CN102509629A - High-specific-area layered pore carbon material as well as preparation method and application thereof - Google Patents
High-specific-area layered pore carbon material as well as preparation method and application thereof Download PDFInfo
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- CN102509629A CN102509629A CN201110300579XA CN201110300579A CN102509629A CN 102509629 A CN102509629 A CN 102509629A CN 201110300579X A CN201110300579X A CN 201110300579XA CN 201110300579 A CN201110300579 A CN 201110300579A CN 102509629 A CN102509629 A CN 102509629A
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Abstract
The invention belongs to the technical field of a material and discloses a high-specific-area layered pore carbon material as well as a preparation method and an application thereof. The preparation method comprises the following steps of: firstly, carrying out a Friedel-Crafts crosslinking reaction on linear polystyrene based on anhydrous carbon tetrachloride as a solvent and a crosslinking agent in the presence of anhydrous aluminum trichloride and then washing, drying and carbonizing to obtain a polystyrene-based layered pore carbon material; and activating the material with KOH, and then washing and drying to obtain the high-specific-area layered pore carbon material. The preparation method is simple in process; the obtained carbon material has a specific layered nano structure; and element carbon rubber particles are piled to form mesopores and macropores, and a large amount of three-dimensional micropores and small mesopores exist in the element carbon rubber particles, various layers of nano pore channels are connected tightly, so that the BET (Brunauer, Emmett and Teller) specific surface area reaches 1820-3100m<2>/g, the pore volume is 1.13-2.18cm<3>/g, wherein the volume of the micropores accounts for 24-51% of the pore volume, and the volumes of the outer mesopores and macropores account for 49-76% of the pore volume. The preparation method disclosed by the invention can be used for preparing an electrode material of an electrochemical capacitor.
Description
Technical field
The invention belongs to the material technology field, particularly a kind of high-specific surface area level hole raw material of wood-charcoal material that utilizes the activating technology preparation.
Background technology
As the carbon nano-material of one type of novelty, level hole raw material of wood-charcoal material has caused widely at material science and has paid close attention to have unique space structure characteristics that micropore, mesopore and macropore ternary aperture rationally distribute concurrently.Synthesizing of level hole raw material of wood-charcoal material adopted template or template-activation combination method usually at present, and this has seriously limited its prospects for commercial application.Main cause is: (1) soft template (for example PEO-PPO-PEO triblock copolymer) costs an arm and a leg; (2) need preparation in advance and technology loaded down with trivial details usually as the nano silicon of hard mould agent or other material, cost is high.
Recently, Chinese patent CN 101698477B (application number 200910193797.0) has realized that through between styrenic, constructing the carbonyl cross-bridge template of exempting from of level hole raw material of wood-charcoal material prepares.This novel level hole raw material of wood-charcoal material with unique nanostructure is made up of primitive charcoal particle; Primitive charcoal colloidal solid inside contain the three-dimensional network micropore (＜2nm); Primitive charcoal colloidal solid pile up each other form the three-dimensional network mesopore (2～50nm) with macropore (＞50nm), each level nano pore is closely continuous.Research shows, through in/microporous network that big hole path is interconnected, be very beneficial for the entering of electrolyte ion; Thereby have ion-transfer ability and electro-chemical activity surface fast efficiently; Therefore, the accumulate performance of these level hole raw material of wood-charcoal material, especially its power characteristic; Obviously be superior to traditional electrode material (for example orderly mesopore charcoal, active carbon and charcoal-aero gel etc.), in fields such as ultracapacitor, demonstrate great application prospect.Yet there is the fault of construction that needs to be resolved hurrily in this material: charcoal matrix porosity rate is low, lacks enough electrochemical energy storage avtive spots.Only contain the micropore that derives from a small quantity in the three-dimensional network type microcellular structure on the polystyrene group hierarchical mesoporous carbon material charcoal skeleton, specific area is merely 500～800m
2/ g, the charcoal skeleton takes up space and is difficult to be utilized to store charge, is unfavorable for the raising of energy density.Therefore; Adopt simple, effective process; In maintenance/the intact prerequisite of macroporous network charcoal skeleton under, increase the quantity of hole on the charcoal skeleton, and then the specific area that improves polystyrene-based level hole charcoal is to increase the electrochemical energy storage active sites; Final high-energy/high power density energy-storage nano raw material of wood-charcoal the material that obtains has important scientific research value and wide application prospect.
Summary of the invention
In order to overcome the deficiency that exists in the prior art, primary and foremost purpose of the present invention is to provide a kind of high-specific surface area level hole charcoal preparation methods.This method is a raw material with polystyrene cheap and easy to get, and preparation is simple.
Another object of the present invention is to the high-specific surface area level hole raw material of wood-charcoal material that provides method for preparing to obtain.
A purpose more of the present invention is to provide the application of above-mentioned high-specific surface area level hole raw material of wood-charcoal material.This high-specific surface area polystyrene group hierarchical mesoporous carbon material can be used for preparing the electrode material of high-energy-density/high power density electrochemical capacitor.
