CN114039034A - Mg2+Pre-embedded magnesium ion battery positive electrode material MgVS4N-TG and application - Google Patents
Mg2+Pre-embedded magnesium ion battery positive electrode material MgVS4N-TG and application Download PDFInfo
- Publication number
- CN114039034A CN114039034A CN202111437488.0A CN202111437488A CN114039034A CN 114039034 A CN114039034 A CN 114039034A CN 202111437488 A CN202111437488 A CN 202111437488A CN 114039034 A CN114039034 A CN 114039034A
- Authority
- CN
- China
- Prior art keywords
- ion battery
- magnesium ion
- mgvs
- positive electrode
- electrode material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910001425 magnesium ion Inorganic materials 0.000 title claims abstract description 57
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 26
- 239000011777 magnesium Substances 0.000 claims abstract description 19
- 239000000243 solution Substances 0.000 claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000010405 anode material Substances 0.000 claims abstract description 10
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 8
- 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
- 239000000463 material Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims abstract description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims abstract description 4
- 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
- 230000008569 process Effects 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
- 230000001939 inductive effect Effects 0.000 claims 1
- 238000003760 magnetic stirring Methods 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 3
- 230000001351 cycling effect Effects 0.000 abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 238000007740 vapor deposition Methods 0.000 abstract 1
- 229910052749 magnesium Inorganic materials 0.000 description 13
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 12
- 150000002500 ions Chemical class 0.000 description 9
- 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
- 239000007772 electrode material Substances 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
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 230000009881 electrostatic interaction Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 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
- 238000012986 modification Methods 0.000 description 1
- 239000007773 negative electrode material Substances 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
- 238000005457 optimization Methods 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 230000010399 physical interaction Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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 Mg2+Pre-embedded magnesium ion battery positive electrode material MgVS4the/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 a hydrothermal reaction at 180 ℃ for 4 hours; drying the product and then electrochemically reacting the dried product over MgSO4Carrying out Mg in solution2+Pre-embedding to obtain the magnesium ion battery anode material MgVS4N-TG. The invention relates to aPerMg2+Pre-embedding of both to expand VS4Inter-strand spacing of, and also can induce V2+And V3+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 wide application prospect.
Description
Technical Field
The invention relates to the technical field of battery materials, in particular to Mg2+Pre-embedded magnesium ion battery positive electrode material MgVS4The preparation method of the novel N-TG and the application thereof.
Background
With the increase of energy consumption and the increase of environmental pollution, the development and popularization of renewable energy storage devices are urgently needed. Magnesium ion batteries have high safety, low cost, and high theoretical volume capacity (3833mAh cm)-3) And the working principle similar to that of the lithium ion battery, and is receiving wide attention. However, during the insertion/extraction process of the magnesium working ions, there is a large polarization between the magnesium working ions and the positive electrode material, resulting in poor stability and low reaction kinetics of the positive electrode material. VS4As an energy storage material, the material has a one-dimensional linear chain structure, extends along a c axis, and has a V center positioned at two S centers2 2-Between dimers and having a diameter greater than the magnesium working ion
The larger chain spacing (0.58nm) is beneficial to the intercalation and deintercalation of magnesium working ions. Furthermore, VS4The adjacent atomic chains interact with each other by van der waals force, and the acting force is weaker, so that the magnesium working ion migration kinetics are greatly improved. Albeit VS4Has very encouraging structural advantages, but VS4Low conductivity and magnesium working ion and VS4Yet fails to make VS due to large electrostatic interactions between4A satisfactory level is achieved in magnesium ion batteries. Therefore, to increase VS4Potential application in magnesium ion batteries, VS is required4Modifications were made to overcome these problems.
