CN101955182A - Ultracapacitor activated carbon in sulfuric acid electrolyte and application thereof - Google Patents
Ultracapacitor activated carbon in sulfuric acid electrolyte and application thereof Download PDFInfo
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- CN101955182A CN101955182A CN 201010292270 CN201010292270A CN101955182A CN 101955182 A CN101955182 A CN 101955182A CN 201010292270 CN201010292270 CN 201010292270 CN 201010292270 A CN201010292270 A CN 201010292270A CN 101955182 A CN101955182 A CN 101955182A
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- Y02E60/13—Energy storage using capacitors
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Abstract
The invention discloses an ultracapacitor activated carbon in sulfuric acid electrolyte and application thereof. The activated carbon is prepared by the following method: charring aromatic polymer, mixing the carbide obtained by charring and an alkali metal compound, and activating at high temperature in an inert atmosphere to prepare the activated carbon, wherein the mass ratio of the carbide to the alkali metal compound is 0.1-15. The prepared activated carbon has the advantages of readily available raw materials, low cost, mild preparation condition, easy industrial production, good electrochemical performance under lead-acid storage battery environment, higher specific capacitance, no obvious capacity attenuation after 10,000 times of circulation, particularly outstanding charging and discharging performance under heavy current, good capacitance property in concentrated sulfuric acid, and capacity of being used as a better candidate material for an ultracapacitor storage battery.
Description
Technical field
The present invention relates to super capacitor material, be specifically related to a kind of ultracapacitor gac that is used for sulfuric acid electrolyte.
Background technology
Ultracapacitor also claims electrochemical capacitor, is a kind of novel energy-storing device that grows up 20th century 70, the eighties.Because advantages such as ultracapacitor has the energy density higher than common batteries, excellent instantaneous charge-discharge performance, have extended cycle life, can be used as free of contamination backup power source and be used for multiple electrical equipment, simultaneously it can form composite power source jointly with battery provides power for electromobile, is subjected to extensive concern in recent years and is rapidly developed.
Lead acid cell experiences 150 years and does not wane, because advantages such as its technology maturation, cheap, safe, renewable circulation, in the decades that novel batteries such as cadmium nickel battery, nickel-hydrogen battery, lithium ion battery go on the market in succession, still can occupy the market share more than half securely.The lead acid cell energy density is higher, but power density is lower, and cycle life is shorter; The ultracapacitor power density is higher, and energy density is lower, has extended cycle life.With lead acid cell and the integrated shortcoming that can avoid separately of ultracapacitor, realize the high current charge-discharge of battery, and in lead acid cell, add the sulphating that the carbon material ultracapacitor can delay lead acid cell, prolong battery work-ing life, such integrated power supply is called super capacitance storage battery (Ultrabattery).
Gac is a kind of important industrial raw material, abundant, with low cost because of its source, as to have prosperity pore texture, bigger specific surface area and surface have the first-selected electrode materials that advantages such as rich functional groups, Stability Analysis of Structures become ultracapacitor, are widely used.
Why super capacitance storage battery can realize that high current charge-discharge is because integrated ultracapacitor possesses very high power density in it, this material (the interval 4-6mol/L sulfuric acid of concentration) under the lead acid storage battery pool environment that just requires to make ultracapacitor has high specific capacitance, and keeps stable in this higher concentration sulfuric acid.By generally can obtain the gac of high-ratio surface to the activation of common charcoal highly basic or phosphoric acid activation, these gacs capacitive properties in strong basicity, neutrality or slightly acidic electrolytic solution improves, but in than the vitriol oil, high-ratio surface, surface have the gac that enriches functional group just can show high specific capacitance, so common carbon source is still waiting research through the activated carbon application that highly basic activates or phosphoric acid activation makes in super capacitance storage battery.
Summary of the invention:
The objective of the invention is to overcome the deficiency of existing gac, provide a kind of bigger than electric capacity, can be applied to the gac in the super capacitance storage battery.
Above-mentioned purpose of the present invention is achieved by the following technical programs:
A kind of gac is prepared from by following method: with the aromatic polymer charing, after carbide that obtains after the charing and the alkali metal compound combination treatment in inert atmosphere high-temperature activation make; The quality ratio of described carbide and alkali metal compound is 0.1～15.
In above-mentioned gac, described aromatic polymer is meant aromatic copolycarbonate, aromatic urethane, poly-phthalic acid glycol ester, polyethylene glycol phthalate, poly-one or more mixture in phenylene-diacetic acid glycol ester, polyethylene terephthalate, the polyethylene terephthalate.