The object of the invention is realized through following technical proposals: a kind of preparation method of high-specific surface area polystyrene group hierarchical mesoporous carbon material comprises following operating procedure:
(1) linear polystyrene is added in the anhydrous carbon tetrachloride, be stirred to linear polystyrene and dissolve fully, obtain the polystyrene carbon tetrachloride solution;
(2) aluminum trichloride (anhydrous) is placed reaction vessel, add anhydrous carbon tetrachloride, after the dissolving that refluxes, add step (1) gained polystyrene carbon tetrachloride solution, reflux is carried out the Friedel-Crafts reaction under the stirring condition;
(3) add ethanol/water mixed solvent and stop the Friedel-Crafts reaction, filter and obtain solid product, after washing, filtration and drying, obtain level hole polystyrene material;
(4) step (3) gained level hole polystyrene material is placed retort, the heating charing obtains polystyrene group hierarchical mesoporous carbon material under inert gas atmosphere;
(5) polystyrene group hierarchical mesoporous carbon material is fully mixed in water/ethanolic solution with KOH, mixture is dry;
(6) mixture with step (5) gained places activation furnace, and high-temperature activation is carried out in heating under inert gas atmosphere, and activation products obtain the high-specific surface area polystyrene group hierarchical mesoporous carbon material after washing, filtration and drying.
Said step (1) to step (3) neutral line polystyrene: aluminum trichloride (anhydrous): anhydrous carbon tetrachloride: the consumption proportion of ethanol/water mixed solvent is 0.2～10g: 3～24g: 100～400ml: 100～200ml, and wherein the consumption of anhydrous carbon tetrachloride is 6～300ml in the step (1).
The consumption proportion of polystyrene group hierarchical mesoporous carbon material: KOH is 1g: 0.5～8g in the said step (5).
Said activation condition is warming up to 500～900 ℃, charing 2～6h for the heating rate with 2～5 ℃/min.
In order to realize the present invention better, reflux has the drying tube that loads anhydrous calcium chloride in the said step (2); Said backflow dissolving is at 30～75 ℃ of dissolving 20～80min that reflux; The condition of said Friedel-Crafts reaction is to react 2～72h down at 30～75 ℃.
In the said step (3) ethanol/water mixed solvent for percent by volume be 95% second alcohol and water by 1～8: 1 volume ratio mixes, and its consumption is that the said filtercondition of 100～200ml is the room temperature decompress filter; Said wash conditions is: use by ethanol and watery hydrochloric acid by 1～5: the solution washing that 1 volume ratio mixes 1～5 time; Use by the second alcohol and water by 1～6: the solution washing that 1 volume ratio mixes 1～6 time; Filter each washing back, and said filtercondition is the room temperature decompress filter; Said ethanol is that percent by volume is 95% ethanol, and said watery hydrochloric acid is that percent by volume is 5% hydrochloric acid; Said water is deionized water; Said drying condition is 105～110 ℃ of down dry 2～24h.
Inert gas atmosphere is the nitrogen atmosphere of 200～800ml/min flow velocity in the said step (4); Said carbonization condition is with the heating rate to 300 of 2～5 ℃/min～900 ℃, charing 2～6h.
Water/ethanolic solution is that 2～20ml water and 2～6ml absolute ethyl alcohol are mixed in the said step (5); Said polystyrene group hierarchical mesoporous carbon material sieves after polystyrene group hierarchical mesoporous carbon material in the step (4) is ground, and obtains 100～400 purpose polystyrene group hierarchical mesoporous carbon materials.
Inert gas atmosphere is the nitrogen atmosphere of 200～800ml/min flow velocity in the said step (6); Temperature with activation products before the said washing is reduced to below 50 ℃; Said wash conditions is: with deionized water and concentrated hydrochloric acid by 5～20: the solution that 1 volume ratio mixes washs under the boiling condition 2～8 times, uses deionized water wash again 1～6 time; Said drying condition is 105～110 ℃ of down dry 6～24h.
A kind of high-specific surface area polystyrene group hierarchical mesoporous carbon material is formed by method for preparing.
Above-mentioned high-specific surface area polystyrene group hierarchical mesoporous carbon material can be used for preparing the electrode material of electrochemical capacitor.
Principle of the present invention is: the present invention at first is reaction raw materials with the linear polystyrene; Anhydrous carbon tetrachloride is solvent and crosslinking agent; Aluminum trichloride (anhydrous) at a certain temperature agitating heating back flow reaction a period of time, stops Friedel-Crafts reaction and hydrolytic reactions subsequently as catalyst; Filtration obtains solid product, after washing and drying, obtains level hole polystyrene material.Then; Charing obtains level hole raw material of wood-charcoal material in inert atmosphere; Group hierarchical mesoporous carbon material with gained stirs in the mixed solvent of ethanol/water with KOH in certain proportion again, obtains high-specific surface area level hole raw material of wood-charcoal material after the pyroreaction in oven dry, inert atmosphere, pickling, filtration, washing neutralization, the drying and other steps.Discover: (1) KOH activation can be effectively carried out etching pore-creating to the polystyrene-based charcoal skeleton of gained level hole raw material of wood-charcoal material, has generated a large amount of micropores and little mesopore, and the specific area of sample is greatly improved, and reaches as high as 3100m
2More than/the g; (2) the KOH activation can not cause the three-dimensional manometer network skeleton of level hole raw material of wood-charcoal material to cave in, so the level pore structure can access effective succession in activation process.
