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    • 专利摘要:
    The present disclosure discloses a Mo-doped VS4 cathode material for a magnesium ion battery and use thereof, and belongs to the technical field of battery materials. Ammonium metavanadate and ammonium molybdate are mixed as a proper proportion, and it is mixed with a solution of excessive thioacetamide, then the mixture solution is transferred into a reaction kettle for a hydrothermal reaction at 200°C for 4 h, the product is washed for 3 times with deionized water and absolute ethanol respectively, and collected through centrifugation, and the obtained product was subjected to vacuum drying to obtain a Mo-doped VS4 electrode material. Then the button battery is assembled with Mo-doped VS4 cathode material and metal magnesium anode. The cathode material prepared by the present disclosure has a morphology of hollow flowerlike microsphere, the enlarged VS4 layer spacing, and rich S vacancies. The magnesium ion battery assembled by it as cathode has good cycling stability and rate performance while a high capacity is maintained, which makes it have broad application prospects in the magnesium ion battery.
    公开号:NL2028807A
    申请号:NL2028807
    申请日:2021-07-22
    公开日:2021-09-16
    发明作者:Dai Xin；Sun Changlong；Li Zhenjiang；Meng Alan；Ding Shiqi
    申请人:Qingdao Univ Of Science And Technology；
    IPC主号:
    专利说明:

    MO-DOPED VS: CATHODE MATERIAL FOR MAGNESIUM ION BATTERYAND USE THEREOF
    TECHNICAL FIELD The present disclosure relates to the technical field of battery materials, and in particular to a Mo-doped VS: cathode material for a magnesium ion battery and use thereof.
    BACKGROUND With the continuous development of economy, science and technology, the human demand for energy is increasing day by day, and renewable energy has great development prospects in the future development. At present, secondary batteries have attracted great attention as a new generation of energy storage devices. Due to the advantages of metal magnesium such as low reduction potential, high theoretical volume capacity, low cost and environmental friendliness, the development of a magnesium ion battery has attracted much attention and it is expected to become the next generation of ion batteries. However, the charge density of a divalent magnesium ion is high, and problems such as relatively more serious polarization phenomenon of a cathode material also exist, which limits the further development of a magnesium ion battery. Therefore, itis still a very challenging work to develop a suitable cathode material to obtain a magnesium ion battery with better electrochemical performance. Among the existing cathode materials, VS:4 possibly becomes a cathode material with an excellent performance for a magnesium ion battery due to its unique linear-chain structure and large interlayer spacing, which is beneficial to the intercalation and deintercalation of a magnesium ion. However, its inherent low conductivity limits the use of VS: in the magnesium ion battery. Therefore, it is a very meaningful work to modify VS. to improve its conductivity, and then apply it in the magnesium ion battery. Ion doping is considered as an effective way to improve the electrochemical performance of an electrode material, since it can change the energy band structure and local electron distribution, showing enhanced electron/ion conductivity or bond polarization and thus improving electrochemical stability and rate performance. Furthermore, the ion doping can induce abundant vacancies, which facilitates the remission of the volume expansion and attenuation of the structural stress and strain, and further provides the additional active sites for absorbing alkali metal ions (see the literature: High valence Mo-doped Naz V2(PO4)3/C as a high rate and stable cycle-life cathode for sodium battery, Xiang Li et al. J. Mater. Chem. A, 2018, 6, 1390-1396). Among numerous metal cations, Mo is a common n-type dopant, it can increase the concentration of free electrons in an active material (see the literature: Ultrafine Mo- doped SnO: nanostructure and derivative Mo-dope Sn/C nanofibers for high- performance lithium-ion batteries, Yanli Chen et al. Nanoscale, 2018, 10, 17378-17387), and Mo ions have a more stable electrochemical interface to enhance a metal bond. Therefore, when Mo as a dopant is doped into the electrode material, it will facilitate the improvement of the conductivity of the material itself, provide more active sites, shorten the diffusion path of the magnesium ion and thus improve the reaction kinetics, and it is also beneficial to maintain the structure stability of the electrode material during charging and discharging. Furthermore, because the radius of the Mo ion is similar to that of V ions, the Mo ion is easily doped into a VS: lattice. However, there are few reports on the application of Mo-doped VS. as the cathode material in the magnesium ion battery.
    In the present disclosure, Mo-doped VS: as the cathode material is prepared by a one-step hydrothermal method for a magnesium ion battery, and its electrochemical performance is studied. The results of the electrochemical performance test show that both the electrochemical cycle performance and rate performance of VS: are improved due to Mo doping. The specific capacity of Mo-doped VS: is still remained at about 120 mAh gt after 350 cycles under a current density of 50 mA gt, and Mo-doped VS: shows relatively better rate performance when the current density reaches 500 mA gt, which is of great significance to the development of a novel cathode material for a magnesium ion battery.
    SUMMARY An objective of the present disclosure is to provide a cathode material for a magnesium ion battery, especially to provide a Mo-doped VS: cathode material for a magnesium ion battery, and to explore use of it in a magnesium ion battery. The cathode material for a magnesium ion battery has the morphology of hollow flower-like microsphere formed by many self-assembled nanosheets, and exhibits the characteristics such as good cycling stability and high rate performance.
