CN114074927A - Two-dimensional material, preparation method thereof and composite membrane - Google Patents
Two-dimensional material, preparation method thereof and composite membrane Download PDFInfo
- Publication number
- CN114074927A CN114074927A CN202010829668.2A CN202010829668A CN114074927A CN 114074927 A CN114074927 A CN 114074927A CN 202010829668 A CN202010829668 A CN 202010829668A CN 114074927 A CN114074927 A CN 114074927A
- Authority
- CN
- China
- Prior art keywords
- dimensional material
- boron nitride
- viscosity
- fluid
- prepared
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/064—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with boron
- C01B21/0648—After-treatment, e.g. grinding, purification
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention discloses a two-dimensional material, a preparation method thereof and a composite membrane, wherein the preparation method comprises the steps of dissolving an improved medium in a polar solvent to prepare an improved fluid; the modified medium is at least one selected from monosaccharide, disaccharide, polysaccharide, polymer, and lipid; the viscosity of the modified fluid is 50 to 10000 mPas, and the viscosity reduction ratio of the viscosity at a shear rate of 100/s to the viscosity at a shear rate of 10/s at 25 ℃ is 0 to 80 percent; uniformly mixing the layered material powder with the improved fluid to prepare a mixed suspension; applying a mechanical peeling force to the mixed suspension to peel the layered material; and then a separation process is performed. The functionalized two-dimensional material with large size and thin thickness can be prepared by the method.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a two-dimensional material, a preparation method thereof and a composite film.
Background
Two-dimensional materials (nanoplatelets) refer to materials having a two-dimensional planar structure and a thickness of less than 10nm, including transition metal chalcogenides, transition metal oxides, and other two-dimensional compounds (e.g., boron nitride, etc.). Since the first acquisition of few-layer and single-layer graphene by means of micromechanical exfoliation by professor heim, manchester university, united kingdom, and professor novoseov, 2004, two-dimensional materials have attracted extensive research interest by scientists of various countries. The novel physical and chemical properties of the composite material have potential application prospects in the aspects of field effect tubes, photoelectric devices, topological insulators, energy storage and the like.
The macroscopic preparation of two-dimensional materials is a prerequisite for their widespread use. In the present stage, the method for massively preparing the two-dimensional material is mainly to strip the layered material by a top-down method, such as micro-mechanical stripping, ball-milling stripping, ultrasonic stripping, high-pressure flow stripping, chemical stripping and the like. The methods have the advantages of low cost, easy processing and the like, and have wide application prospects in various fields, such as energy sources, catalysis, electronic devices and the like. However, the liquid phase stripping method generally produces a two-dimensional material with a low yield, generates a large amount of waste liquid, and has a high treatment cost. At present, the most promising method for realizing large-scale macro-preparation is a mechanical method, such as a ball milling method, a grinding method and the like, and the methods have high yield, simple operation and mature application in industry. However, the mechanical method is difficult to avoid strong mechanical impact force on the two-dimensional material surface, and the obtained sheet layer has the characteristics of small size, large thickness and the like, so that the two-dimensional material is not favorable for film formation, the processability is poor, and the mechanical, thermal and electrical properties of the assembly material are also severely restricted. Therefore, how to effectively improve the traditional mechanical stripping process with low cost to obtain a large-size and thin-thickness two-dimensional material has important significance for industrial application of the two-dimensional material.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides a two-dimensional material, a preparation method thereof and a composite film.
The technical scheme adopted by the invention is as follows:
in a first aspect of the present invention, a method for preparing a two-dimensional material is provided, which comprises the following steps:
s1, dissolving the improved medium in a polar solvent to prepare an improved fluid; the improved medium is selected from at least one of monosaccharide, disaccharide, polysaccharide, polymer and ester; the viscosity of the modified fluid is 50-10000 mPa & s, and the viscosity reduction ratio of the viscosity at the shear rate of 100/s to the viscosity at the shear rate of 10/s at 25 ℃ is 0-80%;
s2, uniformly mixing the layered material powder with the improved fluid to prepare a mixed suspension;
s3, applying mechanical stripping acting force to the mixed suspension to strip the layered material; and then a separation process is performed.
The viscosity of the modified fluid prepared in the above step S1 is preferably 200 to 2000 mPas, and the modified fluid has a specific rheological property (i.e., shear thinning or shear viscosity stabilization property), and the viscosity at a shear rate of 100/S at 25 ℃ is preferably 0 to 40% lower than the viscosity at a shear rate of 10/S. The modified media typically contain polar groups (e.g., hydroxyl, amino, carboxyl, etc.).
According to some embodiments of the invention, in step S2, the mass ratio of the layered material powder to the modified fluid is 1: 100-2: 1; preferably 1: 30-1: 1.
according to some embodiments of the invention, the layered material powder includes, but is not limited to, graphite, hexagonal boron nitride, black phosphorus, metal chalcogenide, double metal hydroxide, clay, mica, or layered metal oxide.
According to some embodiments of the invention, in step S1, the monosaccharide is selected from at least one of glucose, fructose, xylose, lyxose, ribose, arabinose, mannose, galactose, and threose; preferably glucose, fructose or arabinose;
the disaccharide is at least one selected from sucrose, maltose and lactose;
the polysaccharide is selected from at least one of starch, nano-cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose, hyaluronic acid, chitin and agar; preferably, nano-cellulose, sodium carboxymethyl cellulose, agar or hyaluronic acid;
the polymer is selected from at least one of polyvinyl alcohol, polyamide, polyimide, epoxy resin, polysulfone, polyester, polyether, polyethylene glycol, polyvinylpyrrolidone, polyethylene oxide, polyacrylate, polyvinylidene fluoride, aromatic amide, phenolic resin, polycarbonate, poly-p-phenylene terephthalamide and polyvinyl butyral;
the ester substances are selected from at least one of acrylate, phosphate and triglyceride.
According to some embodiments of the invention, in step S1, the polar solvent is selected from at least one of water, glycerol, ethylene glycol, methanol, ethanol, isopropanol, N-butanol, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, dimethylacetamide, N-methylpyrrolidone, benzene, toluene, xylene, simethicone, isoamyl acetate, ethyl acetate, and butyl acetate. The polar solvent is preferably water, glycerol, ethanol, dimethyl sulfoxide or N-methylpyrrolidone.
According to some embodiments of the invention, the mechanical peel force is applied in step S3 in a manner selected from at least one of ball milling, ultrasonication, rolling, milling, sanding, mechanical stirring, high speed shearing, high pressure homogenization, and high speed jetting. Preferably by ball milling, grinding, sanding, high speed shearing or high pressure homogenization.
According to some embodiments of the invention, the mechanical peeling force is applied for a time of 0.5 to 96 hours, preferably 2 to 48 hours.
According to some embodiments of the invention, in step S3, the separation process is at least one selected from centrifugation, natural sedimentation, and filtration. Wherein the filtering comprises positive pressure filtering or negative pressure filtering.
According to some embodiments of the invention, in step S3, the separation process is preceded by a washing process and followed by a drying process; alternatively, the separation treatment is followed by a washing treatment and a drying treatment in this order.
