CN114560449B - Preparation method and application of manganese selenide nano-materials with different morphologies and phases - Google Patents

Preparation method and application of manganese selenide nano-materials with different morphologies and phases Download PDF

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CN114560449B
CN114560449B CN202210171164.5A CN202210171164A CN114560449B CN 114560449 B CN114560449 B CN 114560449B CN 202210171164 A CN202210171164 A CN 202210171164A CN 114560449 B CN114560449 B CN 114560449B
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oleylamine
manganese selenide
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CN114560449A (en
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李娜
封婕
丁书江
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Xian Jiaotong University
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Abstract

A preparation method and application of manganese selenide nanometer materials with different morphologies and phases, wherein the method comprises the following steps: adding a manganese-based precursor, oleylamine and octadecene, or adding the manganese-based precursor, oleylamine, oleic acid and octadecene into a reaction container to form a mixed solution; heating the mixed solution in the reaction vessel, vacuumizing under the temperature condition, stirring to make the mixed solution clear and transparent, and introducing nitrogen to obtain a reaction solution; ultrasonically dispersing selenium powder in a mixed liquid of dodecyl mercaptan and oleylamine to obtain a selenium powder dispersion liquid; the reaction liquid in the reaction vessel is quickly heated, and selenium powder dispersion liquid is injected into the reaction vessel for reaction; cooling the solution in the reaction vessel to room temperature, and transferring the solution in the reaction vessel to a centrifugal device; performing centrifugal separation to achieve washing; and drying the cleaned residues to obtain the powdery manganese selenide nanometer material. The manganese selenide nano material prepared by the method has various shapes, pure components and uniform size, and has good monodispersity and crystallinity.

Description

Preparation method and application of manganese selenide nano-materials with different morphologies and phases
Technical Field
The invention relates to the technical field of nano material synthesis and preparation, in particular to a preparation method and application of manganese selenide nano materials with different morphologies and phases.
Background
In recent years, semiconductor nanocrystals have attracted considerable interest to researchers in the field of basic research and technical applications. In general, the physical and chemical properties of semiconductor nanocrystals are largely dependent on their morphology, size, phase, and crystal structure. Therefore, the morphology, size and phase state of the semiconductor nanocrystals can be effectively regulated, and the properties of the semiconductor nanocrystals in various device applications (electronic devices, photodetectors, solar cells, sensors and the like) can be well regulated, so that the device performance is optimized.
Among the numerous types of nanocrystals, transition metal chalcogenides (sulfides,Selenide, and telluride) have attracted much attention due to their special magnetic, electrical, and optical properties. Manganese selenide (MnSe) is an important class of transition metal chalcogenides with unique magnetic properties based on electron/hole energy bands and Mn 2+ The strong sp-d interaction between 3d electrons can be used as an antiferromagnetic semiconductor and applied to various diluted magnetic semiconductors and magneto-optical devices.
Nanocrystals with different morphologies can exhibit different properties, however, current methods for synthesizing nanocrystals are complex and do not allow for good control of nanocrystal morphology and phase.
Therefore, there is a need to develop a simple synthesis method that can more easily control the nucleation and growth of crystals, thereby adjusting the morphology, size, phase, etc. of the final nanocrystals.
Disclosure of Invention
Based on the method, the invention provides a preparation method of manganese selenide nanometer materials with different morphologies and phases, so as to solve the technical problems that the synthesis method of the nanocrystals in the prior art is complex and the morphologies and phases of the nanocrystals cannot be well controlled.
In order to achieve the above purpose, the invention provides a preparation method of manganese selenide nanometer materials with different morphologies and phases, which comprises the following steps:
1) Adding a manganese-based precursor, oleylamine and octadecene, or adding the manganese-based precursor, oleylamine, oleic acid and octadecene into a reaction container to form a mixed solution;
2) Heating the mixed solution in the reaction vessel to 100-140 ℃, vacuumizing under the temperature condition, stirring for 30-60min, clarifying and transparency, and introducing nitrogen to obtain a reaction solution;
3) Ultrasonically dispersing selenium powder in a mixed liquid of dodecyl mercaptan and oleylamine to obtain a selenium powder dispersion liquid;
4) Under the nitrogen atmosphere, the reaction liquid in the reaction vessel in the step 2) is quickly heated to 210-280 ℃, then the selenium powder dispersion liquid obtained in the step 3) is injected into the reaction vessel for reaction for 30 min-2 h;
5) Cooling the solution in the reaction container to room temperature after the reaction in the step 4), transferring the solution in the reaction container to centrifugal equipment, and performing centrifugal separation at a rotating speed of 8500-9000 rpm for 8-10 min to realize cleaning, repeatedly cleaning for 3-5 times, and adding a cleaning solvent formed by mixing absolute ethyl alcohol and cyclohexane during each cleaning;
6) And 5) placing the residues after the cleaning in the step 5) into a vacuum drying oven to be dried for 10-20 hours at 50-85 ℃ to obtain the powdery manganese selenide nano-material.
