CN111204808B - Preparation method of molybdenum disulfide microcapsule, magnesium ion battery positive electrode and magnesium ion battery - Google Patents

Preparation method of molybdenum disulfide microcapsule, magnesium ion battery positive electrode and magnesium ion battery Download PDF

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CN111204808B
CN111204808B CN202010027488.2A CN202010027488A CN111204808B CN 111204808 B CN111204808 B CN 111204808B CN 202010027488 A CN202010027488 A CN 202010027488A CN 111204808 B CN111204808 B CN 111204808B
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CN111204808A (en
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刘金云
林夕蓉
曾祥兵
朱红
杨在喜
司廷
李金金
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Anhui Normal University
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    • C01G39/00—Compounds of molybdenum
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    • H—ELECTRICITY
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    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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    • 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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    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M2004/028—Positive electrodes
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    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a preparation method of molybdenum disulfide microcapsules, a magnesium ion battery anode and a magnesium ion battery2Nanospheres, and liquid-driven coaxial flow focusing2The nanospheres are encapsulated in the capsule, and the electrode material with good conductivity and high coating rate is obtained through carbonization treatment, so that the problems of low load and poor controllability of the capsule material are solved, and the nanospheres are applied to the positive electrode of the magnesium ion battery, have higher discharge capacity and have long-term circulation stability.

Description

Preparation method of molybdenum disulfide microcapsule, magnesium ion battery positive electrode and magnesium ion battery
Technical Field
The invention relates to the technical field of energy storage materials, in particular to a preparation method of a molybdenum disulfide microcapsule, a magnesium ion battery positive electrode and a magnesium ion battery.
Technical Field
The increasing demand for energy stimulates the widespread development of advanced energy storage devices. Lithium ion batteries are widely used in daily life and modern industry as a main energy carrier. However, the shortage of lithium resources and the inherent safety problem caused by the formation of metallic lithium dendrites during the operation of the battery have prevented the sustainable development of lithium batteries. Accordingly, more and more researchers are turning their attention to the development of other rechargeable metal-ion batteries.
In recent years, there has been great interest in Mg ion batteries with larger theoretical specific capacity (2205mAh g)-1) High negative potential, good operational safety, environmental friendliness, huge material abundance and low price, show potential in large-scale application fields, and are considered as the most promising green power sources for electric vehicles. However, up to now, research on magnesium ion batteries is still in the beginning stage. The main obstacles hindering the practical use of magnesium ion batteries are: 1) slow kinetics of Mg insertion and diffusion in the positive electrode material; 2) mg (magnesium)2+The cation polarization ability is strong, resulting in incompatibility of the negative electrode and the electrolyte. Therefore, it is highly desirable to find suitable anodes and less passivated anodes/electrolytes. Researchers Aurbach et al expressed Chevrel phase Mg in 2000xMo3S4Positive electrode with 0.25M Mg (AlCl)2EtBu)2The THF electrolyte combination achieves excellent magnesium intercalation/deintercalation performance, and pushes the development of the Mg ion battery to a new level.
However, the magnesium ion battery has poor cycle performance and low actual discharge capacity, and the key point for promoting the progress of the magnesium ion battery is to develop a proper positive electrode and less passive negative electrode materials so that the magnesium ion battery has reasonable capacity and cycle capacity.
As a typical layered transition metal, MoS2Has been considered to be a multifunctional energy-related application material. Molybdenum disulfide has a structure similar to graphene, and consists of three stacked atomic layers (S-Mo-S): two S atoms and one Mo atom sandwiched between three layers stacked together by weak van der Waals interactions, the layered structure being such that Mg is present2+The insertion and extraction of ions becomes convenient. Notably, morphology and structure have a significant impact on the electrochemical performance of the electrode material. MoS with special morphology2Has attracted a great deal of attention, and the combination with carbon coatings can greatly enrich the MoS2The electrochemical performance of (2).
Microencapsulation provides a special carbon coating means, and the traditional methods comprise an emulsification method, a layer-by-layer assembly technology, in-situ polymerization, complex coacervation and the like. Although each of these methods has its advantages, there is a limitation that the monomers used in the coating process are highly reactive and often affected by side reactions, and are also very sensitive to temperature and pH, resulting in difficulty in controlling consistent microcapsule formation and low encapsulation efficiency.
Disclosure of Invention
In view of the defects in the prior art, the invention provides a preparation method of a molybdenum disulfide microcapsule, a magnesium ion battery positive electrode and a magnesium ion battery. The invention firstly obtains MoS by a hydrothermal method2Nanospheres, and liquid-driven coaxial flow focusing2The nanospheres are encapsulated in the capsule, and the MoS is obtained after high-temperature carbonization2The microcapsule is applied to a magnesium ion battery positive electrode and a magnesium ion battery. The present invention is directed to MoS2The microcapsule has the defects of poor conductivity and low load capacity, provides a preparation method of the capsule material, which has simple and reliable experimental device, uniform particle size, good reproducibility and real-time control, and has high encapsulation rate, good circulation stability and high rate capability.
The technical scheme adopted by the invention is as follows:
a preparation method of molybdenum disulfide microcapsules, comprising the following steps:
(1) dissolving a molybdenum source and a sulfur source in deionized water, adding a surfactant polyethylene glycol 750 monomethyl ether, stirring and dissolving, carrying out hydrothermal reaction, washing and drying the obtained product to obtain MoS2Dispersing the nano material in a polyvinyl alcohol aqueous solution to obtain MoS2A solution;
(2) stirring and mixing a photoinitiator and an organic light-curing material to obtain a mixed solution A;
(3) in MoS2The solution, the mixed solution A and the polyvinyl alcohol aqueous solution are respectively used as an internal phase, an external phase and a driving phase, and the MoS is obtained by utilizing the liquid-driven coaxial flow focusing technology under the shearing action of the driving phase2Microcapsule liquid drops and curing the liquid drops under ultraviolet irradiation;
(4) the solidified MoS2Washing the microcapsule liquid drops, freeze-drying, and then carbonizing at high temperature under the protection of inert gas to obtain the MoS2And (4) microcapsules.
Further, in the step (1), the molybdenum source is one or two of ammonium molybdate tetrahydrate and sodium molybdate; the sulfur source is one or more of thioacetamide, thiourea, L-cysteine and sodium sulfide.
In the step (1), the concentration of the molybdenum source in deionized water is 0.01-0.1 mol/L, preferably 0.02-0.04 mol/L;
the concentration of the sulfur source in deionized water is 0.25-0.8 mol/L, preferably 0.3-0.5 mol/L;
the mass ratio of the molybdenum source to the sulfur source is more than 1: 2, preferably 1: 12 to 18.
The concentration of the polyethylene glycol 750 monomethyl ether relative to deionized water is 10-17 g/L.
The temperature and the time of the hydrothermal reaction are respectively 160-240 ℃ and 3-48 h, preferably 180-200 ℃ and 3-12 h;
MoS2the concentration of the nano material in the polyvinyl alcohol aqueous solution is 0.01-0.15 g/mL, preferably 0.1-0.5 g/mL;
the mass percentage concentration of the polyvinyl alcohol aqueous solution is 1-10%.
In the step (2), the mass of the photoinitiator is 0.1-10% of that of the organic photocuring material, and preferably 1-5%; the photoinitiator is 2-hydroxy-2-methyl propiophenone.
In the step (2), the organic light-cured material is one or two of ETPTA or PEGDA;
in the step (3), the mass percentage concentration of the polyvinyl alcohol aqueous solution is 0.5-4%, preferably 1.5-2%; the flow rates of the inner phase, the outer phase and the driving phase are respectively 2-20 mL/h, 2-30 mL/h and 200-2000 mL/h, preferably 2-12 mL/h, 4-16 mL/h and 600-120 mL/h.
In the step (3), the wavelength of the ultraviolet light is 365 nm; the curing time is 2-30 min, preferably 5-10 min.
In the step (4), the temperature of the high-temperature carbonization is 450-900 ℃, preferably 480-600 ℃, and the time is 0.5-8 h, preferably 2-3 h.
In the step (4), the freeze drying time is 6-72 hours, preferably 12-24 hours.
The invention also provides a magnesium ion battery anode, and the magnesium ion battery anode is prepared by taking the molybdenum disulfide microcapsule prepared by the preparation method as an anode active substance.
The invention also provides a magnesium ion battery, which is obtained by assembling the magnesium ion battery anode as the anode and has good cycle stability and rate capability.
