CN114804042A - Hexagonal boron nitride nanosheet and preparation method thereof - Google Patents
Hexagonal boron nitride nanosheet and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of design materials, and relates to a hexagonal boron nitride nanosheet and a preparation method thereof. After oxidation treatment, hydrothermal reaction lithium ion intercalation pretreatment, ball milling, ultrasound, centrifugation and washing are carried out on hexagonal boron nitride powder, a large number of hexagonal boron nitride nanosheets below 3nm are stripped, meanwhile, the technical problem of kilogram-level batch production of hexagonal boron nitride nanosheets below 3nm in thickness is solved, the thickness of the prepared hexagonal boron nitride nanosheets is 2-3nm, and the transverse dimension is 0.5-1.5 mu m; when the hexagonal boron nitride nanosheet is stripped, the surface of the lamella of the hexagonal boron nitride nanosheet is functionalized, so that the dispersibility of the hexagonal boron nitride nanosheet in a solvent is greatly improved, and a favorable platform is provided for further surface functionalization. The preparation method of the hexagonal boron nitride nanosheet is simple, the operability is strong, and the yield of the hexagonal boron nitride nanosheet can reach 94%.
Description
Technical Field
The invention belongs to the field of design materials, and relates to a hexagonal boron nitride nanosheet and a preparation method thereof.
Background
Hexagonal boron nitride(hBN) is a graphite-like material of a layered structure in which C atoms are alternately substituted by B atoms and N atoms [2-4] . Hexagonal Boron Nitride Nanosheets (BNNS), also known as white graphene, with boron and nitrogen atoms arranged alternately in a hexagonal structure [5-7] As a novel substitute for graphene. The hexagonal boron nitride nanosheet not only has extremely high thermal conductivity (600-800W/(m.K)), but also has excellent insulating property (forbidden bandwidth of 6 eV) and low dielectric constant (3.9), and has extremely wide application in polymer matrix composite materials due to excellent adsorption performance, high thermal conductivity and ideal mechanical properties, and meanwhile, the hexagonal boron nitride nanosheet is researched in a plurality of fields such as electrocatalysts, hydrogen storage agents, adsorbents and field emitters.
The reported boron nitride synthesis methods can be divided into two types, bottom-up synthesis and top-down stripping. Bottom-up synthesis methods are mainly Chemical Vapor Deposition (CVD) and chemical blowing. In the top-down method, bulk hBN is stripped by mechanical force, hydrothermal reaction, gas, microplasma, supercritical fluid, steam, quadrupole field, etc. to form few-layer BNNS.
However, the above method has the following technical problems: (1) hexagonal boron nitride nanosheets below 3nm are difficult to strip in batches; (2) the batch production (kilogram level) of the hexagonal boron nitride nanosheets is difficult to realize.
In order to solve the problems, a preparation method which can strip a large amount of hexagonal boron nitride nanosheets with the thickness of less than 3nm, can regulate and control the thickness of the hexagonal boron nitride nanosheets and can realize batch production is urgently needed.
Disclosure of Invention
Aiming at the technical problems, the invention provides a hexagonal boron nitride nanosheet and a preparation method thereof. Solves the technical problems that a large amount of hexagonal boron nitride nanosheets below 3nm are difficult to strip and the mass production is difficult to realize in the prior art.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a preparation method of hexagonal boron nitride nanosheets comprises the following steps:
(1) oxidation treatment: calcining the hexagonal boron nitride powder in an air environment to obtain high-temperature hexagonal boron nitride powder;
(2) hydrothermal reaction: carrying out hydrothermal reaction on the high-temperature hexagonal boron nitride powder obtained in the step (1) and a mixed solution to obtain a first slurry;
(3) ball milling treatment: ball-milling the first slurry obtained in the step (2) to obtain a second slurry;
(4) ultrasonic treatment and centrifugal treatment: carrying out ultrasonic treatment and centrifugation on the second slurry obtained in the step (3) at least twice, and separating to obtain a precipitate containing hexagonal boron nitride nanosheets;
(5) washing: and (4) washing the precipitate obtained in the step (4) at least twice, and drying to obtain the hexagonal boron nitride nanosheet.
Further, the lateral dimension of the hexagonal boron nitride powder in the step (1) is less than or equal to 20 μm, and the thickness is 100-1000 nm.
Further, the calcination temperature in the step (1) is 400-1000 ℃, and the calcination time is 0.1-2 h.
Further, the calcination temperature in the step (1) is 800-1000 ℃, and the calcination time is 0.5-1.5 h.
Further, the calcining temperature in the step (1) is 800 ℃, and the calcining time is 1 h.
Further, the temperature of the hydrothermal reaction in the step (2) is 180 ℃, the time of the hydrothermal reaction is 0.5-2h, and the stirring speed is 500 rpm.
Further, the hydrothermal reaction time in the step (2) is 0.5-1.5 h.
Further, the mixed solution in the step (2) is an aqueous solution of an alkaline substance and a salt, wherein the alkaline substance comprises sodium hydroxide, the salt comprises lithium chloride, and the mass ratio of the alkaline substance to the salt is 1: (0.5-2), wherein the concentration of the alkaline substance and the salt is 1% of that of the water solvent, and the mass volume concentration of the hexagonal boron nitride powder is 10-30 mg/mL.
Preferably, the mass ratio of the alkaline substance to the salt in the step (2) is 2: 1.
