CN114956834A - Reinforced graphene composite aerogel and preparation method thereof - Google Patents
Reinforced graphene composite aerogel and preparation method thereof Download PDFInfo
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- 239000011240 wet gel Substances 0.000 claims abstract description 45
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 36
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 32
- 239000012700 ceramic precursor Substances 0.000 claims abstract description 32
- 239000000919 ceramic Substances 0.000 claims abstract description 28
- 239000002245 particle Substances 0.000 claims abstract description 26
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000011148 porous material Substances 0.000 claims abstract description 21
- WOZZOSDBXABUFO-UHFFFAOYSA-N tri(butan-2-yloxy)alumane Chemical compound [Al+3].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] WOZZOSDBXABUFO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
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- 238000002210 supercritical carbon dioxide drying Methods 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 238000000197 pyrolysis Methods 0.000 claims description 23
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 22
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
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- JVKRKMWZYMKVTQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JVKRKMWZYMKVTQ-UHFFFAOYSA-N 0.000 description 1
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- 238000005054 agglomeration Methods 0.000 description 1
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Abstract
The invention belongs to the technical field of composite aerogel, and discloses a wet gel prepared by taking a graphene oxide and polysilazane ceramic precursor as raw materials, taking aluminum sec-butoxide as an aluminum source and divinylbenzene as a cross-linking agent, adding an organic solvent, and then carrying out hydrothermal reaction; by hydrothermal reaction and supercritical CO 2 Drying process combined with ceramic precursor conversion method to prepare high-temperature heat-insulating SiCN-Al with nano interpenetrating structure 2 O 3 the/rGO composite aerogel. The Si isCN‑Al 2 O 3 the/rGO composite aerogel comprises two-dimensional nano graphene sheets, wherein nanoscale SiCN-Al is loaded on the two-dimensional nano graphene sheets 2 O 3 Ceramic particles, SiCN-Al 2 O 3 The ceramic particles are connected with each other, and form a porous framework network with the two-dimensional nano graphene sheet layer, and the porous framework network has nano-scale uniform pores. The composite aerogel disclosed by the invention has excellent mechanical properties and good high-temperature heat-insulating property, and can meet the thermal protection requirement of a novel aircraft in a high-temperature environment.
Description
Technical Field
The invention belongs to the technical field of composite aerogel, and particularly relates to reinforced graphene composite aerogel and a preparation method thereof.
Technical Field
China's aerospace industry is rapidly developing, China's manned aerospace engineering has completely shifted to the phase of space station construction, and the material demand for aerospace engineering is continuously increasing. The novel aerospace craft has the characteristics of high Mach number, long endurance time and the like, and the requirements on a thermal protection system are increasingly strict. Among them, the heat insulating material is one of the key materials for securing various aircrafts.
At present, aerogel materials applied to the field of heat insulation are mostly formed by mutually aggregating nano-scale particles or polymer molecular chains to form a nano-porous structure, although the aerogel materials have higher specific surface area and porosity, the aerogel materials are mostly in an open pore structure, and the probability of collision among gas molecules in the aerogel is higher, so that the efficiency of inhibiting gaseous heat conductivity is lower, and the heat conductivity is higher. In addition, most of traditional ceramic aerogels have poor mechanical properties, have the problems of low strength, high brittleness, easy collapse of an internal nano-pore structure under a high-temperature condition and the like, and are difficult to be independently used as a heat insulation material.
Disclosure of Invention
Aiming at the technical defects of the existing graphene aerogel in the aspects of high-temperature stability, mechanical property, inhibition of gaseous heat conductivity and the like, the invention provides the reinforced graphene composite aerogel and the preparation method thereof. In addition, ceramic aerogel has advantages such as high temperature resistant, chemical stability is high and mechanical shock resistance is good, and the high temperature thermal stability of improvement graphite alkene aerogel that can be good is compound with graphite alkene aerogel, and the mechanical properties of compound aerogel can also further be strengthened to the synergistic toughening effect between graphite alkene nanosheet layer and the ceramic granule.
In order to solve the technical problems, the invention is realized by the following technical scheme:
according to one aspect of the invention, the reinforced graphene composite aerogel comprises two-dimensional nano graphene sheet layers, wherein the two-dimensional nano graphene sheet layers are loaded with nano SiCN-Al 2 O 3 Ceramic particles of SiCN-Al 2 O 3 The ceramic particles are mutually connected and form a nano interpenetrating structure with the two-dimensional nano graphene sheet layer; the SiCN-Al 2 O 3 The ceramic particles and the two-dimensional nano graphene sheet layer form a porous skeleton network, and the porous skeleton network has nanoscale uniform pores.
