CN105271193B - A kind of extremely-low density, the preparation method of superhigh specific surface area elastic conduction aeroge - Google Patents
A kind of extremely-low density, the preparation method of superhigh specific surface area elastic conduction aeroge Download PDFInfo
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Abstract
The invention discloses the preparation method of a kind of extremely-low density, superhigh specific surface area elastic conduction aeroge, the method makes hydrogel by graphene oxide, resorcinol and formaldehyde through cross-linking reaction in aqueous systems, then acidified aging, solvent exchange, supercritical drying, high temperature cabonization are prepared from, this conductive aeroge is mainly made up of hierarchical porous structure carbon graphite alkene nanometer sheet, it has ultralow density, the specific surface area of superelevation, preferably elasticity and electric conductivity.The raw materials used abundance of the present invention, cheap, gained aeroge has preferred application prospect in elasticity sensor, the fields such as absorption, electrode material, hydrogen storage that separate.
Description
Technical field
The invention belongs to porous carbon materials preparing technical field is and in particular to a kind of extremely-low density, superhigh specific surface area bullet
Property conductive aeroge preparation method.
Background technology
Extremely-low density aeroge (≤10mg/cm3) it is that it is due to material in recent years by a kind of new material of extensive concern
Itself very high porosity and extremely-low density, show in fields such as heat-barrier material, energy storage material, catalysis material, adsorbing materials
Splendid application prospect.Wherein, functionalization extremely-low density aeroge has the unique material structure of aeroge and special work(simultaneously
(as elasticity, electric conductivity) people can be enjoyed to favor.
Extremely-low density elastic conduction aeroge is the aeroge porous material that a class has preferably elasticity and electric conductivity, super
The fields such as level capacitor, elasticity sensor, hydrogen storage are widely used.Traditional extremely-low density elastic conduction aeroge is mainly graphite
Alkene aeroge, carbon nanotube aerogel, graphene/carbon nano-tube hybrid aerogel although having good elasticity and electric conductivity,
But the generally low (≤1000m of the specific surface area of material2/ g), in the field such as super capacitor and hydrogen storage, performance is not good enough, example
As patent documentation CN 103274384A discloses, " a kind of graphene oxide strengthens carbon aerogels material and preparation method thereof and answers
With ", the specific surface area of the carbon aerogels of its preparation is up to 1100m2/ g, density the most as little as 0.02g/cm3, patent documentation
CN102774824A disclose " a kind of method that constant pressure and dry prepares Graphene cross-linking type organic aerogel and charcoal-aero gel " its
The specific surface area of the carbon aerogels of preparation is 300～1100m2/ g, density is 0.10-1.2g/cm3, patent documentation
CN104056582A discloses " a kind of graphene oxide/organic aerogel composite and preparation method thereof ", and what it was prepared has
The density of machine aeroge the most as little as 0.14g/cm3.Traditional high-specific surface area conduction aeroge is mainly carbon aerogels, through isophthalic two
Phenol-formaldehyde organic aerogel carbonization is although high-specific surface area (1783m can be possessed2/ g), but density of material is higher
(20mg/cm3), traditional carbon aerogels lack flexibility simultaneously.
It is thus desirable to it is to be noted that although extremely-low density elastic conduction aeroge or high-specific surface area conduction aeroge by
Widely studied, but there is extremely-low density (≤10mg/cm simultaneously3) and superelevation specific surface (>=2000m2/ g) elastic conduction airsetting
Glue material is but rarely reported.This is because give aerogel material extremely-low density, superhigh specific surface area and high resiliency to material simultaneously
The requirement of material design is extremely complex and difficult.For example common carbon aerogels material is piled up by carbon nano-particles and is formed, though tool
There is high specific surface area, but a difficult to reach extremely-low density, material has fragility simultaneously；For example common Graphene or carbon nanometer again
Pipe aeroge, is constituted by the graphene film with good mechanical properties or CNT are three-dimensional netted, have extremely-low density and
Good elasticity, but lead to specific surface area low due to lacking micro structure, affect it in the field such as super capacitor and hydrogen storage
Performance applications.
Therefore, by improving the preparation method of aeroge, composition and the microstructure change of aeroge are controlled, exploitation is ultralow
Density, superhigh specific surface area elastic conduction aeroge are very necessary and meaningful.
Content of the invention
As the result of various extensive and careful researchs and experiment, it has been found by the inventor that by controlling
Response parameter and condition, make hydrogel, Ran Houjing by graphene oxide, resorcinol and formaldehyde through cross-linking reaction in aqueous systems
Supercritical drying, high temperature cabonization can prepare the elastic conduction aeroge of extremely-low density, superhigh specific surface area, based on this
Existing, complete the present invention.
It is an object of the invention to solving at least the above and/or defect, and provide at least will be described later excellent
Point.
