CN113289558A - Discretization preparation method of two-dimensional material aerogel with designable three-dimensional structure - Google Patents
Discretization preparation method of two-dimensional material aerogel with designable three-dimensional structure Download PDFInfo
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Abstract
A discretization preparation method of a two-dimensional material aerogel with a designable three-dimensional structure comprises the steps of firstly, forming hydrogel by cross-linking and combining a two-dimensional material obtained by stripping and a corresponding dispersing agent, and pouring the hydrogel into a pretreated 3D printing and solubilizing mold for adhesion molding; and then freeze-drying, dissolving the resin mold, and obtaining the structured three-dimensional interconnected composite material aerogel through a filling and pouring protection process. The aerogel composite material obtained by the two-dimensional material structured discrete molding process has the characteristics of high structurization, high molding precision, simple preparation process and the like; due to different two-dimensional material choices, the aerogel material has higher mechanical properties, electrical properties, heat conductivity and the like, and has design and manufacturing advantages of quantitatively improving comprehensive properties compared with massive aerogel materials.
Description
Technical Field
The invention is suitable for the technical field of micro-nano manufacturing technology and nano composite material, in particular relates to a discretization preparation method of a two-dimensional material aerogel with a designable three-dimensional structure, particularly relates to a forming process for three-dimensional structuring of two-dimensional materials with different dispersion performances, and provides a demoulding method of a three-dimensional interconnected structure of the two-dimensional material so as to realize discretization forming of a customizable structure.
Background
Two-dimensional materials, also called two-dimensional nanomaterials, are materials in which electrons can move freely in only two dimensions. Since unimorph graphene was obtained from graphite by mechanically peeling it off from graphite with an adhesive tape by Geim et al, manchester university in 2004, two-dimensional materials gradually entered the field of view by virtue of their exceptional physicochemical properties, and the types of materials contained therein have also expanded rapidly, such as graphite, hexagonal boron nitride (h-BN), transition metal disulfides (MoS2, WS2, MoSe2, WSe2 nanosheets), metal halides, metal carbides, layered oxides, layered hydrides, and the like. Due to carrier migration and heat diffusion, the characteristics of two-dimensional materials tend to exhibit unique properties different from bulk materials due to their material dimensions and forming processes. For example, graphene has very high strength, toughness, high thermal conductivity, high carrier mobility, and good optical properties; the single-layer hexagonal boron nitride has high dielectric constant, high thermal conductivity and excellent piezoelectric property; the two-dimensional MoS2 has excellent thermal stability and chemical stability, and is also widely used in the fields of solid lubricants, reaction catalysts, and the like. To date, two-dimensional materials have become a focus hot spot in the fields of material science, chemistry, nanotechnology, and the like, and have received more and more extensive attention and research.
On the basis of various excellent performances of known two-dimensional materials, how to fully exert the advantages thereof and efficiently utilize the properties thereof becomes one of the problems to be solved urgently. From the composition and compositing of two-dimensional materials, a simple two-dimensional material cannot fully exhibit the performance of the material, and auxiliary materials are added to form the composite material, so that the advantages of the composite material are exerted in an oriented manner. Taking graphene as an example, the graphene has properties such as large specific surface area, high chemical stability, high mechanical strength, high thermal conductivity and excellent light transmittance, and if the graphene is made into a device in a disordered stacking manner, the graphene hinders the performance of the characteristics of the graphene, and even is harmful to the properties such as mechanical strength and thermal conductivity of the graphene. In the field of material compounding application, Yang Yang Yang of the university of southern California of America and the group thereof use electric assistance to enable graphene nano sheets to be layered and aligned in the interior of a photocuring resin, so that the 3D printed artificial pearl layer structure shows the specific toughness and strength equivalent to those of a natural pearl layer, and has anisotropic electrical properties. In addition, Kyung-Bum Kim and other people of the korea hanyang university firstly dope a two-dimensional boron nitride nanosheet with piezoelectric properties into a PDMS matrix to prepare a piezoelectric sensor for detecting human body movement, so that the piezoelectric sensor has the characteristics of high transparency, high flexibility, skin friendliness and the like while effectively exerting the piezoelectric properties, and has a wide development prospect in the aspect of wearable electronic sensors.