Dissolving a molybdenum source and a sulfur source in ionic water, adding polyethylene glycol 750 monomethyl ether as a surfactant, and carrying out one-step hydrothermal reaction to obtain MoS2The nanometer ball is used for cleaning and centrifuging the MoS by utilizing a liquid-driven coaxial flow focusing technical device2Nanospheres are ultrasonically dispersed in a PVA aqueous solution to serve as an inner phase, an organic photocuring material containing a photoinitiator serves as an outer phase, a low-concentration PVA aqueous solution serves as a driving phase, and the flow rates of the inner phase, the outer phase and the driving phase are respectively controlled by three injection pumps. When the flow of the driving fluid reaches a threshold value, the inner phase fluid and the outer phase fluid are sheared into coaxial cones under the driving of the driving phase, the coaxial jet flow is finally broken into small liquid drops due to flow instability, and the received small liquid drops are irradiated by an ultraviolet lamp for solidification and then calcined to obtain MoS with excellent conductivity2And (4) microcapsules. On one hand, the microencapsulation solves the problem of low load rate of the carbon coating material; on the other hand, the carbonization process also improves MoS2Is used for the electrical conductivity of (1). Mixing MoS2The microcapsule is applied to the magnesium ion battery anode, and the cycle capacity and the rate capability are improved.
Compared with the prior art, the invention has the following advantages:
(1) the synthesis process is simple, the device is convenient and reliable, and the MoS can be controlled in real time2The microcapsule material has large size and high repeatability, and can be produced in batch.
(2)MoS2The yield of the microcapsules is high and can be directly adjusted by the flow rate of a syringe pumpThe output of capsules is saved.
(3) Can adjust MoS in real time by controlling different flow rates between the internal phase and the external phase2The thickness of the microcapsule carbon shell greatly improves the conductivity.
(4)MoS2MoS inside the microcapsule2The nanosphere has high load rate, is applied to the positive electrode of the magnesium ion battery, and has higher cycle capacity MoS2The microcapsule has uniform grain diameter and good monodispersity.
Drawings
FIG. 1 shows MoS obtained after hydrothermal treatment as prepared in example 12SEM image of nanospheres.
FIG. 2 is a diagram of the carbonized MoS prepared in example 12SEM image of microcapsules.
FIG. 3 is a cured MoS prepared in example 22SEM image of microcapsules.
FIG. 4 is a diagram of the carbonized MoS prepared in example 22SEM image of microcapsules.
FIG. 5 shows the MoS of example 3 after curing but before carbonization2Optical pictures of microcapsules.
FIG. 6 is a carbonized MoS prepared in example 32SEM image of microcapsules.
FIG. 7 shows the MoS of example 4 after curing but before carbonization2Optical pictures of microcapsules.
FIG. 8 is a diagram of the carbonized MoS prepared in example 42SEM image of microcapsules.
FIG. 9 shows MoS obtained after hydrothermal treatment in example 52SEM image of nanospheres.
FIG. 10 shows the MoS of example 5 after curing but before carbonization2Optical pictures of microcapsules.
FIG. 11 is the MoS of example 5 after cure and before carbonization2SEM image of microcapsules.
FIG. 12 is a MoS after carbonization prepared in example 52SEM image of microcapsules.
FIG. 13 is a set of carbonized MoS prepared in example 52XRD pattern of microcapsules.
FIG. 14 is the MoS prepared in example 52The microcapsule is used as a circulation stability test chart and a constant current charge-discharge curve of the magnesium ion battery anode material under the current density of 50 mA/g.
FIG. 15 is the MoS prepared in example 52The microcapsule is used as a constant current charge-discharge curve of the magnesium ion battery anode material under the current density of 50 mA/g.
FIG. 16 is the MoS prepared in step (1) of example 12The nanosphere is used as a cycling stability test chart and a constant current charging and discharging curve of the magnesium ion battery anode material under the current density of 50 mA/g.
Detailed Description
The present invention will be described in detail with reference to examples.