In the method capable of relieving strong electrostatic interaction between magnesium working ions and a positive electrode material and enhancing reaction kinetics, the interlayer regulation and control method can effectively improve the conductivity and prevent the structure from collapsing, thereby improving the electrochemical performance of the magnesium ion battery (see the document: Guest-species-incorporation in manganese/vanadium-based oxides: Towards high performance)aquous zinc-ion batteries, Li et al. Nano Energy,2021,85, 105969). Cation pre-intercalation is a typical interlayer control method, which is to intercalate part of cations into the crystal lattice of an electrode material before cell cycling, and the pre-intercalated cations react with a main framework through chemical and physical interactions and have a remarkable promoting effect on the structural stability of the electrode material and the migration kinetics of carriers (see the literature: pretreatment geometry in organic Oxides for Electrochemical Energy Storage: Review and protocols, adv.mater.,2020,32, e 2002450). However, with respect to Mg2+Pre-embedding of VS grown on nitrogen-doped tubular graphene (N-TG) surface4The research on improving the electrochemical performance of the magnesium ion battery has not been reported.
The invention realizes Mg by an electrochemical method2+Pre-embedded VS4/N-TG and investigation of MgVS4The electrochemical performance of the/N-TG as a positive electrode material applied to the magnesium ion battery. The research result shows that the pre-embedded magnesium ions have the same ionic radius and ionic valence as the working ions, and VS4The chain pitch of (A) is enlarged and a valence change of the V element is induced to make MgVS4The specific capacity and the cycling stability of the/N-TG are improved. At 0.05A g–1At a current density of (1), MgVS4the/N-TG showed 170mAh g–1Higher specific capacity. When the current density is from 0.05Ag-1Increased to 1Ag-1In the process, the specific capacity is 169mAh g-1Change to 107mAh g-1And when the current density dropped back to 0.05A g-1When the specific capacity is recovered to 145mAh g-1The composite material shows excellent rate performance. At 1A g–1At a current density of (1), MgVS4After 1500 cycles of/N-TG treatment, the capacity retention rate is close to 100%.
Disclosure of Invention
The invention aims to provide a magnesium ion battery positive electrode material, in particular to Mg2+Pre-embedded magnesium ion battery positive electrode material MgVS4The preparation method of the novel N-TG and the application thereof.
In order to achieve the aim, the invention provides magnesium ionsAnode material MgVS of sub-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 vertical 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. Electrochemically, with 1M MgSO4Is a solution, at a current density of 20mA cm–2VS under the condition that the voltage window is 0-1.2V4Mg by/N-TG2+Pre-embedding treatment to obtain magnesium ion battery anode material MgVS4/N-TG。
The invention also provides MgVS4The 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, and the current density is 0.05-1 Ag-1。
The magnesium ion battery anode material MgVS provided by the invention4The advantages of the/N-TG are that:
1. the magnesium ion battery anode material MgVS prepared by the invention4N-TG, Pre-Embedded Mg2+VS is enlarged4Chain spacing of, increasing MgVS4The conductivity of the/N-TG promotes the diffusion kinetics of the magnesium working ions and acts as a "backbone" to weaken the electrostatic interaction between the magnesium working ions and the positive electrode material to maintain structural stability, thus MgVS4the/N-TG magnesium-ion battery positive electrode material can show enhanced rate performance and cycle stability.
2. The magnesium ion battery anode material MgVS prepared by the invention4/N-TG，Mg2+Pre-insertion induced V2+And V3+Generation, optimization of MgVS4The electronic structure of/N-TG and provides higher electrochemical reactivity, therefore MgVS4the/N-TG magnesium ion battery positive electrode material can show higher specific capacity.
