CN101531358A - Method for preparing porous carbon electrode material used for super capacitor - Google Patents
Method for preparing porous carbon electrode material used for super capacitor Download PDFInfo
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- CN101531358A CN101531358A CN200910043228A CN200910043228A CN101531358A CN 101531358 A CN101531358 A CN 101531358A CN 200910043228 A CN200910043228 A CN 200910043228A CN 200910043228 A CN200910043228 A CN 200910043228A CN 101531358 A CN101531358 A CN 101531358A
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Abstract
The invention belongs to the technical field of porous carbon material preparation and provides a method for preparing an electrode carbon material used for a super capacitor with excellent specific energy and specific power performance. In the method, phenol compound such as hydroxyphenol and the like reacts with methanol in a hydro-thermal reactor completely in the presence of catalyst and added heat instable polymer polyethyleneglycol in certain proportion to obtain dark red colloid which is dried completely and is carbonized in a tubular furnace under the protection of nitrogen, and a required product is obtained. The quality specific capacitance of the product in aqueous electrolyte can be 170F/g, and the power density and the energy density can be 39KW/Kg and 3.8Wh/Kg respectively. The quality specific capacitance of the product in organic electrolyte can be 120F/g, and the power density and the energy density can be 22KW/Kg and 12Wh/Kg respectively. The electrode carbon material of the super capacitor has the advantages of simple preparation method, high specific capacitance and excellent specific energy and specific power performance.
Description
Affiliated field:
The invention belongs to the porous carbon material preparation field.Be specifically related to a kind of preparation method of porous carbon electrode material used for super capacitor.
Background technology:
Ultracapacitor is the novel energy-storing device of a kind of energy-storage property between traditional capacitor and secondary cell, have the power density higher than secondary cell, than the higher energy density of traditional capacitor, under the high power discharge working condition secondary cell and the incomparable advantage of traditional capacitor are being arranged in short-term.Ultracapacitor is in the transition of important electronic system power supply, and especially there is outstanding application prospect the aspects such as super large pulse power emission power as startup braking power, microwave weapon and the laser weapon of electromobile.
Ultracapacitor has and the similar structure of battery, mainly is made of electrolytic solution and electrode materials.Electrode materials is the important factor that influences its performance.What at present, realize civilian commercialization electrode materials mainly is gac and activated carbon fiber.The general ratio electric capacity of gac in the aqueous electrolysis liquid system is below 150F/g, and energy density is less than 3Wh/Kg.
Ultracapacitor is as a kind of power application product, and the high current charge-discharge ability is to weigh the key factor of its performance quality.The commercialization ultracapacitor is along with charging and discharging currents density improves at present, and the energy density of electrical condenser declines to a great extent, and specific energy-specific power poor performance has limited its further popularization.The major cause one that causes this phenomenon is that ultracapacitor adopts conventional gac as electrode materials, the duct of absorbent charcoal material is narrow and crooked, limited the electrolyte ion diffusive migration of portion within it, electrolyte ion has little time to form the electrostatic double layer store charge when causing high current charge-discharge on the most surfaces of electrode, have only the surface of small part larger aperture hole to obtain utilizing, thereby cause the energy density of electrical condenser to descend.On the other hand, gac internal void aperture is more little, and hole electrolyte inside resistance is big more, and the internal resistance of electrical condenser is big more, and requiring the expenditure of energy during the capacitor stores electric charge overcomes internal resistance, causes capacitor charging/discharging efficient and energy density to reduce.
In theory, the specific surface area of raw material of wood-charcoal material is big more, and its ratio electric capacity that forms the electrostatic double layer store charge is high more, but form electrostatic double layer the hole pore size of raw material of wood-charcoal material is had certain requirement.Simultaneously, the pore size distribution of raw material of wood-charcoal material is one of factor that influences the electrical condenser internal resistance, and the aperture of raw material of wood-charcoal material is big more, and its specific surface area is more little.Raw material of wood-charcoal material specific surface area surpasses 2500m
2During/g, its hole mainly is the micropore distribution that is difficult to form electrostatic double layer.Therefore, make the charcoal based super capacitor under high current density discharges and recharges condition, have good specific energy-specific power performance, must optimize the specific surface area of raw material of wood-charcoal material and the relation of pore size distribution.