In above-mentioned gac, described alkali metal compound is to be selected from following at least a basic metal or this alkali-metal oxide compound, oxyhydroxide, halogenide, phosphoric acid salt, carbonate or nitrate, and described alkali metal compound is to be selected from following at least a alkali-metal compound: lithium, sodium, potassium, rubidium or caesium.
In above-mentioned gac, described charing is with aromatic polymer charing in 200～1000 ℃ of following inert atmospheres.
In above-mentioned gac, preferably 30 minutes～30 hours time that described charing or high-temperature activation are used; Described carbide and alkali metal compound combination treatment be meant carbide and alkali metal compound through ball-milling processing, adding distil water supersound process then, last vacuum impregnation; Described inert atmosphere is meant one or more blended atmosphere in nitrogen, argon gas, helium and the carbonic acid gas; Described high-temperature activation is meant that temperature is between 150～1000 ℃.
Above-mentioned gac can be used to prepare electrode, electrode be by in institute's preparing active carbon, add conductive agent, binding agent solvent to form slurry cream or slurries, it is coated on the collection liquid surface with preset thickness, and collector used herein is the paper tinsel or the sheet of lead, titanium or analogue.After also may be mixed in in other active substances, above-mentioned gac is coated on the electrode that other active electrode surface preparations make new advances, other active substances used herein such as lead powder, other active electrodes used herein such as lead acid cell positive and negative electrode stereotype.The gained electrode can be used for preparing electrochemical capacitor, and uses sulfuric acid as electrolytic solution.The gained electrochemical capacitor can be used to prepare energy storage device.
Compared with prior art, the present invention has following beneficial effect:
The present invention adopts aromatic polymer as starting material, earlier with the aromatic polymer charing, carbide is mixed with the alkali metal compound ball milling, high-temperature activation, alkali metal compound can generate basic metal simple substance with charcoal under the high temperature, and basic metal simple substance will further generate alkaline carbonate with the charcoal reaction, thereby the surface of corrosion charcoal, the specific surface of gac is increased, make activated carbon surface form oxygen-containing functional group simultaneously, thereby make active carbon with high specific surface area.
The raw material that the present invention prepares gac is easy to get, and is with low cost, and the preparation condition gentleness is easy to suitability for industrialized production.The gac of the present invention's preparation is in the existing good electrochemical of lead acid storage battery pool environment following table, have than height ratio electric capacity, 10000 times circulation back capacity does not have obvious decay, charge-discharge performance under big electric current is particularly outstanding, in the vitriol oil, show good capacitive properties, can be used as the better candidate material of super capacitance storage battery.
Embodiment
Embodiment 1
25g is gathered in the phenylene-diacetic acid glycol ester adding porcelain boat, put into tube furnace, logical nitrogen is warming up to 300 ℃, charing 2h.Get carbide after the charing, get this charcoal 2g, Repone K 8g; pour beaker into, in beaker, add distilled water 10ml, supersound process 0.5h behind the stirring 5min; 60 ℃ of following vacuum-drying 10h, dry intact after with the mixture porcelain boat of packing into, under the nitrogen protection; 800 ℃ of calcining 3h; behind the naturally cooling,, extremely neutral with distilled water flushing again with the flushing of 0.1mol/L dilute hydrochloric acid; dry 5h under 60 ℃ promptly gets target product.
Above-mentioned target product specific surface reaches 1800m
2/ g, is 80: 10: 5 with graphite, acetylene black, PVDF in mass ratio with institute's preparing active carbon: 5 ratio is mixed, add NMP furnishing slurry cream, adopt the titanium sheet to do collector, be coated on the titanium sheet, coating thickness 1mm, dry 5h obtains working electrode under 60 ℃, with 4.88mol/L sulfuric acid as electrolytic solution, assembling simulation ultracapacitor cell is carried out cyclic voltammetric and constant current charge-discharge test, 0.1A/g it reaches 130F/g than electric capacity under the current density, 10000 times circulation back capacity keeps 94.5%, and it is very little to decay.Test result shows that this material has higher specific storage and good electrochemical stability under the lead acid storage battery pool environment, is the ideal candidates material of affected super capacitance storage battery.
Embodiment 2
25g is gathered in the phenylene-diacetic acid second diamino ester adding porcelain boat, put into tube furnace, logical nitrogen is warming up to 600 ℃, charing 2h.Get carbide after the charing, get this charcoal 2g, salt of wormwood 8g; pour beaker into, in beaker, add distilled water 10ml, supersound process 0.5h behind the stirring 5min; 60 ℃ of following vacuum-drying 10h, dry intact after with the mixture porcelain boat of packing into, under the nitrogen protection; 600 ℃ of calcining 5h; behind the naturally cooling,, extremely neutral with distilled water flushing again with the flushing of 0.1mol/L dilute hydrochloric acid; dry 5h under 60 ℃ promptly gets target product.