Further, the specific surface area is higher than that of graphene aerogel.
Further, its thermal conductivity is lower than that of graphene aerogel.
Furthermore, the toughness of the alloy is higher than that of SiCN-Al 2 O 3 And (4) performing composite gas condensation.
According to another aspect of the invention, a preparation method of the reinforced graphene composite aerogel is provided, wherein graphene oxide and a polysilazane ceramic precursor are used as raw materials, aluminum sec-butoxide is used as an aluminum source, and divinylbenzene is used as a cross-linking agent, and the wet gel is obtained through a hydrothermal reaction after the graphene oxide and the polysilazane ceramic precursor are dissolved in an organic solvent; subjecting the wet gel to supercritical CO 2 Drying to obtain ceramic precursor/reduced graphene oxide aerogel, and then converting the ceramic precursor aerogel into ceramic aerogel through pyrolysis to prepare SiCN-Al 2 O 3 the/rGO composite aerogel.
Further, the method comprises the following steps:
(1) mixing 2-6 parts of polysilazane ceramic precursor, 1-4 parts of aluminum sec-butoxide, 1-3 parts of divinylbenzene and 10-20 parts of organic solvent according to the mass parts, performing ultrasonic treatment to fully dissolve the mixture, adding 1-4 parts of graphene oxide powder into the uniformly mixed solution, and performing ultrasonic treatment again until the mixture is uniformly dispersed;
(2) carrying out hydrothermal reaction on the dispersion liquid obtained in the step (1) to obtain PSZ-ASB/rGO composite wet gel;
(3) soaking the PSZ-ASB/rGO composite wet gel obtained in the step (2) in ethanol for aging, and then performing supercritical CO 2 Drying to obtain PSZ-ASB/rGO composite aerogel;
(4) the PSZ-ASB/rGO composite aerogel obtained in the step (3) is heated from room temperature to 1000-1400 ℃ for pyrolysis, and then is cooled to room temperature, so that SiCN-Al is finally obtained 2 O 3 a/rGO reinforced graphene composite aerogel material; wherein the heating, the pyrolysis and the cooling are all carried out under the protection of nitrogen or under the vacuum condition.
Further, the organic solvent in step (1) is tetrahydrofuran or ethanol.
Further, the temperature of the hydrothermal reaction in the step (2) is 200 ℃ and 250 ℃ and the time is 8-10 hours.
Further, the temperature rise rate in the step (4) is 2-5 ℃/min
The invention has the beneficial effects that:
the reinforced graphene composite aerogel material is prepared by mutually connecting SiCN-Al 2 O 3 The ceramic particles and the two-dimensional nano graphene sheet layer form a nano interpenetrating structure and form a porous framework network with nano-scale uniform pores. On the one hand, the nanoscale ceramic particles are filled between the two-dimensional nano graphene sheet layers, so that the rich nano pore structure of the traditional aerogel is reserved, the two-dimensional graphene sheet layers are introduced, gas molecules can be mutually separated, gas conduction and gas convection are effectively inhibited, and the gaseous state of the composite aerogel is remarkably reducedThermal conductivity; on the other hand, due to the pulling-out, crack deflection and crack bridging effects of the two-dimensional nano graphene sheet layer, the brittleness of the ceramic matrix composite aerogel is obviously reduced, and the fracture toughness of the ceramic matrix composite aerogel is improved.
The preparation method comprises the steps of taking graphene oxide and polysilazane ceramic precursor as raw materials, taking aluminum sec-butoxide as an aluminum source and divinylbenzene as a cross-linking agent, adding an organic solvent, and carrying out hydrothermal reaction to obtain wet gel; the two-dimensional nano graphene sheet layer and the ceramic precursor are uniformly dispersed and have good assembly effect, and the two-dimensional nano graphene sheet layer and the ceramic precursor are subjected to supercritical CO 2 Drying to obtain ceramic precursor/reduced graphene oxide aerogel, and then converting the ceramic precursor aerogel into ceramic aerogel through pyrolysis to prepare the high-temperature heat-insulation SiCN-Al with the nano interpenetrating structure 2 O 3 the/rGO composite aerogel.
