CN113964321A - K+Magnesium ion battery positive electrode material KVS for pre-embedding induction of multi-electron reaction4N-TG and application - Google Patents
K+Magnesium ion battery positive electrode material KVS for pre-embedding induction of multi-electron reaction4N-TG and application Download PDFInfo
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- 229910001425 magnesium ion Inorganic materials 0.000 title claims abstract description 48
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 34
- 230000006698 induction Effects 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 239000000243 solution Substances 0.000 claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 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
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000007864 aqueous solution Substances 0.000 claims abstract 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 6
- 230000014759 maintenance of location Effects 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000011056 performance test Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims 1
- 238000003760 magnetic stirring Methods 0.000 claims 1
- 239000010405 anode material Substances 0.000 abstract description 8
- 230000001351 cycling effect Effects 0.000 abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 3
- 238000003780 insertion Methods 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 abstract description 2
- 230000037431 insertion Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 abstract 1
- 238000007740 vapor deposition Methods 0.000 abstract 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 7
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 6
- 239000007772 electrode material Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229920000877 Melamine resin Polymers 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000009830 intercalation Methods 0.000 description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 4
- 239000011863 silicon-based powder Substances 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 108090000765 processed proteins & peptides Proteins 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000005347 demagnetization Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
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Classifications
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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
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
-
- 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 a K+Magnesium ion battery positive electrode material KVS for pre-embedding induction of multi-electron reaction4the/N-TG and the application belong to the technical field of battery materials. Preparing ammonium metavanadate into an aqueous solution, mixing the aqueous solution with an excessive thioacetamide glycol solution, transferring the aqueous solution and a carbon sheet which is prepared by a vapor deposition method and grows with N-TG into a reaction kettle, and carrying out hydrothermal reaction for 4 hours at 180 ℃; drying the product and then electrochemically treating the dried product at K2SO4In solution for K+Pre-embedding to obtain the positive electrode material KVS of the magnesium ion battery4N-TG. The invention is based on the discovery that+Is pre-embedded in the insertion layer type anode material, not only can realize multi-electron reaction, but also can maintain the structural stability of the anode material, and improves the magnesium ion electricityElectrochemical performance of the cell. The magnesium ion battery assembled by the composite material has high specific capacity, excellent cycling stability and wide application prospect.
Description
Technical Field
The invention relates to the technical field of battery materials, in particular to a K+Magnesium ion battery positive electrode material KVS for pre-embedding induction of multi-electron reaction4The preparation method of the novel N-TG and the application thereof.
Background
Batteries based on polyvalent metal ions are considered energy storage devices with potential applications due to the abundance of polyvalent elements. The magnesium ion battery is used as a novel energy storage system due to high safety, low cost and high theoretical capacity (3833mAh cm)–3) And the like, and are widely researched. However, the charge migration of the divalent magnesium ion is slow, which causes problems of low structural stability, slow kinetics, and even low specific capacity. To take advantage of the high charge density of divalent magnesium ions, it is necessary to obtain a positive electrode material that can realize multiple electron transfer and maintain structural stability, which is a major challenge in developing magnesium ion batteries with high specific capacity and cycling stability.
