CN114560448A - 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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CN114560448A
CN114560448A CN202210171163.0A CN202210171163A CN114560448A CN 114560448 A CN114560448 A CN 114560448A CN 202210171163 A CN202210171163 A CN 202210171163A CN 114560448 A CN114560448 A CN 114560448A
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manganese selenide
manganese
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CN114560448B (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 a manganese selenide nanometer material are provided, wherein the method comprises the following steps: adding manganese acetate tetrahydrate, selenium powder, ascorbic acid, ethanol and octylamine into a reaction vessel, stirring and uniformly mixing at room temperature, sealing the reaction vessel and preserving heat after the solution is in a suspension emulsion state; after the heat preservation is finished and the reaction container is cooled to the room temperature, transferring the solution in the reaction container to centrifugal equipment, carrying out centrifugal separation to realize cleaning, and adding a cleaning solvent formed by mixing absolute ethyl alcohol and cyclohexane during each cleaning; and (4) drying the cleaned residues in a vacuum drying oven to obtain the powdery manganese selenide nanometer material. According to the preparation method of the manganese selenide nanometer material, the high-quality manganese selenide nanometer material is prepared by a solvothermal synthesis method, and has a high length-diameter ratio; the manganese selenide nanometer material prepared by the method is applied to the anode of a lithium ion battery and the diaphragm of the lithium sulfur battery, and shows excellent cycle performance and rate capability.

Description

Preparation method and application of manganese selenide nano material
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 a manganese selenide nano material.
Background
With the rapid growth of socioeconomic energy storage demands are increasing dramatically. Lithium ion batteries are widely used in the fields of portable notebook computers, mobile phones, electric vehicles, medical microelectronic devices, and the like because of their high energy density and long service life.
In order to meet the next generation of electrochemical energy storage needs, from personal devices to automobiles, there is still a need to increase the energy density of batteries. Lithium-sulfur batteries have a broad prospect in the practical application of electric vehicles, unmanned aircraft, satellites and other energy storage devices working under severe conditions, and have received particular attention from people in the last five or six years, but their specific capacities are low, poor cycling stability and safety problems prevent the development of lithium-sulfur battery technology from laboratory-scale demonstration to large-scale production. In order to manufacture a lithium sulfur battery having a higher energy density and having a long cycle performance, an electrode material excellent in composition and structure has been designed. With the development of the controllable synthesis technology of the nano-crystal, it is found that the performance of the battery can be optimized by compounding sulfur and a nano-wire structure to form an electronic path with a three-dimensional structure and an ion diffusion channel connected with each other.
The conductive nano crystal has small size, large comparative area, porous structure adjustability and unique chemical binding capacity such as adsorption. 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. However, nanocrystals with different morphologies can exhibit different properties, and at the same time, the current synthesis methods for nanocrystals are complex and do not allow good control of the morphology and phase of the nanocrystals. Therefore, the development of a simple synthesis method to enable people to control the nucleation and growth of crystals more easily, thereby adjusting the morphology, size, phase state, etc. of the final nanocrystals is an important subject of current research in the field.
Disclosure of Invention
Based on the above, the invention provides a preparation method and application of a 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 realize the aim, the invention provides a preparation method of a manganese selenide nano 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, uniformly mixing, sealing the reaction container after the solution is in a suspension emulsion, and keeping the temperature of the reaction container in an oven at 150-180 ℃ for 72-120 h, wherein the dosage of each millimole of the selenium powder is taken as a reference, and the dosages corresponding to the other raw materials are 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, after the reaction container is cooled to the room temperature, transferring the solution in the reaction container to centrifugal equipment, 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;
3) and (3) putting the cleaned residues into a vacuum drying oven, and drying for 10-20h at 50-85 ℃ to obtain the powdery manganese selenide nanometer 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 technical scheme of the invention, in the step 2), the amount of the cleaning solvent used in each cleaning is 20-30 ml based on the amount of selenium powder used in each millimole in the step 1).
As a further preferable technical scheme of the invention, in the step 2), anhydrous ethanol and cyclohexane are mixed according to the volume ratio of 1:1 to prepare a cleaning solvent.