Therefore, the SiCN-Al obtained by the invention 2 O 3 the/rGO composite aerogel has excellent mechanical properties and good high-temperature heat-insulating properties; can meet the thermal protection requirement of a novel aircraft in a high-temperature environment, and has important application prospect in the fields of military, aerospace and the like as a novel strategic material.
Drawings
Fig. 1 is a flow chart of the preparation of the reinforced graphene composite aerogel according to the present invention;
fig. 2 is a graph showing (a) a nitrogen adsorption-desorption curve and (b) a pore size distribution curve of the reduced graphene oxide aerogel prepared in example 1 of the present invention;
FIG. 3 shows SiCN-Al prepared in example 5 of the present invention 2 O 3 A nitrogen adsorption-desorption curve and a pore size distribution curve chart of the/rGO composite aerogel;
fig. 4(a) (b) (c) (d) (e) (f) are SEM images of reinforced graphene composite aerogels prepared in examples 2, 3, 5, 7, 4, and 6, respectively;
fig. 5 is a stress-strain curve of the reinforced graphene composite aerogels prepared in examples 5 and 8 of the present invention;
fig. 6 is a TG curve of the reinforced graphene composite aerogel prepared in examples 1, 5, and 9 of the present invention.
Detailed Description
As shown in figure 1, the invention belongs to the technical field of composite materials, and discloses a reinforced graphene (rGO) composite aerogel and a preparation method thereof 2 Drying process combined with ceramic precursor conversion method to prepare high-temperature heat-insulating SiCN-Al with nano interpenetrating structure 2 O 3 the/rGO composite aerogel. The SiCN-Al 2 O 3 the/rGO composite aerogel comprises two-dimensional nano graphene sheet layers, wherein nano SiCN-Al is loaded on the two-dimensional nano graphene sheet layers 2 O 3 Ceramic particles, SiCN-Al 2 O 3 The ceramic particles are mutually connected and form a nano interpenetrating structure with the two-dimensional nano graphene sheet layer; SiCN-Al 2 O 3 The ceramic particles and the two-dimensional nano graphene sheet layer form a porous framework network, and the porous framework network has nano-scale uniform pores.
The invention is described in further detail below by means of specific examples and comparative examples:
example 1
1) Preparation of rGO wet gel: weighing a proper amount of graphene oxide powder, adding the graphene oxide powder into distilled water, performing ultrasonic dispersion for 15min, quickly pouring the uniformly mixed solution into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle in an oven, performing heat preservation for 8 hours at 200 ℃, and taking out the rGO wet gel after the temperature of the reaction kettle is reduced to room temperature;
2) preparation of rGO aerogel: the obtained rGO wet gel was first replaced with water several times to remove the unreacted solvent in the gel, after which the water in the gel was gradually replaced with ethanol (25%, 50%, 75%, 100%), replacing the replacement solution every 8h for 3 days. Finally, the aged rGO wet gel is placed in CO 2 And (3) in a supercritical drying kettle, slowly removing supercritical airflow at the speed of 1bar/min under the supercritical drying conditions of 45 ℃ and 80bar to prepare the rGO aerogel.
Example 2
1) Preparation of PSZ-ASB/rGO composite wet gel: weighing 2g of PSZ, 1g of ASB, 10g of THF and 1g of DVB, mixing, performing ultrasonic dispersion for 15min to fully dissolve the PSZ, 1g of graphene oxide powder, adding the obtained mixture into the uniformly mixed solution, performing ultrasonic dispersion for 15min again, quickly pouring the uniformly mixed dispersion liquid into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle in an oven, keeping the temperature of the hydrothermal reaction kettle at 200 ℃ for 8 hours, and taking out the PSZ-ASB/rGO composite wet gel after the temperature of the hydrothermal reaction kettle is reduced to room temperature;
2) preparing PSZ-ASB/rGO composite aerogel: the GO/PSZ-ASB composite wet gel obtained is firstly replaced by water for multiple times to remove the unreacted solvent in the gel, and then the water in the gel can be gradually replaced by ethanol (25%, 50%, 75%, 100%), and the replacement solution is replaced every 8h for 3 days. Finally, placing the aged PSZ-ASB/rGO composite wet gel in CO 2 And (3) slowly removing supercritical airflow at the speed of 1bar/min in a supercritical drying kettle under the supercritical drying conditions of 45 ℃ and 80bar to prepare the PSZ-ASB/rGO composite aerogel.
