CN113937285A - PVP induced VS4Microstructure-regulated positive electrode material PVP-VS of magnesium ion battery4And applications - Google Patents
PVP induced VS4Microstructure-regulated positive electrode material PVP-VS of magnesium ion battery4And applications Download PDFInfo
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- CN113937285A CN113937285A CN202111159109.6A CN202111159109A CN113937285A CN 113937285 A CN113937285 A CN 113937285A CN 202111159109 A CN202111159109 A CN 202111159109A CN 113937285 A CN113937285 A CN 113937285A
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- 229910001425 magnesium ion Inorganic materials 0.000 title claims abstract description 59
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 35
- 230000001105 regulatory effect Effects 0.000 title claims abstract description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 31
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 31
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 25
- 239000000243 solution Substances 0.000 claims abstract description 12
- 239000013078 crystal Substances 0.000 claims abstract description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 8
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 8
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 7
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 7
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 7
- 239000011593 sulfur Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000007864 aqueous solution Substances 0.000 claims abstract 4
- 238000003756 stirring Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 238000011056 performance test Methods 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 230000014759 maintenance of location Effects 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000009792 diffusion process Methods 0.000 abstract description 8
- 150000002500 ions Chemical class 0.000 abstract description 8
- 230000001351 cycling effect Effects 0.000 abstract description 6
- 239000010405 anode material Substances 0.000 abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract description 3
- 239000011777 magnesium Substances 0.000 description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 7
- 229910052749 magnesium Inorganic materials 0.000 description 7
- 239000011229 interlayer Substances 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 3
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- 239000003365 glass fiber Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
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- 229910052720 vanadium Inorganic materials 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
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- 239000011149 active material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
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- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
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- 230000006698 induction Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
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- 150000003951 lactams Chemical group 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002091 nanocage Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
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- 230000002194 synthesizing effect Effects 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
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- 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
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
- H01M4/604—Polymers containing aliphatic main chain polymers
-
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M4/362—Composites
-
- 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
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses PVP induced VS4Microstructure-regulated positive electrode material PVP-VS of magnesium ion battery4And application thereof, belonging to the technical field of battery materials. Firstly, preparing an aqueous solution with the concentration of 0.167M from ammonium metavanadate and polyvinylpyrrolidone according to the proportion of 1:100, mixing the aqueous solution with an excessive glycol solution of thioacetamide, and carrying out hydrothermal reaction for 4 hours at 200 ℃ in a reaction kettle; then respectively washing the anode material for 3 times by using deionized water and ethanol, and drying to obtain the positive electrode material PVP-VS of the magnesium ion battery4. The invention realizes the embedding of PVP into VS by a one-step hydrothermal method4Interchain, PVP-VS was induced4Chain pitch enlargement, V3+Self-doping, sulfur-rich vacancy formation and high-index crystal face exposure, and realizes Mg2+With MgCl+The co-embedding of ions exposes more active sites, improves the ion diffusion speed, enhances the reaction kinetics and the structural stability, and further improves the electrochemical performance of the magnesium ion battery. The magnesium ion battery assembled by the composite material has high specific capacity, excellent cycling stability and rate performance, and wide application prospect.
Description
Technical Field
The invention relates to the technical field of battery materials, in particular to PVP (polyvinyl pyrrolidone) induced VS (voltage VS)4Microstructure-regulated positive electrode material PVP-VS of magnesium ion battery4And application thereof.
Background
The development of low-cost renewable energy storage technology is undoubtedly an effective approach to solve the energy and environmental crisis faced by the present society. Magnesium ion battery with high volume specific capacity (3833mAh cm)-3) Low cost, high safety, and little environmental impact, and is receiving wide attention (see literature: cu2MoS4 hollow nanocages with fast and stable Mg2+Storage performance, Zhang et al chem.eng.j.,2020,387,124125). Despite the many advantages of magnesium ion batteries, there are still some problems, such as: poor cycle stability, low specific capacity, slow diffusion kinetics and the like of the magnesium ion battery (see the literature: Cation-configuration TiO)2(B) nanowires with proto charge compression for regulating reversible magnesium storage, Luo et al. On the other hand, in a standard chlorine-based electrolyte, MgCl+As the main electro-active species, Mg-Cl bond is hardly destroyed to release Mg2+Participate in the reaction. Therefore, there is still a great challenge to properly modify the cathode material, and the microstructure of the cathode material is controlled to maximize the enlargement of the ion transport channel, improve the structural stability and secure Mg2+And MgCl+Co-insertion and rapid diffusion are of crucial importance.
