CN111097341A - Preparation method of phenolic resin reinforced three-dimensional graphene aerogel - Google Patents
Preparation method of phenolic resin reinforced three-dimensional graphene aerogel Download PDFInfo
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Abstract
The invention relates to a preparation method of a phenolic resin reinforced three-dimensional graphene aerogel, which comprises the following steps: adding a phenolic substance and an aldehyde substance into a graphene oxide aqueous solution to obtain a precursor aqueous solution; adding a phenolic aldehyde reaction catalyst into a precursor water solution, carrying out hydrothermal reaction for 6-24 hours at the temperature of 90-210 ℃, and then washing and drying to obtain the phenolic resin reinforced three-dimensional graphene aerogel.
Description
Technical Field
The invention relates to a preparation method of a phenolic resin reinforced three-dimensional graphene aerogel, and belongs to the field of three-dimensional graphene aerogels.
Background
Graphene is a carbon atom represented by SP2The single-layer crystal material formed by hybridization mode is easy to stack into two-dimensional structure material with low porosity due to the static electricity and pi-pi interaction between graphene sheets, so that the material is easy to stack into two-dimensional structure material with low porosityThe range of use is limited. Therefore, the graphene sheet is constructed into a three-dimensional porous structure to expand the application range thereof, and is attracting more and more attention. The three-dimensional graphene aerogel has the characteristics of low density, high conductivity, high specific surface area, high porosity and the like, and has great application prospects in the fields of energy, environment, electronics and the like. Generally, methods for preparing three-dimensional graphene macroscopic blocks mainly include a self-assembly method, a chemical vapor deposition method, a template method, and the like.
Most of the three-dimensional graphene aerogels reported so far tend to be plastically deformed or brittle fractured when subjected to cyclic stress, which greatly limits the practical use of the three-dimensional graphene aerogels. And the mechanical strength and elasticity can be effectively improved by introducing the polymer into a graphene system to jointly construct the three-dimensional aerogel. And (3) taking the polymer molecules as a skeleton, self-assembling the graphene oxide on the surface of the polymer molecules, and removing the high-molecular skeleton through high-temperature treatment to obtain the three-dimensional graphene foam. Such as: yu et al use polyurethane foam as a skeleton, assemble graphene oxide on the surface of the polymer skeleton by an impregnation method, and then perform high-temperature treatment to obtain graphene foam (Small 2015,11, 2380-2385.). However, in such materials, since the interaction (van der waals force and pi-pi interaction) between graphene and the polymer skeleton is weak, graphene is easily detached from the polymer skeleton, thereby affecting the electrical properties, stability and mechanical properties thereof.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of a stable phenolic resin reinforced three-dimensional graphene aerogel, which comprises the following steps:
adding a phenolic substance and an aldehyde substance into a graphene oxide aqueous solution to obtain a precursor aqueous solution;
adding a phenolic aldehyde reaction catalyst into a precursor water solution, carrying out hydrothermal reaction for 6-24 hours at the temperature of 90-210 ℃, and then washing and drying to obtain the phenolic resin reinforced three-dimensional graphene aerogel.
According to the invention, after phenolic resin monomers (phenolic substances and aldehyde substances capable of being polymerized into phenolic resin) and graphene oxide dispersion liquid are uniformly mixed, due to the electrostatic adsorption effect between graphene nanosheets and phenolic monomers, the monomers are gathered on the surface of graphene sheets, and the phenolic monomers are polymerized into thermosetting phenolic resin under the conditions of a catalyst and high-temperature hydrothermal (90-210 ℃), so that the mechanical strength of the three-dimensional graphene aerogel is greatly improved.
Preferably, the graphene oxide is prepared by adopting an improved Hummers method and is dispersed in deionized water to obtain the graphene oxide aqueous solution.
Preferably, the concentration of the graphene oxide aqueous solution is 1mg/ml to 15 mg/ml.
Preferably, the phenolic substance (R) is at least one selected from phenol, resorcinol, hydroquinone and bisphenol A, and the aldehyde substance (F) is at least one selected from formaldehyde, glutaraldehyde and butyraldehyde.
Preferably, the molar ratio of the phenolic substance to the aldehyde substance is 1: 4-4: 1.
Preferably, the phenolic aldehyde reaction catalyst is at least one selected from sodium hydroxide, barium hydroxide, potassium hydroxide, triethylamine, sodium carbonate, ammonium bicarbonate, zinc chloride, magnesium chloride and calcium chloride, and is preferably ZnCl2One of KOH and ammonium bicarbonate; the addition amount of the phenolic aldehyde reaction catalyst is 1-300 wt% of the total mass of the phenolic substance and the aldehyde substance, and preferably 1-20 wt%.
