CN115212814B - Graphene composite aerogel composition, graphene composite aerogel, and preparation method and application thereof - Google Patents
Graphene composite aerogel composition, graphene composite aerogel, and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 100
- 239000004964 aerogel Substances 0.000 title claims abstract description 72
- 239000002131 composite material Substances 0.000 title claims abstract description 62
- 239000000203 mixture Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title abstract description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000002042 Silver nanowire Substances 0.000 claims abstract description 36
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical class O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000001179 sorption measurement Methods 0.000 claims abstract description 6
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- 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 22
- 238000001035 drying Methods 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000007710 freezing Methods 0.000 claims description 14
- 230000008014 freezing Effects 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 12
- 229960005070 ascorbic acid Drugs 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- 239000002211 L-ascorbic acid Substances 0.000 claims description 9
- 235000000069 L-ascorbic acid Nutrition 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- 238000000354 decomposition reaction Methods 0.000 claims description 5
- 239000012782 phase change material Substances 0.000 claims description 5
- 238000013329 compounding Methods 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000007788 liquid Substances 0.000 description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- 238000000502 dialysis Methods 0.000 description 10
- 238000002791 soaking Methods 0.000 description 10
- 238000000926 separation method Methods 0.000 description 8
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- 230000000052 comparative effect Effects 0.000 description 7
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- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 235000017281 sodium acetate Nutrition 0.000 description 4
- 239000001632 sodium acetate Substances 0.000 description 4
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 3
- 239000012286 potassium permanganate Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
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- 238000011056 performance test Methods 0.000 description 2
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- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 238000011049 filling Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
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Classifications
-
- 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
Abstract
The invention relates to the technical field of aerogel and discloses a graphene composite aerogel composition, a graphene composite aerogel and a preparation method and application thereof. The composition contains the following components which are stored independently or stored in a mixed way: graphene oxide, aminated ferroferric oxide and silver nanowires; based on the total mass of the composition, the content of graphene oxide is 50-90wt%, the content of aminated ferroferric oxide is 10-30wt%, and the content of silver nanowires is 1-5wt%; the average grain diameter of the silver nanowire is 10 mu m-20 mu m, and the average diameter is 100mm-200mm. The graphene composite aerogel obtained by compounding the graphene oxide, the aminated ferroferric oxide and the silver nanowire has a stable three-dimensional structure, and has the characteristics of light weight, large specific surface area and strong adsorption capacity.
Description
Technical Field
The invention relates to the technical field of aerogel, in particular to a graphene composite aerogel composition, a graphene composite aerogel and a preparation method and application thereof.
Background
Aerogel is widely applied to the fields of sewage treatment, heat insulation, electromagnetic shielding, phase change materials, flame retardance and the like due to the structural characteristics of light weight, large surface area, multiple holes and the like.
Graphene single-layer thermal conductivity 5300W/mk and electric conductivity reaching 10 6 S/cm, is widely applied in the fields of electric conduction and heat conduction. If the electric conduction and heat conduction properties of the graphene are fully utilized, the graphene is prepared into aerogel, and the aerogel is used as an electromagnetic shielding material, an adsorption material, a phase change material and other materials, so that the application field of the graphene can be further widened, and the requirements of people on light weight and high performance are met.
However, the graphene aerogel alone has a defect that the three-dimensional structure is not strong. In order to obtain the graphene aerogel with the three-dimensional network structure, researchers generally add other substances when or later in the preparation of the graphene aerogel, and change the performance of the graphene aerogel, so as to obtain an aerogel product with more reactive sites and more stable structure.
CN108940141A discloses a preparation method of graphene composite aerogel, which adopts graphene and carbon spheres as raw materials, and adopts ascorbic acid to assist in reduction synthesis of the graphene composite aerogel, wherein the porosity of the composite aerogel prepared by the method reaches 99.56%, and the bulk density is 9.6mg/cm 3 The particle size of the internal carbon microspheres is less than or equal to 400nm, and the internal carbon microspheres and the graphene sheets are mutually supported to form a mutually crosslinked three-dimensional porous structure, and the pore size of the composite aerogel is less than or equal to 50 mu m.
However, the graphene composite aerogel prepared by the method still has the problems of small specific surface area, complex preparation process and poor stability.
