CN114050256A - Metal-doped vanadium-based oxide nano material and preparation method and application thereof - Google Patents
Metal-doped vanadium-based oxide nano material and preparation method and application thereof Download PDFInfo
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- 239000002086 nanomaterial Substances 0.000 title claims abstract description 26
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 26
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000011777 magnesium Substances 0.000 claims abstract description 27
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000002077 nanosphere Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 5
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 3
- 239000010941 cobalt Substances 0.000 claims abstract description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims abstract description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 39
- 239000002243 precursor Substances 0.000 claims description 33
- 238000000137 annealing Methods 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 14
- 235000006408 oxalic acid Nutrition 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000007774 positive electrode material Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 230000029087 digestion Effects 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 6
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 5
- 239000011654 magnesium acetate Substances 0.000 claims description 5
- 229940069446 magnesium acetate Drugs 0.000 claims description 5
- 235000011285 magnesium acetate Nutrition 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002019 doping agent Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000004729 solvothermal method Methods 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 239000011149 active material Substances 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 238000012876 topography Methods 0.000 claims description 2
- 238000009792 diffusion process Methods 0.000 abstract description 7
- 150000002500 ions Chemical class 0.000 abstract description 7
- 239000013543 active substance Substances 0.000 abstract description 5
- 239000007772 electrode material Substances 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 230000001351 cycling effect Effects 0.000 abstract description 3
- 239000003792 electrolyte Substances 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 239000000872 buffer Substances 0.000 abstract description 2
- 238000012983 electrochemical energy storage Methods 0.000 abstract description 2
- 238000004904 shortening Methods 0.000 abstract description 2
- 238000012546 transfer Methods 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 239000006183 anode active material Substances 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 6
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 5
- 239000006258 conductive agent Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910001425 magnesium ion Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002057 nanoflower Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- ZMLPZCGHASSGEA-UHFFFAOYSA-M zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F ZMLPZCGHASSGEA-UHFFFAOYSA-M 0.000 description 1
- CITILBVTAYEWKR-UHFFFAOYSA-L zinc trifluoromethanesulfonate Substances [Zn+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F CITILBVTAYEWKR-UHFFFAOYSA-L 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
- C01G31/02—Oxides
-
- 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
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to the field of electrochemical energy storage electrode materials, and particularly relates to a metal-doped vanadium-based oxide nano material, a preparation method and application thereof, wherein the chemical formula of the nano material is MxV5O12Wherein M is any one of magnesium, manganese, cobalt and nickel, x is more than or equal to 0.005 and less than or equal to 0.03, and the metal-doped vanadium-based oxide has a porous nano-sphere structure and a larger specific surface area, can provide more active sites and promotes the active substances to be in full contact with electrolyte. The nano structure is beneficial to shortening the ion diffusion path, buffers the deformation generated in the zinc ion embedding and removing process, ensures efficient mass transfer and ion transmission, and enhances the material dynamicsThe energy and the cycling stability.
Description
Technical Field
The invention belongs to the field of electrochemical energy storage electrode materials, and particularly relates to a metal-doped vanadium-based oxide nano material, and a preparation method and application thereof.
Background
People put higher demands on energy storage technology, and energy storage devices are expected to develop towards high energy density, high power density, low cost and environmental protection and safety. Because commercial lithium ion batteries have safety problems such as lithium resource shortage, use of organic electrolyte and the like, the society needs to develop products capable of replacing the lithium ion batteries urgently.
The zinc raw material of the water system Zinc Ion Batteries (ZIBs) is rich in resources, the safety of the batteries is good, the cost is low, and good application prospects are shown. V with vanadium-based material having open framework structure2O5The zinc ion battery cathode material is commonly used as a cathode material of a water system zinc ion battery and has higher specific capacity. However, zinc ions are associated with V when intercalated into the positive electrode material2O5Has strong electrostatic interaction with the host lattice, hindering ion diffusion and leading to V2O5The rate capability of the anode material is reduced, and the repeated embedding of zinc ions can cause pulverization of the anode material and influence the cycle stability of the anode material.
