Nanoscale black phosphorene tablet as well as stripping preparation method and application thereof
By blending micron-scale black phosphorus with additives, dispersing and peeling by ball milling, shearing or discharge method, then diluting and sonicating with solvents, and finally obtaining nano-scale black phosphorusene sheets through solid-liquid separation, solving the problems of unstable production, oxidation and long production time of nano-scale black phosphorusene sheets in the prior art, and achieving high yield and high regularity preparation of nano-scale black phosphorusene sheets.
Patent Information
- Application Number
- CN202411693698.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-25
- Publication Date
- 2025-03-11
AI Technical Summary
The prior art is difficult to produce uniform and stable nano-scale black phosphorene sheets, and it is difficult to prevent oxidative damage of black phosphorus during the treatment process. The production time is too long, the cost and equipment requirements are high, and it is difficult to apply on a large scale.
By blending micron-scale black phosphorus with additives, dispersing and peeling by ball milling, shearing or discharge, followed by dilution and sonication using solvents, and finally obtaining nano-scale black phosphorene sheets by solid-liquid separation.
It improves the yield of nano-scale black phosphorene sheets, shortens the process flow time, ensures the morphological regularity and crystal structure integrity of nano-scale black phosphorene sheets, and enhances its prospects in nanoelectronics and nanophotonics applications.
Smart Images
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Abstract
Description
Technical Field
[0001] The present invention belongs to the field of two-dimensional material applications and relates to a nanoscale black phosphorene sheet and a peeling preparation method and application thereof. Background Art
[0002] As the main allotrope of phosphorus, black phosphorus has attracted great attention in the field of electronics and optoelectronics due to its easy shedding, tunable band gap and high current on / off ratio. In the application of polymer composites, black phosphorus has the most stable structure and the lowest chemical reaction energy under ambient conditions. Therefore, black phosphorus is non-flammable and can coexist well with most solvents without significantly reducing its performance. Compared with red phosphorus, the high specific surface area brought by the unique special two-dimensional layered structure of black phosphorus gives it an outstanding physical barrier effect in flame retardant processes, thereby greatly reducing flammability at low addition amounts. In addition, due to its high specific surface area, black phosphorus can be easily surface modified compared with red phosphorus, and in recent years it has been widely used to improve the fire safety of polymers; although black phosphorus is widely used, how to prepare nanoscale black phosphorene sheets and magnify its high specific surface area advantage has become a hot topic in industry research.
[0003] At present, the more mature preparation methods of nanoscale black phosphorene sheets include mechanical exfoliation, ball milling exfoliation, discharge exfoliation, ultrasonic exfoliation, etc. When they are used to prepare nanoscale black phosphorene sheets, there are the following problems that need to be solved: it is difficult to produce uniform and stable nanoscale black phosphorene sheets, it is difficult to prevent the oxidation damage of black phosphorus during the processing process, the production time is too long, and it is difficult to apply on a large scale under the current cost and equipment requirements. Therefore, it is very necessary to develop a simple and reliable preparation technology for nanoscale black phosphorene sheets. Summary of the invention
[0004] In order to solve the problems existing in the prior art, the present invention provides a nanoscale black phosphorene sheet and its exfoliation preparation method and application, which improves the yield of nanoscale black phosphorene sheets and shortens the process time. The preparation of nanoscale black phosphorene sheets is to use micron-scale black phosphorus and additives to blend, and then use ball milling, shearing or discharge method to disperse and exfoliate the micron-scale black phosphorus in the additives, and use a solvent to dilute the initial product obtained by ball milling, shearing or discharge to obtain a diluted product, and further use an ultrasonic machine to ultrasonically treat it, and use a suction filter or centrifuge to remove the additives and solvent to obtain a nanoscale black phosphorene sheet. This method can ensure the morphological regularity and relatively complete crystal structure of the exfoliated nanoscale black phosphorene sheet, and improve the application prospects of nanoscale black phosphorene sheets in nanoelectronics and nanophotonics.
