CN113929138A - Mo/O co-doped VS4 magnesium ion battery positive electrode material and application thereof - Google Patents
Mo/O co-doped VS4 magnesium ion battery positive electrode material and application thereof Download PDFInfo
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- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910001425 magnesium ion Inorganic materials 0.000 title claims abstract description 54
- 239000007774 positive electrode material Substances 0.000 title claims description 30
- 239000000243 solution Substances 0.000 claims abstract description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 7
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 claims abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 claims abstract description 6
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 239000011593 sulfur Substances 0.000 claims abstract description 6
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims abstract description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 239000007864 aqueous solution Substances 0.000 claims abstract 4
- 230000014759 maintenance of location Effects 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000012360 testing method Methods 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000010405 anode material Substances 0.000 abstract description 13
- 239000010406 cathode material Substances 0.000 abstract description 6
- 230000001351 cycling effect Effects 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 150000001450 anions Chemical class 0.000 description 10
- 150000001768 cations Chemical class 0.000 description 7
- 230000008859 change Effects 0.000 description 7
- 239000011149 active material Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 5
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000009881 electrostatic interaction Effects 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910003003 Li-S Inorganic materials 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001362 electron spin resonance spectrum Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- -1 on one hand Chemical class 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical class N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/006—Compounds containing, besides molybdenum, two or more other elements, with the exception of oxygen or hydrogen
-
- 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
- H01M10/04—Construction or manufacture in general
- H01M10/0422—Cells or battery with cylindrical casing
- H01M10/0427—Button cells
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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
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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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
- H01M4/58—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
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- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- 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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Abstract
The invention discloses Mo/O co-doping VS4A magnesium ion battery anode material and an application thereof belong to the technical field of battery materials. Mixing ammonium metavanadate and ammonium molybdate tetrahydrate according to a molar ratio of 1160: 1, preparing an aqueous solution with the concentration of 0.167M, mixing the aqueous solution with an excessive glycol solution of thioacetamide, and carrying out hydrothermal reaction for 4 hours at the temperature of 200 ℃; drying after cleaning and precipitatingAnd calcining the mixture in a muffle furnace at 100 ℃ for 20min to obtain the magnesium ion battery cathode material MVSO. According to the invention, through Mo/O co-doping, the conductivity of MVSO is improved, the chain spacing of MVSO is enlarged, and abundant oxygen vacancy/sulfur vacancy coexistence and V are induced3+/V4+Coexisting, exposing more active sites, achieving rapid Mg2+Reaction kinetics and stable MVSO structure are maintained, and further the electrochemical performance of the magnesium ion battery is improved. The magnesium ion battery assembled by the composite material has high specific capacity, excellent cycling stability and rate capability, and has wide application prospect.
Description
Technical Field
The invention relates to the technical field of battery materials, in particular to Mo/O co-doping VS4A magnesium ion battery anode material and application thereof.
Background
The abundant reserves and low cost of magnesium metal have led to great interest in developing cathode materials suitable for Magnesium Ion Batteries (MIBs). Semiconductor VS4Has a unique chain structure consisting of octahedron V4+Linked to coordinate dimeric persulfate units of all S having a charge of-1 valence. VS4Has a distance of 0.58nm between adjacent chains and the chains are connected with weak van der Waals force, which is advantageous for Mg2+Is rapidly diffused, therefore, VS4Is a promising positive electrode material of the magnesium ion battery. However, when at VS4When the positive electrode material is applied to a magnesium ion battery, the positive electrode material is Mg2+And VS4High polarization due to strong electrostatic interaction between them, which may lead to VS4Structural collapse and Mg during cycling2+Poor diffusion kinetics and the like, and the long cycle life is difficult to realize. Therefore, it is required to be opposite to VS4The modification is carried out to obtain the magnesium ion battery anode material with high specific capacity, high rate capability and ultra-long cycle life.