As a further preferable technical scheme of the invention, in the step 1), the molar ratio of the manganese-based precursor, the oleylamine, the oleic acid and the octadecene is 0.5-1: 16 to 27.7:0 to 10:6 to 20.
As a further preferable embodiment of the present invention, the manganese-based precursor in step 1) is one or a mixture of two of manganese acetylacetonate and manganese acetate tetrahydrate.
As a further preferable technical scheme of the invention, the molar ratio of the selenium powder taken in the step 3) to the manganese-based precursor taken in the step 1) is 0.5-1: 0.5 to 1.
As a further preferable technical scheme of the invention, in the step 3), the dosage of the corresponding dodecyl mercaptan is 0.1mL and the dosage of the oleylamine is 1.2-3 mL based on the dosage of selenium powder of each 0.5-1 mmol.
As a further preferable technical scheme of the invention, in the step 5), the dosage of the corresponding cleaning solvent for each cleaning is 20-30 ml based on the dosage of the selenium powder of 0.5-1 mmol in the step 3).
As a further preferable technical scheme of the invention, the anhydrous ethanol and the cyclohexane are mixed according to the volume ratio of 1:1 to prepare the cleaning solvent.
As a further preferable embodiment of the present invention, the reaction vessel is a three-necked flask.
As a further preferable embodiment of the present invention, the centrifugal apparatus is a centrifuge tube.
According to another aspect of the invention, the invention further provides an application of the manganese selenide nanometer material, the manganese selenide nanometer material is prepared by the preparation method of the manganese selenide nanometer material with different morphologies and phases, and the manganese selenide nanometer material is applied to a lithium ion battery as a positive electrode material or a lithium sulfur battery as a diaphragm material.
The preparation method of the manganese selenide nanometer material with different morphologies and phases can achieve the following beneficial effects by adopting the technical scheme:
1) The preparation method is simple, and the manganese selenide nano-materials with different morphologies and phases are controllably obtained by adjusting experimental conditions such as reaction time/temperature, types of precursors (manganese acetylacetonate and manganese acetate tetrahydrate), types of surfactants (oleylamine, oleic acid and octadecene) and proportions, wherein the morphologies are cubic particles and quadrangular pyramids, and the phases are alpha and gamma;
2) The size of the prepared manganese selenide nano material is nano-scale and micro-scale, and the size is diversified to meet different requirements, wherein the micro-scale gamma-manganese selenide quadrangular pyramid structure is easier to form a film in the energy application process than the nano-scale gamma-manganese selenide quadrangular pyramid structure;
3) The method has mild reaction conditions, does not need harsh reaction conditions such as high pressure and the like, does not need to add other substances as templates, has low cost, namely can realize the effective control of synthesizing the manganese selenide nano material without using an expensive catalyst;
4) The manganese selenide nano material prepared by the preparation method has various shapes, pure components and uniform size, and has good monodispersity and crystallinity.
Drawings
The invention will be described in further detail with reference to the drawings and the detailed description.
Fig. 1 is a transmission electron microscope image of an α -manganese selenide nanoparticle prepared according to an embodiment of the invention.
Fig. 2 is a transmission electron microscope image of a gamma-manganese selenide nano quadrangular pyramid prepared in the second embodiment of the present invention.
FIG. 3 is an X-ray powder diffraction pattern of a gamma-manganese selenide nanopyramid prepared in example II of the present invention.
Fig. 4 is a transmission electron microscope image of an α -manganese selenide nano-cube prepared in accordance with example three of the invention.
