind of high-energy-density, high-specific-power ultracapacitor usefulness carbon electrode material.
Background technology:
Ultracapacitor with its discharge and recharge speed fast, have extended cycle life, energy density is high and excellent specific property such as pollution-free and become the research focus of new energy field, its application expection at aspects such as hybrid vehicle, solar energy, wind energies will produce the essence influence to energy savings, urban environment control.Electrode material is the core of ultracapacitor.At present the more electrode material of research is based on the carbonaceous porous materials such as super-activated carbon, charcoal-aero gel, CNT (carbon nano-tube) of electric double layer theory.Though electric double layer capacitance is proportional to the effective ratio area of material in theory, but the raising of effective ratio area must be taken all factors into consideration the restriction to electrode performance of pore structure, surface chemical property, resistivity and the density etc. of material, thereby there is limiting value (～200F/g than capacitor C, single electrode, organic system).And, being subject to the preparation process of material, the proof voltage U of its surface texture also only is 2.7V.In the recent period, the researcher carries out orientation control by pore structure, surface chemical property and conductive network to carbonaceous porous electrode material, correspondingly can reach 180F/g than electric capacity, but room for promotion is very limited, causes energy density E (the E ∝ CU of made capacitor
2) only up to 10Wh/kg.Therefore, more the preparation of high-energy-density, specific power carbonaceous electrode material is very important.
Summary of the invention:
The object of the present invention is to provide the preparation method of a kind of ultracapacitor with carbon electrode material.This method technology is simple, the bulk density of made carbon electrode material, conductivity, all more higher than electric capacity, proof voltage.
The present invention realizes by following proposal:
A kind of preparation method of high specific energy super capacitor carbonaceous electrode material is characterized in that, said method comprising the steps of:
(1) be that rich carbon precursor (C content＞60%) particle of 10～500 μ m places retort with particle diameter, the heating rate with 2～10 ℃/min under inert atmosphere is warming up to 400～900 ℃ and constant temperature 0.5～5h, carries out pre-charing and handles;
(2) product that step (1) is obtained carries out ball milling, makes its particle diameter reach 4～30 μ m;
(3) material that step (2) is obtained mixed, floods by mass ratio with KOH (purity is more than 90%) in 1: 3～1: 6, wherein contained the rich carbon matrix precursor of 1g among the KOH of per 10～1000ml;
(4) step (3) gained mixture is placed KOH activation still, successively be warming up to 100～250 ℃, 300～500 ℃, 700～1000 ℃ with the heating rate of 2～10 ℃/min, and equal constant temperature 0.5～3h; Natural cooling is washed to neutrality, obtains required carbon electrode material after the drying.
Wherein, described carbonaceous precursor is a kind of in petroleum coke, pitch coke, coconut husk, apricot shell, shell, the wooden or bamboo class raw material.
The preferred version of technique scheme is as follows:
In the step (4) of such scheme, mixture places before the KOH activation still, adds the slaine of rich carbon precursor quality 5～20wt% earlier in mixture,
Described slaine is a kind of in the salts substances of Fe, Ni, Co, Mg.
Such scheme step (4) gained material can also be placed the charing still, at H
2Under the atmosphere, be warming up to 500～900 ℃ with the heating rate of 2～10 ℃/min and carry out chemical surface treatment 0.5～3h, obtain required carbon electrode material.
Beneficial effect
The invention has the advantages that:, adopt pre-charing or pre-charing and catalytic chemistry collaborative activation multiple techniques or pre-charing, the collaborative activation of catalytic chemistry and H according to the accumulate mechanism of new non-electric double layer capacitance mechanism
2The surface treatment multiple techniques though it is lower to make specific area, its bulk density, conductivity, all is higher than existing ultracapacitor carbon electrode material than electric capacity, proof voltage and mass energy density, volume energy density, specific power.And technology is simple, the cost performance height.Adopt the prepared high specific energy super capacitor carbonaceous electrode material of method of the present invention, novel carbon electrode material for class graphite microcrystal structure, it reaches as high as 180F/g (single electrode), proof voltage for reaching as high as 3.5V than electric capacity, is rich in the ions diffusion passage of aperture 1.5～3nm.
