CN1410350A - Method of increasing mesopore actire carbon specific capacitance by mixing with cheap metal - Google Patents
Method of increasing mesopore actire carbon specific capacitance by mixing with cheap metal Download PDFInfo
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- CN1410350A CN1410350A CN02130062A CN02130062A CN1410350A CN 1410350 A CN1410350 A CN 1410350A CN 02130062 A CN02130062 A CN 02130062A CN 02130062 A CN02130062 A CN 02130062A CN 1410350 A CN1410350 A CN 1410350A
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- activated carbon
- resol
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Abstract
A process for increasing the specific capacitance of mesoporous activated carbon by doping cheap metal includes such steps as proportionally mixing phenolic resin, Cu (CH3COO)2 or Ni(CH3COO)2, ferrocene, hexamethinetetraamine and methanol, solidifying at 150-180 deg.C for 3-5 hr, carbonizing at 700-900 deg.c and activating with steam for 0.5-2 hr. Its advantages are high specific capacitance (130F/g), high charge-discharge efficiency up to 99% or more, and high stability.
Description
Affiliated field:
The invention belongs to a kind of preparation method of mesopore activated carbon.Being specifically related to a kind of is the method for feedstock production electrode material for super capacitor with mesopore activated carbon with resol and cheap organometallic compound.
Ultracapacitor is a kind of novel electrochemical energy accumulating device, has advantages such as high power density, high cycle life and environmentally safe, is widely used in backup power source, electromobile etc.Ultracapacitor is a kind of advanced person's a high-energy storage element, and its power density is far above common batteries, and energy density is far above traditional capacitance, thereby has filled up the blank between these two conventional arts.Ultracapacitor has higher specific power and longer cycle life than traditional rechargeable cell (comprising nickel metal hydride battery and lithium ion battery), and its specific power reaches per kilogram kilowatt more than the order of magnitude, and cycle life is in (working life is more than 5 years) more than ten thousand times.Ultracapacitor expects that from former finished product is all pollution-free, not only can not damage to some extent the environment and the eubiosis, on the contrary because of its substitutability to store battery, has reduced environmental pollution indirectly thereby directly reduced the store battery usage quantity or prolonged its life-span.Therefore, high performance electric chemical super capacitor has of crucial importance and wide application prospect at aspects such as mobile communication, information technology, electromobile, aerospace and science and techniques of defence.
The accumulate mechanism one of super electric electrical condenser is to utilize the bigger specific surface area of electrode materials to form the electrostatic double layer store charge between electrode and electrolytic solution, this process does not have chemical reaction to take place, and material that specific surface area is bigger such as gac, activated carbon fiber, charcoal gel etc. all once were used as active electrode material research and part material (as gac) industrialization.The 2nd, the pseudo-capacitance phenomenon utilizes some metallic compounds (as RuO
2XH
2O etc.) and electrolytic solution the two dimensional oxidation reduction reaction takes place on its surface, electrode is by the stored energy of faraday's electrode reaction fast.The ratio electric capacity of studying compounds such as maximum rutheniums, iridium is higher, but is noble metal, is difficult to bear on price.Discovering in addition on the surface of compounds such as some cheap metals such as copper, cobalt, nickel, manganese also has the pseudo-capacitance phenomenon to take place, but it is lower than electric capacity, and influence is used.
Gac has aboundresources as a kind of relatively inexpensive material, and characteristics such as pore structure distributes well, inactive surfaces, excellent property are suitable for making on a large scale double layer capacitor.Pore size distribution to gac when double layer capacitor discharges and recharges requires than higher.In electrical condenser, the size of the micropore of carbon electrode should help the diffusion of electrolytic solution, and at-25 ℃ low temperature, electrolytic solution viscosity increases especially, more be difficult to flow, the ratio that the above micropore volume of diameter 2nm is equivalent to total micropore volume directly has influence on the low temperature capacity of electrical condenser.The low-temperature performance that therefore will improve electrical condenser just requires the above micropore of more 2nm.Mesopore activated carbon is because the aperture broad helps the turnover of electrolytic solution in charge and discharge process, and the rapid large-current discharge performance is especially superior.But mesopore activated carbon is because specific surface area is less, generally at 1500m
2Below/the g, so energy stored is also less, influences the energy density and the power density of ultracapacitor when large-scale application.In order to improve the ratio electric capacity of mesopore activated carbon, investigator (Y.Sakata, Md.Azhar Uddin, et.a1, Electrochemical and Solid-State Lett.2000; 3:1-3) use cationic exchange resin adsorption Cu
2+Back charing obtains the gac of loaded metal ion, can improve to a certain extent and compare electric capacity.But this method steps is more loaded down with trivial details, and material price is higher, improves the manufacturing cost of electrical condenser during large-scale application greatly.