Above-mentioned target product specific surface reaches 1930m
2/ g, is 80: 10: 5 with graphite, acetylene black, PVDF in mass ratio with institute's preparing active carbon: 5 ratio is mixed, add NMP furnishing slurry cream, adopt the titanium sheet to do collector, be coated on the titanium sheet, coating thickness 1.5mm, dry 5h obtains working electrode under 60 ℃, with 4.88mol/L sulfuric acid as electrolytic solution, assembling simulation ultracapacitor cell is carried out cyclic voltammetric and constant current charge-discharge test, 0.1A/g it reaches 110F/g than electric capacity under the current density, 10000 times circulation back capacity keeps 91.5%, and it is very little to decay.Test result shows that this material has higher specific storage and good electrochemical stability under the lead acid storage battery pool environment, is the ideal candidates material of affected super capacitance storage battery.
Embodiment 3
25g poly terephthalic acid second diamino ester is added in the porcelain boat, put into tube furnace, logical nitrogen is warming up to 600 ℃, charing 1h.Get carbide after the charing, get this charcoal 2g, potassium hydroxide 8g; pour beaker into, in beaker, add distilled water 10ml, supersound process 0.5h behind the stirring 5min; 60 ℃ of following vacuum-drying 10h, dry intact after with the mixture porcelain boat of packing into, under the nitrogen protection; 650 ℃ of calcining 0.5h; behind the naturally cooling,, extremely neutral with distilled water flushing again with the flushing of 0.1mol/L dilute hydrochloric acid; dry 5h under 60 ℃ promptly gets target product.
Embodiment 4
20g is gathered in the phenylene-diacetic acid glycol ester adding porcelain boat, put into tube furnace, logical nitrogen is warming up to 1000 ℃, charing 2h.Get carbide after the charing, get this charcoal 2g, salt of wormwood 15g; pour beaker into, in beaker, add distilled water 10ml, supersound process 0.5h behind the stirring 5min; 60 ℃ of following vacuum-drying 10h, dry intact after with the mixture porcelain boat of packing into, under the nitrogen protection; 500 ℃ of calcining 5h; behind the naturally cooling,, extremely neutral with distilled water flushing again with the flushing of 0.1mol/L dilute hydrochloric acid; dry 5h under 60 ℃ promptly gets target product.
Embodiment 5
The poly-phthalic acid second diamino ester of 25g is added in the porcelain boat, put into tube furnace, logical nitrogen is warming up to 750 ℃, charing 1.5h.Get carbide after the charing, get this charcoal 2g, sodium hydroxide 4g; pour beaker into, in beaker, add distilled water 10ml, supersound process 0.5h behind the stirring 5min; 60 ℃ of following vacuum-drying 10h, dry intact after with the mixture porcelain boat of packing into, under the nitrogen protection; 950 ℃ of calcining 3h; behind the naturally cooling,, extremely neutral with distilled water flushing again with the flushing of 0.1mol/L dilute hydrochloric acid; dry 5h under 60 ℃ promptly gets target product.
Embodiment 6
20g is gathered in the phenylene-diacetic acid glycol ester adding porcelain boat, put into tube furnace, logical nitrogen is warming up to 1000 ℃, charing 2h.Get carbide after the charing, get this charcoal 2g, Potassium peroxide 15g; pour beaker into, in beaker, add distilled water 10ml, supersound process 0.5h behind the stirring 5min; 60 ℃ of following vacuum-drying 10h, dry intact after with the mixture porcelain boat of packing into, under the nitrogen protection; 600 ℃ of calcining 3h; behind the naturally cooling,, extremely neutral with distilled water flushing again with the flushing of 0.1mol/L dilute hydrochloric acid; dry 5h under 60 ℃ promptly gets target product.
Embodiment 7
The poly-phthalic acid second diamino ester of 25g is added in the porcelain boat, put into tube furnace, logical nitrogen is warming up to 750 ℃, charing 1.5h.Get carbide after the charing, get this charcoal 2g, sodium-chlor 10g; pour beaker into, in beaker, add distilled water 10ml, supersound process 0.5h behind the stirring 5min; 60 ℃ of following vacuum-drying 10h, dry intact after with the mixture porcelain boat of packing into, under the nitrogen protection; 750 ℃ of calcining 3h; behind the naturally cooling,, extremely neutral with distilled water flushing again with the flushing of 0.1mol/L dilute hydrochloric acid; dry 5h under 60 ℃ promptly gets target product.