The present invention has following advantage and beneficial effect with respect to prior art:
(1) the present invention etches more energy storage hole through the KOH activating technology on the primitive charcoal colloidal solid of polystyrene group hierarchical mesoporous carbon material, and the BET specific area is 1820～3100m
2/ g, pore volume are 1.13～2.18cm
3/ g, wherein the micropore pore volume accounts for 24～51%, and external holes (being mesopore and macropore) pore volume accounts for 49～76%, and preparation technology is simple, equipment requirements is low, is prone to realize suitability for industrialized production.
(2) under high etching degree, for example, be 6 o'clock at KOH and polystyrene-based level hole charcoal mass ratio, activation does not cause the level pore structure to be caved in, and develops the high-specific surface area polystyrene group hierarchical mesoporous carbon material thus, has a extensive future.
(3) when this material serves as electrode material for super capacitor, the ratio electric capacity that in il electrolyte, obtains is 128～191F/g, and the ratio electric capacity that in organic electrolyte, obtains is 155～253F/g, and specific area is 3080m
2The ratio electric capacity that the commercial ultracapacitor special-purpose activated charcoal of/g is obtained in these two kinds of electrolyte is merely 84F/g and 114F/g respectively, and the material that the present invention developed has tangible excellent effect as electrode material.
Description of drawings
Fig. 1 is the nitrogen adsorption-desorption isotherm figure of the high-specific surface area polystyrene group hierarchical mesoporous carbon material for preparing of embodiment 1.
Fig. 2 is the Electronic Speculum figure of the high-specific surface area polystyrene group hierarchical mesoporous carbon material for preparing of embodiment 1, and wherein, A is a sem photograph, and B is a transmission electron microscope picture.
Embodiment
Below in conjunction with embodiment and accompanying drawing the present invention is described in further detail, but execution mode of the present invention is not limited thereto.
Embodiment 1
A kind of preparation method of high-specific surface area polystyrene group hierarchical mesoporous carbon material may further comprise the steps:
(1) in the 250ml reaction vessel, add the anhydrous carbon tetrachloride of 5.0g linear polystyrene and 100ml successively, stirring at room to polystyrene dissolves fully, obtains the polystyrene carbon tetrachloride solution;
(2) in the 250ml agitated reactor, add catalyst aluminum trichloride (anhydrous) 12.0g and the anhydrous carbon tetrachloride of 100ml earlier; Setting reaction temperature is 75 ℃; Begin to stir after feeding condensed water, load onto the drying tube that is loaded with anhydrous calcium chloride simultaneously, the dissolving 40min that refluxes obtains aluminum trichloride solution; Then under the magnetic agitation condition slowly at the uniform velocity (about 30 seconds of 100ml solution) carry out Friedel-Crafts reaction 48h toward wherein adding step (1) gained polystyrene carbon tetrachloride solution 75 ℃ of following reflux;
(3) add 100ml by ethanol/water mixed solvent (the mixed volume ratio is 4: 1) cessation reaction; The room temperature decompress filter; Use the mixed solution washing 2 times (each 200ml) of ethanol and 5% watery hydrochloric acid (volume ratio is 3: 1) again; The mixed solution washing of 200ml ethanol/water (volume ratio is 3: 1) 1 time is filtered the back in 110 ℃ of dry 12h, obtains level hole polystyrene material; It is 95% ethanol that ethanol is volumn concentration, and watery hydrochloric acid is that volumn concentration is 5% hydrochloric acid;
(4) with the level hole polystyrene material that obtains under the nitrogen atmosphere of 400ml/min flow velocity, be warming up to 500 ℃ with the heating rate of 5 ℃/min, constant temperature charing 3h promptly obtains polystyrene group hierarchical mesoporous carbon material;
(5) 6g KOH is dissolved in 10ml water and the mixed solution of 6ml absolute ethyl alcohol, adds the 300 order polystyrene group hierarchical mesoporous carbon materials that 1g sieves and obtains through grinding, mix, mixture is placed 110 ℃ of dry 12h down;
(6) dried mixture is placed retort; Under the nitrogen atmosphere of 400ml/min flow velocity, be warming up to 900 ℃, activation 3h with the heating rate of 5 ℃/min;, the temperature of retort takes out activation products after the activation when reducing to 50 ℃; With the mixed solution of 100ml deionized water and 10ml 37% hydrochloric acid purging compound 3 times under boiled condition, use the 200ml deionized water wash again 1 time, filter each washing back; After last the filtration with product in 110 ℃ of dry 12h, obtain the high-specific surface area polystyrene group hierarchical mesoporous carbon material.Nitrogen adsorption-the desorption isotherm of the high-specific surface area polystyrene group hierarchical mesoporous carbon material for preparing is as shown in Figure 1.
