CN105271193A - Preparation method of elastic and conductive aerogel with ultralow density and ultrahigh specific surface area - Google Patents
Preparation method of elastic and conductive aerogel with ultralow density and ultrahigh specific surface area Download PDFInfo
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Abstract
The invention discloses a preparation method of elastic and conductive aerogel with ultralow density and an ultrahigh specific surface area. According to the method, graphene oxide, resorcinol and formaldehyde have a crosslinking reaction in a water system, hydrogel is prepared, and the elastic and conductive aerogel is prepared after acidification and aging, solvent exchange, supercritical drying and high-temperature carbonization. The conductive aerogel mainly comprises hierarchical-pore carbon/graphene nanosheets, has ultralow density, ultrahigh specific surface area and better elasticity and conductivity. The raw materials have rich sources and low cost, and the prepared aerogel has broader application prospect in the fields of elastic sensors, separation and adsorption, electrode materials, hydrogen storage and the like.
Description
Technical field
The invention belongs to porous carbon materials preparing technical field, be specifically related to the preparation method of a kind of extremely-low density, superhigh specific surface area elastic conduction aerogel.
Background technology
Extremely-low density aerogel (≤10mg/cm
3) be in recent years by a kind of type material of extensive concern, it, due to the very high porosity of material self and extremely-low density, shows splendid application prospect in fields such as lagging material, energy storage material, catalytic material, sorbing materials.Wherein, functionalization extremely-low density aerogel has the material structure of aerogel uniqueness and special function (as elasticity, electroconductibility) enjoys people to favor simultaneously.
Extremely-low density elastic conduction aerogel is the aerogel porous material that a class has better elasticity and electroconductibility, is widely used in fields such as ultracapacitor, elasticity sensor, Chu Qing.Traditional extremely-low density elastic conduction aerogel mainly graphene aerogel, carbon nanotube aerogel, graphene/carbon nano-tube hybrid aerogel, although have good elasticity and electroconductibility, the specific surface area generally (≤1000m on the low side of material
2/ g), in the field such as super capacitor and Chu Qing, performance is not good enough, such as patent documentation CN103274384A discloses " a kind of graphene oxide strengthens carbon aerogels material and its preparation method and application ", and the specific surface area of its carbon aerogels prepared is up to 1100m
2/ g, density is low to moderate 0.02g/cm most
3, the patent documentation CN102774824A specific surface area that discloses " a kind of method that constant pressure and dry prepares Graphene cross-linking type organic aerogel and charcoal-aero gel " its carbon aerogels prepared is 300 ~ 1100m
2/ g, density is 0.10-1.2g/cm
3, patent documentation CN104056582A discloses " a kind of graphene oxide/organic aerogel composite and preparation method thereof ", the density of its organic aerogel prepared is low to moderate 0.14g/cm most
3.Tradition high-specific surface area conduction aerogel mainly carbon aerogels, through the carbonization of resorcinol-formaldehyde organic aerogel, although can possess high-specific surface area (1783m
2/ g), but the higher (20mg/cm of density of material
3), conventional carbon aerogel lacks flexibility simultaneously.
Although therefore it should be noted that extremely-low density elastic conduction aerogel or high-specific surface area conduction aerogel are widely studied, there is extremely-low density (≤10mg/cm simultaneously
3) and superelevation specific surface (>=2000m
2/ g) elastic conduction aerogel material but rarely have report.This is because it is extremely complicated and difficult for giving aerogel material extremely-low density, superhigh specific surface area and the requirement of snappiness to design of material simultaneously.Such as common carbon aerogels material is piled up by carbon nano-particles and is formed, though have high specific surface area, be difficult to reach extremely-low density, material has fragility simultaneously; Such as common Graphene or carbon nanotube aerogel again, form by the graphene film or carbon nanotube with good mechanical properties are three-dimensional netted, there is extremely-low density and good elasticity, but owing to lacking microstructure and cause specific surface area on the low side, affect its performance applications in the field such as super capacitor and Chu Qing.
Therefore, by improving the preparation method of aerogel, control composition and the microstructure change of aerogel, exploitation extremely-low density, superhigh specific surface area elastic conduction aerogel are very necessary and meaningful.
Summary of the invention
As the result of various extensive and careful research and experiment, the present inventor has been found that, by controlling reaction parameter and condition, hydrogel is made by graphene oxide, Resorcinol and formaldehyde crosslinking reaction in aqueous systems, then the elastic conduction aerogel of extremely-low density, superhigh specific surface area can be prepared through supercritical drying, high temperature cabonization, based on this discovery, complete the present invention.
An object of the present invention is to solve at least the problems referred to above and/or defect, and the advantage will illustrated at least is below provided.