In order to realize according to object of the present invention and further advantage, there is provided a kind of extremely-low density, superelevation specific surface
The preparation method of long-pending elastic conduction aeroge, comprises the following steps：
Step one, take weight than for 1:50～80 resorcinol and deionized water mixing, stir to solution clarification, plus
Enter formalin, after stirring 15～30min, add sodium carbonate liquor, after stirring 15～30min, add graphene oxide dispersion
Liquid；The total mass fraction being subsequently adding deionized water to resorcinol in mixing liquid and formaldehyde is 0.8～1wt%, is divided
Dispersion liquid；The formalin of described addition and the weight of resorcinol are than for 1:0.5～0.8；In the sodium carbonate liquor of described addition
Sodium carbonate is 1 with the mass ratio of resorcinol：100～250；Graphene oxide in the graphene oxide dispersion of described addition
Quality accounts for the 1～4% of resorcinol and formaldehyde gross mass；
Step 2, by dispersion liquid add hermetic container in, under 60～80 DEG C of constant temperature place 3～15 days, obtain
Hydrogel；
Step 3, hydrogel is added carry out being acidified aging in trifluoroacetic acid/acetone mixed solution, acidifying ageing time is
6～8 days；
Step 4, will acidifying aging after hydrogel be placed in equipped with carrying out solvent exchange in the container of fresh acetone, daily
Change fresh acetone, continue 4～6 days；
Step 5, the hydrogel completing solvent exchange are put in supercritical extraction instrument, carry out CO 2 supercritical and do
Dry, obtain organic aerogel；
Step 6, organic aerogel is put in temperature programmed control retort, rises to 150 DEG C of evacuation from room temperature, be incubated 2h,
Then noble gases are passed through with the air velocity of 50mL/min, are warming up to 200～300 DEG C with the speed of 0.5～1 DEG C/min, protect
Warm 25～35min, is then warming up to 400～600 DEG C with the speed of 1～3 DEG C/min, is incubated 30～60min, then with 2～4
DEG C/speed of min is warming up to 700～800 DEG C, is incubated 1～2h, then it is warming up to 900 with the speed of 0.5～1 DEG C/min～
1100 DEG C, it is incubated 1～3h, naturally cools to room temperature, obtain extremely-low density, superhigh specific surface area elastic conduction aeroge.
Preferably, in described step one, the density of formalin is 1.066g/mL, and in formalin, the quality of formaldehyde is divided
Number is 38%.
Preferably, in described step one, the mass concentration of sodium carbonate liquor 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 noble gases in described step 6 are one kind of helium, argon and nitrogen.
Preferably, after obtaining dispersion liquid in described step one, dispersion liquid is placed in ultrasonic 30 in ultrasound wave separating apparatus
～60min, in 500～2000W, supersonic frequency is in 20～60KHz for the range of accommodation of ultrasonic power.
Preferably, complete ultrasonic after, dispersion liquid is delivered to high-voltage pulse with 5～10mL/min flow velocity through peristaltic pump
In electric field processing chamber, using high-pressure pulse electric pretreatment 20～50min, the parameter of high-pressure pulse electric pretreatment is：Pulse
Intensity 1000～1500V/cm, pulse width 60～120 μ s, pulse number 10～30, pulse spacing 300-500ms.
Preferably, after the completion of described step 6, the elastic conduction obtaining aeroge is added in revolving burner, with 2～4
DEG C/the speed microwave heating of min is warming up to 300～500 DEG C, is incubated 10～20min, then with the speed microwave of 1～2 DEG C/min
It is heated to 600～800 DEG C, be incubated 10～20min, be then warming up to 900 with the speed microwave heating of 0.5～1 DEG C/min
～1000 DEG C, it is incubated 1～2h, the process heating up in each stage continues to be passed through vapor with the flow of 20～50mL/min, obtains
Extremely-low density after activation, superhigh specific surface area elastic conduction aeroge；The frequency of described microwave heating is 915MHz；Described rotation
The rotary speed of converter is 10～15r/min.
In step one of the present invention, resorcinol and formaldehyde carry out additive reaction and cross-linking reaction, shape in surface of graphene oxide
Become resorcinol-formaldehyde/Graphene sandwich nanometer chip architecture.The addition of graphene oxide is favorably improved whole reaction system
Gelation rate.
The present invention at least includes following beneficial effect：The carbon aerogels of preparation are mainly received by hierarchical porous structure carbon graphite alkene
Rice piece composition, density is 8mg/cm3, specific surface area is 2650m2/ g, electrical conductivity is 7S/m, and elastic deformation is between 30-70%, institute
Obtain aeroge and there is ultralow density, the specific surface area of superelevation, preferably elastic and higher electrical conductivity, in elastomeric sensor
Device, the fields such as absorption, electrode material, hydrogen storage that separate have preferred application prospect, and the raw materials used abundance of the present invention, valency
Lattice are cheap.
Part is embodied by the further advantage of the present invention, target and feature by description below, and part also will be by this
Invention research and practice and be understood by the person skilled in the art.