Anion or cation doping, which is doped at specific lattice positions and introduces non-uniform atomic points, utilizes the coordinated modulation of electronic structure to change the electrochemical behavior of the host material, such as: the band structure, carrier density and local electron configuration are changed. The conductivity of The electrode material can be improved by doping metal cations in The transition metal compound, so that The electrode material has enhanced rate capability (see The literature: The origin of The two-plated or one-plated open circuit voltage in Li-S batteries, Yuxiao Lin et al Nano Energy,2020,75, 104915). Meanwhile, metal ions with larger radius are doped into the active material, so that the crystal face of the active material can be enlargedSpacing of Mg2+The diffusion of (a) provides a fast and more channel. In addition, the anion is doped into the anion lattice of the active material, which can reduce the electrostatic interaction between magnesium ion and anion lattice, and can effectively adjust the electronic structure and chemical physical property of the active material, thereby improving the electrochemical activity thereof, therefore, the anion doping is also an effective method for improving the electrochemical performance of the positive electrode material (see the documents: Oxygen-doped and nitrogen-modified carbon nitride for the electrochemical activity of light cationic hydrogen evolution, Yuanyuan Yang et al New Journal of Chemistry,2020,44, 16320-. In addition, the doping strategy can also induce to generate abundant defects, so that more active sites are provided, the specific capacity of the active material is improved, and meanwhile, the volume change caused in the magnesium ion de-intercalation process can be relieved, the structural stability of the active material is maintained, and the ultra-long cycle life is realized.
Although doping with anions or cations may improve the electrochemical performance of a magnesium ion battery to some extent, it may also have some negative effects, e.g., with Mg2+The continuous migration to the anode material will cause the phase change of the anode material, not only destroy the structure of the anode material, but also accelerate the capacity decay (see the literature: recovering capacity decay and voltage decay of Li)1.2Ni0.13Co0.13Mn0.54O2 by Mg2+and PO4 3-Dual doping, Yongpeng Liu et al materials Research Bulletin,2020,130,110923). The cation/anion co-doping strategy can combine the advantages of each of the cations and anions, such as: on one hand, the structural change caused by single element doping can be relieved to keep the structural stability and improve the cycle performance; on the other hand, the diffusion kinetics of the ions can be fast. Therefore, co-doping of anions and cations is to modify VS4Better strategy for positive electrode material. For VS4Due to Mo4+And V4+With similar ionic radii, which favors Mo4+Entering VS4In the crystal lattice. Further, Mo4+Has an ionic radius slightly larger than V4+This will favor VS4Enlargement of interplanar spacing with O2-With respect to S2 2-Smaller ionic radius, O2-Can be relieved by doping Mo4 +Doping and the resulting structural change. Therefore, it can be speculated that Mo/O co-doping increases VS4The specific capacity and the rate performance of the composite material can be realized, and meanwhile, the structural stability of the composite material can be kept. However, studies on improving the electrochemical performance of the cathode material of the magnesium ion battery by an anion/cation co-doping strategy have not been reported.
The Mo/O co-doping VS is prepared by a hydrothermal method-calcining method4(MVSO) and researches the electrochemical performance of the magnesium ion battery by using the MVSO as a positive electrode material. Electrochemical performance test results show that the cycle performance and the rate capability of MVSO are improved based on the synergistic effect of series electronic states and microstructure changes brought by Mo/O co-doping. At 50mA g-1MVSO showed 140.5mAh g at current density of (1)-1Higher specific capacity. And when the current density is from 50mA g-1Increased to 1000mA g-1In time, the specific capacity of the MVSO cathode material is 144mAh g-1Change to 75.2mAh g-1When the current density is recovered to 50mA g-1When the specific capacity is recovered to 139.1mAh g-1The retention rate was 95.6% with respect to the initial stage specific capacity, and good rate capability was exhibited. When the MVSO anode material is at 1000mA g-1When the current was cycled at a current density, the capacity retention rate was 92% after 1000 cycles, and excellent cycle stability was exhibited. The invention opens up a new way for the design of the anode material of the future magnesium ion battery.
Disclosure of Invention
The invention aims to provide a magnesium ion battery anode material, and particularly provides Mo/O co-doping VS4A positive electrode material MVSO of a magnesium ion battery and application thereof. VS modified by Mo/O co-doping4The positive electrode material has high specific capacity, good cycling stability, excellent rate capability and the like.