In order to realize, according to these objects of the present invention and other advantage, providing the preparation method of a kind of extremely-low density, superhigh specific surface area elastic conduction aerogel, comprise the following steps:
Step one, get Resorcinol that weight ratio is 1:50 ~ 80 and deionized water mixing, after being stirred to solution clarification, add formaldehyde solution, after stirring 15 ~ 30min, add sodium carbonate solution, after stirring 15 ~ 30min, add graphene oxide dispersion; Then the total mass mark adding Resorcinol and formaldehyde in deionized water to mixing liquid is 0.8 ~ 1wt%, obtains dispersion liquid; The weight ratio of the described formaldehyde solution that adds and Resorcinol is 1:0.5 ~ 0.8; In the described sodium carbonate solution added, the mass ratio of sodium carbonate and Resorcinol is 1:100 ~ 250; In the described graphene oxide dispersion added, the quality of graphene oxide accounts for 1 ~ 4% of Resorcinol and formaldehyde total mass;
Step 2, dispersion liquid is added in encloses container, place 3 ~ 15 days under the constant temperature of 60 ~ 80 DEG C, obtain hydrogel;
Step 3, hydrogel added to carry out acidifying in trifluoroacetic acid/acetone mixing solutions aging, acidifying digestion time is 6 ~ 8 days;
Step 4, acidifying is aging after hydrogel be placed in the container that fresh acetone is housed and carry out exchange of solvent, every day changes fresh acetone, continues 4 ~ 6 days;
Supercritical extraction instrument put into by step 5, hydrogel exchange of solvent completed, and carries out CO 2 supercritical drying, obtains organic aerogel;
Step 6, organic aerogel is put into temperature programmed control charring furnace, rise to 150 DEG C from room temperature to vacuumize, insulation 2h, then rare gas element is passed into the gas velocity of 50mL/min, 200 ~ 300 DEG C are warming up to the speed of 0.5 ~ 1 DEG C/min, insulation 25 ~ 35min, then 400 ~ 600 DEG C are warming up to the speed of 1 ~ 3 DEG C/min, insulation 30 ~ 60min, then 700 ~ 800 DEG C are warming up to the speed of 2 ~ 4 DEG C/min, insulation 1 ~ 2h, then 900 ~ 1100 DEG C are warming up to the speed of 0.5 ~ 1 DEG C/min, insulation 1 ~ 3h, naturally cool to room temperature, obtain extremely-low density, superhigh specific surface area elastic conduction aerogel.
Preferably, in described step one, the density of formaldehyde solution is 1.066g/mL, and in formaldehyde solution, the massfraction of formaldehyde is 38%.
Preferably, in described step one, the mass concentration of sodium carbonate solution is 0.1 ~ 0.3mol/L.
Preferably, in described step one, the concentration of graphene oxide dispersion is 1 ~ 3mg/mL.
Preferably, in described step 3, the volume ratio of trifluoroacetic acid/acetone is 1:30 ~ 35.
Preferably, in described step 5, the condition of supercritical drying is temperature 45 C, pressure 200bar.
Preferably, the rare gas element in described step 6 is the one of helium, argon gas and nitrogen.
Preferably, obtain dispersion liquid in described step one after, dispersion liquid is placed in the ultrasonic 30 ~ 60min of ultrasonic wave separating apparatus, the regulation range of ultrasonic power is at 500 ~ 2000W, and ultrasonic frequency is at 20 ~ 60KHz.
Preferably, complete ultrasonic after, dispersion liquid is delivered in high-voltage pulse electric field processing chamber with 5 ~ 10mL/min flow velocity through peristaltic pump, utilize pulsed electric field pre-treatment 20 ~ 50min, the pretreated parameter of pulsed electric field is: pulse strength 1000 ~ 1500V/cm, pulse width 60 ~ 120 μ s, pulse number 10 ~ 30, recurrent interval 300-500ms.
Preferably, after described step 6 completes, the elastic conduction aerogel obtained is added in rotary oven, 300 ~ 500 DEG C are warming up to the speed microwave heating of 2 ~ 4 DEG C/min, insulation 10 ~ 20min, then 600 ~ 800 DEG C are warming up to the speed microwave heating of 1 ~ 2 DEG C/min, insulation 10 ~ 20min, then 900 ~ 1000 DEG C are warming up to the speed microwave heating of 0.5 ~ 1 DEG C/min, insulation 1 ~ 2h, the process lasts heated up in each stage passes into water vapour with the flow of 20 ~ 50mL/min, obtain the extremely-low density after activating, superhigh specific surface area elastic conduction aerogel, the frequency of described microwave heating is 915MHz, the speed of rotation of described rotary oven is 10 ~ 15r/min.
In step one of the present invention, Resorcinol and formaldehyde carry out addition reaction and crosslinking reaction in surface of graphene oxide, form resorcinol-formaldehyde/Graphene sandwich nanometer sheet structure.Graphene oxide add the gelation rate contributing to improving whole reaction system.