An interlayer control method by introducing organic molecules is one of effective approaches to solve the above problems. The organic molecules can realize the expansion of the interlayer spacing of the anode material through the bonding action between the organic molecules and the anode material, weaken the electrostatic interaction between the organic molecules and the anode material when working ions are rapidly diffused, and relieve the stress change caused in the process of embedding/removing the working ions (see the literature: PVP incorporated with MoS)2 as a Mg ion host with enhanced capacity and durability,Wu et al.J.Mater.Chem.A,2019,7,4426-4430). Further, if the interlayer spacing of the positive electrode material is expanded sufficiently, it is possible to realize Mg2+And MgCl+The co-intercalation of (A) and (B), which will achieve high reversible capacity, excellent cycling stability and good rate performance of magnesium ion batteries (see the literature: Interchain-expanded vanadium tetrasulf iotade with fast kinetics for rechargeable magnesium batteries, Pei et al. ACS appl. mater. inter.,2019,11, 31954-. Polyvinylpyrrolidone (PVP) is used as a nonionic polymer, has high-efficiency coordination capacity, contains a lactam ring, and can interact with other compounds to expand the interlayer spacing of the positive electrode material and keep the structure stable, so that the regulated positive electrode material has high magnesium storage performance.
Besides interlayer organic molecule regulation, autodoping is a promising strategy for improving the electrochemical performance of the magnesium ion battery. Since the difference between the ionic radii of the autodoping material and the host material is small, the lattice distortion caused by the autodoping material is small, and the structural stability of the active material can be maintained. In addition, autodoping can also increase the carrier transport rate to achieve excellent cycling stability and significant rate performance. In addition to autodoping, the formation of abundant vacancies can also serve as electrochemically active sites to adsorb more Mg2+Promoting Mg2+The storage of (2), enhancing charge transfer kinetics. In addition, the exposed high-index crystal face has high surface energy, an open surface structure and abundant unsaturated coordination, is beneficial to enhancing interface charge transfer and adsorbing more magnesium ions, provides a more effective diffusion path for ion diffusion, and improves the specific capacity and rate capability of the magnesium ion battery. Among the numerous magnesium ion battery positive electrode materials, VS4Is considered to be a typical linear chain-like structure host material with two S' S between the V centers2 2-In which V is4+(S2 2-)2The chains are bound by weak van der waals forces, a special linear chain structure and weak van der waals forces that facilitate rapid diffusion and transport of ions/electrons. However, VS4The magnesium-ion battery is still required to be modified by the method so as to enhance the magnesium storage performance of the magnesium-ion battery and be applied to the magnesium-ion battery.
The invention prepares PVP interchain embedded VS by a one-step hydrothermal method4(PVP-VS4) As a positive electrode material of the magnesium ion battery, the electrochemical performance of the magnesium ion battery applied to the magnesium ion battery is studied. Electrochemical performance test results show that VS is embedded between PVP chains4Induced chain spacing enlargement, V3+The synergistic effect of the series of microstructure changes such as self-doping, sulfur-rich vacancy formation and high-index crystal face exposure enables PVP-VS4The specific capacity, the cycle life and the rate capability of the composite material are all improved. At 0.05Ag-1At a current density of PVP-VS4The specific capacity of the alloy is maintained to be 145mAh g-1Left and right. And at a current density of from 0.05Ag-1Increased to 5Ag-1The specific capacity of the electrode material is 151mAh g-1Change to 45mAh g-1When the current density is restored to 0.05Ag-1When the specific capacity is recovered to 138mAh g-1And the high-power-factor performance is shown. In addition, in 5Ag-1At a current density of PVP-VS4After 1500 cycles, the capacity retention rate reaches 80%. The invention provides an innovative feasible way for obtaining the microstructure regulation of the electrode material of the ion battery with high electrochemical performance.