Further, the ball milling in the step (3) is zirconia ball milling, the diameters of the zirconia balls are 2-10mm and 0.2-1mm, and the adding mass of the zirconia balls with the diameters of 2-10mm and 0.2-1mm is 1: 1.
Further, the addition mass of the ball milling is more than or less than 1:1, which can affect the stripping effect, and the addition mass of the ball milling is more than 1:1, which can cause the transverse size of the stripped boron nitride nanosheet to be smaller; ball milling with an addition mass of less than 1:1 resulted in insufficient exfoliation and lower yields.
Further, the rotation speed of ball milling in the step (3) is 200-.
Preferably, the rotation speed of the ball milling in the step (3) is 800-.
Preferably, the rotation speed of the ball mill in the step (3) is 1000 rpm.
Further, the power of the ultrasonic treatment in the step (4) is 100W-600W, and the time of the ultrasonic treatment is 0.5-1 h.
Preferably, the work of the ultrasonic treatment in the step (4) is 250W, and the time of the ultrasonic treatment is 0.5 h.
Further, the rotation speed of the centrifugation in the step (4) is 800-.
Preferably, the centrifugation time in the step (4) is 10-30 min.
Further, the washing solvent in the step (5) is deionized water, and the drying time is 4 h.
Further, after separating the supernatant in the centrifugation step, pouring the same amount of water for next ultrasonic stripping, and performing reciprocating circulation at least twice.
Preferably, the sonication, centrifugation, washing steps are repeated 3-5 times.
Furthermore, the thickness of the hexagonal boron nitride nanosheet prepared by the method is 2-3nm, the transverse size is 0.5-1.5 microns, and hydroxyl groups are modified on the surface of the hexagonal boron nitride nanosheet.
The invention has the following beneficial effects:
1. according to the invention, firstly, hydrothermal reaction lithium ion intercalation is used for pretreating hexagonal boron nitride powder, and then the pretreated boron nitride powder is subjected to ball milling treatment in an alkaline solution, so that higher yield of hexagonal Boron Nitride Nanosheets (BNNS) can be obtained in a shorter time, a large amount of hexagonal boron nitride nanosheets with the size of less than 3nm are obtained, the transverse size of the hexagonal boron nitride nanosheets is 0.5-1.5 mu m, the thickness of the hexagonal boron nitride nanosheets is 2-3nm, and the yield can reach 94%.
2. The method is used for stripping the hexagonal Boron Nitride Nanosheet (BNNS) and simultaneously functionalizing the surface of the lamella of the BNNS, so that the dispersibility of the BNNS in a solvent is greatly improved. The obtained hexagonal boron nitride nanosheet is ultrasonically dispersed in deionized water again, and does not have obvious sedimentation after standing for 16 hours, so that the stability is high, and the dispersibility is good. An advantageous platform is provided for further surface functionalization.
3. The method has the advantages of simple operation steps, strong operability, cheap and easily-obtained treatment raw materials, low toxicity to the environment, realization of batch production, obtainment of the hexagonal boron nitride nanosheet with good performance and great reduction of the production cost.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is an SEM result of hexagonal boron nitride nanosheets obtained in example 1 of the present invention.
FIG. 2 shows AFM results of hexagonal boron nitride nanosheets obtained in example 1 of the present invention.
Fig. 3 shows TEM results of hexagonal boron nitride nanosheets obtained in example 1 of the present invention.
FIG. 4 is the FTIR results for hexagonal boron nitride powder (hBN) as the starting material in example 1 of the present invention and after treatment at high temperature 800 deg.C (hBN-800 deg.C) and the hexagonal Boron Nitride Nanoparticles (BNNS) obtained in example 1.
Fig. 5 shows the dispersibility test result of the hexagonal boron nitride nanosheet obtained in example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Through long-term and intensive research, the inventor can efficiently prepare the hexagonal boron nitride nanosheet in a short time by adopting high-temperature oxidation intercalation pretreatment and combining hydrothermal reaction, a ball milling technology and an ultrasonic stripping technology. On this basis, the inventors have completed the present invention.
Term(s) for
As used herein, the term "high temperature oxidative intercalation" refers to the high temperature treatment of oxygen intercalation, typically at 800-.
As used herein, the term "ultrasonic exfoliation" means that the exfoliation is achieved by ultrasonic treatment.
Example 1
The embodiment is a preparation method of a hexagonal boron nitride nanosheet, and the steps are as follows:
(1) weighing a certain amount of hexagonal boron nitride powder (with the particle size of 10-20 mu m), pouring into a crucible, and calcining for 1h at 800 ℃ in an air environment.
(2) 20g of calcined hexagonal boron nitride powder, 6.67g of sodium hydroxide, 3.37g of lithium chloride and 1000mL of deionized water are weighed and uniformly stirred to form a mixed solution.
(3) The mixed solution was transferred to an autoclave having a tetrafluoroethylene liner, followed by reaction at 180 ℃ and a stirring speed of 500rpm for 2 hours and then naturally cooled to room temperature.
(4) And transferring the reaction product in the reaction kettle to a ball milling tank, and adding an equal amount of zirconia balls (2 mm:0.2mm =1: 1), wherein the ball milling time is 5h, and the ball milling rotating speed is 500 rpm.