The porous micro-nano regulation strategy is proved to increase the number of active sites in the design of the zinc ion battery anode, shorten the diffusion path and further improve the rate capability. And the porous structure is favorable for relieving structural stress and improving the stability of the electrode material. For example, patent document CN 106745252 a discloses a V having a multilayer hollow structure2O5Nanospheres, when applied in lithium ion batteries, as compared to solid V2O5The micron ball (Energy environ. Sci.,2013,6,974) has more excellent rate property and cycle stability.
Furthermore, cation doping has been shown to enhance ion binding capacity and accelerate ion diffusion. For example, Geng et al synthesized Mn0.15V2O5·nH2The O nanoflower accelerates zinc ions through the cooperative work of manganese ions and water molecules embedded between layersDiffusion of (2). Mn at a high Current Density of 10.0A/g0.15V2O5·nH2O nanoflowers exhibit a specific capacity property of 150mAh/g (adv. funct. mater.,2020,30, 1907684). Li et al Synthesis of Ni by hydrothermal method0.25V2O5·nH2The microstructure is changed by the embedding of O nano-plate and nickel ions. When the composite electrode is combined with hydrophilic carbon paper, the obtained composite electrode shows high specific capacity of 402-147 mAh/g at 0.2-5.0A/g (Adv. energy Mater.,2020,10, 2000058).
However, the rate performance and the battery service life of the conventional cathode material are low when the conventional cathode material is used.
Disclosure of Invention
In order to solve the above technical problems, the present invention provides a metal-doped vanadium-based oxide nanomaterial with a chemical formula of MxV5O12Wherein M is any one of magnesium, manganese, cobalt and nickel, and x is more than or equal to 0.005 and less than or equal to 0.03; preferably, 0.008 ≦ x ≦ 0.025; more preferably, 0.01. ltoreq. x.ltoreq.0.02. For example, x is 0.006, 0.008, 0.01, 0.012, 0.016, 0.018, 0.02, 0.022, 0.024.
According to an embodiment of the present invention, the metal doped vanadium-based oxide nanomaterial is, for example, Mg0.02V5O12、Mg0.01V5O12、Co0.006V5O12。
According to the embodiment of the invention, the nanometer material is a nanosphere, for example, the diameter of the nanosphere is 300-1000 nm; preferably, the diameter of the nanosphere is 400-900 nm; more preferably, the diameter of the nanosphere is 500-800 nm; further preferably, the diameter of the nanosphere is 600-700 nm. For example 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm or 1000 nm.
According to the embodiment of the invention, the nanosphere has a porous structure, and the specific surface area of the nanomaterial is 10-100 m2(ii) in terms of/g. Preferably, the nanomaterial has a topography substantially as shown in fig. 1, 4 or 5.
The invention also provides a preparation method of the metal-doped vanadium-based oxide nano material, which comprises the following steps:
s1) mixing V2O5Dissolving oxalic acid in a solvent to obtain a precursor solution A;
s2) adding a dopant M base salt into the precursor liquid A to obtain a precursor liquid B;
s3) adding the precursor liquid B into an alcohol solvent to carry out solvothermal reaction.
According to an embodiment of the present invention, said V in step S1)2O5The molar ratio of oxalic acid to oxalic acid is 1: 2-1: 5; preferably, said V2O5And oxalic acid in a molar ratio of 1:3 to 1:4, for example 1:3, 1:4 or 1: 5.
According to an embodiment of the present invention, the concentration of the precursor liquid A in the step S1) is 0.05-1 mol/L; preferably, the concentration of the precursor liquid A is 0.2-0.8 mol/L; more preferably, the concentration of the precursor liquid A is 0.4 to 0.6 mol/L. For example, 0.08mol/L, 0.1mol/L, 0.3mol/L, 0.5mol/L, 0.6mol/L, 0.7 mol/L, 0.9 mol/L.
