CN103409853A - Method for preparing active carbon fiber material with energy storage characteristic from polyacrylonitrile-based pre-oxidized fiber and application of active carbon fiber material - Google Patents
Method for preparing active carbon fiber material with energy storage characteristic from polyacrylonitrile-based pre-oxidized fiber and application of active carbon fiber material Download PDFInfo
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- CN103409853A CN103409853A CN2013103694471A CN201310369447A CN103409853A CN 103409853 A CN103409853 A CN 103409853A CN 2013103694471 A CN2013103694471 A CN 2013103694471A CN 201310369447 A CN201310369447 A CN 201310369447A CN 103409853 A CN103409853 A CN 103409853A
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Abstract
The invention discloses a method for preparing an active carbon fiber material with energy storage characteristics from a polyacrylonitrile-based pre-oxidized fiber and an application of the active carbon fiber material, and belongs to the technical field of active carbon fiber materials and electrochemical capacitors. The method comprises the following steps of: (1) cleaning the polyacrylonitrile-based pre-oxidized fiber (commercially available) by using water, and drying; (2) mixing the polyacrylonitrile-based pre-oxidized fiber dried from the step (1) with strong alkali in proportion, adding a certain amount of water, uniformly mixing, drying, controlling the temperature rise speed, and activating to obtain an activation product; (3) soaking the activation product obtained from the step (2) in hot water, filtering, washing until the solution is neutral, carrying out vacuum drying, and grinding into powder to obtain the active carbon fiber material capable of being used for the electrochemical capacitors. The active carbon fiber prepared through the method disclosed by the invention achieves the specific area to 1200-2500 m<2>/g, is narrow in pore diameter distribution, achieves the mesoporous ratio by 20%-60%. The prepared active carbon fiber material as an electrode can be used for symmetrical type electrochemical capacitors or dissymmetric type electrochemical capacitors.
Description
Technical field
The invention belongs to active-carbon fibre material and electrochemical capacitor technical field, be specifically related to a kind ofly take the pre-oxygen silk of polyacrylonitrile-radical and be raw material, the highly basic of take is activator, and a step activation preparation has method and the application of the active-carbon fibre material of energy storage feature.
Background technology
Carbon-based material with high specific capacitance performance has been widely used in electrochemical capacitor, as active carbon, activated carbon fiber, charcoal-aero gel, CNT, Graphene etc.Although excellent material performance such as charcoal-aero gel, CNT, Graphenes, Industrialized processing technique is also immature at present, and price is very high, has restricted their commercialization process.The carbon-based material that current commodity are used is mainly active carbon and active-carbon fibre material.
With active carbon, compare, the activated carbon fiber specific discharge capacity is high, good conductivity, good response path can be provided, have the characteristics such as excellent intensity and processability, the application in electrochemical capacitor more and more comes into one's own, but the activated carbon fiber cost is higher, price is 5～100 times of active carbon, has greatly limited the application of activated carbon fiber in electrochemical capacitor.Therefore, current research about high specific capacitance carbon fiber preparation method more concentrates on and reduces costs aspect, if used cheap raw material, simplifies preparation technology etc.
With carbon fibre precursor, be that the activated carbon fiber preparation process that raw material activates is compared, utilize pre-oxygen silk for raw material prepares activated carbon fiber can the decrease cost.Typical preparation method carries out stabilization processes by pre-oxygen silk fiber under low temperature (200～400 ℃), then carry out charing and activation (700～1000 ℃), improve the activated carbon fiber performance by changing the experiment conditions such as activator species, soak time, activation temperature.In Chinese invention patent CN101685713A, adopt viscose cloth as raw material, adopt diammonium hydrogen phosphate as impregnating agent, prepare activated carbon fiber by five step operations such as dipping, oven dry, carbonization, activation, post processings, its specific area is greater than 1500m
2/ g, be used as the capacity that active carbon fiber electrode has effectively improved electrochemical capacitor, reduced the internal resistance of capacitor; Patent CN101562076A discloses a kind of preparation method of ultracapacitor special activated carbon fiber cloth, adopt the mixed liquor of ammonium phosphate type activator and potassium chloride catalyst as impregnating agent, the raw material cloth that dipping is completed carries out the pre-treatment charing under 280 ℃～320 ℃ conditions, then in steam atmosphere, under 800～950 ℃ of conditions, carry out the activation processing process, finally by washing, drying course, prepare electrode material for super capacitor, the product specific area reaches 2000m
2/ g, mesoporous can reach 30%, has that energy storage density is large, the discharge power high.Process route in above two patents all comprises carbonization, activation and aftertreatment technology, process route is many than length, influence factor, although by changing process conditions, obtained comparatively desirable electrochemical energy storage performance, energy consumption increase, cost in the active-carbon fibre material preparation process raise.