With the ASAP2010 absorption appearance nitrogen adsorption method test that U.S. Micromeritics company produces, the specific area of the polystyrene group hierarchical mesoporous carbon material that obtains preparing (BET) is 3023m
2/ g, wherein micropore and external holes (being mesopore and macropore) specific area is respectively 835m
2/ g and 2188m
2/ g; Pore volume is 2.18cm
3/ g, wherein micropore pore volume and external holes pore volume are respectively 0.53cm
3/ g and 1.65cm
3/ g.ESEM and transmission electron microscope observing result show; The nanostructure of gained high-specific surface area polystyrene group hierarchical mesoporous carbon material has unique level; As shown in Figure 2; That is: the three-dimensional network micropore is contained in primitive charcoal colloidal solid inside, and loose the piling up of primitive charcoal colloidal solid compact reactor superimposition forms mesopore and macropore respectively, and each level nano pore is interconnected on three-dimensional.
With gained raw material of wood-charcoal material is electrode material, is electrolyte with 1-butyl-3-methylimidazole hexafluorophosphate ionic liquid, is assembled into electrochemical capacitor, uses galvanostatic charge to record its quality and is 191F/g than electric capacity.
Embodiment 2
A kind of preparation method of high-specific surface area polystyrene group hierarchical mesoporous carbon material may further comprise the steps:
(1) in the container of 250ml, add the anhydrous carbon tetrachloride of 5.0g linear polystyrene and 100ml successively, stirring at room to polystyrene dissolves fully, obtains the polystyrene carbon tetrachloride solution;
(2) in the 250ml agitated reactor, add catalysts aluminum trichloride (anhydrous) 12.0g and the anhydrous carbon tetrachloride of 100ml; The water bath with thermostatic control temperature is set in 75 ℃; Begin to stir behind the feeding condensed water and load onto the drying tube that is loaded with anhydrous calcium chloride simultaneously; Obtain aluminum trichloride solution behind the backflow dissolving 40min; Under the magnetic agitation condition,, carry out Friedel-Crafts reaction 48h 75 ℃ of following reflux slowly at the uniform velocity (about 30 seconds of 100ml solution) toward wherein adding above-mentioned polystyrene carbon tetrachloride solution;
(3) the mixed solvent cessation reaction of adding 100ml 95% ethanol/water (volume ratio is 4: 1); The room temperature decompress filter; Use the mixed solution washing 2 times (each 200ml) of 95% ethanol and 5% watery hydrochloric acid (volume ratio is 3: 1) again; Back dry 12h under 110 ℃ is filtered in the mixed solution washing of 200ml 95% second alcohol and water (volume ratio is 3: 1) 1 time, obtains level hole polystyrene material;
(4) with the level hole polystyrene material that obtains under the nitrogen atmosphere of 400ml/min flow velocity, be warming up to 500 ℃ with the heating rate of 5 ℃/min, charing 3h obtains polystyrene group hierarchical mesoporous carbon material;
(5) 5g KOH is dissolved in the mixed solution of 10ml water and 6ml absolute ethyl alcohol, adds the 300 order polystyrene group hierarchical mesoporous carbon materials that 1g sieves and obtains through grinding then, mix, mixture dry 12h under 110 ℃;
(6) mixture with oven dry places retort, under the nitrogen atmosphere of 400ml/min flow velocity, is warming up to 900 ℃ with the heating rate of 5 ℃/min; Activation 3h; When the temperature of retort is reduced to 50 ℃, take out mixture after the activation,, use the 200ml deionized water wash again 1 time with the mixed solution of 100ml deionized water and 10ml 37% hydrochloric acid purging compound 3 times under the situation of boiling; Filter the back in 110 ℃ of dry 12h, obtain the high-specific surface area polystyrene group hierarchical mesoporous carbon material.
With the ASAP2010 absorption appearance nitrogen adsorption method test that U.S. Micromeritics company produces, its specific area of the polystyrene group hierarchical mesoporous carbon material of preparing (BET) is 3100m
2/ g, wherein micropore and external holes specific area are respectively 1123m
2/ g and 1977m
2/ g; Pore volume is 2.13cm
3/ g, wherein micropore pore volume and external holes pore volume are respectively 0.67cm
3/ g and 1.46cm
3/ g.
With it is electrode material, is electrolyte with 1-butyl-3-methylimidazole hexafluorophosphate ionic liquid, is assembled into electrochemical capacitor, uses galvanostatic charge to record its quality and is 164F/g than electric capacity.