From the functional characteristics and the structuralization of the two-dimensional material, aiming at the electrical characteristics of the two-dimensional material, taking the piezoelectric property of the two-dimensional material doped nano composite material as an example, because the piezoelectric potential output is related to the stress, the three-dimensional microstructure is designed and the micro-morphology of the two-dimensional material is regulated, and compared with a piezoelectric block material, the voltage output of the device can be greatly improved. For example, by spraying a Graphene Nanoribbon (GNR) conductive nanonetwork on the surface of an electrospun Thermoplastic Polyurethane (TPU) fiber membrane, graphene two-dimensional materials improve the structural deformation range and the sensing sensitivity of a device, and a two-dimensional material doped composite material improves the strain range of the sensor to a certain extent compared with an undoped device, thereby facilitating the formation of an electronic transmission path and improving the comprehensive properties of the device such as sensing reliability, tensile stability and the like. Furthermore, if a three-dimensional structure formed by the composite material is designed, the mechanical property can be ensured, the structural efficiency can be improved, and the sensing range of the device can be optimized in the three-dimensional direction. While the construction of a directed tube bundle inside a bulk material is also advantageous for the directed management of heat flow in terms of thermal performance, e.g. Jin Chen et al of Shanghai university of transportation by freeze-drying process using celluloseThe boron nitride nanosheet is internally doped with the interconnected epoxy resin composite material, and under the condition of 9.6% of BNNS doping, the three-dimensional interconnected two-dimensional material improves the heat-conducting property of the composite material by 1400%, and has good electrical insulation property (10)15Omega cm) are widely applied to the aspects of electronic device packaging, heat conduction and the like, and if the flat membrane material is optimized into a three-dimensional space structure with a designable macrostructure by considering the designability of the structure, the adjustable thermal property of the flat membrane material further expands the shapes and the properties of electronic insulation, packaging and heat conduction devices.
In view of the above, the formation of a composite material and a macrostructure formation of a two-dimensional material have become a hot spot of research in the field of nano composite material formation in recent years, and are also necessary requirements for the two-dimensional material to be applied and optimized to devices.
Generally, there are two structured three-dimensional forming processes for two-dimensional materials, namely direct forming and template-assisted forming. For the former, techniques that have been used for directly printing two-dimensional material aerogels include: and (3) ink-jet printing of the two-dimensional material, photocuring 3D printing of photosensitive resin compounded by the two-dimensional material, and rheologically extruding 3D printing of the composite material. However, as the printing material needs to balance the process limitations such as the doping ratio of the matrix and the nano material, the degassing phase, the interface bonding property of the two-dimensional material and the like, so as to ensure the printability and the formability, and meanwhile, the three-dimensional forming precision is restricted by the dispersion of the two-dimensional material, the uniform mixing of the composite material and the properties, the doping and modification of the functional nano material cannot completely meet the requirement of high-precision forming, the performance of the functional nano material cannot be designed and exerted enough, and the comprehensive performance of the direct printing and forming of the two-dimensional material and the two-dimensional material doped composite material is severely limited.
In the latter case, the two-dimensional material is attached to a framework formed on a template material, and the aerogel having a structure similar to that of the template is prepared by freeze-drying, which can fully exert the properties of the two-dimensional material. The method for preparing the two-dimensional material three-dimensional interconnected composite material by the reported 3D printing template comprises the following steps: based on the hollow polymer system structure of high accuracy SLA technique, use acrylonitrile butadiene styrene ink 3D to print degradable support, and the hollow mould support of high impact polystyrene of inversion. However, most of the materials prepared by the process are blocky or irregular polyhedrons, the forming precision is limited by the precision of the degradable materials, and the functional characteristics of a forming die are often mutually restricted with the forming precision; in addition, from the angle of mold filling, the interfacial compatibility characteristics between the two-dimensional material aerogel and the composite material thereof and the degradable template also need to be considered comprehensively, including hydrophilicity, wettability, surface finish, degradation conditions, degradation products and the like, and the performances directly influence the template auxiliary forming process and the synthesis effect of the two-dimensional material aerogel; the mold structure is summarized, the forming method has limitation in the aspect of structural design, due to the restriction of the performance of the high polymer material of the degradable material, most of the materials prepared by the forming process are blocky or irregular polyhedral structures, the forming structure is difficult to carry out secondary processing, the mechanical performance of the forming structure is limited while the structural design capability cannot be improved, and the forming method is to be further optimized and improved.