The construction of the liquid-driven coaxial flow focusing technical device is carried out by referring to the content in Chinese patent CN 206935332U: the coaxial needle head is obtained by utilizing a laser welding technology, the inner needle head is nested in the inner surface of the outer needle head to ensure the coaxiality, and the inner needle head slightly exceeds the outer needle head by 0.1-0.2 mm. The cavity comprises PMMA organic glass pipe (the internal diameter is 19mm, and the external diameter is 25mm, and length is 18mm), and coaxial syringe needle passes through the cork and fixes in the PMMA cavity to align with the aperture on the glass board of bottom (the circular trompil on the probe, its diameter is 0.3mm), adjust the distance between the bottom of coaxial syringe needle and aperture (circular trompil) to 1.2 mm. And three injection pumps are used for controlling the flow of the inner phase, the outer phase and the driving phase respectively.
Example 1
A preparation method of a molybdenum disulfide microcapsule comprises the following steps:
(1) a hydrothermal process: 0.9g of ammonium molybdate tetrahydrate and 1.0g of thioacetamide are weighed and dissolved in 30mL of deionized water, 0.5g of polyethylene glycol 750 monomethyl ether is added into the solution, the solution is continuously stirred for 1 hour and then transferred into a 50mL of polytetrafluoroethylene reaction kettle, and the solution is put into an oven for reacting for 24 hours at 160 ℃. Naturally cooling to room temperature, and using deionized H2And F, centrifugally washing for a plurality of times, and collecting precipitated products. The SEM image is shown in figure 1, and the nano-sphere self-assembled by nano-sheets can be seen from the SEM image, and the size of the nano-sphere is 500 nm. 200mg of the product is taken and ultrasonically dispersed in 10mL of 2 wt% polyvinyl alcohol aqueous solution to obtain MoS with the concentration of 20mg/mL2And (3) solution.
(2) Mixing 0.2g of photoinitiator 2-hydroxy-2-methyl propiophenone with 20g of organic light-curing material ETPTA to obtain a mixed solution A with the mass of the photoinitiator being 1% of that of the organic light-curing material;
(3) utilizing a liquid-driven coaxial flow focusing technology, taking a 2 wt% polyvinyl alcohol (PVA) aqueous solution as a driving phase, and obtaining MoS in the step (1)2The solution is an internal phase, the mixed solution A is an external phase, the flow rate of the internal phase is controlled to be 3mL/h, the flow rate of the external phase is controlled to be 4mL/h, and the flow rate of the driving phase is 1200 mL/h. When the flow of the driving phase fluid reaches a threshold value, the outer phase wraps the inner phase under the shearing action of the polyvinyl alcohol aqueous solution to form microcapsule droplets; collecting, and curing with 365nm ultraviolet lamp for 10 min;
(4) a calcination process: the solidified MoS2Ultrapure H for microcapsules2Washing with O for several times, freeze drying for 12 hr, carbonizing in tubular furnace, and purifying with high purity N2Calcining at 600 ℃ for 3h under the atmosphere, wherein the heating and cooling rate is 3 ℃/min, and the molybdenum disulfide microcapsule can be obtained, wherein the SEM picture is shown in figure 2, and the size is about 30 μm. .
Example 2
A preparation method of a molybdenum disulfide microcapsule comprises the following steps:
(1) a hydrothermal process: 0.8g of ammonium molybdate tetrahydrate and 0.7g of thioacetamide are weighed and dissolved in 30mL of deionized water, 0.5g of polyethylene glycol 750 monomethyl ether is added into the solution, the solution is continuously stirred for 1 hour and then transferred into a 50mL of polytetrafluoroethylene reaction kettle, and the solution is put into an oven for reacting for 24 hours at 160 ℃. Naturally cooling to room temperature, and using deionized H2And F, centrifugally washing for a plurality of times, and collecting precipitated products. 200mg of the product is taken and ultrasonically dispersed in 10mL of 2 wt% polyvinyl alcohol aqueous solution to obtain MoS with the concentration of 20mg/mL2A solution;
(2) mixing 0.4g of photoinitiator 2-hydroxy-2-methyl propiophenone with 20g of organic light-curing material ETPTA to obtain a mixed solution A with the photoinitiator content of 2%;
(3) utilizing a liquid-driven coaxial flow focusing technology, taking a 2 wt% polyvinyl alcohol (PVA) aqueous solution as a driving phase, and obtaining MoS in the step (1)2The solution is the inner phase of the solution,the mixed solution A is an external phase, the flow rate of the internal phase is controlled to be 8mL/h, the flow rate of the external phase is controlled to be 8mL/h, and the flow rate of the driving phase is 900 mL/h. When the flow of the driving phase fluid reaches a threshold value, the outer phase wraps the inner phase under the shearing action of the polyvinyl alcohol aqueous solution to form microcapsule droplets; the material was collected and cured with a 365nm UV lamp for 8min, and the SEM image is shown in FIG. 2 as a uniform spherical shape with a size of about 30 μm.