The present invention at least comprises following beneficial effect: the carbon aerogels of preparation is primarily of hierarchical porous structure carbon/graphene nanometer sheet composition, and density is 8mg/cm
3, specific surface area is 2650m
2/ g, specific conductivity is 7S/m, elastic deformation is between 30-70%, gained aerogel has ultralow density, the specific surface area of superelevation, preferably elasticity and higher specific conductivity, in elasticity sensor, the fields such as absorption, electrode materials, Chu Qing that are separated, there is preferred application prospect, and the raw materials used abundance of the present invention, cheap.
Part is embodied by explanation below by other advantage of the present invention, target and feature, part also will by research and practice of the present invention by those skilled in the art is understood.
Accompanying drawing illustrates:
Fig. 1 is the scanning electron microscope sem figure of conduction aerogel prepared by the embodiment of the present invention 2; As can be seen from the figure the aerogel that conducts electricity forms three-dimensional network by hierarchical porous structure carbon/graphene nanometer sheet self-assembly, and nanometer sheet assembled unit has sandwich structure;
Fig. 2 is the X-ray diffraction XRD spectra of conduction aerogel prepared by the embodiment of the present invention 2; X-ray diffraction peak proves that graphene-based assembled unit is in stripping stacking states;
Fig. 3 is the Raman scattering figure of conduction aerogel prepared by the embodiment of the present invention 2; Raman spectrogram proves the existence of amorphous carbon layer;
Fig. 4 is the nitrogen adsorption curve of conduction aerogel prepared by the embodiment of the present invention 2; This curve proves the existence of a large amount of micropores and mesoporous composition in aerogel;
Fig. 5 is the stress-strain curve of conduction aerogel prepared by the embodiment of the present invention 2; This curve display aerogel has good elasticity performance, can realize the elastic deformation of 30 (a), 50 (b) and 70% (c) respectively.
Embodiment:
Below in conjunction with accompanying drawing, the present invention is described in further detail, can implement according to this with reference to specification sheets word to make those skilled in the art.
Should be appreciated that used hereinly such as " to have ", other element one or more do not allotted in " comprising " and " comprising " term or the existence of its combination or interpolation.
Embodiment 1:
Step one, get 0.647g Resorcinol and be dissolved in 50mL deionized water, after being stirred to solution clarification, adding density is 1.066g/mL, formaldehyde massfraction is the formaldehyde solution 0.871mL of 38%, after stirring 15min, add the sodium carbonate solution 0.147mL that substance withdrawl syndrome is 0.2mol/L, after stirring 15min, add the graphene oxide dispersion 10mL that concentration is 1mg/mL; Then the total mass mark adding Resorcinol and formaldehyde in deionized water to mixing liquid is 1wt%, obtains dispersion liquid;
Step 2, dispersion liquid is added in encloses container, place 4 days under the constant temperature of 80 DEG C, obtain hydrogel; This process mainly plays gel and forms hydrogel;
Step 3, hydrogel added to carry out acidifying in trifluoroacetic acid/acetone mixing solutions that volume ratio is 3:97 aging, acidifying digestion time is 7 days;
Step 4, acidifying is aging after hydrogel be placed in the container that fresh acetone is housed and carry out exchange of solvent, every day changes fresh acetone, continues 5 days;
Supercritical extraction instrument put into by step 5, hydrogel exchange of solvent completed, and is 45 DEG C in temperature, and pressure is carry out CO 2 supercritical drying under the condition of 200bar, obtains organic aerogel;
Step 6, organic aerogel is put into temperature programmed control charring furnace, rise to 150 DEG C from room temperature to vacuumize, insulation 2h, then argon gas is passed into the gas velocity of 50mL/min, 200 DEG C are warming up to the speed of 0.5 DEG C/min, insulation 25min, then 400 DEG C are warming up to the speed of 1 DEG C/min, insulation 30min, is then warming up to 800 DEG C with the speed of 2 DEG C/min, insulation 2h, then 1050 DEG C are warming up to the speed of 1 DEG C/min, insulation 3h, naturally cools to room temperature, obtains extremely-low density, superhigh specific surface area elastic conduction aerogel.