Disclosure of Invention
In order to solve the problem that two-dimensional material aerogel and composite material thereof are difficult to be structured and formed, so as to achieve the purpose of efficiently utilizing the excellent physical and chemical properties of the two-dimensional material, the invention aims to provide a discretization preparation method of the two-dimensional material aerogel with a designable three-dimensional structure, so that the problems of high-precision pouring, demoulding and forming of the two-dimensional material aerogel are solved, the obtained three-dimensional structured two-dimensional material aerogel can maximally exert the performance advantages thereof according to specific requirements, and can be used as an effective process method for forming a three-dimensional interconnected nano composite material doped with the two-dimensional material; the prepared composite material doped with the structured two-dimensional material has the characteristics of high forming precision and high customization, and is suitable for the requirements of microstructure design and commercial production.
In order to achieve the purpose, the invention provides a specific scheme as follows:
a discretization preparation method of a two-dimensional material aerogel with a designable three-dimensional structure comprises the following steps:
(1) preparing a degradable resin mould with a required three-dimensional structure by using a 3D printing technology, and uniformly coating a layer of metal film in an evaporation machine;
(2) fully combining the two-dimensional material with a corresponding stabilizing agent and a cross-linking agent under constant-temperature stirring to form hydrogel, and pouring the hydrogel into a resin mold to form a tightly-filled composite frame;
(3) freezing and drying the two-dimensional material hydrogel attached to the mold to obtain aerogel, placing the aerogel in a packaging material, and forming the aerogel by using a vacuum-assisted dipping method;
(4) removing the metal film coated on one surface of the mold, exposing the degradable resin coated on the metal film, placing the metal film in a solvent of the degradable resin to remove the resin mold, then placing the metal film in a metal dissolving solution to remove the residual metal film, and placing the obtained composite material in a solvent of an encapsulating material or removing the encapsulating material in an etching and heating mode to obtain the three-dimensionally structured two-dimensional material aerogel.
The degradable resin mould is degradable photosensitive resin, and the material preparation comprises the following components in parts by weight: selecting 40-60 parts of comonomer N, N-dimethylacrylamide or acrylamide, 40-60 parts of methacrylic acid, methyl methacrylate or sodium acrylate, 40-50 parts of crosslinking cracking agent methacrylic anhydride or N, N-methylene bisacrylamide, heating in an oil bath at 40-60 ℃, mixing, then gradually adding 90-120 parts of filler polyvinyl alcohol, polyvinylpyrrolidone or methyl cellulose and 10-20 parts of photoinitiator aroylphosphine oxide or bisbenzoylphenylphosphine oxide, and uniformly dispersing.
The wrapped metal film adopts copper or nickel, and the function of the wrapped metal film is to prevent the degradable resin mould from directly contacting with the hydrogel to cause the dissolution of the mould.
The two-dimensional material includes, but is not limited to, one of the following: hexagonal boron nitride, graphite, transition metal dichalcogenides, metal halides, metal carbides, metal nitrides, layered oxides, and layered hydrides.
The stabilizer is cellulose, is dissolved in urea and sodium hydroxide aqueous solution, and is used for adsorbing and connecting the added two-dimensional material.
The cross-linking agent is used for generating cross-linking bonds among cellulose macromolecules, so that the cellulose macromolecules are in a net structure and fix relative positions among the cellulose macromolecules to form a three-dimensional framework, and the cross-linking agent comprises but is not limited to one of the following: formaldehyde, dicarboxylic acids, dialdehydes, epoxides.
The two-dimensional material, the stabilizer and the cross-linking agent are proportioned as follows: 4-8g of two-dimensional material and 2-4g of stabilizer are added into 4mL of cross-linking agent.
The freeze drying treatment method is characterized in that hydrogel is kept in a stable colloidal dispersion state before treatment, and the hydrogel is directly frozen in liquid nitrogen and freeze-dried in a freeze dryer. This is beneficial to preventing the growth of ice crystals, and preventing the ice crystals from destroying the three-dimensional framework of the aerogel.