3)SiCN-Al 2 O 3 Preparation of/rGO composite aerogel: and (3) putting the prepared PSZ-ASB/rGO composite aerogel into a box type sintering furnace, and pyrolyzing the PSZ-ASB/rGO composite aerogel under a vacuum condition, wherein the pyrolysis temperature is 1200 ℃ and the pyrolysis time is 120 min.
Example 3
1) Preparation of PSZ-ASB/rGO composite wet gel: weighing 4g of PSZ, 2g of ASB, 15g of THF and 2g of DVB, mixing, performing ultrasonic dispersion for 15min to fully dissolve the materials, weighing 2g of graphene oxide powder, adding the graphene oxide powder into the uniformly mixed solution, performing ultrasonic dispersion for 15min again, quickly pouring the uniformly mixed dispersion liquid into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle in an oven, preserving heat for 10 hours at 250 ℃, and taking out the PSZ-ASB/rGO composite wet gel after the temperature of the reaction kettle is reduced to room temperature;
2) preparing PSZ-ASB/rGO composite aerogel: the obtained PSZ-ASB/rGO composite wet gel is firstly replaced by water for multiple times to remove the unreacted solvent in the gel, then the water in the gel can be gradually replaced by ethanol (25%, 50%, 75% and 100%), and the replacement solution is replaced every 8h for 3 days. Finally placing the aged PSZ-ASB/rGO composite wet gelIn CO 2 And (3) slowly removing supercritical airflow at the speed of 1bar/min in a supercritical drying kettle under the supercritical drying conditions of 45 ℃ and 80bar to prepare the PSZ-ASB/rGO composite aerogel.
3)SiCN-Al 2 O 3 Preparation of/rGO composite aerogel: placing the prepared PSZ-ASB/rGO composite aerogel in a box type sintering furnace in N 2 Pyrolyzing the mixture under the protection of atmosphere, wherein the pyrolysis temperature is 1200 ℃, and the pyrolysis time is 120 min.
Example 4
1) Preparation of PSZ-ASB/rGO composite wet gel: weighing 6g of PSZ, 3g of ASB, 20g of THF and 3g of DVB, mixing, performing ultrasonic dispersion for 15min to fully dissolve the materials, weighing 3g of graphene oxide powder, adding the graphene oxide powder into the uniformly mixed solution, performing ultrasonic dispersion for 15min again, quickly pouring the uniformly mixed dispersion liquid into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle in an oven, keeping the temperature of the hydrothermal reaction kettle at 250 ℃ for 12 hours, and taking out the PSZ-ASB/rGO composite wet gel after the temperature of the hydrothermal reaction kettle is reduced to room temperature;
2) preparing PSZ-ASB/rGO composite aerogel: the obtained PSZ-ASB/rGO composite wet gel is firstly replaced by water for multiple times to remove the unreacted solvent in the gel, then the water in the gel can be gradually replaced by ethanol (25%, 50%, 75% and 100%), and the replacement solution is replaced every 8h for 3 days. Finally, placing the aged PSZ-ASB/rGO composite wet gel in CO 2 And (3) slowly removing supercritical airflow at the speed of 1bar/min in a supercritical drying kettle under the supercritical drying conditions of 45 ℃ and 80bar to prepare the PSZ-ASB/rGO composite aerogel.
3)SiCN-Al 2 O 3 Preparation of/rGO composite aerogel: and (3) putting the prepared PSZ-ASB/rGO composite aerogel into a box type sintering furnace, and pyrolyzing the composite aerogel under a vacuum condition, wherein the pyrolysis temperature is 1000 ℃ and the pyrolysis time is 120 min.
Example 5
1) Preparation of PSZ-ASB/rGO composite wet gel: weighing 6g of PSZ, 3g of ASB, 20g of THF and 3g of DVB, mixing, performing ultrasonic dispersion for 15min to fully dissolve the materials, weighing 3g of graphene oxide powder, adding the graphene oxide powder into the uniformly mixed solution, performing ultrasonic dispersion for 15min again, quickly pouring the uniformly mixed dispersion liquid into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle in an oven, keeping the temperature of the hydrothermal reaction kettle at 250 ℃ for 12 hours, and taking out the PSZ-ASB/rGO composite wet gel after the temperature of the hydrothermal reaction kettle is reduced to room temperature;
2) preparing PSZ-ASB/rGO composite aerogel: the obtained PSZ-ASB/rGO composite wet gel is firstly replaced by water for multiple times to remove the unreacted solvent in the gel, then the water in the gel can be gradually replaced by ethanol (25%, 50%, 75% and 100%), and the replacement solution is replaced every 8h for 3 days. Finally, placing the aged PSZ-ASB/rGO composite wet gel in CO 2 And (3) slowly removing supercritical airflow at the speed of 1bar/min in a supercritical drying kettle under the supercritical drying conditions of 45 ℃ and 80bar to prepare the PSZ-ASB/rGO composite aerogel.