Embodiment 2:
Step one, get 0.647g Resorcinol and be dissolved in 50mL deionized water, after being stirred to solution clarification, adding density is 1.066g/mL, formaldehyde massfraction is the formaldehyde solution 0.871mL of 38%, after stirring 30min, add the sodium carbonate solution 0.147mL that substance withdrawl syndrome is 0.2mol/L, after stirring 30min, add the graphene oxide dispersion 20mL that concentration is 1mg/mL; Then the total mass mark adding Resorcinol and formaldehyde in deionized water to mixing liquid is 1wt%, obtains dispersion liquid;
Step 2, dispersion liquid is added in encloses container, place 3 days under the constant temperature of 80 DEG C, obtain hydrogel; This process mainly plays gel and forms hydrogel;
Step 3, hydrogel added to carry out acidifying in trifluoroacetic acid/acetone mixing solutions that volume ratio is 3:97 aging, acidifying digestion time is 7 days;
Step 4, acidifying is aging after hydrogel be placed in the container that fresh acetone is housed and carry out exchange of solvent, every day changes fresh acetone, continues 5 days;
Supercritical extraction instrument put into by step 5, hydrogel exchange of solvent completed, and is 45 DEG C in temperature, and pressure is carry out CO 2 supercritical drying under the condition of 200bar, obtains organic aerogel;
Step 6, organic aerogel is put into temperature programmed control charring furnace, rise to 150 DEG C from room temperature to vacuumize, insulation 2h, then argon gas is passed into the gas velocity of 50mL/min, 300 DEG C are warming up to the speed of 1 DEG C/min, insulation 35min, then 500 DEG C are warming up to the speed of 2 DEG C/min, insulation 40min, is then warming up to 800 DEG C with the speed of 3 DEG C/min, insulation 1h, then 1050 DEG C are warming up to the speed of 0.6 DEG C/min, insulation 3h, naturally cools to room temperature, obtains extremely-low density, superhigh specific surface area elastic conduction aerogel.
Embodiment 3:
Step one, get 1g Resorcinol and be dissolved in 80mL deionized water, after being stirred to solution clarification, adding density is 1.066g/mL, formaldehyde massfraction is the formaldehyde solution 1.876mL of 38%, after stirring 30min, add the sodium carbonate solution 0.472mL that substance withdrawl syndrome is 0.2mol/L, after stirring 30min, add the graphene oxide dispersion 35mL that concentration is 1mg/mL; Then the total mass mark adding Resorcinol and formaldehyde in deionized water to mixing liquid is 1wt%, obtains dispersion liquid; Dispersion liquid is placed in the ultrasonic 30min of ultrasonic wave separating apparatus, ultrasonic power is 1200W, and ultrasonic frequency is at 28KHz;
Step 2, the dispersion liquid after ultrasonic is added in encloses container, place 5 days under the constant temperature of 60 DEG C, obtain hydrogel; This process mainly plays gel and forms hydrogel;
Step 3, hydrogel added to carry out acidifying in trifluoroacetic acid/acetone mixing solutions that volume ratio is 3:97 aging, acidifying digestion time is 7 days;
Step 4, acidifying is aging after hydrogel be placed in the container that fresh acetone is housed and carry out exchange of solvent, every day changes fresh acetone, continues 5 days;
Supercritical extraction instrument put into by step 5, hydrogel exchange of solvent completed, and is 45 DEG C in temperature, and pressure is carry out CO 2 supercritical drying under the condition of 200bar, obtains organic aerogel;
Step 6, organic aerogel is put into temperature programmed control charring furnace, rise to 150 DEG C from room temperature to vacuumize, insulation 2h, then argon gas is passed into the gas velocity of 50mL/min, 300 DEG C are warming up to the speed of 1 DEG C/min, insulation 35min, then 500 DEG C are warming up to the speed of 2 DEG C/min, insulation 40min, is then warming up to 800 DEG C with the speed of 3 DEG C/min, insulation 1h, then 1050 DEG C are warming up to the speed of 0.6 DEG C/min, insulation 3h, naturally cools to room temperature, obtains extremely-low density, superhigh specific surface area elastic conduction aerogel.