Summary of the invention:
The objective of the invention is to develop the preparation method of a kind of low cost of manufacture, mesopore content height and the simple doping metals mesopore activated carbon of method.
The preparation method of doping metals mesopore activated carbon is with resol, cheap organic metal salt, ferrocene, hexamethylenetetramine, methanol mixed among the present invention, and stirring and refluxing is cured, charing and activation obtain mesopore activated carbon again.
Preparation method of the present invention comprises the steps: that (1) is with resol, Cu (CH
3COO)
2Or Ni (CH
3COO)
2, ferrocene, hexamethylenetetramine, methyl alcohol be by 100: 0.5～2: 0.3～0.9: 8～15: the weight ratio of 150-200 is mixed, stirring and refluxing 1-2 hour, then methyl alcohol is removed in the mixed solution underpressure distillation, solidified 3-5 hour down at 150-180 ℃; (2) mixture after will solidifying is crushed to granularity＜100 μ m, in 800～900 ℃ of charing 0.5～1hr, and feeds steam activation 0.5～2hr, can make the equally distributed mesopore activated carbon of metal ion.
The present invention adopts the method that adds metal ion in activated carbon precursor, can make metal ion disperse very evenly, as electrical double layer capacitor electrodes the time, utilizes the pseudo-capacitance effect of metal particle can improve the ratio electric capacity of material greatly.The mesopore activated carbon that this method makes is at 1mA/cm
2Be 90～130F/g than electric capacity during charging and discharging currents density.
Embodiments of the invention are as follows:
Comparative Examples
Get 50g resol, mix with 6.2g hexamethylenetetramine, 0.3g ferrocene, put into flask, add 100g methyl alcohol, the 2h that refluxes in 55～60 ℃ water-bath stirs.Remove methyl alcohol 50 ℃ of decompressions then, under 150 ℃ of conditions, solidify 5h.Resin after the curing is pulverized and is granularity＜100m.Get cured resin 5g,, use steam activation 1h, gained gac specific surface area 780m at 800 ℃ of following charing 0.5h
2/ g, pore structure is middle pore distribution, than electric capacity 82F/g.
Embodiment 1
Get 50g resol, mix, put into flask, add 100g methyl alcohol, in 55～60 ℃ water-bath, refluxed 2 hours, stir with 6.2g hexamethylenetetramine, 0.3g ferrocene, 0.25g neutralized verdigris.Remove methyl alcohol 50 ℃ of decompressions then, under 150 ℃ of conditions, solidify 5h.Resin after the curing is pulverized and is granularity＜100m.Get cured resin 5g,, use steam activation 1 hour, gained gac specific surface area 642m 800 ℃ of following charings 0.5 hour
2/ g, pore structure is middle pore distribution, than electric capacity 110F/g.
Embodiment 2
Get 50g resol, mix, put into flask, add 100g methyl alcohol, in 55～60 ℃ water-bath, refluxed 2 hours, stir with 4g hexamethylenetetramine, 0.45g ferrocene, 0.5g neutralized verdigris.Remove methyl alcohol 50 ℃ of decompressions then, under 150 ℃ of conditions, solidified 5 hours.Resin after the curing is pulverized and is granularity＜100m.Get cured resin 5g, 850 ℃ of following charings 1 hour, gained gac specific surface area 436m
2/ g, pore structure is middle pore distribution, than electric capacity 105F/g.
Embodiment 3
Get 50g resol, mix, put into flask, add 100g methyl alcohol, in 55～60 ℃ water-bath, refluxed 2 hours, stir with 7.5g hexamethylenetetramine, 0.15g ferrocene, 0.75g neutralized verdigris.Remove methyl alcohol 50 ℃ of decompressions then, under 180 ℃ of conditions, solidified 3 hours.Resin after the curing is pulverized and is granularity＜100m.Get cured resin 5g,, use steam activation 1.5 hours, gained gac specific surface area 753m 900 ℃ of following charings 0.5 hour
2/ g, pore structure is middle pore distribution, than electric capacity 130F/g.
Embodiment 4
Get 50g resol, mix, put into flask, add 100g methyl alcohol, in 55～60 ℃ water-bath, refluxed 2 hours, stir with 6.2g hexamethylenetetramine, 0.25g ferrocene, 1g neutralized verdigris.Remove methyl alcohol 50 ℃ of decompressions then, under 170 ℃ of conditions, solidified 4 hours.Resin after the curing is pulverized and is granularity＜100m.Get cured resin 5g,, use steam activation 1 hour, gained gac specific surface area 693m 850 ℃ of following charings 1 hour
2/ g, pore structure is middle pore distribution, than electric capacity 120F/g.