As a further preferable technical scheme of the invention, the centrifugal equipment in the step 2) is a centrifugal tube.
According to another aspect of the present invention, the present invention further provides an application of a manganese selenide nanomaterial, wherein the manganese selenide nanomaterial is prepared by the preparation method of any one of the manganese selenide nanomaterials, and the manganese selenide nanomaterial 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) putting the manganese selenide nano-material into a tube furnace, heating to 550-650 ℃ at the heating rate of 3-7 ℃/min under the protection of argon, and preserving the heat for 60-120 min;
2) mixing the manganese selenide nano material subjected to high-temperature treatment with Super P conductive carbon black and polyvinylidene fluoride in a proportion of 7: 2: 1, uniformly grinding, then dropwise adding 350-400 mu L of N-methyl-2-pyrrolidone, and uniformly grinding again to enable the mixed solution to be in a gel state to obtain a gel liquid;
3) coating the uniformly ground gel-like liquid on a current collector copper foil by using a manual film coating instrument, wherein the thickness of the gel-like liquid is 80-120 mu m, and after drying the gel-like liquid at room temperature, placing the copper foil electrode plate in a vacuum drying oven at 50-70 ℃ for heat preservation for 10-12h to obtain a positive electrode plate;
4) and assembling the positive pole piece as a positive pole 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 a manganese selenide nano material and a carboxylated single-walled carbon nanotube according to a mass ratio of 1: 0.025-0.25, then ultrasonically dispersing the mixture in deionized water, and after uniformly mixing, using a sand core funnel to extract a membrane to obtain a membrane;
2) placing the diaphragm in an oven, and drying at 50-60 deg.C for 8-12 h;
3) placing the diaphragm treated in the step 2) in a tube furnace, and preserving the heat for 60-90min at the temperature of 500-800 ℃ under the argon atmosphere condition;
4) punching the diaphragm processed in the step 3) into a preset size, and installing the diaphragm in a lithium-sulfur battery to be used as a battery diaphragm.
As a further preferable technical solution of the present invention, the lithium ion battery and the lithium sulfur battery are button batteries.
By adopting the technical scheme, the preparation method and the application of the manganese selenide nanometer material can achieve the following beneficial effects:
1) according to the preparation method of the manganese selenide nanometer material, the high-quality manganese selenide nanometer material is prepared by a solvothermal synthesis method, and the manganese selenide nanometer material has a very high length-diameter ratio, the diameter of the manganese selenide nanometer material is about 10nm, and the length of the manganese selenide nanometer material is more than ten microns;
2) according to the preparation method of the manganese selenide nanometer material, the manganese selenide nanometer materials with different forms can be obtained by adjusting the material proportion, and the manganese selenide nanometer material is an alpha-manganese selenide nanowire or an alpha-manganese selenide nanorod;
3) the manganese selenide nano material is applied to the positive electrode of the lithium ion battery, and shows excellent cycle performance and rate capability;
4) the manganese selenide nanometer material disclosed by the invention is compounded with the carboxylated single-walled carbon nanotube and then applied to a diaphragm of a lithium-sulfur battery, and shows excellent rate capability and cycle performance.
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 an α -manganese selenide nanowire prepared according to a first embodiment of the present invention;
fig. 2 is an X-ray powder diffraction pattern (XRD) of the α -manganese selenide nanowire prepared in the first embodiment of the present invention;
fig. 3 is X-ray photoelectron spectroscopy (XPS) analysis of different elements in the prepared α -manganese selenide nanowires according to a first embodiment of the present invention, wherein (a) is Mn 2p and (b) is Se 3 d;
FIG. 4 is a TEM image of α -manganese selenide nanorods prepared according to example two of the present invention;
FIG. 5 is a graph of rate capability of a lithium ion battery assembled according to a fourth embodiment of the present invention;
FIG. 6 shows the long cycle performance at a current density of 1C for a lithium ion battery assembled according to a fourth embodiment of the present invention;
fig. 7 is a graph of rate capability of lithium sulfur batteries assembled with different ratios of α -manganese selenide nanowire loading diaphragms in accordance with examples five-eight of the present invention;
fig. 8 shows the long cycle performance of lithium sulfur batteries assembled with different ratios of α -manganese selenide nanowire loading separators according to example five-eight of the present invention at a current density of 1C.