Embodiment 4:
Step one, get 1g Resorcinol and be dissolved in 60mL deionized water, after being stirred to solution clarification with the speed of 300r/min, adding density is 1.066g/mL, formaldehyde massfraction is the formaldehyde solution 1.876mL of 38%, after stirring 20min with the speed of 300r/min, add the sodium carbonate solution 0.472mL that substance withdrawl syndrome is 0.2mol/L, after stirring 20min, add the graphene oxide dispersion 35mL that concentration is 1mg/mL; Then the total mass mark adding Resorcinol and formaldehyde in deionized water to mixing liquid is 1wt%, obtains dispersion liquid; Dispersion liquid is placed in the ultrasonic 50min of ultrasonic wave separating apparatus, ultrasonic power is 1200W, and ultrasonic frequency is at 28KHz; Complete ultrasonic after, dispersion liquid is delivered in high-voltage pulse electric field processing chamber with 10mL/min flow velocity through peristaltic pump, utilize pulsed electric field pre-treatment 50min, the pretreated parameter of pulsed electric field is: pulse strength 1000V/cm, pulse width 60 μ s, pulse number 10, recurrent interval 300ms;
Step 2, dispersion liquid step one processed add in encloses container, place 10 days, obtain hydrogel under the constant temperature of 70 DEG C; This process mainly plays gel and forms hydrogel;
Step 3, hydrogel added to carry out acidifying in trifluoroacetic acid/acetone mixing solutions that volume ratio is 1:35 aging, acidifying digestion time is 8 days;
Step 4, acidifying is aging after hydrogel be placed in the container that fresh acetone is housed and carry out exchange of solvent, every day changes fresh acetone, continues 6 days;
Supercritical extraction instrument put into by step 5, hydrogel exchange of solvent completed, and is 45 DEG C in temperature, and pressure is carry out CO 2 supercritical drying under the condition of 200bar, obtains organic aerogel;
Step 6, organic aerogel is put into temperature programmed control charring furnace, rise to 150 DEG C from room temperature to vacuumize, insulation 2h, then argon gas is passed into the gas velocity of 50mL/min, 250 DEG C are warming up to the speed of 0.6 DEG C/min, insulation 30min, then 400 DEG C are warming up to the speed of 1 DEG C/min, insulation 40min, is then warming up to 700 DEG C with the speed of 2 DEG C/min, insulation 1h, then 1050 DEG C are warming up to the speed of 0.8 DEG C/min, insulation 3h, naturally cools to room temperature, obtains extremely-low density, superhigh specific surface area elastic conduction aerogel.
Embodiment 5:
Step one, get 8g Resorcinol and be dissolved in 400mL deionized water, after being stirred to solution clarification, adding density is 1.066g/mL, formaldehyde massfraction is the formaldehyde solution 15mL of 38%, after stirring 30min, add the sodium carbonate solution 1.26mL that substance withdrawl syndrome is 0.3mol/L, after stirring 30min, add the graphene oxide dispersion 141mL that concentration is 2mg/mL; Then the total mass mark adding Resorcinol and formaldehyde in deionized water to mixing liquid is 1wt%, obtains dispersion liquid; Dispersion liquid is placed in the ultrasonic 60min of ultrasonic wave separating apparatus, ultrasonic power is 1200W, and ultrasonic frequency is at 28KHz;
Step 2, the dispersion liquid after ultrasonic is added in encloses container, place 5 days under the constant temperature of 60 DEG C, obtain hydrogel; This process mainly plays gel and forms hydrogel;
Step 3, hydrogel added to carry out acidifying in trifluoroacetic acid/acetone mixing solutions that volume ratio is 3:97 aging, acidifying digestion time is 7 days;
Step 4, acidifying is aging after hydrogel be placed in the container that fresh acetone is housed and carry out exchange of solvent, every day changes fresh acetone, continues 6 days;
Supercritical extraction instrument put into by step 5, hydrogel exchange of solvent completed, and is 45 DEG C in temperature, and pressure is carry out CO 2 supercritical drying under the condition of 200bar, obtains organic aerogel;
Step 6, organic aerogel is put into temperature programmed control charring furnace, rise to 150 DEG C from room temperature to vacuumize, insulation 2h, then argon gas is passed into the gas velocity of 50mL/min, 300 DEG C are warming up to the speed of 1 DEG C/min, insulation 35min, then 500 DEG C are warming up to the speed of 2 DEG C/min, insulation 40min, is then warming up to 800 DEG C with the speed of 3 DEG C/min, insulation 1h, then 1050 DEG C are warming up to the speed of 0.6 DEG C/min, insulation 3h, naturally cools to room temperature, obtains extremely-low density, superhigh specific surface area elastic conduction aerogel; After carbonization completes, the elastic conduction aerogel obtained is added in rotary oven, 300 DEG C are warming up to the speed microwave heating of 4 DEG C/min, insulation 10min, is then warming up to 600 DEG C with the speed microwave heating of 1 DEG C/min, insulation 10min, then 1000 DEG C are warming up to the speed microwave heating of 0.5 DEG C/min, insulation 1h, the process lasts heated up in each stage passes into water vapour with the flow of 20mL/min, obtains extremely-low density, superhigh specific surface area elastic conduction aerogel after activating; The frequency of described microwave heating is 915MHz; The speed of rotation of described rotary oven is 10r/min.
