CN102838115A - Preparation method of petroleum coke base high specific surface area activated carbon used for supercapacitor - Google Patents
Preparation method of petroleum coke base high specific surface area activated carbon used for supercapacitor Download PDFInfo
- Publication number
- CN102838115A CN102838115A CN2012103803421A CN201210380342A CN102838115A CN 102838115 A CN102838115 A CN 102838115A CN 2012103803421 A CN2012103803421 A CN 2012103803421A CN 201210380342 A CN201210380342 A CN 201210380342A CN 102838115 A CN102838115 A CN 102838115A
- Authority
- CN
- China
- Prior art keywords
- petroleum coke
- refinery coke
- surface area
- activated carbon
- specific surface
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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 relates to a preparation method of petroleum coke base high specific surface area activated carbon used for a supercapacitor. The method comprises the following steps of: crushing, grinding and screening petroleum coke, and carbonizing powdered petroleum coke at a certain temperature to obtain carbonized petroleum coke; carrying out oxidation treatment on the carbonized petroleum coke by using H2O2 by adopting a hydrothermal method to obtain oxidized petroleum coke; mixing KOH and the oxidized petroleum coke according to a certain mass ratio, then activating, boiling a product with an HCL aqueous solution, and cleaning with deionized water to obtain activated carbon. The preparation method has the advantages that the activation difficulty of the petroleum coke is reduced through adjusting the structure of petroleum coke graphite crystallite so as to improve the properties of specific surface area, specific volume and the like of the activated carbon.
Description
Technical field
The present invention relates to the preparation method of a kind of ultracapacitor with the refinery coke matrix activated carbon.
Background technology
Ultracapacitor has very wide application field and enormous and latent market as the novel energy-storing element, enjoys national governments and enterprises pay attention.According to the difference of energy storage principle, ultracapacitor can be divided into double layer capacitor and fake capacitance device.The electrode materials of fake capacitance device has two types of MOX and conductive polymerss, and the electrode materials of double layer capacitor mainly is various high-specific surface area carbon materials.The electrode materials that the ultracapacitor of industrialization at present uses mainly is a gac.Refinery coke is owing to abundant raw material, high, low, the cheap desirable feedstock that becomes the preparation active carbon with high specific surface area of ash content of carbon content.The effective ways of refinery coke matrix activated carbon preparation at present are to be acvator with KOH, carry out chemical activation.But because the refinery coke compact structure, the activation difficulty has limited the raising of its specific surface area and specific volume.The present invention carries out preparatory charing to refinery coke, and the charing refinery coke is carried out H
2O
2Hydrothermal oxidization is handled, and the structure of the inner graphite microcrystal of adjustment refinery coke reduces the activation difficulty, performances such as the specific surface area of raising gac and specific volume.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of ultracapacitor, through to preparatory charing of refinery coke and H with the refinery coke matrix activated carbon
2O
2Hydrothermal oxidization, the structure of the inner graphite microcrystal of adjustment refinery coke is controlled preparatory carbonization temperature, time, H in the oxide treatment
2O
2Concentration, temperature of reaction, parameters such as alkali carbon ratio, activation temperature, time in the activation, the gac of preparation high-specific surface area and high specific volume.
The present invention realizes like this, it is characterized in that method steps is: refinery coke is broken, to grind, and the screening granularity is that the petroleum coke powder of 104 ~ 124 μ m is a raw material.Petroleum coke powder is put into crucible oven, and the speed with 20 ℃/min under the nitrogen protection is warming up to 400 ~ 450 ℃, and insulation charing 1 h obtains the charing refinery coke.Add massfraction in the charing refinery coke and be 20 ~ 30% H
2O
2, pour in the autoclave in 80-100 ℃ of reaction 8 h, with the product suction filtration, flushing obtains petroleum oxidate Jiao to neutral repeatedly.With KOH and petroleum oxidate Jiao is the mixed of KOH: refinery coke=3:1 according to mass ratio; Mixture is put into crucible oven; Under nitrogen protection, be warmed up to 800-850 ℃ with identical heat-up rate, insulation activation 2 ~ 3 h boil 5 min with product with the HCl aqueous solution; Clean repeatedly to neutrality with deionized water, obtain gac.
Advantage of the present invention is: through the structure of adjustment refinery coke graphite microcrystal, reduce refinery coke activation difficulty, performances such as the specific surface area of raising gac and specific volume.
Description of drawings
Fig. 1 is Comparative Examples 1 a gained gac XRD figure spectrum.
Fig. 2 is Comparative Examples 1 a gained activated carbon electrodes cyclic voltammetry curve.
Fig. 3 is embodiment 1 a gained gac XRD figure spectrum.
Fig. 4 is embodiment 1 a gained activated carbon electrodes cyclic voltammetry curve.