According to an embodiment of the present invention, the dopant M-based salt described in step S2) is an M-based acetate or an M-based nitrate, for example, at least one of magnesium acetate, manganese acetate, cobalt acetate, nickel acetate, magnesium nitrate, manganese nitrate, cobalt nitrate, and nickel nitrate.
According to an embodiment of the present invention, in the step S2), the molar ratio of M to V is 1:200 to 1: 35; preferably, the molar ratio of M to V is 1: 150-1: 50; more preferably, the molar ratio of M to V is from 1:100 to 1: 60; more preferably, the molar ratio of M to V is 1:80 to 1:70, for example 1:200, 1:150, 1:50 or 1: 40.
According to an embodiment of the present invention, the alcoholic solvent described in step S3) is selected from at least one of methanol, ethanol, and isopropanol.
According to an embodiment of the present invention, the volume ratio of the precursor liquid B to the alcohol solvent in step S3) is 1:5 to 1: 20; preferably, the volume ratio of the precursor liquid B to the alcohol solvent is 1:10 to 1:15, for example, 1: 18.
According to the embodiment of the invention, the reaction temperature in the step S3) is 160-200 ℃, and the reaction time is 1-24 h; preferably, the reaction temperature is 170-190 ℃, and the reaction time is 4-20 h; more preferably, the reaction temperature is 175-185 ℃, and the reaction time is 10-15 h.
According to an embodiment of the invention, the reaction of step S3) is carried out in a high pressure digestion tank.
According to an embodiment of the present invention, said step S3) is further followed by: and annealing the reaction product obtained in the step S3) to obtain the metal-doped vanadium-based oxide porous nanospheres.
According to the embodiment of the invention, the temperature of the annealing treatment is 150-300 ℃, and the time is 1-12 h; for example, the temperature of the annealing treatment is 180-250 ℃, and the time is 2-10 h; and if the temperature of the annealing treatment is 200-230 ℃, the time is 4-7 h.
According to an embodiment of the present invention, the temperature increase rate of the annealing treatment is 1-5 ℃/min, for example, the temperature increase rate of the annealing treatment is 2-4 ℃/min, and is exemplified by 1 ℃/min, 2 ℃/min, 3 ℃/min, 4 ℃/min, 5 ℃/min.
According to an embodiment of the invention, the annealing treatment is performed under an air atmosphere.
According to an embodiment of the invention, the annealing treatment is performed in a tube furnace.
The invention also provides application of the metal-doped vanadium-based oxide nano material as an active material (also called as an active substance). It is preferably used as a positive electrode active material, for example, as a positive electrode active material for a zinc ion battery.
The invention provides a positive electrode active material or a positive electrode, which comprises the metal-doped vanadium-based oxide nano material.
According to an embodiment of the present invention, the positive electrode further includes a conductive agent and a binder. The conductive agent and the binder, and the amount of the conductive agent and the binder are not particularly limited, and those skilled in the art can select the known conductive agent and binder, for example, the conductive agent may be conductive carbon black, and the binder may be polyvinylidene fluoride.
According to an embodiment of the invention, the positive electrode further comprises a current collector. The person skilled in the art can select known current collectors, such as titanium foils.
The invention also provides a zinc ion battery which comprises the metal-doped vanadium-based oxide nano material, the positive electrode active material and/or the positive electrode.
According to an embodiment of the present invention, the zinc-ion battery substantially has the cycle performance curve shown in fig. 8 at a current density of 5.0A/g.
According to an embodiment of the present invention, the zinc-ion battery substantially has a cyclic specific capacity diagram shown in fig. 10 at a current density of 10.0A/g.
Advantageous effects
1. The method for synthesizing the metal-doped vanadium-based oxide by the one-step solvothermal method has a porous nanosphere structure, the synthesis mode is simple and easy to control, and the reaction condition is mild.