3. The magnesium ion battery anode material MgVS prepared by the invention4the/N-TG shows excellent electrochemical performance: at 0.05Ag-1At a current density of (1), MgVS4the/N-TG showed 170mAh g-1High specific capacity of (2). When the current density is from 0.05Ag-1Increased to 1Ag-1In the process, the specific capacity is 169mAh g-1Change to 107mAh g-1And when the current density drops back to 0.05Ag-1When the specific capacity is recovered to 145mAh g-1The composite material shows excellent rate performance. In 1Ag-1The capacity retention rate of the electrode material is close to 100% after 1500 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 MgVS of the magnesium-ion battery obtained in the example4XRD pattern of/N-TG;
FIG. 2 shows the positive electrode material MgVS of the magnesium-ion battery obtained in the example4of/N-TG(110) Crystal face HRTEM picture;
FIG. 3 shows the positive electrode material MgVS of the magnesium-ion battery obtained in the example4XPS spectrum of/N-TG;
FIG. 4 shows the positive electrode material MgVS of the magnesium-ion battery obtained in the example4V high resolution XPS spectra of/N-TG;
FIG. 5 shows the positive electrode material MgVS of the magnesium-ion battery obtained in the example4The electrochemical performance curve of/N-TG;
FIG. 6 shows the positive electrode material MgVS of the magnesium-ion battery obtained in the example4(iv) 1Ag for N-TG-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, reacting 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 the saturated calomel electrode and the platinum wire electrode is 1M MgSO4Using electrochemical method in solution at 20mA cm–2The current density of the anode material is within the range of 0-1.2V voltage window for three-stage circulation, after the reaction is finished, the sample is washed for 3 times by deionized water, and the sample is dried to obtain the magnesium ion battery anode material MgVS4/N-TG。
After hydrothermal reaction and electrochemical reaction, Mg2+Successful embedding into a 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 map, which can prove that Mg2+Pre-embedding expands VS4The chain pitch of (A), this result may also be at MgVS4In the HRTEM picture of (2), the enlargement of the (110) interplanar spacing was confirmed (fig. 2). Mg, V, S, C and N elements can be simultaneously observed in the XPS map (figure 3), and further proves that Mg2+Pre-embedding into VS4In the/N-TG lattice. The high resolution XPS spectrum of V (FIG. 4) shows that the elements of V are in addition to V4+In addition to the peak, V is also shown2+And V3+Peak of (2), indicating Mg2+Pre-embedding induces V2+And V3+Is generated.
MgVS prepared4The 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, and the current density is 0.05-1 Ag-1。
The obtained magnesium ion battery anode material MgVS4The current density of the/N-TG is 0.05Ag-1It showed 170mAh g-1High specific capacity and when the current density is from 0.05Ag-1Increased to 1Ag-1In the process, the specific capacity is 169mAh g-1Change to 107mAh g-1And when the current density drops back to 0.05Ag-1When the specific capacity is recovered to 145mAh g-1The excellent rate capability was exhibited (fig. 5). At a current density of 1A g-1When, MgVS4After 1500 cycles, the capacity retention rate of the/N-TG magnesium-ion battery positive electrode material is close to 100%, and excellent cycle stability is shown (figure 6).
Claims (3)
1. Mg2+Pre-embedded magnesium ion battery positive electrode material MgVS4The 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 (2) is in a voltage range of 0-1.2V and is 1M MgSO4Carrying out Mg in solution2+Pre-embedding, after the reaction is finished, washing the sample with deionized water for 3 times, and drying in vacuum to obtain Mg2+Pre-embedded magnesium ion battery positive electrode material MgVS4/N-TG。
The obtained magnesium ion battery anode material MgVS4And assembling the/N-TG into the button type magnesium ion battery to carry out electrochemical performance test.
2. Mg according to claim 12+Pre-embedded magnesium ion battery positive electrode material MgVS4N-TG and use thereof, characterised by pre-embedded Mg2+VS can be enlarged4And inducing V2+And V3+Is present.
