CN114560448B - Preparation method and application of manganese selenide nano material - Google Patents

Preparation method and application of manganese selenide nano material Download PDF

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CN114560448B
CN114560448B CN202210171163.0A CN202210171163A CN114560448B CN 114560448 B CN114560448 B CN 114560448B CN 202210171163 A CN202210171163 A CN 202210171163A CN 114560448 B CN114560448 B CN 114560448B
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manganese selenide
manganese
cleaning
nano material
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CN114560448A (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
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    • 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
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
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    • C01P2004/00—Particle morphology
    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/10—Energy storage using batteries

Abstract

A preparation method and application of manganese selenide nanometer material, wherein the method comprises the following steps: adding manganese acetate tetrahydrate, selenium powder, ascorbic acid, ethanol and octylamine into a reaction container, stirring at room temperature, mixing, sealing the reaction container after the solution presents suspension emulsion, and preserving heat; after the heat preservation is finished and the reaction vessel is cooled to room temperature, transferring the solution in the reaction vessel to centrifugal equipment, and centrifugally separating to realize cleaning, wherein a cleaning solvent formed by mixing absolute ethyl alcohol and cyclohexane is added during each cleaning; and (3) placing the cleaned residues in a vacuum drying oven for drying to obtain the powdery manganese selenide nanometer material. The preparation method of the manganese selenide nano material utilizes a solvothermal synthesis method to prepare the high-quality manganese selenide nano material, and the high-quality manganese selenide nano material has very high length-diameter ratio; the manganese selenide nano material prepared by the method is applied to the positive electrode of a lithium ion battery and the diaphragm of a lithium sulfur battery, and has excellent cycle performance and rate performance.

Description

Preparation method and application of manganese selenide nano material
Technical Field
The invention relates to the technical field of nano material synthesis and preparation, in particular to a preparation method and application of a manganese selenide nano material.
Background
With the rapid growth of socioeconomic, there is a dramatic increase in energy storage demand. The lithium ion battery has higher energy density and longer service life, so that the lithium ion battery is widely applied to the fields of portable notebook computers, mobile phones, electric automobiles, medical microelectronic devices and the like.
In order to meet the next generation electrochemical energy storage demands from personal devices to automobiles, there is still a need to increase the energy density of batteries. Optimizing lithium ion batteries and exploring high-energy substitutes that can surpass lithium ion batteries, lithium sulfur batteries have received particular attention in the last five and six years due to wide prospects in practical applications of electric automobiles, unmanned aerial vehicles, satellites and other energy storage devices operating under severe conditions, but the development of lithium sulfur battery technology from laboratory-scale demonstration to mass production has been prevented by low specific capacity, poor cycling stability, safety problems and the like. In order to manufacture lithium sulfur batteries having higher energy density and long cycle performance, electrode materials having excellent composition and structure have been designed. With the development of nanocrystal controlled synthesis technology, it was discovered that the recombination of sulfur with nanowire structures to form electron paths with three-dimensional structures and interconnecting ion diffusion channels could optimize the performance of the cell.
The conductive nanocrystals have small size, large comparative area, porous structure adjustability, and unique chemical binding capability such as adsorption. Among the vast variety of nanocrystals, transition metal chalcogenides (sulfides, selenides, and tellurides) have attracted much attention due to their unique magnetic, electrical, and optical properties. However, nanocrystals with different morphologies may exhibit different properties, and at the same time, the current synthesis method for nanocrystals is complex, and the morphology and phase state of the nanocrystals cannot be well controlled. Therefore, developing a simple synthesis method that allows one to more easily control the nucleation and growth of crystals, thereby adjusting the morphology, size, phase, etc. of the final nanocrystals is an important topic of current research in the art.
Disclosure of Invention
Based on the above, the invention provides a preparation method and application of manganese selenide nano-material, so as to solve the technical problems that the synthesis method of the nano-crystal in the prior art is complex and the morphology and phase state of the nano-crystal cannot be well controlled.
In order to achieve the above purpose, the invention provides a preparation method of manganese selenide nanometer material, which comprises the following steps:
1) Adding manganese acetate tetrahydrate, selenium powder, ascorbic acid, ethanol and octylamine into a reaction container, stirring at room temperature for 30-60min, mixing uniformly, sealing the reaction container after the solution presents suspension emulsion, and preserving heat in an oven at 150-180 ℃ for 72-120 h, wherein the consumption of the selenium powder per millimole is taken as a reference, and the consumption of the corresponding other raw materials is as follows: 1-2 mmol of manganese acetate tetrahydrate, 0-50 mg of ascorbic acid, 0-5 mL of ethanol and 15-18 mL of octylamine;
2) After the heat preservation is finished, cooling the reaction vessel to room temperature, transferring the solution in the reaction vessel to a centrifugal device, 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;
3) And (3) placing the cleaned residues in a vacuum drying oven, and drying at 50-85 ℃ for 10-20 hours to obtain the powdery manganese selenide nano material.
As a further preferable technical scheme of the invention, the reaction vessel in the step 1) is a polytetrafluoroethylene reaction kettle.
As a further preferable embodiment of the present invention, in the step 2), the amount of the cleaning solvent used for each cleaning is 20 to 30ml based on the amount of the selenium powder used in the step 1) per millimole.
In step 2), anhydrous ethanol and cyclohexane are mixed according to a volume ratio of 1:1 to prepare the cleaning solvent.
As a further preferable embodiment of the present invention, the centrifugal apparatus in the step 2) 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, 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.
As a further preferable technical scheme of the invention, the manganese selenide nanometer material is applied to a lithium ion battery as a positive electrode material, and specifically comprises the following steps:
1) Placing the manganese selenide nano material in a tube furnace, heating to 550-650 ℃ at a heating rate of 3-7 ℃/min under the protection of argon, and preserving heat for 60-120min;
2) Mixing the manganese selenide nano material subjected to high-temperature treatment with Super P conductive carbon black and polyvinylidene fluoride according to the proportion of 7:2:1, uniformly grinding, then dropwise adding 350-400 mu L of N-methyl-2-pyrrolidone, uniformly grinding again, and enabling the mixed solution to be gel-like to obtain gel-like liquid;
3) Coating the gel-like liquid which is uniformly ground on a current collector copper foil by using a manual film coating instrument, wherein the thickness is 80-120 mu m, airing at room temperature, and then placing the copper foil electrode plate in a vacuum drying oven at 50-70 ℃ for heat preservation for 10-12 hours to obtain a positive electrode plate;
4) And the positive electrode plate is used as a positive electrode to be assembled in the lithium ion battery.
As a further preferable technical scheme of the invention, the manganese selenide nanometer material is applied to a lithium sulfur battery as a diaphragm material, and specifically comprises the following steps:
1) Mixing manganese selenide nano material and carboxylated single-walled carbon nano tube according to the mass ratio of 1:0.025-0.25, then ultrasonically dispersing the mixture in deionized water, and pumping the membrane by using a sand core funnel after uniformly mixing the mixture to obtain a membrane;
2) Placing the diaphragm in an oven, and drying for 8-12h at 50-60 ℃;
3) Placing the membrane treated in the step 2) in a tube furnace, and preserving heat for 60-90min at 500-800 ℃ under the condition of argon atmosphere;
4) And (3) punching the membrane processed in the step (3) into a preset size, and then installing the membrane in a lithium-sulfur battery to serve as a battery membrane.
As a further preferable technical scheme of the invention, the lithium ion battery and the lithium sulfur battery are button batteries.