Announced that as granted patent " a kind of preparation method of meso-porous carbon material " (patent No. 2006100223663.0) a kind of solgel reaction system of tensio-active agent self-assembly of utilizing prepares high specific surface area and mesoporous raw material of wood-charcoal material technology, the raw material of wood-charcoal material specific surface area of preparation reaches 2400m
2/ g, mean pore size reaches 8nm, and the ratio electric capacity in the aqueous electrolyte is between 120-200F/g, and the ratio electric capacity in the organic electrolyte is at 90-130F/g.Publication " the porous carbon electrode preparation method of high rate charge-discharge performance ultracapacitor " (number of patent application 200810053475.1) has been announced a kind of porous carbon material technology of preparing that adopts the preparation of template charring to be applicable to high rate charge-discharge performance ultracapacitor, the electrode of this raw material of wood-charcoal material preparation is in aqueous electrolyte, when working with the current density of 24A/g, still can reach 110F/g than electric capacity, power density reaches 12KW/Kg.The defective of this method is to need to remove inorganic template in preparation raw material of wood-charcoal material process, and is of a high price.
As seen, adopt appropriate means that the pore texture of electrode of super capacitor raw material of wood-charcoal material is controlled, can reach the purpose of improving its specific energy-specific power performance.
Summary of the invention:
The present invention aims to provide the electrode of super capacitor raw material of wood-charcoal preparation method for material of a kind of specific energy-specific power excellent performance.The raw material of wood-charcoal material that adopts this method to prepare is fit to be applied to the ultracapacitor of high power density work.
The preparation process of method provided by the invention is as follows:
The mass ratio of control phenol compound such as Resorcinol and total water amount is 1:(5～20).Earlier with phenol compound such as Resorcinol and formaldehyde in molar ratio 1:2 be dissolved in a small amount of distilled water, be 1:(25～200 in mol ratio with phenol compound such as Resorcinol) ratio add catalyzer.Above-mentioned solution is fully reaction at a certain temperature, and can make atresia phenolic aldehyde xerogel after dehydrating.According to the mass ratio with phenolic aldehyde xerogel theoretical yield is (1～8): 1 scope, and the weighing polyoxyethylene glycol, and it is dissolved in the distilled water of residual content.Two kinds of solution are mixed, stir after 0.5～12 hour, inject hydrothermal reaction kettle, placed 72 hours for 50～70 ℃, placed 96 hours for 60～90 ℃ again, obtain the garnet transparent colloid.The colloid thorough drying, nitrogen protection in the tube furnace, charing is 1～4 hour under 700～1000 ℃ of temperature, obtains desired product.
The phenol monomer of the synthetic carbon precursor polymkeric substance that the present invention is used comprises Resorcinol, meta-cresol, mixture cresol etc.
The catalyzer of using among the present invention is yellow soda ash, sodium hydroxide, potassium hydroxide etc.
The molecular weight of the polyoxyethylene glycol that uses among the present invention is between 400～20000.
General polymer mixes the mixed with polymers charing that charring is utilized two kinds of thermostability differences, can be formed micro phase separation structure, the polymkeric substance that thermostability is high becomes carbon matrix through high temperature carbonization, the polymkeric substance that thermostability is low then decomposes gasification in heat treatment process, stay hole in carbonizing production.The blending ratio of polymkeric substance and the consistency difference between the polymkeric substance cause the phase separation structure difference, thereby can be implemented in nm～mm scope the pore texture of raw material of wood-charcoal material are effectively regulated.
The present invention mixes on the charring basis at general polymer, in the organic monomer solution of synthetic carbon precursor polymkeric substance, sneak into thermal unstable polymer with perforating action, set about from the adding proportion and molecular size three aspects of control carbon precursor polymer molecule network structure and mixing gasifying polymkeric substance, reach the pore texture of more effectively controlling the raw material of wood-charcoal material, satisfy the needs of the ultracapacitor of high power density work.
The raw material of wood-charcoal material of processing method preparation of the present invention all has higher ratio electric capacity in water-based or organic electrolyte, and has excellent specific energy-specific power performance, still can keep high energy density when high power density is worked.The raw material of processing method of the present invention is easy to get, technology is simple, cost is lower, the improved performance of ultracapacitor is had important realistic meaning, thereby the present invention has the potential application value.
Description of drawings
Accompanying drawing 1 is the pore size distribution curve of embodiment 1 gained porous charcoal.
Accompanying drawing 2 is the charging and discharging curve of embodiment 1 gained porous charcoal in aqueous electrolyte.
Accompanying drawing 3 is the curve that the specific storage of embodiment 1 gained porous charcoal in aqueous electrolyte changes with working current density.
Embodiment:
Taking by weighing Resorcinol 11g, is that the ratio of 1:2 is measured formaldehyde solution in the mol ratio with Resorcinol, is dissolved in 30 ml waters, adds yellow soda ash 0.15g.Get molecular weight and be 4000 polyoxyethylene glycol 30g, it is dissolved in 40 ml waters.Two kinds of solution mix, and stir 30 minutes, inject hydrothermal reaction kettle, place 72 hours for 55 ℃, place 96 hours for 85 ℃ again.The colloid that obtains is placed thorough drying in the air, changes tube furnace over to, nitrogen protection, and 900 ℃ are incubated 1 hour, obtain product.The specific surface area that obtains the raw material of wood-charcoal material is 740m
2/ g, pore volume are 0.70cm
3/ g, mean pore size is about 3.0nm.When working with the 0.1A/g current density in aqueous electrolyte, the quality of product is 132F/g than electric capacity, and the workload current density improves 100 times, and the quality of product still has 97F/g than electric capacity.
Embodiment 2
Taking by weighing Resorcinol 11g, is that the ratio of 1:2 is measured formaldehyde solution in the mol ratio with Resorcinol, is dissolved in 30 ml waters, adds sodium hydroxide 0.10g.Get molecular weight and be 4000 polyoxyethylene glycol 50g, it is dissolved in 50 ml waters.Two kinds of solution mix, and stir 2 hours, inject hydrothermal reaction kettle, place 72 hours for 60 ℃, place 96 hours for 80 ℃ again.The colloid that obtains is placed thorough drying in the air, changes tube furnace over to, nitrogen protection, and 900 ℃ are incubated 2 hours, obtain product.The specific surface area that obtains the raw material of wood-charcoal material is 910m
2/ g, pore volume are 1.15cm
3/ g, mean pore size is about 2.5nm, and when working with the 0.1A/g current density in aqueous electrolyte, the quality of product is 170F/g than electric capacity, and the workload current density improves 100 times, and the quality of product is 100F/g than electric capacity.
Embodiment 3
Take by weighing Resorcinol 11g,, be dissolved in 30 ml waters, add yellow soda ash 0.20g in measuring formaldehyde solution for the 1:2 ratio with the mol ratio of Resorcinol.Get molecular weight and be 20000 polyoxyethylene glycol 30g, it is dissolved in 60 ml waters.Two kinds of solution mix, and stir 2 hours, inject hydrothermal reaction kettle, place 72 hours for 60 ℃, place 96 hours for 90 ℃ again.The colloid that obtains is placed thorough drying in the air, changes tube furnace over to, nitrogen protection, and 900 ℃ are incubated 2 hours, obtain product.The specific surface area that obtains the raw material of wood-charcoal material is 750m
2/ g, pore volume are 0.80cm
3/ g, mean pore size is about 5.5nm.When working with the 0.1A/g current density in aqueous electrolyte, the quality of product is 150F/g than electric capacity, and the workload current density improves 100 times, and the quality of product is 110F/g than electric capacity.