The packaging material includes but is not limited to one of the following: epoxy resin, PDMS, polyurethane, elastic silicon rubber, paraffin and rosin. Because the obtained two-dimensional material aerogel is fragile and can be decomposed when meeting water, the obtained three-dimensional structure aerogel is fixed by the packaging material, and the problem that the obtained three-dimensional structure aerogel is damaged by a dissolving agent in the subsequent dissolving of a die is avoided.
The dissolving agent of the degradable resin adopts aqueous solution of sodium hydroxide and other alkaline solution.
The metal dissolving solution is prepared from dilute nitric acid, dilute hydrochloric acid, dilute sulfuric acid, ferric trichloride solution and ammonia alkaline solution under the condition that the metal dissolving solution can fully dissolve a plated metal film and does not react with a two-dimensional material.
The dissolving agent of the packaging material is used for fully dissolving the packaging material and does not react with the two-dimensional material.
The invention has the beneficial effects that:
(1) the two-dimensional material aerogel structured forming process realizes structural design from micro to macro and from two to three dimensions. The microcosmic two-dimensional material is made into aerogel and is formed in a macroscopic three-dimensional structure, so that the excellent properties of the aerogel are kept to the maximum degree, the additional performance of the three-dimensional structure is realized, and the potential of structural forming of the two-dimensional material is further developed.
(2) The discretization forming process provided by the invention solves the forming problems that parts are difficult to process and form two-dimensional materials, and provides a new thought for the structural forming of the two-dimensional material aerogel. In addition, the required mold can be designed in a micrometer scale due to the fact that the photocuring 3D printing technology is used, the structure of the mold can be randomly selected according to the use requirement, the mold is convenient and fast, the characteristics of high precision and good flexibility are achieved, the application range of the two-dimensional material aerogel is greatly widened, the two-dimensional material aerogel also meets the commercial production requirement, and the mold has good economic benefits.
(3) The two-dimensional material hydrogel infusion process aims at discretization infusion molding of a two-dimensional material. Compared with the traditional integrated forming process, the material appearance and the spatial arrangement composition can be controlled under an external condition, so that the mechanical property, the electrical property, the heat-conducting property and the like of the material can be fully designed and optimized to achieve better performance indexes.
Drawings
Fig. 1 is a technical scheme of a two-dimensional material aerogel structured molding process provided by the present invention.
Fig. 2 is a schematic view of the light-cured 3D printing of the degradable photosensitive resin according to the present invention.
Fig. 3 is a schematic view of a degradable resin mold provided by the present invention.
FIG. 4 is a schematic diagram of the preparation of a two-dimensional hydrogel material provided by the present invention.
Fig. 5 is a schematic view of a two-dimensional hydrogel/degradable resin mold composite provided by the invention.
FIG. 6 is a schematic view of a structured two-dimensional material aerogel provided by the present invention.
Fig. 7 is a physical diagram of a boron nitride two-dimensional material aerogel provided in the present invention, including the ultra-light weight characteristics that the aerogel exhibits on a flower.
Fig. 8 is a physical diagram of a structured boron nitride two-dimensional material aerogel provided by the present invention, which includes a three-dimensional structure 8(a) formed without removing a metal film, and a three-dimensional structure aerogel 8(b) with a metal film removed.
Fig. 9 is a scanning electron microscope image of the boron nitride two-dimensional material aerogel provided by the present invention, fig. 9(a) is a porous boron nitride nanosheet aerogel under low magnification, and fig. 9(b) is a schematic view of an aerogel showing a layered structure of boron nitride nanosheets under high magnification.
Detailed Description
The present invention will be described in further detail with reference to preferred examples thereof.
It should be added that the specific examples described herein are only used for explaining the discretization preparation method of the two-dimensional material aerogel with programmable three-dimensional structure according to the present invention, and are not used to limit the present invention and its embodiments.
Example 1
The embodiment aims to realize three-dimensional structural molding of the hexagonal boron nitride nanosheet aerogel, and the specific preparation process, referring to fig. 1, comprises the following steps:
first, a resin mold is prepared.