(5) Dispersing the ball-milled slurry in deionized water, carrying out 250W ultrasonic stripping on the obtained mixed solution for 30min, centrifuging the obtained mixture after the ultrasonic stripping is finished (the centrifugal rotation speed is 3000rpm, and the centrifugal time is 10 min), and slowly pouring out the supernatant.
(6) And dispersing the centrifuged precipitate in deionized water again, carrying out 250W ultrasonic stripping on the obtained mixed solution for 30min, centrifuging the obtained mixture after the ultrasonic treatment is finished (the centrifugal rotation speed is 3000rpm, and the centrifugal time is 10 min), slowly pouring out the supernatant, and repeating the steps twice.
(7) The collected supernatant was filtered (filter pore size: 0.1 μm), washed repeatedly with deionized water at room temperature to wash the base and salts (e.g., sodium hydroxide and lithium chloride) clean, and the resulting product was freeze-dried.
Fig. 1 shows SEM results of hexagonal boron nitride nanosheets obtained in this example. FIG. 2 shows AFM results of hexagonal boron nitride nanosheets obtained in this example. As can be seen from fig. 1 and 2: the size of the obtained hexagonal boron nitride nanosheet is 0.5-1.5um, and the thickness is about 2-3 nm.
Fig. 3 shows TEM results of hexagonal boron nitride nanosheets obtained in this example. As can be seen from fig. 3: hexagonal boron nitride powder has been successfully exfoliated into hexagonal boron nitride nanoplates.
FIG. 4 shows FTIR results for hexagonal boron nitride powder (hBN) as a starting material and treated at 800 deg.C (hBN-800 deg.C) and hexagonal Boron Nitride Nanoparticles (BNNS) obtained in example 1. As can be seen from fig. 4: the surface of the obtained hexagonal boron nitride nanosheet is modified with hydroxyl.
Fig. 5 shows the dispersion test result of the hexagonal boron nitride nanosheets obtained in this example. As can be seen from fig. 5: and ultrasonically dispersing the obtained hexagonal boron nitride nanosheet in deionized water again, and standing for 16 hours without obvious sedimentation.
The test method of hexagonal boron nitride nanosheets prepared in example 1 was compared to other prior art methods, and the concentrations and yields are shown in table 1, where the yield values in the present invention are the average of the yields in the examples of the present invention. The references are given below.
TABLE 1 yield and concentration of BNNS obtained by different stripping methods
The yield and the size of the hexagonal boron nitride nanosheets prepared by the present invention are summarized as shown in table 2, wherein H in H-1% B-BNNS represents hydrothermal method, B represents ball milling, and 1% represents the concentration of sodium hydroxide and lithium chloride of 1%.
TABLE 2 yield and size of inventive samples
Example 2
The difference from example 1 is that: the addition amounts of sodium hydroxide and lithium chloride in step (2) were 5g and 5g, respectively.
The embodiment is a preparation method of a hexagonal boron nitride nanosheet, and the steps are as follows:
(1) weighing a certain amount of hexagonal boron nitride powder (with the particle size of 10-20 mu m), pouring into a crucible, and calcining for 1h at 800 ℃ in an air environment.
(2) Weighing 20g of calcined hexagonal boron nitride powder, 5g of sodium hydroxide, 5g of lithium chloride and 1000mL of deionized water, and uniformly stirring to obtain a mixed solution.
(3) The mixed solution was transferred to an autoclave having a tetrafluoroethylene liner, followed by reaction at 180 ℃ and a stirring speed of 500rpm for 2 hours and then naturally cooled to room temperature.
(4) And transferring the reaction product in the reaction kettle to a ball milling tank, and adding an equal amount of zirconia balls (2 mm:0.2mm =1: 1), wherein the ball milling time is 5h, and the ball milling rotating speed is 500 rpm.
(5) Dispersing the ball-milled slurry in deionized water, carrying out 250W ultrasonic stripping on the obtained mixed solution for 30min, centrifuging the obtained mixture after the ultrasonic stripping is finished (the centrifugal rotation speed is 3000rpm, and the centrifugal time is 10 min), and slowly pouring out the supernatant.
(6) And dispersing the centrifuged precipitate in deionized water again, carrying out 250W ultrasonic stripping on the obtained mixed solution for 30min, centrifuging the obtained mixture after the ultrasonic treatment is finished (the centrifugal rotation speed is 3000rpm, and the centrifugal time is 10 min), slowly pouring out the supernatant, and repeating the steps twice.
(7) The collected supernatant was filtered (filter pore size: 0.1 μm), washed repeatedly with deionized water at room temperature to wash the base and salts (e.g., sodium hydroxide and lithium chloride) clean, and the resulting product was freeze-dried.
Example 3
The difference from example 1 is that: in step (2), the amounts of sodium hydroxide and lithium chloride added were 3.34g and 6.67g, respectively.
The embodiment is a preparation method of a hexagonal boron nitride nanosheet, and the steps are as follows:
(1) weighing a certain amount of hexagonal boron nitride powder (with the particle size of 10-20 mu m), pouring into a crucible, and calcining for 1h at 800 ℃ in an air environment.
(2) 20g of calcined hexagonal boron nitride powder, 3.34g of sodium hydroxide, 6.67g of lithium chloride and 1000mL of deionized water are weighed and uniformly stirred to form a mixed solution.