Embodiment 3
A kind of preparation method of high-specific surface area polystyrene group hierarchical mesoporous carbon material may further comprise the steps:
(1) in the container of 250ml, add the anhydrous carbon tetrachloride of 5.0g linear polystyrene and 100ml successively, stirring at room to polystyrene dissolves fully, obtains the polystyrene carbon tetrachloride solution;
(2) in the 250ml agitated reactor, add catalysts aluminum trichloride (anhydrous) 12.0g and the anhydrous carbon tetrachloride of 100ml, the water bath with thermostatic control temperature is set in 75 ℃, begin to stir behind the feeding condensed water and load onto the drying tube that is loaded with anhydrous calcium chloride simultaneously; Obtain aluminum trichloride solution behind the backflow dissolving 40min, under the magnetic agitation condition,, carry out Friedel-Crafts reaction 48h in 75 ℃ of reflux slowly at the uniform velocity (about 30 seconds of 100ml solution) toward wherein adding above-mentioned polystyrene carbon tetrachloride solution;
(3) the mixed solvent cessation reaction of adding 100ml 95% ethanol/water (volume ratio is 4: 1); The room temperature decompress filter; Use the mixed solution washing 2 times (each 200ml) of 95% ethanol and 5% watery hydrochloric acid (volume ratio is 3: 1) again; The mixed solution washing of 200ml 95% second alcohol and water (volume ratio is 3: 1) 1 time is filtered the back in 110 ℃ of dry 12h, obtains level hole polystyrene material;
(4) with the level hole polystyrene material that obtains under the nitrogen atmosphere of 400ml/min flow velocity, be warming up to 500 ℃ with the heating rate of 5 ℃/min, charing 3h promptly obtains polystyrene group hierarchical mesoporous carbon material;
(5) 4g KOH is dissolved in the mixed solution of 8ml water and 4ml absolute ethyl alcohol, adds the 300 order polystyrene group hierarchical mesoporous carbon materials that 1g sieves and obtains through grinding then, mix, mixture is placed 110 ℃ of dry 12h down;
(6) dried mixture is placed retort, under the nitrogen atmosphere of 400ml/min flow velocity, be warming up to 900 ℃ with the heating rate of 5 ℃/min; Activation 3h; When the temperature of retort is reduced to 50 ℃, take out mixture after the activation,, use the 200ml deionized water wash again 1 time with 100ml deionized water and 10ml 37% hydrochloric acid mixed solution purging compound 3 times under the situation of boiling; Filter the back in 110 ℃ of dry 12h, obtain the high-specific surface area polystyrene group hierarchical mesoporous carbon material.
With the ASAP2010 absorption appearance nitrogen adsorption method test that U.S. Micromeritics company produces, its specific area of the polystyrene group hierarchical mesoporous carbon material of preparing (BET) is 2602m
2/ g, wherein micropore and external holes specific area are respectively 1088m
2/ g and 1514m
2/ g; Pore volume is 1.85cm
3/ g, wherein micropore pore volume and external holes pore volume are respectively 0.61cm
3/ g and 1.24cm
3/ g.
With it is electrode material, is electrolyte with 1-butyl-3-methylimidazole hexafluorophosphate ionic liquid, is assembled into electrochemical capacitor, uses galvanostatic charge to record its quality and is 159F/g than electric capacity.
Embodiment 4
A kind of preparation method of high-specific surface area polystyrene group hierarchical mesoporous carbon material may further comprise the steps:
(1) in the container of 250ml, add the anhydrous carbon tetrachloride of 5.0g linear polystyrene and 100ml successively, stirring at room to polystyrene dissolves fully, obtains the polystyrene carbon tetrachloride solution;
(2) in the agitated reactor of 250ml, add catalysts aluminum trichloride (anhydrous) 12.0g and the anhydrous carbon tetrachloride of 100ml, the water bath with thermostatic control temperature is set in 75 ℃, begin to stir behind the feeding condensed water and load onto the drying tube that is loaded with anhydrous calcium chloride simultaneously; Obtain aluminum trichloride solution behind the backflow dissolving 40min, under the magnetic agitation condition,, carry out Friedel-Crafts reaction 48h in 75 ℃ of reflux slowly at the uniform velocity (about 30 seconds of 100ml solution) toward wherein adding above-mentioned polystyrene solution;
(3) the mixed solvent cessation reaction of adding 100ml 95% ethanol/water (volume ratio is 4: 1); The room temperature decompress filter; Use the mixed solution washing 2 times (each 200ml) of 95% ethanol and 5% watery hydrochloric acid (volume ratio is 3: 1) again; The mixed solution washing of 200ml 95% second alcohol and water (volume ratio is 3: 1) 1 time is filtered the back in 110 ℃ of dry 12h, obtains level hole polystyrene material;
(4) with the level hole polystyrene material that obtains under the nitrogen atmosphere of 400ml/min flow velocity, be warming up to 500 ℃ with the heating rate of 5 ℃/min, charing 3h promptly obtains polystyrene group hierarchical mesoporous carbon material;
(5) 3g KOH is dissolved in the mixed solution of 8ml water and 4ml absolute ethyl alcohol, adds the 300 order polystyrene group hierarchical mesoporous carbon materials that 1g sieves and obtains through grinding then, mix, mixture is placed 110 ℃ of dry 12h down;
(6) dried mixture is placed retort, under the nitrogen atmosphere of 400ml/min flow velocity, be warming up to 900 ℃ with the heating rate of 5 ℃/min; Activation 3h; When the temperature of retort is reduced to 50 ℃, take out mixture after the activation,, use the 200ml deionized water wash again 1 time with 100ml deionized water and 10ml 37% hydrochloric acid mixed solution purging compound 3 times under the situation of boiling; Filter the back in 110 ℃ of dry 12h, obtain the high-specific surface area polystyrene group hierarchical mesoporous carbon material.