Disclosure of Invention
The invention aims to solve the problems of small specific surface area and poor stability of graphene composite aerogel in the prior art.
In order to achieve the above object, according to a first aspect of the present invention, there is provided a graphene composite aerogel composition comprising the following components, each independently stored or stored in a mixed manner of two or more:
graphene oxide, aminated ferroferric oxide and silver nanowires;
based on the total mass of the composition, the content of graphene oxide is 50-90wt%, the content of aminated ferroferric oxide is 10-30wt%, and the content of silver nanowires is 1-5wt%;
the average grain diameter of the silver nanowire is 10 mu m-20 mu m, and the average diameter is 100mm-200mm.
Preferably, the content of the graphene oxide is 70-85wt%, the content of the aminated ferroferric oxide is 10-25wt% and the content of the silver nanowire is 3-5wt%, based on the total mass of the composition.
The second aspect of the present invention provides a method for preparing a graphene composite aerogel, the method comprising: mixing the components of the composition of the first aspect;
wherein the operation of mixing the components of the composition comprises the steps of:
(1) In the presence of a solvent I, carrying out first mixing on graphene oxide, aminated ferroferric oxide and silver nanowires to obtain a first mixed solution, and carrying out heating treatment on the first mixed solution to obtain a second mixed solution;
(2) Carrying out a first contact reaction on the second mixed solution and the L-ascorbic acid to obtain hydrogel;
(3) And sequentially performing freezing treatment and first drying treatment on the hydrogel.
Preferably, in step (1), the conditions of the first mixing include at least: the ultrasonic frequency is 30-40kHz, the temperature is 25-45 ℃ and the time is 1.5-3h.
Preferably, in step (1), the conditions of the heating treatment include at least: the temperature is 65-80 ℃ and the time is 2-3h.
Preferably, in step (2), the conditions of the first contact reaction include at least: the temperature is 40-50 ℃ and the time is 10-16h.
Preferably, in step (3), the conditions of the freezing treatment include at least: the temperature is from-196 ℃ to-210 ℃ and the time is 2-3min.
Preferably, in step (3), the conditions of the first drying treatment include at least: the temperature is between minus 56 ℃ and minus 65 ℃ for 20-30 hours.
The third aspect of the invention provides the graphene composite aerogel prepared by the method of the second aspect.
Preferably, the specific surface area of the graphene composite aerogel is 440-600m 2 The initial decomposition temperature per gram is 400-450 ℃.
The fourth aspect of the invention provides an application of the graphene composite aerogel in electromagnetic shielding materials, adsorption materials or phase change materials and the like.
The graphene composite aerogel obtained by compounding the graphene oxide, the aminated ferroferric oxide and the silver nanowire has a stable three-dimensional structure, and has the characteristics of light weight, large specific surface area and strong adsorption capacity.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In the present invention, unless otherwise stated, the room temperature or the normal temperature represents 25.+ -. 2 ℃.
As described above, the first aspect of the present invention provides a graphene composite aerogel composition, which contains the following components stored independently or in a mixed manner of two or more:
graphene oxide, aminated ferroferric oxide and silver nanowires;
based on the total mass of the composition, the content of graphene oxide is 50-90wt%, the content of aminated ferroferric oxide is 10-30wt%, and the content of silver nanowires is 1-5wt%;
the average grain diameter of the silver nanowire is 10 mu m-20 mu m, and the average diameter is 100mm-200mm.
The average particle diameter of the silver nanowire means "average value of the length of the silver nanowire".
The average diameter of the silver nanowires refers to "average value of cross-sectional diameters of silver nanowires".
The method for detecting the average particle diameter of the silver nanowires and the average diameter of the silver nanowires is not particularly required, and the method can be obtained by detecting the average particle diameter of the silver nanowires by adopting a method known in the art, and the average particle diameter and the average diameter of the silver nanowires are obtained by adopting a scanning electron microscope.
Preferably, the content of the graphene oxide is 70-85wt%, the content of the aminated ferroferric oxide is 10-25wt% and the content of the silver nanowire is 3-5wt%, based on the total mass of the composition. The inventor finds that in the specific embodiment in the preferred case, the graphene composite aerogel with larger specific surface area can be obtained on the premise of keeping thermal stability.