Preferably, the precursor aqueous solution further comprises a cross-linking agent and a curing accelerator, wherein the cross-linking agent is at least one of hexamethylenetetramine (hexamethylenetetramine), hydroxymethyl urea and propylene carbonate, and the curing accelerator is at least one of tosyl chloride and benzene sulfonyl chloride; preferably, the mass ratio of the crosslinking agent to the phenolic substance is 1: (4-20), wherein the mass ratio of the curing accelerator to the phenolic substance is 1: (8-20). In addition, due to the addition of the cross-linking agent and the curing accelerator, the cross-linking degree of the phenolic resin is further improved under the action of the cross-linking agent (such as hexamethylenetetramine) and the phenolic resin can be further fully cross-linked with the graphene nanosheet under the promotion of the cross-linking agent.
Preferably, the mass ratio of the phenolic substance to the graphene oxide is (0.05-2): 1; preferably, the mass ratio of the phenolic substance (or aldehyde substance) to the graphene oxide is (0.1-1): 1. within the range, the mechanical strength can be improved, and the conductivity and the specific surface area of the aerogel can be greatly improved. Specifically, within this ratio range, the strength of the carbon aerogel gradually increases as the phenolic content increases, the electrical conductivity increases after heat treatment, the specific surface area increases, and beyond this range, the density of the material increases too much, and the material becomes brittle, and the specific surface area decreases.
Preferably, the washing is washing with deionized water.
Preferably, the phenolic resin reinforced three-dimensional graphene aerogel is subjected to annealing treatment at the temperature of 200-1200 ℃. The aerogel is annealed at a lower temperature, so that the mechanical strength is high, the conductivity is low, the density is high, and the specific surface area is low; high specific surface area, good conductivity, low density and relatively low strength by annealing treatment at high temperature. The main purposes of annealing thereof include: on one hand, the catalyst for pore forming and participation in phenolic aldehyde polymerization, especially, part of the catalyst selected in the invention can play a role in activating pore forming in the subsequent annealing treatment, thereby improving the specific surface area of the aerogel. On the other hand, the phenolic resin has higher conductivity after carbonization along with the increase of temperature.
According to the invention, after the phenolic resin in the phenolic resin reinforced three-dimensional graphene aerogel is annealed at a high temperature of 200-1200 ℃, the improvement on the electrical property of the three-dimensional graphene aerogel is very favorable, so that the three-dimensional graphene aerogel has a lower density (13-70 mg/cm)3) Large specific surface area (500-1600 m)2G) and a high conductivity (20 to 100S/m).
Has the advantages that:
the preparation of the three-dimensional graphene aerogel with high mechanical strength can be realized by adopting a simple hydrothermal method, the degree of phenolic resin polymerization can be regulated and controlled by adjusting the type and content of the added phenolic monomer, the reaction time, the reaction temperature and the like, the mechanical strength of the three-dimensional graphene is further improved, and high elasticity (before annealing treatment,hydrogel state) to a high hardness (after annealing) material. Meanwhile, the preparation method is simple and feasible, and can realize the macro preparation of the three-dimensional graphene. The three-dimensional graphene prepared by the method has lower density (13-70 mg/cm)3) Larger specific surface area (500- & lt1600 m-)2(g) and higher conductivity (20-100S/m) (which is data after annealing treatment), and has great application prospect in the fields of catalysis, environmental management, adsorption and energy. In the invention, the mechanical strength of the three-dimensional graphene and graphene aerogel is enhanced mainly by using the phenolic resin, and the density (15-50 mg/cm) of the aerogel is not obviously influenced3) And has better electrical property and higher specific surface area. In addition, the invention also adopts ZnCl2Or KOH can play a role in catalysis in the system and can also play a role in activating and pore-forming in the subsequent heat treatment process, so that the prepared three-dimensional graphene aerogel with enhanced mechanical strength has a higher specific surface area (500-1600 m)2In terms of/g). For another example, ammonia bicarbonate can be used as a catalyst or decomposed to produce NH during heating3、CO2And the gases endow the system with more pore channel structures, and can be doped. In addition, besides the advantage of catalyst selection, the use of the cross-linking agent (hexamethylenetetramine) and the curing accelerator (tosyl chloride or benzene sulfonyl chloride) is that the material has more cross-linking points inside, forms more macromolecular cross-linked networks and has stronger mechanical properties. The use of the cross-linking agent (curing agent) can also improve the nitrogen doping amount of the final three-dimensional graphene, and is beneficial to the improvement of the adsorption performance of the three-dimensional graphene.