Brief description：
Fig. 1 is the scanning electron microscope sem figure of the conductive aeroge of the embodiment of the present invention 2 preparation；As can be seen from the figure conductive
Aeroge is self-assembly of three-dimensional network by hierarchical porous structure carbon graphite alkene nanometer sheet, and nanometer sheet module unitss have sandwich
Structure；
Fig. 2 is the X-ray diffraction XRD spectra of the conductive aeroge of the embodiment of the present invention 2 preparation；X-ray diffraction peak proves
Graphene-based module unitss are in stripping stacking states；
Fig. 3 is the Raman scattering figure of the conductive aeroge of the embodiment of the present invention 2 preparation；Raman spectrogram proves amorphous carbon layer
Presence；
Fig. 4 is the nitrogen adsorption curve of the conductive aeroge of the embodiment of the present invention 2 preparation；This curve proves big in aeroge
Amount micropore and the presence of mesoporous composition；
Fig. 5 is the load-deformation curve of the conductive aeroge of the embodiment of the present invention 2 preparation；This curve display aeroge tool
There is good elastic performance, the elastic deformation of 30% (a), 50% (b) and 70% (c) can be realized respectively.
Specific embodiment：
The present invention is described in further detail below in conjunction with the accompanying drawings, to make those skilled in the art with reference to description literary composition
Word can be implemented according to this.
Embodiment 1：
Step one, take 0.647g resorcinol to be dissolved in 50mL deionized water, stir to solution clarification, add the density to be
1.066g/mL, formaldehyde mass fraction is 38% formalin 0.871mL, and after stirring 15min, addition substance withdrawl syndrome is
The sodium carbonate liquor 0.147mL of 0.2mol/L, after stirring 15min, adds the graphene oxide dispersion that concentration is 1mg/mL
10mL；The total mass fraction being subsequently adding deionized water to resorcinol in mixing liquid and formaldehyde is 1wt%, is disperseed
Liquid；
Step 2, by dispersion liquid add hermetic container in, under 80 DEG C of constant temperature place 4 days, obtain hydrogel；This
The effect that individual process has been mainly gel forms hydrogel；
Step 3, by hydrogel add volume ratio be 3:Carry out being acidified aging in 97 trifluoroacetic acid/acetone mixed solution,
Acidifying ageing time is 7 days；
Step 4, will acidifying aging after hydrogel be placed in equipped with carrying out solvent exchange in the container of fresh acetone, daily
Change fresh acetone, continue 5 days；
Step 5, the hydrogel completing solvent exchange are put in supercritical extraction instrument, are 45 DEG C in temperature, and pressure is
Carry out carbon dioxide supercritical fluid drying under conditions of 200bar, obtain organic aerogel；
Step 6, organic aerogel is put in temperature programmed control retort, rises to 150 DEG C of evacuation from room temperature, be incubated 2h,
Then argon is passed through with the air velocity of 50mL/min, is warming up to 200 DEG C with the speed of 0.5 DEG C/min, be incubated 25min, then
It is warming up to 400 DEG C with the speed of 1 DEG C/min, is incubated 30min, is then warming up to 800 DEG C with the speed of 2 DEG C/min, be incubated 2h, so
It is warming up to 1050 DEG C with the speed of 1 DEG C/min afterwards, be incubated 3h, naturally cool to room temperature, obtain extremely-low density, superhigh specific surface area
Elastic conduction aeroge.
Embodiment 2：
Step one, take 0.647g resorcinol to be dissolved in 50mL deionized water, stir to solution clarification, add the density to be
1.066g/mL, formaldehyde mass fraction is 38% formalin 0.871mL, and after stirring 30min, addition substance withdrawl syndrome is
The sodium carbonate liquor 0.147mL of 0.2mol/L, after stirring 30min, adds the graphene oxide dispersion that concentration is 1mg/mL
20mL；The total mass fraction being subsequently adding deionized water to resorcinol in mixing liquid and formaldehyde is 1wt%, is disperseed
Liquid；
Step 2, by dispersion liquid add hermetic container in, under 80 DEG C of constant temperature place 3 days, obtain hydrogel；This
The effect that individual process has been mainly gel forms hydrogel；
Step 3, by hydrogel add volume ratio be 3:Carry out being acidified aging in 97 trifluoroacetic acid/acetone mixed solution,
Acidifying ageing time is 7 days；
Step 4, will acidifying aging after hydrogel be placed in equipped with carrying out solvent exchange in the container of fresh acetone, daily
Change fresh acetone, continue 5 days；
Step 5, the hydrogel completing solvent exchange are put in supercritical extraction instrument, are 45 DEG C in temperature, and pressure is
Carry out carbon dioxide supercritical fluid drying under conditions of 200bar, obtain organic aerogel；
Step 6, organic aerogel is put in temperature programmed control retort, rises to 150 DEG C of evacuation from room temperature, be incubated 2h,
Then argon is passed through with the air velocity of 50mL/min, is warming up to 300 DEG C with the speed of 1 DEG C/min, be incubated 35min, then with 2
DEG C/speed of min is warming up to 500 DEG C, it is incubated 40min, is then warming up to 800 DEG C with the speed of 3 DEG C/min, be incubated 1h, then
It is warming up to 1050 DEG C with the speed of 0.6 DEG C/min, be incubated 3h, naturally cool to room temperature, obtain extremely-low density, superhigh specific surface area
Elastic conduction aeroge.