As previously described, a second aspect of the present invention provides a method of preparing a graphene composite aerogel, the method comprising: mixing the components of the composition of the first aspect;
wherein the operation of mixing the components of the composition comprises the steps of:
(1) In the presence of a solvent I, carrying out first mixing on graphene oxide, aminated ferroferric oxide and silver nanowires to obtain a first mixed solution, and carrying out heating treatment on the first mixed solution to obtain a second mixed solution;
(2) Carrying out a first contact reaction on the second mixed solution and the L-ascorbic acid to obtain hydrogel;
(3) And sequentially performing freezing treatment and first drying treatment on the hydrogel.
Preferably, in step (1), the conditions of the first mixing include at least: the ultrasonic frequency is 30-40kHz, the temperature is 25-45 ℃ and the time is 1.5-3h.
Preferably, in step (1), the conditions of the heating treatment include at least: the temperature is 65-80 ℃ and the time is 2-3h.
Preferably, in step (2), the conditions of the first contact reaction include at least: the temperature is 40-50 ℃ and the time is 10-16h.
Preferably, in step (2), the amount of L-ascorbic acid is 1-5g relative to 1g of the composition.
Preferably, in step (3), the conditions of the freezing treatment include at least: the temperature is from-196 ℃ to-210 ℃ and the time is 2-3min.
The particular manner in which the freezing process is performed is not particularly critical and may be carried out using methods known in the art, and illustratively the invention employs liquid nitrogen freezing.
Preferably, in step (3), the conditions of the first drying treatment include at least: the temperature is between minus 56 ℃ and minus 65 ℃ for 20-30 hours.
In order to keep the hydrogel from shrinking, in step (3), the method further comprises: before the hydrogel is frozen, the hydrogel is soaked, and the soaked hydrogel is dialyzed.
Preferably, in step (3), the conditions of the soaking treatment include at least: the temperature is 3-8deg.C, and the time is 20-30h.
The type and the amount of the solvent used in the soaking treatment are not particularly required, the soaking treatment can be performed by using a solvent known in the art, and the hydrogel is only required to be completely soaked, and the soaking treatment is performed by using distilled water in an exemplary manner.
The type of solvent used in the dialysis treatment is not particularly limited, and the dialysis treatment may be performed using solvents known in the art, and the present invention uses ethanol having a concentration of 10 to 20wt% as an example.
The invention has no special requirement on the solvent dosage adopted in the dialysis treatment, and only needs to meet the requirement of the invention, and the invention adopts a dialysis bag for dialysis treatment, and the solvent dosage can completely exceed the dialysis bag.
Preferably, in step (3), the conditions of the dialysis treatment include at least: the temperature is 20-40 ℃ and the time is 0.5-2h.
Preferably, the graphene oxide is prepared by a method comprising the following steps:
s1, in the presence of an acid solvent I, reacting graphite with potassium permanganate to obtain a mixed solution I;
s2, reacting the mixed solution I with hydrogen peroxide to obtain a mixed solution II, and performing solid-liquid separation I on the mixed solution II to obtain a solid material I containing graphene oxide;
s3, drying the solid material I.
Preferably, in step S1, the acid solvent I is sulfuric acid and phosphoric acid in a dosage volume ratio of 4-10:1.
More preferably, in step S1, the concentration of the phosphoric acid is not less than 70wt% and the concentration of the phosphoric acid is not less than 80wt%.
Preferably, in step S1, the graphite is expanded graphite, and the mass ratio of the amount of the expanded graphite to the amount of the potassium permanganate is 1:4-8.
Preferably, in step S1, the conditions of reaction I include at least: the stirring speed is 400-600rpm, the temperature is 40-60 ℃ and the time is 8-20h.
Preferably, in step S2, the conditions of reaction II include at least: the stirring speed is 200-400rpm, the temperature is 20-40 ℃ and the time is 8-20h.
The specific operation method of the solid-liquid separation I is not particularly limited, and the solid-liquid separation I can be performed by a method known in the art, and the solid-liquid separation I is performed by centrifugation, for example.
Preferably, in step S3, the conditions of the drying process I include at least: the temperature is 60-90 ℃ and the time is 15-30h.