The solvent used in the washing treatment is water, alcohols (such as methanol, ethanol, isopropanol, etc.), ketones (such as acetone, butanone, etc.), lipids (such as ethyl acetate, butyl acetate, etc.), or aromatic hydrocarbons (such as benzene, toluene, xylene, etc.). The washing treatment can adopt repeated washing for many times, and the washing times can be 1-10 times, preferably 2-5 times. The drying treatment can be air drying, vacuum drying, freeze drying, spray drying, supercritical drying, etc. Further, the solid powder obtained by drying can be dispersed in a solvent to prepare a dispersion liquid.
In a second aspect of the present invention, there is provided a two-dimensional material prepared by the method for preparing any one of the two-dimensional materials provided in the first aspect of the present invention.
In a third aspect of the invention, there is provided a composite film comprising any one of the two-dimensional materials provided in the second aspect of the invention.
The embodiment of the invention has the beneficial effects that:
the embodiment of the invention provides a preparation method of a two-dimensional material, which adopts the mixing of improved fluid and layered material powder and then carries out mechanical stripping. On one hand, the improved fluid has specific viscosity and rheological property (namely the property of shear thinning or shear viscosity stabilization), the laminar material is mechanically peeled in the improved fluid medium, the mechanical impact force can be well converted into the shear force to peel the laminar material under the environment of the improved fluid medium, the tearing effect brought by the flow of the improved fluid is also peeled along the plane of the laminar material, the in-plane structure of the laminar material cannot be damaged, the peeling efficiency is high, the obtained two-dimensional nano material has large plane size, thin thickness and good film forming property, and the electric conduction, heat conduction, blocking and reinforcing functions of the two-dimensional nano material are favorably exerted. On the other hand, because the impact and friction action of mechanical force in the traditional solid phase mechanical grinding process can cause the problems of high temperature, high noise, much dust and the like of a reaction system, the embodiment of the invention can provide a uniform and continuous chemical reaction space by introducing the improved fluid as a medium, compared with the common solid phase mechanical grinding, the invention can more efficiently and uniformly cause the reaction to be uniform and mild, reduce the reaction temperature, reduce the noise during collision, and eliminate dust pollution, has simple preparation method, and is a macro preparation method with great industrial prospect. Furthermore, the modified fluid contains polar functional groups, and can react with the fresh surface and the section of the stripped two-dimensional nano material to graft the polar functional groups on the modified fluid so as to prepare a functionalized two-dimensional material, and the dispersibility of the two-dimensional material in a polar solvent can be improved through the functionalization, and the modified fluid can be used for subsequent processing without chemical modification; and because the functionalization degree is improved, the material has stronger interaction with common dispersing matrixes (such as polymer monomers, polymers, thermoplastic plastics, dimethyl silicone oil and the like), and the mechanical property of the material is improved. And the introduction of the functional group can reduce the interface thermal resistance between the two-dimensional material and the dispersion matrix and improve the thermal conductivity of the material.
Drawings
FIG. 1 is a schematic diagram of a conventional mechanical stripping process for producing two-dimensional materials and the present invention process for producing two-dimensional materials by adding a modified fluid-assisted mechanical stripping process;
FIG. 2 is an SEM photograph of the boron nitride powder used in example 1 and the two-dimensional material produced;
FIG. 3 is an XPS curve of a two-dimensional material prepared in example 1;
FIG. 4 is an FTIR profile of the boron nitride powder used and the two-dimensional material produced in example 1;
FIG. 5 is a TGA curve of the boron nitride powder used and the two-dimensional material produced in example 1;
FIG. 6 is a graph of the rheology of the modified liquids prepared in example 1 and comparative example 1;
FIG. 7 is a TEM image of a two-dimensional material obtained in example 1;
FIG. 8 is a TEM image of a two-dimensional material prepared in comparative example 1;
FIG. 9 is a TEM image of a two-dimensional material prepared in comparative example 2;
FIG. 10 is a TEM image of a two-dimensional material prepared in comparative example 3;
FIG. 11 is a TEM image of a two-dimensional material obtained in example 3;
FIG. 12 is an AFM image of the two-dimensional material prepared in example 3;
FIG. 13 is a TEM image of a two-dimensional material obtained in example 3;
FIG. 14 is an SEM photograph of a two-dimensional material prepared in example 4;
FIG. 15 is an SEM photograph of a two-dimensional material prepared in example 5;
FIG. 16 is an SEM photograph of a two-dimensional material prepared in example 6;
FIG. 17 is an SEM photograph of a two-dimensional material prepared in example 7;
FIG. 18 is an SEM image of a two-dimensional material prepared in comparative example 4;
FIG. 19 is an SEM image of a two-dimensional material prepared in comparative example 5;
FIG. 20 is an SEM photograph of a two-dimensional material prepared in example 8;
FIG. 21 is an SEM photograph of a two-dimensional material prepared in comparative example 6;
FIG. 22 is an SEM photograph of a two-dimensional material prepared in example 9;
FIG. 23 is an SEM photograph of a two-dimensional material prepared in example 10;
FIG. 24 is an SEM photograph of a two-dimensional material prepared in example 11; (ii) a
FIG. 25 is an SEM photograph of a two-dimensional material prepared in example 12;
FIG. 26 is a SEM photograph showing a cross-section of a flexible composite film obtained in example 13.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
Referring to fig. 1, (a) of fig. 1 shows a schematic diagram of a conventional mechanical stripping process for preparing a two-dimensional material, and (b) of fig. 1 shows a schematic diagram of a two-dimensional material prepared by adding a modified fluid-assisted mechanical stripping process according to the present invention. As shown in fig. 1 (a), the conventional mechanical peeling of two-dimensional materials can generate strong mechanical impact force in the plane of the layered material. As shown in (b) of FIG. 1, the improved fluid with specific viscosity and rheological property is used as a medium, so that the mechanical impact force in the mechanical stripping process can be converted into mechanical shearing force, the improved system can tear the layered material to strip the layered material, and the layered material can be functionalized while being stripped, so that a large-size functionalized two-dimensional material can be prepared, wherein the planar size range of the prepared two-dimensional material is 0.1-10 μm, and the thickness of the prepared two-dimensional material is 0.33-50 nm.
The following examples are provided to illustrate the preparation of the two-dimensional material of the present invention.
Example 1
A method of preparing a two-dimensional material, comprising the steps of:
s1, weighing 75g of glucose and 25g of water, heating in a water bath at 90 ℃ to promote dissolution, and mixing uniformly to obtain the improved fluid. The viscosity of the modified fluid was 1400 mPas as measured at 25 ℃ with an NDJ-5S rotational viscometer.
S2, 20mL of modified fluid, 1g of boron nitride powder, 100g of 95% zirconia balls with the diameter of 10mm and 25g of zirconia balls with the diameter of 1mm are added into a 250mL zirconia ball milling tank together, and after sealing, the mixture is ball milled for 24h on a QM-3SP2 planetary ball mill at the speed of 500 rpm.