60g of comonomer N, N-dimethylacrylamide is weighed by an electronic scale and poured into a beaker for later use, then 60g of comonomer methyl methacrylate is weighed and poured into the beaker for mixing with the N, N-dimethylacrylamide, and then 45g of crosslinking cracking agent methacrylic anhydride is weighed and poured into the beaker for fully mixing the three. And (3) putting the beaker containing the mixed solution into a magnetic stirring water bath kettle, and stirring for 30 minutes in an oil bath at the temperature of 50 ℃. 120g of bulking agent polyvinylpyrrolidone and 15g of photosensitizer aroylphosphine oxide were then added stepwise. Continuously stirring for 3 hours at the temperature of 50 ℃ to obtain the degradable photosensitive resin. Referring to fig. 2, using the surface projection micro-stereolithography technique, a resin material 4 is placed in a resin tank 1, and every time a forming platform 3 is lowered by one layer thickness, an ultraviolet light emitter 2 exposes a corresponding shape of the layer, and the operation is repeated until the desired three-dimensional shape is completed. Referring to fig. 3, the resin mold is printed, and a front view 5, a left side sectional view 6, and a top sectional view 7 are used to show the internal structure thereof. And cleaning and drying the resin mold by deionized water, and placing the resin mold in a copper film evaporation machine for 1 minute to obtain the copper/resin composite material with the surface coated with a layer of copper film.
And secondly, pouring the two-dimensional material composite material.
Preparation of two-dimensional material: 2g of hexagonal boron nitride powder having a particle size of about 3 μm and 20g of sucrose were put into a planetary ball mill containing 20g of small balls, 20g of medium balls and 25g of large balls, and ball-milled at 200rpm for 6 hours. The powder obtained was added to 100ml of deionized water, mixed well and placed in a cell disruptor for 1 hour with 20% power ratio at the tip of the needle. The sonicated solution was then centrifuged in a centrifuge at 2000rpm for 20 minutes and the supernatant was taken. 20ml of 12mol/L concentrated hydrochloric acid was added to the obtained supernatant, and the mixture was sufficiently stirred until the precipitation was completed. And filtering, washing and drying the precipitate, and then putting the precipitate into an electric heating furnace at 900 ℃ for pyrolysis for 4 hours to obtain a white powdery two-dimensional hexagonal Boron Nitride Nanosheet (BNNS).
Referring to fig. 4, 0.8g of sodium hydroxide, 1.5g of urea and 10mL of deionized water are mixed, 0.4mL of epichlorohydrin is added, the mixture is placed in a magnetic stirrer at-10 ℃ and stirred for 1 hour, then 0.6g of prepared BNNS and 0.3g of cellulose are added, and stirring is continued for 1 hour, so that a mixed solution 8 of the stabilizer and the urea/sodium hydroxide/two-dimensional material is obtained. And (3) preserving the temperature of the obtained colloid for 3 hours at 50 ℃, and washing the colloid for 2-3 times by using deionized water to obtain the cellulose/BNNS hydrogel 9. The obtained cellulose/BNNS hydrogel was suction-filtered into a resin mold, and a two-dimensional material hydrogel/degradable resin mold complex including a two-dimensional material hydrogel 10, a copper film 11, and a degradable resin mold 12 was obtained with reference to fig. 5.
And thirdly, freezing and drying to form the aerogel.
Freezing the obtained two-dimensional material hydrogel/degradable resin mold complex in liquid nitrogen, and freeze-drying for 72 hours in a freeze dryer (-60 ℃, 10Pa) to obtain the cellulose/BNNS aerogel. The liquid paraffin was melted in a water bath at 60 ℃ and the resulting cellulose/BNNS aerogel was completely immersed for 1 hour together with the resin mold and left to cure for 2 hours at-10 ℃ and then the surface was scraped free of excess paraffin.
And fourthly, demolding the two-dimensional material composite material.
And (3) grinding the metal film on the outer surface of one side of the resin mold by using sand paper, and standing in a sodium hydroxide solution with the mass fraction of 5% for 2 hours until the resin is completely dissolved. And (2) washing with deionized water, placing the composite material in a mixed solution of 50ml of 10 mass percent hydrogen peroxide solution and 50ml of 20 mass percent dilute hydrochloric acid until the coated copper film is completely dissolved, washing, drying, placing the composite material in a constant-temperature oven at 60 ℃ until paraffin is completely melted, taking out, and blowing hot air until paraffin is completely removed, and referring to fig. 6, obtaining the three-dimensional structured two-dimensional material aerogel which comprises an aerogel cavity 13 and a three-dimensional interconnected two-dimensional material 14.