Preferably, the aminated ferroferric oxide is prepared by a method comprising the following steps:
y1. reacting ferric chloride hexahydrate, sodium acetate and triethylenetetramine in the presence of a solvent A to obtain a mixed solution A, and carrying out solid-liquid separation on the mixed solution A to obtain a solid material A containing ferroferric oxide;
y2. the solid material a was subjected to drying treatment a.
Preferably, in step Y1, the solvent a is absolute ethanol.
Preferably, in step Y1, the solvent A is used in an amount of 15 to 30mL, the sodium acetate is used in an amount of 1 to 5g, and the triethylenetetramine is used in an amount of 1 to 10mL, relative to 1g of the ferric chloride hexahydrate.
Preferably, in step Y1, the conditions of reaction a include at least: the temperature is 180-220 ℃ and the time is 8-10h.
The specific operation method of the solid-liquid separation A is not particularly limited, and the solid-liquid separation A can be carried out by adopting a method known in the art, and the solid-liquid separation I is carried out by magnetic attraction by way of example.
Preferably, in step Y2, the conditions of the drying treatment a include at least: the temperature is 50-60 ℃ and the time is 24-30h.
As previously described, a third aspect of the present invention provides a graphene composite aerogel prepared by the method of the second aspect.
Preferably, the specific surface area of the graphene composite aerogel is 440-600m 2 The initial decomposition temperature per gram is 400-450 ℃.
As described above, the fourth aspect of the present invention provides an application of the graphene composite aerogel according to the third aspect in electromagnetic shielding materials, adsorption materials or phase change materials.
The invention will be described in detail below by way of examples. In the following examples, all of the raw materials used were commercial products unless otherwise specified.
The preparation method of graphene oxide used in the following examples comprises the following steps:
4g of graphite, 450mL of concentrated sulfuric acid (98 wt% strength) and 54mL of concentrated phosphoric acid (85 wt% strength) were added to a three-necked flask, followed by slow addition of 24g of KMnO to the three-necked flask 4 After the raw materials are added, the temperature is increased to 50 ℃, the stirring speed is 500rpm, the stirring time is 12 hours, and after the reaction is finished, the temperature is reduced to room temperature, so as to obtain a mixed solution I;
adding the mixed solution I into a beaker filled with 1000mL of deionized water at room temperature, adding hydrogen peroxide into the beaker, stirring at 300rpm until the color of the mixture turns golden yellow, standing for 10 hours, removing supernatant, sequentially centrifugally washing with hydrochloric acid and deionized water until the pH value is 7, and washing with absolute ethyl alcohol to obtain a solid material I containing graphene oxide;
finally, placing the solid material I in a vacuum oven at 70 ℃ for drying for 24 hours, wherein the obtained brown product is graphene oxide;
the preparation method of the aminated ferroferric oxide applied in the following examples comprises the following steps:
1.1g of FeCl 3 ·6H 2 Adding O into 25mL of absolute ethyl alcohol under stirring condition (stirring speed is 400 rpm) to form a uniform solution, then adding 3g of sodium acetate and 5mL of triethylenetetramine into the solution, continuously stirring until solid substances are completely dissolved, transferring the solution into a Teflon-lined stainless steel autoclave, placing the solution into an oven, and adjusting the temperature of the oven to 200 ℃ for 10 hours to obtain a mixed solution A;
transferring the mixed solution A into a beaker, washing with deionized water for 5 times, magnetically sucking each washing to obtain a solid material A, and treating the solid material A in an oven at 60 ℃ for 28 hours;
silver nanowires: the average particle diameter is 15um, the average diameter is 150nm, and the nanometer material is purchased from Jiangsu Xianfeng nanometer materials science and technology Co., ltd;
graphite: expanded graphite flakes having an average particle size of 300 mesh, available from peninsula Xin Co., ltd;
in the following examples, phosphoric acid, sulfuric acid, potassium permanganate, hydrogen peroxide, ferric chloride hexahydrate, ethanol, and sodium acetate were all purchased from Chengdu Kelong chemical reagent plants; l-ascorbic acid, triethylenetetramine were analytically pure and purchased from Sigma-Aldrich.