Summary of the invention
The object of the invention is to disclose and a kind ofly take commercially available PAN-based stabilized fiber and be activator as raw material, the highly basic of take, a step activation method preparation has the method for the active-carbon fibre material of energy storage feature.The concrete steps of the method are as follows:
(1) the pre-oxygen silk of polyacrylonitrile-radical (commercially available) is washed to drying;
(2) the dried pre-oxygen silk of above-mentioned steps (1) is mixed in proportion with highly basic, add certain water gaging to mix, dry, control programming rate, activation, obtain activation products;
(3) activation products that above-mentioned steps (2) obtained, with in hot water, soaking, are filtered, and washing is extremely neutral, vacuumize, and grind into powder must can be used for the active-carbon fibre material of electrochemical capacitor.
In said method, in described step (1), described baking temperature is 80-120 ℃;
Highly basic in described step (2) is at least a in potassium hydroxide or NaOH, and carbide and highly basic mass ratio are 1:(2-5), programming rate is 2-15 ℃/min, and activation temperature is 700-900 ℃, and soak time is 0.5-3h;
In described step (3), the hot water temperature is controlled at 70-100 ℃, and baking temperature is 40-80 ℃, and be 12-24h drying time.
Active-carbon fibre material specific area prepared by above method can reach 1200-2500m2/g, and pore-size distribution is narrow, and mesoporous can reach 20%～60%.
Active-carbon fibre material prepared by above method can be used for symmetric form electrochemical capacitor or asymmetrical type electrochemical capacitor as electrode material, and electrolyte can be the aqueous solution such as acid, neutral, alkaline, can be also organic electrolyte.
Beneficial effect:
The present invention prepared the activated carbon fiber specific area be 1200-2500m
2/ g, pore-size distribution is narrow, and mesoporous can reach 20%～60%.Prepared active carbon fiber electrode can be for symmetric form electrochemical capacitor or asymmetrical type electrochemical capacitor, electrolyte can be the aqueous solution such as acid, neutral, alkaline, it can be also organic electrolyte, have larger than electric capacity and less internal resistance, charge-discharge performance, cyclical stability excellence.The method preparation flow is short, simple to operate, reduces energy consumption, has greatly reduced the preparation cost of active-carbon fibre material, has improved the preparation efficiency of active-carbon fibre material.
The accompanying drawing explanation
Fig. 1 is the graph of pore diameter distribution that the nitrogen absorption under low temperature test of the polyacrylonitrile based activated carbon fiber of the embodiment of the present invention 1 preparation obtains.
Fig. 2 is the stereoscan photograph of the polyacrylonitrile-radical active-carbon fibre material of the embodiment of the present invention 1 preparation.
Fig. 3 is electrochemical capacitor constant current charge-discharge curve under current density 0.5A/g that the polyacrylonitrile-radical active-carbon fibre material of the embodiment of the present invention 1 preparation is assembled into.
The specific embodiment:
The invention will be further described below in conjunction with example.
Embodiment 1
(1) the pre-oxygen silk of polyacrylonitrile-radical (commercially available) is washed to dry 24h when temperature is 120 ℃;
(2) the dried pre-oxygen silk of above-mentioned steps (1) is placed in to nickel crucible, than (mass ratio) 1:2, adds the potassium hydroxide solid by carbon alkali, add certain water gaging to mix, dry, control 5 ℃/min of programming rate, activate 1h under 800 ℃, naturally cool to room temperature, obtain activation products;
(3) activation products that above-mentioned steps (2) obtained, with in 100 ℃ of hot water, soaking, are filtered, and washing, to neutral, is placed in 60 ℃ of dry 24h in vacuum drying chamber, obtains active-carbon fibre material, specific area 2503m
2/ g, average pore size 2.65nm, mesoporous are 60%, grind into powder must can be used for the active-carbon fibre material of electrochemical capacitor.
(4) powdered activated carbon fiber above-mentioned steps (3) made, by active carbon: binding agent (polytetrafluoroethylene (PTFE))=95:5(mass ratio) be distributed in ethanol, add thermal agitation, roll-in is in blocks;
(5) electrode slice above-mentioned steps (4) made is pressed on nickel foam under 15MPa, be assembled into the symmetric form electrochemical capacitor, electrolyte is 6M KOH, is under 0.5A/g, to carry out the constant current charge-discharge test in current density, and prepared active-carbon fibre material is 288.6F/g than electric capacity.