And (4) physical property characterization of the two-dimensional material aerogel. Referring to fig. 7, the prepared boron nitride aerogel was placed on the blade, exhibiting ultra-light-weight characteristics.
And (3) microstructure characterization of the two-dimensional material aerogel. Referring to fig. 8, a structured boron nitride two-dimensional material aerogel real object is obtained, which comprises a three-dimensional structure (a) formed without removing the metal film, and a three-dimensional structure aerogel (b) with the metal film removed. Observing the obtained structured two-dimensional material aerogel by using a scanning electron microscope under different magnification factors to obtain the porous boron nitride nanosheet aerogel under low magnification factor as shown in figure 9(a), wherein the microstructure of the porous and loose aerogel is shown. And the layered two-dimensional boron nitride nanosheet shown in fig. 9(b) is observed under high magnification, and a good three-dimensional interconnection effect of the two-dimensional material is shown.
Example 2
The embodiment aims to realize three-dimensional structural molding of the graphene aerogel, and the specific preparation process comprises the following steps:
first, a resin mold is prepared.
50g of the comonomer acrylamide was weighed by an electronic scale and poured into a beaker for future use, then 60g of the comonomer methyl methacrylate was weighed and poured into a beaker for mixing with N, N-dimethylacrylamide, and then 40g of the crosslinking cleavage agent methacrylic anhydride was weighed and poured into a beaker for thorough mixing of the three. And (3) putting the beaker containing the mixed solution into a magnetic stirring water bath kettle, and carrying out oil bath stirring for 30 minutes at the temperature of 40 ℃. 100g of filler polyvinyl alcohol and 20g of photosensitizer aroylphosphine oxide are then added stepwise. Continuously stirring for 3 hours at the temperature of 50 ℃ to obtain the degradable photosensitive resin. And printing the resin mold by using a surface projection micro-stereolithography technology. And cleaning and drying the resin mold by deionized water, and placing the resin mold in a copper film evaporation machine for 1 minute to obtain the copper/resin composite material with the surface coated with a layer of copper film.
And secondly, pouring the two-dimensional material composite material.
And (4) preparing a two-dimensional material. 20g of graphite particles with the particle size of about 150 mu m, 20g of sodium cholate and 100ml of N-methyl-2-pyrrolidone (NMP) with the purity of 99.5 percent are added into 400ml of deionized water and evenly mixed. The mixed solution was placed in a high shear mixing emulsifier and run at 4500rpm for 3 hours using a 32mm rotor. And centrifuging the solution in a centrifuge at the rotating speed of 2000rpm for 1 hour, filtering out precipitates, and placing the residual liquid in a constant-temperature oven at 90 ℃ for 3 hours to obtain the two-dimensional graphene.
0.8g of sodium hydroxide, 1.5g of urea, 10mL of deionized water and 0.4mL of formaldehyde are mixed, placed in a magnetic stirrer at the temperature of-10 ℃ and stirred for 1 hour, and then 0.5g of prepared two-dimensional graphene and 0.2g of cellulose are added and stirring is continued for 1 hour. And (3) keeping the obtained colloid at 50 ℃ for 3 hours, washing the colloid for 2-3 times by using deionized water to obtain cellulose/graphene hydrogel, and performing suction filtration on the obtained cellulose/graphene hydrogel into a resin mold.
Third, freeze drying to form aerogel
Freezing the obtained two-dimensional material hydrogel/degradable resin mold complex in liquid nitrogen, and freeze-drying for 72 hours in a freeze dryer (-60 ℃, 10Pa) to obtain the cellulose/graphene aerogel. The liquid paraffin was melted in a water bath at 60 ℃, and then the resulting cellulose/graphene aerogel was completely immersed for 1 hour together with the resin mold and placed at 0 ℃ for curing for 2 hours, followed by scraping off the excess paraffin on the surface.
And fourthly, demolding the two-dimensional material composite material.
And (3) grinding the metal film on the outer surface of one side of the resin mold by using sand paper, and standing in a sodium hydroxide solution with the mass fraction of 5% for 2 hours until the resin is completely dissolved. And (2) washing with deionized water, placing the composite material in a mixed solution of 50ml of 10% hydrogen peroxide solution and 50ml of 10% dilute sulfuric acid until the coated copper film is completely dissolved, washing, drying, placing the composite material in a constant-temperature oven at 60 ℃ until paraffin is completely melted, taking out, and blowing hot air until paraffin is completely removed, thus obtaining the three-dimensional structured two-dimensional graphene aerogel.