Example 1
The embodiment provides a method for preparing graphene composite aerogel, which comprises the following steps:
(1) Adding 0.42g of graphene oxide, 0.06g of aminated ferroferric oxide and 0.02g of silver nanowire into 18mL of deionized water for first mixing to obtain a first mixed solution, heating the first mixed solution to obtain a second mixed solution, and cooling to room temperature;
wherein, the first mixing condition is: the ultrasonic frequency is 30kHz, the temperature is 30 ℃, and the time is 2 hours;
the conditions of the heating treatment are as follows: the temperature is 70 ℃ and the time is 3 hours;
(2) Adding 1.2g of L-ascorbic acid into all the cooled second mixed solution, replacing a glass bottle cap with tinfoil, performing a first contact reaction to obtain hydrogel, cooling to room temperature, and cleaning the hydrogel by using distilled water;
wherein, the conditions of the first contact reaction are as follows: the temperature is 50 ℃ and the time is 10 hours;
(3) Soaking the washed hydrogel in distilled water, sealing, placing in a refrigerator, keeping for 24 hours, dialyzing with 10wt% ethanol, freezing with liquid nitrogen, and placing the frozen hydrogel in a freeze dryer for a first drying treatment to obtain cylindrical graphene composite aerogel S1;
wherein, the conditions of the soaking treatment are as follows: the temperature is 5 ℃ and the time is 24 hours;
the conditions for the dialysis treatment were: the temperature is room temperature and the time is 1h;
the conditions of the freezing treatment are as follows: the temperature is below 196 ℃ below zero and the time is 3min;
the conditions of the first drying treatment were: the temperature is 65 ℃ below zero and the time is 24 hours.
Example 2
The embodiment provides a method for preparing graphene composite aerogel, which comprises the following steps:
(1) Adding 0.40g of graphene oxide, 0.08g of aminated ferroferric oxide and 0.02g of silver nanowire into 18mL of deionized water for first mixing to obtain a first mixed solution, heating the first mixed solution to obtain a second mixed solution, and cooling to room temperature;
wherein, the first mixing condition is: the ultrasonic frequency is 40kHz, the temperature is 40 ℃, and the time is 1.5 hours;
the conditions of the heating treatment are as follows: the temperature is 70 ℃ and the time is 3 hours;
(2) Adding 1.2g of L-ascorbic acid into all the cooled second mixed solution, replacing a glass bottle cap with tinfoil, performing a first contact reaction to obtain hydrogel, cooling to room temperature, and cleaning the hydrogel by using distilled water;
wherein, the conditions of the first contact reaction are as follows: the temperature is 50 ℃ and the time is 10 hours;
(3) Soaking the washed hydrogel in distilled water, sealing, placing in a refrigerator, keeping for 24 hours, dialyzing with 10wt% ethanol, freezing with liquid nitrogen, and placing the frozen hydrogel in a freeze dryer for a first drying treatment to obtain cylindrical graphene composite aerogel S2;
wherein, the conditions of the soaking treatment are as follows: the temperature is 5 ℃ and the time is 24 hours;
the conditions for the dialysis treatment were: the temperature is room temperature and the time is 1h;
the conditions of the freezing treatment are as follows: the temperature is minus 200 ℃ and the time is 3min;
the conditions of the first drying treatment were: the temperature is 65 ℃ below zero and the time is 24 hours.
Example 3
The embodiment provides a method for preparing graphene composite aerogel, which comprises the following steps:
(1) Adding 0.38g of graphene oxide, 0.1g of aminated ferroferric oxide and 0.02g of silver nanowire into 18mL of deionized water for first mixing to obtain a first mixed solution, heating the first mixed solution to obtain a second mixed solution, and cooling to room temperature;
wherein, the first mixing condition is: the ultrasonic frequency is 35kHz, the temperature is 45 ℃, and the time is 1.5 hours;
the conditions of the heating treatment are as follows: the temperature is 80 ℃ and the time is 2 hours;
(2) Adding 1.2g of L-ascorbic acid into all the cooled second mixed solution, replacing a glass bottle cap with tinfoil, performing a first contact reaction to obtain hydrogel, cooling to room temperature, and cleaning the hydrogel by using distilled water;
wherein, the conditions of the first contact reaction are as follows: the temperature is 40 ℃ and the time is 15 hours;
(3) Soaking the washed hydrogel in distilled water, sealing, placing in a refrigerator, keeping for 24 hours, dialyzing with 10wt% ethanol, freezing with liquid nitrogen, and placing the frozen hydrogel in a freeze dryer for a first drying treatment to obtain cylindrical graphene composite aerogel S3;
wherein, the conditions of the soaking treatment are as follows: the temperature is 5 ℃ and the time is 24 hours;
the conditions for the dialysis treatment were: the temperature is room temperature and the time is 1h;
the conditions of the freezing treatment are as follows: the temperature is below 210 ℃ and the time is 2min;
the conditions of the first drying treatment were: the temperature is minus 56 ℃ and the time is 24 hours.