Embodiment 5
Get 50g resol, mix, put into flask, add 75g methyl alcohol, in 55～60 ℃ water-bath, refluxed 2 hours, stir with 5g hexamethylenetetramine, 0.4g ferrocene, 0.5g nickel acetate.Remove methyl alcohol 50 ℃ of decompressions then, under 180 ℃ of conditions, solidified 3 hours.Resin after the curing is pulverized and is granularity＜100m.Get cured resin 5g,, use steam activation 1h, gained gac specific surface area 715m at 800 ℃ of following charing 0.5h
2/ g, pore structure is middle pore distribution, than electric capacity 102F/g.
Embodiment 6
Get 50g resol, mix, put into flask, add 100g methyl alcohol, in 55～60 ℃ water-bath, refluxed 2 hours, stir with 6g hexamethylenetetramine, 0.2g ferrocene, 1g nickel acetate.Remove methyl alcohol 50 ℃ of decompressions then, under 150 ℃ of conditions, solidified 5 hours.Resin after the curing is pulverized and is granularity＜100m.Get cured resin 5g,, use steam activation 2h, gained gac specific surface area 885m at 900 ℃ of following charing 0.5h
2/ g, pore structure is middle pore distribution, than electric capacity 118F/g.
Claims (3)
1. the preparation method of the mesopore activated carbon of an even doping cheap metal, it is to be raw material with resol, by adding organometallic compound, make activated carbon precursor after mixing, solidifying the back is activator with water vapour, carries out carbonization-activation at 700～900 ℃ and makes the homodisperse mesopore activated carbon of metal.
2. the method for claim 1 is characterized in that the thorough mixing in methanol solution with organometallic compound and resol.Wherein resol, Cu (CH
3COO)
2Or Ni (CH
3COO)
2, ferrocene, hexamethylenetetramine, methyl alcohol be by 100: 0.5～2: 0.3～0.9: 8～15: the mixed of 150-200.
3. method as claimed in claim 2 is characterized in that used organometallic compound is neutralized verdigris, nickel acetate.
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| CNB021300623A CN1171782C (en) | 2002-08-19 | 2002-08-19 | Method of increasing mesopore actire carbon specific capacitance by mixing with cheap metal |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1753116B (en) * | 2004-09-20 | 2010-04-28 | 中国科学院电工研究所 | Carbon base porous electrode film used in super capacitor and its preparation method |
| CN102097620A (en) * | 2011-01-13 | 2011-06-15 | 华南师范大学 | Lead-loaded carbon aerogel and preparation method thereof |
| CN101604580B (en) * | 2009-04-03 | 2011-10-05 | 中国科学院上海硅酸盐研究所 | Method for preparing porous carbon electrode material by method decomposing monophyletic compound at one step |
| CN103803545A (en) * | 2014-01-18 | 2014-05-21 | 复旦大学 | Method for preparing copper-doped activated carbon by utilizing complexing process |
| CN106449145A (en) * | 2016-11-08 | 2017-02-22 | 铜陵市启动电子制造有限责任公司 | Supercapacitor electrode material added with manganese cobalt oxide foamed nickel composite material |
| CN106853968A (en) * | 2016-12-19 | 2017-06-16 | 河南超威电源有限公司 | A kind of preparation method of multielement codope lead carbon battery activated carbon |
-
2002
- 2002-08-19 CN CNB021300623A patent/CN1171782C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1753116B (en) * | 2004-09-20 | 2010-04-28 | 中国科学院电工研究所 | Carbon base porous electrode film used in super capacitor and its preparation method |
| CN101604580B (en) * | 2009-04-03 | 2011-10-05 | 中国科学院上海硅酸盐研究所 | Method for preparing porous carbon electrode material by method decomposing monophyletic compound at one step |
| CN102097620A (en) * | 2011-01-13 | 2011-06-15 | 华南师范大学 | Lead-loaded carbon aerogel and preparation method thereof |
| CN103803545A (en) * | 2014-01-18 | 2014-05-21 | 复旦大学 | Method for preparing copper-doped activated carbon by utilizing complexing process |
| CN106449145A (en) * | 2016-11-08 | 2017-02-22 | 铜陵市启动电子制造有限责任公司 | Supercapacitor electrode material added with manganese cobalt oxide foamed nickel composite material |
| CN106853968A (en) * | 2016-12-19 | 2017-06-16 | 河南超威电源有限公司 | A kind of preparation method of multielement codope lead carbon battery activated carbon |
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| Publication number | Publication date |
|---|---|
| CN1171782C (en) | 2004-10-20 |
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