Example 3
The embodiment is to realize the three-dimensional structural molding of the molybdenum disulfide composite material, and the specific preparation process comprises the following steps:
first, a resin mold is prepared.
60g of comonomer N, N-dimethylacrylamide is weighed by an electronic scale and poured into a beaker for later use, 50g of comonomer methyl methacrylate is weighed and poured into the beaker for mixing with the N, N-dimethylacrylamide, and 50g of crosslinking cracking agent methacrylic anhydride is weighed and poured into the beaker for fully mixing the three. And (3) putting the beaker containing the mixed solution into a magnetic stirring water bath kettle, and stirring for 30 minutes in an oil bath at the temperature of 50 ℃. Subsequently, 100g of the filler methylcellulose and 10g of the photosensitizer bis-benzoylphenylphosphine oxide were added stepwise. Continuously stirring for 3 hours at the temperature of 60 ℃ to obtain the degradable photosensitive resin. And printing the resin mold by using a surface projection micro-stereolithography technology. And cleaning and drying the resin mold by deionized water, and placing the resin mold in a copper film evaporation machine for 1 minute to obtain the copper/resin composite material with the surface coated with a layer of copper film.
And secondly, pouring the two-dimensional material composite material.
And (4) preparing a two-dimensional material. 10g of molybdenum disulfide powder with the particle size of about 2 mu m and 50mg of sodium hydroxide are taken and added into 200ml of 1-methyl-2-pyridone, and the mixture is placed into an ultrasonic cleaner for ultrasonic treatment for 4 hours at the frequency of 50kHz and the power of 100W after being uniformly mixed. The sonicated solution was then centrifuged in a centrifuge at 2000rpm for 30 minutes to obtain a supernatant. And (3) drying the obtained solution in a vacuum drying oven at 90 ℃ for 2 hours, washing the powder for 2-3 times by using 1-methyl-2-pyridone to remove residual sodium hydroxide, and fully drying to obtain black powdery two-dimensional molybdenum disulfide.
1g of sodium hydroxide, 1.5g of urea, 10mL of deionized water and 0.4mL of epoxy chloropropane are mixed, placed in a magnetic stirrer for stirring for 1 hour at the temperature of minus 10 ℃, and then 0.8g of prepared molybdenum disulfide and 0.3g of cellulose are added for continuous stirring for 1 hour. And (3) keeping the temperature of the obtained colloid at 50 ℃ for 3 hours, washing the colloid for 2-3 times by using deionized water to obtain cellulose/molybdenum disulfide hydrogel, and carrying out suction filtration on the obtained cellulose/molybdenum disulfide hydrogel into a resin mold.
Third, freeze drying to form aerogel
Freezing the obtained two-dimensional material hydrogel/degradable resin mold complex in liquid nitrogen, and freeze-drying for 72 hours in a freeze dryer (-60 ℃, 10Pa) to obtain the cellulose/molybdenum disulfide aerogel. Epoxy resin monomer, curing agent (MHHPA) and catalyst were mixed at room temperature at 100: 80: 0.6, then the resulting cellulose/molybdenum disulfide aerogel was completely immersed in the resin mold for 2 hours and then transferred to a vacuum oven for 12 hours to remove air. The surface was then scraped free of excess epoxy and left to cure at 140 ℃ for 3 hours.
And fourthly, demolding the two-dimensional material composite material.
And (3) grinding the metal film on the outer surface of one side of the resin mold by using sand paper, and standing in a sodium hydroxide solution with the mass fraction of 5% for 2 hours until the resin is completely dissolved. And washing with deionized water, putting the composite material into a mixed solution of 50ml of 10 mass percent hydrogen peroxide solution and 50ml of 20 mass percent dilute hydrochloric acid until the coated copper film is completely dissolved, and washing and drying to obtain the three-dimensional structured two-dimensional molybdenum disulfide composite material.
The present invention includes but is not limited to the embodiments described above, and any equivalent or partial modifications made under the spirit of the present invention are considered to be within the scope of the present invention.