2. The metal-doped vanadium-based oxide synthesized by the method has a porous nanosphere structure and a larger specific surface area, can provide more active sites for energy storage reaction, and promotes the active substances to be in full contact with electrolyte. And the nano structure is beneficial to shortening an ion diffusion path, buffering deformation generated in the process of embedding and removing zinc ions, ensuring efficient mass transfer and ion transmission, and enhancing the dynamic performance and the cycling stability of the material.
3. When the metal-doped vanadium-based oxide porous nanosphere electrode material synthesized by the invention is applied to the anode of a water-based zinc ion battery, the embedding of metal ions increases oxygen defects, weakens the electrostatic repulsion between zinc ions to be embedded and main crystal lattices, and ensures the rapid diffusion of the zinc ions, so that the metal-doped vanadium-based oxide porous nanosphere electrode material has higher capacity and better rate performance.
Drawings
FIG. 1 shows Mg in example 1 of the present invention0.02V5O12Field Emission Scanning Electron Microscopy (FESEM) images of (a);
FIG. 2 shows Mg in example 1 of the present invention0.02V5O12X-ray diffraction (XRD) pattern of (a);
FIG. 3 shows Mg in example 1 of the present invention0.02V5O12The nitrogen adsorption and desorption curve diagram;
FIG. 4 shows Co in example 3 of the present invention0.006V5O12FESEM image of (B);
FIG. 5 shows Mg in example 4 of the present invention0.026V5O12FESEM image of (B);
FIG. 6 shows V in comparative example 1 of the present invention2O5XRD pattern of (a);
FIG. 7 shows Mg @ V in comparative example 2 of the present invention2O5FESEM image of (B);
FIG. 8 shows Mg in example 1 of the present invention0.02V5O12Comparative example 1, V2O5Comparative example 2 Mg @ V2O5A cycle performance curve at a current density of 5.0A/g;
FIG. 9 shows Mg in example 10.02V5O12Comparative example 1, V2O5The cycle performance curve of (a);
FIG. 10 shows Mg in example 10.02V5O12Cycle performance curve of (a).
Detailed Description
The technical scheme, the preparation method and the application of the invention are further described in detail by combining specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Example 1: mg (magnesium)0.02V5O12Preparation of anode active material of water-based zinc ion battery
Will be commercial V2O5And oxalic acid in a molar ratio of 1:3 is dissolved in deionized water to obtain a precursor solution A with the concentration of 0.33 mol/L. Then adding magnesium acetate (Mg: V molar ratio is 1: 50) into the precursor liquid A) To obtain precursor liquid B containing magnesium ions. 1.2mL of the precursor solution B was added to a high pressure digestion tank containing 20mL of isopropanol and reacted at 200 ℃ for 2 h. Placing the obtained product in a tube furnace, heating to 250 ℃ at 1 ℃/min under the air atmosphere, and annealing for 2h to obtain Mg0.02V5O12The porous nanosphere structure, FESEM is shown in figure 1, and XRD is shown in figure 2. The nitrogen adsorption and desorption curves are shown in FIG. 3, and the BET specific surface area is 39.83m2/g。
Example 2: mg (magnesium)0.01V5O12Preparation of anode active material of water-based zinc ion battery
Will be commercial V2O5And oxalic acid in a molar ratio of 1:3 is dissolved in deionized water to obtain a precursor solution A with the concentration of 0.33 mol/L. Then, magnesium acetate (Mg: V molar ratio of 1:100) was added to the precursor solution A to obtain a precursor solution B containing magnesium ions. 2.4mL of the precursor solution B was added to a high pressure digestion tank containing 50mL of isopropanol solvent and reacted at 200 ℃ for 2 h. Placing the obtained product in a tube furnace, heating to 250 ℃ at 1 ℃/min under the air atmosphere, and annealing for 2h to obtain Mg0.01V5O12A porous nanosphere structure.
Example 3: co0.006V5O12Preparation of anode active material of water-based zinc ion battery
Will be commercial V2O5And oxalic acid in a molar ratio of 1:2 is dissolved in deionized water to obtain a precursor solution A with the concentration of 0.5 mol/L. Then, cobalt acetate (molar ratio of Co: V: 1:150) was added to the precursor solution A to obtain a precursor solution B containing cobalt ions. 1.2mL of the precursor solution B was added to a high pressure digestion tank containing 20mL of isopropanol solvent and reacted at 200 ℃ for 2.5 h. Placing the obtained product in a tube furnace, heating to 250 ℃ at the rate of 1 ℃/min under the air atmosphere, and annealing for 2h to obtain Co0.006V5O12The porous nanosphere structure, FESEM is shown in FIG. 4.
Example 4: mg (magnesium)0.026V5O12Preparation of anode active material of water-based zinc ion battery
Will be commercial V2O5And oxalic acid in a molar ratio of 1:3 dissolving in deionized water to obtain concentrateThe precursor solution A with the degree of 0.33 mol/L. Then, 25.6Mg of magnesium nitrate (Mg: V molar ratio of 1:65) was added to each of the precursor solutions A to obtain a precursor solution B containing magnesium ions. 1.2mL of the precursor solution B was added to a high pressure digestion tank containing 20mL of isopropanol solvent and reacted at 200 ℃ for 2 h. Placing the obtained product in a tube furnace, heating to 250 ℃ at 1 ℃/min under the air atmosphere, and annealing for 2h to respectively obtain Mg0.026V5O12The porous nanosphere structure, FESEM is shown in FIG. 5.
Comparative example 1: v2O5Preparation of anode active material of water-based zinc ion battery
Will be commercial V2O5And oxalic acid in a molar ratio of 1:3 is dissolved in deionized water to obtain a precursor solution A with the concentration of 0.33 mol/L. 1.2mL of the precursor solution A was added to a high pressure digestion tank containing 20mL of isopropanol solvent and reacted at 200 ℃ for 2 h. Placing the obtained product in a tube furnace, heating to 250 ℃ at 1 ℃/min under the air atmosphere, and annealing for 2h to obtain V2O5The porous nanosphere structure has XRD shown in figure 6.
Comparative example 2: magnesium ion doped commercial V2O5Preparation of anode active material of water-based zinc ion battery
Will be commercial V2O5Dissolving powder (1.2g) in 5ml of deionized water, adding 28.3Mg of magnesium acetate (the molar ratio of Mg: V is 1:50, the difference between the comparative example and the example 1 is that no oxalic acid is added), stirring until the mixture is uniformly mixed, drying, raising the temperature to 250 ℃ at 1 ℃/min under an air atmosphere, and annealing for 2h to obtain magnesium ion doped V2O5The product was taken as comparative example 2(Mg @ V)2O5) FESEM is shown in FIG. 7, which shows non-spherical dense particles.
Test example 1
Mg prepared in example 10.02V5O12V prepared in comparative example 12O5Porous nanospheres, Mg @ V prepared in comparative example 22O5Respectively taking the nano particles as active substances, uniformly mixing the active substances (70 wt%), conductive carbon black Super-P (20 wt%) and polyvinylidene fluoride (PVDF) binder (10 wt%), and coating the mixture on a titanium foil to serve as zinc ionsAnd (3) assembling the button cell by taking the zinc foil as the negative electrode, the glass fiber membrane as the diaphragm and 3mol/L zinc trifluoromethanesulfonate solution as electrolyte. The cycle performance curve at a current density of 5.0A/g is shown in FIG. 8. Can be obtained as Mg0.02V5O12Has a capacity higher than V2O5Porous nanospheres and Mg @ V2O5The cycle performance of the nano-particles is obviously improved. The embedding of metal ions is beneficial to improving the zinc ion diffusion, the unique nano-sphere structure can effectively buffer the deformation generated in the zinc ion embedding and removing process, and the two have good rate performance and cycling stability under the synergistic effect.