Embodiment 6:
Step one, get 8g Resorcinol and be dissolved in 480mL deionized water, after being stirred to solution clarification with the speed of 300r/min, adding density is 1.066g/mL, formaldehyde massfraction is the formaldehyde solution 15mL of 38%, after stirring 20min with the speed of 300r/min, add the sodium carbonate solution 1.26mL that substance withdrawl syndrome is 0.3mol/L, after stirring 20min, add the graphene oxide dispersion 141mL that concentration is 2mg/mL; Then the total mass mark adding Resorcinol and formaldehyde in deionized water to mixing liquid is 1wt%, obtains dispersion liquid; Dispersion liquid is placed in the ultrasonic 50min of ultrasonic wave separating apparatus, ultrasonic power is 1200W, and ultrasonic frequency is at 28KHz; Complete ultrasonic after, dispersion liquid is delivered in high-voltage pulse electric field processing chamber with 5mL/min flow velocity through peristaltic pump, utilize pulsed electric field pre-treatment 30min, the pretreated parameter of pulsed electric field is: pulse strength 1200V/cm, pulse width 80 μ s, pulse number 20, recurrent interval 350ms;
Step 2, dispersion liquid step one processed add in encloses container, place 10 days, obtain hydrogel under the constant temperature of 70 DEG C; This process mainly plays gel and forms hydrogel;
Step 3, hydrogel added to carry out acidifying in trifluoroacetic acid/acetone mixing solutions that volume ratio is 1:35 aging, acidifying digestion time is 8 days;
Step 4, acidifying is aging after hydrogel be placed in the container that fresh acetone is housed and carry out exchange of solvent, every day changes fresh acetone, continues 6 days;
Supercritical extraction instrument put into by step 5, hydrogel exchange of solvent completed, and is 45 DEG C in temperature, and pressure is carry out CO 2 supercritical drying under the condition of 200bar, obtains organic aerogel;
Step 6, organic aerogel is put into temperature programmed control charring furnace, rise to 150 DEG C from room temperature to vacuumize, insulation 2h, then argon gas is passed into the gas velocity of 50mL/min, 250 DEG C are warming up to the speed of 0.6 DEG C/min, insulation 30min, then 400 DEG C are warming up to the speed of 1 DEG C/min, insulation 40min, is then warming up to 700 DEG C with the speed of 2 DEG C/min, insulation 1h, then 1050 DEG C are warming up to the speed of 0.8 DEG C/min, insulation 3h, naturally cools to room temperature, obtains extremely-low density, superhigh specific surface area elastic conduction aerogel; The elastic conduction aerogel obtained is added in rotary oven, 500 DEG C are warming up to the speed microwave heating of 3 DEG C/min, insulation 10min, then 700 DEG C are warming up to the speed microwave heating of 2 DEG C/min, insulation 20min, is then warming up to 950 DEG C with the speed microwave heating of 1 DEG C/min, insulation 1h, the process lasts heated up in each stage passes into water vapour with the flow of 30mL/min, obtains extremely-low density, superhigh specific surface area elastic conduction aerogel after activating; The frequency of described microwave heating is 915MHz; The speed of rotation of described rotary oven is 10r/min.
Embodiment 7:
Step one, get 0.647g Resorcinol and be dissolved in 50mL deionized water, after being stirred to solution clarification, adding density is 1.066g/mL, formaldehyde massfraction is the formaldehyde solution 0.871mL of 38%, after stirring 30min, add the sodium carbonate solution 0.147mL that substance withdrawl syndrome is 0.2mol/L, after stirring 30min, add the graphene oxide dispersion 20mL that concentration is 1mg/mL; Then the total mass mark adding Resorcinol and formaldehyde in deionized water to mixing liquid is 1wt%, obtains dispersion liquid;
Step 2, dispersion liquid is added in encloses container, place 3 days under the constant temperature of 80 DEG C, obtain hydrogel; This process mainly plays gel and forms hydrogel;
Step 3, hydrogel added to carry out acidifying in trifluoroacetic acid/acetone mixing solutions that volume ratio is 1:30 aging, acidifying digestion time is 7 days;
Step 4, acidifying is aging after hydrogel be placed in the container that fresh acetone is housed and carry out exchange of solvent, every day changes fresh acetone, continues 5 days;
Supercritical extraction instrument put into by step 5, hydrogel exchange of solvent completed, and is 45 DEG C in temperature, and pressure is carry out CO 2 supercritical drying under the condition of 200bar, obtains organic aerogel;
Step 6, organic aerogel is put into temperature programmed control charring furnace, rise to 150 DEG C from room temperature to vacuumize, insulation 2h, then argon gas is passed into the gas velocity of 50mL/min, 300 DEG C are warming up to the speed of 0.6 DEG C/min, insulation 35min, then 600 DEG C are warming up to the speed of 2 DEG C/min, insulation 40min, is then warming up to 800 DEG C with the speed of 3 DEG C/min, insulation 1h, then 1050 DEG C are warming up to the speed of 0.6 DEG C/min, insulation 3h, naturally cools to room temperature, obtains extremely-low density, superhigh specific surface area elastic conduction aerogel; The elastic conduction aerogel obtained is added in rotary oven, 500 DEG C are warming up to the speed microwave heating of 4 DEG C/min, insulation 15min, then 700 DEG C are warming up to the speed microwave heating of 2 DEG C/min, insulation 20min, is then warming up to 1000 DEG C with the speed microwave heating of 1 DEG C/min, insulation 1h, the process lasts heated up in each stage passes into water vapour with the flow of 50mL/min, obtains extremely-low density, superhigh specific surface area elastic conduction aerogel after activating; The frequency of described microwave heating is 915MHz; The speed of rotation of described rotary oven is 10 ~ 15r/min.