The preparation method and the application of the manganese selenide nanometer material can achieve the following beneficial effects by adopting the technical scheme:
1) The preparation method of the manganese selenide nanometer material utilizes a solvothermal synthesis method to prepare the high-quality manganese selenide nanometer material, and the high-quality manganese selenide nanometer material has very high length-diameter ratio, the diameter of the high-quality manganese selenide nanometer material is about 10nm, and the length of the high-quality manganese selenide nanometer material is more than ten micrometers;
2) According to the preparation method of the manganese selenide nano material, the manganese selenide nano material with different forms can be obtained by adjusting the material proportion, and the manganese selenide nano material is an alpha-manganese selenide nanowire or an alpha-manganese selenide nanorod;
3) The manganese selenide nano material provided by the invention is applied to the anode of a lithium ion battery, and has excellent cycle performance and rate performance;
4) The manganese selenide nano material and the carboxylated single-walled carbon nano tube are compounded and then applied to a diaphragm of a lithium sulfur battery, and the manganese selenide nano material has excellent rate capability and cycle performance.
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 nanowire prepared in accordance with an embodiment of the invention;
FIG. 2 is an X-ray powder diffraction pattern (XRD) of an α -manganese selenide nanowire prepared in accordance with an embodiment of the invention;
FIG. 3 shows X-ray photoelectron spectroscopy (XPS) analysis of different elements in an α -manganese selenide nanowire prepared according to an embodiment of the invention, wherein (a) is Mn 2p and (b) is Se 3d;
FIG. 4 is a transmission electron microscope image of an α -manganese selenide nanorod prepared according to example two of the invention;
fig. 5 shows the rate performance of a lithium ion battery assembled according to the fourth embodiment of the invention;
fig. 6 shows the long cycle performance of the assembled lithium ion battery according to the fourth embodiment of the invention at a current density of 1C;
FIG. 7 is a graph showing the rate capability of lithium sulfur batteries assembled in accordance with examples five-eight of the present invention with different proportions of alpha-manganese selenide nanowire supported separators;
fig. 8 is a graph showing the long cycling performance of lithium sulfur batteries assembled in the five-eight examples of the present invention with different ratios of alpha-manganese selenide nanowire supported separators at a current density of 1C.
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 acetate tetrahydrate, 1mmol of selenium powder and 50mg of ascorbic acid are weighed and added into the liner of a 20mL polytetrafluoroethylene reaction kettle;
(2) Respectively transferring 5mL of ethanol and 15mL of octylamine by using a liquid transferring gun, adding the mixture into the inner container of the tetrafluoroethylene reaction kettle in the step (1), stirring the mixture at room temperature for 30min, and after the solution presents suspension emulsion, loading the inner container of the polytetrafluoroethylene reaction kettle into a stainless steel shell, and preserving heat for 72h by using a 180 ℃ oven;
(3) After the reaction of the step (2) is finished, cooling the reaction kettle to room temperature, transferring the cooled solution into a 50mL centrifuge tube, adding 20mL of cleaning solvent formed by mixing absolute ethanol and cyclohexane according to the volume ratio of 1:1, performing centrifugal separation at 8500rpm for 9min to realize cleaning, and repeatedly cleaning for 3 times;
(4) And (3) placing the residues after the cleaning in the step (3) in a vacuum drying oven, and drying at 65 ℃ for 12 hours to obtain a powdery manganese selenide nano-material sample.
The sample of the manganese selenide nano material prepared by the embodiment is an alpha-manganese selenide nano wire, and the morphological characterization of the alpha-manganese selenide nano wire by using a transmission electron microscope is shown as shown in figure 1, and the nano wire has a very high length-diameter ratio, the diameter of the nano wire is about 10nm, and the length of the nano wire is tens of micrometers.