Disclosure of Invention
The invention aims to provide a magnesium ion battery positive electrode material, in particular to a PVP (polyvinyl pyrrolidone) -induced VS (positive electrode material)4Microstructure-regulated positive electrode material PVP-VS of magnesium ion battery4And application thereof. PVP at VS4Induces an enlargement of the chain spacing, V3+The PVP-VS is caused by the microstructural changes of self doping, the formation of sulfur-rich vacancy, the exposure of high-index crystal face and the like4And the material has the characteristics of high specific capacity, excellent cycling stability, high rate capability and the like.
In order to achieve the aim, the invention provides a positive electrode material PVP-VS of a magnesium ion battery4The preparation process is as follows:
1. respectively weighing polyvinylpyrrolidone (PVP) and ammonium metavanadate according to the mass ratio of 1:100, dissolving the PVP and the ammonium metavanadate in deionized water, and magnetically stirring at a constant temperature of 60 ℃ until the PVP and the ammonium metavanadate are completely dissolved to obtain a solution A with the concentration of 0.167M;
2. weighing excessive thioacetamide, dissolving in glycol with the same volume as the solution A, and magnetically stirring at normal temperature until the thioacetamide is completely dissolved to obtain a solution B;
3. mixing the solution B and the solution A, and magnetically stirring at a constant temperature of 60 ℃ until the two solutions are completely mixed;
4. transferring the fully mixed solution into a 100ml reaction kettle, heating to 200 ℃, reacting for 4 hours, and cooling to room temperature along with the furnace after the reaction is finished;
5. respectively washing with deionized water and anhydrous ethanol for 3 times, centrifuging, collecting precipitate, placing the precipitate in a vacuum drying oven, and drying at 60 deg.C for 12 hr to obtain positive electrode material PVP-VS of magnesium ion battery4。
The invention also provides PVP-VS4The composite material is used as a positive electrode material in a magnesium ion battery, and is assembled with a metal magnesium negative electrode, a glass fiber diaphragm and an APC-THF electrolyte to form a button battery. Standing the assembled battery for 24 hours, and then carrying out electrochemical performance test on a CT2001A battery program-controlled tester, wherein the test voltage window is 0.2-2.1V, and the current density is 50-5000 mAg-1。
The invention provides a positive electrode material PVP-VS of a magnesium ion battery4Has the advantages that:
1. the positive electrode material PVP-VS of the magnesium ion battery synthesized by the invention4Due to PVP embedding in VS4Interchain, enlarging PVP-VS4Not only increase PVP-VS4The contact area with the electrolyte exposes more active sites and Mg can be realized2+And MgCl+Co-embedding and attenuating the same in PVP-VS4The polarization in the structure enhances the diffusion dynamics and improves the specific capacity and the rate capability of the magnesium ion battery;
2. the positive electrode material PVP-VS of the magnesium ion battery prepared by the invention4Due to PVP embedding in VS4Between chains, induce V3+Self-doping, formation of sulfur-rich vacancy, exposure of high-index crystal face and other series of microstructure changes. Wherein, V3+Self-doping canSo as to improve the conductivity of the anode material and accelerate the reaction kinetics; sulfur-rich vacancy formation can increase active sites and can mitigate PVP-VS induction during cycling4Maintaining structural stability; the exposure of the high-index crystal face is beneficial to increasing the active sites and accelerating the diffusion speed of ions; the specific capacity, the cycle life and the rate capability of the magnesium ion battery are improved under the synergistic effect of the microstructure changes.
3. The positive electrode material PVP-VS of the magnesium ion battery prepared by the invention4Shows excellent electrochemical performance: at 0.05A g-1The specific capacity is maintained to 145mAh g at the current density of-1Left and right. And at a current density of from 0.05A g-1Increased to 5A g-1The specific capacity of the electrode material is 151mAh g-1Change to 45mAh g-1When the current density is restored to 0.05A g-1The specific capacity is recovered to 138mAh g-1And the high-power-factor performance is shown. Further, at 5A g-1The capacity retention rate reached 80% after 1500 cycles at the current density of (1).