Table 1 shows the performance test data of the elastic conduction aerogel of preparation in embodiment 1 ~ 7.Wherein the quality of the aerogel material of embodiment 1 ~ 7 gained is recorded by 100,000/balance, size is recorded by vernier callipers, specific surface area is recorded by full-automatic adsorption instrument, and stress-strain curve is recorded by dynamic mechanical analysis tester, and specific conductivity is recorded by four probe method.
Table 1
The present invention is by controlling reaction parameter and condition, hydrogel is made by graphene oxide, Resorcinol and formaldehyde crosslinking reaction in aqueous systems, then can prepare the elastic conduction aerogel of extremely-low density, superhigh specific surface area through supercritical drying, high temperature cabonization, aerogel is primarily of hierarchical porous structure carbon/graphene nanometer sheet composition.The raw material adopted in the process of preparation is in ratio of the present invention, and parameters is in described scope, as shown in table 1, and the carbon aerogels density of preparation is lower than 8.5mg/cm
3, specific surface area is greater than 2580m
2/ g, specific conductivity is 7S/m, elastic deformation is between 30-70%, gained aerogel has ultralow density, the specific surface area of superelevation, preferably elasticity and higher specific conductivity, in elasticity sensor, the fields such as absorption, electrode materials, Chu Qing that are separated, there is preferred application prospect, and the raw materials used abundance of the present invention, cheap.In addition, adopt and ultrasonicly to process dispersion liquid, ultrasonic energy discharges huge energy, localized hyperthermia's hyperbaric environment of generation and have the microjet of strong impacts, easily realize each phase Homogeneous phase mixing, elimination partial concn is uneven, improves speed of response, stimulates the formation of cenotype, and can also shearing action be played to reunion, be conducive to the formation of micro-nano laminated structure, reaction product is dispersed in microemulsion with the form of micro-nano laminated structure, and existence that can be stable.In addition adopt the process of pulsed electric field, reaction product is dispersed in microemulsion with the laminated structure of micro-nano-scale, and existence that can be more stable, the sandwich nanometer sheet size of generation is homogeneous, after carbonization completes, carry out activation treatment, activation treatment effectively can improve the pore structure of carbon aerogels, the significant specific surface area improving carbon aerogels, and in the process of activation, adopt temperature programming, temperature programming can play the greatest benefit of each temperature section, reduce the medial temperature of whole process, reduce total power loss, improve overall capacity usage ratio, meanwhile, temperature programming decreases the heating unit working hour at high temperature, thus the requirement reduced heating unit high-temperature stability, improve rate of utilization and the reliability of heating installation, activation simultaneously adopts microwave heating, microwave is a kind of hertzian wave with special property, its frequency is between radiowave and light wave, its heating rate is fast, raw material can be made in short-term, to reach carbonization and activate temperature required, therefore energy consumption is lower, time is also shorter, simultaneously in microwave heating process, material is self-heating, relative to the mode of existing air conduction, the projecting envrionment temperature of temperature of charge, therefore microwave heating is adopted to reduce sintering temperature, and the hot environment of material inside and outside homogeneous temperature is provided, fully can penetrate into the inside of material, improve substance characteristics, adjustment material structure and shape, obtain high-quality product.
Although embodiment of the present invention are open as above, but it is not restricted to listed in specification sheets and embodiment utilization, it can be applied to various applicable the field of the invention completely, for those skilled in the art, can easily realize other amendment, therefore do not deviating under the universal that claim and equivalency range limit, the present invention is not limited to specific details and illustrates here and the legend described.