The alpha-manganese selenide nanowire obtained in the example is subjected to phase analysis and element valence analysis, and the method comprises the following steps of:
(1) X-ray powder diffraction analysis (XRD). 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,
Figure BDA0003517695540000041
) The scanning rate of the test is 5 DEG/min and the scanning range is 20 DEG to 90 deg. The results are shown in FIG. 2, several of the XRD diffraction patterns of the samplesThe main diffraction peak is matched with the peak position (JCPCDS: 11-0683) on the PDF standard card of the alpha-manganese selenide, which proves that the alpha-manganese selenide belongs to a cubic phase crystal system, the crystal space group is Fm-3m, and the lattice constant is +.>
Figure BDA0003517695540000042
(2) X-ray photoelectron spectroscopy (XPS). And analyzing the valence states of two elements Mn and Se in the alpha-manganese selenide nanowire by using XPS. As shown in FIG. 3 a, the 2p electron orbitals of the element Mn have two characteristic peaks of 2p respectively 3/2 And 2p 1/2 Peaks 640.8eV and 652.6eV correspond to Mn, respectively 2+ 2p of (2) 3/2 And 2p 1/2 Track binding energy. B in fig. 3 is an XPS data curve of Se in an α -MnSe nanowire, and it can be seen from the graph that the peak value of the Se 3d orbital is 54.9eV.
By combining XRD and XPS data analysis, the powder sample synthesized in the embodiment is proved to be alpha phase, and the chemical composition is MnSe, namely alpha-MnSe is obtained.
Example two
The embodiment comprises the following steps:
(1) Weighing 2mmol of manganese acetate tetrahydrate and 1mmol of selenium powder, and adding the manganese acetate tetrahydrate and the selenium powder into a liner of a 20mL polytetrafluoroethylene reaction kettle;
(2) Transferring 16mL of octylamine by a liquid transferring gun, adding the octylamine into the inner container of the polytetrafluoroethylene reaction kettle in the step (1), stirring for 60 minutes at room temperature, filling the inner container of the polytetrafluoroethylene reaction kettle into a stainless steel shell for sealing after the solution presents suspension emulsion, and preserving heat for 120 hours in a baking oven at 150 ℃;
(3) After the reaction in the step (2) is finished, cooling the polytetrafluoroethylene reaction kettle to room temperature, transferring the cooled solution into a 50mL centrifuge tube, adding 25mL of cleaning solvent formed by mixing absolute ethanol and cyclohexane according to the volume ratio of 1:1, performing centrifugal separation at 8000rpm for 10min to realize cleaning, and repeatedly cleaning for 4 times;
(4) And (3) placing the residues after the cleaning in the step (3) in a vacuum drying oven, and drying at 65 ℃ for 12 hours to obtain a powdery manganese selenide nano-material sample.
The manganese selenide nano-material sample prepared by the method of the embodiment is an alpha-manganese selenide nano-rod, and the morphology characterization of the alpha-manganese selenide nano-rod by using a transmission electron microscope is shown as shown in figure 4, and the alpha-manganese selenide nano-rod can be seen to have the length of 500nm and the diameter of about 20nm.
Example III
The embodiment comprises the following steps:
(1) 1.5mmol of manganese acetate tetrahydrate, 1mmol of selenium powder and 50mg of ascorbic acid are weighed and added into the liner of a 20mL polytetrafluoroethylene reaction kettle;
(2) Transferring 18mL of octylamine by a liquid transferring gun, adding the octylamine into the inner container of the polytetrafluoroethylene reaction kettle in the step (1), stirring for 30min at room temperature, and after the solution presents suspension emulsion, loading the inner container of the polytetrafluoroethylene reaction kettle into a stainless steel shell, and preserving heat for 96h by a 180 ℃ oven;
(3) After the reaction is finished, cooling the polytetrafluoroethylene reaction kettle to room temperature, transferring the cooled solution into a 50mL centrifuge tube, adding 20mL of absolute ethyl alcohol and cyclohexane into the centrifuge tube, and performing centrifugal separation at 9000rpm for 8min to realize cleaning, and repeatedly cleaning for 5 times;
(4) And (3) placing the cleaned sample in the step (3) in a vacuum drying oven, and drying at 65 ℃ for 12 hours to obtain a powder manganese selenide nano-material sample.
Example IV
The alpha-manganese selenide nanowire prepared based on the first embodiment is applied to a lithium ion battery anode material, and comprises the following specific steps:
(1) Preparing a positive electrode plate: weighing 70mg of alpha-manganese selenide nanowire, 10mg of conductive carbon black and 10mg of polyvinylidene fluoride, mixing, uniformly grinding, dropwise adding 400 mu L of N-methyl-2-pyrrolidone, and uniformly grinding again to enable the mixed solution to be gel; coating the gel-like liquid which is uniformly ground on a current collector copper foil by using a manual film coating instrument, wherein the thickness is 100 mu m, airing at room temperature, and then placing the copper foil electrode plate in a vacuum drying oven at 60 ℃ for preserving heat for 12 hours;
(2) Assembling the button cell, namely assembling the button cell in a glove box filled with argon gas (the moisture content is less than 0.1ppm, and the oxygen content is less than 0.1 ppm) according to the sequence of a positive electrode shell, a positive electrode plate, an electrolyte, a diaphragm, a lithium sheet, a gasket, a spring piece and a negative electrode shell;
(3) The assembled battery tests the charge and discharge performance on a battery constant temperature measurement system (NEWARE), and the voltage test interval is 0.01-3.0V;
the electrolyte in the step (2) is 1mmol ml -1 LiPF 6 The electrolyte is added in an amount of 100 mu L, the negative electrode is a lithium sheet with a diameter of 12mm, the battery shell is CR 2025, and the diaphragm is Celgard 2325.
The rate capability of the assembled cell in this example is shown in FIG. 5, and when the current density is increased stepwise from 0.2C to 5C and then back to 0.2C, the capacity of the α -MnSe nanowire electrode can be restored to 349.7mA h g -1 . The long cycle performance of the assembled battery at a current density of 1C is shown in FIG. 6, and the battery capacity remains at 228.4mAh g after 160 long cycles -1 And the coulomb efficiency is still kept around 100%, and the long-cycle performance is better.
Example five
The alpha-manganese selenide nanowire prepared based on the first embodiment is applied to a lithium sulfur battery diaphragm material, and comprises the following specific steps:
(1) Preparation of a positive electrode material: 70mg of sulfur powder and 30mg of long-range ordered mesoporous carbon are weighed respectively, and ground for 10min by using a mortar. The milled mixture was filled into glass bottles and sealed with aluminum foil. Then the whole glass bottle is put into a stainless steel reaction kettle for encapsulation, and the temperature is kept for 12 hours at 155 ℃. 80mg of the 70% S/CMK-3 mixture, 10mg of Super P conductive carbon black and 10mg of polyvinylidene fluoride binder are weighed into a ball milling tank, then 500 mu L of N-methyl-2-pyrrolidone solution is removed by using a pipette, added into the ball milling tank, and put into a ball mill for uniform mixing of electrode slurry. The electrode slurry thus mixed was uniformly coated on an aluminum foil with a thickness of 100 μm using a manual film coater. Naturally airing at room temperature, and then placing the dried product in a vacuum drying oven at 60 ℃ for 12 hours to obtain an electrode slice;
(2) Preparation of lithium-sulfur battery separator: weighing 1.1mg of alpha-manganese selenide nanowire, 20mg of ultra-pure carboxylated single-walled carbon nanotube, dispersing in 30mL of deionized water for 1h by ultrasonic treatment, performing suction filtration by using a sand core funnel, placing the pumped diaphragm (5% Mn) in an oven, and drying for 12h at 60 ℃; placing the obtained diaphragm in a tube furnace, heating to 600 ℃ at a heating rate of 5 ℃/min, and preserving heat for 90min;
(3) Punching the electrode plate obtained in the step (1) into a round electrode plate with the diameter of 12mm, punching the diaphragm obtained in the step (2) into a wafer with the diameter of 19mm, assembling the button cell, and assembling the button cell in a glove box filled with argon gas according to the sequence of positive electrode shell, electrode plate, electrolyte, diaphragm, lithium plate, gasket, spring piece and negative electrode shell, wherein the moisture content is less than 0.1ppm and the oxygen content is less than 0.1 ppm;
(4) The assembled battery was tested for charge and discharge performance on a battery constant temperature measurement system (NEWARE) with a voltage test interval of 1.7-2.6V.