The above; only for the preferable preparation method of the present invention, but protection scope of the present invention is not limited thereto, and anyly is familiar with those skilled in the art in the technical scope that the embodiment of the invention discloses; the variation that can expect easily or replacement all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claim.
Claims (10)
1. gac is characterized in that being prepared from by following method: with the aromatic polymer charing, after carbide that obtains after the charing and the alkali metal compound combination treatment in inert atmosphere high-temperature activation make; The quality ratio of described carbide and alkali metal compound is 0.1～15.
2. gac as claimed in claim 1 is characterized in that described aromatic polymer is meant aromatic copolycarbonate, aromatic urethane, poly-phthalic acid glycol ester, polyethylene glycol phthalate, poly-one or more mixture in phenylene-diacetic acid glycol ester, polyethylene terephthalate, the polyethylene terephthalate.
3. gac as claimed in claim 1 is characterized in that described alkali metal compound is to be selected from following at least a basic metal or this alkali-metal oxide compound, oxyhydroxide, halogenide, phosphoric acid salt, carbonate or nitrate; Described basic metal is selected from: lithium, sodium, potassium, rubidium or caesium.
4. gac as claimed in claim 1 is characterized in that described charing is with aromatic polymer charing in 200～1000 ℃ of following inert atmospheres.
5. gac as claimed in claim 1 is characterized in that the used time of described charing or high-temperature activation is 30 minutes～30 hours; Described carbide and alkali metal compound combination treatment be meant carbide and alkali metal compound through ball-milling processing, adding distil water supersound process then, last vacuum impregnation; Described inert atmosphere is meant one or more blended atmosphere in nitrogen, argon gas, helium and the carbonic acid gas; Described high-temperature activation is meant that temperature is between 150～1000 ℃.
6. slurries, it contains as the described gac of arbitrary claim in the claim 1 to 5.
7. starch cream for one kind, it contains as the described gac of arbitrary claim in the claim 1 to 5.
8. electrode, it contains each described gac of claim 1 to 5.
9. electrochemical capacitor, it has the described electrode of claim 8, and it uses sulfuric acid as electrolytic solution.
10. energy storage device, it comprises the described electrochemical capacitor of claim 9.
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| CN2010102922706A CN101955182B (en) | 2010-09-21 | 2010-09-21 | Ultracapacitor activated carbon in sulfuric acid electrolyte and application thereof |
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| CN2010102922706A CN101955182B (en) | 2010-09-21 | 2010-09-21 | Ultracapacitor activated carbon in sulfuric acid electrolyte and application thereof |
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| CN101955182A true CN101955182A (en) | 2011-01-26 |
| CN101955182B CN101955182B (en) | 2012-11-21 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103121678A (en) * | 2012-12-14 | 2013-05-29 | 大连理工大学 | Method for preparing nitrogen-doped activated carbon by utilizing PET (polyethylene terephthalate) waste material |
| CN108516532A (en) * | 2018-06-20 | 2018-09-11 | 苏州大学 | Porous carbon materials and its preparation based on two-dimensional polymer and application |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101648706A (en) * | 2009-06-24 | 2010-02-17 | 吴江飞乐天和电子材料有限公司 | Production method of active carbon for super capacitors |
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2010
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101648706A (en) * | 2009-06-24 | 2010-02-17 | 吴江飞乐天和电子材料有限公司 | Production method of active carbon for super capacitors |
Non-Patent Citations (2)
| Title |
|---|
| 《中国化学会第27届学术年会第10分会场摘要集》 20100620 彭亮波等 硫酸电解液中超级电容器碳材料的制备及性能 第82页 1－10 , 2 * |
| 《炭素》 20091231 陈再华 微波并用加热制备高品质活性炭及其特性 第3－8页 1－10 , 第4期 2 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103121678A (en) * | 2012-12-14 | 2013-05-29 | 大连理工大学 | Method for preparing nitrogen-doped activated carbon by utilizing PET (polyethylene terephthalate) waste material |
| CN103121678B (en) * | 2012-12-14 | 2014-12-24 | 大连理工大学 | Method for preparing nitrogen-doped activated carbon by utilizing PET (polyethylene terephthalate) waste material |
| CN108516532A (en) * | 2018-06-20 | 2018-09-11 | 苏州大学 | Porous carbon materials and its preparation based on two-dimensional polymer and application |
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| CN101955182B (en) | 2012-11-21 |
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