S3, washing and ultrasonically treating the ball-milled product with 200mL of deionized water, filtering with a microporous filter membrane, and fully washing for 3-5 times; then ultrasonically dispersing the filter cake with 200mL of deionized water, standing, and then sucking supernatant to prepare boron nitride nanosheet dispersion liquid; filtering a proper amount of the dispersion liquid, and drying the dispersion liquid in vacuum at the temperature of 60 ℃ for 12 hours to obtain a two-dimensional material, namely boron nitride nanosheet powder.
The boron nitride powder used in example 1 and the prepared boron nitride nanosheets were subjected to morphological analysis using a scanning electron microscope, and the results are shown in fig. 2 (a) and (b), respectively. As shown in fig. 2, the boron nitride powder is broken and thinned under the action of mechanical force during the ball milling process to obtain the boron nitride nanosheet. The elemental composition of the boron nitride nanosheet powder prepared in example 1 is analyzed by X-ray photoelectron spectroscopy, and the obtained result is shown in fig. 3, which shows that a certain oxygen atom exists in the boron nitride nanosheet powder and forms a boron-oxygen bond with the boron atom, thereby indicating that the prepared boron nitride nanosheet contains a certain oxygen-containing functional group; infrared spectroscopic analysis was performed on the boron nitride nanosheet powder prepared in example 1 by fourier transform infrared spectroscopy, and the obtained result is shown in fig. 4, which indicates that a certain amount of hydroxyl groups are present in the boron nitride nanosheet powder. Thermogravimetric testing was performed on the boron nitride nanosheet prepared in example 1 under a nitrogen atmosphere by using a thermogravimetric method, and the obtained result is shown in fig. 5, which indicates that the group content in the boron nitride nanosheet powder is about 5%. It can be seen that, in the ball milling process, boron nitride undergoes mechanochemical reaction with the modifying fluid under the action of mechanical force, so that organic functional groups are grafted on the boron nitride in the surface or the edge.
Comparative example 1
A method of producing a two-dimensional material, the comparative example two-dimensional material being produced substantially in the same manner as the two-dimensional material of example 1, except that: in this comparative example, in step S1, 30g of glucose was weighed and mixed with 70g of water to prepare a conventional fluid, and the viscosity of the conventional fluid was measured at room temperature and 25 ℃ by means of an NDJ-5S rotational viscometer to be 10 mPas; then, in substantially the same operation as in steps S2 and S3 of example 1, the conventional fluid prepared by this comparative example was used in place of the modified fluid of example 1, and mixed with boron nitride powder and ground to obtain boron nitride nanosheet powder.
The rheological characteristics of the fluids prepared in example 1 and the fluids prepared in comparative example 1 are respectively researched, the two-dimensional material preparation process and the finally prepared two-dimensional material are observed and researched, and the fact that the fluids adopted by the two fluids are different and influence the grinding process and the performance of a final product is found.
First, the rheological properties of the fluids prepared in example 1 and comparative example 1 were investigated at 25 ℃ using the rotational rheology test method (MCR 502-. As can be seen from FIG. 6, the modified fluid prepared in example 1 had a viscosity of 1423 mPas at a shear rate of 10/s, a viscosity stabilized at 1379 mPas at a shear rate of 100/s, and a viscosity drop of 3%; the conventional fluid prepared in comparative example 1 had a viscosity of 10 mPas at shear rates of 10/s and 100/s.
Secondly, in step S2 of example 1, the improved fluid with viscosity of 1400mPa · S is mixed with the boron nitride powder for ball milling treatment, and the materials in the ball milling tank are uniform and have no agglomeration during the ball milling process, which indicates sufficient ball milling and high efficiency; in comparative example 1, the fluid with viscosity of 10mPa · s was mixed and ball milled, and the viscosity of the fluid was low, so the shearing force during ball milling was poor and the peeling effect was poor.
Further, observing the boron nitride nanosheet dispersions further prepared after washing the ball-milled products in step S3 of comparative example 1 and comparative example 1, it was found that the boron nitride nanosheet dispersion in example 1 had better dispersibility, indicating that the boron nitride nanosheets stripped with improved fluid assistance in example 1 had better dispersibility than the boron nitride nanosheets stripped with conventional fluid assistance in comparative example 1.
Comparative example 2
A method of producing a two-dimensional material, the comparative example two-dimensional material being produced substantially in the same manner as the two-dimensional material of example 1, except that: in this comparative example, in step S1, 82g of glucose was weighed and mixed with 18g of water to prepare a conventional fluid, and the viscosity of the conventional fluid was 18760 mPas as measured at room temperature and 25 ℃ with an NDJ-5S rotational viscometer; then, in substantially the same operation as in steps S2 and S3 of example 1, the conventional fluid prepared by this comparative example was used in place of the modified fluid of example 1, and mixed with boron nitride powder and ground to obtain boron nitride nanosheet powder.
In comparative example 2, the fluid with the viscosity of 18760mPa · s is mixed and ball-milled, and the viscosity of the fluid is too high, so that the energy of the grinding ball is absorbed by the fluid, the acting force during the ball-milling process is low, and the peeling effect is poor.
Comparative example 3
A method of preparing a two-dimensional material, the comparative example differing from example 1 mainly in that: in the comparative example, glucose dry powder is directly used to replace the improved fluid in example 1, and the improved fluid and boron nitride powder are mixed and ball-milled to prepare boron nitride nanosheet powder.
The two-dimensional materials obtained in example 1 and comparative examples 1, 2 and 3 were observed with a Transmission Electron Microscope (TEM), and the results are shown in fig. 7 to 10, respectively, (a) and (b) in fig. 8 and 9 are TEM images at different magnifications, respectively, and (b) in fig. 10 is an enlarged view of M in (a). As can be seen from FIG. 7, the boron nitride nanosheet prepared in example 1 is almost transparent, has a very small thickness, and has a planar size of 1-1.5 μm; as can be seen from FIG. 8, the boron nitride nanosheet prepared in comparative example 1 is thick, and the plane size is 2-3 μm; as can be seen from FIG. 9, the boron nitride nanosheet prepared in comparative example 2 is thick, and the plane size is also 2-3 μm; as can be seen from FIG. 10, the boron nitride nanosheet sphere prepared in comparative example 3 is crushed and destroyed by the impact of the grinding balls, and the size is 100-200 nm; thus, it is clear that the gain effect of using the improved fluid-assisted ball milling exfoliation in example 1 is very significant.
Example 2
A method of preparing a two-dimensional material, comprising the steps of:
s1, weighing 6g of glucose and 94g of glycerol, uniformly mixing, and heating in a water bath at 120 ℃ to obtain the improved fluid. The viscosity of the modified fluid was 1600 mPas at a shear rate of 10/s and 1587 mPas at a shear rate of 100/s at a 1% reduction as measured at 25 ℃ using MCR 502-702 rotational rheometer.