[0005] In order to achieve the above object, the technical solution adopted by the present invention is as follows:
[0006] The present invention provides a method for preparing a nanoscale black phosphorene sheet by exfoliation, which achieves the above-mentioned purpose by means of a variety of optional additives through ball milling, shearing or discharge, and specifically comprises the following steps:
[0007] S1: Dispersion and exfoliation of micron-sized black phosphorus
[0008] Using a stripping method, micron-sized black phosphorus is dispersed and stripped in an additive and / or a solvent to obtain a nano-sized black phosphorus primary product;
[0009] The stripping method is selected from ball milling, shearing or discharge method;
[0010] When the stripping method is ball milling or shearing, a liquid additive or (solid additive + solvent) is selected; when the stripping method is discharge method, a solvent is selected;
[0011] In the S1, the liquid additive is one or more of ED2003, Triton X-100 or N-methyl-2-pyrrolidone; the solid additive is one or more of tannic acid or vitamin C; and the solvent is one or more of anhydrous ethanol, N,N-dimethylformamide, and dimethyl sulfoxide.
[0012] In S1, when the stripping method is ball milling or shearing, the mixed material may be ground before the ball milling or shearing begins.
[0013] In the above S1, the stripping method is one of the following methods:
[0014] The first method is to mix micron-sized black phosphorus and liquid additives, and transfer them into a planetary ball mill for ball milling or into a wall breaking machine for shearing to obtain a nano-sized black phosphorus primary product;
[0015] The second method is to mix and grind the micron-sized black phosphorus with the liquid additive, and then transfer the mixture into a planetary ball mill for ball milling or transfer the mixture into a wall breaking machine for shearing to obtain a nano-sized black phosphorus primary product.
[0016] The third method is to mix micron-sized black phosphorus and solid additives, add solvent to dilute, transfer to a planetary ball mill for ball milling or transfer to a wall breaking machine for shearing, and obtain a nano-sized black phosphorus primary product;
[0017] The fourth method is to mix and grind the micron-sized black phosphorus with the solid additive, add a solvent to dilute it, and then transfer it to a planetary ball mill for ball milling or a wall breaking machine for shearing to obtain a nano-sized black phosphorus primary product;
[0018] The fifth method is to mix micron-sized black phosphorus with a solvent, place it in positive and negative electrodes for discharge treatment, and obtain a nano-sized black phosphorus primary product;
[0019] The grinding time is 1 to 2 hours.
[0020] The ball milling time is 3 to 10 hours, a steel tank is selected for the ball milling process, a zirconia ball or a stainless steel ball is selected for the ball milling speed is 400 to 1000 rpm, and the ball milling program is selected to ball mill for 20 minutes and pause for 10 minutes.
[0021] The shearing time is 1 to 6 hours, a high-speed wall breaking machine is selected for the shearing process, the shearing speed is 20000 to 30000 rpm, and the shearing program is selected to shear for 20 minutes and pause for 10 minutes.
[0022] The discharge time is 1 to 5 hours, the positive and negative electrodes are selected during the discharge process, the voltage applied to the anode is +5 to +10V, and the current is maintained at 0.4 to 1A.
[0023] In the S1, according to the solid-liquid ratio, micron-sized black phosphorus: liquid additive = 100 mg: (1-5) ml. According to the mass ratio, micron-sized black phosphorus: solid additive = 1: (0.2-1), according to the mass ratio, micron-sized black phosphorus: solvent = 1: (5-20).
[0024] S2: Dilution
[0025] Adding the obtained nanoscale black phosphorus primary product to a solvent for dilution to obtain a diluted product; wherein the volume ratio of the nanoscale black phosphorus primary product to the solvent is 1:(10-40);
[0026] S3: Low temperature ultrasound
[0027] The diluted product is sealed and placed in an ultrasonic machine for 2 to 5 hours to obtain an ultrasonically treated product;
[0028] In the above-mentioned S3, the role of ultrasonic treatment is to promote the interlayer separation of black phosphorus and improve the yield;
[0029] In the above-mentioned S3, the ultrasonic vibration frequency is preferably 45-55kHz, and the temperature of the ultrasonic process is controlled not to exceed 20°C.
[0030] S4: Solid-liquid separation
[0031] The product after ultrasonic treatment is separated into solid and liquid, and the additives and / or solvents are removed to obtain nanoscale black phosphorene sheets.
[0032] In the S4, the solid-liquid separation is performed by centrifugal separation using a high-speed centrifuge or by filtration separation using a suction filter to remove additives and / or solvents to obtain nanoscale black phosphorene sheets, and the solid-liquid separation treatment time is 20 to 40 minutes.
[0033] In the above S4, the high-speed centrifuge selected for centrifugal separation has a centrifugal speed of 5000 to 20000 rpm.
[0034] The nanoscale black phosphorene sheet of the present invention is prepared by the above-mentioned peeling preparation method, has a regular morphology with a radial dimension of 50 to 1000 nm, a thickness of 1 to 30 nm, a high degree of complete regularity of the crystal structure, and no obvious defects on the surface.