Embodiment
Comparative Examples 1
Refinery coke is broken, to grind, the screening granularity is that the powder of 104 ~ 124 μ m is a raw material.KOH and powder refinery coke according to the mixed of mass ratio KOH: refinery coke=3:1, are put into crucible oven with mixture, and the speed with 20 ℃/min under nitrogen protection is warming up to 400 ℃; Be incubated 1 h; Continuation is warmed up to 800 ℃ with identical heat-up rate, and insulation activation 2 h boil 5 min with product with the HCl aqueous solution; Clean repeatedly to neutrality with deionized water, obtain gac.Fig. 1 is the XRD figure spectrum of refinery coke.Diffraction peak about 25 ° is the d002 peak of graphite microcrystal.Table 1 is the structural parameter of refinery coke graphite microcrystal, its spacing (d
002) be 0.344 nm, crystallite thickness (Lc) is 2.34 nm, the microcrystalline carbon atom number of plies (N) is 8.Table 2 is the porosity parameter of gac.Total pore volume (V
t) be 1.17 mL/g, micropore pore volume (V wherein
Micro) be 0.97 mL/g, the micropore pore volume accounts for the ratio (V of total pore volume
Micro/ V
t) be 82.49%; Specific surface area (S
BET) be 2216 m
2/ g, wherein micropore specific area (S
Micro) be 1978, micropore specific area accounts for the ratio (S of total specific surface area
Micro/ S
BET) be 89.2%; Mean pore size (L
0) be 1.92 nm.
The preparation of activated carbon electrodes and test: the mixed of gac, carbon black and ptfe emulsion being pressed mass ratio 70:25:5 is even, is prepared into the electrode slice of about 0.5 mm of thickness, and electrode slice is put into 120 ℃ of vacuum drying oven vacuum-dryings 24 hours.With the Ag/AgCl electrode is reference electrode, and the platinized platinum electrode is a counter electrode, and electrolytic solution is the 6M KOH aqueous solution, on German IM6ex electrochemical workstation, carries out the cyclic voltammetric characteristic test of activated carbon electrodes, and by the specific volume of cyclic voltammetry curve integral and calculating gac.Fig. 2 is the cyclic voltammetry curve of activated carbon electrodes when sweep velocity is 0.5 mV/s.Can find out that sample has good rectangular characteristic, its capacity is described mainly from electric double layer capacitance, calculating its specific volume is 278F/g.
Refinery coke is broken, to grind, the screening granularity is that the powder of 104 ~ 124 μ m is a raw material.The powder refinery coke is put into crucible oven, and the speed with 20 ℃/min under nitrogen protection is warming up to 400 ℃, and insulation charing 1 h obtains the charing refinery coke.Add massfraction in the charing refinery coke and be 20% H
2O
2, and pour in the autoclave in 80 ℃ of reaction 8 h, with the product suction filtration, flushing obtains petroleum oxidate Jiao to neutral repeatedly.With KOH and petroleum oxidate Jiao is the mixed of KOH: refinery coke=3:1 according to mass ratio; Mixture is put into crucible oven; Under nitrogen protection, be warmed up to 800 ℃ with identical heat-up rate, insulation activation 2 h boil 5 min with product with the HCl aqueous solution; Clean repeatedly to neutrality with deionized water, obtain gac.Fig. 3 is the XRD figure spectrum of refinery coke.Compare with Comparative Examples, trickle moving to left appears in the burnt diffraction peak of petroleum oxidate, and obvious wideization of diffraction peak, explains that oxidation modification increases refinery coke graphite microcrystal interlamellar spacing, and crystallite thickness reduces simultaneously.Table 3 is the structural parameter of the burnt graphite microcrystal of petroleum oxidate, compares with Comparative Examples, and its spacing increases to 0.356 nm by 0.344 nm, and crystallite thickness is reduced to 1.69 nm by 2.34 nm, and the microcrystalline carbon atomic shell is reduced to 6 layers by 8 layers.This variation of graphite microcrystal helps follow-up activation, can make the refinery coke activation more abundant, increasing specific surface area and specific volume.Table 4 is the porosity parameter of gac.Compare with Comparative Examples, total pore volume increases to 1.61 mL/g by 1.17 mL/g, and specific surface area is by 2216 m
2/ g is increased to 3097 m
2/ g, mean pore size increases to 2.08 nm by 1.92 nm.The raising of specific surface area helps obtaining high specific volume, and the increase of mean pore size helps obtaining high power density simultaneously.And high specific volume and the high power density developing goal of ultracapacitor just.