With the ASAP2010 absorption appearance nitrogen adsorption method test that U.S. Micromeritics company produces, its specific area of the polystyrene group hierarchical mesoporous carbon material of preparing (BET) is 2653m
2/ g, wherein micropore and external holes specific area are respectively 1265m
2/ g and 1388m
2/ g; Pore volume is 1.73cm
3/ g, wherein micropore pore volume and external holes pore volume are respectively 0.70cm
3/ g and 1.03cm
3/ g.
With it is electrode material, is electrolyte with 1-butyl-3-methylimidazole hexafluorophosphate ionic liquid, is assembled into electrochemical capacitor, uses galvanostatic charge to record its quality and is 145F/g than electric capacity.
Embodiment 5
A kind of preparation method of high-specific surface area polystyrene group hierarchical mesoporous carbon material may further comprise the steps:
(1) in the container of 250ml, add the anhydrous carbon tetrachloride of 5.0g linear polystyrene and 100ml successively, stirring at room to polystyrene dissolves fully, obtains the polystyrene carbon tetrachloride solution;
(2) in the agitated reactor of 250ml, add catalysts aluminum trichloride (anhydrous) 12.0g and the anhydrous carbon tetrachloride of 100ml, the water bath with thermostatic control temperature is set in 75 ℃, begin to stir behind the feeding condensed water and load onto the drying tube that is loaded with anhydrous calcium chloride simultaneously; Obtain aluminum trichloride solution behind the backflow dissolving 40min, under the magnetic agitation condition,, carry out Friedel-Crafts reaction 48h in 75 ℃ of following reflux slowly at the uniform velocity (about 30 seconds of 100ml solution) toward wherein adding above-mentioned polystyrene solution;
(3) the mixed solvent cessation reaction of adding 100ml 95% ethanol/water (volume ratio is 4: 1); The room temperature decompress filter; Use the mixed solution washed twice (each 200ml) of 95% ethanol and 5% watery hydrochloric acid (volume ratio is 3: 1) again; The mixed solution washing of 200ml 95% second alcohol and water (volume ratio is 3: 1) is once filtered the back in 110 ℃ of dry 12h, obtains level hole polystyrene material;
(4) with the level hole polystyrene material that obtains under the nitrogen atmosphere of 400ml/min flow velocity, with the heating rate to 500 of 5 ℃/min ℃, charing 3h promptly obtains polystyrene group hierarchical mesoporous carbon material;
(5) 2g KOH is dissolved in the mixed solution of 5ml water and 3ml absolute ethyl alcohol, adds the 300 order polystyrene group hierarchical mesoporous carbon materials that 1g sieves and obtains through grinding then, mix, mixture is placed 110 ℃ of dry 12h down;
(6) dried mixture is placed retort, under the nitrogen atmosphere of 400ml/min flow velocity, be warming up to 900 ℃ with the heating rate of 5 ℃/min; Through 900 ℃ of activation 3h; When the temperature of retort is reduced to 50 ℃, take out mixture after the activation,, use the 200ml deionized water wash again 1 time with 100ml deionized water and 10ml 37% hydrochloric acid mixed solution purging compound 3 times under the situation of boiling; Filter the back in 110 ℃ of dry 12h, obtain the high-specific surface area polystyrene group hierarchical mesoporous carbon material.
With the ASAP2010 absorption appearance nitrogen adsorption method test that U.S. Micromeritics company produces, its specific area of the polystyrene group hierarchical mesoporous carbon material of preparing (BET) is 1986m
2/ g, wherein micropore and external holes specific area are respectively 1141m
2/ g and 845m
2/ g; Pore volume is 1.22cm
3/ g, wherein micropore pore volume and external holes pore volume are respectively 0.60cm
3/ g and 0.62cm
3/ g.
With it is electrode material, is electrolyte with 1-butyl-3-methylimidazole hexafluorophosphate ionic liquid, is assembled into electrochemical capacitor, uses galvanostatic charge to record its quality and is 140F/g than electric capacity.
