CN114560449A - Preparation method and application of manganese selenide nano-materials with different shapes and phases - Google Patents

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

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CN114560449A
CN114560449A CN202210171164.5A CN202210171164A CN114560449A CN 114560449 A CN114560449 A CN 114560449A CN 202210171164 A CN202210171164 A CN 202210171164A CN 114560449 A CN114560449 A CN 114560449A
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manganese
manganese selenide
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CN114560449B (en
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李娜
封婕
丁书江
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Xian Jiaotong University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B19/00—Selenium; Tellurium; Compounds thereof
    • C01B19/007—Tellurides or selenides of metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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    • C01—INORGANIC CHEMISTRY
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    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2004/01—Particle morphology depicted by an image
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    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

A preparation method and application of manganese selenide nanometer materials with different shapes and phases are provided, 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 container, vacuumizing at the temperature, stirring to ensure that the mixed solution is 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; quickly heating the reaction solution in the reaction container, and injecting the selenium powder dispersion solution into the reaction container for reaction; cooling the solution in the reaction container to room temperature, and transferring the solution in the reaction container to a centrifugal device; performing centrifugal separation to realize cleaning; and drying the cleaned residue to obtain the powdery manganese selenide nanometer material. The manganese selenide nano material prepared by the method has various shapes, pure components, uniform size, good monodispersity and good crystallinity.

Description

Preparation method and application of manganese selenide nano-materials with different shapes and phases
Technical Field
The invention relates to the technical field of synthesis and preparation of nano materials, in particular to a preparation method and application of manganese selenide nano materials with different shapes and phases.
Background
In recent years, semiconductor nanocrystals have attracted considerable interest to researchers in the areas of basic research and technological applications. In general, the physical and chemical properties of semiconductor nanocrystals depend to a large extent on their morphology, size, phase state, and crystal structure. Therefore, the characteristics of the semiconductor nanocrystal (such as electronic equipment, a photoelectric detector, a solar cell, a sensor and the like) in various equipment applications can be well adjusted by effectively regulating the appearance, the size and the phase state of the semiconductor nanocrystal, so that the equipment performance is optimized.
Among the numerous types of nanocrystals, transition metal chalcogenides (sulfides, selenides, and tellurides) have attracted much attention due to their exceptional 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 Mn2+The strong sp-d mutual exchange effect 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 good control of the morphology and phase of the nanocrystals.
Therefore, there is a need to develop a simple synthesis method to control the nucleation and growth of the crystal more easily, so as to adjust the morphology, size, phase state, etc. of the final nanocrystal.
Disclosure of Invention
Based on the above, the invention provides a preparation method of manganese selenide nanometer materials with different shapes and phases, so as to solve the technical problems that the synthesis method of the nanometer crystal in the prior art is complex and the shape and phase of the nanometer crystal cannot be well controlled.
In order to achieve the purpose, the invention provides a preparation method of manganese selenide nanometer materials with different shapes 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 container to 140 ℃ at 100 ℃, vacuumizing at the temperature, stirring for 30-60min to ensure that the mixed solution is clear and transparent, 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) rapidly heating the reaction liquid in the reaction container in the step 2) to 210-280 ℃ in a nitrogen atmosphere, then injecting the selenium powder dispersion liquid obtained in the step 3) into the reaction container, and reacting for 30 min-2 h;
5) after the reaction in the step 4) is finished, cooling the solution in the reaction container to room temperature, transferring the solution in the reaction container to a centrifugal device, carrying out centrifugal separation for 8-10 min at the rotating speed of 8500-9000 rpm 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 (3) drying the residue cleaned in the step 5) in a vacuum drying oven at 50-85 ℃ for 10-20h 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, oleylamine, oleic acid and octadecene is 0.5-1: 16-27.7: 0-10: 6-20, and mixing.
As a further preferable technical scheme of the invention, the manganese-based precursor in the 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 obtained in the step 3) to the manganese-based precursor obtained in the step 1) is 0.5-1: 0.5 to 1.
As a further preferable technical scheme, in the step 3), the dosage of the corresponding dodecanethiol is 0.1mL and the dosage of the oleylamine is 1.2-3 mL based on the dosage of each 0.5-1 mmol of selenium powder.
As a further preferable technical scheme of the invention, in the step 5), the dosage of the cleaning solvent corresponding to 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 absolute ethyl alcohol and the cyclohexane are mixed according to the volume ratio of 1:1 to prepare a cleaning solvent.