(4) A calcination process: the solidified MoS2Ultrapure H for microcapsules2Washing with O for several times, freeze drying for 24 hr, carbonizing in tubular furnace, and purifying with high purity N2Calcining for 1h at 900 ℃ in the atmosphere, wherein the heating and cooling rate is 5 ℃/min, and obtaining the molybdenum disulfide microcapsule, wherein an SEM picture of the molybdenum disulfide microcapsule is shown in figure 4.
Example 3
A preparation method of a molybdenum disulfide microcapsule comprises the following steps:
(1) a hydrothermal process: 0.8g of ammonium molybdate tetrahydrate and 0.7g of thioacetamide are weighed and dissolved in 30mL of deionized water, 0.5g of polyethylene glycol 750 monomethyl ether is added into the solution, the solution is continuously stirred for 1 hour and then transferred into a 50mL of polytetrafluoroethylene reaction kettle, and the solution is put into an oven for reacting for 24 hours at 160 ℃. Naturally cooling to room temperature, and using deionized H2And F, centrifugally washing for a plurality of times, and collecting precipitated products. Ultrasonically dispersing 800mg of product in 10mL of 2 wt% polyvinyl alcohol aqueous solution to obtain MoS with the concentration of 80mg/mL2A solution;
(2) mixing 0.6g of photoinitiator 2-hydroxy-2-methyl propiophenone with 20g of organic light-curing material ETPTA to obtain a mixed solution A with the mass of the photoinitiator being 3% of that of the organic light-curing material;
(3) utilizing a liquid-driven coaxial flow focusing technology, taking a 2 wt% polyvinyl alcohol (PVA) aqueous solution as a driving phase, and obtaining MoS in the step (1)2The solution is an internal phase, the mixed solution A is an external phase, the flow rate of the internal phase is controlled to be 4mL/h, the flow rate of the external phase is controlled to be 14mL/h, and the flow rate of the driving phase is controlled to be 800 mL/h. When the flow of the driving phase fluid reaches a threshold value, the outer phase wraps the inner phase under the shearing action of the polyvinyl alcohol aqueous solution to form microcapsule droplets; collecting, curing with 365nm ultraviolet lamp for 3min, and obtaining an optical picture as shown in FIG. 5 which is a uniform ballThe shape, size is 80-100 μm, wherein the shell thickness is 20 μm;
(4) a calcination process: the solidified MoS2Ultrapure H for microcapsules2And washing for a plurality of times by using O, freeze-drying for 72h, putting into a tube furnace for carbonization, calcining for 4h at 550 ℃ under the high-purity Ar atmosphere, and heating and cooling at the rate of 3 ℃/min to obtain the molybdenum disulfide microcapsule, wherein an SEM image of the molybdenum disulfide microcapsule is shown in figure 6.