(3) The mixed solution was transferred to an autoclave having a tetrafluoroethylene liner, followed by reaction at 180 ℃ and a stirring speed of 500rpm for 2 hours and then naturally cooled to room temperature.
(4) And transferring the reaction product in the reaction kettle to a ball milling tank, and adding an equal amount of zirconia balls (2 mm:0.2mm =1: 1), wherein the ball milling time is 5h, and the ball milling rotating speed is 500 rpm.
(5) Dispersing the ball-milled slurry in deionized water, carrying out 250W ultrasonic stripping on the obtained mixed solution for 30min, centrifuging the obtained mixture after the ultrasonic stripping is finished (the centrifugal rotation speed is 3000rpm, and the centrifugal time is 10 min), and slowly pouring out the supernatant.
(6) And dispersing the centrifuged precipitate in deionized water again, carrying out 250W ultrasonic stripping on the obtained mixed solution for 30min, centrifuging the obtained mixture after the ultrasonic treatment is finished (the centrifugal rotation speed is 3000rpm, and the centrifugal time is 10 min), slowly pouring out the supernatant, and repeating the steps twice.
(7) The collected supernatant was filtered (filter pore size: 0.1 μm), washed repeatedly with deionized water at room temperature to wash the base and salts (e.g., sodium hydroxide and lithium chloride) clean, and the resulting product was freeze-dried.
Example 4
The difference from example 1 is that: the high-temperature oxidation temperature in the step (1) is 400 ℃.
The embodiment is a preparation method of a hexagonal boron nitride nanosheet, and the steps are as follows:
(1) weighing a certain amount of hexagonal boron nitride powder (with the particle size of 10-20 mu m), pouring into a crucible, and calcining for 1h at 400 ℃ in an air environment.
(2) 20g of calcined hexagonal boron nitride powder, 6.67g of sodium hydroxide, 3.37g of lithium chloride and 1000mL of deionized water are weighed and uniformly stirred to form a mixed solution.
(3) The mixed solution was transferred to an autoclave having a tetrafluoroethylene liner, followed by reaction at 180 ℃ and a stirring speed of 500rpm for 2 hours and then naturally cooled to room temperature.
(4) And transferring the reaction product in the reaction kettle to a ball milling tank, and adding an equal amount of zirconia balls (2 mm:0.2mm =1: 1), wherein the ball milling time is 5h, and the ball milling rotating speed is 500 rpm.
(5) Dispersing the ball-milled slurry in deionized water, carrying out 250W ultrasonic stripping on the obtained mixed solution for 30min, centrifuging the obtained mixture after the ultrasonic stripping is finished (the centrifugal rotation speed is 3000rpm, and the centrifugal time is 10 min), and slowly pouring out the supernatant.
(6) And dispersing the centrifuged precipitate in deionized water again, carrying out 250W ultrasonic stripping on the obtained mixed solution for 30min, centrifuging the obtained mixture after the ultrasonic treatment is finished (the centrifugal rotation speed is 3000rpm, and the centrifugal time is 10 min), slowly pouring out the supernatant, and repeating the steps twice.
(7) The collected supernatant was filtered (filter pore size: 0.1 μm), washed repeatedly with deionized water at room temperature to wash the base and salts (e.g., sodium hydroxide and lithium chloride) clean, and the resulting product was freeze-dried.
Example 5
The difference from example 1 is that: the high-temperature oxidation temperature in the step (1) is 1000 ℃.
The embodiment is a preparation method of a hexagonal boron nitride nanosheet, and the steps are as follows:
(1) weighing a certain amount of hexagonal boron nitride powder (with the particle size of 10-20 mu m), pouring the hexagonal boron nitride powder into a crucible, and calcining for 1h at 1000 ℃ in an air environment.
(2) 20g of calcined hexagonal boron nitride powder, 6.67g of sodium hydroxide, 3.37g of lithium chloride and 1000mL of deionized water are weighed and uniformly stirred to form a mixed solution.
(3) The mixed solution was transferred to an autoclave having a tetrafluoroethylene liner, followed by reaction at 180 ℃ and a stirring speed of 500rpm for 2 hours and then naturally cooled to room temperature.
(4) And transferring the reaction product in the reaction kettle to a ball milling tank, and adding an equal amount of zirconia balls (2 mm:0.2mm =1: 1), wherein the ball milling time is 5h, and the ball milling rotating speed is 500 rpm.
(5) Dispersing the ball-milled slurry in deionized water, carrying out 250W ultrasonic stripping on the obtained mixed solution for 30min, centrifuging the obtained mixture after the ultrasonic stripping is finished (the centrifugal rotation speed is 3000rpm, and the centrifugal time is 10 min), and slowly pouring out the supernatant.
(6) And dispersing the centrifuged precipitate in deionized water again, carrying out 250W ultrasonic stripping on the obtained mixed solution for 30min, centrifuging the obtained mixture after the ultrasonic treatment is finished (the centrifugal rotation speed is 3000rpm, and the centrifugal time is 10 min), slowly pouring out the supernatant, and repeating the steps twice.
(7) The collected supernatant was filtered (filter pore size: 0.1 μm), washed repeatedly with deionized water at room temperature to wash the base and salts (e.g., sodium hydroxide and lithium chloride) clean, and the resulting product was freeze-dried.
Example 6
The difference from example 1 is that: the addition amount of the hexagonal boron nitride powder in the step (2) is 10 g.