In a further preferred embodiment of the present invention, the reaction vessel is a three-necked flask.
In a further preferred embodiment of the present invention, the centrifugal apparatus is a centrifugal tube.
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 any one of the manganese selenide nanometer materials with different shapes 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.
By adopting the technical scheme, the preparation method of the manganese selenide nanometer materials with different shapes and phases can achieve the following beneficial effects:
1) the preparation method is simple, and the manganese selenide nanometer materials with different shapes and phases can be obtained controllably by adjusting the reaction time/temperature, the types (manganese acetylacetonate, manganese acetate tetrahydrate) of the precursor, the types (oleylamine, oleic acid and octadecene) and the proportion of the surfactant and other experimental conditions, wherein the shapes of the manganese selenide nanometer materials are cubic particles and quadrangular pyramids, and the phases of the manganese selenide nanometer materials are alpha and gamma;
2) the size of the manganese selenide nanometer material prepared by the invention is nano-scale and micron-scale, and the size is diversified so as to meet different requirements, wherein compared with the nano-scale gamma-manganese selenide quadrangular pyramid structure, the micron-scale gamma-manganese selenide quadrangular pyramid structure is easier to form a film in the energy application process;
3) the method has mild reaction conditions, does not need severe reaction conditions such as high pressure and the like, does not need to add other substances as templates, has low cost, and can realize effective control synthesis of the manganese selenide nano material without using expensive catalysts;
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 present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
Fig. 1 is a transmission electron microscope image of the α -manganese selenide nanoparticles prepared in the first embodiment of the present invention.
Fig. 2 is a transmission electron microscope image of a gamma-manganese selenide nanopyramid prepared in the second embodiment of the present invention.
Fig. 3 is an X-ray powder diffraction pattern of the gamma-manganese selenide nano-quadrangular pyramid prepared in the second embodiment of the present invention.
Fig. 4 is a transmission electron microscope image of small α -manganese selenide nano-cubes prepared in the third embodiment of the present invention.
Fig. 5 is a transmission electron microscope image of nano-cubic α -manganese selenide prepared in example four of the present invention.
Fig. 6 is an X-ray powder diffraction pattern of the α -manganese selenide nanomaterial prepared in the first, third, and fourth embodiments of the present invention.
Fig. 7 is a transmission electron microscope image of a gamma-manganese selenide micron quadrangular pyramid prepared in the sixth embodiment of the invention.
The objects, features and advantages of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
The invention will be further described with reference to the accompanying drawings and specific embodiments. In the preferred embodiments, the terms "upper", "lower", "left", "right", "middle" and "a" are used for clarity of description only, and are not used to limit the scope of the invention, and the relative relationship between the terms and the terms is not changed or modified substantially without changing the technical content of the invention.
Example one
The embodiment comprises the following steps:
(1) weighing 1mmol of manganese acetylacetonate, and adding into a 50mL three-necked bottle;
(2) adding 20mmol of oleylamine and 20mmol of octadecene into the three-necked bottle in the step (1);
(3) heating the mixed solution in the step (2) to 120 ℃, vacuumizing and stirring for 60min at 120 ℃, introducing nitrogen gas after the solution is clear and transparent, so that the subsequent reaction is carried out in the nitrogen atmosphere, and obtaining reaction liquid;
(4) weighing 1mmol of selenium powder, and ultrasonically dispersing the selenium powder in a mixed liquid of 0.1mL of dodecanethiol and 3mL of oleylamine to obtain a selenium powder dispersion liquid;
(5) quickly heating the reaction liquid in the three-necked bottle in the step (3) to 220 ℃, quickly 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 cold solution in the three-necked bottle into a 50mL centrifuge tube, carrying out centrifugal separation at 8500rpm for 9min, repeatedly cleaning for 3 times, adding 20mL cleaning solvent during each cleaning, and mixing absolute ethyl alcohol and cyclohexane according to the volume ratio of 1:1 to prepare the cleaning solvent;
(7) and (4) placing the substance cleaned in the step (6) in a vacuum drying oven, and drying at 65 ℃ for 12h to obtain a powdery manganese selenide nanometer material sample.
The manganese selenide nano-material sample prepared by the method is alpha-manganese selenide nano-particles in an alpha phase state, and the appearance of the manganese selenide nano-material sample is represented by using a transmission electron microscope as shown in figure 1, so that the prepared nano-particles have good monodispersity and the uniform size of the particles is about 25 nm.
Example two
The embodiment comprises the following steps:
(1) weighing 0.5mmol of manganese acetate tetrahydrate and adding the manganese acetate tetrahydrate into a 50mL three-necked bottle;
(2) adding 16mmol of oleylamine, 2mmol of oleic acid and 6mmol of octadecene into the three-necked bottle in the step (1);
(3) and (3) heating the mixed solution obtained in the step (2) to 120 ℃, vacuumizing and stirring for 60min at 120 ℃, introducing nitrogen gas after the solution is clear and transparent, and carrying out subsequent reaction in the nitrogen atmosphere.
(4) Weighing 0.5mmol of selenium powder, and ultrasonically dispersing the selenium powder in a mixed liquid of 0.1mL of dodecanethiol and 1.2mL of oleylamine to obtain a selenium powder dispersion liquid;
(5) quickly heating the reaction liquid in the three-necked bottle in the step (3) to 210 ℃, quickly 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 25mL of cleaning solvent prepared by mixing absolute ethyl alcohol and cyclohexane, performing centrifugal separation at 8000rpm for 10min, and repeatedly cleaning for 4 times;
(7) and (4) drying the sample cleaned in the step (6) in a vacuum drying oven at 65 ℃ for 12 hours to obtain a powdery manganese selenide nanometer material sample.
The manganese selenide nanometer material sample prepared by the method of the embodiment is a gamma-manganese selenide nanometer quadrangular pyramid (the length of the side is at the nanometer level) in a gamma phase state, and the appearance of the manganese selenide nanometer material sample is represented by a transmission electron microscope as shown in figure 2, so that the diameter of four support legs of the gamma-manganese selenide nanometer quadrangular pyramid is about 10nm, and the length of the four support legs is about 100 nm.
The gamma-manganese selenide nano-quadrangular pyramid prepared in the embodiment is subjected to X-ray powder diffraction analysis: the samples prepared in the experiment were ground to powder using a mortar and spread on a sample table for XRD testing. The target is bombarded with a high-energy electron beam of Cu (Cu K alpha,
Figure BDA0003517695680000051
) The scan rate of the test was 5 °/min, the scan range was 20 ° -70 °, and the result is shown in fig. 3, which is analyzed by several main diffraction peaks (100), (002), (101), (110), (103), and (112) in the XRD diffractogram, the manganese selenide was hexagonal phase γ -manganese selenide with a lattice constant of 5 °/min
Figure BDA0003517695680000052
EXAMPLE III
The embodiment comprises the following steps:
(1) weighing 1mmol of manganese acetylacetonate, and adding the manganese acetylacetonate into a 50mL three-necked bottle;
(2) adding 20.0mmoL oleylamine and 20.0mmoL octadecene into the three-necked bottle in the step (1);
(3) heating the mixed solution in the step (2) to 120 ℃, vacuumizing and stirring for 60min at 120 ℃, introducing nitrogen gas after the solution is clear and transparent, and carrying out subsequent reaction under the nitrogen atmosphere;
(4) weighing 0.5mmol of selenium powder, and ultrasonically dispersing the selenium powder in a mixed liquid of 0.1mL of dodecanethiol and 3.0mL of oleylamine to obtain a selenium powder dispersion liquid;
(5) quickly heating the reaction liquid in the three-necked bottle in the step (3) to 280 ℃, quickly 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 cleaning solvent prepared by mixing absolute ethyl alcohol and cyclohexane, performing centrifugal separation at 9000rpm for 8min, and repeatedly cleaning for 5 times;
(7) and (5) drying the sample cleaned in the step (6) in a vacuum drying oven at 65 ℃ for 12 hours to obtain a powdery manganese selenide nanometer material sample.
The manganese selenide nanometer material sample prepared by the method is an alpha-phase alpha-manganese selenide nanometer small cube, the appearance of the sample is characterized by using a transmission electron microscope, and the side length of the prepared nanometer small cube is about 50nm as shown in figure 4.
Example four
The embodiment comprises the following steps:
(1) weighing 0.5mmol of manganese acetate tetrahydrate and adding the manganese acetate tetrahydrate into a 50mL three-necked bottle;
(2) adding 26.6mmol of oleylamine, 3.4mmol of oleic acid and 10mmol of octadecene into the three-necked bottle in the step (1);
(3) heating the mixed solution in the step (2) to 120 ℃, vacuumizing and stirring for 60min at 120 ℃, introducing nitrogen gas after the solution is clear and transparent, and carrying out subsequent reaction under the nitrogen atmosphere;
(4) weighing 0.5mmol of selenium powder, and ultrasonically dispersing the selenium powder in a mixed liquid of 0.1mL of dodecanethiol and 3.0mL of oleylamine to obtain a selenium powder dispersion liquid for later use;
(5) quickly heating the reaction liquid in the three-necked bottle in the step (3) to 220 ℃, quickly 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 cleaning solvent prepared by mixing absolute ethyl alcohol and cyclohexane, performing centrifugal separation at 8500rpm for 9min, and repeatedly cleaning for 3 times;
(7) and (4) drying the sample cleaned in the step (6) in a vacuum drying oven at 65 ℃ for 12 hours to obtain a powdery manganese selenide nanometer material sample.
The manganese selenide nanometer material sample prepared by the method of the embodiment is an alpha-manganese selenide nanometer large cube, the appearance and the size of the prepared nanometer large cube are uniform, and the side length of the cube is about 100nm, wherein the appearance and the size of the prepared nanometer large cube are represented as shown in figure 5 by using a transmission electron microscope.
Three groups of manganese selenide nanometer material samples prepared in the first example (nanometer particles), the third example (small cubic blocks) and the fourth example (large cubic blocks) are respectively subjected to X-ray powder diffraction analysis, and the details are as follows: the manganese selenide nanometer material sample prepared in the experiment is ground into powder by using a mortar and is flatly paved on a sample table for XRD test. The target is bombarded with a high-energy electron beam of Cu (Cu K alpha,
Figure BDA0003517695680000061
) The scan rate tested was 5 deg./min, the scan range was 20 deg. -80 deg., and the results are shown in fig. 6. The manganese selenide nano material sample is cubic phase alpha-MnSe (NaCl-type, space group: Fm-3m, JCPDS: 11-0683) and has a lattice constant of
Figure BDA0003517695680000062
It can be seen from the figure that the XRD diffraction peak intensities of the alpha-MnSe nanometer materials with different shapes and sizes are different, and the XRD diffraction peak intensity is enhanced along with the increase of the size of the nanometer materials. The nanometer cubic block of the manganese selenide has higher XRD diffraction peak intensity, thereby proving that the size of the nanometer cubic block is larger.
EXAMPLE five
The embodiment comprises the following steps:
(1) weighing 0.5mmol of manganese acetylacetonate, and adding the manganese acetylacetonate into a 50mL three-necked bottle;
(2) adding 16mmol of oleylamine, 2mmol of oleic acid and 6mmol of octadecene into the three-necked bottle in the step (1);
(3) heating the mixed solution in the step (2) to 120 ℃, vacuumizing and stirring for 60min at 120 ℃, introducing nitrogen gas after the solution is clear and transparent, and carrying out subsequent reaction under the nitrogen atmosphere;
(4) weighing 0.5mmol of selenium powder, and ultrasonically dispersing the selenium powder in a mixed liquid of 0.1mL of dodecanethiol and 1.2mL of oleylamine to obtain a selenium powder dispersion liquid;
(5) quickly heating the reaction liquid in the three-necked bottle in the step (3) to 210 ℃, quickly 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 to a 50mL centrifuge tube, adding 30mL of cleaning solvent prepared by mixing absolute ethyl alcohol and cyclohexane, performing centrifugal separation at 9000rpm for 8min, and repeatedly cleaning for 4 times;
(7) and (4) drying the sample cleaned in the step (6) in a vacuum drying oven at 65 ℃ for 12 hours to obtain a powdery manganese selenide nanometer material sample.
The manganese selenide nanometer material sample prepared by the method is a gamma-manganese selenide quadrangular pyramid (the length of the side is in micron scale), and the appearance representation by using a transmission electron microscope is shown in fig. 7, so that the length of four supporting legs of the micron gamma-manganese selenide quadrangular pyramid is obviously in micron scale, and compared with the nano gamma-manganese selenide quadrangular pyramid structure, the micron 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) weighing 0.5mmol of manganese acetate tetrahydrate and adding the manganese acetate tetrahydrate into a 50mL three-necked bottle;
(2) adding 26.6mmol of oleylamine, 3.4mmol of oleic acid and 10mmol of octadecene into the three-necked bottle in the step (1);
(3) heating the mixed solution in the step (2) to 120 ℃, vacuumizing and stirring for 60min at 120 ℃, introducing nitrogen gas after the solution is clear and transparent, and carrying out subsequent reaction under the nitrogen atmosphere;
(4) weighing 1mmol of selenium powder, and ultrasonically dispersing the selenium powder in a mixed liquid of 0.1mL of dodecanethiol and 3mL of oleylamine to obtain a selenium powder dispersion liquid for later use;
(5) quickly heating the reaction liquid in the three-necked bottle in the step (3) to 220 ℃, quickly 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 a cleaning solvent prepared by mixing anhydrous ethanol and cyclohexane, performing centrifugal separation at 8500rpm for 9min, and repeatedly cleaning for 3 times;
(7) and (4) drying the sample cleaned in the step (6) in a vacuum drying oven at 65 ℃ for 12 hours to obtain a powdery manganese selenide nanometer material sample.
EXAMPLE seven
The embodiment comprises the following steps:
(1) weighing 0.5mmol of manganese acetate tetrahydrate and adding the manganese acetate tetrahydrate into a 50mL three-necked bottle;
(2) adding 20mmol of oleylamine, 10mmol of oleic acid and 10mmol of octadecene into the three-necked bottle in the step (1);
(3) heating the mixed solution in the step (2) to 120 ℃, vacuumizing and stirring for 60min at 120 ℃, introducing nitrogen gas after the solution is clear and transparent, and carrying out subsequent reaction under the nitrogen atmosphere;
(4) weighing 0.5mmol of selenium powder, and ultrasonically dispersing the selenium powder in a mixed solution of 0.1mL of dodecanethiol and 3mL of oleylamine for later use;
(5) quickly heating the reaction liquid in the three-necked bottle in the step (3) to 230 ℃, quickly 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 cleaning solvent prepared by mixing absolute ethyl alcohol and cyclohexane, performing centrifugal separation at 8000rpm for 10min, and repeatedly cleaning for 4 times;
(7) and (4) drying the sample cleaned in the step (6) in a vacuum drying oven at 65 ℃ for 12 hours to obtain a powdery manganese selenide nanometer material sample.
Example eight
The embodiment comprises the following steps:
(1) weighing 0.5mmol of manganese acetate tetrahydrate and adding the manganese acetate tetrahydrate into a 50mL three-necked bottle;
(2) adding 27.7mmol of oleylamine, 2.3mmol of oleic acid and 10mmol of octadecene into the three-necked bottle in the step (1);
(3) heating the mixed solution in the step (2) to 120 ℃, vacuumizing and stirring for 60min at 120 ℃, introducing nitrogen gas after the solution is clear and transparent, and carrying out subsequent reaction under the nitrogen atmosphere;
(4) weighing 0.5mmol of selenium powder, and ultrasonically dispersing the selenium powder in a mixed liquid of 0.1mL of dodecanethiol and 3mL of oleylamine to obtain a selenium powder dispersion liquid;
(5) quickly heating the reaction liquid in the three-necked bottle in the step (3) to 220 ℃, quickly 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 to a 50mL centrifuge tube, adding 20mL cleaning solvent prepared by mixing absolute ethyl alcohol and cyclohexane, performing centrifugal separation at 8500rpm for 9min, and repeatedly cleaning for 3 times;
(7) and (4) drying the sample cleaned in the step (6) in a vacuum drying oven at 65 ℃ for 12 hours to obtain a powdery manganese selenide nanometer material sample.
Comprehensive analysis on the first embodiment to the eighth embodiment shows that the preparation method disclosed by the invention is mild in reaction conditions, does not need severe reaction conditions such as high pressure and the like, does not need to add other substances as a template, is low in cost, and can realize effective control and synthesis of the manganese selenide nanometer material without using an expensive catalyst; the manganese selenide material prepared by the preparation method of the manganese selenide nanometer material has various shapes, pure components and uniform size, and the prepared manganese selenide nanometer material has good monodispersity and crystallinity; the method can control nucleation and growth of crystals more easily, and can controllably obtain manganese selenide nano materials (alpha-manganese selenide nanocubes, alpha-manganese selenide nano particles and gamma-manganese selenide nano tetrapyramids) with different shapes and phases by adjusting experimental conditions such as reaction time/temperature, types of precursors (manganese acetylacetonate, manganese acetate tetrahydrate), types of surfactants (oleylamine, oleic acid, octadecene) and proportion, namely, the shapes, sizes, phases and the like of final nano crystals can be adjusted to meet different application requirements.
According to another aspect of the present invention, the present invention further provides an application of a manganese selenide nanometer material, wherein the manganese selenide nanometer material is prepared by the preparation method of the manganese selenide nanometer materials with different morphologies and phases described in any embodiment, 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.
Although specific embodiments of the present invention have been described above, it will be appreciated by those skilled in the art that these are merely examples 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 in the appended claims.

Claims (10)

1. A preparation method of manganese selenide nanometer materials with different shapes 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;
2) heating the mixed solution in the reaction container to 140 ℃ at 100 ℃, vacuumizing at the temperature, stirring for 30-60min to ensure that the mixed solution is clear and transparent, 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) in the nitrogen atmosphere, quickly heating the reaction liquid in the reaction container in the step 2) to 210-280 ℃, then injecting the selenium powder dispersion liquid obtained in the step 3) into the reaction container, and reacting for 30 min-2 h;
5) after the reaction in the step 4) is finished, cooling the solution in the reaction container to room temperature, transferring the solution in the reaction container to a centrifugal device, carrying out centrifugal separation for 8-10 min at the rotating speed of 8500-9000 rpm 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 (3) drying the residue cleaned in the step 5) in a vacuum drying oven at 50-85 ℃ for 10-20h to obtain the powdery manganese selenide nano material.
2. The preparation method of manganese selenide nano-materials with different morphologies and phases according to claim 1, wherein in the step 1), the molar ratio of the manganese-based precursor, oleylamine, oleic acid and octadecene is 0.5-1: 16-27.7: 0-10: 6-20, and mixing.
3. The method for preparing manganese selenide nano-materials with different morphologies and phases according to claim 2, wherein the manganese-based precursor in the step 1) is one or a mixture of two of manganese acetylacetonate and manganese acetate tetrahydrate.
4. The preparation method of manganese selenide nano-materials with different morphologies and phases according to claim 1, wherein 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.
5. The preparation method of manganese selenide nano-materials with different morphologies and phases according to claim 1, wherein in the step 3), the dosage of corresponding dodecanethiol is 0.1mL and the dosage of oleylamine is 1.2-3 mL based on the dosage of each 0.5-1 mmol of selenium powder.
6. The preparation method of manganese selenide nano-materials with different morphologies and phases according to claim 1, wherein in the step 5), the amount of cleaning solvent used for each cleaning is 20-30 ml based on the amount of selenium powder used in each 0.5-1 mmol in the step 3).
7. The method for preparing manganese selenide nano-materials with different morphologies and phases according to claim 1, wherein the absolute ethanol and the cyclohexane are mixed according to a volume ratio of 1:1 to prepare a cleaning solvent.
8. The method for preparing manganese selenide nanometer materials with different morphologies and phases as claimed in claim 1, wherein the reaction vessel is a three-necked flask.
9. The method for preparing manganese selenide nanometer materials with different morphologies and phases as claimed in any one of claims 1 to 8, wherein the centrifugal device is a centrifugal tube.
10. An application of a manganese selenide nanometer material, wherein the manganese selenide nanometer material is prepared by the preparation method of the manganese selenide nanometer material with different shapes and phases as claimed in any one of claims 1 to 9, 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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Publication number Priority date Publication date Assignee Title
JPS5659461A (en) * 1979-10-22 1981-05-22 Nippon Telegr & Teleph Corp <Ntt> Battery
CN102637890A (en) * 2012-03-30 2012-08-15 中国科学院青岛生物能源与过程研究所 Lithium metal flow battery system and preparation method for same
CN106430121A (en) * 2016-09-27 2017-02-22 南京工程学院 Wurtzite manganese selenide nanosheet material and preparation method thereof
CN112875657A (en) * 2021-02-03 2021-06-01 吉林大学 Preparation method and application of manganese selenide/reduced graphene oxide nanocomposite
CN113594625A (en) * 2021-07-20 2021-11-02 烟台大学 Preparation and application of 3D self-supporting film for lithium-sulfur battery

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5659461A (en) * 1979-10-22 1981-05-22 Nippon Telegr & Teleph Corp <Ntt> Battery
CN102637890A (en) * 2012-03-30 2012-08-15 中国科学院青岛生物能源与过程研究所 Lithium metal flow battery system and preparation method for same
CN106430121A (en) * 2016-09-27 2017-02-22 南京工程学院 Wurtzite manganese selenide nanosheet material and preparation method thereof
CN112875657A (en) * 2021-02-03 2021-06-01 吉林大学 Preparation method and application of manganese selenide/reduced graphene oxide nanocomposite
CN113594625A (en) * 2021-07-20 2021-11-02 烟台大学 Preparation and application of 3D self-supporting film for lithium-sulfur battery

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