Example 4
A preparation method of a molybdenum disulfide microcapsule comprises the following steps:
(1) a hydrothermal process: 0.8g of ammonium molybdate tetrahydrate and 0.7g of thioacetamide are weighed and dissolved in 30mL of deionized water, 0.5g of polyethylene glycol 750 monomethyl ether is added into the solution, the solution is continuously stirred for 1 hour and then transferred into a 50mL of polytetrafluoroethylene reaction kettle, and the solution is put into an oven for reacting for 24 hours at 160 ℃. Naturally cooling to room temperature, and using deionized H2And F, centrifugally washing for a plurality of times, and collecting precipitated products. Naturally cooling to room temperature, and using deionized H2O centrifugal washing is carried out for a plurality of times, the precipitated product is collected, 1.2g of the product is taken to be ultrasonically dispersed in 10mL of 2 wt% polyvinyl alcohol aqueous solution, and MoS with the concentration of 120mg/mL is obtained2A solution;
(2) mixing 0.8g of photoinitiator 2-hydroxy-2-methyl propiophenone with 20g of organic light-curing material ETPTA to obtain a mixed solution A with the mass of the photoinitiator being 4% of that of the organic light-curing material;
(3) utilizing a liquid-driven coaxial flow focusing technology, taking a 2 wt% polyvinyl alcohol (PVA) aqueous solution as a driving phase, and obtaining MoS in the step (1)2The solution is an internal phase, the mixed solution A is an external phase, the flow rate of the internal phase is controlled to be 10mL/h, the flow rate of the external phase is controlled to be 8mL/h, and the flow rate of the driving phase is controlled to be 700 mL/h. When the flow of the driving phase fluid reaches a threshold value, the outer phase wraps the inner phase under the shearing action of the polyvinyl alcohol aqueous solution to form microcapsule droplets; collecting, curing with 365nm ultraviolet lamp for 20min, and making into uniform spherical shape with size of 70-90 μm and shell thickness of 10 μm as shown in FIG. 7;
(4) a calcination process: the solidified MoS2Ultrapure H for microcapsules2Washing with O for several times, freeze drying for 36 hr, and placing into tubeCarbonizing in a furnace, calcining for 1h at 700 ℃ under the atmosphere of high-purity Ar, and obtaining the molybdenum disulfide microcapsule with the heating and cooling rate of 5 ℃/min, wherein an SEM picture is shown in figure 8.
Example 5
A preparation method of a molybdenum disulfide microcapsule comprises the following steps:
(1) a hydrothermal process: 0.87g of ammonium molybdate tetrahydrate and 0.89g of thioacetamide are weighed and dissolved in 30mL of deionized water, 0.5g of polyethylene glycol 750 monomethyl ether is added into the solution, the solution is continuously stirred for 1 hour and then transferred into a 50mL of polytetrafluoroethylene reaction kettle, and the reaction kettle is placed into an oven for reaction at 180 ℃ for 3 hours. Naturally cooling to room temperature, and using deionized H2And O, centrifugally washing for several times. The SEM image is shown in FIG. 9, which is about 300nm in size. Taking 900mg of product, and ultrasonically dispersing the product in 10mL of 2 wt% polyvinyl alcohol aqueous solution to obtain MoS with the concentration of 90mg/mL2And (3) solution.
(2) Mixing 1.0g of photoinitiator 2-hydroxy-2-methyl propiophenone with 20g of organic light-curing material ETPTA to obtain a mixed solution A with the mass of the photoinitiator being 5% of that of the organic light-curing material;
(3) utilizing a liquid-driven coaxial flow focusing technology, taking a 2 wt% polyvinyl alcohol (PVA) aqueous solution as a driving phase, and obtaining MoS in the step (1)2The solution is an internal phase, the mixed solution A is a driving phase, the flow rate of the internal phase is controlled to be 3mL/h, the flow rate of the external phase is controlled to be 4mL/h, and the flow rate of the driving phase is controlled to be 700 mL/h. When the flow of the driving phase fluid reaches a threshold value, the outer phase wraps the inner phase under the shearing action of the polyvinyl alcohol aqueous solution to form microcapsule droplets; collecting, and curing with 365nm ultraviolet lamp for 5min, wherein the optical picture is shown in FIG. 10, and is uniform spherical, and has size of 20-30 μm, and shell thickness of 5 μm; the SEM image is shown in FIG. 11;
(4) a calcination process: the solidified MoS2Ultrapure H for microcapsules2Washing with O for several times, freeze drying for 24 hr, carbonizing in tubular furnace, and purifying with high purity N2Calcining for 2h at 500 ℃ in the atmosphere, wherein the heating and cooling rate is 2 ℃/min, and thus obtaining the molybdenum disulfide microcapsule. The SEM thereof is shown in FIG. 12, the size is about 20-30 μm, and the results are shown in FIG. 13, which are confirmed to be hexagonal crystals, by characterization with XRDIs a structure.
Example 6
MoS2Application of microcapsule in magnesium ion battery
The final products MoS obtained in step (4) of example 5 were separately subjected to2Microcapsules and MoS obtained in step (1) of example 12The mass ratio of the nanospheres to the conductive carbon black and PVDF is 80: 10: 10A uniform slurry was prepared in N-methylpyrrolidone (NMP) solvent, coated on 304 stainless steel foil, and dried overnight at 60 ℃ under vacuum. Tabletting the dried electrode slice by a roller machine or a tablet press, cutting the electrode slice by a mechanical cutting machine to obtain a round electrode slice with uniform size, wherein the round electrode slice is used as a positive electrode, a high-purity Mg slice is used as a counter electrode, glass fiber is used as a diaphragm, and 0.4M (PhMgCl)2-AlCl3THF (APC) as electrolyte. Assembled into a CR2032 type battery in a glove box.