3)SiCN-Al 2 O 3 Preparation of/rGO composite aerogel: and (3) putting the prepared PSZ-ASB/rGO composite aerogel into a box type sintering furnace, and pyrolyzing the PSZ-ASB/rGO composite aerogel under a vacuum condition, wherein the pyrolysis temperature is 1200 ℃ and the pyrolysis time is 120 min.
Example 6
1) Preparation of PSZ-ASB/rGO composite wet gel: weighing 6g of PSZ, 3g of ASB, 20g of THF and 3g of DVB, mixing, performing ultrasonic dispersion for 15min to fully dissolve the materials, weighing 3g of graphene oxide powder, adding the graphene oxide powder into the uniformly mixed solution, performing ultrasonic dispersion for 15min again, quickly pouring the uniformly mixed dispersion liquid into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle in an oven, keeping the temperature of the hydrothermal reaction kettle at 250 ℃ for 12 hours, and taking out the PSZ-ASB/rGO composite wet gel after the temperature of the hydrothermal reaction kettle is reduced to room temperature;
2) preparing PSZ-ASB/rGO composite aerogel: the obtained PSZ-ASB/rGO composite wet gel is firstly replaced by water for multiple times to remove the unreacted solvent in the gel, then the water in the gel can be gradually replaced by ethanol (25%, 50%, 75% and 100%), and the replacement solution is replaced every 8h for 3 days. Finally, placing the aged PSZ-ASB/rGO composite wet gel in CO 2 And (3) slowly removing supercritical airflow at the speed of 1bar/min in a supercritical drying kettle under the supercritical drying conditions of 45 ℃ and 80bar to prepare the PSZ-ASB/rGO composite aerogel.
3)SiCN-Al 2 O 3 Preparation of/rGO composite aerogel: preparing the prepared PSZ-ASB/rGO composite aerogelAnd putting the mixture into a box type sintering furnace, and pyrolyzing the mixture under the vacuum condition, wherein the pyrolysis temperature is 1400 ℃ and the pyrolysis time is 120 min.
Example 7
1) Preparation of PSZ-ASB/rGO composite wet gel: weighing 8g of PSZ, 4g of ASB, 25g of THF and 4g of DVB, mixing, performing ultrasonic dispersion for 15min to fully dissolve the PSZ, 4g of graphene oxide powder, adding the graphene oxide powder into the uniformly mixed solution, performing ultrasonic dispersion for 15min again, quickly pouring the uniformly mixed dispersion liquid into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle in an oven, preserving heat for 12 hours at 250 ℃, and taking out PSZ-ASB/rGO composite wet gel after the temperature of the reaction kettle is reduced to room temperature;
2) preparing PSZ-ASB/rGO composite aerogel: the obtained PSZ-ASB/rGO composite wet gel is firstly replaced by water for multiple times to remove the unreacted solvent in the gel, then the water in the gel can be gradually replaced by ethanol (25%, 50%, 75% and 100%), and the replacement solution is replaced every 8h for 3 days. Finally, placing the aged PSZ-ASB/rGO composite wet gel in CO 2 And (3) slowly removing supercritical airflow at the speed of 1bar/min in a supercritical drying kettle under the supercritical drying conditions of 45 ℃ and 80bar to prepare the PSZ-ASB/rGO composite aerogel.
3)SiCN-Al 2 O 3 Preparation of rGO composite aerogel: and (3) putting the prepared PSZ-ASB/rGO composite aerogel into a box type sintering furnace, and pyrolyzing the PSZ-ASB/rGO composite aerogel under a vacuum condition, wherein the pyrolysis temperature is 1200 ℃ and the pyrolysis time is 120 min.