    In order to achieve the aforementioned objective of the present disclosure, a process for preparing a Mo-doped VS; as the cathode material of a magnesium ion battery provided by the invention comprises the following steps:
    1. weighing ammonium metavanadate and ammonium molybdate tetrahydrate respectively according to the ratio of 1160:1 and formulating the two agents into an aqueous solution with a concentration of 0.167 M, and magnetically stirring the mixture at a constant temperature of 60°C for 30 min until they are completely dissolved, so as to obtain a solution A;
    2. weighing excessive thioacetamide and dissolving in 30 ml ethylene glycol, and IO magnetically stirring the mixture at ambient temperature for 30 min until it is completely dissolved, so as to obtain a solution B;
    3. pouring the solution B into the solution A, and magnetically stirring the mixture at a constant temperature of 60°C for 30 min until the two solutions are completely mixed;
    4. transferring the mixed solution into a 100 ml reaction kettle for a hydrothermal reaction at a hydrothermal reaction temperature of 200°C for a reaction time of 4 h, and furnace cooling to room temperature after the reaction is finished; and
    5. washing the precipitate with deionized water and absolute ethanol respectively for 3 times, centrifuging and collecting the precipitate, and putting the obtained precipitate into a vacuum drying oven for drying treatment at a drying temperature of 60°C for a drying time of 12 h, so as to obtain a Mo-doped VS: compound.
    The present disclosure also provides use of Mo-doped VS: as a cathode material for a magnesium ion battery. The Mo-doped VS: is made into a cathode sheet, and it is assembled with a metal magnesium anode material, a glass fiber separator and an APC- THF electrolyte to form a button battery. The assembled battery is allowed to stand for 24 h, and then tested for the electrochemical performance on a CT2001A battery program-controlled tester. The test has a voltage window of 0.2-2.1 V and a current density of 20-500 mA gt.
    The Mo-doped VS4 cathode material for a magnesium ion battery as provided by the present disclosure has the following advantages:
    1. the employed Mo-doped VS4 cathode material synthesized by the present disclosure for a magnesium ion battery has the morphology of regular hollow flower- like microsphere;
    2. the employed Mo-doped VS: cathode material prepared by the present disclosure for a magnesium ion battery possess the enlarged VS: layer spacing, forms abundant sulfur vacancies, and provides more active sites due to Mo doping, improving the conductivity of the Mo-doped VS; material, shortening the diffusion distance of the magnesium ion in the Mo-doped VS: electrode material, which is beneficial to the storage and diffusion of the magnesium ion; and
    3. the employed Mo-doped VS: prepared by the present disclosure as the cathode material for a magnesium ion battery exhibits an excellent electrochemical performance: it can achieve a long cycle life of 350 cycles under a current density of 50 mAh gt, and keep the specific capacity at about 120 mAh gt; and when the current density reaches 500 mA g'!, it exhibits a good rate performance.
    The conception, morphology, structure and resultant technical effects of the present disclosure will be further explained hereafter in connection with the accompanying drawings.
    BRIEF DESCRIPTION OF THE DRAWINGS The accompanying drawings are intended to provide a further understanding of the present disclosure and form a part of the specification, and are used together with the following detailed description to explain the present disclosure, but do not constitute a limitation of the present disclosure. In the accompanying drawings: FIG. 1 shows an SEM image of a Mo-doped VS: cathode material for a magnesium ion battery as obtained in Example 1; FIG. 2 shows a TEM image of the Mo-doped VS: cathode material for a magnesium ion battery as obtained in Example 1; FIG. 3 shows an XRD spectrum of the Mo-doped VS4 cathode material for a magnesium ion battery as obtained in Example 1; FIG. 4 shows an EDS spectrum of the Mo-doped VS: cathode material for a magnesium ion battery as obtained in Example 1; FIG. 5 shows a Mo high-resolution XPS spectrum of the Mo-doped VS: cathode material for a magnesium ion battery as obtained in Example 1; FIG. 6 shows a S high-resolution XPS spectrum of the Mo-doped VS: cathode material for a magnesium ion battery as obtained in Example 1; and
    FIG. 7 shows a cycle performance curve and a rate performance curve of the Mo- doped VS; cathode material for a magnesium ion battery as obtained in Example 1.
    DETAILED DESCRIPTION 5 The present disclosure will be further described in detail in connection with specific examples below, but these examples do not limit the scope of the present disclosure in any way.