Embodiment 3：
Step one, take 1g resorcinol to be dissolved in 80mL deionized water, stir to solution clarification, add the density to be
1.066g/mL, formaldehyde mass fraction is 38% formalin 1.876mL, and after stirring 30min, addition substance withdrawl syndrome is
The sodium carbonate liquor 0.472mL of 0.2mol/L, after stirring 30min, adds the graphene oxide dispersion that concentration is 1mg/mL
35mL；The total mass fraction being subsequently adding deionized water to resorcinol in mixing liquid and formaldehyde is 1wt%, is disperseed
Liquid；Dispersion liquid is placed in ultrasonic 30min in ultrasound wave separating apparatus, ultrasonic power is 1200W, and supersonic frequency is in 28KHz；
Step 2, will be ultrasonic after dispersion liquid add hermetic container in, under 60 DEG C of constant temperature place 5 days, obtain
Hydrogel；The effect that this process has been mainly gel forms hydrogel；
Step 3, by hydrogel add volume ratio be 3:Carry out being acidified aging in 97 trifluoroacetic acid/acetone mixed solution,
Acidifying ageing time is 7 days；
Step 4, will acidifying aging after hydrogel be placed in equipped with carrying out solvent exchange in the container of fresh acetone, daily
Change fresh acetone, continue 5 days；
Step 5, the hydrogel completing solvent exchange are put in supercritical extraction instrument, are 45 DEG C in temperature, and pressure is
Carry out carbon dioxide supercritical fluid drying under conditions of 200bar, obtain organic aerogel；
Step 6, organic aerogel is put in temperature programmed control retort, rises to 150 DEG C of evacuation from room temperature, be incubated 2h,
Then argon is passed through with the air velocity of 50mL/min, is warming up to 300 DEG C with the speed of 1 DEG C/min, be incubated 35min, then with 2
DEG C/speed of min is warming up to 500 DEG C, it is incubated 40min, is then warming up to 800 DEG C with the speed of 3 DEG C/min, be incubated 1h, then
It is warming up to 1050 DEG C with the speed of 0.6 DEG C/min, be incubated 3h, naturally cool to room temperature, obtain extremely-low density, superhigh specific surface area
Elastic conduction aeroge.
Embodiment 4：
Step one, take 1g resorcinol to be dissolved in 60mL deionized water, stirred to solution clarification with the speed of 300r/min
Afterwards, density is added to be 1.066g/mL, formaldehyde mass fraction is 38% formalin 1.876mL, stirs with the speed of 300r/min
After mixing 20min, add the sodium carbonate liquor 0.472mL that substance withdrawl syndrome is 0.2mol/L, after stirring 20min, add concentration
Graphene oxide dispersion 35mL for 1mg/mL；It is subsequently adding deionized water total to resorcinol in mixing liquid and formaldehyde
Mass fraction is 1wt%, obtains dispersion liquid；Dispersion liquid is placed in ultrasonic 50min in ultrasound wave separating apparatus, ultrasonic power is
1200W, supersonic frequency is in 28KHz；Complete ultrasonic after, dispersion liquid is delivered to high-tension pulse with 10mL/min flow velocity through peristaltic pump
Rush in electric field processing chamber, using high-pressure pulse electric pretreatment 50min, the parameter of high-pressure pulse electric pretreatment is：Pulse is strong
Degree 1000V/cm, pulse width 60 μ s, pulse number 10, pulse spacing 300ms；
Step 2, the dispersion liquid completing step one process add in hermetic container, place under 70 DEG C of constant temperature
10 days, obtain hydrogel；The effect that this process has been mainly gel forms hydrogel；
Step 3, by hydrogel add volume ratio be 1:Carry out being acidified aging in 35 trifluoroacetic acid/acetone mixed solution,
Acidifying ageing time is 8 days；
Step 4, will acidifying aging after hydrogel be placed in equipped with carrying out solvent exchange in the container of fresh acetone, daily
Change fresh acetone, continue 6 days；
Step 5, the hydrogel completing solvent exchange are put in supercritical extraction instrument, are 45 DEG C in temperature, and pressure is
Carry out carbon dioxide supercritical fluid drying under conditions of 200bar, obtain organic aerogel；
Step 6, organic aerogel is put in temperature programmed control retort, rises to 150 DEG C of evacuation from room temperature, be incubated 2h,
Then argon is passed through with the air velocity of 50mL/min, is warming up to 250 DEG C with the speed of 0.6 DEG C/min, be incubated 30min, then
It is warming up to 400 DEG C with the speed of 1 DEG C/min, is incubated 40min, is then warming up to 700 DEG C with the speed of 2 DEG C/min, be incubated 1h, so
It is warming up to 1050 DEG C with the speed of 0.8 DEG C/min afterwards, be incubated 3h, naturally cool to room temperature, obtain extremely-low density, superelevation specific surface
Long-pending elastic conduction aeroge.
Embodiment 5：
Step one, take 8g resorcinol to be dissolved in 400mL deionized water, stir to solution clarification, add the density to be
1.066g/mL, formaldehyde mass fraction is 38% formalin 15mL, and after stirring 30min, addition substance withdrawl syndrome is
The sodium carbonate liquor 1.26mL of 0.3mol/L, after stirring 30min, adds the graphene oxide dispersion that concentration is 2mg/mL
141mL；The total mass fraction being subsequently adding deionized water to resorcinol in mixing liquid and formaldehyde is 1wt%, is disperseed
Liquid；Dispersion liquid is placed in ultrasonic 60min in ultrasound wave separating apparatus, ultrasonic power is 1200W, and supersonic frequency is in 28KHz；
Step 2, will be ultrasonic after dispersion liquid add hermetic container in, under 60 DEG C of constant temperature place 5 days, obtain
Hydrogel；The effect that this process has been mainly gel forms hydrogel；
Step 3, by hydrogel add volume ratio be 3:Carry out being acidified aging in 97 trifluoroacetic acid/acetone mixed solution,
Acidifying ageing time is 7 days；
Step 4, will acidifying aging after hydrogel be placed in equipped with carrying out solvent exchange in the container of fresh acetone, daily
Change fresh acetone, continue 6 days；
Step 5, the hydrogel completing solvent exchange are put in supercritical extraction instrument, are 45 DEG C in temperature, and pressure is
Carry out carbon dioxide supercritical fluid drying under conditions of 200bar, obtain organic aerogel；
Step 6, organic aerogel is put in temperature programmed control retort, rises to 150 DEG C of evacuation from room temperature, be incubated 2h,
Then argon is passed through with the air velocity of 50mL/min, is warming up to 300 DEG C with the speed of 1 DEG C/min, be incubated 35min, then with 2
DEG C/speed of min is warming up to 500 DEG C, it is incubated 40min, is then warming up to 800 DEG C with the speed of 3 DEG C/min, be incubated 1h, then
It is warming up to 1050 DEG C with the speed of 0.6 DEG C/min, be incubated 3h, naturally cool to room temperature, obtain extremely-low density, superhigh specific surface area
Elastic conduction aeroge；After the completion of carbonization, the elastic conduction obtaining aeroge is added in revolving burner, with the speed of 4 DEG C/min
Microwave heating is warming up to 300 DEG C, is incubated 10min, is then warming up to 600 DEG C with the speed microwave heating of 1 DEG C/min, insulation
10min, is then warming up to 1000 DEG C with the speed microwave heating of 0.5 DEG C/min, is incubated 1h, and the process heating up in each stage continues
Vapor is passed through with the flow of 20mL/min, the extremely-low density after being activated, superhigh specific surface area elastic conduction aeroge；Institute
The frequency stating microwave heating is 915MHz；The rotary speed of described revolving burner is 10r/min.
Embodiment 6：
Step one, take 8g resorcinol to be dissolved in 480mL deionized water, stirred to solution clarification with the speed of 300r/min
Afterwards, density is added to be 1.066g/mL, formaldehyde mass fraction is 38% formalin 15mL, with the speed stirring of 300r/min
After 20min, add the sodium carbonate liquor 1.26mL that substance withdrawl syndrome is 0.3mol/L, after stirring 20min, addition concentration is
Graphene oxide dispersion 141mL of 2mg/mL；It is subsequently adding deionized water total to resorcinol in mixing liquid and formaldehyde
Mass fraction is 1wt%, obtains dispersion liquid；Dispersion liquid is placed in ultrasonic 50min in ultrasound wave separating apparatus, ultrasonic power is
1200W, supersonic frequency is in 28KHz；Complete ultrasonic after, dispersion liquid is delivered to high-tension pulse with 5mL/min flow velocity through peristaltic pump
Rush in electric field processing chamber, using high-pressure pulse electric pretreatment 30min, the parameter of high-pressure pulse electric pretreatment is：Pulse is strong
Degree 1200V/cm, pulse width 80 μ s, pulse number 20, pulse spacing 350ms；
Step 2, the dispersion liquid completing step one process add in hermetic container, place under 70 DEG C of constant temperature
10 days, obtain hydrogel；The effect that this process has been mainly gel forms hydrogel；
Step 3, by hydrogel add volume ratio be 1:Carry out being acidified aging in 35 trifluoroacetic acid/acetone mixed solution,
Acidifying ageing time is 8 days；
Step 4, will acidifying aging after hydrogel be placed in equipped with carrying out solvent exchange in the container of fresh acetone, daily
Change fresh acetone, continue 6 days；
Step 5, the hydrogel completing solvent exchange are put in supercritical extraction instrument, are 45 DEG C in temperature, and pressure is
Carry out carbon dioxide supercritical fluid drying under conditions of 200bar, obtain organic aerogel；
Step 6, organic aerogel is put in temperature programmed control retort, rises to 150 DEG C of evacuation from room temperature, be incubated 2h,
Then argon is passed through with the air velocity of 50mL/min, is warming up to 250 DEG C with the speed of 0.6 DEG C/min, be incubated 30min, then
It is warming up to 400 DEG C with the speed of 1 DEG C/min, is incubated 40min, is then warming up to 700 DEG C with the speed of 2 DEG C/min, be incubated 1h, so
It is warming up to 1050 DEG C with the speed of 0.8 DEG C/min afterwards, be incubated 3h, naturally cool to room temperature, obtain extremely-low density, superelevation specific surface
Long-pending elastic conduction aeroge；The elastic conduction obtaining aeroge is added in revolving burner, with the speed microwave heating liter of 3 DEG C/min
Temperature, to 500 DEG C, is incubated 10min, is then warming up to 700 DEG C with the speed microwave heating of 2 DEG C/min, is incubated 20min, then with 1
DEG C/the speed microwave heating of min is warming up to 950 DEG C, is incubated 1h, the process heating up in each stage continues with the flow of 30mL/min
It is passed through vapor, the extremely-low density after being activated, superhigh specific surface area elastic conduction aeroge；The frequency of described microwave heating
For 915MHz；The rotary speed of described revolving burner is 10r/min.
Embodiment 7：
Step one, take 0.647g resorcinol to be dissolved in 50mL deionized water, stir to solution clarification, add the density to be
1.066g/mL, formaldehyde mass fraction is 38% formalin 0.871mL, and after stirring 30min, addition substance withdrawl syndrome is
The sodium carbonate liquor 0.147mL of 0.2mol/L, after stirring 30min, adds the graphene oxide dispersion that concentration is 1mg/mL
20mL；The total mass fraction being subsequently adding deionized water to resorcinol in mixing liquid and formaldehyde is 1wt%, is disperseed
Liquid；
Step 2, by dispersion liquid add hermetic container in, under 80 DEG C of constant temperature place 3 days, obtain hydrogel；This
The effect that individual process has been mainly gel forms hydrogel；
Step 3, by hydrogel add volume ratio be 1:Carry out being acidified aging in 30 trifluoroacetic acid/acetone mixed solution,
Acidifying ageing time is 7 days；
Step 4, will acidifying aging after hydrogel be placed in equipped with carrying out solvent exchange in the container of fresh acetone, daily
Change fresh acetone, continue 5 days；
Step 5, the hydrogel completing solvent exchange are put in supercritical extraction instrument, are 45 DEG C in temperature, and pressure is
Carry out carbon dioxide supercritical fluid drying under conditions of 200bar, obtain organic aerogel；
Step 6, organic aerogel is put in temperature programmed control retort, rises to 150 DEG C of evacuation from room temperature, be incubated 2h,
Then argon is passed through with the air velocity of 50mL/min, is warming up to 300 DEG C with the speed of 0.6 DEG C/min, be incubated 35min, then
It is warming up to 600 DEG C with the speed of 2 DEG C/min, is incubated 40min, is then warming up to 800 DEG C with the speed of 3 DEG C/min, be incubated 1h, so
It is warming up to 1050 DEG C with the speed of 0.6 DEG C/min afterwards, be incubated 3h, naturally cool to room temperature, obtain extremely-low density, superelevation specific surface
Long-pending elastic conduction aeroge；The elastic conduction obtaining aeroge is added in revolving burner, with the speed microwave heating liter of 4 DEG C/min
Temperature, to 500 DEG C, is incubated 15min, is then warming up to 700 DEG C with the speed microwave heating of 2 DEG C/min, is incubated 20min, then with 1
DEG C/the speed microwave heating of min is warming up to 1000 DEG C, is incubated 1h, the process heating up in each stage continues with the stream of 50mL/min
Amount is passed through vapor, the extremely-low density after being activated, superhigh specific surface area elastic conduction aeroge；The frequency of described microwave heating
Rate is 915MHz；The rotary speed of described revolving burner is 10～15r/min.
Table 1 shows the performance test data of the elastic conduction aeroge of preparation in embodiment 1～7.Wherein embodiment 1～
The quality of the aerogel material of 7 gained is recorded by 100,000/balance, and size is recorded by slide gauge, and specific surface area is by entirely certainly
Dynamic adsorption instrument records, and load-deformation curve is recorded by dynamic mechanical analysis tester, and electrical conductivity is recorded by four probe method.