The electrolyte in the step (2) was a mixed solution of 1, 3-Dioxolane (DOL) and 1, 2-ethyleneglycol dimethyl ether (DME) with a concentration of 1mmol ml-1 of lithium bistrifluoromethane sulfonyl imide (LiTFSI) to which 1wt% lithium nitrate (LiNO 3) was added (volume ratio: DOL/dme=1/1), 10 μl of the electrolyte was added to 1mg of sulfur powder, the positive electrode was S/CMK-3, the negative electrode was a lithium sheet with a diameter of 12mm, and the battery case was CR 2025.
Example six
The alpha-manganese selenide nanowire prepared based on the first embodiment is applied to a lithium sulfur battery diaphragm material, and comprises the following specific steps:
(1) Preparing a positive electrode material in the same manner as in the step (1) of the fifth embodiment;
(2) Preparation of lithium-sulfur battery separator: weighing 2.2mg of alpha-manganese selenide nanowire, 20mg of ultra-pure carboxylated single-walled carbon nanotube, dispersing in 40mL of deionized water for 1.3 hours by ultrasonic treatment, carrying out suction filtration by using a sand core funnel, placing a suction diaphragm (10% Mn) in an oven, and drying for 12 hours at 60 ℃; placing the obtained diaphragm in a tube furnace, heating to 600 ℃ at a heating rate of 5 ℃/min, and preserving heat for 90min;
(3) Punching the electrode plate obtained in the step (1) into a round electrode plate with the diameter of 12mm, punching the diaphragm obtained in the step (2) into a wafer with the diameter of 19mm, assembling the button cell, and assembling the button cell in a glove box filled with argon gas according to the sequence of positive electrode shell, electrode plate, electrolyte, diaphragm, lithium plate, gasket, spring piece and negative electrode shell, wherein the moisture content is less than 0.1ppm and the oxygen content is less than 0.1ppm, and the battery assembling requirement is the same as that of the fifth embodiment;
(4) The assembled battery was tested for charge and discharge performance on a battery constant temperature measurement system (NEWARE) with a voltage test interval of 1.7-2.6V.
Example seven
The alpha-manganese selenide nanowire prepared based on the first embodiment is applied to a lithium sulfur battery diaphragm material, and comprises the following specific steps:
(1) Preparing a positive electrode material in the same manner as in the step (1) of the fifth embodiment;
(2) Preparation of lithium-sulfur battery separator: weighing 5mg of alpha-manganese selenide nanowire, 20mg of ultra-pure carboxylated single-walled carbon nanotube, dispersing in 50mL of deionized water for 1.7 hours by ultrasonic treatment, carrying out suction filtration by using a sand core funnel, placing the sucked diaphragm (20% Mn) in an oven, and drying for 12 hours at 60 ℃; placing the obtained diaphragm in a tube furnace, heating to 600 ℃ at a heating rate of 5 ℃/min, and preserving heat for 90min;
(3) Punching the electrode plate obtained in the step (1) into a round electrode plate with the diameter of 12mm, punching the diaphragm obtained in the step (2) into a wafer with the diameter of 19mm, assembling the button cell, and assembling the button cell in a glove box filled with argon gas according to the sequence of positive electrode shell, electrode plate, electrolyte, diaphragm, lithium plate, gasket, spring piece and negative electrode shell, wherein the moisture content is less than 0.1ppm and the oxygen content is less than 0.1ppm, and the battery assembling requirement is the same as that of the fifth embodiment;
(4) The assembled battery was tested for charge and discharge performance on a battery constant temperature measurement system (NEWARE) with a voltage test interval of 1.7-2.6V.