The concept, shape, structure and technical effects of the present invention will be further described with reference to the accompanying drawings.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 shows the positive electrode material PVP-VS of the magnesium-ion battery obtained in example 14XRD pattern of (a);
FIG. 2 shows the positive electrode material PVP-VS of the magnesium-ion battery obtained in example 14XPS spectra of (a);
FIG. 3 shows the positive electrode material PVP-VS of the magnesium-ion battery obtained in example 14V high resolution XPS spectra of (a);
FIG. 4 shows the positive electrode material PVP-VS of the magnesium-ion battery obtained in example 14An EPR map of (a);
FIG. 5 shows the positive electrode material PVP-VS of the magnesium-ion battery obtained in example 14HRTEM picture of (020) crystal face;
FIG. 6 shows the positive electrode material PVP-VS of the magnesium-ion battery obtained in example 14The electrochemical performance curve of (a);
FIG. 7 shows the positive electrode material PVP-VS of the magnesium-ion battery obtained in example 14At 5Ag-1Cycling performance curve at current density.
Detailed Description
The present invention will be described in further detail with reference to specific examples, which, however, should not be construed as limiting the scope of the present invention in any way.
Examples
Weighing 0.58g of ammonium metavanadate and 0.0058g of polyvinylpyrrolidone, dissolving in 30ml of deionized water, and magnetically stirring at a constant temperature of 60 ℃ until the ammonium metavanadate and the polyvinylpyrrolidone are completely dissolved to obtain a solution A; meanwhile, weighing excessive thioacetamide, dissolving the thioacetamide in 30ml of ethylene glycol, and magnetically stirring at normal temperature until the thioacetamide is completely dissolved to obtain a solution B; the solution A and the solution B were mixed well under magnetic stirring at a constant temperature of 60 ℃. Then, transferring the mixed solution into a 100ml reaction kettle, reacting for 4 hours at 200 ℃, and cooling to room temperature along with the furnace; washing the precipitate with deionized water and anhydrous ethanol for 3 times, respectively, placing into a vacuum drying oven, and drying at 60 deg.C for 12 hr to obtain positive electrode material PVP-VS of magnesium ion battery4。
After hydrothermal reaction, PVP is embedded into VS4Interchain, and enlarging PVP-VS4The results are shown in XRD (FIG. 1), as can be seen in FIG. 1, except for VS4Is outside the characteristic peaks, no new phase is formed, and PVP-VS4The diffraction peak of (A) is shifted to a low angle relative to the standard pattern, indicating that PVP is embedded in VS4The chain space is enlarged among chains. From PVP-VS4VS was observed simultaneously in the XPS summary spectrum (FIG. 2)4Element V and S in PVP and element C, N, O in PVP prove that PVP-VS4And (4) synthesizing. The high resolution XPS spectrum of V shows that V has both +3 and +4 valency states (FIG. 3), indicating that PVP-VS4In has V3+Self-doping of (3). PVP-VS4The EPR spectrum (FIG. 4) of (C) shows that PVP-VS at g ═ 1.9534Has a significantly higher VS4Peak of (2), descriptionIn PVP-VS4Rich sulfur vacancies exist in the alloy. The HRTEM image in FIG. 5 clearly shows that several layers of PVP-VS with the same orientation and the lattice spacing of 0.52nm are all observed4Nanosheets, corresponding to the (020) crystal plane, indicated that the high index crystal plane was exposed.
The prepared PVP-VS4And (3) as a positive electrode material of the magnesium ion battery, respectively using the polished magnesium foil and the glass fiber filter membrane as a negative electrode and a diaphragm of the magnesium ion battery, using 0.4M APC-THF as an electrolyte, and assembling the magnesium foil and the glass fiber filter membrane into a button battery in a glove box filled with argon. Standing the assembled magnesium ion battery for 24 hours, and then carrying out electrochemical performance test on a CT2001A battery program-controlled tester, wherein the test voltage window is 0.2-2.1V, and the current density is 0.05-5A g-1。
The obtained positive electrode material PVP-VS of the magnesium ion battery4See fig. 6 for rate capability and cycling performance at current densities from 0.05A g-1To 5A g-1In the process, the specific capacity is 151mAh g-1Change to 45mAh g-1And when the current density dropped to 0.05A g-1When the specific capacity is recovered to 134mAh g-1And excellent rate performance is shown. Cycling Performance shown in FIG. 6 at a current density of 0.05A g-1The specific capacity is stabilized at 145mAh g-1Left and right. 5A g-1The cycle performance under the current density is shown in fig. 7, and it can be seen that after 1500 cycles, the capacity can still keep about 80% of the initial capacity value, and good cycle stability performance is shown.
Claims (3)
1. PVP induced VS4Microstructure-regulated positive electrode material PVP-VS of magnesium ion battery4The application is characterized in that the preparation process is as follows:
respectively weighing polyvinylpyrrolidone and ammonium metavanadate according to the mass ratio of 1:100, and magnetically stirring at a constant temperature of 60 ℃ to prepare an aqueous solution with the concentration of 0.167M; then weighing excessive thioacetamide and dissolving the thioacetamide in glycol with the same volume as the aqueous solution; mixing the two solutions completely, transferring into a reaction kettle, reacting at 200 deg.C for 4 hr, and respectively using deionized water after reactionWashing the precipitate with water and absolute ethyl alcohol for 3 times, and vacuum drying to obtain positive electrode material PVP-VS of the magnesium ion battery4；
The obtained positive electrode material PVP-VS of the magnesium ion battery4The button type magnesium ion battery is assembled, the voltage window for electrochemical performance test is 0.2-2.1V, and the current density is 0.05-5 Ag-1。
2. A PVP-induced VS according to claim 14Microstructure-regulated positive electrode material PVP-VS of magnesium ion battery4And use, characterized in that PVP is embedded in VS4Interchain, PVP-VS was induced4Enlargement of chain spacing, V3+Self-doping, formation of sulfur-rich vacancy, exposure of high-index crystal face and the like.
3. A PVP-induced VS according to claim 14Microstructure-regulated positive electrode material PVP-VS of magnesium ion battery4And the application is characterized in that when the prepared material is used as the anode of the magnesium ion battery, the current density is 0.05A g-1The specific capacity is stabilized at 145mAh g-1Left and right; at 5A g-1Under the current density, after 1500 cycles, the capacity retention rate reaches 80%, and the high-power-factor performance is achieved.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111159109.6A CN113937285B (en) | 2021-09-30 | 2021-09-30 | PVP (polyvinyl pyrrolidone) induced VS (voltage VS) 4 Microstructure-regulated positive electrode material PVP-VS of magnesium ion battery 4 |
| ZA2022/00085A ZA202200085B (en) | 2021-09-30 | 2022-01-03 | Magnesium ions battery cathode material pvp-vs4 acquired by pvp inducing microstructure modulation of vs4 and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111159109.6A CN113937285B (en) | 2021-09-30 | 2021-09-30 | PVP (polyvinyl pyrrolidone) induced VS (voltage VS) 4 Microstructure-regulated positive electrode material PVP-VS of magnesium ion battery 4 |
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| CN113937285A true CN113937285A (en) | 2022-01-14 |
| CN113937285B CN113937285B (en) | 2023-02-28 |
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| CN202111159109.6A Active CN113937285B (en) | 2021-09-30 | 2021-09-30 | PVP (polyvinyl pyrrolidone) induced VS (voltage VS) 4 Microstructure-regulated positive electrode material PVP-VS of magnesium ion battery 4 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112242526A (en) * | 2020-10-20 | 2021-01-19 | 青岛科技大学 | Mo-doped VS4Magnesium ion battery positive electrode material and application thereof |
| CN112259733A (en) * | 2020-10-21 | 2021-01-22 | 湘潭大学 | Nanotube-shaped magnesium ion battery positive electrode material and preparation method thereof |
| CN112490438A (en) * | 2020-11-27 | 2021-03-12 | 青岛科技大学 | Magnesium ion battery positive electrode material Mo-VS4N-GNTs and uses thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112242526A (en) * | 2020-10-20 | 2021-01-19 | 青岛科技大学 | Mo-doped VS4Magnesium ion battery positive electrode material and application thereof |
| CN112259733A (en) * | 2020-10-21 | 2021-01-22 | 湘潭大学 | Nanotube-shaped magnesium ion battery positive electrode material and preparation method thereof |
| CN112490438A (en) * | 2020-11-27 | 2021-03-12 | 青岛科技大学 | Magnesium ion battery positive electrode material Mo-VS4N-GNTs and uses thereof |
Non-Patent Citations (1)
| Title |
|---|
| HAN TANG: "PVP incorporated MoS2 as a Mg ion host with enhanced capacity and durability", 《JOURNAL MATERIALS CHEMISTRY A》 * |
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| ZA202200085B (en) | 2022-03-30 |
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