Table 1
The present invention passes through to control response parameter and condition, by graphene oxide, resorcinol and formaldehyde through handing in aqueous systems
Hydrogel is made in connection reaction, then can prepare the bullet of extremely-low density, superhigh specific surface area through supercritical drying, high temperature cabonization
Property conductive aeroge, aeroge is mainly made up of hierarchical porous structure carbon graphite alkene nanometer sheet.Adopt during preparation is former
In ratio of the present invention, in described scope, as shown in table 1, the carbon aerogels density of preparation is less than parameters material
8.5mg/cm3, specific surface area is more than 2580m2/ g, electrical conductivity is 7S/m, and elastic deformation has between 30-70%, gained aeroge
Ultralow density, the specific surface area of superelevation, preferably elastic and higher electrical conductivity, in elasticity sensor, separate absorption, electricity
The fields such as pole material, hydrogen storage have preferred application prospect, and the raw materials used abundance of the present invention, cheap.Additionally, adopting
With ultrasonic, dispersion liquid is processed, ultrasonic wave energy discharges huge energy, localized hyperthermia's environment under high pressure of generation and having
The microjet of strong impacts, easily realize each mutually uniformly mix, eliminate local concentration uneven, improve response speed, stimulate
The formation of cenotype, and shear action be may also operate as to reunion, be conducive to the formation of micro-nano lamellar structure, product is with micro-
The form of lamellar structure received is dispersed in microemulsion, and can be stable presence.In addition adopt the process of high-pressure pulse electric, instead
Answer product to be dispersed in microemulsion with the lamellar structure of micro-nano-scale, and can be more stable presence, the three of generation
Mingzhi's nanometer sheet size is homogeneous；After the completion of carbonization, carry out activation processing, activation processing can effectively improve carbon aerogels
Pore structure, significantly improves the specific surface area of carbon aerogels；And adopt temperature programming, temperature programming energy during activation
Enough play the greatest benefit of each temperature section, reduce the mean temperature of whole process, reduce total energy loss, improve entirety
Capacity usage ratio, meanwhile, temperature programming decreases the heater working time at high temperature, thus reducing to heater
The requirement of high-temperature stability, improves utilization rate and the reliability of firing equipment；Activation adopts microwave heating simultaneously, and microwave is one
Plant the electromagnetic wave with special nature, between radio wave and light wave, its rate of heat addition is fast, can make raw material short for its frequency
When interior reach carbonization and activation temperature required, therefore energy consumption is relatively low, and the time is also shorter, and simultaneously in microwave heating process, material is
Self-heating, with respect to the mode of existing air conduction, the projecting ambient temperature of temperature of charge, therefore adopt microwave heating
Sintering temperature can be reduced, and provide material inside and outside temperature uniform hot environment, can fully penetrate into the inside of material, improve thing
Matter characteristic, adjustment material structure and shape, obtain high-quality product.
Although embodiment of the present invention is disclosed as above, it is not restricted to listed in description and embodiment
With, it can be applied to various suitable the field of the invention completely, for those skilled in the art, can be easily
Realize other modification, therefore under the general concept being limited without departing substantially from claim and equivalency range, the present invention does not limit
In specific details with shown here as the legend with description.
Claims (10)
1. the preparation method of a kind of extremely-low density, superhigh specific surface area elastic conduction aeroge is it is characterised in that include following walking
Suddenly：
Step one, take weight than for 1:50～80 resorcinol and deionized water mixing, stir to solution clarification, add first
Aldehyde solution, after stirring 15～30min, adds sodium carbonate liquor, after stirring 15～30min, adds graphene oxide dispersion；So
Addition deionized water is 0.8～1wt% to the total mass fraction of resorcinol in mixing liquid and formaldehyde afterwards, obtains dispersion liquid；
The formalin of described addition and the weight of resorcinol are than for 1:0.5～0.8；Sodium carbonate in the sodium carbonate liquor of described addition
Mass ratio with resorcinol is 1：100～250；In the graphene oxide dispersion of described addition, the quality of graphene oxide accounts for
Resorcinol and the 1～4% of formaldehyde gross mass；
Step 2, by dispersion liquid add hermetic container in, under 60～80 DEG C of constant temperature place 3～15 days, obtain water-setting
Glue；
Step 3, hydrogel is added carry out being acidified aging in trifluoroacetic acid/acetone mixed solution, acidifying ageing time is 6～8
My god；
Step 4, will be aging for acidifying after hydrogel be placed in and carry out solvent exchange equipped with the container of fresh acetone, daily change
Fresh acetone, continues 4～6 days；
Step 5, the hydrogel completing solvent exchange are put in supercritical extraction instrument, carry out carbon dioxide supercritical fluid drying, obtain
To organic aerogel；
Step 6, organic aerogel is put in temperature programmed control retort, rise to 150 DEG C of evacuation from room temperature, be incubated 2h, then
Noble gases are passed through with the air velocity of 50mL/min, are warming up to 200～300 DEG C with the speed of 0.5～1 DEG C/min, be incubated 25
～35min, is then warming up to 400～600 DEG C with the speed of 1～3 DEG C/min, is incubated 30～60min, then with 2～4 DEG C/min
Speed be warming up to 700～800 DEG C, be incubated 1～2h, be then warming up to 900～1100 DEG C with the speed of 0.5～1 DEG C/min, protect
Warm 1～3h, naturally cools to room temperature, obtains extremely-low density, superhigh specific surface area elastic conduction aeroge.
2. extremely-low density as claimed in claim 1, the preparation method of superhigh specific surface area elastic conduction aeroge, its feature exists
In in described step one, the density of formalin is 1.066g/mL, and in formalin, the mass fraction of formaldehyde is 38%.