The embodiment is a preparation method of a hexagonal boron nitride nanosheet, and the steps are as follows:
(1) weighing a certain amount of hexagonal boron nitride powder (with the particle size of 10-20 mu m), pouring into a crucible, and calcining for 1h at 800 ℃ in an air environment.
(2) 10g of calcined hexagonal boron nitride powder, 6.67g of sodium hydroxide, 3.37g of lithium chloride and 1000mL of deionized water are weighed and uniformly stirred to form a mixed solution.
(3) The mixed solution was transferred to an autoclave having a tetrafluoroethylene liner, followed by reaction at 180 ℃ and a stirring speed of 500rpm for 2 hours and then naturally cooled to room temperature.
(4) And transferring the reaction product in the reaction kettle to a ball milling tank, and adding an equal amount of zirconia balls (2 mm:0.2mm =1: 1), wherein the ball milling time is 5h, and the ball milling rotating speed is 500 rpm.
(5) Dispersing the slurry after ball milling in deionized water, carrying out 250W ultrasonic stripping on the obtained mixed solution for 30min, centrifuging the obtained mixture after the ultrasonic stripping is finished (the centrifugal speed is 3000rpm, and the centrifugal time is 10 min), and slowly pouring out the supernatant.
(6) And dispersing the centrifuged precipitate in deionized water again, carrying out 250W ultrasonic stripping on the obtained mixed solution for 30min, centrifuging the obtained mixture after the ultrasonic treatment is finished (the centrifugal rotation speed is 3000rpm, and the centrifugal time is 10 min), slowly pouring out the supernatant, and repeating the steps twice.
(7) The collected supernatant was filtered (filter pore size: 0.1 μm), washed repeatedly with deionized water at room temperature to wash the base and salts (e.g., sodium hydroxide and lithium chloride) clean, and the resulting product was freeze-dried.
Example 7
The difference from example 1 is that: the reaction time in step (3) is 1 h.
The embodiment is a preparation method of a hexagonal boron nitride nanosheet, and the steps are as follows:
(1) weighing a certain amount of hexagonal boron nitride powder (with the particle size of 10-20 mu m), pouring into a crucible, and calcining for 1h at 800 ℃ in an air environment.
(2) 20g of calcined hexagonal boron nitride powder, 6.67g of sodium hydroxide, 3.37g of lithium chloride and 1000mL of deionized water are weighed and uniformly stirred to form a mixed solution.
(3) The mixed solution was transferred to an autoclave having a tetrafluoroethylene liner, followed by reaction at 180 ℃ and a stirring speed of 500rpm for 1 hour and then naturally cooled to room temperature.
(4) And transferring the reaction product in the reaction kettle to a ball milling tank, and adding an equal amount of zirconia balls (2 mm:0.2mm =1: 1), wherein the ball milling time is 5h, and the ball milling rotating speed is 500 rpm.
(5) Dispersing the ball-milled slurry in deionized water, carrying out 250W ultrasonic stripping on the obtained mixed solution for 30min, centrifuging the obtained mixture after the ultrasonic stripping is finished (the centrifugal rotation speed is 3000rpm, and the centrifugal time is 10 min), and slowly pouring out the supernatant.
(6) And dispersing the centrifuged precipitate in deionized water again, carrying out 250W ultrasonic stripping on the obtained mixed solution for 30min, centrifuging the obtained mixture after the ultrasonic treatment is finished (the centrifugal rotation speed is 3000rpm, and the centrifugal time is 30 min), slowly pouring out the supernatant, and repeating the steps twice.
(7) The collected supernatant was filtered (filter pore size: 0.1 μm), washed repeatedly with deionized water at room temperature to wash the base and salts (e.g., sodium hydroxide and lithium chloride) clean, and the resulting product was freeze-dried.
Example 8
The difference from example 1 is that: the reaction time in step (3) was 0.5 h.
The embodiment is a preparation method of a hexagonal boron nitride nanosheet, and the steps are as follows:
(1) weighing a certain amount of hexagonal boron nitride powder (with the particle size of 10-20 mu m), pouring into a crucible, and calcining for 1h at 800 ℃ in an air environment.
(2) 20g of calcined hexagonal boron nitride powder, 6.67g of sodium hydroxide, 3.37g of lithium chloride and 1000mL of deionized water are weighed and uniformly stirred to form a mixed solution.
(3) The mixed solution was transferred to an autoclave having a tetrafluoroethylene liner, followed by reaction at 180 ℃ and a stirring speed of 500rpm for 0.5h and then naturally cooled to room temperature.
(4) And transferring the reaction product in the reaction kettle to a ball milling tank, and adding an equal amount of zirconia balls (2 mm:0.2mm =1: 1), wherein the ball milling time is 0.5h, and the ball milling rotating speed is 500 rpm.
(5) Dispersing the ball-milled slurry in deionized water, carrying out 250W ultrasonic stripping on the obtained mixed solution for 30min, centrifuging the obtained mixture after the ultrasonic stripping is finished (the centrifugal rotation speed is 3000rpm, and the centrifugal time is 10 min), and slowly pouring out the supernatant.
(6) And dispersing the centrifuged precipitate in deionized water again, carrying out 250W ultrasonic stripping on the obtained mixed solution for 30min, centrifuging the obtained mixture after the ultrasonic treatment is finished (the centrifugal rotation speed is 3000rpm, and the centrifugal time is 10 min), slowly pouring out the supernatant, and repeating the steps twice.
(7) The collected supernatant was filtered (filter pore size: 0.1 μm), washed repeatedly with deionized water at room temperature to wash the base and salts (e.g., sodium hydroxide and lithium chloride) clean, and the resulting product was freeze-dried.
Example 9
The difference from example 1 is that: the ball milling time in the step (4) is 2 hours.
The embodiment is a preparation method of a hexagonal boron nitride nanosheet, and the steps are as follows:
(1) weighing a certain amount of hexagonal boron nitride powder (with the particle size of 10-20 mu m), pouring into a crucible, and calcining for 1h at 800 ℃ in an air environment.
(2) 20g of calcined hexagonal boron nitride powder, 6.67g of sodium hydroxide, 3.37g of lithium chloride and 1000mL of deionized water are weighed and uniformly stirred to form a mixed solution.
(3) The mixed solution was transferred to an autoclave having a tetrafluoroethylene liner, followed by reaction at 180 ℃ and a stirring speed of 500rpm for 2 hours and then naturally cooled to room temperature.
(4) And transferring the reaction product in the reaction kettle to a ball milling tank, and adding the same amount of zirconia balls (2 mm:0.2mm =1: 1), wherein the ball milling time is 2h, and the ball milling rotating speed is 500 rpm.
(5) Dispersing the ball-milled slurry in deionized water, carrying out 250W ultrasonic stripping on the obtained mixed solution for 30min, centrifuging the obtained mixture after the ultrasonic stripping is finished (the centrifugal rotation speed is 3000rpm, and the centrifugal time is 10 min), and slowly pouring out the supernatant.
(6) And dispersing the centrifuged precipitate in deionized water again, carrying out 250W ultrasonic stripping on the obtained mixed solution for 30min, centrifuging the obtained mixture after the ultrasonic treatment is finished (the centrifugal rotation speed is 3000rpm, and the centrifugal time is 10 min), slowly pouring out the supernatant, and repeating the steps twice.
(7) The collected supernatant was filtered (filter pore size: 0.1 μm), washed repeatedly with deionized water at room temperature to wash the base and salts (e.g., sodium hydroxide and lithium chloride) clean, and the resulting product was freeze-dried.
Example 10
The difference from example 1 is that: the ball milling time in the step (4) is 1 h.
The embodiment is a preparation method of a hexagonal boron nitride nanosheet, and the steps are as follows:
(1) weighing a certain amount of hexagonal boron nitride powder (with the particle size of 10-20 mu m), pouring into a crucible, and calcining for 1h at 800 ℃ in an air environment.
(2) 20g of calcined hexagonal boron nitride powder, 6.67g of sodium hydroxide, 3.37g of lithium chloride and 1000mL of deionized water are weighed and uniformly stirred to form a mixed solution.
(3) The mixed solution was transferred to an autoclave having a tetrafluoroethylene liner, followed by reaction at 180 ℃ and a stirring speed of 500rpm for 2 hours and then naturally cooled to room temperature.
(4) And transferring the reaction product in the reaction kettle to a ball milling tank, and adding the same amount of zirconia balls (2 mm:0.2mm =1: 1), wherein the ball milling time is 1h, and the ball milling rotating speed is 500 rpm.
(5) Dispersing the ball-milled slurry in deionized water, carrying out 250W ultrasonic stripping on the obtained mixed solution for 30min, centrifuging the obtained mixture after the ultrasonic stripping is finished (the centrifugal rotation speed is 3000rpm, and the centrifugal time is 10 min), and slowly pouring out the supernatant.
(6) And dispersing the centrifuged precipitate in deionized water again, carrying out 250W ultrasonic stripping on the obtained mixed solution for 30min, centrifuging the obtained mixture after the ultrasonic treatment is finished (the centrifugal rotation speed is 3000rpm, and the centrifugal time is 10 min), slowly pouring out the supernatant, and repeating the steps twice.
(7) The collected supernatant was filtered (filter pore size: 0.1 μm), washed repeatedly with deionized water at room temperature to wash the base and salts (e.g., sodium hydroxide and lithium chloride) clean, and the resulting product was freeze-dried.
Example 11
The difference from example 1 is that: the centrifugation speed in step (5) was 800 rpm.
The embodiment is a preparation method of a hexagonal boron nitride nanosheet, and the steps are as follows:
(1) weighing a certain amount of hexagonal boron nitride powder (with the particle size of 10-20 mu m), pouring into a crucible, and calcining for 1h at 800 ℃ in an air environment.
(2) 20g of calcined hexagonal boron nitride powder, 6.67g of sodium hydroxide, 3.37g of lithium chloride and 1000mL of deionized water are weighed and uniformly stirred to form a mixed solution.
(3) The mixed solution was transferred to an autoclave having a tetrafluoroethylene liner, followed by reaction at 180 ℃ and a stirring speed of 500rpm for 2 hours and then naturally cooled to room temperature.
(4) And transferring the reaction product in the reaction kettle to a ball milling tank, and adding an equal amount of zirconia balls (2 mm:0.2mm =1: 1), wherein the ball milling time is 5h, and the ball milling rotating speed is 500 rpm.
(5) Dispersing the ball-milled slurry in deionized water, carrying out 250W ultrasonic stripping on the obtained mixed solution for 30min, centrifuging the obtained mixture after the ultrasonic stripping is finished (the centrifugal rotation speed is 800rpm, and the centrifugal time is 10 min), and slowly pouring out the supernatant.
(6) And dispersing the centrifuged precipitate in deionized water again, carrying out 250W ultrasonic stripping on the obtained mixed solution for 30min, centrifuging the obtained mixture after the ultrasonic treatment is finished (the centrifugal rotation speed is 3000rpm, and the centrifugal time is 10 min), slowly pouring out the supernatant, and repeating the steps twice.
(7) The collected supernatant was filtered (filter pore size: 0.1 μm), washed repeatedly with deionized water at room temperature to wash the base and salts (e.g., sodium hydroxide and lithium chloride) clean, and the resulting product was freeze-dried.
Example 12
The difference from example 1 is that: the centrifugation speed in step (5) was 1000 rpm.
The embodiment is a preparation method of a hexagonal boron nitride nanosheet, and the steps are as follows:
(1) weighing a certain amount of hexagonal boron nitride powder (with the particle size of 10-20 mu m), pouring into a crucible, and calcining for 1h at 800 ℃ in an air environment.
(2) 20g of calcined hexagonal boron nitride powder, 6.67g of sodium hydroxide, 3.37g of lithium chloride and 1000mL of deionized water are weighed and uniformly stirred to form a mixed solution.
(3) The mixed solution was transferred to an autoclave having a tetrafluoroethylene liner, followed by reaction at 180 ℃ and a stirring speed of 500rpm for 2 hours and then naturally cooled to room temperature.
(4) And transferring the reaction product in the reaction kettle to a ball milling tank, and adding an equal amount of zirconia balls (2 mm:0.2mm =1: 1), wherein the ball milling time is 5h, and the ball milling rotating speed is 500 rpm.
(5) Dispersing the ball-milled slurry in deionized water, carrying out 250W ultrasonic stripping on the obtained mixed solution for 30min, centrifuging the obtained mixture after the ultrasonic stripping is finished (the centrifugal rotation speed is 1000rpm, and the centrifugal time is 10 min), and slowly pouring out the supernatant.
(6) And dispersing the centrifuged precipitate in deionized water again, carrying out 250W ultrasonic stripping on the obtained mixed solution for 30min, centrifuging the obtained mixture after the ultrasonic treatment is finished (the centrifugal rotation speed is 3000rpm, and the centrifugal time is 10 min), slowly pouring out the supernatant, and repeating the steps twice.
(7) The collected supernatant was filtered (filter pore size: 0.1 μm), washed repeatedly with deionized water at room temperature to wash the base and salts (e.g., sodium hydroxide and lithium chloride) clean, and the resulting product was freeze-dried.
Example 13
The difference from example 1 is that: the centrifugation time in step (5) was 30 min.
The embodiment is a preparation method of a hexagonal boron nitride nanosheet, and the steps are as follows:
(1) weighing a certain amount of hexagonal boron nitride powder (with the particle size of 10-20 mu m), pouring into a crucible, and calcining for 1h at 800 ℃ in an air environment.
(2) 20g of calcined hexagonal boron nitride powder, 6.67g of sodium hydroxide, 3.37g of lithium chloride and 1000mL of deionized water are weighed and uniformly stirred to form a mixed solution.
(3) The mixed solution was transferred to an autoclave having a tetrafluoroethylene liner, followed by reaction at 180 ℃ and a stirring speed of 500rpm for 2 hours and then naturally cooled to room temperature.
(4) The reaction product in the reaction kettle is transferred to a ball milling tank, and an equal amount of zirconia balls (2 mm:0.2mm =1: 1) are added, wherein the ball milling time is 5 h.
(5) Dispersing the ball-milled slurry in deionized water, carrying out 250W ultrasonic stripping on the obtained mixed solution for 30min, centrifuging the obtained mixture after the ultrasonic stripping is finished (the centrifugal rotation speed is 3000rpm, and the centrifugal time is 30 min), and slowly pouring out the supernatant.
(6) And dispersing the centrifuged precipitate in deionized water again, carrying out 250W ultrasonic stripping on the obtained mixed solution for 30min, centrifuging the obtained mixture after the ultrasonic treatment is finished (the centrifugal rotation speed is 3000rpm, and the centrifugal time is 30 min), slowly pouring out the supernatant, and repeating the steps twice.
(7) The collected supernatant was filtered (filter pore size: 0.1 μm), washed repeatedly with deionized water at room temperature to wash the base and salts (e.g., sodium hydroxide and lithium chloride) clean, and the resulting product was freeze-dried.
Reference to the literature
[1] Zhao. HR, Ding. JH, Shao. ZZ, Xu. BY, Zhou. QB, Yu. HB. High-Quality Boron Nitride Nanosheets and Their Bioinspired Thermally Conductive Papers. 11Acs Applied Materials & Interfaces. （2019）37247-37255. https://10.1021/acsami.9b11180.
[2] Wang. N, Yang. G, Wang. HX, Yan. CZ, Sun. R, Wong. CP. A universal method for large-yield and high-concentration exfoliation of two-dimensional hexagonal boron nitride nanosheets. 27Materials Today. （2019）33-42.https://10.1016/j.mattod.2018.10.039.
[3] Ding. JH, Zhao. HR, Yu. HB. High-yield synthesis of extremely high concentrated and few-layered boron nitride nanosheet dispersions. 52D Materials. （2018）. https://10.1088/2053-1583/aad51a.
[4] Sun. ZM, Lin. L, Yuan. MW, Li. HF, Sun. GB, Ma. SL, Yang. XJ. High-purity production of ultrathin boron nitride nanosheets via shock chilling and their enhanced mechanical performance and transparency in nanocomposite hydrogels. 29Nanotechnology. （2018）. https://10.1088/1361-6528/aab503.
[5] Wang. Y, Mayorga-Martinez. CC, Chia. XY, Sofer. Z, Pumera. M. Nonconductive layered hexagonal boron nitride exfoliation by bipolar electrochemistry. 10Nanoscale. （2018）7298-7303. https://10.1039/c8nr00082d.
[6] Ding. JH, Zhao. HR, Zheng. Y, Wang. QL, Chen. H, Dou. HM, Yu. HB. Efficient exfoliation of layered materials by waste liquor. 29Nanotechnology. （2018）. https://10.1088/1361-6528/aaa05f.
[7] Kovtyukhova. NI, Perea-Lopez. N, Terrones. M, Mallouk. TE. Atomically Thin Layers of Graphene and Hexagonal Boron Nitride Made by Solvent Exfoliation of Their Phosphoric Acid Intercalation Compounds. 11Acs Nano. （2017）6746-6754. https://10.1021/acsnano.7b01311.
[8] Li. XL, Hao. XP, Zhao. MW, Wu. YZ, Yang. JX, Tian. YP, Qian. GD. Exfoliation of Hexagonal Boron Nitride by Molten Hydroxides. 25Advanced Materials. （2013）2200-2204. https://10.1002/adma.201204031.
[9] Wang. Y, Shi. ZX, Yin. J. Boron nitride nanosheets: large-scale exfoliation in methanesulfonic acid and their composites with polybenzimidazole. 21Journal Of Materials Chemistry. （2011）11371-11377. https://10.1039/c1jm10342c.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A preparation method of hexagonal boron nitride nanosheets is characterized by comprising the following steps:
(1) oxidation treatment: calcining the hexagonal boron nitride powder in an air environment to obtain high-temperature hexagonal boron nitride powder;
(2) hydrothermal reaction: carrying out hydrothermal reaction on the high-temperature hexagonal boron nitride powder obtained in the step (1) and a mixed solution to obtain a first slurry;
(3) ball milling treatment: ball-milling the first slurry obtained in the step (2) to obtain a second slurry;
(4) ultrasonic treatment and centrifugal treatment: carrying out ultrasonic treatment and centrifugation on the second slurry obtained in the step (3) at least twice, and separating to obtain a precipitate containing hexagonal boron nitride nanosheets;
(5) washing: and (4) washing the precipitate obtained in the step (4) at least twice, and drying to obtain the hexagonal boron nitride nanosheet.
2. A method of preparing hexagonal boron nitride nanoplates as defined in claim 1, wherein: in the step (1), the lateral size of the hexagonal boron nitride powder is less than or equal to 20 microns, and the thickness is 100-1000 nm.
3. A method of preparing hexagonal boron nitride nanoplates as defined in claim 2, wherein: the calcination temperature in the step (1) is 400-1000 ℃, and the calcination time is 0.1-2 h.
4. A method of preparing hexagonal boron nitride nanoplates as defined in claim 3, wherein: the temperature of the hydrothermal reaction in the step (2) is 180 ℃, and the time of the hydrothermal reaction is 0.5-2 h.
5. A method of preparing hexagonal boron nitride nanosheets according to claim 4, wherein: the mixed solution in the step (2) is an aqueous solution of an alkaline substance and salt, wherein the alkaline substance comprises sodium hydroxide, the salt comprises lithium chloride, and the mass ratio of the alkaline substance to the salt is 1: (0.5-2), wherein the concentration of the alkaline substance and the salt is 1% of that of the water solvent, and the mass volume concentration of the hexagonal boron nitride powder is 10-30 mg/mL.
6. A method of preparing hexagonal boron nitride nanoplates as defined in claim 5, wherein: the ball milling in the step (3) is zirconia ball milling, the diameters of the zirconia balls are 2-10mm and 0.2-1mm, the adding mass of the zirconia balls with the diameters of 2-10mm and 0.2-1mm is 1:1, the rotating speed of the ball milling is 200-1000rpm, and the ball milling time is 1-10 h.
7. A method of preparing hexagonal boron nitride nanoplates as defined in claim 6, wherein: the power of ultrasonic treatment in the step (4) is 100W-600W, and the time of ultrasonic treatment is 0.5-1 h.
8. A method of preparing hexagonal boron nitride nanoplates as defined in claim 7, wherein: the rotating speed of the centrifugation in the step (4) is 800-3000rpm, and the time of the centrifugation is 10-60 min.
9. A method of producing hexagonal boron nitride nanoplates as defined in claim 8, wherein: and (3) in the step (5), the washing solvent is deionized water, and the drying time is 4 h.
10. Hexagonal boron nitride nanoplates prepared by any of the methods of claims 1-9, characterized in that: the thickness of the hexagonal boron nitride nanosheet is 2-3nm, the transverse dimension is 0.5-1.5 microns, and hydroxyl groups are modified on the surface of the hexagonal boron nitride nanosheet.
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