In recent years, in the multi-electron reaction in the ion battery, the capability of improving the storage capacity of the battery due to the participation of a plurality of electrons in the reaction has attracted extensive attention of researchers. However, the majority of the multi-electron reactions occur in the conventional conversion electrode materials, and the modification of the electrode materials is difficult to exceed the reaction mechanism of the intercalation electrode materials and is limited to single-electron reactions (see the literature: Nanphthalalene diimides as a two-electron anode for aqueous and neutral pH redox flow batteries, Messalmi et al J.Mater. chem.A., 2020,8, 11218-11223). From the viewpoint of electrode design, vanadium element shows more electrochemical diversity and multiple electron cloud state density in different crystal structures. VS4As a typical vanadium-based sulfide, the valence of the V element is +4, and when the electronic environment is changed, the chemical valence can be changed from +2 to + 5. Furthermore, VS4Has a unique linear chain structure, and the distance between adjacent chains is 0.56nm, which is beneficial to the adsorption of magnesium ions. Therefore, VS4Is considered to be a positive electrode material of a magnesium ion battery with research significance. However, VS4Is a typical intercalation type anode material with single electron transfer, which is verified in the existing report (see the literature: Morphology-dependent electrochemical)performance of VS4for recoverable magnesium battery and its magnetization/demagnetization mechanism, Li et al.j.power Sources,2020,451,227815) can be used to insert the layer into the VS4The modification is carried out to realize multi-electron reaction so as to improve the specific capacity of the material. However, the large volume change caused during the multi-electron reaction makes it difficult to maintain the structural stability of the host material, which limits the cycle reversibility and stability of the magnesium-ion battery (see literature: Hetero-layered MoS)2/C composites enabling ultrafast and durable Na storage,Li et al.Energy Storage Mater.2019,21,115-123)。
The invention realizes K by an electrochemical method+Pre-embedded VS4N-TG and study of KVS4the/N-TG is used as a positive electrode material in the multi-electron reaction process and the electrochemical performance of the magnesium ion battery. The serial characterization results show that K+Pre-insertion induced V2+Appearance, V2+Is such that V2+/V4+、V4+/V5+The reaction process is carried out to promote the reaction at KVS4The multi-electron reaction is realized in the positive electrode material of the/N-TG magnesium ion battery. Electrochemical performance shows that K is+Pre-intercalation induced multiple electron responses and pre-intercalated K+KVS, a synergistic effect as a strut to maintain structural stability4The specific capacity and the cycle performance of the/N-TG are improved. At 0.05A g-1At current density of (KVS)4the/N-TG showed 190mAh g-1Higher specific capacity. And at 1A g-1At current density of (KVS)4After 2000 cycles of the/N-TG treatment, the capacity retention rate is close to 100 percent.
Disclosure of Invention
The invention aims to provide a magnesium ion battery positive electrode material, in particular to K+Magnesium ion battery positive electrode material KVS for pre-embedding induction of multi-electron reaction4The preparation method of the novel N-TG and the application thereof. Through K+Pre-embedded modified KVS4The positive electrode material of the/N-TG magnesium ion battery realizes multi-electron reaction and maintains the structure of the positive electrode material without changing the intercalation reaction mechanismStable, shows higher specific capacity and better cycling stability.
In order to realize the aim, the invention provides a positive electrode material KVS of a magnesium ion battery4The preparation process of the/N-TG is as follows:
1. according to the mass ratio of 9: 1, weighing melamine and silicon powder, fully grinding, putting the melamine and the silicon powder together with a carbon sheet dropwise added with a catalyst into a vacuum atmosphere furnace for calcining, and cooling to normal temperature to obtain nitrogen-doped tubular graphene (N-TG) uniformly growing on the surface of the carbon sheet;
2. dissolving ammonium metavanadate in deionized water at 60 ℃ under stirring to obtain a solution A with the concentration of 0.167M;
3. weighing excessive thioacetamide, dissolving in glycol with the same volume as the solution A, and stirring until the thioacetamide is completely dissolved to obtain a solution B;
4. mixing the solution A and the solution B, and stirring at 60 ℃ until the two solutions are completely mixed;
5. transferring the fully mixed solution and the carbon sheet with the grown N-TG into a 100ml reaction kettle, heating to 180 ℃, reacting for 4 hours, and cooling to room temperature along with the furnace after the reaction is finished;
6. taking out the reacted sample, washing with deionized water and anhydrous ethanol for 3 times, respectively, placing the obtained product into a vacuum drying oven, and drying at 60 ℃ for 12h to obtain VS4/N-TG。
7. By electrochemical means, at 1M K2SO4Is a solution, at a current density of 20mA cm–2VS under the condition that the voltage window is 0-1.2V4K on/N-TG+Pre-embedding treatment to obtain positive electrode material KVS of magnesium ion battery4/N-TG。
The invention also provides KVS4The button cell is assembled by the aid of the/N-TG as a positive electrode material, a metal magnesium negative electrode, a glass fiber diaphragm and an APC-THF electrolyte. 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, the current density is 0.05 and 1Ag-1。
The magnesium ion battery anode material KVS provided by the invention4The advantages of the/N-TG are that:
1. the magnesium ion battery anode material KVS prepared by the invention4/N-TG，K+Pre-insertion induced V2+Generation of V2+Is such that V2+/V4+、V4+/V5+The reaction process is carried out at KVS4Multiple electron reaction is realized in the positive electrode material of the/N-TG magnesium ion battery, so that KVS4the/N-TG magnesium ion battery positive electrode material can show higher specific capacity.