The preparation of activated carbon electrodes and test: the mixed of gac, carbon black and ptfe emulsion being pressed mass ratio 70:25:5 is even, is prepared into the electrode slice of about 0.5 mm of thickness, and electrode slice is put into 120 ℃ of vacuum drying oven vacuum-dryings 24 hours.With the Ag/AgCl electrode is reference electrode, and the platinized platinum electrode is a counter electrode, and electrolytic solution is the 6M KOH aqueous solution, on German IM6ex electrochemical workstation, carries out the cyclic voltammetric characteristic test of activated carbon electrodes, and by the specific volume of cyclic voltammetry curve integral and calculating gac.Fig. 4 is the cyclic voltammetry curve of activated carbon electrodes when sweep velocity is 0.5 mV/s.Compare with Comparative Examples, when the electric potential scanning direction was reversed, sample had better current response characteristic, explained that its power characteristic is better, and calculating its specific volume simultaneously is 423F/g, exceeded 52.16% than the specific volume of Comparative Examples gac 278F/g.
Generally speaking, through preparatory charing of refinery coke and H
2O
2The hydrothermal oxidization modification, under the identical situation of other processing condition, the specific surface area of gac is by 2216 m
2/ g brings up to 3097 m
2/ g, specific volume is brought up to 423F/g by 278F/g.
Table 1 is Comparative Examples 1 gained refinery coke graphite microcrystal structural parameter.
Table 2 is the porosity parameter of Comparative Examples 1 gained gac.
Table 3 is the structural parameter of the burnt graphite microcrystal of embodiment 1 gained petroleum oxidate.
Table 4 is the porosity parameter of embodiment 1 gained gac.
Table 1
Table 2
Table 3
Table 4
Claims (1)
1. ultracapacitor is characterized in that with the high specific surface area active charcoal based preparation method of refinery coke method steps is: refinery coke is broken, grind; The screening granularity is that the petroleum coke powder of 104 ~ 124 μ m is a raw material; Petroleum coke powder is put into crucible oven, and the speed with 20 ℃/min under the nitrogen protection is warming up to 400 ~ 450 ℃, insulation charing 1 h; Obtain the charing refinery coke, add massfraction in the charing refinery coke and be 20 ~ 30% H
2O
2, pour in the autoclave in 80-100 ℃ of reaction 8 h, with the product suction filtration; Flushing obtains petroleum oxidate Jiao to neutral repeatedly, is the mixed of KOH: refinery coke=3:1 according to mass ratio with KOH and petroleum oxidate Jiao; Mixture is put into crucible oven, under nitrogen protection, be warmed up to 800-850 ℃, insulation activation 2 ~ 3 h with identical heat-up rate; Product is boiled 5 min with the HCl aqueous solution, clean repeatedly to neutrality, obtain gac with deionized water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210380342.1A CN102838115B (en) | 2012-10-10 | 2012-10-10 | Preparation method of petroleum coke base high specific surface area activated carbon used for supercapacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210380342.1A CN102838115B (en) | 2012-10-10 | 2012-10-10 | Preparation method of petroleum coke base high specific surface area activated carbon used for supercapacitor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102838115A true CN102838115A (en) | 2012-12-26 |
| CN102838115B CN102838115B (en) | 2015-04-29 |
Family
ID=47365883
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210380342.1A Expired - Fee Related CN102838115B (en) | 2012-10-10 | 2012-10-10 | Preparation method of petroleum coke base high specific surface area activated carbon used for supercapacitor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102838115B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103990430A (en) * | 2014-04-25 | 2014-08-20 | 重庆文理学院 | Pecan shell/sorghum straw bio-char and preparation method thereof |
| CN104192838A (en) * | 2014-09-09 | 2014-12-10 | 哈尔滨工业大学 | Preparation method for coal-based activated carbon by carrying out combined gas activation by stages |
| CN105236404A (en) * | 2015-08-20 | 2016-01-13 | 深圳市贝特瑞新能源材料股份有限公司 | Petroleum coke based activated carbon for electrode material of supercapacitor, preparation method therefor and use thereof |
| CN105826087A (en) * | 2016-04-11 | 2016-08-03 | 汪晓伟 | Preparation method of active carbon powder used for manufacturing supercapacitor electrode |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1593744A (en) * | 2004-06-24 | 2005-03-16 | 中国海洋大学 | Method for preparing active carbon materials SO#-[2] absorbent by medicament activation method |
| CN1843906A (en) * | 2006-03-22 | 2006-10-11 | 大连理工大学 | Method for preparing high-specific surface area active carbon by petroleum coke |
| CN101844069A (en) * | 2010-04-23 | 2010-09-29 | 成都益盛环境工程科技有限责任公司 | Method for preparing high surface-activity adsorbing carbon material through catalysis and activation synchronous process |