Fig. 5 is a transmission electron microscope image of a-manganese selenide nano-cube prepared in accordance with example four of the invention.
Fig. 6 is an X-ray powder diffraction pattern of the α -manganese selenide nanomaterial prepared in example one, example three, and example four of the present invention.
Fig. 7 is a transmission electron microscope image of a gamma-manganese selenide micro-quadrangular pyramid prepared in example five of the present invention.
The achievement of the objects, functional features and advantages of the present invention will be further described with reference to the accompanying drawings, in conjunction with the embodiments.
Detailed Description
The invention will be further described with reference to the drawings and detailed description. The terms such as "upper", "lower", "left", "right", "middle" and "a" in the preferred embodiments are merely descriptive, but are not intended to limit the scope of the invention, as the relative relationship changes or modifications may be otherwise deemed to be within the scope of the invention without substantial modification to the technical context.
Example 1
The embodiment comprises the following steps:
(1) 1mmol of manganese acetylacetonate is weighed and added into a 50mL three-necked bottle;
(2) Adding 20mmol of oleylamine and 20mmol of octadecene into the three-necked flask in the step (1);
(3) Heating the mixed solution in the step (2) to 120 ℃, vacuumizing and stirring for 60min at 120 ℃, and introducing nitrogen gas after the solution is clarified and transparent so as to enable the subsequent reaction to be carried out under the nitrogen atmosphere, thus obtaining a reaction solution;
(4) 1mmol of selenium powder is weighed and dispersed in 0.1mL of mixed liquid of dodecyl mercaptan and 3mL of oleylamine by ultrasonic to obtain selenium powder dispersion;
(5) Rapidly heating the reaction liquid in the three-necked bottle in the step (3) to 220 ℃, rapidly injecting the selenium powder dispersion liquid obtained in the step (4) into the reaction liquid, and reacting for 2 hours at 220 ℃;
(6) After the reaction is finished and the three-necked bottle in the step (5) is cooled to room temperature, transferring the solution in the three-necked bottle into a 50mL centrifuge tube, centrifugally separating at 8500rpm for 9min, repeatedly cleaning for 3 times, adding 20mL of cleaning solvent during each cleaning, and mixing the cleaning solvent with absolute ethyl alcohol and cyclohexane according to the volume ratio of 1:1;
(7) And (3) placing the cleaned substance in the step (6) in a vacuum drying oven, and drying at 65 ℃ for 12 hours to obtain a powder manganese selenide nano-material sample.
The manganese selenide nano material sample prepared by the method is alpha-manganese selenide nano particles in an alpha phase state, the morphology characterization of the nano particles is shown in figure 1 by using a transmission electron microscope, and the prepared nano particles have good monodispersity and uniform particle size of about 25nm.
Example two
The embodiment comprises the following steps:
(1) 0.5mmol of manganese acetate tetrahydrate is weighed and added into a 50mL three-necked bottle;
(2) 16mmol of oleylamine, 2mmol of oleic acid and 6mmol of octadecene are added to the three-necked flask in the step (1);
(3) Heating the mixed solution in the step (2) to 120 ℃, vacuumizing and stirring for 60min at 120 ℃, clarifying and transparentizing the solution, and then introducing nitrogen gas to carry out the subsequent reaction under the nitrogen atmosphere.
(4) Weighing 0.5mmol selenium powder, and ultrasonically dispersing the selenium powder into 0.1mL mixed liquid of dodecyl mercaptan and 1.2mL oleylamine to obtain a selenium powder dispersion;
(5) Rapidly heating the reaction liquid in the three-necked bottle in the step (3) to 210 ℃, rapidly injecting the selenium powder dispersion liquid obtained in the step (4) into the reaction liquid, and reacting for 2 hours at 210 ℃;
(6) After the three-necked bottle in the step (5) is cooled to room temperature after the reaction is finished, transferring the solution in the three-necked bottle into a 50mL centrifuge tube, adding 25mL of cleaning solvent prepared by mixing absolute ethanol and cyclohexane into the centrifuge tube, centrifugally separating the mixture at 8000rpm for 10min, and repeatedly cleaning the mixture for 4 times;
(7) And (3) placing the sample cleaned in the step (6) in a vacuum drying oven, and drying at 65 ℃ for 12 hours to obtain a powder manganese selenide nano-material sample.
The sample of the manganese selenide nano material prepared by the method of the embodiment is gamma-manganese selenide nano quadrangular cone in gamma phase state (the edge length is in nano level), and the appearance characterization of the sample is shown in figure 2 by using a transmission electron microscope, so that the diameter of four supporting legs of the gamma-manganese selenide nano quadrangular cone is about 10nm, and the length is about 100nm.
The gamma-manganese selenide nano quadrangular pyramid prepared in the embodiment is subjected to X-ray powder diffraction analysis: the experimentally prepared samples were ground to powder using a mortar and tiled on a sample stage for XRD testing. The target is bombarded with Cu as a high energy electron beam (Cu ka,) The scan rate was measured at 5 °/min and the scan range was 20 ° -70 °, with the result that as shown in fig. 3, the several main diffraction peaks (100), (002), (101), (110), (103) and (112) in the XRD diffractogram were analyzed, and the manganese selenide was hexagonal phase gamma-manganese selenide with a lattice constant +.>
Example III
The embodiment comprises the following steps:
(1) 1mmol of manganese acetylacetonate is weighed and added into a 50mL three-necked bottle;
(2) Adding 20.0mmoL of oleylamine and 20.0mmoL of octadecene into the three-necked flask in the step (1);
(3) Heating the mixed solution in the step (2) to 120 ℃, vacuumizing and stirring for 60min at 120 ℃, and introducing nitrogen gas after the solution is clarified and transparent, so that the subsequent reaction is carried out under the nitrogen atmosphere;
(4) Weighing 0.5mmol selenium powder, and ultrasonically dispersing the selenium powder into 0.1mL mixed liquid of dodecyl mercaptan and 3.0mL oleylamine to obtain a selenium powder dispersion;
(5) Rapidly heating the reaction liquid in the three-necked bottle in the step (3) to 280 ℃, rapidly injecting the selenium powder dispersion liquid obtained in the step (4) into the reaction liquid, and reacting for 30min at 280 ℃;
(6) After the reaction is finished and the three-necked bottle in the step (5) is cooled to room temperature, transferring the solution in the three-necked bottle into a 50mL centrifuge tube, adding 20mL of cleaning solvent prepared by mixing absolute ethanol and cyclohexane into the centrifuge tube, centrifugally separating at 9000rpm for 8min, and repeatedly cleaning for 5 times;
(7) And (3) placing the sample cleaned in the step (6) in a vacuum drying oven, and drying at 65 ℃ for 12 hours to obtain a powder manganese selenide nano-material sample.
The sample of the manganese selenide nano material prepared by the method is an alpha-manganese selenide nano small cube in an alpha phase state, the morphological characterization of the nano small cube is shown in figure 4 by using a transmission electron microscope, and the side length of the prepared nano small cube is about 50nm.
Example IV
The embodiment comprises the following steps:
(1) 0.5mmol of manganese acetate tetrahydrate is weighed and added into a 50mL three-necked bottle;
(2) 26.6mmol of oleylamine, 3.4mmol of oleic acid and 10mmol of octadecene are introduced into a three-necked flask in the step (1);
(3) Heating the mixed solution in the step (2) to 120 ℃, vacuumizing and stirring for 60min at 120 ℃, and introducing nitrogen gas after the solution is clarified and transparent, so that the subsequent reaction is carried out under the nitrogen atmosphere;
(4) Weighing 0.5mmol selenium powder, and ultrasonically dispersing the selenium powder into 0.1mL mixed liquid of dodecyl mercaptan and 3.0mL oleylamine to obtain a selenium powder dispersion liquid for later use;
(5) Rapidly heating the reaction liquid in the three-necked bottle in the step (3) to 220 ℃, rapidly injecting the selenium powder dispersion liquid obtained in the step (4) into the reaction liquid, and reacting for 2 hours at 220 ℃;
(6) After the reaction is finished and the three-necked bottle in the step (5) is cooled to room temperature, transferring the solution in the three-necked bottle into a 50mL centrifuge tube, adding 30mL of cleaning solvent prepared by mixing absolute ethyl alcohol and cyclohexane into the centrifuge tube, centrifugally separating the mixture at 8500rpm for 9min, and repeatedly cleaning the mixture for 3 times;
(7) And (3) placing the sample cleaned in the step (6) in a vacuum drying oven, and drying at 65 ℃ for 12 hours to obtain a powder manganese selenide nano-material sample.
The manganese selenide nano material sample prepared by the method is an alpha-manganese selenide nano large cube, the appearance characterization of the nano large cube is shown in figure 5 by using a transmission electron microscope, the appearance and the size of the prepared nano large cube are uniform, and the side length of the cube is about 100nm.
The three groups of manganese selenide nanomaterial samples prepared in example one (nanoparticle), example three (small cube), and example four (large cube) were each subjected to X-ray powder diffraction analysis, as follows: and grinding the experimentally prepared manganese selenide nano-material sample into powder by using a mortar, and laying the powder on a sample table for XRD test. The target is bombarded with Cu as a high energy electron beam (Cu ka,) The scan rate was measured at 5 °/min and the scan range was 20 ° -80 °, with the results shown in fig. 6. The manganese selenide nanomaterial sample was cubic phase alpha-MnSe (NaCl-type, space group: fm-3m, JCPDS: 11-0683) with lattice constant +.>It can be seen from the figure that the XRD diffraction peak intensities of the α -MnSe nanomaterials of different morphologies and sizes are different, and the XRD diffraction peak intensities are enhanced as the nanomaterial size is increased. The alpha-manganese selenide nanometer big cube has higher XRD diffraction peak intensity, thereby proving that the size is larger.
Example five
The embodiment comprises the following steps:
(1) Weighing 0.5mmol of manganese acetylacetonate, and adding into a 50mL three-necked bottle;
(2) 16mmol of oleylamine, 2mmol of oleic acid and 6mmol of octadecene are added to the three-necked flask in the step (1);
(3) Heating the mixed solution in the step (2) to 120 ℃, vacuumizing and stirring for 60min at 120 ℃, and introducing nitrogen gas after the solution is clarified and transparent, so that the subsequent reaction is carried out under the nitrogen atmosphere;
(4) Weighing 0.5mmol selenium powder, and ultrasonically dispersing the selenium powder into 0.1mL mixed liquid of dodecyl mercaptan and 1.2mL oleylamine to obtain a selenium powder dispersion;
(5) Rapidly heating the reaction liquid in the three-necked bottle in the step (3) to 210 ℃, rapidly injecting the selenium powder dispersion liquid obtained in the step (4) into the reaction liquid, and reacting for 2 hours at 210 ℃;
(6) After the reaction is finished and the three-necked bottle in the step (5) is cooled to room temperature, transferring the solution in the three-necked bottle into a 50mL centrifuge tube, adding 30mL of cleaning solvent prepared by mixing absolute ethanol and cyclohexane into the centrifuge tube, centrifugally separating at 9000rpm for 8min, and repeatedly cleaning for 4 times;
(7) And (3) placing the sample cleaned in the step (6) in a vacuum drying oven, and drying at 65 ℃ for 12 hours to obtain a powder manganese selenide nano-material sample.
The sample of the manganese selenide nano material prepared by the method is gamma-manganese selenide quadrangular pyramid (the edge length is in the micron level), and the morphological characterization of the sample is shown in fig. 7 by using a transmission electron microscope, so that the length of four supporting legs of the micron-level gamma-manganese selenide quadrangular pyramid is obviously in the micron level, and compared with the nano-level gamma-manganese selenide quadrangular pyramid structure, the micron-level gamma-manganese selenide quadrangular pyramid structure is easier to form a film in the energy application process.
Example six
The embodiment comprises the following steps:
(1) 0.5mmol of manganese acetate tetrahydrate is weighed and added into a 50mL three-necked bottle;
(2) 26.6mmol of oleylamine, 3.4mmol of oleic acid and 10mmol of octadecene are introduced into a three-necked flask in the step (1);
(3) Heating the mixed solution in the step (2) to 120 ℃, vacuumizing and stirring for 60min at 120 ℃, and introducing nitrogen gas after the solution is clarified and transparent, so that the subsequent reaction is carried out under the nitrogen atmosphere;
(4) 1mmol of selenium powder is weighed and dispersed in 0.1mL of mixed liquid of dodecyl mercaptan and 3mL of oleylamine in an ultrasonic way, and the obtained selenium powder dispersion liquid is reserved;
(5) Rapidly heating the reaction liquid in the three-necked bottle in the step (3) to 220 ℃, rapidly injecting the selenium powder dispersion liquid obtained in the step (4) into the reaction liquid, and reacting for 2 hours at 220 ℃;
(6) After the reaction is finished and the three-necked bottle in the step (5) is cooled to room temperature, transferring the solution in the three-necked bottle into a 50mL centrifuge tube, adding a cleaning solvent prepared by mixing 30mL of ethanol with cyclohexane, centrifuging at 8500rpm for 9min, and repeatedly cleaning for 3 times;
(7) And (3) placing the sample cleaned in the step (6) in a vacuum drying oven, and drying at 65 ℃ for 12 hours to obtain a powder manganese selenide nano-material sample.
Example seven
The embodiment comprises the following steps:
(1) 0.5mmol of manganese acetate tetrahydrate is weighed and added into a 50mL three-necked bottle;
(2) To the three-necked flask in step (1) were added 20mmol of oleylamine, 10mmol of oleic acid and 10mmol of octadecene;
(3) Heating the mixed solution in the step (2) to 120 ℃, vacuumizing and stirring for 60min at 120 ℃, and introducing nitrogen gas after the solution is clarified and transparent, so that the subsequent reaction is carried out under the nitrogen atmosphere;
(4) Weighing 0.5mmol selenium powder, and dispersing the selenium powder in 0.1mL mixed solution of dodecyl mercaptan and 3mL of oleylamine for later use;
(5) Rapidly heating the reaction liquid in the three-necked bottle in the step (3) to 230 ℃, rapidly injecting the selenium powder dispersion liquid obtained in the step (4) into the reaction liquid, and reacting for 2 hours at 230 ℃;
(6) After the reaction is finished and the three-necked bottle in the step (5) is cooled to room temperature, transferring the solution in the three-necked bottle into a 50mL centrifuge tube, adding 30mL of cleaning solvent prepared by mixing absolute ethanol and cyclohexane into the centrifuge tube, centrifugally separating at 8000rpm for 10min, and repeatedly cleaning for 4 times;
(7) And (3) placing the sample cleaned in the step (6) in a vacuum drying oven, and drying at 65 ℃ for 12 hours to obtain a powder manganese selenide nano-material sample.
Example eight
The embodiment comprises the following steps:
(1) 0.5mmol of manganese acetate tetrahydrate is weighed and added into a 50mL three-necked bottle;
(2) To the three-necked flask in step (1) were added 27.7mmol of oleylamine, 2.3mmol of oleic acid and 10mmol of octadecene;
(3) Heating the mixed solution in the step (2) to 120 ℃, vacuumizing and stirring for 60min at 120 ℃, and introducing nitrogen gas after the solution is clarified and transparent, so that the subsequent reaction is carried out under the nitrogen atmosphere;
(4) Weighing 0.5mmol selenium powder, and ultrasonically dispersing the selenium powder into 0.1mL mixed liquid of dodecyl mercaptan and 3mL oleylamine to obtain a selenium powder dispersion;
(5) Rapidly heating the reaction liquid in the three-necked bottle in the step (3) to 220 ℃, rapidly injecting the selenium powder dispersion liquid obtained in the step (4) into the reaction liquid, and reacting for 2 hours at 220 ℃;
(6) After the reaction is finished and the three-necked bottle in the step (5) is cooled to room temperature, transferring the solution in the three-necked bottle into a 50mL centrifuge tube, adding 20mL of cleaning solvent prepared by mixing absolute ethyl alcohol and cyclohexane into the centrifuge tube, centrifugally separating the mixture at 8500rpm for 9min, and repeatedly cleaning the mixture for 3 times;
(7) And (3) placing the sample cleaned in the step (6) in a vacuum drying oven, and drying at 65 ℃ for 12 hours to obtain a powder manganese selenide nano-material sample.
According to comprehensive analysis of the first to eighth embodiments, the preparation method provided by the invention has the advantages of mild reaction conditions, no need of harsh reaction conditions such as high pressure and the like, no need of adding other substances as templates, low cost, no need of using expensive catalysts, and capability of effectively controlling the synthesis of the manganese selenide nano material; the manganese selenide material prepared by the preparation method of the manganese selenide nano material has various shapes, pure components and uniform size, and the prepared manganese selenide nano material has good monodispersity and crystallinity; the invention can control the nucleation and growth of crystal more easily, and can obtain the manganese selenide nano-material (alpha-manganese selenide nanocube, alpha-manganese selenide nano-particle and gamma-manganese selenide nano-tetrapod) with different morphology and phase state controllably by adjusting the experimental conditions of reaction time/temperature, the types of precursors (manganese acetylacetonate, manganese acetate tetrahydrate), the types of surfactants (oleylamine, oleic acid, octadecene) and the proportion, and the like, namely, the morphology, the size, the phase state and the like of the final nano-crystal are adjusted so as to meet different application requirements.
According to another aspect of the invention, the invention further provides an application of the manganese selenide nanometer material, wherein the manganese selenide nanometer material is prepared by the preparation method of the manganese selenide nanometer material with different morphologies and phases, and the manganese selenide nanometer material is applied to a lithium ion battery as a positive electrode material or a lithium sulfur battery as a diaphragm material.
While particular embodiments of the present invention have been described above, it will be appreciated by those skilled in the art that these are merely illustrative, and that many variations or modifications may be made to the embodiments without departing from the principles and spirit of the invention, the scope of which is defined only by the appended claims.

Claims (5)

1. The preparation method of the manganese selenide nanometer material with different morphologies and phases is characterized by comprising the following steps:
1) Adding a manganese-based precursor, oleylamine and octadecene, or adding the manganese-based precursor, oleylamine, oleic acid and octadecene into a reaction container to form a mixed solution; the molar ratio of the manganese-based precursor to the oleylamine to the oleic acid to the octadecene is 0.5-1: 16 to 27.7:0 to 10: 6-20, wherein the manganese-based precursor is one or two of manganese acetylacetonate and manganese acetate tetrahydrate;
2) Heating the mixed solution in the reaction vessel to 100-140 ℃, vacuumizing under the temperature condition, stirring for 30-60min, clarifying and transparency, and introducing nitrogen to obtain a reaction solution;
3) Taking selenium powder to be ultrasonically dispersed in mixed liquid of dodecyl mercaptan and oleylamine to obtain selenium powder dispersion liquid, wherein the dosage of the corresponding dodecyl mercaptan is 0.1mL and the dosage of the oleylamine is 1.2-3 mL based on the dosage of selenium powder of every 0.5-1 mmol; the molar ratio of the selenium powder obtained in the step 3) to the manganese-based precursor obtained in the step 1) is 0.5-1: 0.5 to 1;
4) Under the nitrogen atmosphere, the reaction liquid in the reaction vessel in the step 2) is quickly heated to 210-280 ℃, then the selenium powder dispersion liquid obtained in the step 3) is injected into the reaction vessel for reaction for 30 min-2 h;
5) Cooling the solution in the reaction container to room temperature after the reaction in the step 4), transferring the solution in the reaction container to centrifugal equipment, and performing centrifugal separation at a rotating speed of 8500-9000 rpm for 8-10 min to realize cleaning, repeatedly cleaning for 3-5 times, and adding a cleaning solvent formed by mixing absolute ethyl alcohol and cyclohexane during each cleaning;
6) And 5) placing the residues after the cleaning in the step 5) into a vacuum drying oven to be dried for 10-20 hours at 50-85 ℃ to obtain the powdery manganese selenide nano-material.
2. The method for preparing the manganese selenide nanometer material with different morphologies and phases according to claim 1, wherein the anhydrous ethanol and the cyclohexane are mixed according to a volume ratio of 1:1 to prepare a cleaning solvent.
3. The method for preparing the manganese selenide nanometer material with different morphologies and phases according to claim 1, wherein the reaction vessel is a three-necked bottle.
4. A method of preparing manganese selenide nanomaterials of different morphologies and phases according to any one of claims 1 to 3, wherein the centrifuge apparatus is a centrifuge tube.
5. The application of the manganese selenide nanometer material is characterized in that the manganese selenide nanometer material is prepared by the preparation method of the manganese selenide nanometer material with different morphologies and phases according to any one of claims 1-4, and the manganese selenide nanometer material is applied to a lithium ion battery as a positive electrode material or a lithium sulfur battery as a diaphragm material.
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