2. The magnesium ion battery anode material KVS prepared by the invention4N-TG, Pre-Embedded K+Also acting as a "pillar" in the structure, maintaining structural stability by weakening the polarization between the magnesium ions and the positive electrode material, thus KVS4the/N-TG magnesium-ion battery positive electrode material can show enhanced cycle stability.
3. The magnesium ion battery anode material KVS prepared by the invention4the/N-TG shows excellent electrochemical performance: at 0.05A g-1At current density of (KVS)4the/N-TG showed 190mAh g-1High specific capacity of (2). At 1A g-1The capacity retention rate of the electrode material is close to 100% after 2000 cycles, and the electrode material shows excellent cycle stability.
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 shows the positive electrode material KVS of the magnesium-ion battery obtained in example 14XRD pattern of/N-TG;
FIG. 2 shows the positive electrode material KVS of the magnesium-ion battery obtained in example 14XPS spectrum of/N-TG;
FIG. 3 shows the positive electrode material KVS of the magnesium-ion battery obtained in example 14V high resolution XPS spectra of/N-TG;
FIG. 4 shows the positive electrode material KVS of the magnesium-ion battery obtained in example 14V high resolution XPS spectra of/N-TG at different cut-off voltages;
FIG. 5 shows the positive electrode material KVS of the magnesium-ion battery obtained in example 14The ratio of the concentration of the peptide to the concentration of the peptide is 0.05A g in terms of N-TG-1A cycle performance curve at current density;
FIG. 6 shows the positive electrode material KVS of the magnesium-ion battery obtained in example 14The ratio of the concentration of the acid to the concentration of 1A 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
Weighing 12.6g of melamine and 1.4g of silicon powder, fully grinding, putting the melamine and the silicon powder together with a carbon sheet dropwise added with a nickel nitrate catalyst into a vertical vacuum atmosphere furnace, reacting for 30min at 1250 ℃, and cooling to room temperature along with the furnace to obtain N-TG uniformly growing on the carbon sheet; weighing 0.5814g of ammonium metavanadate, dissolving in 30ml of deionized water, and stirring at 60 ℃ until the ammonium metavanadate is completely dissolved to obtain a solution A; weighing excessive thioacetamide, dissolving the thioacetamide in 30ml of ethylene glycol, and stirring at normal temperature until the thioacetamide is completely dissolved to obtain a solution B; fully mixing the solution B and the solution A at 60 ℃; transferring the mixed solution and the carbon sheet with N-TG growth into a 100ml reaction kettle, carrying out hydrothermal reaction for 4 hours at 180 ℃, and cooling to room temperature along with the furnace; taking out the sample, washing with deionized water and anhydrous ethanol for 3 times, respectively, and oven drying at 60 deg.C for 12 hr in a vacuum drying oven to obtain VS4N-TG; (ii) the obtained VS4the/N-TG is used as a working electrode, the saturated calomel electrode and the platinum wire electrode are respectively used as a reference electrode and a counter electrode, and the concentration of K is 1M2SO4Using electrochemical method in solution at 20mA cm–2Under the current density, three-stage circulation is carried out within the range of 0-1.2V voltage window, after the reaction is finished, the sample is washed for 3 times by deionized water, and the KVS as the magnesium ion battery anode material is obtained by drying4/N-TG。
After hydrothermal reaction and electrochemical reaction, K+SuccessfulEmbedded into VS4in/N-TG, it can be observed in XRD results (FIG. 1) except for VS4And outside the characteristic peaks of N-TG, no new phase is formed, and VS4The diffraction peak of (A) is shifted to a low angle relative to the standard spectrum, which can prove that K is+Pre-embedding expands VS4Chain spacing of/N-TG. K, V, S, C, N elements were observed simultaneously in the XPS spectra (FIG. 2), further demonstrating K+Pre-embedding into VS4In the/N-TG lattice. The high resolution XPS spectrum of V (FIG. 3) shows that the elements of V are in addition to V4+In addition to the peak, V is also shown2+Peak of (2), description of K+Pre-embedding induces V2+Is generated. By pairing KVS4Analysis of the V high resolution XPS spectra at different cut-off voltages for/N-TG (FIG. 4) gives the result that V is present during discharge2+Gradually disappear, V5+Gradually appeared and has no V3+The valence of the element V during charging is also from V5+Change to V4+Then from V4+Directly to V2+In the middle, there is no V3+Evidence of KVS4V of/N-TG cathode material2+/V4+、V4+/V5+The reaction process further proves that the multi-electron reaction process occurs in KVS4In the/N-TG cathode material.