S2, 20mL of modified fluid, 1g of boron nitride powder, 100g of 95% zirconia balls with the diameter of 10mm and 25g of zirconia balls with the diameter of 1mm are added into a 250mL zirconia ball milling tank together, and after sealing, the mixture is ball milled for 24h on a QM-3SP2 planetary ball mill at the speed of 500 rpm. The materials in the ball milling tank are uniform and have no caking in the ball milling process, which indicates that the ball milling is sufficient and efficient.
S3, ultrasonically washing the ball-milled product with 200mL of deionized water, filtering with a microporous filter membrane, and fully washing for 3-5 times; then ultrasonically dispersing the filter cake with 200mL of deionized water, standing, and sucking supernatant to prepare a dispersion liquid of the boron nitride nanosheet, wherein the dispersion uniformity of the dispersion liquid is high; and filtering a proper amount of the dispersion liquid, and drying the dispersion liquid in vacuum at the temperature of 60 ℃ for 12 hours to obtain boron nitride nanosheet powder.
The two-dimensional material prepared in this example was observed and tested by a Transmission Electron Microscope (TEM) and an Atomic Force Microscope (AFM), and the results are shown in fig. 11 and fig. 12, respectively, where (a) in fig. 12 is an atomic force scanning image of a boron nitride nanosheet, and (b) is a height curve of the boron nitride nanosheet marked in (a). As can be seen from FIG. 11, the thickness of the prepared boron nitride nanosheet is small, and the plane size is 1-1.5 μm; as can be seen from FIG. 12, the thickness of the prepared boron nitride nanosheet is about 2 nm.
Example 3
A method of preparing a two-dimensional material, comprising the steps of:
s1, weighing 6g of glucose and 94g of glycerol, uniformly mixing, and heating in a water bath at 120 ℃ to obtain the improved fluid. The viscosity of the modified fluid was 1600 mPas at a shear rate of 10/s and 1587 mPas at a shear rate of 100/s at a 1% reduction as measured at 25 ℃ using MCR 502-702 rotational rheometer.
S2, 20mL of modified fluid, 1g of 325 mesh graphite powder, 100g of 95% zirconia balls with the diameter of 10mm and 25g of zirconia balls with the diameter of 1mm are added into a 250mL zirconia ball milling tank together, and after sealing, the mixture is ball milled for 24h on a QM-3SP2 planetary ball mill at the speed of 500 rpm. The materials in the ball milling tank are uniform and have no agglomeration in the ball milling process.
S3, ultrasonically washing the ball-milled product with 200mL of deionized water, filtering with a microporous filter membrane, and fully washing for 3-5 times; then ultrasonically dispersing the filter cake with 200mL of deionized water, standing, and sucking supernatant to prepare a dispersion liquid of the graphene nanosheet, wherein the dispersion uniformity of the dispersion liquid is high; and filtering a proper amount of the dispersion liquid, and drying the dispersion liquid in vacuum at the temperature of 60 ℃ for 12 hours to obtain graphene nanosheet powder.
The two-dimensional material prepared in this example was observed and tested by a Transmission Electron Microscope (TEM), and the results are shown in fig. 13, respectively, which shows that the thickness is small and the plane size is 2 to 3 μm.
Example 4
A method of preparing a two-dimensional material, comprising the steps of:
s1, weighing 79g of glucose and 21g of water, uniformly mixing, and heating in a water bath at 95 ℃ to obtain the improved fluid. The viscosity of the modified fluid was 9640 mPas at a shear rate of 10/s, 8360 mPas at a shear rate of 100/s, as measured at 25 ℃ in MCR 502-702 rotational rheometer, with a 13% reduction.
S2, 20mL of modified fluid, 1g of boron nitride powder, 100g of 95% zirconia balls with the diameter of 10mm and 25g of zirconia balls with the diameter of 1mm are added into a 250mL zirconia ball milling tank together, and after sealing, the mixture is ball milled for 24h on a QM-3SP2 planetary ball mill at the speed of 500 rpm.
S3, ultrasonically washing the ball-milled product with 200mL of deionized water, filtering with a microporous filter membrane, and fully washing for 3-5 times; then ultrasonically dispersing the filter cake with 200mL of deionized water, standing, and sucking supernatant to prepare a dispersion liquid of the boron nitride nanosheet, wherein the dispersion uniformity of the dispersion liquid is high; and filtering a proper amount of the dispersion liquid, and drying the dispersion liquid in vacuum at the temperature of 60 ℃ for 12 hours to obtain boron nitride nanosheet powder.
The two-dimensional material prepared in this example was observed and tested by a Scanning Electron Microscope (SEM), and the obtained result is shown in fig. 14, which shows that the thickness of the prepared boron nitride nanosheet is small, and the planar size is 0.8-1.7 μm.
Example 5
A method of preparing a two-dimensional material, comprising the steps of:
s1, weighing 41g of glucose and 59g of water, uniformly mixing, and heating in a water bath at 95 ℃ to obtain the improved fluid. The viscosity of the modified fluid was measured at 25 ℃ at a shear rate of 10/s and 74 mPas at a shear rate of 100/s using MCR 502-702 rotational rheometer.
S2, 20mL of modified fluid, 1g of boron nitride powder, 100g of 95% zirconia balls with the diameter of 10mm and 25g of zirconia balls with the diameter of 1mm are added into a 250mL zirconia ball milling tank together, and after sealing, the mixture is ball milled for 24h on a QM-3SP2 planetary ball mill at the speed of 500 rpm.
S3, ultrasonically washing the ball-milled product with 200mL of deionized water, filtering with a microporous filter membrane, and fully washing for 3-5 times; then ultrasonically dispersing the filter cake with 200mL of deionized water, standing, and sucking supernatant to prepare a dispersion liquid of the boron nitride nanosheet, wherein the dispersion uniformity of the dispersion liquid is high; and filtering a proper amount of the dispersion liquid, and drying the dispersion liquid in vacuum at the temperature of 60 ℃ for 12 hours to obtain boron nitride nanosheet powder.
The two-dimensional material prepared in this example was observed and tested by a Scanning Electron Microscope (SEM), and the obtained result is shown in fig. 15, which shows that the thickness of the prepared boron nitride nanosheet is small, and the planar size is 0.6-1.4 μm.
Example 6
A method of preparing a two-dimensional material, comprising the steps of:
s1, weighing 150g of glucose and 50g of water, mixing uniformly, and heating in a water bath at 95 ℃ to obtain the improved fluid. The viscosity of the modified fluid was 1423 mPas at a shear rate of 10/s, 1379 mPas at a shear rate of 100/s, and the decrease rate was 3%, as measured at 25 ℃ at room temperature using MCR 502-702 rotational rheometer.
S2, taking 100mL of modified fluid, 1g of boron nitride powder, 100g of 95% zirconia balls with the diameter of 10mm and 25g of zirconia balls with the diameter of 1mm, adding the mixture into a 250mL zirconia ball milling tank, sealing the tank, and ball milling the mixture for 36h on a QM-3SP2 planetary ball mill at the speed of 500 rpm.