Embodiment
[Comparative Examples]
The petroleum coke powder and the KOH solution of mass concentration more than 90% of 300 μ m particle diameters were flooded 24 hours, and wherein the weight ratio of petroleum coke and KOH is 1: 4.Under nitrogen protection; programming rate with 5 ℃/min is warming up to 100 ℃ of low-temperature physics dehydration 1h earlier; rise to 400 ℃ of chemical dehydration 1.5h with identical programming rate then; activate 2h after continuing again to be warming up to 800 ℃; naturally cool to 30 ℃, be washed to neutrality then, after the drying; make the active carbon of superhigh specific surface area, its BET specific area is 2573m
2/ g, the aperture is concentrated and is distributed in 0.5～2.5nm.When being electrolyte with tetraethyl amine tetrafluoride boron, the ratio electric capacity of this electrode material is 157F/g, and proof voltage is 2.5V.
[embodiment one]
The petroleum coke powder 500g of 300 μ m particle diameters is placed retort, at N
2Heating rate with 5 ℃/min under the atmosphere is warming up to 800 ℃ and constant temperature 2h, carries out pre-charing and handles.After KOH solution more than 90% flooded 24 hours with above-mentioned product and mass concentration, wherein the weight ratio of petroleum coke and KOH was 1: 4, at N
2Under the atmosphere, programming rate with 5 ℃/min is warming up to 100 ℃ of low-temperature physics dehydration 1h earlier, rise to 400 ℃ of chemical dehydration 1.5h with identical programming rate then, activate 2h after continuing again to be warming up to 800 ℃, naturally cool to 30 ℃, be washed to neutrality then, after the drying, make the carbonaceous material of class graphite microcrystal structure, its BET specific area is 209m
2/ g, pore volume are 0.19ml/g.When being electrolyte with tetraethyl amine tetrafluoride boron, the ratio electric capacity of this electrode material is 177F/g, and proof voltage 3.2V, specific energy are 8Wh/Kg.
[embodiment two]
On the basis of embodiment one, in KOH solution and petroleum coke powder dipping, add the Ni (NO of 40g
3)
2, the specific area of gained carbonaceous porous material is 279m
2/ g, pore volume are 0.28ml/g, and wherein mesopore volume is 0.21ml/g.When being electrolyte with tetraethyl amine tetrafluoride boron, the ratio electric capacity of this carbon electrode material is 183F/g, and proof voltage 3.1V, specific energy are 10Wh/Kg.
[embodiment three]
On the basis of embodiment two, products therefrom is placed the charing still, at H
2Under the atmosphere, be warming up to 750 ℃ with the heating rate of 5 ℃/min and carry out chemical surface treatment 2h, be cooled to 30 ℃ then naturally, get material, and be washed to neutrality.The specific area of gained carbonaceous porous material is 261m
2/ g, pore volume are 0.26ml/g, and mesopore volume is 0.20ml/g.When being electrolyte with tetraethyl amine tetrafluoride boron, the ratio electric capacity of this carbon electrode material is 180F/g, and proof voltage 3.5V, specific energy are 10Wh/Kg.
[embodiment four]
When being raw material with the coconut husk, adopt the same process of [embodiment one], making the BET specific area is 509m
2/ g, pore volume are the carbonaceous material of 0.39ml/g.When being electrolyte with tetraethyl amine tetrafluoride boron, the ratio electric capacity of this carbon electrode material is 147F/g, and proof voltage 2.5V, specific energy are 5Wh/Kg.
Claims (4)
1, a kind of preparation method of high specific energy super capacitor carbonaceous electrode material is characterized in that, said method comprising the steps of:
(1) be that the rich carbon precursor particle of 10～500 μ m places retort with particle diameter, the heating rate with 2～10 ℃/min under inert atmosphere is warming up to 400～900 ℃ and constant temperature 0.5～5h, carries out pre-charing and handles;
(2) product that step (1) is obtained carries out ball milling, makes its particle diameter reach 4～30 μ m;
(3) the powder material with step (2) gained mixed, floods by mass ratio with the KOH of mass concentration more than 90% in 1: 3～1: 6, wherein contained the rich carbon matrix precursor of 1g among the KOH of per 10～1000ml;
(4) step (3) gained mixture is placed KOH activation still, being warming up to 100～250 ℃ respectively with the heating rate of 2～10 ℃/min carries out physics dehydration, 300～500 ℃ and carries out chemical dehydration, 700～1000 ℃ of catalyzing cooperations activation pore-creating, and equal constant temperature 0.5～3h, natural cooling, be washed to neutrality, obtain required carbon electrode material after the drying;
Wherein, described carbonaceous precursor is a kind of in petroleum coke, pitch coke, coconut husk, apricot shell, shell, the wooden or bamboo class raw material.
2, the preparation method of super capacitor carbonaceous electrode material as claimed in claim 1 is characterized in that, in described step (4), mixture places before the KOH activation still, adds the slaine of rich carbon precursor quality 5～20wt% earlier in mixture.
3, the preparation method of super capacitor carbonaceous electrode material as claimed in claim 2 is characterized in that, described slaine is a kind of in the salts substances of Fe, Ni, Co, Mg.
4, the preparation method of super capacitor carbonaceous electrode material as claimed in claim 1 or 2 is characterized in that, described step (4) gained material is placed the charing still, at H
2Under the atmosphere, be warming up to 500～900 ℃ with the heating rate of 2～10 ℃/min and carry out chemical surface treatment.
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| CNA2008100385352A CN101295587A (en) | 2008-06-05 | 2008-06-05 | Production method of high specific energy super capacitor carbonaceous electrode material |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101556868B (en) * | 2009-05-20 | 2011-05-04 | 河南理工大学 | Method for preparing carbon electrode material of oxygen-enriched super-capacitor |
| CN102354613A (en) * | 2011-09-14 | 2012-02-15 | 中国第一汽车股份有限公司 | Electrode material of supercapacitor and preparation method for electrode material |
| CN102509629A (en) * | 2011-09-29 | 2012-06-20 | 中山大学 | High-specific-area layered pore carbon material as well as preparation method and application thereof |
| CN103021674A (en) * | 2012-12-08 | 2013-04-03 | 天津大学 | Carbon-based ionic intercalation energy-storage electrode material and preparation process thereof |
| CN104064369A (en) * | 2014-06-28 | 2014-09-24 | 北京航空航天大学 | Preparation of natural nutshell carbon material and application of natural nutshell carbon material in electrochemical capacitors |
| CN108455604A (en) * | 2018-01-29 | 2018-08-28 | 中钢集团鞍山热能研究院有限公司 | A kind of carboxyl asphaltic base porous charcoal and preparation method thereof and purposes |
| CN108473319A (en) * | 2016-01-19 | 2018-08-31 | 迪睿合株式会社 | Porous carbon material and its manufacturing method and filter, sheet material and carriers for catalysts |
| CN111883369A (en) * | 2020-06-28 | 2020-11-03 | 南京林业大学 | Based on supported TiO2Preparation method of super capacitor with apricot shell activated carbon electrode |
-
2008
- 2008-06-05 CN CNA2008100385352A patent/CN101295587A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101556868B (en) * | 2009-05-20 | 2011-05-04 | 河南理工大学 | Method for preparing carbon electrode material of oxygen-enriched super-capacitor |
| CN102354613A (en) * | 2011-09-14 | 2012-02-15 | 中国第一汽车股份有限公司 | Electrode material of supercapacitor and preparation method for electrode material |
| CN102509629A (en) * | 2011-09-29 | 2012-06-20 | 中山大学 | High-specific-area layered pore carbon material as well as preparation method and application thereof |
| CN103021674A (en) * | 2012-12-08 | 2013-04-03 | 天津大学 | Carbon-based ionic intercalation energy-storage electrode material and preparation process thereof |
| CN104064369A (en) * | 2014-06-28 | 2014-09-24 | 北京航空航天大学 | Preparation of natural nutshell carbon material and application of natural nutshell carbon material in electrochemical capacitors |
| CN104064369B (en) * | 2014-06-28 | 2017-01-18 | 北京航空航天大学 | Preparation of natural nutshell carbon material and application of natural nutshell carbon material in electrochemical capacitors |
| CN108473319A (en) * | 2016-01-19 | 2018-08-31 | 迪睿合株式会社 | Porous carbon material and its manufacturing method and filter, sheet material and carriers for catalysts |
| CN108455604A (en) * | 2018-01-29 | 2018-08-28 | 中钢集团鞍山热能研究院有限公司 | A kind of carboxyl asphaltic base porous charcoal and preparation method thereof and purposes |
| CN111883369A (en) * | 2020-06-28 | 2020-11-03 | 南京林业大学 | Based on supported TiO2Preparation method of super capacitor with apricot shell activated carbon electrode |
| CN111883369B (en) * | 2020-06-28 | 2022-04-19 | 南京林业大学 | Based on supported TiO2Preparation method of super capacitor with apricot shell activated carbon electrode |
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Open date: 20081029 |