Claims (10)
1. a preparation method for extremely-low density, superhigh specific surface area elastic conduction aerogel, is characterized in that, comprise the following steps:
Step one, get Resorcinol that weight ratio is 1:50 ~ 80 and deionized water mixing, after being stirred to solution clarification, add formaldehyde solution, after stirring 15 ~ 30min, add sodium carbonate solution, after stirring 15 ~ 30min, add graphene oxide dispersion; Then the total mass mark adding Resorcinol and formaldehyde in deionized water to mixing liquid is 0.8 ~ 1wt%, obtains dispersion liquid; The weight ratio of the described formaldehyde solution that adds and Resorcinol is 1:0.5 ~ 0.8; In the described sodium carbonate solution added, the mass ratio of sodium carbonate and Resorcinol is 1:100 ~ 250; In the described graphene oxide dispersion added, the quality of graphene oxide accounts for 1 ~ 4% of Resorcinol and formaldehyde total mass;
Step 2, dispersion liquid is added in encloses container, place 3 ~ 15 days under the constant temperature of 60 ~ 80 DEG C, obtain hydrogel;
Step 3, hydrogel added to carry out acidifying in trifluoroacetic acid/acetone mixing solutions aging, acidifying digestion time is 6 ~ 8 days;
Step 4, acidifying is aging after hydrogel be placed in the container that fresh acetone is housed and carry out exchange of solvent, every day changes fresh acetone, continues 4 ~ 6 days;
Supercritical extraction instrument put into by step 5, hydrogel exchange of solvent completed, and carries out CO 2 supercritical drying, obtains organic aerogel;
Step 6, organic aerogel is put into temperature programmed control charring furnace, rise to 150 DEG C from room temperature to vacuumize, insulation 2h, then rare gas element is passed into the gas velocity of 50mL/min, 200 ~ 300 DEG C are warming up to the speed of 0.5 ~ 1 DEG C/min, insulation 25 ~ 35min, then 400 ~ 600 DEG C are warming up to the speed of 1 ~ 3 DEG C/min, insulation 30 ~ 60min, then 700 ~ 800 DEG C are warming up to the speed of 2 ~ 4 DEG C/min, insulation 1 ~ 2h, then 900 ~ 1100 DEG C are warming up to the speed of 0.5 ~ 1 DEG C/min, insulation 1 ~ 3h, naturally cool to room temperature, obtain extremely-low density, superhigh specific surface area elastic conduction aerogel.
2. the preparation method of extremely-low density as claimed in claim 1, superhigh specific surface area elastic conduction aerogel, it is characterized in that, in described step one, the density of formaldehyde solution is 1.066g/mL, and in formaldehyde solution, the massfraction of formaldehyde is 38%.
3. the preparation method of extremely-low density as claimed in claim 1, superhigh specific surface area elastic conduction aerogel, it is characterized in that, in described step one, the mass concentration of sodium carbonate solution is 0.1 ~ 0.3mol/L.
4. the preparation method of extremely-low density as claimed in claim 1, superhigh specific surface area elastic conduction aerogel, it is characterized in that, in described step one, the concentration of graphene oxide dispersion is 1 ~ 3mg/mL.
5. the preparation method of extremely-low density as claimed in claim 1, superhigh specific surface area elastic conduction aerogel, it is characterized in that, in described step 3, the volume ratio of trifluoroacetic acid/acetone is 1:30 ~ 35.
6. the preparation method of extremely-low density as claimed in claim 1, superhigh specific surface area elastic conduction aerogel, it is characterized in that, in described step 5, the condition of supercritical drying is temperature 45 C, pressure 200bar.
7. the preparation method of extremely-low density as claimed in claim 1, superhigh specific surface area elastic conduction aerogel, it is characterized in that, the rare gas element in described step 6 is the one of helium, argon gas and nitrogen.
8. the preparation method of extremely-low density as claimed in claim 1, superhigh specific surface area elastic conduction aerogel, it is characterized in that, obtain dispersion liquid in described step one after, dispersion liquid is placed in the ultrasonic 30 ~ 60min of ultrasonic wave separating apparatus, the regulation range of ultrasonic power is at 500 ~ 2000W, and ultrasonic frequency is at 20 ~ 60KHz.
9. the preparation method of extremely-low density as claimed in claim 8, superhigh specific surface area elastic conduction aerogel, it is characterized in that, complete ultrasonic after, dispersion liquid is delivered in high-voltage pulse electric field processing chamber with 5 ~ 10mL/min flow velocity through peristaltic pump, utilize pulsed electric field pre-treatment 20 ~ 50min, the pretreated parameter of pulsed electric field is: pulse strength 1000 ~ 1500V/cm, pulse width 60 ~ 120 μ s, pulse number 10 ~ 30, recurrent interval 300-500ms.
10. extremely-low density as claimed in claim 1, the preparation method of superhigh specific surface area elastic conduction aerogel, it is characterized in that, after described step 6 completes, the elastic conduction aerogel obtained is added in rotary oven, 300 ~ 500 DEG C are warming up to the speed microwave heating of 2 ~ 4 DEG C/min, insulation 10 ~ 20min, then 600 ~ 800 DEG C are warming up to the speed microwave heating of 1 ~ 2 DEG C/min, insulation 10 ~ 20min, then 900 ~ 1000 DEG C are warming up to the speed microwave heating of 0.5 ~ 1 DEG C/min, insulation 1 ~ 2h, the process lasts heated up in each stage passes into water vapour with the flow of 20 ~ 50mL/min, obtain the extremely-low density after activating, superhigh specific surface area elastic conduction aerogel, the frequency of described microwave heating is 915MHz, the speed of rotation of described rotary oven is 10 ~ 15r/min.
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