Utilize battery tester to carry out charge-discharge performance test, MoS2The microcapsule is used as the anode material of a magnesium ion battery and is 50mA g-1The results of the cycle stability test at current density are shown in fig. 14, and the cycle stability of the battery is good. As can be seen from the constant current charge-discharge curve of FIG. 15, the battery capacity is still stabilized at 129mAh g after 100 times of circulation-1。MoS2The nanospheres have cycling performance shown in FIG. 16 at 50mA g-1The capacity is only maintained at 80mAh g after 100 cycles under the current density of (1)-1。
The above detailed description of the method for preparing molybdenum disulfide microcapsules, the positive electrode for magnesium ion batteries, and the magnesium ion battery with reference to the examples is illustrative and not restrictive, and several examples can be cited within the scope of the present invention, so that variations and modifications thereof can be made without departing from the general concept of the present invention.

Claims (9)

1. A preparation method of a molybdenum disulfide microcapsule is characterized by comprising the following steps:
(1) dissolving a molybdenum source and a sulfur source in ionized water, adding polyethylene glycol 750 monomethyl ether, stirring and dissolving,performing hydrothermal reaction, washing and drying the obtained product nano material to obtain MoS2Dispersing the nano material in a polyvinyl alcohol aqueous solution to obtain MoS2A solution;
(2) stirring and mixing a photoinitiator and an organic light-curing material to obtain a mixed solution A;
(3) in MoS2The solution, the mixed solution A and the polyvinyl alcohol aqueous solution are respectively used as an internal phase, an external phase and a driving phase, and the MoS is obtained by utilizing the liquid-driven coaxial flow focusing technology under the shearing action of the driving phase2Microcapsule liquid drops and curing the liquid drops under ultraviolet irradiation;
(4) the solidified MoS2Washing the microcapsule liquid drops, freeze-drying, and then carbonizing at high temperature under the protection of inert gas to obtain the MoS2Microcapsules;
the organic light-cured material is one or two of ETPTA or PEGDA.
2. The preparation method according to claim 1, wherein in the step (1), the molybdenum source is one or two of ammonium molybdate and sodium molybdate; the sulfur source is one or more of thioacetamide, thiourea, L-cysteine and sodium sulfide.
3. The preparation method according to claim 1 or 2, wherein in the step (1), the concentration of the molybdenum source in the deionized water is 0.01-0.1 mol/L; the concentration of the sulfur source in deionized water is 0.25-0.8 mol/L; the temperature and the time of the hydrothermal reaction are respectively 160-240 ℃ and 3-48 h; MoS2The concentration of the nano material in the polyvinyl alcohol aqueous solution is 0.01-0.15 g/mL; the mass percentage concentration of the polyvinyl alcohol aqueous solution is 1-10%.
4. The preparation method according to claim 1, wherein in the step (2), the mass of the photoinitiator is 0.1-10% of the mass of the organic light-cured material; the photoinitiator is 2-hydroxy-2-methyl propiophenone.
5. The preparation method according to claim 1 or 2, wherein in the step (3), the concentration of the polyvinyl alcohol aqueous solution is 0.5-4% by mass; the flow rates of the inner phase, the outer phase and the driving phase are respectively 2-20 mL/h, 2-30 mL/h and 200-2000 mL/h.
6. The preparation method according to claim 1, wherein in the step (3), the wavelength of the ultraviolet light is 365nm, and the curing time is 2-30 min.
7. The preparation method according to claim 1, wherein in the step (4), the temperature of the high-temperature carbonization is 450-900 ℃ and the time is 0.5-8 h.
8. A magnesium ion battery positive electrode, characterized in that, the magnesium ion battery positive electrode is prepared by using the molybdenum disulfide microcapsule prepared by the preparation method of any one of claims 1 to 7 as a positive electrode active material.
9. A magnesium-ion battery, wherein the magnesium-ion battery is obtained by assembling the magnesium-ion battery positive electrode according to claim 8 as a positive electrode.
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