3. extremely-low density as claimed in claim 1, the preparation method of superhigh specific surface area elastic conduction aeroge, its feature
It is, in described step one, the molar concentration of sodium carbonate liquor is 0.1～0.3mol/L.
4. extremely-low density as claimed in claim 1, the preparation method of superhigh specific surface area elastic conduction aeroge, its feature exists
In in described step one, the concentration of graphene oxide dispersion is 1～3mg/mL.
5. extremely-low density as claimed in claim 1, the preparation method of superhigh specific surface area elastic conduction aeroge, its feature exists
In in described step 3, the volume ratio of trifluoroacetic acid/acetone is 1：30～35.
6. extremely-low density as claimed in claim 1, the preparation method of superhigh specific surface area elastic conduction aeroge, its feature exists
In in described step 5, the condition of supercritical drying is temperature 45 C, pressure 200bar.
7. extremely-low density as claimed in claim 1, the preparation method of superhigh specific surface area elastic conduction aeroge, its feature exists
In the noble gases in described step 6 are one kind of helium, argon and nitrogen.
8. extremely-low density as claimed in claim 1, the preparation method of superhigh specific surface area elastic conduction aeroge, its feature exists
In obtaining being placed in dispersion liquid after dispersion liquid ultrasonic 30～60min in ultrasound wave separating apparatus, ultrasonic work(in described step one
, in 500～2000W, supersonic frequency is in 20～60kHz for the range of accommodation of rate.
9. extremely-low density as claimed in claim 8, the preparation method of superhigh specific surface area elastic conduction aeroge, its feature exists
In, complete ultrasonic after, dispersion liquid is delivered in high-voltage pulse electric field processing chamber with 5～10mL/min flow velocity through peristaltic pump,
Using high-pressure pulse electric pretreatment 20～50min, the parameter of high-pressure pulse electric pretreatment is：Pulse strength 1000～
1500V/cm, pulse width 60～120 μ s, pulse number 10～30, pulse spacing 300-500ms.
10. extremely-low density as claimed in claim 1, the preparation method of superhigh specific surface area elastic conduction aeroge, its feature
It is, after the completion of described step 6, the elastic conduction obtaining aeroge is added in revolving burner, with the speed of 2～4 DEG C/min
Microwave heating is warming up to 300～500 DEG C, is incubated 10～20min, is then warming up to the speed microwave heating of 1～2 DEG C/min
600～800 DEG C, it is incubated 10～20min, is then warming up to 900～1000 DEG C with the speed microwave heating of 0.5～1 DEG C/min, protect
Warm 1～2h, the process heating up in each stage continues to be passed through vapor with the flow of 20～50mL/min, ultralow after being activated
Density, superhigh specific surface area elastic conduction aeroge；The frequency of described microwave heating is 915MHz；The rotation speed of described revolving burner
Spend for 10～15r/min.
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| CN106365142B (en) * | 2016-09-13 | 2019-01-25 | 同济大学 | A kind of preparation method of the compound carbon aerogels of high-specific surface area High conductivity graphene based on chemical crosslinking |
| CN106542517A (en) * | 2016-12-06 | 2017-03-29 | 绵阳泛博新材料科技有限公司 | The preparation method of carbon aerogels |
| CN107026028A (en) * | 2017-03-03 | 2017-08-08 | 南京林业大学 | A kind of method that utilization biological material quickly prepares ultracapacitor carbon aerogels |
| CN107973283B (en) * | 2017-11-01 | 2021-05-14 | 华南理工大学 | Elastic carbon aerogel and preparation method and application thereof |
| CN108601316B (en) * | 2018-01-18 | 2019-12-10 | 航天特种材料及工艺技术研究所 | Preparation method and application of electromagnetic shielding material |
| CN110165151A (en) * | 2018-02-05 | 2019-08-23 | 北京欧美中科学技术研究院 | A kind of graphene aerogel negative electrode material of high capacity and preparation method thereof |
| CN111229136B (en) * | 2018-11-29 | 2022-02-08 | 昆山科技大学 | Method for detecting gas by using carbon aerogel adsorption material |
| CN110407208A (en) * | 2019-08-07 | 2019-11-05 | 贵州梅岭电源有限公司 | A kind of preparation method of mesoporous graphene-based charcoal-aero gel |
| CN110817871A (en) * | 2019-10-09 | 2020-02-21 | 贵州梅岭电源有限公司 | Preparation method and application of nitrogen-doped graphene-based carbon aerogel microspheres |
| CN114506839A (en) * | 2022-02-24 | 2022-05-17 | 西安理工大学 | Electrically conductive aerogel sheet and method of making same |
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| CN104056582A (en) * | 2013-03-18 | 2014-09-24 | 北京化工大学 | Graphene oxide/organic aerogel composite material and preparation method thereof |
| CN103274384A (en) * | 2013-04-24 | 2013-09-04 | 中科院广州化学有限公司 | Graphene oxide reinforced carbon aerogel material, and preparation method and application thereof |
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