S3, ultrasonically washing the ball-milled product with 200mL of deionized water, filtering with a microporous filter membrane, and fully washing for 3-5 times; then ultrasonically dispersing the filter cake with 200mL of deionized water, standing, and sucking supernatant to prepare a dispersion liquid of the boron nitride nanosheet, wherein the dispersion uniformity of the dispersion liquid is high; and filtering a proper amount of the dispersion liquid, and drying the dispersion liquid in vacuum at the temperature of 60 ℃ for 12 hours to obtain boron nitride nanosheet powder.
The two-dimensional material prepared in this example was observed and tested by a Scanning Electron Microscope (SEM), and the obtained result is shown in fig. 16, which shows that the thickness of the prepared boron nitride nanosheet is small, and the planar size is 1 to 1.5 μm.
Example 7
S1, weighing 75g of glucose and 25g of water, uniformly mixing, and heating in a water bath at 95 ℃ to obtain the improved fluid. The viscosity of the modified fluid was 1423 mPas at a shear rate of 10/s, 1379 mPas at a shear rate of 100/s, and the decrease rate was 3%, as measured at 25 ℃ at room temperature using MCR 502-702 rotational rheometer.
S2, 0.5mL of modified fluid, 1g of boron nitride powder, 100g of 95% zirconia balls with the diameter of 10mm and 25g of zirconia balls with the diameter of 1mm are added into a 250mL zirconia ball milling tank together, and after sealing, the mixture is ball milled for 24h on a QM-3SP2 planetary ball mill at the speed of 500 rpm.
S3, ultrasonically washing the ball-milled product with 200mL of deionized water, filtering with a microporous filter membrane, and fully washing for 3-5 times; then ultrasonically dispersing the filter cake with 200mL of deionized water, standing, and sucking supernatant to prepare a dispersion liquid of the boron nitride nanosheet, wherein the dispersion uniformity of the dispersion liquid is high; and filtering a proper amount of the dispersion liquid, and drying the dispersion liquid in vacuum at the temperature of 60 ℃ for 12 hours to obtain boron nitride nanosheet powder.
Comparative example 4
A method of preparing a two-dimensional material, the comparative example two-dimensional material being prepared substantially as in example 7, except that: in this comparative example, in step S2, 0.2mL of the modified fluid, 1g of boron nitride powder, 100g of 95% zirconia balls having a diameter of 10mm, and 25g of zirconia balls having a diameter of 1mm were charged together into a 250mL zirconia ball mill jar, and after sealing, ball-milled in a QM-3SP2 planetary ball mill at a speed of 500rpm for 24 hours; then, in substantially the same operation as in steps S1 and S3 in example 7, boron nitride nanosheet powder was prepared.
Comparative example 5
A method of preparing a two-dimensional material, the comparative example two-dimensional material being prepared substantially as in example 7, except that: in this comparative example, in step S2, 100mL of the modified fluid, 0.2g of boron nitride powder, 100g of 95% zirconia balls having a diameter of 10mm, and 25g of zirconia balls having a diameter of 1mm were charged together into a 250mL zirconia ball mill pot, and after sealing, they were ball-milled in a QM-3SP2 planetary ball mill at 500rpm for 24 hours; then, in substantially the same operation as in steps S1 and S3 in example 7, boron nitride nanosheet powder was prepared.
The two-dimensional materials obtained in example 7 and comparative examples 4 and 5 were observed and tested by a Scanning Electron Microscope (SEM), and the results are shown in fig. 17 to 19, respectively. As can be seen from FIG. 17, the boron nitride nanosheets prepared in Experimental example 7 are relatively small in thickness and have a planar size of 1-1.5 μm; as can be seen from FIG. 18, the boron nitride nanosheet prepared in comparative example 4 has a small thickness and a planar dimension of 100-200 nm, and as can be seen from FIG. 19, the boron nitride nanosheet prepared in comparative example 5 has a large thickness and a planar dimension of 2-3 μm. Therefore, the boron nitride powder and the improved fluid in the proportion of example 7 are used for ball milling and stripping, and the effect is better; in comparative example 4, the addition of the modified fluid is too little, and the function of assisting ball milling is difficult to be achieved, so that boron nitride is highly crushed by impact force; the modified fluid in comparative example 5 was added too much, resulting in difficulty in applying force to the boron nitride powder and poor peeling effect.
Example 8
S1, weighing 50g of polyethylene glycol (6000 molecular weight) and 50g of water, uniformly mixing, and heating in a water bath at 60 ℃ to obtain the improved fluid. The viscosity of the modified fluid was 165 mPas at a shear rate of 10/s, 117 mPas at a shear rate of 100/s, and the decrease rate was 29%, as measured at 25 ℃ using MCR 502-702 rotational rheometer.
S2, 20mL of modified fluid, 1g of boron nitride powder, 100g of 95% zirconia balls with the diameter of 10mm and 25g of zirconia balls with the diameter of 1mm are added into a 250mL zirconia ball milling tank together, and after sealing, the mixture is ball milled for 24h on a QM-3SP2 planetary ball mill at the speed of 500 rpm.
S3, ultrasonically washing the ball-milled product with 200mL of deionized water, filtering with a microporous filter membrane, and fully washing for 3-5 times; then ultrasonically dispersing the filter cake with 200mL of deionized water, standing, and sucking supernatant to prepare a dispersion liquid of the boron nitride nanosheet, wherein the dispersion uniformity of the dispersion liquid is high; and filtering a proper amount of the dispersion liquid, and drying the dispersion liquid in vacuum at the temperature of 60 ℃ for 12 hours to obtain boron nitride nanosheet powder.
Comparative example 6
A method of producing a two-dimensional material, the comparative example two-dimensional material being produced substantially in the same manner as the two-dimensional material of example 8, except that: in this comparative example, in step S1, 1g of polyethylene glycol (6000 molecular weight) was weighed and mixed with 99g of water to prepare a conventional fluid, and the viscosity of the conventional fluid was 2 mPas at a shear rate of 10/S and 2 mPas at a shear rate of 100/S, as measured at 25 ℃ with MCR 502-702 rotational rheometer; then, in substantially the same operation as in steps S2 and S3 of example 1, the conventional fluid prepared by this comparative example was used in place of the modified fluid of example 1, and mixed with boron nitride powder and ground to obtain boron nitride nanosheet powder.
The two-dimensional materials obtained in example 8 and comparative example 6 were observed and tested by a Scanning Electron Microscope (SEM), and the results are shown in fig. 20 and 21, respectively. As can be seen from FIG. 20, the boron nitride nanosheets prepared in Experimental example 7 are relatively small in thickness and have a planar size of 0.7-1.3 μm; as can be seen from FIG. 21, the boron nitride nanosheet prepared in comparative example 4 has a large thickness and a planar dimension of 2 to 3 μm. Therefore, the boron nitride powder and the improved fluid in the proportion of the embodiment 8 have good ball-milling stripping effect, and the 50% polyethylene glycol solution can well assist the ball milling of the two-dimensional material; comparative example 5 has a low fluid viscosity and is difficult to perform a ball milling assistance function, and thus the peeling effect is poor.