-
2012
- 2012-10-10 CN CN201210380342.1A patent/CN102838115B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1593744A (en) * | 2004-06-24 | 2005-03-16 | 中国海洋大学 | Method for preparing active carbon materials SO#-[2] absorbent by medicament activation method |
| CN1843906A (en) * | 2006-03-22 | 2006-10-11 | 大连理工大学 | Method for preparing high-specific surface area active carbon by petroleum coke |
| CN101844069A (en) * | 2010-04-23 | 2010-09-29 | 成都益盛环境工程科技有限责任公司 | Method for preparing high surface-activity adsorbing carbon material through catalysis and activation synchronous process |
Non-Patent Citations (2)
| Title |
|---|
| 蒋宝城: "《高比表面积活性炭的制备及其初步应用》", 《中国硕士学位论文全文数据库》 * |
| 邓梅根等: "《石油焦制备超级电容器用中孔活性炭研究》", 《第九届全国化学工艺学术年会论文集》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103990430A (en) * | 2014-04-25 | 2014-08-20 | 重庆文理学院 | Pecan shell/sorghum straw bio-char and preparation method thereof |
| CN104192838A (en) * | 2014-09-09 | 2014-12-10 | 哈尔滨工业大学 | Preparation method for coal-based activated carbon by carrying out combined gas activation by stages |
| CN104192838B (en) * | 2014-09-09 | 2016-05-11 | 哈尔滨工业大学 | The active carbon from coal preparation method of combination of gases activation stage by stage |
| CN105236404A (en) * | 2015-08-20 | 2016-01-13 | 深圳市贝特瑞新能源材料股份有限公司 | Petroleum coke based activated carbon for electrode material of supercapacitor, preparation method therefor and use thereof |
| CN105826087A (en) * | 2016-04-11 | 2016-08-03 | 汪晓伟 | Preparation method of active carbon powder used for manufacturing supercapacitor electrode |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102838115B (en) | 2015-04-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Fan et al. | Fe3O4@ carbon nanosheets for all-solid-state supercapacitor electrodes | |
| Samdani et al. | Self-assembled Bi2MoO6 nanopetal array on carbon spheres toward enhanced supercapacitor performance | |
| Farma et al. | Preparation of highly porous binderless activated carbon electrodes from fibres of oil palm empty fruit bunches for application in supercapacitors | |
| Zhou et al. | Ordered assembly of NiCo2O4 multiple hierarchical structures for high-performance pseudocapacitors | |
| Ghodbane et al. | Microstructural effects on charge-storage properties in MnO2-based electrochemical supercapacitors | |
| JP5599186B2 (en) | Activated carbon for electric double layer capacitor electrode and manufacturing method thereof | |
| JP5473282B2 (en) | Carbon material for electric double layer capacitor and manufacturing method thereof | |
| JP5344972B2 (en) | Carbon material for electric double layer capacitor electrode and manufacturing method thereof | |
| KR102159201B1 (en) | Activated carbon for electric double layer capacitor electrode and production method for same | |
| Gouda et al. | Nickel and cobalt oxides supported on activated carbon derived from willow catkin for efficient supercapacitor electrode | |
| WO2009005170A1 (en) | Process for producing activated carbon for electric double layer capacitor electrode | |
| WO2011122309A1 (en) | Activated charcoal for electric double-layer capacitor electrode and method for producing the same | |
| WO2005038836A1 (en) | Electric double layer capacitor, activated carbon for electrode thereof and method for producing same | |
| CN102838115B (en) | Preparation method of petroleum coke base high specific surface area activated carbon used for supercapacitor | |
| JP4576374B2 (en) | Activated carbon, its production method and its use | |
| JP5242090B2 (en) | Method for producing activated carbon for electric double layer capacitor electrode | |
| Li et al. | Nitrogen/sulfur-codoped carbon materials from chitosan for supercapacitors | |
| CN102826549A (en) | Preparation method of activated carbon for supercapacitor | |
| KR20160120671A (en) | Carbon Material for Power Storage Device Electrode and Manufacturing Method Thereof | |
| JP5242216B2 (en) | Carbon material for electric double layer capacitor electrode and manufacturing method thereof | |
| Srinivasan et al. | Construction of Fe2O3 Nanoparticles Decorated for a Highly Efficient Oxygen Evolution Reaction Activity | |
| TW201634387A (en) | Activated carbon and electric double layer capacitor thereof | |
| Moorthi et al. | Morphological Impact of Perovskite-Structured Lanthanum Cobalt Oxide (LaCoO3) Nanoflakes Toward Supercapacitor Applications | |
| Suryani et al. | Ag nanoparticles effect on BaTiO3-Graphite-AC/Aluminum foil symmetric supercapacitor | |
| JP2006216748A (en) | Carbon composite powder for electrode for electric dipole layer capacitor and manufacturing method for carbon composite powder and electric dipole layer capacitor using carbon composite powder |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150429 Termination date: 20151010 |
|
| EXPY | Termination of patent right or utility model |