Example 8
1) Preparation of PSZ-ASB composite wet gel: weighing 6g of PSZ, 3g of ASB, 20g of THF and 3g of DVB, mixing, performing ultrasonic treatment for 15min to fully dissolve the PSZ, 3g of ASB, 20g of THF and 3g of DVB, quickly pouring the uniformly mixed dispersion liquid into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle in an oven, keeping the temperature of the hydrothermal reaction kettle at 250 ℃ for 12 hours, and taking out the PSZ-ASB composite wet gel after the temperature of the reaction kettle is reduced to room temperature;
2) preparing PSZ-ASB composite aerogel: the obtained PSZ-ASB composite wet gel is firstly replaced by water for a plurality of times to remove the unreacted solvent in the gel, and then the water in the gel can be gradually replaced by ethanol (25%, 50%, 75% and 100%), and the replacement solution is replaced every 8h for 3 days.Finally placing the aged PSZ-ASB composite wet gel in CO 2 And (3) slowly removing the supercritical airflow at the speed of 1bar/min in a supercritical drying kettle under the supercritical drying conditions of 45 ℃ and 80bar to prepare the PSZ-ASB composite aerogel.
3)SiCN-Al 2 O 3 Preparing the composite aerogel: and (3) putting the prepared PSZ-ASB composite aerogel into a box type sintering furnace, and pyrolyzing the PSZ-ASB composite aerogel under the vacuum condition, wherein the pyrolysis temperature is 1200 ℃ and the pyrolysis time is 120 min.
Example 9
1) Preparation of PSZ-ASB/rGO composite wet gel: weighing 6g of PSZ, 3g of ASB, 20g of THF and 3g of DVB, mixing, performing ultrasonic dispersion for 15min to fully dissolve the materials, weighing 3g of graphene oxide powder, adding the graphene oxide powder into the uniformly mixed solution, performing ultrasonic dispersion for 15min again, quickly pouring the uniformly mixed dispersion liquid into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle in an oven, preserving heat for 12 hours at 250 ℃, and taking out PSZ-ASB/rGO composite wet gel after the temperature of the reaction kettle is reduced to room temperature;
2) preparing PSZ-ASB/rGO composite aerogel: the obtained PSZ-ASB/rGO composite wet gel is firstly replaced by water for multiple times to remove the unreacted solvent in the gel, then the water in the gel can be gradually replaced by ethanol (25%, 50%, 75% and 100%), and the replacement solution is replaced every 8h for 3 days. Finally, placing the aged PSZ-ASB/rGO composite wet gel in CO 2 And (3) slowly removing supercritical airflow at the speed of 1bar/min in a supercritical drying kettle under the supercritical drying conditions of 45 ℃ and 80bar to prepare the PSZ-ASB/rGO composite aerogel.
And (3) performance test results:
the ceramic aerogel sample is tested by a Beijing Behcard instruments science and technology limited 3H-2000PS1 model specific surface area and aperture tester. Fig. 2 is a graph showing (a) a nitrogen adsorption-desorption curve and (b) a pore size distribution curve of a reduced graphene oxide aerogel prepared in example 1 of the present invention, and fig. 3 is a graph showing SiCN — Al prepared in example 5 of the present invention 2 O 3 The (a) nitrogen adsorption-desorption curves and (b) pore size distribution profiles of the/rGO composite aerogels are plotted and the corresponding values are listed in table 1.
TABLE 1
As can be seen from the test results, the SiCN-Al prepared by the invention 2 O 3 the/rGO composite aerogel is of a mesoporous structure, and the specific surface area of the/rGO composite aerogel is higher than that of a pure reduced graphene oxide aerogel.
The obtained enhanced graphene composite aerogel is subjected to morphology analysis by a SM-7800F type ultra-high resolution thermal field emission scanning electron microscope of Japan electronic Co., Ltd, so as to obtain a graph shown in FIG. 4. Wherein (a), (b), (c), (d), (e) and (f) are SEM images of the reinforced graphene composite aerogel prepared in examples 2, 3, 5, 7, 4 and 6 of the present invention, respectively. As can be seen from the test results, SiCN-Al 2 O 3 The pore size of the pore structure of the/rGO composite aerogel is uniform, the nanoparticles are connected to form a porous skeleton network, and the graphene sheet layers are inserted among the nanoparticles. Nanoscale SiCN-Al 2 O 3 The ceramic particles are mutually connected and interpenetrated with the two-dimensional nano graphene sheet layer to form a porous framework network. In addition, as can be seen from the comparison of graphs (a-e), SiCN-Al increased with the increase in the content of the ceramic precursor 2 O 3 The skeleton network of the/rGO composite aerogel is gradually compact, and larger ceramic precursor particles appear. As can be seen from the graphs (c), (e) and (f), as the cracking temperature increases, the neck region between the ceramic precursor particles is extended, the ceramic precursor particles are fused, the length and size of the particles become larger, and meanwhile, the graphene sheet layer covered by the ceramic precursor particles starts to be exposed, and the ceramic precursor particles are agglomerated at the graphene sheet layer enrichment position. At further elevated temperatures, the ceramic precursor particles begin to crack into inorganic ceramics, the pore structure tends to densify, but the aerogel after cracking at 1400 ℃ still has a good pore structure.