In order to achieve the purpose, the preparation process of the positive electrode material MVSO of the magnesium ion battery provided by the invention is as follows:
1. according to the molar ratio of 1160: 1, weighing ammonium metavanadate and ammonium molybdate tetrahydrate according to the proportion, dissolving in deionized water, and magnetically stirring at 60 ℃ until the ammonium metavanadate and the ammonium molybdate tetrahydrate 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 until the thioacetamide is completely dissolved to obtain a solution B;
3. mixing the solution B and the solution A, and magnetically stirring at 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. washing the precipitate with deionized water and anhydrous ethanol for 3 times, centrifuging to collect the precipitate, vacuum drying at 60 deg.C for 12 hr to obtain Mo-doped VS4；
6. Doping the obtained Mo with VS4Heating the mixture to 100 ℃ in a muffle furnace, and preserving the heat for 20min to obtain the magnesium ion battery positive electrode material MVSO.
The invention also provides application of MVSO as a positive electrode material in a magnesium ion battery, and the MVSO, a metal magnesium negative electrode, a glass fiber diaphragm and an APC-THF electrolyte are assembled into a button cell. 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 50-1000 mA-1
g-1。
The positive electrode material MVSO of the magnesium ion battery provided by the invention has the advantages that:
1. the prepared magnesium ion battery positive electrode material MVSO and Mo/O co-doping improve the conductivity of the MVSO positive electrode material and accelerate Mg2+The diffusion speed is increased, and the reaction kinetics are improved; in addition, Mo/O codoping increases VS4Chain pitch of to enlarge Mg2+The diffusion channel can also maintain the stability of the structure, therefore, Mo/O co-doping can improve VS4Reaction kinetics and cycle stability.
2. The invention is madeThe prepared magnesium ion battery anode material MVSO, Mo/O co-doping induced oxygen vacancy and sulfur vacancy coexist, and V3+/V4+Coexisting with the changes of the microstructure and the electronic state of the same series. Wherein the coexistence of oxygen-rich vacancy and sulfur-rich vacancy can expose more Mg2+Adsorb active sites and mitigate the presence of positive electrode material in Mg2+The volume change caused in the de-intercalation process is beneficial to improving the specific capacity and the cycling stability; v3+/V4+The coexistence is beneficial to improving the conductivity of the anode material and accelerating the reaction kinetics; based on the synergistic effect of the microstructure and the electronic state change caused by Mo/O co-doping, the MVSO magnesium ion battery anode material can show enhanced specific capacity, cycling stability and rate capability.
3. The magnesium ion battery anode material MVSO prepared by the invention has excellent electrochemical performance: at 50mA g-1MVSO showed 140.5mAh g at current density of (1)-1The specific capacity of (A). At a current density of 50mA g-1Increased to 1000mA g-1The specific capacity of the electrode material is 144mAh g-1Change to 75.2mAh g-1When the current density is recovered to 50mA g-1When the specific capacity is higher than the specific capacity value in the initial stage, the average specific capacity reaches 95.6%, and the good rate performance is shown. And at 1000mA g-1Under the current density, the capacity retention rate of the electrode material can reach 92% after 1000 cycles, and excellent cycle stability is shown.
The concept, 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 is an XRD spectrum of MVSO of the cathode material of the magnesium ion battery obtained in example 1;
FIG. 2 is an XPS spectrum of the positive electrode material MVSO of the magnesium ion battery obtained in example 1;
FIG. 3 is a V high resolution XPS spectrum of the positive electrode material MVSO of the magnesium ion battery obtained in example 1;
FIG. 4 is an EPR spectrum of the positive electrode material MVSO of the magnesium ion battery obtained in example 1;
FIG. 5 is a graph showing the electrochemical performance of the positive electrode material MVSO of the magnesium ion battery obtained in example 1;
FIG. 6 shows that the MVSO content of the positive electrode material of the magnesium-ion battery obtained in example 1 is 1000mA g-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
0.5814g of ammonium metavanadate and 0.0265g of ammonium molybdate tetrahydrate are weighed and dissolved in 30ml of deionized water, and the solution is magnetically stirred at the temperature of 60 ℃ until the ammonium metavanadate and the ammonium molybdate tetrahydrate are completely dissolved to obtain a solution A; weighing excessive thioacetamide, dissolving the thioacetamide in 30ml of ethylene glycol, and magnetically stirring until the thioacetamide is completely dissolved to obtain a solution B; fully mixing the solution B with the solution A under the magnetic stirring at 60 ℃; transferring the mixed solution into a 100ml reaction kettle, carrying out hydrothermal reaction for 4 hours at the temperature of 200 ℃, and cooling to room temperature along with the furnace; and (3) respectively cleaning and precipitating with deionized water and absolute ethyl alcohol for 3 times by adopting a centrifugal method, putting into a vacuum drying oven, drying at 60 ℃ for 12h, calcining in a muffle furnace at 100 ℃ for 20min, and cooling along with the furnace to obtain the magnesium ion battery cathode material MVSO.