[0035] The application of the nanoscale black phosphorene sheet of the present invention is used in nanoelectronic devices, nanophotonic devices or as a fireproof filler for polymers after surface modification.
[0036] The method mainly realizes the stripping of nano-scale black phosphorus by ball milling, shearing or discharge method; the materials required for the stripping method include micron-scale black phosphorus, additives and / or solvents, the micron-scale black phosphorus is stripped at the nano-scale by the additives and / or solvents, and the additives are removed by the solvents;
[0037] Additives and / or solvents are processed together with the raw material micron-sized black phosphorus and used in the process of ball milling, shearing or discharge, so that the micron-sized black phosphorus tends to separate between layers rather than break at will; the solvent is used to dissolve the additives remaining after the ball milling or shearing, thereby realizing the collection of nano-sized black phosphorene sheets, or the solvent is used as a conductive medium in the discharge process.
[0038] The nanoscale black phosphorene sheet and its exfoliation preparation method and application of the present invention have the following beneficial effects:
[0039] 1. The present invention provides a method for preparing a nanoscale black phosphorene sheet by exfoliation, which has a simple preparation process and a short process time, and can greatly shorten the production time of the nanoscale black phosphorene sheet.
[0040] 2. The present invention provides a method for preparing a nanoscale black phosphorene sheet by exfoliation, which can better protect the exfoliated black phosphorene nanosheets, prevent their oxidative decomposition, and protect the structural integrity of the exfoliated nanoscale black phosphorene sheets to the greatest extent under operating conditions suitable for factory production. BRIEF DESCRIPTION OF THE DRAWINGS
[0041] picture Figure 1 The present invention is a schematic diagram of the process of exfoliating a nanoscale black phosphorene sheet.
[0042] Figure 2 This is the XRD image of the nanoscale black phosphorene sheet prepared in Example 1 of the present invention.
[0043] Figure 3 This is an XPS image of the nanoscale black phosphorene sheet prepared in Example 1 of the present invention.
[0044] Figure 4 The AFM image of the nanoscale black phosphorene sheet prepared in Example 1 of the present invention and the corresponding sheet thickness analysis.
[0045] Figure 5The AFM image of the nanoscale black phosphorene sheet prepared in Example 1 of the present invention and the corresponding sheet thickness analysis. DETAILED DESCRIPTION
[0046] The present invention is further described in detail below in conjunction with embodiments.
[0047] In the following examples, the additive is one of polyetheramine (ED2003), Triton X-100, N-methyl-2-pyrrolidone, tannic acid, or vitamin C.
[0048] In the following examples, the solvent is one or more of anhydrous ethanol, N,N-dimethylformamide, and dimethyl sulfoxide.
[0049] Example 1
[0050] A method for preparing a nanoscale black phosphorene sheet by exfoliation, the schematic diagram of the preparation process is shown in Figure 1 , including the following steps:
[0051] Step 1:
[0052] The weighed micron-sized black phosphorus and the liquid additive-ED2003 were mixed, ground in the labware for 1 hour at room temperature, and then moved into a planetary ball mill. A steel tank was selected for the ball milling process, a zirconia ball was selected for the ball milling, the ball milling speed was 500 rpm, the ball milling program selected ball milling for 20 minutes, paused for 10 minutes, and the ball milling time was 3 hours to obtain a nano-sized black phosphorus primary product; wherein, according to the solid-liquid ratio, micron-sized black phosphorus: liquid additive-ED2003 = 100 mg: 1 ml;
[0053] Step 2:
[0054] The nanoscale black phosphorus primary product obtained in the ball milling process is diluted with a solvent, N,N-dimethylformamide, to obtain a diluted product; wherein the volume ratio of the nanoscale black phosphorus primary product to the solvent is 1:10;
[0055] Step 3:
[0056] The diluted product is sealed with a film and placed in an ultrasonic machine. The ultrasonic treatment time is 3 hours, the ultrasonic vibration frequency is preferably 50 kHz, and the temperature of the ultrasonic process is controlled not to exceed 20°C;
[0057] Step 4:
[0058] The product after ultrasonic treatment is filtered using a suction filter to remove additives and solvents to obtain nanoscale black phosphorene sheets.
[0059] The nanoscale black phosphorene sheet prepared in this embodiment was tested, and its XRD pattern is shown in Figure 2 , XRS chart see Figure 3 , AFM images are shown in Figure 4 and Figure 5 ,pass Figure 2-Figure 5 It can be seen that the exfoliation of the nanoscale black phosphorene sheet is irregular, with a thickness of 20.027 nm and a longitudinal dimension of 52.814 nm.
[0060] Example 2
[0061] A method for preparing a nanoscale black phosphorene sheet by exfoliation comprises the following steps:
[0062] Step 1:
[0063] The weighed micron-sized black phosphorus and liquid additive-N-methyl-2-pyrrolidone were mixed and transferred into a planetary ball mill. The steel tank was selected for the ball milling process, the zirconia ball was selected for the ball milling, the ball milling speed was 500rpm, the ball milling program was selected to ball mill for 20min, pause for 10min, and the ball milling time was 5h to obtain the nano-sized black phosphorus primary product; wherein, micron-sized black phosphorus: additive = 100mg: 1ml;
[0064] Step 2:
[0065] The nanoscale black phosphorus primary product obtained in the ball milling process is diluted with a solvent, N,N-dimethylformamide, to obtain a diluted product; wherein the volume ratio of the nanoscale black phosphorus primary product to the solvent is 1:10;
[0066] Step 3:
[0067] The diluted product is sealed with a film and placed in an ultrasonic machine. The ultrasonic treatment time is 3 hours, the ultrasonic vibration frequency is preferably 50 kHz, and the temperature of the ultrasonic process is controlled not to exceed 20°C;
[0068] Step 4:
[0069] The product after ultrasonic treatment is filtered using a suction filter to remove additives and solvents to obtain nanoscale black phosphorene sheets.
[0070] Example 3
[0071] A method for preparing a nanoscale black phosphorene sheet by exfoliation, the schematic diagram of the preparation process is shown in Figure 1 , including the following steps:
[0072] Step 1:
[0073] The weighed micron-sized black phosphorus and liquid additive-ED2003 were mixed, ground in a mortar at room temperature for 1 hour, and transferred into a high-speed wall breaking machine, with a shearing speed of 28000rpm, a shearing program of 20 minutes of wall breaking, a pause of 10 minutes, and a shearing time of 2 hours, to obtain a nano-sized black phosphorus primary product; wherein, micron-sized black phosphorus: additive = 100mg: 1ml;
[0074] Step 2:
[0075] The nanoscale black phosphorus primary product obtained in the cell wall breaking process is diluted with solvent-N,N-dimethylformamide to obtain a diluted product; wherein the volume ratio of the nanoscale black phosphorus primary product: solvent = 1:10;
[0076] Step 3:
[0077] The diluted product is sealed with a film and placed in an ultrasonic machine. The ultrasonic treatment time is 3 hours, the ultrasonic vibration frequency is preferably 50 kHz, and the temperature of the ultrasonic process is controlled not to exceed 20°C;
[0078] Step 4:
[0079] The product after ultrasonic treatment is filtered using a suction filter to remove additives and solvents to obtain nanoscale black phosphorene sheets.
[0080] Example 4
[0081] A method for preparing a nanoscale black phosphorene sheet by exfoliation comprises the following steps:
[0082] Step 1:
[0083] The weighed micron-sized black phosphorus and solid additive tannic acid were mixed, dissolved in a solvent, ground in a grinder at room temperature for 1 hour, and transferred to a high-speed wall breaking machine with a shearing speed of 28000 rpm. The shearing program selected wall breaking for 20 minutes, pause for 10 minutes, and shearing for 3 hours to obtain a nano-sized black phosphorus primary product. The preparation process diagram is shown in Figure 1 ; Among them, micron-sized black phosphorus: additive = 1g: 0.5g, micron-sized black phosphorus: solvent = 1g: 10g;
[0084] Step 2:
[0085] The nanoscale black phosphorus primary product obtained in the cell wall breaking process is diluted with solvent-N,N-dimethylformamide to obtain a diluted product; wherein the volume ratio of the nanoscale black phosphorus primary product: solvent = 1:10;
[0086] Step 3:
[0087] The diluted product is sealed with a film and placed in an ultrasonic machine. The ultrasonic treatment time is 3 hours, the ultrasonic vibration frequency is preferably 50 kHz, and the temperature of the ultrasonic process is controlled not to exceed 20°C;
[0088] Step 4:
[0089] The product after ultrasonic treatment is filtered using a suction filter to remove additives and solvents to obtain nanoscale black phosphorene sheets.
[0090] Example 5
[0091] A method for preparing a nanoscale black phosphorene sheet by exfoliation comprises the following steps:
[0092] Step 1:
[0093] The weighed micron-sized black phosphorus and solid additive vitamin C were mixed, and the solvent N,N-dimethylformamide was added to dissolve, and the mixture was transferred into a planetary ball mill. A steel tank was selected for the ball milling process, a zirconium oxide ball was selected for the ball milling, the ball milling speed was 500 rpm, and the ball milling program was selected to ball mill for 20 minutes, pause for 10 minutes, and the ball milling time was 6 hours to obtain a nano-sized black phosphorus primary product; wherein, micron-sized black phosphorus: solid additive = 1g: 0.5g, micron-sized black phosphorus: solvent = 1g: 10g;
[0094] Step 2:
[0095] The nanoscale black phosphorus primary product obtained in the ball milling process is diluted with a solvent, N,N-dimethylformamide, to obtain a diluted product; wherein the volume ratio of the nanoscale black phosphorus primary product to the solvent is 1:10;
[0096] Step 3:
[0097] The diluted product is sealed with a film and placed in an ultrasonic machine. The ultrasonic treatment time is 3 hours, the ultrasonic vibration frequency is preferably 50 kHz, and the temperature of the ultrasonic process is controlled not to exceed 20°C;
[0098] Step 4:
[0099] The product after ultrasonic treatment is filtered using a suction filter to remove additives and solvents to obtain nanoscale black phosphorene sheets.
[0100] Example 6
[0101] A method for preparing a nanoscale black phosphorene sheet by exfoliation comprises the following steps:
[0102] Step 1:
[0103] The weighed micron-scale black phosphorus was diluted and mixed with the solvent N,N-dimethylformamide, and placed in the positive and negative electrodes for discharge treatment. The anode voltage was +5V, the current was maintained at 0.42A, and the discharge time was 1.5h to obtain the initial product of nanoscale black phosphorus. The schematic diagram of its preparation process is shown in Figure 1 ; Wherein, micron-sized black phosphorus: solvent = 1g: 10g;
[0104] Step 2:
[0105] The nanoscale black phosphorus primary product obtained in the discharge process is diluted with a solvent, N,N-dimethylformamide, to obtain a diluted product; wherein the volume ratio of the nanoscale black phosphorus primary product to the solvent is 1:10;
[0106] Step 3:
[0107] The diluted product is transferred into an ultrasonic machine, the ultrasonic treatment time is 3 hours, the ultrasonic vibration frequency is preferably 50 kHz, and the temperature of the ultrasonic process is controlled not to exceed 20°C;
[0108] Step 4:
[0109] The product after ultrasonic treatment is centrifuged in a high-speed centrifuge to remove the solvent at a centrifugal speed of 10,000 rpm to obtain nanoscale black phosphorene sheets.
[0110] Comparative Example 1
[0111] The same as Example 5, except that the solid additive vitamin C is not added, and the micron-sized black phosphorus is directly added to the solvent N,N-dimethylformamide for dissolution, and the subsequent steps are the same as Example 5. The obtained nanoscale black phosphorene sheet is the same as the nanoscale black phosphorene sheet prepared in Example 5, but has the disadvantages of partial oxidation of the nanoscale black phosphorene sheet and reduced yield.
[0112] Comparative Example 2
[0113] The same as Example 1, except that there is no dilution process in step 2, so too much additive residue remains.
[0114] Comparative Example 3
[0115] The same as Example 1, except that the temperature of ultrasound is high, that is, above 20° C., so that the nanoscale black phosphorene sheet is partially oxidized and the yield is reduced.
[0116] Comparative Example 4
[0117] The same as Example 1, except that there is no ultrasonic process in step 3, so some products of the nanoscale black phosphorene sheet are not completely separated from each other, and the purity and yield are reduced.
Claims
1. A method for preparing a nanoscale black phosphorene sheet by exfoliation, characterized in that: The exfoliation preparation method of the nanoscale black phosphorene sheet mainly adopts an exfoliation method to disperse and exfoliate micron-scale black phosphorus in an additive and / or a solvent, and then combines a low-temperature ultrasonic method to prepare the nanoscale black phosphorene sheet; The stripping method is selected from one of ball milling, shearing or discharge method; When the stripping method is ball milling or shearing, a liquid additive or (solid additive + solvent) is selected; when the stripping method is discharge method, a solvent is selected.
2. The method for preparing a nanoscale black phosphorene sheet by exfoliation according to claim 1, characterized in that: in, Micron-scale black phosphorus is exfoliated at the nanoscale by using additives and / or solvents, and the additives are removed by solvents; The additive and the micron-sized black phosphorus are ball-milled or sheared together to achieve the micron-sized black phosphorus tending to separate into layers rather than being randomly broken; The solvent and the micron-sized black phosphorus are subjected to discharge treatment together to achieve interlayer separation of the micron-sized black phosphorus; The solvent is used to dissolve the additives remaining after the ball milling or shearing method, so as to collect the nanoscale black phosphorene sheets or serve as a conductive medium during the discharge process.
3. A method for preparing a nanoscale black phosphorene sheet by exfoliation, characterized in that: The following steps are involved: S1: Dispersion and exfoliation of micron-sized black phosphorus Using a stripping method, micron-sized black phosphorus is dispersed and stripped in an additive and / or a solvent to obtain a nano-sized black phosphorus primary product; The stripping method is selected from ball milling, shearing or discharge method; When the stripping method is ball milling or shearing, a liquid additive or (solid additive + solvent) is selected; when the stripping method is discharge method, a solvent is selected; S2: Dilution The obtained nanoscale black phosphorus primary product is diluted with a solvent to obtain a diluted product; wherein the volume ratio of the ball-milled primary product to the solvent is 1: (10-40); S3: Low temperature ultrasound The diluted product is sealed and placed in an ultrasonic machine for 2 to 5 hours. During the ultrasonic process, the temperature of the diluted product is controlled not to exceed 20° C. to obtain a product after ultrasonic treatment. S4: Solid-liquid separation The product after ultrasonic treatment is separated into solid and liquid, and the additives and / or solvents are removed to obtain nanoscale black phosphorene sheets.
4. The method for preparing a nanoscale black phosphorene sheet by exfoliation according to claim 3, characterized in that: The liquid additive is selected from one or more of ED2003, Triton X-100 or N-methyl-2-pyrrolidone, the solid additive is selected from tannic acid and / or vitamin C; the solvent is selected from one or more of anhydrous ethanol, N,N-dimethylformamide, and dimethyl sulfoxide.
5. The method for preparing a nanoscale black phosphorene sheet by exfoliation according to claim 3, characterized in that: In the S1, according to the solid-liquid ratio, micron-sized black phosphorus: liquid additive = 100 mg: (1-5) ml; according to the mass ratio, micron-sized black phosphorus: solid additive = 1: (0.2-1); according to the mass ratio, micron-sized black phosphorus: solvent = 1: (5-20).
6. The method for preparing a nanoscale black phosphorene sheet by exfoliation according to claim 3, characterized in that: The ball milling time is 3 to 10 hours, a steel tank is selected for the ball milling process, a zirconia ball or a stainless steel ball is selected for the ball milling speed is 400 to 1000 rpm, and the ball milling program is selected to ball mill for 20 minutes and pause for 10 minutes; And / or, the shearing time is 1 to 6 hours, a high-speed wall breaking machine is selected for the shearing process, the shearing speed is 20000 to 30000 rpm, and the shearing program is selected to shear for 20 minutes and pause for 10 minutes; And / or, the discharge time is 1 to 5 hours, the positive and negative electrodes are selected during the discharge process, the voltage applied to the anode is +5 to +10V, and the current is maintained at 0.4 to 1A.
7. The method for preparing a nanoscale black phosphorene sheet by exfoliation according to claim 3, characterized in that: In the S2, the solvent is selected from one or more of anhydrous ethanol, N,N-dimethylformamide, and dimethyl sulfoxide; and / or, in the S3, the ultrasonic vibration frequency is 45-55kHz.
8. The method for preparing a nanoscale black phosphorene sheet by exfoliation according to claim 3, characterized in that: In the above S4, the solid-liquid separation is carried out by high-speed centrifugal separation or suction filtration separation; the solid-liquid separation time is 20 to 40 minutes; When centrifugation is performed using a high-speed centrifuge, the centrifugal speed of the high-speed centrifuge is 5000 to 20000 rpm.
9. A nanoscale black phosphorene sheet, characterized in that: The nanoscale black phosphorene sheet is prepared by the exfoliation preparation method according to any one of claims 1 to 8, and has a regular radial size of 50 to 1000 nm, a thickness of 1 to 30 nm, a complete and regular crystal structure, and no obvious defects on the surface.
10. The use of the nanoscale black phosphorene sheet as claimed in claim 9 in nanoelectronic devices, nanophotonic devices or as a fireproof filler for polymers after surface modification.