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 descriptive purposes only and are not intended to limit the scope of the present invention, and the relative relationships thereof may be changed or modified without substantial change in technical content.
Example one
The embodiment comprises the following steps:
(1) weighing 1mmol of manganese acetate tetrahydrate, 1mmol of selenium powder and 50mg of ascorbic acid, and adding the manganese acetate tetrahydrate, the 1mmol of selenium powder and the 50mg of ascorbic acid into a liner of a 20mL polytetrafluoroethylene reaction kettle;
(2) respectively transferring 5mL of ethanol and 15mL of octylamine by using a liquid transfer gun, adding the ethanol and the octylamine into the liner of the tetrafluoroethylene reaction kettle in the step (1), stirring for 30min at room temperature, putting the liner of the polytetrafluoroethylene reaction kettle into a stainless steel shell after the solution is in a suspension state emulsion, and keeping the temperature of an oven at 180 ℃ for 72 h;
(3) after the reaction in the step (2) is finished, cooling the reaction kettle to room temperature, transferring the cooled solution into a 50mL centrifuge tube, adding 20mL of a cleaning solvent formed by mixing absolute ethyl alcohol and cyclohexane according to a volume ratio of 1:1, performing centrifugal separation at 8500rpm for 9min to realize cleaning, and repeatedly cleaning for 3 times;
(4) and (4) drying the residue cleaned in the step (3) in a vacuum drying oven at 65 ℃ for 12h to obtain a powdery manganese selenide nano material sample.
The manganese selenide nanometer material sample prepared by the embodiment is an alpha-manganese selenide nanowire, and the appearance representation by using a transmission electron microscope is shown in fig. 1, and it can be seen that the nanowire has a very high length-diameter ratio, the diameter of the nanowire is about 10nm, and the length of the nanowire is more than ten microns.
The phase analysis and the element valence analysis of the alpha-manganese selenide nanowire obtained in the example are as follows:
(1) x-ray powder diffraction analysis (XRD). The samples prepared in the experiment were ground to powder using a mortar and spread on a sample table for XRD testing. The target was bombarded with Cu as a high energy electron beam (Cu ka,
Figure BDA0003517695540000041
) The scanning speed of the test is 5 degrees/min, and the scanning range is 20 degrees to 90 degrees. The result is shown in figure 2, several main diffraction peaks in the XRD diffractogram of the sample are consistent with the peak positions on the PDF standard card of the alpha-manganese selenide (JCPDS: 11-0683), 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 Fm-3m
Figure BDA0003517695540000042
(2) X-ray photoelectron spectroscopy (XPS). And analyzing the valence states of Mn and Se in the alpha-manganese selenide nanowire by XPS. As shown in a in FIG. 3, the 2p electron orbital of the element Mn has two characteristic peaks of 2p3/2And 2p1/2The peaks 640.8eV and 652.6eV correspond to Mn, respectively2+2p of3/2And 2p1/2The track binding energy. B in fig. 3 is an XPS data curve of Se in the α -MnSe nanowire, from which it can be seen that the peak of the Se 3d orbital is 54.9 eV.
Combined XRD and XPS data analysis demonstrated that the powder sample synthesized in this example was alpha phase and had a chemical composition of MnSe, i.e., the resulting alpha-MnSe.
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 1mmol of selenium powder into a liner of a polytetrafluoroethylene reaction kettle of 20 mL;
(2) transferring 16mL of octylamine by using a liquid transfer gun, adding the octylamine into the inner container of the polytetrafluoroethylene reaction kettle obtained in the step (1), stirring at room temperature for 60min, putting the inner container of the polytetrafluoroethylene reaction kettle into a stainless steel shell for sealing after the solution is in a suspension state emulsion, and keeping the temperature of a 150 ℃ oven for 120 h;
(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 cleaning solvent formed by mixing absolute ethyl alcohol 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 (4) drying the residue cleaned in the step (3) in a vacuum drying oven at 65 ℃ for 12h 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 nanorod, and the appearance of the manganese selenide nano-material sample is represented by using a transmission electron microscope as shown in figure 4, which shows that the length of the alpha-manganese selenide nanorod is 500nm, and the diameter of the alpha-manganese selenide nanorod is about 20 nm.