Example 4
A graphene composite aerogel was prepared in accordance with the method of example 1, except that in step (1), 0.45g of graphene oxide was used and 0.03g of aminated ferroferric oxide was used. .
The rest steps are the same as in example 1, and graphene composite aerogel S4 is prepared.
Example 5
A graphene composite aerogel was prepared according to the method of example 1, except that in step (1), 0.34g of graphene oxide was used and 0.14g of aminated ferroferric oxide was used.
The rest steps are the same as in example 1, and graphene composite aerogel S5 is prepared.
Example 6
A graphene composite aerogel was prepared as in example 1, except that in step (2), an equal mass of hydrazine (N 2 H 4 ) The ascorbic acid is replaced by L-ascorbic acid.
The rest steps are the same as in example 1, and graphene composite aerogel S6 is prepared.
Comparative example 1
A graphene composite aerogel was prepared as in example 1, except that in step (1), no silver nanowires were applied, i.e., 0.42g of graphene oxide was applied and 0.08g of aminated ferroferric oxide was applied.
The rest steps are the same as those of the embodiment 1, and the graphene composite aerogel DS1 is prepared.
Comparative example 2
A graphene composite aerogel was prepared according to the method of example 1, except that in step (1), no aminated ferroferric oxide was applied, i.e., 0.48g of graphene oxide was applied and 0.02g of silver nanowire was applied.
The rest steps are the same as those of the embodiment 1, and the graphene composite aerogel DS2 is prepared.
Comparative example 3
A graphene composite aerogel was prepared as in example 1, except that in step (1), the aminated ferroferric oxide was replaced with an equal mass of ferroferric oxide.
The rest steps are the same as in example 1, and graphene composite aerogel DS3 is prepared.
Comparative example 4
A graphene composite aerogel was prepared as in example 1, except that in step (1), the aminated ferroferric oxide was replaced with an equal mass of copper powder.
The rest steps are the same as in example 1, and graphene composite aerogel DS4 is prepared.
Comparative example 5
A graphene composite aerogel was prepared according to the method of example 1, except that in step (1), 0.46g of graphene oxide was used and 0.02g of aminated ferroferric oxide was used.
The rest steps are the same as in example 1, and graphene composite aerogel DS5 is prepared.
Comparative example 6
A graphene composite aerogel was prepared according to the method of example 1, except that in step (1), 0.2g of graphene oxide was used and 0.28g of aminated ferroferric oxide was used.
The rest steps are the same as in example 1, and graphene composite aerogel DS6 is prepared.
Test case
The graphene composite aerogel prepared in the examples and the comparative examples is subjected to performance test, wherein the performance test comprises specific surface area and initial decomposition temperature, and specific test results are shown in table 1.
The initial decomposition temperature is tested by adopting thermogravimetric analysis (the model of the thermogravimetric analyzer is TA-Q50, purchased from TA company of America), and the specific method is as follows: cutting the graphene composite aerogel into square fragments with the size of 2mm multiplied by 2mm, testing the square fragments with the mass of 5mg, placing a weighed sample into an aluminum oxide crucible for testing, wherein the air flow speed of nitrogen is 50cm under the nitrogen environment during testing 3 The temperature rising rate is set to 20 ℃/min, and the temperature range of the test is 100-900 ℃;
the specific surface area was measured using a specific surface area analyzer (model Autosorb-1-1, available from Kang Da, U.S.A.), and the specific test method was: weighing a certain amount of graphene composite aerogel to be measured, filling the graphene composite aerogel into a sample tube, and weighing the condition (the product of the mass of the sample and the estimated specific surface area should be 20-100m 2 And the volume of the sample in the sample tube cannot exceed two thirds, the loading quantity of the sample is required to be more than 100mg, and the sample tube with the sample is placed in a specific surface area analyzer for detection.