As can be seen from FIG. 9, the specific capacities of example 1 at current densities of 0.2, 0.5, 1.0, 2.0, 3.0 and 5.0A/gA were 520, 480, 440, 410, 390 and 360mAh/g, respectively. Comparative example 1 has specific capacities of 450, 410, 370, 335, 310, 280mAh/g at current densities of 0.2, 0.5, 1.0, 2.0, 3.0, 5.0A/g, respectively. Example 1 the capacity remained at 360mAh/g after 25-fold current expansion, indicating Mg0.02V5O12Has excellent rate performance.
As can be seen from FIG. 10, example 1 cycled 5000 cycles at 10A/g, the capacity remained at 100mAh/g and the initial capacity was close (102mAh/g), indicating a long cycle life.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A metal doped vanadium-based oxide nano material is characterized in that the chemical formula of the material is MxV5O12Wherein M is any one of magnesium, manganese, cobalt and nickel, and x is more than or equal to 0.005 and less than or equal to 0.03.
2. The metal-doped vanadium-based oxide nanomaterial according to claim 1, wherein the nanomaterial is nanospheres having a diameter of 300-1000 nm.
Preferably, the nanospheres have a porous structure.
Preferably, the specific surface area of the nano material is 10-100 m2/g。
Preferably, the nanomaterial has a topography substantially as shown in fig. 1, 4 or 5.
Preferably, the metal-doped vanadium-based oxide nano material is Mg0.02V5O12、Mg0.01V5O12、Co0.006V5O12。
3. A method for preparing the metal-doped vanadium-based oxide nanomaterial as claimed in claim 1 or 2, comprising the steps of:
s1) mixing V2O5Dissolving oxalic acid in a solvent to obtain a precursor solution A;
s2) adding a dopant M base salt into the precursor liquid A to obtain a precursor liquid B;
s3) adding the precursor liquid B into an alcohol solvent to carry out solvothermal reaction.
4. The method according to claim 3, wherein V is the same as V in step S1)2O5The molar ratio of oxalic acid to oxalic acid is 1: 2-1: 5.
Preferably, the concentration of the precursor liquid A in the step S1) is 0.05-1 mol/L.
5. The method according to claim 3 or 4, wherein the M-based salt of the dopant in step S2) is M-based acetate or nitrate; preferably, it is at least one of magnesium acetate, manganese acetate, cobalt acetate, nickel acetate, magnesium nitrate, manganese nitrate, cobalt nitrate, and nickel nitrate.
Preferably, in the step S2), the molar ratio of M to V is 1:200 to 1: 35.
6. The method according to any one of claims 3 to 5, wherein the alcoholic solvent in step S3) is at least one selected from methanol, ethanol and isopropanol.
Preferably, the volume ratio of the precursor liquid B to the alcohol solvent in the step S3) is 1: 5-1: 20.
Preferably, the reaction temperature in the step S3) is 160-200 ℃, and the reaction time is 1-24 h.
Preferably, the reaction of step S3) is carried out in a high pressure digestion tank.
7. The method according to any one of claims 3 to 6, wherein the step S3) is further followed by: and annealing the reaction product obtained in the step S3) to obtain the metal-doped vanadium-based oxide porous nanospheres.
Preferably, the temperature of the annealing treatment is 150-300 ℃, and the time is 1-12 h.
Preferably, the temperature rise rate of the annealing treatment is 1-5 ℃/min.
Preferably, the annealing treatment is performed under an air atmosphere.
8. Use of the metal doped vanadium-based oxide nanomaterial of claim 1 or 2 as an active material. Preferably, the metal-doped vanadium-based oxide nanomaterial is used as a positive active material, for example, as a positive active material for a zinc battery.
9. A positive electrode active material or a positive electrode comprising the metal-doped vanadium-based oxide nanomaterial of claim 1 or 2.
10. A zinc ion battery comprising the metal-doped vanadium-based oxide nanomaterial of claim 1 or 2, the above positive active material, and/or a positive electrode.
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