The prepared KVS4The button cell is assembled by taking the/N-TG as the positive electrode material of the magnesium ion cell, the polished magnesium foil as the negative electrode material, the glass fiber filter membrane as the diaphragm of the magnesium ion cell and 0.4M APC-THF as the electrolyte in a glove box filled with high-purity 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, the current density is 0.05 and 1A g-1。
The obtained positive electrode material KVS of the magnesium ion battery4The current density of the/N-TG is 0.05A g-1It showed 190mAh g-1High specific capacity (fig. 5). At a current density of 1A g-1Time, KVS4After 2000 cycles of the/N-TG magnesium-ion battery positive electrode material, the capacity retention rate is close to 100 percent, and the excellent cycle stability is shown (Fig. 6).
Claims (3)
1. K+Magnesium ion battery positive electrode material KVS for pre-embedding induction of multi-electron reaction4The preparation method is characterized by comprising the following steps:
dissolving ammonium metavanadate in water at 60 ℃ under magnetic stirring 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 two solutions and a carbon sheet with N-TG growth into a reaction kettle, reacting for 4 hours at 180 ℃, cleaning the carbon sheet for 3 times by using deionized water and absolute ethyl alcohol respectively after the reaction is finished, and drying in vacuum; electrochemically, at 20mA cm–2The current density of (1M) is in the voltage range of 0-1.2V2SO4In solution for K+Pre-embedding, after the reaction is finished, washing the sample with deionized water for 3 times, and drying in vacuum to obtain K+Pre-embedded magnesium ion battery positive electrode material KVS4/N-TG。
The obtained positive electrode material KVS of the magnesium ion battery4The button magnesium ion battery is assembled by the aid of the/N-TG, the voltage window of an electrochemical performance test is 0.2-2.1V, the current density is 0.05 and 1A g-1。
2. A K according to claim 1+Magnesium ion battery positive electrode material KVS for pre-embedding induction of multi-electron reaction4the/N-TG and the use thereof, characterized in that K+Pre-embedding can both act as a "pillar" to maintain structural stability and induce multiple electron responses.
3. A K according to claim 1+Magnesium ion battery positive electrode material KVS for pre-embedding induction of multi-electron reaction4the/N-TG and the application are 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 190mAh g-1Left and right; at 1A g-1At current density, KVS4After 2000 cycles/N-TG, capacityThe retention rate is close to 100%.
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|---|---|---|---|---|
| CN111029172A (en) * | 2019-12-31 | 2020-04-17 | 青岛科技大学 | Two-dimensional layered supercapacitor electrode material Ti3C2Interlayer structure regulation and control method of MXene |
| 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 |
| 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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2021
- 2021-10-21 CN CN202111224763.0A patent/CN113964321B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111029172A (en) * | 2019-12-31 | 2020-04-17 | 青岛科技大学 | Two-dimensional layered supercapacitor electrode material Ti3C2Interlayer structure regulation and control method of MXene |
| 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 |
| 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: "Alkali ions pre-intercalated layered vanadium oxide nanowires for stable magnesium ions storage", 《NANO ENERGY》 * |
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