TABLE 1
As can be seen from the results in table 1, the graphene composite aerogel with large specific surface area and stable thermal property can be prepared by compounding the graphene oxide, the aminated ferroferric oxide and the silver nanowire according to a specific ratio.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. The composite aerogel composition for preparing the graphene is characterized by comprising the following components which are stored independently or stored in a mixed manner by more than two of the following components:
graphene oxide, aminated ferroferric oxide and silver nanowires;
based on the total mass of the composition, the content of graphene oxide is 70-85wt%, the content of aminated ferroferric oxide is 10-25wt%, and the content of silver nanowires is 3-5wt%;
the average grain diameter of the silver nanowire is 10 mu m-20 mu m, and the average grain diameter is 100nm-150nm;
the average particle diameter of the silver nanowire means "average value of the length of the silver nanowire".
2. A method of preparing a graphene composite aerogel, the method comprising: mixing the components of the composition of claim 1;
the method comprises the following steps:
(1) In the presence of a solvent I, carrying out first mixing on graphene oxide, aminated ferroferric oxide and silver nanowires to obtain a first mixed solution, and carrying out heating treatment on the first mixed solution to obtain a second mixed solution;
(2) Carrying out a first contact reaction on the second mixed solution and the L-ascorbic acid to obtain hydrogel;
(3) And sequentially performing freezing treatment and first drying treatment on the hydrogel.
3. The method of claim 2, wherein in step (1), the first mixing conditions include at least: the ultrasonic frequency is 30-40kHz, the temperature is 25-45 ℃ and the time is 1.5-3h.
4. A method according to claim 2 or 3, wherein in step (1), the conditions of the heat treatment comprise at least: the temperature is 65-80 ℃ and the time is 2-3h.
5. A method according to claim 2 or 3, wherein in step (2) the conditions of the first contact reaction comprise at least: the temperature is 40-50 ℃ and the time is 10-16h.
6. A method according to claim 2 or 3, wherein in step (3), the conditions of the freezing treatment comprise at least: the temperature is from-196 ℃ to-210 ℃ and the time is 2-3min.
7. A method according to claim 2 or 3, wherein in step (3), the conditions of the first drying treatment comprise at least: the temperature is between minus 56 ℃ and minus 65 ℃ for 20-30 hours.
8. A graphene composite aerogel prepared by the method of any one of claims 2-7.
9. The graphene composite aerogel of claim 8, wherein the specific surface area of the graphene composite aerogel is 440-600m 2 The initial decomposition temperature per gram is 400-450 ℃.
10. Use of the graphene composite aerogel according to claim 8 or 9 in an electromagnetic shielding material, an adsorption material or a phase change material.
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| CN108976718A (en) * | 2018-08-13 | 2018-12-11 | 西北工业大学 | A kind of epoxy resin base electro-magnetic screen composite material and preparation method thereof |
| CN109592964A (en) * | 2018-12-01 | 2019-04-09 | 浙江大学 | Electromagnetic shielding elastic controllable grapheme aeroge and preparation method thereof |
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| US8975326B2 (en) * | 2010-03-15 | 2015-03-10 | Lei Zhai | Carbon nanotube or graphene-based aerogels |
| CN107913674B (en) * | 2017-10-27 | 2020-08-04 | 苏州大学 | MOF-loaded 3D ruthenium/graphene aerogel composite material, preparation method thereof and application thereof in continuous CO treatment |
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| CN102824883A (en) * | 2012-08-27 | 2012-12-19 | 北京理工大学 | Composite aerogel of graphene/Prussian-blue complexes, and preparation method and application thereof |
| CN108976718A (en) * | 2018-08-13 | 2018-12-11 | 西北工业大学 | A kind of epoxy resin base electro-magnetic screen composite material and preparation method thereof |
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