After a hydrothermal-calcining method, Mo and O elements are successfully and jointly doped into VS4In XRD results (FIG. 1) can be observed, except for VS4Is outside the characteristic peak of (1), no new phase is generated, and VS4The diffraction peak shifts to a low angle relative to the standard map, which can prove that the Mo/O codoping expands VS4The chain pitch of (1). Mo, O, V and S elements can be simultaneously observed in an XPS spectrum (figure 2), and further prove that the Mo and O elements are jointly doped into VS4In the crystal lattice. High resolution XPS spectra of V (FIG. 3) show that V has both V and V3+And V4+Valence state, which shows that Mo/O co-doping induces V3+Is generated. The EPR profile of MVSO (FIG. 4) is shown ing-1.96 and g-1.98 correspond to sulfur and oxygen vacancies, respectively, indicating that abundant sulfur and oxygen vacancies are present in MVSO at the same time.
And (3) assembling the button cell by taking the prepared MVSO as a positive electrode material of the magnesium ion battery, taking the polished magnesium foil as a negative electrode material, taking a glass fiber filter membrane as a diaphragm of the magnesium ion battery, taking 0.4M APC-THF as electrolyte and filling the diaphragm with high-purity argon in a glove box. 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 50-1000 mA g-1。
The electrochemical properties of the obtained positive electrode material MVSO of the magnesium ion battery are shown in figure 5, and the current density is 50mA g-1MVSO showed 140.5mAh g-1High specific capacity of (2). And when the current density is from 50mA g-1Gradually increased to 1000mA g-1The specific capacity of MVSO is 144mAh g-1Gradually changing to 75.2mAh g-1And when the current density is restored to 50mA g-1When the specific capacity is higher than the initial stable specific capacity by 95.6%, the specific capacity shows better rate performance. MVSO is 1000mA g-1The capacity retention rate after 1000 cycles is as high as 92% at the current density (see fig. 6), and good cycle stability is shown.
Claims (3)
1. Mo/O co-doping VS4The magnesium ion battery positive electrode material and the application thereof are characterized in that the preparation process is as follows:
respectively weighing ammonium metavanadate and ammonium molybdate tetrahydrate according to the ratio of 1160: 1, and magnetically stirring at 60 ℃ to prepare an aqueous solution with the concentration of 0.167M; weighing excessive thioacetamide and dissolving in glycol with the same volume as the aqueous solution; completely mixing the two solutions, transferring the mixture into a reaction kettle, and reacting for 4 hours at 200 ℃; cleaning, precipitating, drying, heating to 100 deg.C in a muffle furnace, calcining for 20min, and cooling to obtain Mo/O co-doped VS4The positive electrode material MVSO of the magnesium ion battery;
assembling the obtained positive electrode material MVSO of the magnesium ion battery into a button magnesium ion battery with electrochemical performanceThe test voltage window is 0.2-2.1V, and the current density is 50-1000 mA g-1。
2. The Mo/O co-doped VS according to claim 14The magnesium ion battery positive electrode material and the application thereof are characterized in that Mo/O codoping improves the conductivity of MVSO, enlarges the chain spacing and induces V3+/V4+Coexists and forms a series of microstructures such as rich oxygen/sulfur vacancy and the like and changes of electronic states.
3. The Mo/O co-doped VS according to claim 14The magnesium ion battery positive electrode material and the application thereof are characterized in that when the obtained material is used as the magnesium ion battery positive electrode, the positive electrode material is at 50mA g-1The specific capacity under the current density is 140.5mAh g-1(ii) a The current density is from 50mA g-1Increase to 1000mA g-1Then the voltage is restored to 50mA g-1The specific capacity retention rate is 95.6 percent; at 1000mA g-1The capacity retention rate can reach 92% after 1000 cycles of circulation under the current density.
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