Example eight
The alpha-manganese selenide nanowire prepared based on the first embodiment is applied to a lithium sulfur battery diaphragm material, and comprises the following specific steps:
(1) Preparing a positive electrode material in the same manner as in the step (1) of the fifth embodiment;
(2) Preparation of lithium-sulfur battery separator: weighing 13.3mg of alpha-manganese selenide nanowire, 20mg of ultra-pure carboxylated single-walled carbon nanotube, dispersing in 60mL of deionized water for 2 hours by ultrasonic treatment, carrying out suction filtration by using a sand core funnel, placing the pumped diaphragm (40% Mn) in an oven, and drying for 12 hours at 60 ℃; placing the obtained diaphragm in a tube furnace, heating to 600 ℃ at a heating rate of 5 ℃/min, and preserving heat for 90min;
(3) Punching the electrode plate obtained in the step (1) into a round electrode plate with the diameter of 12mm, punching the diaphragm obtained in the step (2) into a wafer with the diameter of 19mm, assembling the button cell, and assembling the button cell in a glove box filled with argon gas according to the sequence of positive electrode shell, positive electrode plate, electrolyte, diaphragm, lithium plate, gasket, spring piece and negative electrode shell, wherein the moisture content is less than 0.1ppm and the oxygen content is less than 0.1ppm, and the battery assembling requirement is the same as that of the fifth embodiment;
(4) The assembled battery was tested for charge and discharge performance on a battery constant temperature measurement system (NEWARE) with a voltage test interval of 1.7-2.6V.
In the fifth to eighth embodiments, the effect of heating to 600 ℃ at a heating rate of 5 ℃/min and preserving heat for 90min is to remove oleylamine/oleic acid molecules coated on the surface of europium selenide, thereby improving the electronic and ionic conductivity of the material.
The rate performance of the battery measured in examples five to eight is shown in fig. 7, and when the content of the α -MnSe nanowires in the separator increases from 5% to 20% at current densities of 0.2, 0.5, 1,2, 3 and 5C, the rate performance of the lithium sulfur battery is gradually improved (i.e., the capacity and stability at different current densities), and the capacity retention rate and stability of the lithium sulfur battery are best at the content of the α -MnSe nanowires of 20%.
The long cycle performance of the cells measured in examples five-eight at a current density of 1C is shown in fig. 8, with the best long cycle performance of the lithium sulfur cell at a 20% alpha-MnSe nanowire content.
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 is characterized by comprising the following steps of:
1) Adding manganese acetate tetrahydrate, selenium powder, ascorbic acid, ethanol and octylamine into a reaction container, stirring at room temperature for 30-60min, mixing uniformly, sealing the reaction container after the solution presents suspension emulsion, and preserving heat in an oven at 150-180 ℃ for 72-120 h, wherein the consumption of the selenium powder per millimole is taken as a reference, and the consumption of the corresponding other raw materials is as follows: 1-2 mmol of manganese acetate tetrahydrate, 0-50 mg of ascorbic acid, 0-5 mL of ethanol and 15-18 mL of octylamine;
2) After the heat preservation is finished, cooling the reaction vessel to room temperature, transferring the solution in the reaction vessel to a centrifugal device, 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;
3) And (3) placing the cleaned residues in a vacuum drying oven, and drying at 50-85 ℃ for 10-20 hours to obtain the powdery manganese selenide nano material.
2. The method for preparing the manganese selenide nanometer material according to claim 1, wherein the reaction vessel in the step 1) is a polytetrafluoroethylene reaction kettle.
3. The method for preparing the manganese selenide nanometer material according to claim 1, wherein in the step 2), the amount of the cleaning solvent used for each cleaning is 20-30 ml based on the amount of the selenium powder used in each millimole in the step 1).
4. The method for preparing a manganese selenide nanomaterial according to claim 3, wherein in the step 2), anhydrous ethanol and cyclohexane are mixed in a volume ratio of 1:1 to prepare the cleaning solvent.
5. The method for preparing a manganese selenide nanomaterial according to claim 1, wherein the centrifugal device in step 2) is a centrifuge tube.
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