Embodiment 6
A kind of preparation method of high-specific surface area polystyrene group hierarchical mesoporous carbon material may further comprise the steps:
(1) in the container of 250ml, add the anhydrous carbon tetrachloride of 5.0g linear polystyrene and 100ml successively, stirring at room to polystyrene dissolves fully, obtains the polystyrene carbon tetrachloride solution;
(2) in the agitated reactor of 250ml, add catalysts aluminum trichloride (anhydrous) 12.0g and the anhydrous carbon tetrachloride of 100ml, the water bath with thermostatic control temperature is set in 75 ℃, begin to stir behind the feeding condensed water and load onto the drying tube that is loaded with anhydrous calcium chloride simultaneously; Slowly at the uniform velocity (about 30 seconds of 100ml solution) toward wherein adding above-mentioned polystyrene solution, Friedel-Crafts reaction 48h is carried out in 75 ℃ of backflows of heating under the magnetic agitation condition behind the backflow dissolving 40min;
(3) the mixed solvent cessation reaction of adding 100ml 95% ethanol/water (volume ratio is 4: 1); The room temperature decompress filter; Use the mixed solution washed twice (each 200ml) of 95% ethanol and 5% watery hydrochloric acid (volume ratio is 3: 1) again; The mixed solution washing of 200ml 95% second alcohol and water (volume ratio is 3: 1) is once filtered the back in 110 ℃ of dry 12h, obtains level hole polystyrene material;
(4) with the level hole polystyrene material that obtains under the nitrogen atmosphere of 400ml/min flow velocity, with the heating rate to 500 of 5 ℃/min ℃, charing 3h promptly obtains polystyrene group hierarchical mesoporous carbon material;
(5) 1g KOH is dissolved in the mixed solution of 10ml water and 6ml absolute ethyl alcohol, adds the 300 order polystyrene group hierarchical mesoporous carbon materials that 1g sieves and obtains through grinding then, mix, mixture is placed 110 ℃ of dry 12h down;
(6) dried mixture is placed retort, under the nitrogen atmosphere of 400ml/min flow velocity, be warming up to 900 ℃ with the heating rate of 5 ℃/min; Through 900 ℃ of activation 3h; When the temperature of retort is reduced to 50 ℃, take out mixture after the activation,, use the 200ml deionized water wash again 1 time with the mixed solution of 100ml deionized water and 10ml 37% hydrochloric acid purging compound 3 times under the situation of boiling; Filter the back in 110 ℃ of dry 12h, obtain the high-specific surface area polystyrene group hierarchical mesoporous carbon material.
With the ASAP2010 absorption appearance nitrogen adsorption method test that U.S. Micromeritics company produces, its specific area of the polystyrene group hierarchical mesoporous carbon material of preparing (BET) is 1820m
2/ g, wherein micropore and external holes specific area are respectively 1197m
2/ g and 623m
2/ g; Pore volume is 1.13cm
3/ g, wherein micropore pore volume and external holes pore volume are respectively 0.58cm
3/ g and 0.55cm
3/ g.
With it is electrode material, is electrolyte with 1-butyl-3-methylimidazole hexafluorophosphate ionic liquid, is assembled into electrochemical capacitor, uses galvanostatic charge to record its quality and is 128F/g than electric capacity.
Embodiment 7
With the high-specific surface area polystyrene group hierarchical mesoporous carbon material of embodiment 2 preparation as electrode material; With tetraethyl ammonium tetrafluoroborate/carbonic allyl ester solution is electrolyte; Be assembled into electrochemical capacitor, use cyclic voltammetry to record its quality and be 253F/g than electric capacity.
Embodiment 8
With the high-specific surface area polystyrene group hierarchical mesoporous carbon material of embodiment 4 preparation as electrode material; With tetraethyl ammonium tetrafluoroborate/carbonic allyl ester solution is electrolyte; Be assembled into electrochemical capacitor, use cyclic voltammetry to record its quality and be 208F/g than electric capacity.
Embodiment 9
With the high-specific surface area polystyrene group hierarchical mesoporous carbon material of embodiment 5 preparation as electrode material; With tetraethyl ammonium tetrafluoroborate/carbonic allyl ester solution is electrolyte; Be assembled into electrochemical capacitor, use cyclic voltammetry to record its quality and be 175F/g than electric capacity.
Embodiment 10
With the high-specific surface area polystyrene group hierarchical mesoporous carbon material of embodiment 6 preparation as electrode material; With tetraethyl ammonium tetrafluoroborate/carbonic allyl ester solution is electrolyte; Be assembled into electrochemical capacitor, use cyclic voltammetry to record its quality and be 155F/g than electric capacity.
The foregoing description is a preferred implementation of the present invention; But execution mode of the present invention is not restricted to the described embodiments; Other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; All should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (9)
1. high-specific surface area level hole charcoal preparation methods; It is characterized in that: this method comprises following operating procedure: linear polystyrene and anhydrous carbon tetrachloride generation Friedel-Crafts cross-linking reaction are prepared polystyrene group hierarchical mesoporous carbon material, then the activation of gained polystyrene group hierarchical mesoporous carbon material is prepared the high-specific surface area polystyrene group hierarchical mesoporous carbon material; The activator that said activation is adopted is KOH.
