CN102838115B - 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
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- CN102838115B CN102838115B CN201210380342.1A CN201210380342A CN102838115B CN 102838115 B CN102838115 B CN 102838115B CN 201210380342 A CN201210380342 A CN 201210380342A CN 102838115 B CN102838115 B CN 102838115B
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- petroleum coke
- activated carbon
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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
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- Electric Double-Layer Capacitors Or The Like (AREA)
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 a kind of preparation method of ultracapacitor petroleum coke matrix activated carbon.
Background technology
Ultracapacitor, as novel energy-storing element, has application widely and huge potential market, enjoys national governments and enterprises pay attention.According to the difference of energy storage principle, ultracapacitor can be divided into double electric layer capacitor and pseudocapacitors.The electrode material of pseudocapacitors has metal oxide and conducting polymer two class, the electrode material mainly various high-specific surface area material with carbon element of double electric layer capacitor.The electrode material mainly active carbon of the ultracapacitor use of current industrialization.Petroleum coke due to abundant raw material, carbon content is high, ash content is low, cheap and become the desirable feedstock preparing active carbon with high specific surface area.Effective ways prepared by current petroleum coke matrix activated carbon take KOH as activator, carries out chemical activation.But due to petroleum coke compact structure, activation difficulty, limits the raising of its specific area and specific volume.The present invention carbonizes in advance to petroleum coke, and carries out H to charing petroleum coke
2o
2hydrothermal oxidization process, the structure of the inner graphite microcrystal of adjustment petroleum coke, reduces activation difficulty, the performances such as the specific area of raising active carbon and specific volume.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of ultracapacitor petroleum coke matrix activated carbon, by carbonizing in advance and H petroleum coke
2o
2hydrothermal oxidization, the structure of the inner graphite microcrystal of adjustment petroleum coke, controls pre-carbonization temperature, time, H in oxidation processes
2o
2concentration, reaction temperature, in activation, the parameter such as alkali carbon ratio, activation temperature, time, prepares the active carbon of high-ratio surface sum Fabrication of High Specific Capacitance.
The present invention is achieved like this, and it is characterized in that method step is: petroleum coke is broken, grinding, and screening granularity is the petroleum coke powder of 104 ~ 124 μm is raw material.Petroleum coke powder is put into crucible furnace, is warming up to 400 ~ 450 DEG C under nitrogen protection with the speed of 20 DEG C/min, insulation charing 1 h, obtains carbonizing petroleum coke.The H that mass fraction is 20 ~ 30% is added in charing petroleum coke
2o
2, pour in 80-100 DEG C of reaction 8 h in autoclave, by product suction filtration, repeatedly rinse extremely neutral, obtain petroleum oxidate Jiao.By burnt to KOH and petroleum oxidate be KOH according to mass ratio: the ratio of petroleum coke=3:1 mixes; mixture is put into crucible furnace; 800-850 DEG C is warmed up under nitrogen protection with identical programming rate; insulation activation 2 ~ 3 h; the product HCl aqueous solution is boiled 5 min; repeatedly clean to neutrality with deionized water, obtain active carbon.
Advantage of the present invention is: by the structure of adjustment petroleum coke graphite microcrystal, reduces petroleum coke activation difficulty, the performances such as the specific area of raising active carbon and specific volume.
Accompanying drawing explanation
Fig. 1 is comparative example 1 gained active carbon XRD collection of illustrative plates.
Fig. 2 is comparative example 1 gained activated carbon electrodes cyclic voltammetry curve.
Fig. 3 is embodiment 1 gained active carbon XRD collection of illustrative plates.
Fig. 4 is embodiment 1 gained activated carbon electrodes cyclic voltammetry curve.
Embodiment
comparative example 1
Petroleum coke is broken, and grinding, screening granularity is the powder of 104 ~ 124 μm is raw material.By KOH with powder petroleum coke according to mass ratio KOH: the ratio of petroleum coke=3:1 mixes; mixture is put into crucible furnace; 400 DEG C are warming up under nitrogen protection with the speed of 20 DEG C/min; be incubated 1 h; continue to be warmed up to 800 DEG C with identical programming rate, insulation activation 2 h, boils 5 min by the product HCl aqueous solution; repeatedly clean to neutrality with deionized water, obtain active carbon.Fig. 1 is the XRD collection of illustrative plates of petroleum coke.The diffraction maximum of about 25 ° is the d002 peak of graphite microcrystal.Table 1 is the structural parameters of petroleum coke graphite microcrystal, its interplanar distance (d
002) be 0.344 nm, crystallite thickness (Lc) is 2.34 nm, and the microcrystalline carbon atom number of plies (N) is 8.Table 2 is the porosity parameter of active carbon.Total pore volume (V
t) be 1.17 mL/g, wherein Micropore volume (V
micro) be 0.97 mL/g, Micropore volume accounts for the ratio (V of total pore volume
micro/ V
t) be 82.49%; Specific 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 area
micro/ S
bET) be 89.2%; Average pore size (L
0) be 1.92 nm.
The preparation of activated carbon electrodes and test: the ratio of active carbon, carbon black and ptfe emulsion 70:25:5 is in mass ratio mixed, is prepared into the electrode slice of thickness about 0.5 mm, electrode slice is put into 120 DEG C of vacuum drying chamber vacuumizes 24 hours.With Ag/AgCl electrode for reference electrode, platinum plate electrode is to electrode, and electrolyte is the 6M KOH aqueous solution, and German IM6ex electrochemical workstation carries out the Cyclic voltamogram test of activated carbon electrodes, and by the specific volume of cyclic voltammetry curve integral and calculating active carbon.Fig. 2 is the cyclic voltammetry curve of activated carbon electrodes when sweep speed is 0.5 mV/s.Can find out that sample has good rectangular characteristic, illustrate that its capacity is mainly from electric double layer capacitance, calculating its specific volume is 278F/g.
embodiment 1
Petroleum coke is broken, and grinding, screening granularity is the powder of 104 ~ 124 μm is raw material.Powder petroleum coke is put into crucible furnace, is warming up to 400 DEG C under nitrogen protection with the speed of 20 DEG C/min, insulation charing 1 h, obtains carbonizing petroleum coke.The H that mass fraction is 20% is added in charing petroleum coke
2o
2, and pour in 80 DEG C of reaction 8 h in autoclave, by product suction filtration, repeatedly rinse extremely neutral, obtain petroleum oxidate Jiao.By burnt to KOH and petroleum oxidate be KOH according to mass ratio: the ratio of petroleum coke=3:1 mixes; mixture is put into crucible furnace; 800 DEG C are warmed up under nitrogen protection with identical programming rate; insulation activation 2 h; the product HCl aqueous solution is boiled 5 min; repeatedly clean to neutrality with deionized water, obtain active carbon.Fig. 3 is the XRD collection of illustrative plates of petroleum coke.Compared with comparative example, there is trickle moving to left in the diffraction maximum of petroleum oxidate Jiao, and the obvious broadening of diffraction maximum, illustrates that oxidation modification makes petroleum coke graphite microcrystal interlamellar spacing increase, and crystallite thickness reduces simultaneously.Table 3 is the structural parameters of the burnt graphite microcrystal of petroleum oxidate, and compared with comparative example, its interplanar distance increases to 0.356 nm by 0.344 nm, and crystallite thickness is reduced to 1.69 nm by 2.34 nm, and microcrystalline carbon atomic layer is reduced to 6 layers by 8 layers.This change of graphite microcrystal, is conducive to follow-up activation, petroleum coke can be made to activate more abundant, increasing specific surface area and specific volume.Table 4 is the porosity parameter of active carbon.Compare with comparative example, total pore volume increases to 1.61 mL/g by 1.17 mL/g, and specific area is by 2216 m
2/ g is increased to 3097 m
2/ g, average pore size increases to 2.08 nm by 1.92 nm.The raising of specific area is conducive to obtaining Fabrication of High Specific Capacitance, simultaneously the increase of average pore size, is conducive to obtaining high power density.And the developing goal of Fabrication of High Specific Capacitance and high power density ultracapacitor just.
The preparation of activated carbon electrodes and test: the ratio of active carbon, carbon black and ptfe emulsion 70:25:5 is in mass ratio mixed, is prepared into the electrode slice of thickness about 0.5 mm, electrode slice is put into 120 DEG C of vacuum drying chamber vacuumizes 24 hours.With Ag/AgCl electrode for reference electrode, platinum plate electrode is to electrode, and electrolyte is the 6M KOH aqueous solution, and German IM6ex electrochemical workstation carries out the Cyclic voltamogram test of activated carbon electrodes, and by the specific volume of cyclic voltammetry curve integral and calculating active carbon.Fig. 4 is the cyclic voltammetry curve of activated carbon electrodes when sweep speed is 0.5 mV/s.Compare with comparative example, when reversing in electric potential scanning direction, sample has better current response characteristic, and illustrate that its power characteristic is better, calculate its specific volume is 423F/g simultaneously, exceeds 52.16% compared with the specific volume of comparative example active carbon 278F/g.
Generally speaking, carbonized in advance and H by petroleum coke
2o
2hydrothermal oxidization modification, when other process conditions are identical, the specific area of active carbon is by 2216 m
2/ g brings up to 3097 m
2/ g, specific volume brings up to 423F/g by 278F/g.
Table 1 is comparative example 1 gained petroleum coke structural parameters of graphite crystallites.
Table 2 is the porosity parameter of comparative example 1 gained active carbon.
Table 3 is the structural parameters of the burnt graphite microcrystal of embodiment 1 gained petroleum oxidate.
Table 4 is the porosity parameter of embodiment 1 gained active carbon.
Table 1
Table 2
Table 3
Table 4
Claims (1)
1. the preparation method of ultracapacitor High-specific Area Activated Carbon; it is characterized in that method step is: petroleum coke is broken; grinding; screening granularity is the petroleum coke powder of 104 ~ 124 μm is raw material; petroleum coke powder is put into crucible furnace, under nitrogen protection, is warming up to 400 ~ 450 DEG C with the speed of 20 DEG C/min, insulation charing 1 h; obtain carbonizing petroleum coke, in charing petroleum coke, add the H that mass fraction is 20 ~ 30%
2o
2pour in 80-100 DEG C of reaction 8 h in autoclave, by product suction filtration, repeatedly rinse to neutral; obtain petroleum oxidate Jiao; by burnt to KOH and petroleum oxidate be KOH according to mass ratio: the ratio of petroleum coke=3:1 mixes, and mixture is put into crucible furnace, is warmed up to 800-850 DEG C under nitrogen protection with identical programming rate; insulation activation 2 ~ 3 h; the product HCl aqueous solution is boiled 5 min, repeatedly cleans to neutrality with deionized water, obtain active carbon.
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| CN103990430B (en) * | 2014-04-25 | 2016-02-10 | 重庆文理学院 | A kind of green shell/broomcorn straw biological carbon and preparation method thereof |
| 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 |
Citations (3)
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|---|---|---|---|---|
| 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 |
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| 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 |
|---|
| 《石油焦制备超级电容器用中孔活性炭研究》;邓梅根等;《第九届全国化学工艺学术年会论文集》;20051231;第1556页 * |
| 《高比表面积活性炭的制备及其初步应用》;蒋宝城;《中国硕士学位论文全文数据库》;20081231;正文第36-40页 * |
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