CN102826549A - Preparation method of activated carbon for supercapacitor - Google Patents
Preparation method of activated carbon for supercapacitor Download PDFInfo
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- CN102826549A CN102826549A CN2012103802607A CN201210380260A CN102826549A CN 102826549 A CN102826549 A CN 102826549A CN 2012103802607 A CN2012103802607 A CN 2012103802607A CN 201210380260 A CN201210380260 A CN 201210380260A CN 102826549 A CN102826549 A CN 102826549A
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- refinery coke
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Abstract
The invention provides a preparation method of activated carbon for a supercapacitor, comprising the following steps: crushing petroleum coke, grinding, screening, and carbonizing the power petroleum coke under a certain temperature, so that carbonized petroleum coke can be obtained; treating the carbonized petroleum coke by HNO3 solution under a certain temperature, cleaning, drying under a low temperature, and puffing under a certain temperature, so that puffed petroleum coke can be obtained; and mixing KOH and the puffed petroleum coke according to a certain weight ratio and activating, boiling a product by HCl water solution, and cleaning by ionized water, so that the activated carbon can be obtained. The preparation method has the advantages that due to the puffing treatment, the distances among petroleum coke graphite microcrystal layers can be increased, the graphite microcrystal thickness can be reduced, the petroleum coke activating difficulty can be reduced, and the performances of the activated carbon such as the specific surface area, the specific volume and the like can be improved.
Description
Technical field
The present invention relates to a kind of preparation method of activated carbon for super capacitors.
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 puffing, increases the graphite microcrystal interlamellar spacing, reduces crystallite thickness, 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 a kind of preparation method of activated carbon for super capacitors,, increase the graphite microcrystal interlamellar spacing, reduce crystallite thickness, control preparatory carbonization temperature, time, HNO in the puffing through refinery coke is carried out preparatory charing and puffing
3Concentration, 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 30 ~ 50% HNO
3The aqueous solution, in 30-50 ℃ of stirring reaction 4 h, with the product suction filtration, flushing is to neutral repeatedly, and 50 ℃ of dryings are carried out expanded in 130-160 ℃ then.With KOH and popping oil 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 increasing the graphite microcrystal interlamellar spacing, reduce crystallite thickness, 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 activated carbon electrodes cyclic voltammetry curve.
Fig. 2 for the specific volume of Comparative Examples 1 gained activated carbon electrodes with sweeping fast change curve.
Fig. 3 is embodiment 1 a gained activated carbon electrodes cyclic voltammetry curve.
Fig. 4 for the specific volume of embodiment 1 gained activated carbon electrodes with sweeping fast change 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.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. 1 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.Fig. 2 is the change curve of gac normalization method specific volume with scan speed.When sweeping speed when increasing to 8 mV/s, when its specific volume is 0.5 mV/s 67.61% of specific volume.
Refinery coke is broken, to 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 ℃, and insulation charing 1 h obtains the charing refinery coke.Add massfraction in the charing refinery coke and be 40% HNO
3, in 40 ℃ of stirring reaction 4 h, with the product suction filtration, flushing is to neutral repeatedly, 50 ℃ of dryings, and carry out expandedly in 150 ℃, obtain popping oil Jiao.With KOH and popping oil 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.Table 3 is the structural parameter of the burnt graphite microcrystal of popping oil.Compare with Comparative Examples, its spacing increases to 0.361 nm by 0.344 nm, and crystallite thickness is reduced to 1.43 nm by 2.34 nm, and the microcrystalline carbon atomic shell is reduced to 5 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 1.66 mL/g by 1.17 mL/g, and specific surface area is by 2216 m
2/ g is increased to 3089 m
2/ g, mean pore size increases to 2.15 nm by 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. 3 is the cyclic voltammetry curve of activated carbon electrodes when sweep velocity is 0.5 mV/s.Curve has kept good rectangular characteristic equally, compares with Comparative Examples, and when the electric potential scanning direction was reversed, sample had better current response characteristic, explained that its power characteristic is better.The specific volume that calculates sample is 456F/g, exceeds 64.03% than the specific volume of the gac 278F/g of Comparative Examples preparation.Fig. 4 is the change curve of activated carbon electrodes normalization method specific volume with scan speed.When sweeping speed when increasing to 8 mV/s; When its specific volume is 0.5 mV/s 73.21% of specific volume, be higher than the specific volume conservation rate of comparison sample 67.61%, the sample of illustrative embodiment has better power characteristic; This is because in the gac of embodiment preparation; The external surface area proportion is higher, and mean pore size is also bigger, helps the migration of electrolyte ion.