Drawings
Fig. 1 is a phenolic resin reinforced three-dimensional graphene hydrogel prepared in example 3 of the present invention;
fig. 2 is a three-dimensional graphene aerogel prepared in example 3 of the present invention;
fig. 3 is a scanning electron microscope image of the annealed three-dimensional graphene aerogel prepared in embodiment 3 of the present invention.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
In the invention, the preparation of the phenolic resin reinforced three-dimensional graphene aerogel is realized by adopting a simple process. The prepared three-dimensional graphene aerogel has high mechanical strength, large specific surface area and high conductivity. The preparation process is simple and easy to implement, and the production process is environment-friendly and harmless.
The following exemplarily illustrates a method for preparing a phenol resin reinforced three-dimensional graphene aerogel.
And preparing the graphene oxide by adopting an improved Hummers method. It should be noted that other methods in the art may also be used to prepare graphene oxide, such as the Brodietz method, Staudenmaier method, electrochemical exfoliation method, and the like.
And dispersing the graphene oxide in deionized water to obtain a graphene oxide aqueous solution. The dispersion mode can be ultrasonic dispersion, and the ultrasonic dispersion time can be 0.5-4 hours. The concentration of the obtained graphene oxide aqueous solution can be 1mg/ml-15 mg/ml.
Adding a certain amount of phenolic substances, aldehyde substances (or adding a cross-linking agent and a curing accelerator) and a phenolic reaction catalyst into the graphene oxide dispersion liquid in sequence according to a certain proportion, and stirring uniformly to obtain a mixed solution. Wherein the mass ratio of the phenolic substances to the graphene oxide (0.05-2) is as follows: 1, the mass ratio of the aldehyde substance to the graphene oxide is (0.1-1): 1. within this ratio range, the strength of the carbon aerogel gradually increases with an increase in the phenolic content, and after heat treatment, the electrical conductivity increases and the specific surface area increases, and beyond this range, the density of the material increases too much, and at the same time, the material becomes brittle and the specific surface area decreases. Wherein the cross-linking agent is one of hexamethylene tetramine, hydroxymethyl urea and propylene carbonate. The curing accelerator can be at least one of tosyl chloride and benzene sulfonyl chloride. The mass ratio of the cross-linking agent to the phenolic substance is 1: (4-20). The molar ratio (or mass ratio) of the cure accelerator to the phenolic may be 1: (8-20).
In alternative embodiments, the phenolic substance may be one or a mixture of phenol, resorcinol, hydroquinone and bisphenol a, and the aldehyde substance may be one or a mixture of formaldehyde, glutaraldehyde and butyraldehyde. Wherein the molar ratio of the phenols to the aldehydes can be 1:4 to 4: 1.
In an alternative embodiment, the phenolic reaction catalyst is selected from the group consisting of: sodium hydroxide, barium hydroxide, triethylamine, sodium carbonate, ammonium carbonate, zinc chloride, magnesium chloride, calcium chloride, and the like. Wherein the addition amount of the phenolic aldehyde reaction catalyst can be 1-20% of the total mass of the phenolic substance and the aldehyde substance.
And transferring the mixed solution into a reaction kettle to perform hydrothermal reaction at a certain temperature, and washing and drying to obtain the phenolic resin reinforced three-dimensional graphene aerogel. Wherein the hydrothermal reaction temperature can be 90-210 ℃, and the reaction time can be 6-24 hours. The solvent used for washing was deionized water. The drying method can be freeze drying, vacuum drying, supercritical drying, heating drying, etc.
As a detailed example of a preparation method of the phenolic resin reinforced three-dimensional graphene aerogel, the method specifically comprises the following steps: (1) ultrasonically dispersing graphene oxide in deionized water to obtain a graphene oxide aqueous solution; (2) then adding phenols, a cross-linking agent, a curing accelerator, aldehydes and a phenolic aldehyde reaction catalyst into the graphene oxide dispersion liquid in the step (1) in sequence according to a certain proportion, stirring uniformly, transferring the mixed solution into a reaction kettle, and carrying out hydrothermal reaction at a certain temperature; (3) after reacting for a period of time, cooling the reaction kettle in the step (2) to room temperature, taking out the reacted hydrogel, and repeatedly washing the hydrogel with deionized water to remove unreacted phenol and aldehyde monomers; (4) and (4) freeze-drying the hydrogel in the step (3) to obtain the phenolic resin reinforced three-dimensional graphene aerogel.