Embodiment 4
Take by weighing Resorcinol 11g,, be dissolved in 20 ml waters, add potassium hydroxide 0.10g in measuring formaldehyde solution for the 1:2 ratio with the mol ratio of Resorcinol.Get molecular weight and be 20000 polyoxyethylene glycol 40g, it is dissolved in 90 ml waters.Two kinds of solution mix, and stir 3 hours, inject hydrothermal reaction kettle, place 72 hours for 70 ℃, place 96 hours for 90 ℃ again.The colloid that obtains is placed thorough drying in the air, changes tube furnace over to, nitrogen protection, and 900 ℃ are incubated 3 hours, obtain product.The specific surface area that obtains the raw material of wood-charcoal material is 870m
2/ g, pore volume are 1.32cm
3/ g, mean pore size is about 4.8nm.When working with the 0.1A/g current density in aqueous electrolyte, the quality of product is 170F/g than electric capacity, and the workload current density improves 100 times, and the quality of product is 130F/g than electric capacity.Power density and energy density can reach 39KW/Kg, 3.8Wh/Kg respectively.
Take by weighing Resorcinol 11g,, be dissolved in 20 ml waters, add yellow soda ash 0.35g in measuring formaldehyde solution for the 1:2 ratio with the mol ratio of Resorcinol.Get molecular weight and be 20000 polyoxyethylene glycol 50g, it is dissolved in 100 ml waters.Two kinds of solution mix, and stir 4 hours, inject hydrothermal reaction kettle, place 72 hours for 70 ℃, place 96 hours for 85 ℃ again.The colloid that obtains is placed thorough drying in the air, changes tube furnace over to, nitrogen protection, and 900 ℃ are incubated 4 hours, obtain product.The specific surface area that obtains the raw material of wood-charcoal material is 1100m
2/ g, pore volume are 1.56cm
3/ g, mean pore size is about 4.4nm.When working with the 0.1A/g current density in aqueous electrolyte, the quality of product is 215F/g than electric capacity, and the workload current density improves 100 times, and the quality of product is 165F/g than electric capacity.Power density and energy density can reach 38KW/Kg, 4.9Wh/Kg respectively.When working with the 0.1A/g current density in organic electrolyte, the quality of product is 120F/g than electric capacity, and the workload current density improves 100 times, and the quality of product is 75F/g than electric capacity.Power density and energy density can reach 22KW/Kg, 12Wh/Kg respectively.
Claims (6)
1, a kind of preparation method of porous carbon electrode material used for super capacitor is characterized in that comprising the steps:
(1) mass ratio of control phenol compound such as Resorcinol and total water amount is 1:(5～20).Earlier with phenol compound such as Resorcinol and formaldehyde in molar ratio 1:2 be dissolved in a small amount of distilled water, be 1:(25～200 in mol ratio with phenol compound such as Resorcinol) ratio add catalyzer, obtain the carbon precursor reaction soln.
(2) carbon precursor reaction soln fully reaction at a certain temperature, and can make atresia phenolic aldehyde xerogel after dehydrating.According to the mass ratio (1～8) of phenolic aldehyde xerogel theoretical yield: 1 scope, weighing polyoxyethylene glycol, and it is dissolved in the distilled water of residual content.
(3) (1), (2) two kinds of solution are mixed, stir after 0.5～12 hour, inject hydrothermal reaction kettle, placed 72 hours for 50～70 ℃, placed 96 hours for 60～90 ℃ again, obtain the garnet transparent colloid.The colloid thorough drying, nitrogen protection in the tube furnace, charing is 1～4 hour under 700～1000 ℃ of temperature, obtains desired product.
2, the method for claim 1, the phenol monomer that it is characterized in that synthetic carbon precursor polymkeric substance comprise can with the Resorcinol of formaldehyde generation polycondensation, meta-cresol, mixture cresol etc.