SiCN-Al obtained in example 5 was subjected to an electronic universal tester 2 O 3 PerGO composite aerogel and SiCN-Al obtained in example 8 2 O 3 The ceramic aerogel was subjected to a compression performance test by applying a pressure in the longitudinal direction, to obtain fig. 5. SiCN-Al 2 O 3 Ceramic aerogel and SiCN-Al 2 O 3 The composite aerogel/rGO has fracture behavior after reaching the highest stress value, which shows that the composite aerogel has certain brittleness, but the compressive strength of the rGO aerogel is enhanced by introducing the ceramic precursor, and the strength is increased mainly because the pore structure of the ceramic precursor tends to be densified after high-temperature cracking. Notably, SiCN-Al 2 O 3 rGO composite aerogel and SiCN-Al 2 O 3 There is also a yield stage for ceramic aerogels. SiCN-Al 2 O 3 The first brittle fracture of the/rGO composite aerogel occurs after the highest stress value is reached, but this fracture behavior is not for SiCN-Al 2 O 3 SiCN-Al, a severe damage caused by/rGO composite aerogels 2 O 3 the/rGO composite aerogel can also bear lower pressure until a second brittle fracture occurs to cause SiCN-Al 2 O 3 the/rGO composite aerogel structure was completely destroyed. This phenomenon is mainly due to the synergistic toughening effect between the ceramic precursor particles and the nano-graphene sheets. The nano graphene sheet layers inserted between the ceramic precursor particles can deflect the direction of crack expansion, so that the stress is weakened. In addition, as the graphene sheet layers are embedded between the ceramic precursors in a bent and wrinkled shape and have enlarged specific surface area and extremely high toughness, the friction resistance between the graphene sheet layers and the ceramic precursors during fracture is very large, and SiCN-Al is enhanced to a certain extent 2 O 3 The toughness of the/rGO composite aerogel improves the mechanical property of the aerogel.
Thermal stability analysis was performed on the samples using a thermogravimetric analyzer, and fig. 6 is a thermogravimetric curve of examples 1, 5, and 9. From the test results, it can be seen that the uncracked SiCN-Al 2 O 3 The mass loss process of the/rGO composite aerogel, namely PSZ-ASB/rGO composite aerogel can be divided into three stages. The first stage is that the temperature is lower than 203.02 ℃, the mass loss in the first stage is mainly caused by that water is adsorbed on PSZ-ASB/rGO composite aerogel and residual low-boiling-point organic solvent is evaporated, no chemical reaction occurs, the weight loss rate is small and is about 4.4%; the second stage is 203.02-403.16 deg.C, and the mass loss in this stage is mainlyIf the removal of active oxygen-containing groups such as hydroxyl, carboxyl and the like on the nano graphene sheet layer also causes partial mass loss; the third stage is that the temperature is higher than 403.16 ℃, thermal decomposition begins to occur in the third stage, including the pyrolysis of the ceramic precursor to release a large amount of small molecule gas and the removal of oxygen-containing groups on the nano graphene sheet layer, and the ceramic precursor begins to crack inorganic products by organic matters. And SiCN-Al after pyrolysis 2 O 3 The quality of the/rGO composite aerogel is almost not lost, which shows that the composite aerogel has good high-temperature stability.
The samples were tested for thermal conductivity using a thermal conductivity meter and the results are shown in table 2.