Embodiment 2
(1) the pre-oxygen silk of polyacrylonitrile-radical (commercially available) is washed to dry 24h when temperature is 100 ℃;
(2) the dried pre-oxygen silk of above-mentioned steps (1) is placed in to nickel crucible, than (mass ratio) 1:3, adds sodium hydrate solid by carbon alkali, add certain water gaging to mix, dry, control 10 ℃/min of programming rate, activate 1h under 900 ℃, naturally cool to room temperature, obtain activation products;
(3) activation products that above-mentioned steps (2) obtained, with in 90 ℃ of hot water, soaking, are filtered, and washing, to neutral, is placed in 65 ℃ of dry 24h in vacuum drying chamber, obtains active-carbon fibre material, specific area 2238m
2/ g, average pore size 2.46nm, mesoporous are 51%, grind into powder must can be used for the active-carbon fibre material of electrochemical capacitor.
(4) powdered activated carbon fiber above-mentioned steps (3) made, by active carbon: binding agent (polytetrafluoroethylene (PTFE))=95:5(mass ratio) be distributed in ethanol, add thermal agitation, roll-in is in blocks;
(5) electrode slice above-mentioned steps (4) made is being pressed on the stainless (steel) wire sheet under 15MPa, is assembled into the symmetric form electrochemical capacitor, and electrolyte is 1M H
2SO
4, in current density, be under 0.5A/g, to carry out the constant current charge-discharge test, prepared active-carbon fibre material is 248.9F/g than electric capacity.
Embodiment 3
(1) the pre-oxygen silk of polyacrylonitrile-radical (commercially available) is washed to dry 24h when temperature is 80 ℃;
(2) the dried pre-oxygen silk of above-mentioned steps (1) is placed in to nickel crucible, than (mass ratio) 1:3, adds the potassium hydroxide solid by carbon alkali, add certain water gaging to mix, dry, control 8 ℃/min of programming rate, activate 0.5h under 850 ℃, naturally cool to room temperature, obtain activation products;
(3) activation products that above-mentioned steps (2) obtained, with in 70 ℃ of hot water, soaking, are filtered, and washing, to neutral, is placed in 75 ℃ of dry 24h in vacuum drying chamber, obtains active-carbon fibre material, specific area 1249m
2/ g, average pore size 1.86nm, mesoporous are 35%, grind into powder must can be used for the active-carbon fibre material of electrochemical capacitor.
(4) powdered activated carbon fiber above-mentioned steps (3) made, by active carbon: binding agent (polytetrafluoroethylene (PTFE))=95:5(mass ratio) be distributed in ethanol, add thermal agitation, roll-in is in blocks;
(5) electrode slice above-mentioned steps (4) made is pressed on nickel foam under 15MPa, be assembled into the symmetric form electrochemical capacitor, and electrolyte is 1M Na
2SO4, be under 0.5A/g, to carry out the constant current charge-discharge test in current density, and prepared active-carbon fibre material is 226.7F/g than electric capacity.
Embodiment 4
(1) the pre-oxygen silk of polyacrylonitrile-radical (commercially available) is washed to dry 24h when temperature is 90 ℃;
(2) the dried pre-oxygen silk of above-mentioned steps (1) is placed in to nickel crucible, than (mass ratio) 1:4, adds the potassium hydroxide solid by carbon alkali, add certain water gaging to mix, dry, control 3 ℃/min of programming rate, activate 2h under 750 ℃, naturally cool to room temperature, obtain activation products;
(3) activation products that above-mentioned steps (2) obtained, with in 80 ℃ of hot water, soaking, are filtered, and washing, to neutral, is placed in 50 ℃ of dry 24h in vacuum drying chamber, obtains active-carbon fibre material, specific area 1653m
2/ g, average pore size 1.93nm, mesoporous are 40%, grind into powder must can be used for the active-carbon fibre material of electrochemical capacitor.
(4) powdered activated carbon fiber above-mentioned steps (3) made, by activated carbon fiber: binding agent (polytetrafluoroethylene (PTFE))=95:5(mass ratio) be distributed in NMP, the aluminium foil of take is made electrode as collector, electrolyte is 1M TEA-BF4/AN, in glove box, be assembled into the symmetric form electrochemical capacitor, in current density, be under 0.5A/g, to carry out the constant current charge-discharge test, prepared active-carbon fibre material is 201.2F/g than electric capacity.
Claims (6)
1. one kind has the method for the active-carbon fibre material of energy storage feature from the pre-oxygen silk preparation of polyacrylonitrile-radical, comprises the following steps at least:
(1) the pre-oxygen silk of polyacrylonitrile-radical is washed to drying;
(2) the dried pre-oxygen silk of above-mentioned steps (1) is mixed in proportion with highly basic, add certain water gaging to mix, dry, control programming rate, activation, obtain activation products;
(3) activation products that above-mentioned steps (2) obtained, with in hot water, soaking, are filtered, and washing is extremely neutral, vacuumize, and grind into powder must can be used for the active-carbon fibre material of electrochemical capacitor.
2. according to claim 1 a kind ofly have the method for the active-carbon fibre material of energy storage feature from the preparation of the pre-oxygen silk of polyacrylonitrile-radical, and it is characterized in that: the pre-oxygen silk of polyacrylonitrile-radical of take in described step (1) is raw material, and baking temperature is 80～120 ℃.
3. according to claim 1 a kind ofly have the method for the active-carbon fibre material of energy storage feature from the preparation of the pre-oxygen silk of polyacrylonitrile-radical, it is characterized in that: the highly basic in described step (2) is at least a in potassium hydroxide or NaOH, pre-oxygen silk and highly basic mass ratio are 1:(2～5), programming rate is 2-15 ℃/min, activation temperature is 700～900 ℃, and soak time is 0.5～3h.
4. according to claim 1 a kind ofly have the method for the active-carbon fibre material of energy storage feature from the preparation of the pre-oxygen silk of polyacrylonitrile-radical, it is characterized in that: in described step (3), the hot water temperature is controlled at 70-100 ℃, and baking temperature is 40～80 ℃, and be 12-24h drying time.
5. according to claim 1 a kind ofly have the method for the active-carbon fibre material of energy storage feature from the preparation of the pre-oxygen silk of polyacrylonitrile-radical, it is characterized in that: the active-carbon fibre material specific area of preparation can reach 1200-2500m2/g, pore-size distribution is narrow, and mesoporous can reach 20%～60%.
6. one kind can be used for symmetric form electrochemical capacitor or asymmetrical type electrochemical capacitor with the prepared active-carbon fibre material out of either method in claim 1-5 as electrode material, electrolyte can be the aqueous solution such as acid, neutral, alkaline, can be also organic electrolyte.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103806130A (en) * | 2014-02-24 | 2014-05-21 | 钟春燕 | Preparation method for bacterial cellulose-based nano active carbon fibers |
| CN104148031A (en) * | 2014-07-30 | 2014-11-19 | 华南理工大学 | Method for preparing poly-dopamine carbon material with high specific surface area |
| CN112342644A (en) * | 2020-11-26 | 2021-02-09 | 湖北亿纬动力有限公司 | Porous carbon fiber and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4082694A (en) * | 1975-12-24 | 1978-04-04 | Standard Oil Company (Indiana) | Active carbon process and composition |
| CN1291587A (en) * | 2000-09-05 | 2001-04-18 | 天津大学 | Process for preparing activated carbon to make electrode of super capacitor |
| CN1948147A (en) * | 2006-11-10 | 2007-04-18 | 华南理工大学 | Preparation method of high specific surface area coal mass active carbon |
| CN1970444A (en) * | 2006-12-07 | 2007-05-30 | 湖南大学 | Microwave radiation method for preparing activated carbon with high specific surface area |
| CN101503189A (en) * | 2008-02-05 | 2009-08-12 | 产业技术研究所股份有限公司 | Active carbon and method for manufacturing double-layer capacitor |
| CN101844765A (en) * | 2010-06-02 | 2010-09-29 | 天津大学 | Active carbon for preparing carbon electrode of super capacitor and preparation method thereof |
-
2013
- 2013-08-22 CN CN2013103694471A patent/CN103409853A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4082694A (en) * | 1975-12-24 | 1978-04-04 | Standard Oil Company (Indiana) | Active carbon process and composition |
| CN1291587A (en) * | 2000-09-05 | 2001-04-18 | 天津大学 | Process for preparing activated carbon to make electrode of super capacitor |
| CN1948147A (en) * | 2006-11-10 | 2007-04-18 | 华南理工大学 | Preparation method of high specific surface area coal mass active carbon |
| CN1970444A (en) * | 2006-12-07 | 2007-05-30 | 湖南大学 | Microwave radiation method for preparing activated carbon with high specific surface area |
| CN101503189A (en) * | 2008-02-05 | 2009-08-12 | 产业技术研究所股份有限公司 | Active carbon and method for manufacturing double-layer capacitor |
| CN101844765A (en) * | 2010-06-02 | 2010-09-29 | 天津大学 | Active carbon for preparing carbon electrode of super capacitor and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103806130A (en) * | 2014-02-24 | 2014-05-21 | 钟春燕 | Preparation method for bacterial cellulose-based nano active carbon fibers |
| CN103806130B (en) * | 2014-02-24 | 2016-02-10 | 钟春燕 | A kind of preparation method of bacteria cellulose-base nanometer activated carbon fiber |
| CN104148031A (en) * | 2014-07-30 | 2014-11-19 | 华南理工大学 | Method for preparing poly-dopamine carbon material with high specific surface area |
| CN112342644A (en) * | 2020-11-26 | 2021-02-09 | 湖北亿纬动力有限公司 | Porous carbon fiber and preparation method and application thereof |
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Application publication date: 20131127 |