EXAMPLE III
The embodiment comprises the following steps:
(1) weighing 1.5mmol of manganese acetate tetrahydrate, 1mmol of selenium powder and 50mg of ascorbic acid, and adding the manganese acetate tetrahydrate, the 1mmol of selenium powder and the 50mg of ascorbic acid into a liner of a 20mL polytetrafluoroethylene reaction kettle;
(2) transferring 18mL of octylamine by using a liquid transfer gun, adding into the inner container of the polytetrafluoroethylene reaction kettle obtained in the step (1), stirring at room temperature for 30min, after the solution is in a suspension state emulsion, putting the inner container of the polytetrafluoroethylene reaction kettle into a stainless steel shell, and keeping the temperature of an oven at 180 ℃ for 96 h;
(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 absolute ethyl alcohol and cyclohexane into the centrifuge tube, performing centrifugal separation at 9000rpm for 8min to realize cleaning, and repeatedly cleaning for 5 times;
(4) and (4) drying the sample cleaned in the step (3) in a vacuum drying oven at 65 ℃ for 12h to obtain a powdery manganese selenide nano-material sample.
Example four
The alpha-manganese selenide nanowire prepared based on the first embodiment is applied to a lithium ion battery anode material, and the specific steps are as follows:
(1) preparing a positive pole piece: weighing 70mg of alpha-manganese selenide nanowires, 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 in a gel state; coating the uniformly ground gel-like liquid on a current collector copper foil by using a manual film coating instrument, wherein the thickness of the gel-like liquid is 100 mu m, and after drying the gel-like liquid at room temperature, placing the copper foil electrode plate in a vacuum drying oven at 60 ℃ for heat preservation for 12 hours;
(2) assembling a button battery in a glove box filled with argon (the moisture content is less than 0.1ppm, the oxygen content is less than 0.1ppm) according to the sequence of a positive electrode shell, a positive electrode piece, electrolyte, a diaphragm, a lithium sheet, a gasket, a spring piece and a negative electrode shell;
(3) testing the charge and discharge performance of the assembled battery on a battery constant temperature measurement system (NEWARE), wherein the voltage test interval is 0.01-3.0V;
the electrolyte in the step (2) is 1 mmol/ml-1LiPF6The electrolyte solution (volume ratio: EC/DMC: 1/1) was added in an amount of 100 μ L, the negative electrode was a lithium sheet with a diameter of 12mm, the battery case was CR 2025, and the separator was Celgard 2325.
The rate capability of the assembled cell in this example is shown in fig. 5, and the capacity of the α -MnSe nanowire electrode can be restored to 349.7mA hg when the current density is increased from 0.2C to 5C and then returned to 0.2C in steps-1. The long-cycle performance of the assembled battery at a current density of 1C is shown in FIG. 6, and the battery capacity is maintained at 228.4mAh g after 160 cycles of long cycle-1And the coulombic efficiency is still kept about 100%, and the good long-cycle performance is shown.