2. high-specific surface area level hole charcoal preparation methods is characterized in that specifically comprising following operating procedure:
(1) linear polystyrene is added in the anhydrous carbon tetrachloride, be stirred to linear polystyrene and dissolve fully, obtain the polystyrene carbon tetrachloride solution;
(2) aluminum trichloride (anhydrous) is placed reaction vessel, add anhydrous carbon tetrachloride, after the dissolving that refluxes, add step (1) gained polystyrene carbon tetrachloride solution, reflux is carried out the Friedel-Crafts reaction under the stirring condition;
(3) add ethanol/water mixed solvent and stop the Friedel-Crafts reaction, filter and obtain solid product, after washing, filtration and drying, obtain level hole polystyrene material;
(4) step (3) gained level hole polystyrene material is placed retort, the heating charing obtains polystyrene group hierarchical mesoporous carbon material under inert gas atmosphere;
(5) polystyrene group hierarchical mesoporous carbon material is fully mixed in water/ethanolic solution with KOH, mixture is dry;
(6) the dried mixture of step (5) is placed activation furnace, under inert gas atmosphere, carry out high-temperature activation, activation products obtain the high-specific surface area polystyrene group hierarchical mesoporous carbon material after washing, filtration and drying;
Said step (1) to step (3) neutral line polystyrene: aluminum trichloride (anhydrous): anhydrous carbon tetrachloride: the consumption proportion of ethanol/water mixed solvent is 0.2～10g: 3～24g: 100～400ml: 100～200ml, and wherein the consumption of anhydrous carbon tetrachloride is 6～300ml in the step (1);
The consumption proportion of polystyrene group hierarchical mesoporous carbon material and KOH is 1g: 0.5～8g in the said step (5);
Activation condition is warming up to 500～900 ℃, activation 2～6h for the heating rate with 2～5 ℃/min in the said step (6).
3. the preparation method of a kind of high-specific surface area polystyrene group hierarchical mesoporous carbon material according to claim 1 is characterized in that: reflux has the drying tube that loads anhydrous calcium chloride described in the step (2); Said backflow dissolving is at 30～75 ℃ of dissolving 20～80min that reflux; The condition of said Friedel-Crafts reaction is to react 2～72h down at 30～75 ℃.
4. the preparation method of a kind of high-specific surface area polystyrene group hierarchical mesoporous carbon material according to claim 1; It is characterized in that: in the said step (3) ethanol/water mixed solvent for percent by volume be 95% second alcohol and water by 1～8: 1 volume ratio mixes, and its consumption is 100～200ml; Said filtercondition is the room temperature decompress filter; Said wash conditions is: use earlier by ethanol and watery hydrochloric acid by 1～5: the solution washing that 1 volume ratio mixes 1～5 time; Use again by the second alcohol and water by 1～6: the solution washing that 1 volume ratio mixes 1～6 time; Said ethanol is that percent by volume is 95% ethanol, and said watery hydrochloric acid is that percent by volume is 5% hydrochloric acid; Said water is deionized water; Said drying condition is 105～110 ℃ of down dry 2～24h.
5. the preparation method of a kind of high-specific surface area polystyrene group hierarchical mesoporous carbon material according to claim 1 is characterized in that: inert gas atmosphere is the nitrogen atmosphere of 200～800ml/min flow velocity in the said step (4); Said carbonization condition is with the heating rate to 300 of 2～5 ℃/min～900 ℃, charing 2～6h.
6. the preparation method of a kind of high-specific surface area polystyrene group hierarchical mesoporous carbon material according to claim 1 is characterized in that: water/ethanolic solution is that 2～20ml water and 2～6ml absolute ethyl alcohol are mixed in the said step (5); Said polystyrene group hierarchical mesoporous carbon material sieves after the polystyrene group hierarchical mesoporous carbon material in the step (4) is ground, and obtains 100～400 purpose polystyrene group hierarchical mesoporous carbon materials.
7. the preparation method of a kind of high-specific surface area polystyrene group hierarchical mesoporous carbon material according to claim 1 is characterized in that: inert gas atmosphere is the nitrogen atmosphere of 200～800ml/min flow velocity in the said step (6); Temperature with activation products before the said washing is reduced to below 50 ℃; Said wash conditions is: with deionized water and concentrated hydrochloric acid by 5～20: the solution that 1 volume ratio mixes washs under the boiling condition 2～8 times, uses deionized water wash again 1～4 time; Said drying condition is 105～110 ℃ of down dry 6～24h.
8. high-specific surface area polystyrene group hierarchical mesoporous carbon material for preparing according to each said method of claim 1～7, it is characterized in that: the BET specific area of this material is 1820～3100m
2/ g, pore volume are 1.13～2.18cm
3/ g, wherein the micropore pore volume accounts for 24～51%, and outside mesopore and macropore pore volume account for 49～76%.
9. the application of a kind of high-specific surface area polystyrene group hierarchical mesoporous carbon material according to claim 8 in the electrode material of preparation electrochemical capacitor.
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Application publication date: 20120620 |