3, the method for claim 1 is characterized in that using heat-labile polyoxyethylene glycol to be the pore-forming polymkeric substance that gasifies.
4, the method for claim 1, the molecular weight that it is characterized in that the polyoxyethylene glycol that uses is between 400～20000.
5, the method for claim 1, it is characterized in that (1), (2) two kinds of solution mix and fully stir after, under the condition that has thermal unstable polymer to exist, in hydrothermal reaction kettle, finish the formation reaction of carbon precursor polymkeric substance.
6, the method for claim 1 is characterized in that being warming up to 700～1000 ℃ with the temperature rise rate of 5～20 ℃/min, and is incubated 1～4 hour.
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Cited By (8)
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|---|---|---|---|---|
| CN101947422A (en) * | 2010-08-24 | 2011-01-19 | 天津大学 | Alkaline solution gel and preparation method as well as application thereof |
| CN101950683A (en) * | 2010-09-09 | 2011-01-19 | 江西财经大学 | Preparation method of semi-spherical active carbon electrode material of super capacitor |
| CN101697322B (en) * | 2009-10-15 | 2011-01-26 | 青岛大学 | Method for preparing porous carbon electrode material |
| WO2012070013A1 (en) * | 2010-11-26 | 2012-05-31 | Basf Se | Process for manufacturing nitrogen-containing porous carbonaceous material |
| CN102592698A (en) * | 2010-11-23 | 2012-07-18 | 哈钦森公司 | Sulphur-modified porous carbon material, method for preparing same and uses thereof for storing and redelivering power |
| CN105523539A (en) * | 2016-01-25 | 2016-04-27 | 新余学院 | Preparation method of porous carbon material |
| CN106365140A (en) * | 2015-07-22 | 2017-02-01 | 中国人民解放军63971部队 | High electric conductivity mesoporous carbon preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101697322B (en) * | 2009-10-15 | 2011-01-26 | 青岛大学 | Method for preparing porous carbon electrode material |
| CN101947422A (en) * | 2010-08-24 | 2011-01-19 | 天津大学 | Alkaline solution gel and preparation method as well as application thereof |
| CN101947422B (en) * | 2010-08-24 | 2012-06-13 | 天津大学 | Alkaline solution gel and preparation method as well as application thereof |
| CN101950683A (en) * | 2010-09-09 | 2011-01-19 | 江西财经大学 | Preparation method of semi-spherical active carbon electrode material of super capacitor |
| CN101950683B (en) * | 2010-09-09 | 2012-07-11 | 江西财经大学 | Preparation method of semi-spherical active carbon electrode material of super capacitor |
| CN102592698A (en) * | 2010-11-23 | 2012-07-18 | 哈钦森公司 | Sulphur-modified porous carbon material, method for preparing same and uses thereof for storing and redelivering power |
| CN102592698B (en) * | 2010-11-23 | 2016-06-01 | 哈钦森公司 | The modified Integrate porous carbon-based material of sulfur, its preparation method, and application thereof |
| WO2012070013A1 (en) * | 2010-11-26 | 2012-05-31 | Basf Se | Process for manufacturing nitrogen-containing porous carbonaceous material |
| CN106365140A (en) * | 2015-07-22 | 2017-02-01 | 中国人民解放军63971部队 | High electric conductivity mesoporous carbon preparation method |
| CN105523539A (en) * | 2016-01-25 | 2016-04-27 | 新余学院 | Preparation method of porous carbon material |
| CN108584915A (en) * | 2018-06-03 | 2018-09-28 | 湖南科技大学 | A kind of cellular carbon nanomaterial of regular hexagon and preparation method thereof |
| CN108584915B (en) * | 2018-06-03 | 2021-09-14 | 湖南科技大学 | Regular hexagonal honeycomb-shaped carbon nano material and preparation method thereof |
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Open date: 20090916 |