CN114162828A - Preparation method of graphene/silicon dioxide composite aerogel - Google Patents
Preparation method of graphene/silicon dioxide composite aerogel Download PDFInfo
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- CN114162828A CN114162828A CN202111660996.5A CN202111660996A CN114162828A CN 114162828 A CN114162828 A CN 114162828A CN 202111660996 A CN202111660996 A CN 202111660996A CN 114162828 A CN114162828 A CN 114162828A
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 152
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 117
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 239000004964 aerogel Substances 0.000 title claims abstract description 116
- 239000002131 composite material Substances 0.000 title claims abstract description 67
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 66
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 230000033444 hydroxylation Effects 0.000 claims abstract description 4
- 238000005805 hydroxylation reaction Methods 0.000 claims abstract description 4
- 239000011259 mixed solution Substances 0.000 claims description 53
- 239000007864 aqueous solution Substances 0.000 claims description 45
- 239000000843 powder Substances 0.000 claims description 38
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 34
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 30
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 28
- 239000004965 Silica aerogel Substances 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 20
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 238000000889 atomisation Methods 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 15
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- 238000001914 filtration Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 239000004593 Epoxy Substances 0.000 claims description 12
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 12
- 239000002356 single layer Substances 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- 239000010410 layer Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
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- 229910052710 silicon Inorganic materials 0.000 abstract description 23
- 239000010703 silicon Substances 0.000 abstract description 23
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 20
- 238000000034 method Methods 0.000 abstract description 7
- 238000002156 mixing Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
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- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000001694 spray drying Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 30
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- 230000000052 comparative effect Effects 0.000 description 9
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- 229910052682 stishovite Inorganic materials 0.000 description 9
- 229910052905 tridymite Inorganic materials 0.000 description 9
- 230000002378 acidificating effect Effects 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 125000003700 epoxy group Chemical group 0.000 description 6
- 230000002209 hydrophobic effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000004005 microsphere Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
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- 239000000126 substance Substances 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
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- FXXMDJFRMDVSCF-RXSVEWSESA-N (2r)-2-[(1s)-1,2-dihydroxyethyl]-3,4-dihydroxy-2h-furan-5-one;hydrate Chemical compound O.OC[C@H](O)[C@H]1OC(=O)C(O)=C1O FXXMDJFRMDVSCF-RXSVEWSESA-N 0.000 description 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
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- 125000003277 amino group Chemical group 0.000 description 1
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- 125000004432 carbon atom Chemical group C* 0.000 description 1
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- 239000000945 filler Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
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- 239000011343 solid material Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/157—After-treatment of gels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0091—Preparation of aerogels, e.g. xerogels
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/157—After-treatment of gels
- C01B33/159—Coating or hydrophobisation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/32—Thermal properties
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses a preparation method of graphene/silicon dioxide composite aerogel. The composite aerogel is prepared by firstly carrying out hydroxylation and coupling treatment on silicon dioxide aerogel, then mixing the silicon dioxide aerogel with graphene oxide, wrapping the silicon dioxide aerogel and the graphene together through bonding, and finally carrying out spray drying. The graphene/silicon dioxide composite aerogel prepared by the invention has low heat conductivity coefficient, high hydrophobicity and high porosity under the condition of only adding a small amount of graphene, and the addition of the graphene can effectively absorb impact, reduce the damage of external force to a silicon aerogel matrix structure, greatly improve the problem of high brittleness of the silicon dioxide aerogel, and has the advantages of low possibility of abrasion and stable structure. The method has the advantages of simple process, low cost, strong operability, environmental protection, no pollution in the preparation process and obvious practical value.
Description
Technical Field
The invention belongs to the technical field of material preparation, and particularly relates to graphene/silicon dioxide composite aerogel and a preparation method thereof.
Background
Silicon dioxide (SiO)2) The aerogel is a low-density porous solid material formed by aggregating nano-scale particles, is filled with a gaseous dispersion medium, has the characteristics of high porosity, high specific surface area, low thermal conductivity, low optical refractive index, light material and the like, and shows unique properties in various fields of heat insulation, optics, electrics and the like. But due to SiO2The aerogel has the advantages of large brittleness, poor mechanical property and easiness in abrasion and breakage, so that the structure of the aerogel is damaged and the original performance of the aerogel is lost, thereby seriously limiting the large-scale application of the aerogel; in addition, SiO2The hydrophobic property of the aerogel is one of the important factors influencing the heat insulation property, because a large amount of silicon hydroxyl exists on the inner surface of a hole of the aerogel, when the aerogel contacts with water in the air, the silicon hydroxyl can adsorb water to crack, collapse and pulverize the surface of the aerogel, so that the property of the aerogel is seriously reduced, and the heat conductivity coefficient of water is greater than that of the air, so that the heat insulation property of the aerogel is greatly reduced. Therefore, it is necessary to use SiO2The aerogel is enhanced and improved. Currently for SiO2The research on aerogel composites has mainly focused on two aspects, namely the research on multicomponent aerogels, which are carried out in the sol phase and other solsCompounding in a certain mode to obtain composite sol, and then drying and other operations to obtain the composite aerogel material: on the other hand is SiO2The research on the improvement of the mechanical properties of the aerogel is mostly carried out by mixing SiO2The aerogel and the fiber porous ceramic and other reinforcing materials are compounded by a mechanical or chemical mode, or the nano filler is added into SiO2Reinforcement is performed in the aerogel nanostructures to produce a reinforced aerogel composite.
The graphene is a novel two-dimensional structure material formed by single-layer or few-layer sp2 hybridized carbon atoms, and has excellent electrical properties, mechanical properties, thermal properties, high specific surface area and the like. The excellent characteristics of graphene are introduced into SiO2In the field of aerogels, development of high-performance, special functional SiO2Aerogels are currently a focus of research. According to Chinese patent CN201910556360.2, namely an ordinary pressure preparation method of high-specific-surface-area strong-hydrophobicity graphene oxide/silicon dioxide composite aerogel, ethyl orthosilicate is used as a precursor, a silane coupling agent aminopropyltriethoxysilane is used for replacing a traditional alkaline catalyst, graphene oxide turbid liquid is added under an acidic condition, basic group amino contained in a system is easier to be combined with acidic group carboxyl in graphene oxide through chemical bonds, the binding force is enhanced, the gel forming time can be greatly reduced, and the graphene oxide/silicon dioxide aerogel with high specific surface area, strong hydrophobicity and low thermal conductivity coefficient is obtained through ordinary pressure drying. Patent CN201710255537.6 "a graphene/silica composite aerogel material and its preparation method" prepares composite aerogel with good high-temperature hydrophobic property and the like and possibly enduring temperature of more than 400 ℃ through processes of graphene oxide/silica system hydrogel, alcogel, supercritical drying, high-temperature treatment and the like. However, in the solutions of the two patents, graphene oxide is added in the silicon source stage, and the graphene oxide is easily aggregated and reduced in the presence of an amino group, an alkali and a poor solvent, which may deteriorate the dispersibility of the graphene oxide in the system, and after undergoing a mixing and bonding process, the original oxidation of the graphene oxide may be affected by the lamellar structure of the graphene oxideDue to the formation of the silicon aerogel structure, the graphene can present different distributions of each position in the structure of the aerogel, so that the hydrophobic property and the thermal conductivity coefficient property are not greatly improved. The other two patents need to undergo the steps of mixing, gelling, aging and the like, and in addition, the patent CN201710255537.6 scheme also needs supercritical drying and high-temperature reduction under inert gas, so that the problems of high temperature and high pressure, inflammability of organic reagents, higher equipment cost, higher energy consumption, more complicated steps and the like exist.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a graphene/silicon dioxide composite aerogel. The composite aerogel has low heat conductivity coefficient, high hydrophobicity and high porosity, and the problem of high brittleness of the silicon dioxide aerogel is greatly improved by adding the graphene, so that the composite aerogel is not easy to wear and has a stable structure.
The purpose of the invention is realized by the following technical scheme:
(1) dispersing 100 parts by weight of silicon dioxide aerogel powder in a mixed solution of concentrated sulfuric acid and hydrogen peroxide for hydroxylation treatment;
(2) filtering, washing, dispersing into an aqueous solution containing 100-500 parts by weight of epoxy siloxane, and stirring;
(3) adding 0.1-20 parts by weight of graphene oxide, adjusting the pH value to be less than 3, and mechanically stirring at 50 ℃;
(4) adding an ascorbic acid aqueous solution, heating to 80 ℃, and maintaining for 10-30 min; then heating to 150 ℃, and maintaining for 1-3 h;
(5) adjusting the viscosity to 200-600 cp, and then obtaining the graphene/silicon dioxide composite aerogel powder by an atomization drying method.
Further, the silicon dioxide aerogel powder is nano aerogel powder, the particle size is 5-50 mu m, and the aperture is 10-30 nm.
Further, the graphene oxide is one or more of single-layer graphene oxide, double-layer graphene oxide and multi-layer graphene oxide. The transverse size of the graphene oxide sheet diameter is 2-50 mu m.
Further, the acid solution is one or more of 10wt% acetic acid, 10wt% oxalic acid, 20wt% citric acid and 5wt% ethylene diamine tetraacetic acid aqueous solution.
The invention has the beneficial effects that:
the method can enable the combination of the graphene and the silicon aerogel to be more compact, does not damage the structure of the silicon aerogel, can improve the problem of high brittleness of the silicon aerogel due to the addition of the graphene, has good mechanical property and strong stability, can effectively absorb impact due to the support of the graphene, and reduces the damage of external force to the silicon aerogel matrix structure. The graphene/silicon dioxide composite aerogel has excellent performances of low thermal conductivity, high hydrophobicity, high porosity and the like under the condition of only adding a small amount of graphene.
Drawings
Fig. 1 is a sample diagram of raw silica aerogel powder, graphene/silica composite aerogel of examples 2, 5, 8;
fig. 2 is a graph of the hydrophobic properties of the raw silica aerogel powder and the graphene/silica composite aerogels of examples 2, 5 and 8.
Detailed Description
According to the invention, firstly, the silica aerogel is subjected to hydroxylation treatment by using a mixed solution of concentrated sulfuric acid and hydrogen peroxide, and then the silica aerogel is slowly added into an epoxy siloxane aqueous solution, so that the hydroxyl on the surface of the silica aerogel can be uniformly combined with epoxy siloxane, epoxy groups can be exposed outside, and the combination of the aerogel and other substances is facilitated; the pH value is adjusted to be less than 3 by using acid, the epoxy group is facilitated to be subjected to ring opening at 50 ℃, the epoxy group is tightly combined with graphene oxide, graphene oxide sheets are tightly wrapped on the surfaces of aerogel microspheres by modifying the bonding force of the surfaces of the silicon aerogel, the graphene has good mechanical property, the problems of high brittleness and the like of the silicon aerogel can be solved, ascorbic acid is used as a weak reducing agent, the graphene oxide sheets wrap the aerogel microspheres and are attached between the aerogel microspheres and the graphene oxide sheets in a molecular form, the graphene oxide can be slightly reduced by wrapping the aerogel microspheres on the surfaces of the graphene oxide sheets and reducing the volume expansion, the temperature is raised later, part of the reducing agent reacts with oxygen-containing functional groups between the surfaces of the graphene oxide sheets and the surfaces of the silicon aerogel, a product is removed along with the volatilization of a solvent, and the reduction reaction can be slowly carried out at the temperature of 80 ℃ in the first section to carry out slight reduction, the problem that the graphene sheet is separated from the silicon aerogel due to volume expansion caused by reduction is solved, and hydroxyl on the surface of the composite aerogel can be reduced better at the high temperature of 150 ℃ in the second section, so that the hydrophobicity is increased; the composite aerogel mixed solution is controlled to be at a certain viscosity, the phenomenon that composite aerogel is accumulated due to too high viscosity can be avoided through an atomization drying method, and uniform composite aerogel particles can be prepared.
The present invention is described in detail by the following embodiments, which are only used for further illustration of the present invention and should not be construed as limiting the scope of the present invention, and the non-essential changes and modifications made by the person skilled in the art according to the above disclosure are within the scope of the present invention.
Example 1
(1) 100 parts of silica aerogel powder (particle size of 5 μm and pore size of 10nm) was dispersed in a mixed solution of concentrated sulfuric acid and hydrogen peroxide by mechanical stirring to hydroxylate silica. The mixed solution of concentrated sulfuric acid and hydrogen peroxide had a sulfuric acid concentration of 18mol/L and a hydrogen peroxide concentration of 10mol/L (the same applies to examples below).
(2) And (2) filtering and washing the mixed solution in the step (1). Then dispersed into 100 parts of an aqueous solution of epoxysiloxane with stirring, and the mass ratio of the epoxysiloxane to water is 0.5: 100.
(3) Subsequently, 0.5 part of monolayer graphene oxide (average lateral dimension of 5 μm) was added in step (2), and 1 part of 10wt% aqueous acetic acid was further added to adjust the pH to 1.9. Mechanically stirring at 50 deg.C, slowly adding 2 parts of ascorbic acid water solution, heating to 80 deg.C, maintaining for 30min, heating to 150 deg.C, and maintaining for 2 hr.
(4) And (4) adding pure water into the mixed solution obtained in the step (3) to dilute the mixed solution until the viscosity is about-300 cp, and then obtaining the graphene/silicon dioxide composite aerogel powder through an atomization drying method.
The graphene/silicon dioxide composite aerogel is obtained through the steps, and the performances are shown in table 1.
Example 2
(1) 100 parts of silica aerogel powder (particle size of 5 μm and pore size of 10nm) was dispersed in a mixed solution of concentrated sulfuric acid and hydrogen peroxide by mechanical stirring.
(2) And (2) filtering and washing the mixed solution in the step (1). And then dispersed into an aqueous solution of 300 parts of epoxysiloxane with stirring, wherein the mass ratio of the epoxysiloxane to water is 5: 100.
(3) And (3) adding 0.5 part of single-layer graphene oxide (the average transverse dimension is 5 microns) in the step (2), adding 1 part of 10wt% acetic acid aqueous solution, adjusting the pH value to 2.3, mechanically stirring at 50 ℃, slowly adding 2 parts of ascorbic acid aqueous solution, heating to 80 ℃, maintaining for 30min, heating to 150 ℃, and maintaining for 2 h.
(4) And (4) adding pure water into the mixed solution obtained in the step (3) to dilute the mixed solution until the viscosity is about-300 cp, and then obtaining the graphene/silicon dioxide composite aerogel powder through an atomization drying method.
The graphene/silicon dioxide composite aerogel is obtained through the steps, and the performances are shown in table 1.
Example 3
(1) 100 parts of silica aerogel powder (particle size of 5 μm and pore size of 10nm) was dispersed in a mixed solution of concentrated sulfuric acid and hydrogen peroxide by mechanical stirring.
(2) And (2) filtering and washing the mixed solution in the step (1). And then dispersed into an aqueous solution of 500 parts of epoxysiloxane to stir the epoxysiloxane to water at a mass ratio of 8: 100.
(3) And (3) adding 0.5 part of single-layer graphene oxide (the average transverse dimension is 5 microns) in the step (2), adding 1 part of 10wt% acetic acid aqueous solution, adjusting the pH value to 2.6, mechanically stirring at 50 ℃, slowly adding 2 parts of ascorbic acid aqueous solution, heating to 80 ℃, maintaining for 30min, heating to 150 ℃, and maintaining for 2 h.
(4) And (4) adding pure water into the mixed solution obtained in the step (3) to dilute the mixed solution until the viscosity is about-300 cp, and then obtaining the graphene/silicon dioxide composite aerogel powder through an atomization drying method.
The graphene/silicon dioxide composite aerogel is obtained through the steps, and the performances are shown in table 1.
Example 4
(1) 100 parts of silica aerogel powder (particle size 25 μm, pore size 20nm) was dispersed in a mixed solution of concentrated sulfuric acid and hydrogen peroxide by mechanical stirring.
(2) And (2) filtering and washing the mixed solution in the step (1). And then dispersed into 250 parts of an aqueous solution of epoxysiloxane with stirring, wherein the mass ratio of the epoxysiloxane to water is 5: 100.
(3) And (3) adding 0.8 part of single-layer graphene oxide (the average transverse dimension is 10 microns) in the step (2), adding 0.1 part of 10wt% oxalic acid aqueous solution, adjusting the pH value to 2.8, mechanically stirring at 50 ℃, slowly adding 3 parts of ascorbic acid aqueous solution, heating to 80 ℃, maintaining for 30min, heating to 150 ℃, and maintaining for 3 h.
(4) And (4) adding pure water into the mixed solution obtained in the step (3) to dilute the mixed solution until the viscosity is about 400cp, and then obtaining the graphene/silicon dioxide composite aerogel powder through an atomization drying method.
The graphene/silicon dioxide composite aerogel is obtained through the steps, and the performances are shown in table 1.
Example 5
(1) 100 parts of silica aerogel powder (particle size 25 μm, pore size 20nm) was dispersed in a mixed solution of concentrated sulfuric acid and hydrogen peroxide by mechanical stirring.
(2) And (2) filtering and washing the mixed solution in the step (1). And then dispersed into 250 parts of an aqueous solution of epoxysiloxane with stirring, wherein the mass ratio of the epoxysiloxane to water is 5: 100.
(3) And (3) adding 0.8 part of single-layer graphene oxide (the average transverse dimension is 10 microns) in the step (2), adding 1 part of 10wt% oxalic acid aqueous solution, adjusting the pH value to 2.2, mechanically stirring at 50 ℃, slowly adding 3 parts of ascorbic acid aqueous solution, heating to 80 ℃, maintaining for 30min, heating to 150 ℃, and maintaining for 3 h.
(4) And (4) adding pure water into the mixed solution obtained in the step (3) to dilute the mixed solution until the viscosity is about 400cp, and then obtaining the graphene/silicon dioxide composite aerogel powder through an atomization drying method.
The graphene/silicon dioxide composite aerogel is obtained through the steps, and the performances are shown in table 1.
Example 6
(1) 100 parts of silica aerogel powder (particle size 25 μm, pore size 20nm) was dispersed in a mixed solution of concentrated sulfuric acid and hydrogen peroxide by mechanical stirring.
(2) And (2) filtering and washing the mixed solution in the step (1). And then dispersed into 250 parts of an aqueous solution of epoxysiloxane with stirring, wherein the mass ratio of the epoxysiloxane to water is 5: 100.
(3) And (3) adding 0.8 part of single-layer graphene oxide (the average transverse dimension is 10 microns) in the step (2), adding 5 parts of 10wt% oxalic acid aqueous solution, adjusting the pH value to 1.3, mechanically stirring at 50 ℃, slowly adding 3 parts of ascorbic acid aqueous solution, heating to 80 ℃, maintaining for 30min, heating to 150 ℃, and maintaining for 3 h.
(4) And (4) adding pure water into the mixed solution obtained in the step (3) to dilute the mixed solution until the viscosity is about 400cp, and then obtaining the graphene/silicon dioxide composite aerogel powder through an atomization drying method.
The graphene/silicon dioxide composite aerogel is obtained through the steps, and the performances are shown in table 1.
Example 7
(1) 100 parts of silica aerogel powder (particle size of 10 μm and pore size of 10nm) was dispersed in a mixed solution of concentrated sulfuric acid and hydrogen peroxide by mechanical stirring.
(2) And (2) filtering and washing the mixed solution in the step (1), and then dispersing into 300 parts of an aqueous solution of epoxysiloxane and stirring, wherein the mass ratio of the epoxysiloxane to water is 5: 100.
(3) Then, 0.2 part of graphene oxide (average transverse dimension of 30 μm) is added in the step (2), 4 parts of 10wt% acetic acid aqueous solution is added, the pH value is adjusted to 1.7, mechanical stirring is carried out at 50 ℃, 4 parts of ascorbic acid aqueous solution is slowly added, the temperature is raised to 80 ℃, the temperature is raised to 150 ℃ after 30min, and the temperature is maintained for 3 h.
(4) And (4) adding pure water into the mixed solution obtained in the step (3) to dilute the mixed solution until the viscosity is about 400cp, and then obtaining the graphene/silicon dioxide composite aerogel powder through an atomization drying method.
The graphene/silicon dioxide composite aerogel is obtained through the steps, and the performances are shown in table 1.
Example 8
(1) 100 parts of silica aerogel powder (particle size of 10 μm and pore size of 10nm) was dispersed in a mixed solution of concentrated sulfuric acid and hydrogen peroxide by mechanical stirring.
(2) And (2) filtering and washing the mixed solution in the step (1), and then dispersing into 300 parts of an aqueous solution of epoxysiloxane and stirring, wherein the mass ratio of the epoxysiloxane to water is 5: 100.
(3) And (3) adding 2 parts of graphene oxide (the average transverse dimension is 30 microns) in the step (2), adding 4 parts of 10wt% acetic acid aqueous solution, adjusting the pH value to 1.5, mechanically stirring at 50 ℃, slowly adding 4 parts of ascorbic acid aqueous solution, heating to 80 ℃, maintaining for 30min, then heating to 150 ℃, and maintaining for 3 h.
(4) And (4) adding pure water into the mixed solution obtained in the step (3) to dilute the mixed solution until the viscosity is about 400cp, and then obtaining the graphene/silicon dioxide composite aerogel powder through an atomization drying method.
The graphene/silicon dioxide composite aerogel is obtained through the steps, and the performances are shown in table 1.
Example 9
(1) 100 parts of silica aerogel powder (particle size of 10 μm and pore size of 10nm) was dispersed in a mixed solution of concentrated sulfuric acid and hydrogen peroxide by mechanical stirring.
(2) And (2) filtering and washing the mixed solution in the step (1), and then dispersing into 300 parts of an aqueous solution of epoxysiloxane and stirring, wherein the mass ratio of the epoxysiloxane to water is 5: 100.
(3) And (3) adding 15 parts of graphene oxide (the average transverse dimension is 30 microns) in the step (2), adding 4 parts of 10wt% acetic acid aqueous solution, adjusting the pH value to 1.1, mechanically stirring at 50 ℃, slowly adding 4 parts of ascorbic acid aqueous solution, heating to 80 ℃, maintaining for 30min, then heating to 150 ℃, and maintaining for 3 h.
(4) And (4) adding pure water into the mixed solution obtained in the step (3) to dilute the mixed solution until the viscosity is about 400cp, and then obtaining the graphene/silicon dioxide composite aerogel powder through an atomization drying method.
The graphene/silicon dioxide composite aerogel is obtained through the steps, and the performances are shown in table 1.
Comparative example 10
(1) 100 parts of silica aerogel powder (particle size of 5 μm and pore size of 10nm) was dispersed in a mixed solution of concentrated sulfuric acid and hydrogen peroxide by mechanical stirring.
(2) And (2) filtering, washing and dispersing the mixed solution in the step (1) in water.
(3) And (3) adding 0.5 part of single-layer graphene oxide (the average transverse dimension is 5 microns) in the step (2), adding 1 part of 10wt% acetic acid aqueous solution, adjusting the pH value to 2.2, mechanically stirring at 50 ℃, slowly adding 2 parts of ascorbic acid aqueous solution, heating to 80 ℃, maintaining for 30min, heating to 150 ℃, and maintaining for 2 h.
(4) And (4) adding pure water into the mixed solution obtained in the step (3) to dilute the mixed solution until the viscosity is about-300 cp, and then obtaining the graphene/silicon dioxide composite aerogel powder through an atomization drying method.
The graphene/silicon dioxide composite aerogel is obtained through the steps, and the performances are shown in table 1.
Comparative example 11
(1) 100 parts of silica aerogel powder (particle size 25 μm, pore size 20nm) was dispersed in a mixed solution of concentrated sulfuric acid and hydrogen peroxide by mechanical stirring.
(2) And (2) filtering and washing the mixed solution in the step (1), and then dispersing into 300 parts of an aqueous solution of epoxysiloxane and stirring, wherein the mass ratio of the epoxysiloxane to water is 5: 100.
(3) And (3) adding 0.8 part of single-layer graphene oxide (with the average transverse dimension of 10 microns) in the step (2), mechanically stirring at 50 ℃, slowly adding 3 parts of ascorbic acid aqueous solution, heating to 80 ℃, maintaining for 30min, heating to 150 ℃, and maintaining for 3 h.
(4) And (4) adding pure water into the mixed solution obtained in the step (3) to dilute the mixed solution until the viscosity is about 400cp, and then obtaining the graphene/silicon dioxide composite aerogel powder through an atomization drying method.
The graphene/silicon dioxide composite aerogel is obtained through the steps, and the performances are shown in table 1.
Comparative example 12
(1) 100 parts of silica aerogel powder (particle size of 10 μm and pore size of 10nm) was dispersed in a mixed solution of concentrated sulfuric acid and hydrogen peroxide by mechanical stirring.
(2) And (2) filtering and washing the mixed solution in the step (1), and then dispersing into 300 parts of an aqueous solution of epoxysiloxane and stirring, wherein the mass ratio of the epoxysiloxane to water is 5: 100.
(3) And (3) adding 4 parts of 10wt% acetic acid aqueous solution in the step (2), adjusting the pH value to 1.8, mechanically stirring at 50 ℃, slowly adding 4 parts of ascorbic acid aqueous solution, heating to 80 ℃, maintaining for 30min, heating to 150 ℃, and maintaining for 3 h.
(4) And (4) adding pure water into the mixed solution obtained in the step (3) to dilute the mixed solution until the viscosity is about 400cp, and then obtaining the graphene/silicon dioxide composite aerogel powder through an atomization drying method.
The graphene/silicon dioxide composite aerogel is obtained through the steps, and the performances are shown in table 1.
Comparative example 13
TEOS、EtOH、H2Adding 0.1mol/L oxalic acid solution into the precursor solution according to the mol ratio of 1:8:3.75, adjusting the pH value to 3-4, stirring for 60min under a magnetic stirrer, and hydrolyzing for 16h in a water bath kettle at constant temperature; adding 0.5mol/L ammonia water solution, adjusting the pH value to 7-8, adding the graphene oxide suspension, placing the graphene oxide suspension in an ultrasonic cleaner for ultrasonic treatment for about 30min, stirring, standing, adding ethanol solution after gelation, and aging for 12 h; solvent exchange is carried out for 1-2 d, ethanol is carried out for 1 time and n-hexane is carried out for 2 times in sequence, then HMDZ is adopted to modify wet gel, n-hexane is used to wash away residual modified liquid, finally the wet gel is placed into a drying box and dried for 3 hours at the temperature of 80 ℃, and after drying is finished, hydrophobic graphene modified SiO can be obtained2And (3) compounding the aerogel.
Specific properties are shown in table 1.
TABLE 1 composite aerogel Performance Table of the examples
Remarking: the contact angle measurement refers to GB/T30693-.
According to the contact angles of the above cases, the contact angles of the products (examples 1 to 9) of the present invention are higher than that of the raw silica aerogel, fig. 1 and 2 are respectively a sample diagram and a hydrophobic property diagram of the raw silica aerogel powder, the graphene/silica composite aerogels of examples 2, 5 and 8, it can be found from fig. 1 that the graphene/silica composite aerogel samples of examples 2, 5 and 8 have color uniformity and are consistent with the state of the raw silica aerogel powder, fig. 2 can find that obvious depressions appear when water drops drop on the raw silica aerogel powder, and the water drops drop on the graphene/silica composite aerogel samples of examples 2, 5 and 8, and can be stabilized on the sample without depressions, and the method of the present invention realizes the coating of the graphene on the silica aerogel, the reason for this is probably that silicon hydroxyl groups generated after hydrolysis of epoxy siloxane and modified silica aerogel are adsorbed on the surface of the silica aerogel under the action of hydrogen bonds in aqueous solution, so that epoxy groups are exposed to the outside, and the epoxy groups are helpful for ring opening of the epoxy groups under the conditions of acid solution and certain temperature, like a tentacle with claws, when graphene oxide is added, due to the fact that the surface of the graphene oxide has a plurality of functional groups, the graphene oxide can be effectively caught, and the graphene oxide can be bonded with oxygen-containing functional groups on the surface of the graphene oxide, so that the graphene oxide is wrapped on the surface of the silica aerogel. In the traditional preparation method, graphene oxide is added into a silicon source, graphene oxide sheets exist in a silicon source solution, and an integral composite material is formed through the processes of gelling, aging, drying and the like.
Further comparing the coated product of the present invention with the composite product of the conventional method, the product of the present invention (examples 1 to 9) has a greatly improved compressive strength and the like as compared with the silica aerogel as the raw material and comparative examples 11 to 13. The reason is that the reduced graphene has good mechanical properties and strong stability, and the graphene serving as a support on the surface of the silicon aerogel can effectively absorb impact, so that the damage of external force to the silicon aerogel matrix structure is reduced, the problem of high brittleness of the silicon aerogel can be solved, and the compressive strength of the silicon dioxide aerogel is improved.
Further comparing the coated product of the present invention with the composite product of the conventional method, the product of the present invention (examples 1 to 9) maintains the porosity of the silica aerogel powder itself, and the low porosity of the conventional method is due to the collapse of the pore structure or the inhibition of the formation of pores caused by the change of the structure of the original silica aerogel after doping the graphene sheet.
Further, as can be seen from examples 1 to 9 and comparative examples 10 to 12, when the addition amounts of the epoxy siloxane, the acidic aqueous solution and the graphene oxide are regulated, the related performance of the composite aerogel is improved, and the regulation of the amount of the epoxy siloxane in examples 1 to 3 and comparative example 10 improves the related performance, and has an obvious effect on the compressive strength of the composite silicon aerogel along with the increase of the amount; the amount of the acidic aqueous solution is regulated and controlled in examples 4-6 and comparative example 11, the related performance is improved, and the contact angle and the compressive strength of the composite silicon aerogel are obviously influenced along with the increase of the amount; examples 7-9 and comparative example 12 regulate the amount of epoxy siloxane, improve the relevant performance, and have obvious effects on the contact angle, compressive strength, porosity and thermal conductivity of the composite silicone aerogel with the increase of the amount, and the possible reasons for the above effects are that the addition of epoxy siloxane and an acidic aqueous solution both contribute to the combination of graphene oxide and GO, so that more graphene sheets are tightly wrapped on the surface of the silicone aerogel to form a stable structure, which contributes to the improvement of the relevant performance of the composite silicone aerogel. However, when the addition amounts of the epoxy siloxane and the acidic aqueous solution reach a certain amount, the related performance of the composite aerogel is not obviously improved, because the number of the epoxy siloxane connected to the surface of the silicon aerogel is limited and reaches saturation, and the performance cannot be well influenced by changing the addition amounts of the epoxy siloxane and the acidic aqueous solution, in addition, when the addition amount of the graphene is too high, a plurality of sheets cannot be completely wrapped on the surface of the silicon aerogel, and free graphene sheets exist and can form stacking, so that the overall performance of the composite aerogel is influenced.
Claims (4)
1. The graphene/silicon dioxide composite aerogel is characterized by being prepared by the following steps:
(1) dispersing 100 parts by weight of silicon dioxide aerogel powder in a mixed solution of concentrated sulfuric acid and hydrogen peroxide for hydroxylation treatment;
(2) filtering, washing, dispersing into an aqueous solution containing 100-500 parts by weight of epoxy siloxane, and stirring;
(3) adding 0.1-20 parts by weight of graphene oxide, adjusting the pH value to be less than 3, and mechanically stirring at 50 ℃;
(4) adding an ascorbic acid aqueous solution, heating to 80 ℃, and maintaining for 10-30 min; then heating to 150 ℃, and maintaining for 1-3 h;
(5) adjusting the viscosity to 200-600 cp, and then obtaining the graphene/silicon dioxide composite aerogel powder by an atomization drying method.
2. The graphene/silica composite aerogel according to claim 1, wherein the silica aerogel powder is a nano aerogel powder, and has a particle size of 5 to 50 μm and a pore size of 10 to 30 nm.
3. The graphene/silica composite aerogel according to claim 1, wherein the graphene oxide is formed from one or more of a single layer of graphene oxide, a double layer of graphene oxide, and a multi-layer of graphene oxide; the transverse size of the graphene oxide sheet diameter is 2-50 mu m.
4. The graphene/silica composite aerogel according to claim 1, wherein the acid solution is one or more of 10wt% acetic acid, 10wt% oxalic acid, 20wt% citric acid, and 5wt% ethylenediaminetetraacetic acid aqueous solution.
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