EXAMPLE five
The alpha-manganese selenide nanowire prepared based on the first embodiment is applied to a lithium-sulfur battery diaphragm material, and the method comprises the following specific steps:
(1) preparing a positive electrode material: 70mg of sulfur powder and 30mg of long-range ordered mesoporous carbon were weighed and ground for 10min using a mortar. The ground mixture was filled into a glass bottle and sealed with aluminum foil. Then the whole glass bottle is placed in a stainless steel reaction kettle for packaging, and the temperature is kept for 12h under the condition of 155 ℃. Weighing 80mg of 70% S/CMK-3 mixture, 10mg of Super P conductive carbon black and 10mg of polyvinylidene fluoride binder, adding into a ball milling tank, then using a liquid transfer gun to transfer 500 mu L of N-methyl-2-pyrrolidone solution into the ball milling tank, and putting into a ball mill to uniformly mix electrode slurry. The uniformly mixed electrode slurry was uniformly coated on an aluminum foil with a thickness of 100 μm using a manual film coating apparatus. Naturally airing at room temperature, and then placing the electrode slice in a vacuum drying oven for heat preservation for 12 hours at 60 ℃ to obtain an electrode slice;
(2) preparation of lithium-sulfur battery separator: weighing 1.1mg of alpha-manganese selenide nanowires and 20mg of ultra-pure carboxylated single-walled carbon nanotubes, ultrasonically dispersing the nanowires in 30mL of deionized water for 1 hour, performing suction filtration by using a sand core funnel, placing a pumped diaphragm (5% Mn) in an oven, and drying the diaphragm for 12 hours at the temperature of 60 ℃; placing the obtained diaphragm in a tube furnace, heating to 600 ℃ at the heating rate of 5 ℃/min, and preserving heat for 90 min;
(3) punching the electrode slice obtained in the step (1) into a circular electrode slice with the diameter of 12mm, punching the diaphragm obtained in the step (2) into a circular slice with the diameter of 19mm, assembling the button cell, and 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 0.1ppm) according to the sequence of a positive electrode shell, a pole piece, electrolyte, a diaphragm, a lithium sheet, a gasket, a spring piece and a negative electrode shell;
(4) the assembled battery is tested for the charge and discharge performance on a battery constant temperature measurement system (NEWARE), and the voltage test interval is 1.7-2.6V.
The electrolyte in the step (2) is a mixed solution of 1, 3-Dioxolane (DOL) and 1, 2-Dimethoxyethane (DME) with a concentration of 1mmol ml-1 of lithium bistrifluoromethanesulfonylimide (LiTFSI) added with 1 wt% of lithium nitrate (LiNO3) (volume ratio: DOL/DME ═ 1/1), 10 μ L of electrolyte is added to 1mg of sulfur powder, the positive electrode is S/CMK-3, the negative electrode is a lithium sheet with a diameter of 12mm, and the battery case is 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 the specific steps are as follows:
(1) the preparation of the positive electrode material was the same as in step (1) of example five;
(2) preparing a lithium-sulfur battery diaphragm: weighing 2.2mg of alpha-manganese selenide nanowires and 20mg of ultra-pure carboxylated single-walled carbon nanotubes, dispersing in 40mL of deionized water by ultrasonic treatment for 1.3h, performing suction filtration by using a sand core funnel, placing the extracted diaphragm (10% Mn) in an oven, and drying for 12h at the temperature of 60 ℃; placing the obtained diaphragm in a tubular furnace, heating to 600 ℃ at a heating rate of 5 ℃/min, and preserving heat for 90 min;
(3) punching the electrode plate obtained in the step (1) into a circular electrode plate with the diameter of 12mm, punching the diaphragm obtained in the step (2) into a circular sheet with the diameter of 19mm, assembling the button cell, and assembling the button cell in a glove box filled with argon gas (wherein the water content is less than 0.1ppm, and the oxygen content is less than 0.1ppm) according to the sequence of a positive electrode shell, a pole piece, electrolyte, a diaphragm, a lithium sheet, a gasket, a spring piece and a negative electrode shell, wherein the battery assembly requirement is the same as that of the fifth embodiment;
(4) the assembled battery is tested for the charge and discharge performance on a battery constant temperature measurement system (NEWARE), and the voltage test interval is 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 the specific steps are as follows:
(1) the preparation of the positive electrode material was the same as in step (1) of example five;
(2) preparation of lithium-sulfur battery separator: weighing 5mg of alpha-manganese selenide nanowires and 20mg of ultra-pure carboxylated single-walled carbon nanotubes, ultrasonically dispersing the nanowires in 50mL of deionized water for 1.7h, performing suction filtration by using a sand core funnel, placing the extracted diaphragm (20% Mn) in an oven, and drying the diaphragm for 12h at the temperature of 60 ℃; placing the obtained diaphragm in a tubular furnace, heating to 600 ℃ at a heating rate of 5 ℃/min, and preserving heat for 90 min;
(3) punching the electrode plate obtained in the step (1) into a circular electrode plate with the diameter of 12mm, punching the diaphragm obtained in the step (2) into a circular plate with the diameter of 19mm, assembling the button cell, and assembling the button cell in a glove box filled with argon (wherein the water content is less than 0.1ppm, and the oxygen content is less than 0.1ppm) according to the sequence of a positive electrode shell, a pole piece, electrolyte, a diaphragm, a lithium sheet, a gasket, a spring piece and a negative electrode shell, wherein the battery assembling requirement is the same as that in the fifth embodiment;
(4) the assembled battery is tested for the charge and discharge performance on a battery constant temperature measurement system (NEWARE), and the voltage test interval is 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 the specific steps are as follows:
(1) the preparation of the positive electrode material was the same as in step (1) of example five;
(2) preparing a lithium-sulfur battery diaphragm: weighing 13.3mg of alpha-manganese selenide nanowires and 20mg of ultra-pure carboxylated single-walled carbon nanotubes, ultrasonically dispersing the nanowires in 60mL of deionized water for 2h, performing suction filtration by using a sand core funnel, placing the extracted diaphragm (40% Mn) in an oven, and drying the diaphragm for 12h at the temperature of 60 ℃; placing the obtained diaphragm in a tubular furnace, heating to 600 ℃ at a heating rate of 5 ℃/min, and preserving heat for 90 min;
(3) punching the electrode plate obtained in the step (1) into a circular electrode plate with the diameter of 12mm, punching the diaphragm obtained in the step (2) into a circular plate with the diameter of 19mm, assembling the button cell, and assembling the button cell in a glove box filled with argon gas (wherein the moisture content is less than 0.1ppm, and the oxygen content is less than 0.1ppm) according to the sequence of a positive electrode shell, a positive electrode plate, electrolyte, a diaphragm, a lithium plate, a gasket, a spring piece and a negative electrode shell, wherein the assembling requirement of the cell is the same as that of the fifth embodiment;
(4) the assembled battery is tested for the charge and discharge performance on a battery constant temperature measurement system (NEWARE), and the voltage test interval is 1.7-2.6V.
In the fifth to eighth embodiments, the effect of raising the temperature to 600 ℃ at a temperature raising rate of 5 ℃/min and maintaining the temperature 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.
As shown in fig. 7, the rate performance of the battery measured in the fifth to eighth examples is that the rate performance of the lithium-sulfur battery is gradually improved (i.e., the capacity and stability at different current densities) when the content of the α -MnSe nanowires in the separator is increased from 5% to 20% at current densities of 0.2, 0.5, 1, 2, 3, and 5C, and the capacity retention rate and stability of the lithium-sulfur battery are the best at the content of the α -MnSe nanowires of 20%.
The long-cycling performance of the cells at a current density of 1C as measured in examples five-eight is shown in fig. 8, with the long-cycling performance of the lithium-sulfur cell being best at a 20% alpha-MnSe nanowire content.
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 (9)

1. A preparation method of a manganese selenide nanometer material is characterized by comprising 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, uniformly mixing, sealing the reaction container after the solution is in a suspension emulsion, and keeping the temperature of the reaction container in an oven at 150-180 ℃ for 72-120 h, wherein the dosage of each millimole of the selenium powder is taken as a reference, and the dosages corresponding to the other raw materials are 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, after the reaction container is cooled to the room temperature, transferring the solution in the reaction container to centrifugal equipment, 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;
3) and (3) drying the cleaned residues in a vacuum drying oven at the temperature of 50-85 ℃ for 10-20h to obtain the powdery manganese selenide nano material.
2. The method for preparing manganese selenide nanometer material according to claim 1, wherein the reaction vessel in the step 1) is a polytetrafluoroethylene reaction kettle.
3. The preparation method of the manganese selenide nanomaterial 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 manganese selenide nanometer material according to claim 3, wherein in the step 2), absolute ethyl alcohol and cyclohexane are mixed according to the volume ratio of 1:1 to prepare a cleaning solvent.
5. The method for preparing manganese selenide nanometer material according to claim 1, wherein the centrifugal device in the step 2) is a centrifugal tube.
6. An application of a manganese selenide nano material, wherein the manganese selenide nano material is prepared by the preparation method of the manganese selenide nano material as claimed in any one of claims 1 to 5, and the manganese selenide nano material is applied to a lithium ion battery as a positive electrode material or a lithium sulfur battery as a diaphragm material.
7. The application of the manganese selenide nanometer material in the battery, wherein the manganese selenide nanometer material is applied to the lithium ion battery as the anode material, and the method specifically comprises the following steps:
1) putting the manganese selenide nano-material into a tube furnace, heating to 550-650 ℃ at the heating rate of 3-7 ℃/min under the protection of argon, and preserving the heat for 60-120 min;
2) mixing the manganese selenide nano material subjected to high-temperature treatment with Super P conductive carbon black and polyvinylidene fluoride in a ratio of 7: 2: 1, uniformly grinding, dripping 350-400 mu L of N-methyl-2-pyrrolidone, uniformly grinding again to enable the mixed solution to be in a gel state to obtain a gel liquid;
3) coating the uniformly ground gel-like liquid on a current collector copper foil by using a manual film coating instrument, wherein the thickness of the gel-like liquid 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 10-12h to obtain a positive electrode plate;
4) and assembling the positive pole piece as a positive pole in the lithium ion battery.
8. The application of the manganese selenide nanometer material in the battery, wherein the manganese selenide nanometer material is applied to the lithium-sulfur battery as a diaphragm material, and the method specifically comprises the following steps:
1) mixing a manganese selenide nano material and a carboxylated single-walled carbon nanotube according to a mass ratio of 1: 0.025-0.25, then ultrasonically dispersing the mixture in deionized water, and after uniform mixing, using a sand core funnel to extract a membrane to obtain a membrane;
2) placing the diaphragm in an oven, and drying at 50-60 deg.C for 8-12 h;
3) placing the diaphragm treated in the step 2) in a tube furnace, and preserving the heat for 60-90min at the temperature of 500-800 ℃ under the argon atmosphere condition;
4) punching the diaphragm processed in the step 3) into a preset size, and installing the diaphragm in a lithium-sulfur battery to be used as a battery diaphragm.
9. The use of manganese selenide nanomaterials of any one of claims 6 to 8 in batteries, wherein the lithium ion batteries and the lithium sulfur batteries are button cells.
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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
CN102557059A (en) * 2012-01-11 2012-07-11 复旦大学 Manganese diselenide manometer bar as well as synthetic method and application thereof
CN109560277A (en) * 2018-11-29 2019-04-02 重庆文理学院 A kind of preparation method of nanometer of linear manganese selenide/carbon composite
CN109830649A (en) * 2019-01-14 2019-05-31 湘潭大学 A kind of preparation process of long circulation life, height ratio capacity flexible electrode
CN114050265A (en) * 2021-11-22 2022-02-15 安徽师范大学 Cross-linked nano carbon sheet loaded nickel selenide/manganese selenide nanocomposite and preparation method thereof, and sodium ion battery cathode

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
CN102557059A (en) * 2012-01-11 2012-07-11 复旦大学 Manganese diselenide manometer bar as well as synthetic method and application thereof
CN109560277A (en) * 2018-11-29 2019-04-02 重庆文理学院 A kind of preparation method of nanometer of linear manganese selenide/carbon composite
CN109830649A (en) * 2019-01-14 2019-05-31 湘潭大学 A kind of preparation process of long circulation life, height ratio capacity flexible electrode
CN114050265A (en) * 2021-11-22 2022-02-15 安徽师范大学 Cross-linked nano carbon sheet loaded nickel selenide/manganese selenide nanocomposite and preparation method thereof, and sodium ion battery cathode

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