And annealing the phenolic resin reinforced three-dimensional graphene aerogel to enhance the electrical property of the phenolic resin reinforced three-dimensional graphene aerogel. Wherein, the annealing treatment temperature of the three-dimensional graphene can be 200-1200 ℃, and the time can be 1-4 hours. According to the invention, the density of the phenolic resin reinforced three-dimensional graphene aerogel subjected to annealing treatment is 12-70 mg/cm3Preferably 13 to 70mg/cm3The specific surface area is 500-1600m measured by a specific surface area tester2(g) it was determined by the four-probe methodThe conductivity is 20-100S/m (preferably 37-100S/m), and the compressive strength of the phenolic resin reinforced three-dimensional graphene aerogel measured by an electronic universal tester is 0.09-2 MPa, preferably 0.20-0.6 MPa.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like (time, charge amount, etc.) in the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the process parameters and the like within suitable ranges through the description herein, and are not limited to the specific values in the following examples.
Example 1
First, graphene oxide was prepared by a modified Hummers method, and a 4mg/ml aqueous graphene oxide solution was prepared by means of ultrasonic and mechanical stirring, followed by mixing phenol (62mg) and formaldehyde (18mg) in a molar ratio of 1: adding the graphene oxide dispersion solution (160ml) with the concentration of 5mg/ml into the mixture according to the proportion of 1, then adding potassium hydroxide accounting for 10% of the total mass of the phenolic substances and the aldehyde substances, performing ultrasonic treatment, stirring uniformly, and transferring into a reaction kettle. And (3) reacting the reaction kettle filled with the mixed solution at 160 ℃ for 8 hours to obtain the phenolic resin reinforced graphene hydrogel. And washing the hydrogel with deionized water and freeze-drying for 48 hours to obtain the phenolic resin reinforced three-dimensional graphene aerogel. Then placing the phenolic resin reinforced three-dimensional graphene aerogel into a quartz tube, heating to 800 ℃ under the protection of 200sccm argon, carrying out annealing treatment for 2 hours, and cooling the furnace to room temperature to obtain the three-dimensional graphene aerogel with the density of 12mg/cm3The specific surface area is 821cm2The electrical conductivity was 31S/m.
Example 2
First, graphene oxide was prepared by a modified Hummers method, and a 4mg/ml aqueous graphene oxide solution was prepared by means of ultrasonic and mechanical stirring, followed by mixing phenol (62mg) and formaldehyde (18mg) in a molar ratio of 1: ratio of 1For example, the graphene oxide dispersion liquid (160ml) with the concentration of 5mg/ml is added, then potassium hydroxide with the mass of 10% of the total mass of the phenolic substance and the aldehyde substance is added, 10mg of hexamethylenetetramine and 5mg of benzenesulfonyl chloride are added after stirring for 30min, and the mixture is transferred into a reaction kettle after ultrasonic treatment and uniform stirring. And (3) reacting the reaction kettle filled with the mixed solution at 160 ℃ for 8 hours to obtain the phenolic resin reinforced graphene hydrogel. And washing the hydrogel with deionized water and freeze-drying for 48 hours to obtain the phenolic resin reinforced three-dimensional graphene aerogel. Then placing the phenolic resin reinforced three-dimensional graphene aerogel into a quartz tube, heating to 800 ℃ under the protection of 200sccm argon, carrying out annealing treatment for 2 hours, and cooling the furnace to room temperature to obtain the three-dimensional graphene aerogel with the density of 15mg/cm3The specific surface area is 867cm2(ii)/g, conductivity was 37S/m.
Example 3
Firstly, preparing graphene oxide by adopting an improved Hummers method, preparing 6mg/ml graphene oxide aqueous solution by adopting an ultrasonic and mechanical stirring mode, then adding phenol (62mg) and formaldehyde (18mg) into graphene oxide dispersion liquid (5mg/ml, 160ml) according to a molar ratio of 1:1, fully and uniformly stirring, then adding glutaraldehyde with the mass fraction (relative to the formaldehyde) of 10%, then adding potassium hydroxide aqueous solution with the total mass of phenolic substances and aldehyde substances of 10 wt%, stirring for 30min, then adding 10mg hexamethylenetetramine and 5mg benzenesulfonyl chloride, further performing ultrasonic and uniform stirring, and transferring into a reaction kettle. And (3) reacting the reaction kettle filled with the mixed solution at 160 ℃ for 8 hours to obtain the phenolic resin reinforced graphene hydrogel. And washing the hydrogel with deionized water and freeze-drying for 48 hours to obtain the thermosetting phenolic resin reinforced three-dimensional graphene aerogel. Placing the three-dimensional graphene aerogel into a quartz tube, heating to 800 ℃ under the protection of 200sccm argon, carrying out annealing treatment for 2 hours, and cooling the furnace to room temperature to obtain the three-dimensional graphene aerogel with the density of 21mg/cm3The specific surface area is 863cm2The specific conductivity was 41S/m.
Example 4
Firstly, preparing graphene oxide by adopting an improved Hummers method, and preparing the graphene oxide by adopting an ultrasonic and mechanical stirring modePreparing 6mg/ml graphene oxide aqueous solution, adding resorcinol (78mg) and formaldehyde (42mg) into graphene oxide dispersion liquid (5mg/ml, 160ml) according to the molar ratio of 1:2, fully and uniformly stirring, then adding glutaraldehyde with the mass fraction (relative to formaldehyde) of 5%, and then adding ZnCl containing 50% of total mass of phenolic substances and aldehyde substances2Stirring the aqueous solution for 30min, adding 10mg of hexamethylenetetramine and 5mg of tosyl chloride, performing ultrasonic treatment, stirring uniformly, and transferring into a reaction kettle. And (3) reacting the reaction kettle filled with the mixed solution at 160 ℃ for 8 hours to obtain the phenolic resin reinforced graphene hydrogel. And washing the hydrogel with deionized water and freeze-drying for 48 hours to obtain the thermosetting phenolic resin reinforced three-dimensional graphene aerogel. Placing the three-dimensional graphene aerogel into a quartz tube, heating to 350 ℃ under the protection of 200sccm argon, carrying out annealing treatment for 2 hours, and cooling the furnace to room temperature to obtain the three-dimensional graphene aerogel with the density of 31g/cm3Specific surface area of 713cm2The electrical conductivity was 52S/m.
Example 5
Firstly, graphene oxide is prepared by adopting a modified Hummers method, a 6mg/ml graphene oxide aqueous solution is prepared by means of ultrasonic and mechanical stirring, resorcinol (63mg) and glutaraldehyde (57mg) are added into a graphene oxide GO dispersion liquid (5mg/ml, 160ml) according to a molar ratio of 1:1, and ZnCl containing 50% of total mass of phenolic substances and aldehyde substances is added2Stirring the aqueous solution for 30min, adding 10mg of hexamethylenetetramine and 5mg of tosyl chloride, performing ultrasonic treatment, stirring uniformly, and transferring into a reaction kettle. And (3) reacting the reaction kettle filled with the mixed solution at 160 ℃ for 8 hours to obtain the phenolic resin reinforced graphene hydrogel. And washing the hydrogel with deionized water and freeze-drying for 48 hours to obtain the thermosetting phenolic resin reinforced three-dimensional graphene aerogel. Then placing the three-dimensional graphene aerogel into a quartz tube, heating to 350 ℃ under the protection of 200sccm argon, carrying out annealing treatment for 2 hours, and cooling the furnace temperature to room temperature to obtain the three-dimensional graphene aerogel with the density of 47g/cm3The specific surface area is 791cm2The specific conductivity was 50S/m.
Table 1 shows the preparation method and performance parameters of the phenolic resin reinforced graphene aerogel prepared in examples 1 to 4 of the present invention:
FIG. 1 is a schematic diagram of a phenolic resin reinforced three-dimensional graphene hydrogel prepared in example 3 of the present invention, from which a graphene hydrogel with a stable morphology and few defects can be prepared by the method of the present invention;
fig. 2 is a three-dimensional graphene aerogel prepared in example 3 of the present invention (after annealing), and it can be seen from the figure that the structure of the three-dimensional graphene aerogel after annealing treatment still remains intact, and the size can be adjusted according to the size of the hydrothermal reaction kettle (diameter 1-3cm, height 1-5 cm);
fig. 3 is a scanning electron microscope image of the annealed three-dimensional graphene aerogel prepared in embodiment 3 of the present invention, and it can be seen that the sheet-like graphene is cross-linked and stacked, so as to improve the mechanical strength of the material; meanwhile, a certain gap is still reserved between the sheets, so that the sheets have lower density.
Industrial applicability: the three-dimensional graphene disclosed by the invention has excellent mechanical properties, a simple preparation process and strong controllability, and the prepared material has rich pore diameters and has great application prospects in the fields of adsorption and environmental management.
Claims (10)
1. A preparation method of a phenolic resin reinforced three-dimensional graphene aerogel is characterized by comprising the following steps:
adding a phenolic substance and an aldehyde substance into a graphene oxide aqueous solution to obtain a precursor aqueous solution;
adding a phenolic aldehyde reaction catalyst into a precursor water solution, carrying out hydrothermal reaction for 6-24 hours at the temperature of 90-210 ℃, and then washing and drying to obtain the phenolic resin reinforced three-dimensional graphene aerogel.
2. The preparation method according to claim 1, wherein the graphene oxide is prepared by a modified Hummers method and dispersed in deionized water to obtain the graphene oxide aqueous solution.
3. The method according to claim 1 or 2, wherein the concentration of the aqueous graphene oxide solution is 1mg/ml to 15 mg/ml.
4. The method according to any one of claims 1 to 3, wherein the phenolic substance is at least one selected from phenol, resorcinol, hydroquinone and bisphenol A, and the aldehyde substance is at least one selected from formaldehyde, butyraldehyde and glutaraldehyde.
5. The method according to any one of claims 1 to 4, wherein the molar ratio of the phenolic substance to the aldehyde substance is 1:4 to 4: 1.
6. The method according to any one of claims 1 to 5, wherein the phenolic reaction catalyst is at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, barium hydroxide, triethylamine, sodium carbonate, ammonium bicarbonate, zinc chloride, magnesium chloride, and calcium chloride, and preferably is ZnCl2One of KOH and ammonium bicarbonate; the addition amount of the phenolic aldehyde reaction catalyst is 1-300 wt% of the total mass of the phenolic substance and the aldehyde substance, and preferably 1-20 wt%.
7. The preparation method according to any one of claims 1 to 6, further comprising a cross-linking agent and a curing accelerator, wherein the cross-linking agent is at least one of hexamethylenetetramine, methylol urea and propylene carbonate, and the curing accelerator is at least one of tosyl chloride and benzene sulfonyl chloride; preferably, the mass ratio of the crosslinking agent to the phenolic substance is 1: (4-20), wherein the mass ratio of the curing accelerator to the phenolic substance is 1: (8-20).
8. The preparation method according to any one of claims 1 to 7, wherein the mass ratio of the phenolic substance to the graphene oxide is (0.05-2): 1; preferably, the mass ratio of the aldehyde substance to the graphene oxide is (0.1-1): 1.
9. the method of any one of claims 1-8, wherein the washing is with deionized water.
10. The preparation method according to any one of claims 1 to 9, wherein the obtained phenolic resin reinforced three-dimensional graphene aerogel is subjected to annealing treatment at 200 to 1200 ℃.
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| WO2022233626A1 (en) * | 2021-05-04 | 2022-11-10 | Consejo Superior De Investigaciones Científicas (Csic) | 3d graphene aerogels |
| LU502730B1 (en) | 2022-08-30 | 2024-02-29 | Fyzikalni Ustav Av Cr V V I | Highly thermally insulating and electrically conductive graphene aerogel and method of manufacturing thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111760557A (en) * | 2020-07-01 | 2020-10-13 | 青岛科技大学 | Magnetic lignin graphene oxide composite aerogel |
| WO2022233626A1 (en) * | 2021-05-04 | 2022-11-10 | Consejo Superior De Investigaciones Científicas (Csic) | 3d graphene aerogels |
| CN114572973A (en) * | 2022-05-03 | 2022-06-03 | 营口理工学院 | Method for preparing graphene composite aerogel by intercalation-in-situ polymerization synergistic method |
| CN114572973B (en) * | 2022-05-03 | 2024-04-09 | 营口理工学院 | Method for preparing graphene composite aerogel by intercalation-in-situ polymerization synergistic method |
| LU502730B1 (en) | 2022-08-30 | 2024-02-29 | Fyzikalni Ustav Av Cr V V I | Highly thermally insulating and electrically conductive graphene aerogel and method of manufacturing thereof |
| EP4332061A1 (en) | 2022-08-30 | 2024-03-06 | Fyzikální ústav AV CR, v. v. i. | Highly thermally insulating and electrically conductive graphene aerogel and method of manufacturing thereof |
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