TABLE 2
As can be seen from the test results, SiCN-Al obtained in example 5 2 O 3 The thermal conductivity of the/rGO composite aerogel is 0.037W/(m.K), and the composite aerogel shows good thermal insulation performance compared with a pure graphene aerogel. The three-dimensional pore framework is formed by overlapping graphene sheet layers, and simultaneously, nano-scale ceramic particles are uniformly filled between the graphene sheet layers and connected to form a similar SiO 2 The 'bead necklace' shaped pore network of the aerogel greatly prolongs the solid heat transfer path, thereby weakening the solid heat transfer capacity. In addition, due to the filling of the nano ceramic particles, the graphene sheet layers are fully isolated, the shrinkage and agglomeration of the graphene sheet layers in the heat treatment process are avoided, and the solid-state thermal conductivity is greatly reduced. And as the nano-scale ceramic particles are uniformly filled between the graphene sheet layers, the porosity of the composite aerogel is greatly increased, and the pore diameter of pores is reduced, so that the heat conduction and heat convection of gas molecules are more effectively inhibited, and the gaseous heat conductivity is reduced.
Although the preferred embodiments of the present invention have been described, the present invention is not limited to the above embodiments, which are only illustrative and not restrictive, and those skilled in the art can make many changes and modifications without departing from the spirit and scope of the invention as claimed.
Claims (9)
1. The reinforced graphene composite aerogel is characterized by comprising two-dimensional nano graphene sheet layers, wherein nano SiCN-Al is loaded on the two-dimensional nano graphene sheet layers 2 O 3 Ceramic particles of SiCN-Al 2 O 3 The ceramic particles are mutually connected and form a nano interpenetrating structure with the two-dimensional nano graphene sheet layer; the SiCN-Al 2 O 3 The ceramic particles and the two-dimensional nano graphene sheet layer form a porous framework network, and the porous framework network has nanoscale uniform pores.
2. The reinforced graphene composite aerogel according to claim 1, wherein the specific surface area of the reinforced graphene composite aerogel is higher than that of the graphene aerogel.
3. The reinforced graphene composite aerogel according to claim 1, wherein the thermal conductivity of the reinforced graphene composite aerogel is lower than that of graphene aerogel.
4. The reinforced graphene composite aerogel according to claim 1, wherein the toughness of the reinforced graphene composite aerogel is higher than that of SiCN-Al 2 O 3 And (4) performing composite gas condensation.
5. The preparation method of the reinforced graphene composite aerogel according to any one of claims 1 to 4, wherein graphene oxide and a polysilazane ceramic precursor are used as raw materials, aluminum sec-butoxide is used as an aluminum source, and divinylbenzene is used as a crosslinking agent, and an organic solvent is added to the raw materials to obtain a wet gel through a hydrothermal reaction; subjecting the wet gel to supercritical CO 2 Drying to obtain ceramic precursor/reduced graphene oxide aerogel, and converting the ceramic precursor aerogel into ceramic aerogel by pyrolysis to obtain the final productTo SiCN-Al 2 O 3 the/rGO composite aerogel.
6. The preparation method of the reinforced graphene composite aerogel according to claim 5, which is carried out according to the following steps:
(1) mixing 2-6 parts of polysilazane ceramic precursor, 1-4 parts of aluminum sec-butoxide, 1-3 parts of divinylbenzene and 10-20 parts of organic solvent according to the mass parts, performing ultrasonic treatment to fully dissolve the mixture, adding 1-4 parts of graphene oxide powder into the uniformly mixed solution, and performing ultrasonic treatment again until the mixture is uniformly dispersed;
(2) carrying out hydrothermal reaction on the dispersion liquid obtained in the step (1) to obtain PSZ-ASB/rGO composite wet gel;
(3) soaking the PSZ-ASB/rGO composite wet gel obtained in the step (2) in ethanol for aging, and then performing supercritical CO 2 Drying to obtain PSZ-ASB/rGO composite aerogel;
(4) the PSZ-ASB/rGO composite aerogel obtained in the step (3) is heated from room temperature to 1000-1400 ℃ for pyrolysis, and then is cooled to room temperature, so that SiCN-Al is finally obtained 2 O 3 a/rGO reinforced graphene composite aerogel material; wherein the heating, the pyrolysis and the cooling are all carried out under the protection of nitrogen or under the vacuum condition.
7. The preparation method of the reinforced graphene composite aerogel according to claim 6, wherein the organic solvent in the step (1) is tetrahydrofuran or ethanol.
8. The preparation method of the reinforced graphene composite aerogel according to claim 6, wherein the temperature of the hydrothermal reaction in the step (2) is 200-250 ℃, and the time is 8-10 hours.
9. The preparation method of the reinforced graphene composite aerogel according to claim 6, wherein the temperature rise rate in the step (4) is 2-5 ℃/min.
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Application publication date: 20220830 |