Example 9
A method of preparing a two-dimensional material, comprising the steps of:
s1, weighing 75g of glucose and 25g of water, uniformly mixing, and heating in a water bath at 95 ℃ to obtain the improved fluid. The viscosity of the modified fluid was 1400 mPas at a shear rate of 10/s, 980 mPas at a shear rate of 100/s, and a 30% reduction, as measured at 25 ℃ using MCR 502-702 rotational rheometer.
S2, taking 20mL of modified fluid, 1g of black phosphorus powder, 100g of 95% zirconia balls with the diameter of 10mm and 25g of zirconia balls with the diameter of 1mm, adding the mixture into a 250mL zirconia ball milling tank, sealing the tank, and carrying out ball milling on a QM-3SP2 planetary ball mill for 24h at the speed of 500 rpm.
S3, ultrasonically washing the ball-milled product with 200mL of deionized water, filtering with a microporous filter membrane, and fully washing for 3-5 times; then ultrasonically dispersing the filter cake with 200mL of deionized water, standing, and sucking supernatant to prepare a dispersion liquid of the black phosphorus nanosheet, wherein the dispersion uniformity of the dispersion liquid is high; and filtering a proper amount of the dispersion liquid, and drying the dispersion liquid in vacuum at the temperature of 60 ℃ for 12 hours to obtain black phosphorus nanosheet powder.
The two-dimensional material prepared in this embodiment is observed and tested by a Scanning Electron Microscope (SEM), and the obtained result is shown in fig. 22, which shows that the thickness of the prepared black phosphorus nanosheet is small, and the plane size is 0.6-1.2 μm.
Example 10
A method of preparing a two-dimensional material, comprising the steps of:
s1, weighing 75g of glucose and 25g of water, uniformly mixing, and heating in a water bath at 95 ℃ to obtain the improved fluid. The viscosity of the modified fluid was 1423 mPas at a shear rate of 10/s, 1379 mPas at a shear rate of 100/s, and the decrease rate was 3%, as measured at 25 ℃ at room temperature using MCR 502-702 rotational rheometer.
S2, 20mL of modified fluid, 1g of molybdenum disulfide powder, 100g of 95% zirconia balls with the diameter of 10mm and 25g of zirconia balls with the diameter of 1mm are added into a 250mL zirconia ball milling tank together, and ball milling is carried out on a QM-3SP2 planetary ball mill for 24h at the speed of 300rpm after sealing.
S3, ultrasonically washing the ball-milled product with 200mL of deionized water, filtering with a microporous filter membrane, and fully washing for 3-5 times; then ultrasonically dispersing the filter cake with 200mL of deionized water, standing, and sucking supernatant to prepare a dispersion liquid of the molybdenum disulfide nanosheet, wherein the dispersion uniformity of the dispersion liquid is high; and filtering a proper amount of the dispersion liquid, and drying the dispersion liquid in vacuum at the temperature of 60 ℃ for 12 hours to obtain molybdenum disulfide nanosheet powder.
The two-dimensional material prepared in this embodiment is observed and tested by a Scanning Electron Microscope (SEM), and the obtained result is shown in fig. 23, which shows that the thickness of the prepared molybdenum disulfide nanosheet is small, and the plane size is 0.3-0.8 μm.
Example 11
A method of preparing a two-dimensional material, comprising the steps of:
s1, weighing 75g of glucose and 25g of water, uniformly mixing, and heating in a water bath at 95 ℃ to obtain the improved fluid. The viscosity of the modified fluid was 1423 mPas at a shear rate of 10/s, 1379 mPas at a shear rate of 100/s, and the decrease rate was 3%, as measured at 25 ℃ at room temperature using MCR 502-702 rotational rheometer.
S2, 20mL of modified fluid, 1g of mica powder, 100g of 95% zirconia balls with the diameter of 10mm and 25g of zirconia balls with the diameter of 1mm are added into a 250mL zirconia ball milling tank together, and after sealing, the mixture is ball milled for 24h on a QM-3SP2 planetary ball mill at the speed of 400 rpm.
S3, ultrasonically washing the ball-milled product with 200mL of deionized water, filtering with a microporous filter membrane, and fully washing for 3-5 times; then ultrasonically dispersing the filter cake with 200mL of deionized water, standing, and sucking supernatant to prepare a dispersion liquid of the mica nanosheets, wherein the dispersion uniformity of the dispersion liquid is high; and filtering a proper amount of the dispersion liquid, and drying the dispersion liquid for 12 hours in vacuum at the temperature of 60 ℃ to obtain mica nanosheet powder.
The two-dimensional material prepared in this example was observed and tested by a Scanning Electron Microscope (SEM), and the obtained result is shown in fig. 24, which indicates that the prepared mica nanosheet has a small thickness and a planar size of 0.9-1.7 μm.
Example 12
A method of preparing a two-dimensional material, comprising the steps of:
s1, weighing 75g of glucose and 25g of water, uniformly mixing, and heating in a water bath at 95 ℃ to obtain the improved fluid. The viscosity of the modified fluid was 1423 mPas at a shear rate of 10/s, 1379 mPas at a shear rate of 100/s, and the decrease rate was 3%, as measured at 25 ℃ at room temperature using MCR 502-702 rotational rheometer.
S2, taking 20mL of modified fluid, 1g of aluminum magnesium layered double hydroxide powder, 100g of 95% zirconia balls with the diameter of 10mm and 25g of zirconia balls with the diameter of 1mm, adding the mixture into a 250mL zirconia ball milling tank, sealing the tank, and ball milling the mixture for 48h on a QM-3SP2 planetary ball mill at the speed of 200 rpm.
S3, ultrasonically washing the ball-milled product with 200mL of deionized water, filtering with a microporous filter membrane, and fully washing for 3-5 times; then ultrasonically dispersing the filter cake with 200mL of deionized water, standing, and sucking supernatant to prepare a dispersion liquid of the aluminum-magnesium bimetal layered hydroxide nanosheet, wherein the dispersion liquid is high in dispersion uniformity; and filtering a proper amount of the dispersion liquid, and drying the dispersion liquid in vacuum at the temperature of 60 ℃ for 12 hours to obtain the aluminum-magnesium bimetal layered hydroxide nanosheet powder.
The two-dimensional material prepared in this embodiment is observed and tested by a Scanning Electron Microscope (SEM), and the obtained result is shown in fig. 25, which shows that the thickness of the prepared aluminum-magnesium bimetal layered hydroxide nanosheet is small, and the plane size is 0.8-1.7 μm.
Example 13
A flexible composite film can be used for heat dissipation of radio frequency devices. The preparation method comprises the following steps: the dispersion of boron nitride nanosheets prepared in step S3 of example 1 was mixed with an aqueous polyvinyl alcohol (PVA) solution in the following proportions of boron nitride: mixing PVA in a mass ratio of 80:20, ultrasonically dispersing, filtering by using a microporous filter membrane, and removing after drying to obtain the self-supporting boron nitride nanosheet/PVA flexible composite membrane.
The Scanning Electron Microscope (SEM) is used to observe the cross section of the flexible composite film prepared in this embodiment, and the obtained result is shown in fig. 26, where (a) and (b) in fig. 26 are SEM images at different magnifications, respectively, it can be seen that boron nitride nanosheets are sequentially stacked along the film plane direction, so that the interaction force between the nanosheets is increased, the phonon scattering between the nanosheets is effectively reduced, and the mechanical strength and the thermal conductivity of the composite film are improved.
Comparative example 7
A flexible composite film was produced in the same manner as in example 9 except that the boron nitride nanosheet dispersion produced in comparative example 3 was used. The boron nitride nanosheet layer of comparative example 3 was smaller in size.
The composite films in the experimental example 9 and the comparative example 7 were tested for thermal diffusivity, density and specific heat capacity by a flash test method, a drainage method and a differential scanning calorimetry method, and the thermal conductivities were calculated to be 37W m respectively-1K-1And 8Wm-1K-1(ii) a Tensile strength tests were conducted on the composite films of Experimental example 9 and comparative example 7 using a universal mechanical testing machine, and the results were 43MPa and 19MPa, respectively. Thus, the boron nitride nanosheets prepared using the modified fluid in the present invention were verified to have excellent thermal conductivity and mechanical properties after being assembled.
Claims (10)
1. A preparation method of a two-dimensional material is characterized by comprising the following steps:
s1, dissolving the improved medium in a polar solvent to prepare an improved fluid; the improved medium is selected from at least one of monosaccharide, disaccharide, polysaccharide, polymer and ester; the viscosity of the modified fluid is 50-10000 mPa & s, and the viscosity reduction ratio of the viscosity at the shear rate of 100/s to the viscosity at the shear rate of 10/s at 25 ℃ is 0-80%;
s2, uniformly mixing the layered material powder with the improved fluid to prepare a mixed suspension;
s3, applying mechanical stripping acting force to the mixed suspension to strip the layered material; and then a separation process is performed.
2. The method for preparing a two-dimensional material according to claim 1, wherein in step S2, the mass ratio of the laminar material powder to the modified fluid is 1: 100-2: 1.
3. the method of claim 2, wherein the layered powder is graphite, hexagonal boron nitride, black phosphorus, metal chalcogenide, double metal hydroxide, clay, mica, or layered metal oxide.
4. The method for preparing a two-dimensional material according to claim 1, wherein in step S1, the monosaccharide is at least one selected from glucose, fructose, xylose, lyxose, ribose, arabinose, mannose, galactose, and threose;
the disaccharide is at least one selected from sucrose, maltose and lactose;
the polysaccharide is selected from at least one of starch, nano-cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose, hyaluronic acid, chitin and agar;
the polymer is selected from at least one of polyvinyl alcohol, polyamide, polyimide, epoxy resin, polysulfone, polyester, polyether, polyethylene glycol, polyvinylpyrrolidone, polyethylene oxide, polyacrylate, polyvinylidene fluoride, aromatic amide, phenolic resin, polycarbonate, poly-p-phenylene terephthalamide and polyvinyl butyral;
the ester substances are selected from at least one of acrylate, phosphate and triglyceride.
5. The method for preparing a two-dimensional material according to claim 1, wherein in step S1, the polar solvent is at least one selected from the group consisting of water, glycerol, ethylene glycol, methanol, ethanol, isopropanol, N-butanol, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, dimethylacetamide, N-methylpyrrolidone, benzene, toluene, xylene, simethicone, isoamyl acetate, ethyl acetate, and butyl acetate.
6. The method of claim 1, wherein the mechanical peeling force is applied in step S3 by at least one selected from the group consisting of ball milling, ultrasonication, rolling, grinding, sanding, mechanical stirring, high-speed shearing, high-pressure homogenization, and high-speed jet.
7. The method for preparing a two-dimensional material according to claim 1, wherein in step S3, the separation process is at least one selected from the group consisting of centrifugation, natural sedimentation, and filtration.
8. The method for producing a two-dimensional material according to any one of claims 1 to 7, wherein in step S3, the separation treatment is preceded by a washing treatment and is followed by a drying treatment; alternatively, the separation treatment is followed by a washing treatment and a drying treatment in this order.
9. A two-dimensional material, characterized by being produced by the method for producing a two-dimensional material according to any one of claims 1 to 8.
10. A composite film comprising the two-dimensional material of claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010829668.2A CN114074927B (en) | 2020-08-18 | 2020-08-18 | Two-dimensional material, preparation method thereof and composite membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010829668.2A CN114074927B (en) | 2020-08-18 | 2020-08-18 | Two-dimensional material, preparation method thereof and composite membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114074927A true CN114074927A (en) | 2022-02-22 |
| CN114074927B CN114074927B (en) | 2023-02-03 |
Family
ID=80281299
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010829668.2A Active CN114074927B (en) | 2020-08-18 | 2020-08-18 | Two-dimensional material, preparation method thereof and composite membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114074927B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114316376A (en) * | 2022-01-11 | 2022-04-12 | 陕西科技大学 | CNF/BNNS composite dispersion liquid, film and preparation method |
| CN114957805A (en) * | 2022-05-24 | 2022-08-30 | 南京林业大学 | Two-dimensional cellulose nano fluid channel membrane and preparation method and application thereof |
| CN115197513A (en) * | 2022-08-09 | 2022-10-18 | 清华大学深圳国际研究生院 | Composite doped with two-dimensional material and preparation method thereof |
| CN115321551A (en) * | 2022-07-29 | 2022-11-11 | 清华-伯克利深圳学院筹备办公室 | Intercalation method of clay material, two-dimensional material, preparation method and application thereof |
| CN115321599A (en) * | 2022-06-22 | 2022-11-11 | 佛山(华南)新材料研究院 | Preparation method of two-dimensional material nanosheet based on non-Newtonian fluid |
| CN115449133A (en) * | 2022-08-19 | 2022-12-09 | 清华大学深圳国际研究生院 | Composite gel and preparation method and application thereof |
| CN115678274A (en) * | 2022-10-26 | 2023-02-03 | 中国科学技术大学 | Shell-like polyimide-nano boron nitride insulating paper and preparation method thereof |
| CN115889141A (en) * | 2022-07-29 | 2023-04-04 | 武汉大学 | Method for improving insulation performance of metal/insulator by using two-dimensional material |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015036928A2 (en) * | 2013-09-10 | 2015-03-19 | Amrita Vishwa Vidyapeetham | Graphene exfoliation method |