3. Mg according to claim 12+Pre-embedded magnesium ion battery positive electrode material MgVS4the/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 170mAh g-1Left and right; when the current density is from 0.05A g-1Increased to 1A g-1In the process, the specific capacity is 169mAh g-1Change to 107mAh g-1And when the current density dropped back to 0.05A g-1When the specific capacity is recovered to 145mAh g-1(ii) a At 1A g-1At current density, MgVS4After 1500 cycles of/N-TG treatment, the capacity retention rate is close to 100%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111437488.0A CN114039034B (en) | 2021-11-29 | 2021-11-29 | Mg (magnesium) 2+ Pre-embedded magnesium ion battery anode material MgVS 4 N-TG and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111437488.0A CN114039034B (en) | 2021-11-29 | 2021-11-29 | Mg (magnesium) 2+ Pre-embedded magnesium ion battery anode material MgVS 4 N-TG and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114039034A true CN114039034A (en) | 2022-02-11 |
| CN114039034B CN114039034B (en) | 2023-10-10 |
Family
ID=80145991
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111437488.0A Active CN114039034B (en) | 2021-11-29 | 2021-11-29 | Mg (magnesium) 2+ Pre-embedded magnesium ion battery anode material MgVS 4 N-TG and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114039034B (en) |
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 |
-
2021
- 2021-11-29 CN CN202111437488.0A patent/CN114039034B/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》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114039034B (en) | 2023-10-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105914374B (en) | Composite material of nitrogen-doped carbon cladding selenizing molybdenum/graphene nucleocapsid array interlayer structure and its preparation method and application | |
| CN104993125B (en) | A kind of lithium ion battery negative material Fe3O4The preparation method of/Ni/C | |
| CN112490438B (en) | Mo-VS4Positive electrode material of/N-GNTs magnesium ion battery | |
| CN112242526B (en) | Mo-doped VS4 magnesium ion battery positive electrode material | |
| CN112886004A (en) | Cathode material of water-based zinc ion battery and matched electrolyte | |
| CN112010291B (en) | Preparation method and application of nickel-doped molybdenum disulfide/graphene three-dimensional composite material | |
| CN113526483A (en) | Ferro-phosphorus sodalite type cathode material and preparation method and application thereof | |
| CN112142030A (en) | Preparation method of low-cost low-temperature lithium iron phosphate | |
| CN109244459A (en) | A kind of codope flexibility sodium-ion battery positive material and preparation method thereof | |
| CN107634223A (en) | A kind of preparation method of Carbon negative electrode material of sodium ion battery | |
| CN104852029A (en) | Lithium ion battery cathode material without binder and conductive agent and preparation method therefor | |
| CN109279663B (en) | Borate sodium-ion battery negative electrode material and preparation and application thereof | |
| CN110233251A (en) | A kind of preparation method and applications of porous silicon/carbon composite material | |
| CN107134575A (en) | A kind of preparation method of anode material of lithium-ion battery | |
| CN106784803A (en) | A kind of cobalt acid nickel nanocube material and its preparation method and application | |
| CN111261870B (en) | NASICON structure Na4CrMn(PO4)3Method for producing materials and use thereof | |
| CN108598463A (en) | A kind of preparation method of nano-sheet lithium-rich manganese-based anode material | |
| CN108417824B (en) | Preparation method of high-performance lithium battery cathode material carbon-coated lithium titanate | |
| CN105720268A (en) | Lithium ion battery anode material and preparation method of lithium ion battery anode material | |
| CN114039034A (en) | Mg2+Pre-embedded magnesium ion battery positive electrode material MgVS4N-TG and application | |
| CN115064657A (en) | High-entropy layered metal oxide and preparation method and application thereof | |
| CN114243007A (en) | Nickel disulfide/carbon nanotube composite electrode material and preparation method and application thereof | |
| CN114014330A (en) | Energy storage electrode material K3Nb3Si2O13Preparation method and application of | |
| CN113929138A (en) | Mo/O co-doped VS4 magnesium ion battery positive electrode material and application thereof | |
| CN105070900A (en) | Technology for preparing lithium-rich manganese-based electrode material by electrolytic manganese anode slime |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |