CN113772642B - Electrochemical preparation method of few-layer black phosphorus nanosheets - Google Patents
Electrochemical preparation method of few-layer black phosphorus nanosheets Download PDFInfo
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- CN113772642B CN113772642B CN202111121334.0A CN202111121334A CN113772642B CN 113772642 B CN113772642 B CN 113772642B CN 202111121334 A CN202111121334 A CN 202111121334A CN 113772642 B CN113772642 B CN 113772642B
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Abstract
An electrochemical preparation method of a few-layer black phosphorus nanosheet, which belongs to the technical field of inorganic nanomaterial preparation. The method solves the problems of low efficiency, poor controllability and difficult industrial production of the existing method for preparing the few-layer black phosphorus. The method comprises the following steps: 1. preparing an electrolyte; 2. applying a circulating voltage in an electrolytic cell by taking block black phosphorus as a cathode to obtain an electrolyzed material; 3. and after ultrasonic dispersion, centrifugally washing, collecting supernatant and vacuum drying to obtain the few-layer black phosphorus nano-sheets. The invention adopts the electrochemical cathode intercalation method of the polar aprotic solvent system to realize the efficient preparation of the few-layer black phosphorus nanosheet material, has controllable current and voltage, simple preparation process and equipment, is easy for industrial production and is suitable for large-scale popularization; the few-layer black phosphorus nanosheet material obtained by the method has the advantages of complete structure, large transverse size and higher quality and application value. The prepared few-layer black phosphorus nanosheet material is used as a nonmetallic nanosheet material.
Description
Technical Field
The invention belongs to the technical field of inorganic nano material preparation; in particular to an electrochemical preparation method of a few-layer black phosphorus nano-sheet.
Background
Black phosphorus is an emerging two-dimensional material and has considerable application prospect in the research fields of electronic, photoelectric, thermoelectric, gas-sensitive devices and the like. Unlike zero bandgap semiconductors such as graphene, black phosphorus has a direct bandgap, and the smaller the number of layers, the more its bandgap. Therefore, how to prepare high-quality ultrathin black phosphorus materials becomes a research hot spot.
Researchers have used mechanical stripping and ultrasonic liquid phase stripping to obtain thinner black phosphorus nanoplatelets. However, the mechanical stripping method has the defects of limited sample size, low preparation efficiency, difficult control of thickness and difficult industrialized popularization, is only suitable for basic research in a laboratory, but the ultrasonic stripping method can realize large-scale preparation of the black phosphorus nano sheet, but has the defects of long experimental process, low yield, poor controllability and the like, and structural damage caused by long-time ultrasonic action can prevent the prepared sample from being applied to electronic equipment. In addition, chemical vapor deposition methods for preparing two-dimensional materials such as graphene are limited by the lack of suitable substrates with appropriate interactions and lattice constants for growing black phosphorus. This severely restricts the application of the few-layer black phosphorus in the preparation of photoelectric devices and the like.
Disclosure of Invention
The invention aims to solve the problems of low efficiency, poor controllability and difficult industrial production of the existing method for preparing the few-layer black phosphorus, and provides an electrochemical preparation method of the few-layer black phosphorus nanosheets.
The electrochemical preparation method of the few-layer black phosphorus nano-sheet is realized by the following steps:
1. dissolving ammonium salt in a polar aprotic solvent, and uniformly mixing to obtain an electrolyte;
2. placing the block black phosphorus in a platinum sheet electrode clamp of a double-electrode system, keeping a working distance with a platinum sheet electrode, then placing the platinum sheet electrode clamp in a glass electrolytic cell filled with the electrolyte, and applying a circulating voltage to the block black phosphorus by taking the block black phosphorus as a cathode to obtain an electrolyzed material;
3. and (3) carrying out ultrasonic dispersion on the electrolyzed material, then centrifugally washing, collecting supernatant, and carrying out vacuum drying to obtain a few-layer black phosphorus nano sheet, thereby completing the preparation method.
The invention prepares the small-layer black phosphorus nano sheet material with large transverse size and complete structure by adopting an electrochemical method with high preparation efficiency, controllable current and voltage and simple preparation process and equipment, and solves the problems of lower preparation efficiency, poor controllability and difficult industrialized popularization existing in the prior preparation technology.
The ammonium cations in the invention have large diameter, are easy to be inserted between the black phosphorus material layers with larger interlayer spacing, and the polar aprotic solvent is easy to electrolyze to generate gas, so that the ultra-rapid expansion and stripping of the black phosphorus are driven, and the further insertion of the ammonium cations is facilitated; the electrochemical cathode intercalation method adopting the polar aprotic solvent system can realize the efficient and controllable preparation of the few-layer black phosphorus nano sheet material, and the obtained few-layer black phosphorus nano sheet material has complete structure, large transverse size and higher quality and application value.
The prepared few-layer black phosphorus nanosheet material is used as a nonmetallic nanosheet material.
Drawings
FIG. 1 is a diagram of the preparation process of a few-layer black phosphorus nanoplatelet in the examples;
FIG. 2 is a CV plot of a few-layer black phosphorus nanoplatelet in an example;
FIG. 3 is an SEM image of a few-layer black phosphorus nanoplatelet according to the example;
fig. 4 is a TEM image of a few-layer black phosphorus nanoplatelet in an example.
Detailed Description
The technical scheme of the invention is not limited to the specific embodiments listed below, and also includes any combination of the specific embodiments.
The first embodiment is as follows: the electrochemical preparation method of the few-layer black phosphorus nanosheets is realized according to the following steps:
1. dissolving ammonium salt in a polar aprotic solvent, and uniformly mixing to obtain an electrolyte;
2. placing the block black phosphorus in a platinum sheet electrode clamp of a double-electrode system, keeping a working distance with a platinum sheet electrode, then placing the platinum sheet electrode clamp in a glass electrolytic cell filled with the electrolyte, and applying a circulating voltage to the block black phosphorus by taking the block black phosphorus as a cathode to obtain an electrolyzed material;
3. and (3) carrying out ultrasonic dispersion on the electrolyzed material, then centrifugally washing, collecting supernatant, and carrying out vacuum drying to obtain a few-layer black phosphorus nano sheet, thereby completing the preparation method.
The second embodiment is as follows: in a first difference from the specific embodiment, the ammonium salt in the first step is tetraethylammonium hexafluorophosphate, tetrapropylammonium hexafluorophosphate, tetrabutylammonium hexafluorophosphate, tetraethylammonium tetrafluoroborate, tetrapropylammonium tetrafluoroborate or tetrabutylammonium tetrafluoroborate. Other steps and parameters are the same as in the first embodiment.
And a third specific embodiment: this embodiment differs from the one or two embodiments in that the polar aprotic solvent in step one is DMSO, DMF, or NMP. Other steps and parameters are the same as in the first or second embodiment.
The specific embodiment IV is as follows: this embodiment differs from one to three embodiments in that the concentration of the electrolyte in the first step is 0.01 to 0.1M. Other steps and parameters are the same as in one to three embodiments.
Fifth embodiment: the difference between the first embodiment and the fourth embodiment is that the working distance in the second step is 1-2 cm. Other steps and parameters are the same as in one to four embodiments.
Specific embodiment six: the difference between the present embodiment and the first to fifth embodiments is that the cyclic voltage in the second step is (1V-4V) to (-5V to (-7V)), and the application time is 60-120 min. Other steps and parameters are the same as in one of the first to fifth embodiments.
Seventh embodiment: the difference between the present embodiment and one to six embodiments is that the ultrasonic dispersion time in the third step is 5 to 10 minutes. Other steps and parameters are the same as in one of the first to sixth embodiments.
Eighth embodiment: this embodiment differs from one of the first to seventh embodiments in that the centrifugal washing in the third step is performed 3 to 5 times with a polar aprotic solvent and absolute ethanol, respectively. Other steps and parameters are the same as those of one of the first to seventh embodiments.
Detailed description nine: the difference between the present embodiment and one to eight embodiments is that the rotational speed of the centrifugal washing in the third step is 8000-12000 r/min, and the time is 10-30 min. Other steps and parameters are the same as in one to eight of the embodiments.
Detailed description ten: the difference between the present embodiment and one of the first to ninth embodiments is that the temperature of the vacuum drying in the third step is 50 to 70 ℃ and the time is 8 to 12 hours. Other steps and parameters are the same as in one of the first to ninth embodiments.
The beneficial effects of the invention are verified by the following examples:
examples:
the electrochemical preparation method of the few-layer black phosphorus nano-sheet is realized by the following steps:
1. dissolving ammonium salt in a polar aprotic solvent, and uniformly mixing to obtain an electrolyte;
2. placing the block black phosphorus in a platinum sheet electrode clamp of a double-electrode system, keeping a working distance with a platinum sheet electrode, then placing the platinum sheet electrode clamp in a glass electrolytic cell filled with the electrolyte, and applying a circulating voltage to the block black phosphorus by taking the block black phosphorus as a cathode to obtain an electrolyzed material;
3. and (3) carrying out ultrasonic dispersion on the electrolyzed material, then centrifugally washing, collecting supernatant, and carrying out vacuum drying to obtain a few-layer black phosphorus nano sheet, thereby completing the preparation method.
The ammonium salt in step one of this example is tetrabutylammonium hexafluorophosphate.
The polar aprotic solvent in step one of this example is DMSO.
The concentration of the electrolyte in step one of this example was 0.05M.
In the second embodiment, the working distance is 2cm.
In the second embodiment, the cyclic voltage is 1V to-5V, and the application time is 90min.
The time of ultrasonic dispersion in the third step of this embodiment is 5min.
The centrifugal washing in step three of this example was performed 3 times with DMSO and absolute ethanol, respectively.
In the third step of the embodiment, the rotational speed of the centrifugal washing is 10000r/min, and the time is 30min.
In the third embodiment, the temperature of the vacuum drying is 60 ℃ and the time is 12 hours.
In the preparation process of the few-layer black phosphorus nanoplatelets prepared in this example, as shown in fig. 1, as the power-on time increases (0 min for part a, 5min for part b, 10min for part c, and 15min for part d in fig. 1), the bulk black phosphorus expands significantly, black powder falls off, and the color of the solution becomes gradually darker.
The CV curve of the resulting few-layer black phosphorus nanoplatelets prepared in this example, as shown in FIG. 2, can be seen to appear at about-0.5V with TBA + Positive intercalation related clear cathode peak current, indicating TBA + The cation was successfully inserted into the bulk BP, and the ion generated by TBA appeared at about-0.5V during the reverse scan + New peaks due to cation deintercalation.
As shown in fig. 3, the SEM image of the few-layer black phosphorus nanoplatelets prepared in this example shows that the layered structure of black phosphorus is gradually opened with the application of voltage, the gap between layers is gradually expanded into an accordion shape, the expanded gap is favorable for further permeation of cations, and finally the BP nanoplatelets are peeled off.
The TEM image of the obtained few-layer black phosphorus nanoplatelets prepared in this example, as shown in fig. 4, can be seen that the block-shaped black phosphorus is peeled into an ultrathin black phosphorus nanoplatelet with large transverse dimension and complete structure.
The black phosphorus nano sheet material is prepared by adopting a method with high preparation efficiency (high macroscopic speed), controllable current and voltage and simple preparation process and equipment; the obtained few-layer black phosphorus nano-sheet has high yield, large transverse size and complete structure, and is suitable for industrialized popularization.
Claims (5)
1. The electrochemical preparation method of the few-layer black phosphorus nanosheets is characterized by comprising the following steps of:
1. dissolving ammonium salt in a polar aprotic solvent, and uniformly mixing to obtain an electrolyte;
2. placing the block black phosphorus in a platinum sheet electrode clamp of a double-electrode system, keeping a working distance with a platinum sheet electrode, then placing the platinum sheet electrode clamp in a glass electrolytic cell filled with the electrolyte, and applying a circulating voltage to the block black phosphorus by taking the block black phosphorus as a cathode to obtain an electrolyzed material;
3. taking the electrolyzed material to carry out ultrasonic dispersion, then centrifugally washing, collecting supernatant and carrying out vacuum drying to obtain a few-layer black phosphorus nano-sheet, thereby completing the preparation method;
wherein the ammonium salt in the first step is tetraethylammonium hexafluorophosphate, tetrapropylammonium hexafluorophosphate, tetraethylammonium tetrafluoroborate or tetrapropylammonium tetrafluoroborate;
in the first step, the polar aprotic solvent is DMSO;
the concentration of the electrolyte in the first step is 0.05-0.1M;
the cyclic voltage in the second step is (1V-4V) to (-5V-7V), and the application time is 60-120 min;
and in the third step, the centrifugal washing is carried out by adopting a polar aprotic solvent and absolute ethyl alcohol for 3-5 times respectively.
2. The electrochemical preparation method of the few-layer black phosphorus nanoplatelets according to claim 1, wherein the working distance in the second step is 1-2 cm.
3. The electrochemical preparation method of the few-layer black phosphorus nanoplatelets according to claim 1, wherein the ultrasonic dispersion time in the step three is 5-10 min.
4. The electrochemical preparation method of the few-layer black phosphorus nanoplatelets according to claim 1, wherein the rotational speed of centrifugal washing in the step three is 8000-12000 r/min for 10-30 min.
5. The electrochemical preparation method of the few-layer black phosphorus nanoplatelets according to claim 1, wherein the vacuum drying temperature in the step three is 50-70 ℃ for 8-12 h.
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| CN104876199B (en) * | 2015-04-21 | 2017-03-15 | 合肥国轩高科动力能源有限公司 | A kind of ultrasound peels off the method that black phosphorus prepares the black scale of few layer |
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