    Example 1 Use of Mo-doped VS; cathode material for a magnesium ion battery
    0.5814 g of ammonium metavanadate and 0.0265 g of ammonium molybdate tetrahydrate were weighed. The two agents were dissolved in 30 ml of deionized water, and stirred magnetically at a constant temperature of 60°C for 30 min until they are completely dissolved, so as to obtain a solution A. Meanwhile, excessive thioacetamide was weighed and dissolved in 30 ml of ethylene glycol, and stirred magnetically at ambient temperature for 30 min until it was completely dissolved, so as to obtain a solution B. The solution B was poured into the solution A and mixed, and magnetically stirred at a constant temperature of 60°C for 30 min until the two solutions were completely mixed. The fully mixed solution was transferred into a 100 ml reaction kettle for a hydrothermal reaction at a hydrothermal reaction temperature of 200°C for a reaction time of 4 h, and fumace-cooled to room temperature after the reaction was finished. The product was washed for 3 times with deionized water and absolute ethanol, respectively, and collected through centrifugation. The obtained product was put into a vacuum drying oven for drying at 60°C for 12 h, so as to obtain a Mo-doped VS4 compound.
    The Mo-doped VS; material had a morphology of hollow flower-like microsphere that was self-assembled by many nanosheets, as shown in a SEM image (FIG. 1) and a TEM image (FIG. 2). The XRD result (FIG. 3) showed that the obtained product was VS,, and the EDS result (FIG. 4) showed the existence of a Mo element, so Mo was doped into the lattice of VSa4. Furthermore, the diffraction peak of the XRD spectrum shifts towards a lower angle relative to a standard spectrum, and the Mo high-resolution XPS spectrum showed that the valence state of Mo is +4 (FIG. 5), so Mo is doped into the lattice of VSa4 in the valence state of Mo**, and thus the VS. interlayer spacing was enlarged. The S high-resolution XPS spectrum (FIG. 6) showed that S existed in both -
    1 and -2 valences, which indicated that rich sulfur vacancies were formed after Mo doping. The synthesized Mo-doped VS4 powder was used as an active cathode material, which was uniformly mixed with carbon black and a binder (polyvinylidene fluoride, PVDF) according to a mass ratio of 8:1:1, then an organic solvent of 1-methyl-2- pyrrolidone was added and ground to a viscous state. The slurry was coated onto a conductive current-collector carbon paper with an H-shaped scraper, and then put into a vacuum oven at 60°C for 12 h for drying. The dried electrode sheet was cut by a slitting machine into discs with a diameter of 12 mm, which were used as the cathode of the IO magnesium ion battery. A magnesium foil with a thickness of 0.1 mm was sanded with a sandpaper to remove the oxide layer on the surface, then it was cut into discs with a diameter of 16 mm by a slitting machine, which were used as the anode of the magnesium ion battery, at same time, a glass fiber filter membrane was used as diaphragm, and 0.4 M APC/THF was used as the electrolyte, for assembling a button battery in a glove box in argon atmosphere. The assembled button battery was allowed to stand for 24 h, and then tested for the electrochemical performance on a CT2001A battery program-controlled tester. The test was carried out under the voltage window of
    0.2-2.1 V and a current density of 20-500 mA gt. The electrochemical performance of the obtained product, Mo-doped VS4, was shown in FIG. 7 of the specification. Under the current density of 50 mA g™!, the Mo- doped VS had achieved 350 cycles, and the specific capacity was kept at about 120 mAh gt during the cycle, and the coulombic efficiency was close to 100%. Meanwhile, the Mo-doped VS; exhibited an excellent rate performance, when the current density reached 500 mA gt, the specific capacity could still be maintained at about 70 mAh gt, and the capacity of it could rise back to about 130 mAh gt when the current density was risen back to 20 mA gl.
    权利要求:
    Claims (3)
    [1]
    A Mo-doped VS4 cathode material for a magnesium ion battery and use thereof, wherein: a preparation process of the cathode material comprises the steps of: weighing ammonium metavanadate and ammonium molybdate tetrahydrate in the ratio of 1160:1, respectively, adding them to deionized water, and magnetic stirring at a constant temperature of 60°C for 30 min until completely dissolved, so as to prepare an aqueous solution with a concentration of 0.167 M; weighing and dissolving excess thioacetamide in 30 ml of ethylene glycol, and magnetically stirring at ambient temperature for 30 min until completely dissolved; mixing the above two solutions and magnetically stirring at a constant temperature of 60°C for 30 min until the two solutions are completely mixed; transferring the mixed solution into a reaction vessel for a hydrothermal reaction at a reaction temperature of 200°C for a reaction time of 4 hours, and oven cooling after the reaction is completed; washing 3 times with deionized water and absolute ethanol, respectively, collecting a product by centrifugation, subjecting the obtained product to vacuum drying to obtain the Mo-doped VS4 cathode material; and assembling the Mo-doped VS4 as a cathode material in a magnesium ion button battery, wherein the electrochemical performance is tested under a voltage window of 0.2-2.1 V and a current density of 20-500 mA gt.
    [2]
    The Mo-doped VS4 cathode material for a magnesium ion battery and the use thereof according to claim 1, wherein the obtained sample exhibits the morphology of hollow flower-like microsphere.
    [3]
    The Mo-doped VSi cathode material for a magnesium ion battery and the use thereof according to claim 1, wherein the obtained material used in a magnesium ion battery has a specific capacity of 120 mAh g, a life of 350 cycles and good quality performance.
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    法律状态:
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