Claims (10)
1. A discretization preparation method of a two-dimensional material aerogel with a designable three-dimensional structure is characterized by comprising the following steps:
(1) preparing a degradable resin mould with a required three-dimensional structure by using a 3D printing technology, and uniformly coating a layer of metal film in an evaporation machine;
(2) fully combining the two-dimensional material with a corresponding stabilizing agent and a cross-linking agent under constant-temperature stirring to form hydrogel, and pouring the hydrogel into a resin mold to form a tightly-filled composite frame;
(3) freezing and drying the two-dimensional material hydrogel attached to the mold to obtain aerogel, placing the aerogel in a packaging material, and forming the aerogel by using a vacuum auxiliary impregnation method;
(4) removing the metal film coated on one surface of the mold, exposing the degradable resin coated on the metal film, placing the metal film in a solvent of the degradable resin to remove the resin mold, then placing the metal film in a metal dissolving solution to remove the residual metal film, and placing the obtained composite material in a solvent of an encapsulating material or removing the encapsulating material in an etching and heating mode to obtain the three-dimensionally structured two-dimensional material aerogel.
2. The discretization preparation method of the aerogel of two-dimensional material with designable three-dimensional structure of claim 1, wherein the degradable resin mold is a degradable photosensitive resin, and the material preparation comprises, by weight: selecting 40-60 parts of comonomer N, N-dimethylacrylamide or acrylamide, 40-60 parts of methacrylic acid, methyl methacrylate or sodium acrylate, 40-50 parts of crosslinking cracking agent methacrylic anhydride or N, N-methylene bisacrylamide, heating in an oil bath at 40-60 ℃, mixing, then gradually adding 90-120 parts of filler polyvinyl alcohol, polyvinylpyrrolidone or methyl cellulose and 10-20 parts of photoinitiator aroylphosphine oxide or bisbenzoylphenylphosphine oxide, and uniformly dispersing.
3. The discretization method for preparing aerogel of two-dimensional material with designable three-dimensional structure according to claim 1, characterized in that said wrapped metal film is made of copper or nickel.
4. The discretization method for the aerogel of two-dimensional materials with programmable three-dimensional structure according to claim 1, characterized in that said two-dimensional materials include but are not limited to one of the following: hexagonal boron nitride, graphite, transition metal dichalcogenides, metal halides, metal carbides, metal nitrides, layered oxides, and layered hydrides.
5. The discretization method for the aerogel of two-dimensional material with programmable three-dimensional structure as claimed in claim 1, characterized in that said stabilizer is cellulose, which is dissolved in the urea and sodium hydroxide aqueous solution, for the adsorption and connection of the added two-dimensional material.
6. The discretization preparation method of the aerogel of two-dimensional material with designable three-dimensional structure as claimed in claim 1, wherein said cross-linking agent is used to generate cross-linking bonds between cellulose macromolecules, so as to form a network structure and fix the relative positions of the cellulose macromolecules, forming a three-dimensional framework, including but not limited to one of the following: formaldehyde, dicarboxylic acids, dialdehydes, epoxides.
7. The discretization preparation method of the aerogel of two-dimensional material with designable three-dimensional structure according to claim 1, characterized in that the proportions of said two-dimensional material, stabilizer and cross-linking agent are as follows: 4-8g of two-dimensional material and 2-4g of stabilizer are added into 4mL of cross-linking agent.
8. The discretization method for preparing the aerogel of two-dimensional material with programmable three-dimensional structure as claimed in claim 1, wherein said freeze-drying treatment method comprises maintaining the hydrogel in a stable colloidal dispersion state before treatment, directly freezing the hydrogel in liquid nitrogen, and freeze-drying the hydrogel in a freeze-dryer.
9. The discretization method for preparing aerogel of two-dimensional material with programmable three-dimensional structure as claimed in claim 1, wherein said encapsulating material includes but is not limited to one of the following: epoxy resin, PDMS, polyurethane, elastic silicon rubber, paraffin and rosin. The dissolving agent of the degradable resin adopts aqueous solution of sodium hydroxide and other alkaline solution.
10. The metal dissolving solution is used for fully dissolving the metal film without reacting with the two-dimensional material and comprises dilute nitric acid, dilute hydrochloric acid, dilute sulfuric acid, ferric trichloride solution and ammonia alkaline solution;
the dissolving agent of the packaging material is used for fully dissolving the packaging material and does not react with the two-dimensional material.
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