In a word, through the preparatory charing and the puffing and modifying of refinery coke, under the identical situation of other processing condition, the specific surface area of gac is by 2216 m
2/ g brings up to 3089 m
2/ g, specific volume is brought up to 456 F/g by 278 F/g, and when sweep velocity had 0.5 mV/s to increase to 8 mV/s, the specific volume conservation rate brought up to 73.21% by 67.61%.
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 popping oil.
Table 4 is the porosity parameter of embodiment 1 gained gac.
Table 1
Table 2
Table 3
Table 4
Claims (1)
1. an activated carbon for super capacitors preparation method is characterized in that method steps is:, grind the refinery coke fragmentation; 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 30 ~ 50% HNO
3The aqueous solution, in 30-50 ℃ of stirring reaction 4 h, with the product suction filtration, flushing is to neutral repeatedly; 50 ℃ of dryings are carried out expandedly then in 130-160 ℃, be the mixed of KOH: refinery coke=3:1 according to mass ratio with KOH and popping oil 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.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11083468B2 (en) | 2004-07-09 | 2021-08-10 | Stryker Corporation | Surgical blade assembly including a guide bar and a blade |
| US11090061B2 (en) | 2005-09-10 | 2021-08-17 | Stryker Corporation | Surgical saw blade |
| US11160561B2 (en) | 2015-05-12 | 2021-11-02 | Stryker European Holdings I, Llc | Surgical sagittal blade cartridge with a guide bar |
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| CN1215694A (en) * | 1997-10-29 | 1999-05-05 | 胡福昌 | Method for producing high performance active carbon from nut shell |
| CN1935641A (en) * | 2006-09-13 | 2007-03-28 | 大连理工大学 | Method for preparing carbon molecular sieve by intercalation of petrol coke |
| CN101468797A (en) * | 2007-12-24 | 2009-07-01 | 徐文东 | Preparation of super active carbon material |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1215694A (en) * | 1997-10-29 | 1999-05-05 | 胡福昌 | Method for producing high performance active carbon from nut shell |
| CN1935641A (en) * | 2006-09-13 | 2007-03-28 | 大连理工大学 | Method for preparing carbon molecular sieve by intercalation of petrol coke |
| CN101468797A (en) * | 2007-12-24 | 2009-07-01 | 徐文东 | Preparation of super active carbon material |
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| 时志强等: "预炭化对KOH活化石油焦的结构及电容性能的影响", 《无机材料学报》 * |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11083468B2 (en) | 2004-07-09 | 2021-08-10 | Stryker Corporation | Surgical blade assembly including a guide bar and a blade |
| US11090061B2 (en) | 2005-09-10 | 2021-08-17 | Stryker Corporation | Surgical saw blade |
| US12029436B2 (en) | 2005-09-10 | 2024-07-09 | Stryker European Operations Holdings Llc | Surgical saw for actuating a saw blade with an oscillating head, the saw having a coupling assembly for releasably holding the saw blade |
| US11160561B2 (en) | 2015-05-12 | 2021-11-02 | Stryker European Holdings I, Llc | Surgical sagittal blade cartridge with a guide bar |
| US11241240B2 (en) | 2015-05-12 | 2022-02-08 | Stryker European Operations Holdings Llc | Surgical sagittal blade cartridge with a reinforced guide bar |
| US11890021B2 (en) | 2015-05-12 | 2024-02-06 | Stryker European Operations Holdings Llc | Surgical sagittal blade cartridge with a reinforced guide bar |
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Application publication date: 20121219 |