| CN106698386A (en) * | 2015-08-18 | 2017-05-24 | 中国科学院上海微***与信息技术研究所 | Method for preparing graphene from graphite through HPLC (high performance liquid chromatography) stripping |
| CN108163847A (en) * | 2018-01-12 | 2018-06-15 | 昂星新型碳材料常州有限公司 | The preparation method of large stretch of diameter graphene and large stretch of diameter graphene |
| CN108793140A (en) * | 2018-07-10 | 2018-11-13 | 清华大学深圳研究生院 | A kind of high quality large scale two-dimensional material and preparation method thereof |
| CN110143586A (en) * | 2019-03-26 | 2019-08-20 | 上海烯望材料科技有限公司 | A kind of preparation method of the graphene of single layer or few layer |
| CN113247868A (en) * | 2021-04-14 | 2021-08-13 | 佛山市晟鹏科技有限公司 | Two-dimensional material and preparation method and application thereof |
-
2020
- 2020-08-18 CN CN202010829668.2A patent/CN114074927B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015036928A2 (en) * | 2013-09-10 | 2015-03-19 | Amrita Vishwa Vidyapeetham | Graphene exfoliation method |
| CN106698386A (en) * | 2015-08-18 | 2017-05-24 | 中国科学院上海微***与信息技术研究所 | Method for preparing graphene from graphite through HPLC (high performance liquid chromatography) stripping |
| CN108163847A (en) * | 2018-01-12 | 2018-06-15 | 昂星新型碳材料常州有限公司 | The preparation method of large stretch of diameter graphene and large stretch of diameter graphene |
| CN108793140A (en) * | 2018-07-10 | 2018-11-13 | 清华大学深圳研究生院 | A kind of high quality large scale two-dimensional material and preparation method thereof |
| CN110143586A (en) * | 2019-03-26 | 2019-08-20 | 上海烯望材料科技有限公司 | A kind of preparation method of the graphene of single layer or few layer |
| CN113247868A (en) * | 2021-04-14 | 2021-08-13 | 佛山市晟鹏科技有限公司 | Two-dimensional material and preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| YAGO CHAMOUN F.SOARES;ET AL.: "Influence of Oxidation Degree of Graphene Oxide on the shear Rheology of Poly(ethylene glycol) Suspensions", 《FLUIDS》 * |
| 任文才等: "石墨烯的化学气相沉积法制备", 《新型炭材料》 * |
| 邵姣婧等: "二维纳米材料的自上而下制备：可控液相剥离", 《新型炭材料》 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114316376A (en) * | 2022-01-11 | 2022-04-12 | 陕西科技大学 | CNF/BNNS composite dispersion liquid, film and preparation method |
| CN114316376B (en) * | 2022-01-11 | 2022-12-27 | 陕西科技大学 | CNF/BNNS composite dispersion liquid, film and preparation method |
| CN114957805A (en) * | 2022-05-24 | 2022-08-30 | 南京林业大学 | Two-dimensional cellulose nano fluid channel membrane and preparation method and application thereof |
| CN114957805B (en) * | 2022-05-24 | 2023-11-24 | 南京林业大学 | Two-dimensional cellulose nano fluid channel membrane and preparation method and application thereof |
| CN115321599A (en) * | 2022-06-22 | 2022-11-11 | 佛山(华南)新材料研究院 | Preparation method of two-dimensional material nanosheet based on non-Newtonian fluid |
| CN115321551A (en) * | 2022-07-29 | 2022-11-11 | 清华-伯克利深圳学院筹备办公室 | Intercalation method of clay material, two-dimensional material, preparation method and application thereof |
| CN115889141A (en) * | 2022-07-29 | 2023-04-04 | 武汉大学 | Method for improving insulation performance of metal/insulator by using two-dimensional material |
| CN115321551B (en) * | 2022-07-29 | 2023-12-05 | 清华-伯克利深圳学院筹备办公室 | Intercalation method of clay material, two-dimensional material, preparation method and application thereof |
| CN115889141B (en) * | 2022-07-29 | 2024-03-29 | 武汉大学 | Method for improving insulation performance of metal/insulator by using two-dimensional material |
| CN115197513A (en) * | 2022-08-09 | 2022-10-18 | 清华大学深圳国际研究生院 | Composite doped with two-dimensional material and preparation method thereof |
| CN115449133A (en) * | 2022-08-19 | 2022-12-09 | 清华大学深圳国际研究生院 | Composite gel and preparation method and application thereof |
| CN115678274A (en) * | 2022-10-26 | 2023-02-03 | 中国科学技术大学 | Shell-like polyimide-nano boron nitride insulating paper and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114074927B (en) | 2023-02-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114074927B (en) | Two-dimensional material, preparation method thereof and composite membrane | |
| Wang et al. | Highly thermal conductive, anisotropically heat-transferred, mechanically flexible composite film by assembly of boron nitride nanosheets for thermal management | |
| Wu et al. | Preparation of a thermally conductive biodegradable cellulose nanofiber/hydroxylated boron nitride nanosheet film: the critical role of edge-hydroxylation | |
| Norazlina et al. | Graphene modifications in polylactic acid nanocomposites: a review | |
| KR101666478B1 (en) | Preparation method of graphene and dispersed composition of graphene | |
| Ye et al. | Green fabrication of cellulose/graphene composite in ionic liquid and its electrochemical and photothermal properties | |
| KR101700355B1 (en) | Preparation method of carbon nanotube and dispersed composition of carbon nanotube | |
| CN110845870A (en) | Surface covalent grafting modified hexagonal boron nitride nanosheet and preparation method thereof | |
| WO2016002254A1 (en) | Graphite-type carbon material used as graphene precursor and method for producing same | |
| Rajasekar et al. | Electrostatically assembled layer-by-layer composites containing graphene oxide for enhanced hydrogen gas barrier application | |
| Wang et al. | Preparation and properties of poly (vinylidene fluoride) nanocomposites blended with graphene oxide coated silica hybrids. | |
| Huang et al. | Study on the PMMA/GO nanocomposites with good thermal stability prepared by in situ Pickering emulsion polymerization | |
| CN111232967A (en) | Preparation method of aminated graphene oxide | |
| CN110709447A (en) | Nanocomposite material comprising boron nitride nanoplates and method of making the same | |
| Tsou et al. | High-performance antibacterial nanocomposite films with a 3D network structure prepared from carboxylated graphene and modified polyvinyl alcohol | |
| CN103408895A (en) | Preparation method of graphene/epoxy resin composite material | |
| Cui et al. | Preparation of poly (propylene carbonate)/graphite nanoplates-spherical nanocrystal cellulose composite with improved glass transition temperature and electrical conductivity | |
| Gumel et al. | Carbon nanofibers-poly-3-hydroxyalkanoates nanocomposite: ultrasound-assisted dispersion and thermostructural properties | |
| Ou et al. | Highly mechanical nanostructured aramid-composites with gradient structures | |
| Liu et al. | High-yield, high-conductive graphene/nanocellulose hybrids prepared by Co-exfoliation of low-oxidized expanded graphite and microfibrillated cellulose | |
| CN108529609A (en) | A kind of graphene aqueous solution and preparation method thereof | |
| Hu et al. | Functionalized graphene nanosheets with fewer defects prepared via sodium alginate assisted direct exfoliation of graphite in aqueous media for lithium-ion batteries | |
| CN113247868B (en) | Two-dimensional material and preparation method and application thereof | |
| Yufei et al. | Characteristics and properties of TiO2/EP-PU composite | |
| Basavaraja et al. | Characterization and AC electrical conductivity for the dispersed composites containing alginate-multiwalled carbon nanotubes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |