CN115124080B - Vanadium oxide nanosheet array and preparation method and application thereof - Google Patents
Vanadium oxide nanosheet array and preparation method and application thereof Download PDFInfo
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- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910001935 vanadium oxide Inorganic materials 0.000 title claims abstract description 54
- 239000002135 nanosheet Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 18
- 238000006722 reduction reaction Methods 0.000 claims abstract description 15
- 239000012429 reaction media Substances 0.000 claims abstract description 6
- 239000002064 nanoplatelet Substances 0.000 claims description 16
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 235000010323 ascorbic acid Nutrition 0.000 claims description 6
- 229960005070 ascorbic acid Drugs 0.000 claims description 6
- 239000011668 ascorbic acid Substances 0.000 claims description 6
- 239000007774 positive electrode material Substances 0.000 claims description 6
- 239000011229 interlayer Substances 0.000 claims description 4
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 3
- 239000004289 sodium hydrogen sulphite Substances 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 25
- 239000011701 zinc Substances 0.000 abstract description 9
- 229910052725 zinc Inorganic materials 0.000 abstract description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 7
- 239000002243 precursor Substances 0.000 abstract description 7
- 239000003792 electrolyte Substances 0.000 abstract description 6
- 238000003860 storage Methods 0.000 abstract description 5
- 230000009467 reduction Effects 0.000 abstract description 4
- 239000006183 anode active material Substances 0.000 abstract description 3
- 230000008569 process Effects 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- GNTDGMZSJNCJKK-UHFFFAOYSA-N Vanadium(V) oxide Inorganic materials O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000001994 activation Methods 0.000 description 4
- 239000011149 active material Substances 0.000 description 4
- 238000003491 array Methods 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000002127 nanobelt Substances 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005464 sample preparation method Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
- C01G31/02—Oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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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
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
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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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- 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
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides a vanadium oxide nano-sheet array, a preparation method and application thereof, wherein the preparation method comprises the step of carrying out reduction reaction on V 2O5 and a reducing agent in a reaction medium to prepare the vanadium oxide nano-sheet array. According to the invention, the vanadium oxide nano-sheet array is prepared by reducing the precursor commercial V 2O5 under mild reaction conditions, and meanwhile, the phase structure and the microstructure of the vanadium oxide nano-sheet array are changed, so that the electrochemical performance of the vanadium oxide nano-sheet array is integrally improved; the one-step reduction method has simple procedures, is convenient to operate and is easy to industrialize; the vanadium oxide nano-sheet array obtained by the preparation method has larger specific surface area, distinct and uniform layers, stable material structure and excellent electrochemical performance, can be used as an anode active material for a zinc ion battery, can be more fully contacted with electrolyte to provide more active sites, and can store more zinc ions at larger lattice spacing, so that the zinc storage performance of the vanadium oxide nano-sheet array is integrally improved.
Description
Technical Field
The invention relates to the technical field of electrode materials, in particular to a vanadium oxide nano-sheet array and a preparation method and application thereof.
Background
With the continuous development of human society, the demand for renewable energy is more urgent. Electrochemical energy storage systems have attracted attention and have been rapidly developed by researchers in order to increase the utilization of renewable energy sources. Among them, lithium Ion Batteries (LIBs) have been widely used in our lives due to their high energy density and other advantages. However, the further application of the lithium metal is greatly limited by the defects of limited metal lithium resource, high cost, high toxicity, inflammability, explosiveness and the like of the used organic electrolyte. The water-based zinc ion battery (AZIBs) is expected to be widely used in large-scale energy storage equipment due to the advantages of low oxidation-reduction potential (-0.76V vs. SHE) of metal zinc, high theoretical capacity (820 mAh g -1), abundant reserve, low cost, high safety and the like, and the development of high-performance positive electrode materials becomes a key for developing the water-based zinc ion battery.
Vanadium has various valence states (+5, +4, +3, +2), can realize multi-electron transfer in an electrochemical process, so that higher reversible capacity is obtained, meanwhile, vanadium oxide has a layered structure or a tunnel structure, can provide a diffusion channel for zinc ions in the electrochemical process, shortens the diffusion path, and is considered as a very promising zinc ion battery positive electrode material.
In recent years, a great deal of research has been done to develop various types of vanadium oxide positive electrode materials, including V 2O5,VO2, and metal doped vanadium oxides such as Na 2V6O16·3H2 O and Zn 0.25V2O5·nH2 O. However, since vanadium oxide has problems of dissolution of vanadium in an aqueous electrolyte, structural collapse and retarded kinetics, it greatly reduces its zinc storage performance. For example, commercial vanadium pentoxide generally exhibits long activation processes, low conductivity, low diffusion efficiency, and cycling stability. Generally, two-dimensional materials (nano-sheets, nano-belts and the like) have very high specific surface area, are favorable for diffusing zinc ions and promoting electrochemical reaction kinetics, but at the same time, the high specific surface energy of the two-dimensional materials is easy to cause stacking and agglomeration phenomena, and an active site is embedded to prevent substance transmission.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a vanadium oxide nanosheet array, and a preparation method and application thereof, which are used for solving the problems of long activation process and poor cycle stability of the existing commercial vanadium pentoxide in the electrochemical process.
To achieve the above and other related objects, the present invention provides a method for preparing a vanadium oxide nanosheet array, comprising the steps of: and carrying out reduction reaction on V 2O5 and a reducing agent in a reaction medium to obtain the vanadium oxide nano-sheet array.
According to the invention, the vanadium oxide nano-sheet array is prepared by reducing the precursor commercial V 2O5 under mild reaction conditions, and meanwhile, the phase structure and the microstructure of the vanadium oxide nano-sheet array are changed, so that the electrochemical performance of the vanadium oxide nano-sheet array is integrally improved; the one-step reduction method has simple procedures, is convenient to operate and is easy to industrialize.
Preferably, the reducing agent is an acidic reducing agent.
Preferably, the reducing agent is a weakly acidic strong reducing agent selected from one of ascorbic acid, sodium bisulphite and hydrogen peroxide.
In the invention, the selection of the reducing agent is critical, if the selected reducing agent is too acidic, excessive corrosion can cause the collapse of the whole structure of the vanadium oxide in the conversion process, and the formed V 10O24·12H2 O can further react with the acid; if the acidity of the selected reducing agent is too weak, the morphology of the reduced V 10O24·12H2 O is similar to that of the precursor V 2O5, and the V 10O24·12H2 O is in a block shape; if the reducibility is too weak, V 2O5 cannot be reduced to V 10O24·12H2 O; if the reducibility is too strong, V 2O5 is reduced to vanadium oxide with lower valence, such as V 2O3.
Preferably, the mass ratio of V 2O5 to the reducing agent is (1-10): 1, such as (1-3): 1. (3-5): 1. (5-10): 1.
More preferably, the reducing agent is ascorbic acid, and the ascorbic acid not only has strong reducibility, but also can easily dissociate enol or hydroxyl in the structure to release H +, which is beneficial to slow weak etching reaction at the interlayer position of commercial V 2O5 and is beneficial to the formation of an accordion structure. In addition, commercial V 2O5 was insufficient to convert to V 10O24·12H2 O, and commercial V 2O5 was too high to convert to mixtures of other vanadium oxides. Thus, the feed mass ratio of ascorbic acid to commercial V 2O5 is optimally 1:5.
Preferably, the temperature of the reduction reaction is 60 to 120℃and the time of the reduction reaction is 0.5 to 10 hours, more preferably 5 hours. The reduction reaction time is too short, and the precursor commercial V 2O5 is insufficient to be converted into a nano-sheet array structure (accordion structure), so that the number of active sites of the nano-sheet array structure is greatly reduced; too long a reduction reaction time will lead to disintegration of the nanoplatelet array structure.
Preferably, the reaction medium is selected from one or more of N, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetonitrile and water.
More preferably, after the reduction, the method further comprises impurity removal and drying processes. The impurity removal can be centrifugal washing by adopting deionized water and ethanol; the temperature of the drying may be 60 to 80 ℃.
The second object of the present invention is to provide a vanadium oxide nanosheet array manufactured by the above manufacturing method.
Preferably, the molecular formula of the vanadium oxide nano-sheet array is V 10O24·12H2 O.
Preferably, the specific surface area of the vanadium oxide nano-sheet array is 6-10 m 2/g.
Preferably, in the vanadium oxide nano-sheet array, the thickness of the nano-sheet is 10-20 nm, and the interlayer spacing of the nano-sheet is 50-200 nm.
The invention further aims to provide an application of the vanadium oxide nano-sheet array as a positive electrode active material in a zinc ion battery.
The vanadium oxide nano-sheet array obtained by the preparation method has larger specific surface area, distinct and uniform layers, stable material structure and excellent electrochemical performance. When the active material is applied to a zinc ion battery as an anode active material, the active material can be more fully contacted with electrolyte to provide more active sites, and meanwhile, more zinc ions can be stored in the larger lattice spacing of the active material, so that the zinc storage performance of the active material is improved as a whole.
A fourth object of the invention is to provide a zinc ion battery comprising a positive electrode comprising conductive carbon black, a binder and an array of vanadium oxide nanoplatelets, a negative electrode and a separator.
As described above, the vanadium oxide nanosheet array and the preparation method and application thereof have the following beneficial effects: according to the invention, the vanadium oxide nano-sheet array is prepared by reducing the precursor commercial V 2O5 under mild reaction conditions, and meanwhile, the phase structure and the microstructure of the vanadium oxide nano-sheet array are changed, so that the electrochemical performance of the vanadium oxide nano-sheet array is integrally improved; the one-step reduction method has simple procedures, is convenient to operate and is easy to industrialize; the vanadium oxide nano-sheet array obtained by the preparation method has larger specific surface area, distinct and uniform layers, stable material structure and excellent electrochemical performance, can be used as an anode active material for a zinc ion battery, can be more fully contacted with electrolyte to provide more active sites, and can store more zinc ions at larger lattice spacing, so that the zinc storage performance of the vanadium oxide nano-sheet array is integrally improved.
Drawings
Fig. 1 shows SEM images of the vanadium oxide nanoplatelet arrays (a, b) and commercial V 2O5 (c, d) prepared in example 1.
FIG. 2 shows nitrogen adsorption and desorption isotherms for the vanadium oxide nanoplatelet array prepared in example 1 and commercial V 2O5.
Figure 3 shows XRD patterns for the vanadium oxide nanoplatelet arrays and commercial V 2O5 produced in example 1.
Fig. 4 shows a graph comparing electrochemical cycling stability at a current density of 2A g -1 for the vanadium oxide nanoplatelet array prepared in example 1 and commercial V 2O5.
Detailed Description
Other advantages and effects of the present invention will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present invention with reference to specific examples. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention.
It should be understood that the process equipment or devices not specifically identified in the examples below are all conventional in the art.
Furthermore, it is to be understood that the reference to one or more method steps in this disclosure does not exclude the presence of other method steps before or after the combination step or the insertion of other method steps between these explicitly mentioned steps, unless otherwise indicated; it should also be understood that the combined connection between one or more devices/means mentioned in the present invention does not exclude that other devices/means may also be present before and after the combined device/means or that other devices/means may also be interposed between these two explicitly mentioned devices/means, unless otherwise indicated. Moreover, unless otherwise indicated, the numbering of the method steps is merely a convenient tool for identifying the method steps and is not intended to limit the order of arrangement of the method steps or to limit the scope of the invention in which the invention may be practiced, as such changes or modifications in their relative relationships may be regarded as within the scope of the invention without substantial modification to the technical matter.
In the following examples of the application, commercial V 2O5, commercially available from belvedere technologies, 99% purity, product number 972308, was used for the V 2O5.
Example 1
The embodiment provides a preparation method of a vanadium oxide nano-sheet array, which comprises the following steps:
100mg of commercial V 2O5 is dispersed in 40mL of deionized water and stirred continuously for 30min under the oil bath condition at 90 ℃, then 20mg of ascorbic acid is added and stirred continuously for 5h, finally, the mixture is washed once by centrifugation respectively with deionized water and ethanol, and then dried for 12h in a vacuum oven at 60 ℃ to obtain the vanadium oxide nanosheet array.
The following characterization and testing was performed on the vanadium oxide nanoplatelet arrays prepared in this example:
(1) Morphology characterization:
SEM characterization was performed on a HITACHI S-4700 scanning electron microscope using the following sample preparation method: and placing the dried accordion-structured V 10O24·12H2 O nano-sheet array on the surface of a supporting table stuck with conductive adhesive, and then placing the supporting table in an SEM (scanning electron microscope) chamber for testing.
Nitrogen adsorption and desorption isothermal curve test conditions: the sample was subjected to pretreatment at 300℃under vacuum for 10 hours, and then subjected to nitrogen desorption test at 77k liquid nitrogen for 8 hours at 300 ℃.
The SEM of the vanadium oxide nanoplatelet array prepared in example 1 is shown in fig. 1, and it can be observed from fig. 1a and b that the V 10O24·12H2 O nanoplatelet array exhibits a unique accordion structure morphology, the nanoplatelets retain the length and width of the precursor V 2O5, the thickness is about 15nm, and the interlayer spacing of the nanoplatelets is 50-200 nm. As shown in FIG. 2, the morphology has a larger specific surface area (9.1764 m 2/g) which is higher than that of the precursor commercial V 2O5(4.1611m2/g), so that a large number of active sites are provided, and the electrochemical reaction kinetics can be remarkably enhanced. While FIGS. 1c, d are SEM's of commercial V 2O5, which exhibit larger blocky irregularities and thus show retarded reaction kinetics compared to V 10O24·12H2 O.
(2) Characterization of the composition:
XRD testing was performed on an X' Pert Pro type X-ray diffractometer, and samples to be tested were prepared as follows: and placing the dried accordion structure V 10O24·12H2 O nano sheet array into a frosted groove formed above the quartz sheet for testing.
The XRD spectra of V 10O24·12H2 O and commercial V 2O5, respectively, are shown in FIG. 3, and all diffraction peaks of the XRD spectra are consistent with monoclinic V 10O24·12H2 O (JCPCDS 25-1006), which proves that the material is successfully prepared. And a very obvious diffraction peak is arranged at the position of 2 theta = 6.22 DEG, the corresponding crystal face is (002), and the lattice spacing isSuch a large lattice spacing facilitates intercalation and deintercalation of zinc ions, promoting reaction kinetics thereof.
(3) Electrochemical performance test of zinc ion battery
V 10O24·12H2 O and commercial V 2O5 prepared in this example were mixed with conductive carbon black and PVDF respectively to prepare a positive electrode, a zinc sheet as a negative electrode, WHATMAN GF/D glass fiber as a separator, and 3M Zn (CF 3SO3)2 solution as electrolyte to assemble CR 2032 type battery.
Fig. 4 is a graph showing the electrochemical cycling stability of the V 10O24·12H2 O nanoplatelet array and commercial V 2O5 prepared in this example at a current density of 2Ag -1, respectively, and it can be seen that V 10O24·12H2 O can reach the highest specific capacity of 370.3mAh g -1 after a short cycle, and the specific capacity still reaches 274.1mAh g -1 after a cycle of 650 cycles, the capacity retention rate is 74.0%, while commercial V 2O5 can reach 307.2mAh g -1 after a longer electrochemical activation process, and it is notable that a short circuit occurs and causes battery damage when commercial V 2O5 electrode is cycled to 325 cycles, and the specific capacity at this time is 186.8mAh g -1, and the capacity retention rate is only 60.8%, which is significantly lower than V 10O24·12H2 O. We theorize that this may be due to irreversible destruction of the material structure by commercial V 2O5 during prolonged electrochemical activation, which in turn leads to degradation of cycling stability and ultimately to shorting of the cell.
Through the above test and characterization, it can be obviously seen that the V 10O24·12H2 O nanosheet array prepared in this embodiment has more excellent electrochemical performance, can be used as a positive electrode active material in a zinc ion battery, and can be more fully contacted with an electrolyte to provide more active sites, and meanwhile, the larger lattice spacing can store more zinc ions, so that the zinc storage performance of the nanosheet array is integrally improved.
Example 2
Example 2 differs from example 1 in that the reaction medium is different, N-Dimethylformamide (DMF) is used and the rest of the process is identical.
Example 3
Example 3 differs from example 1 in that the reducing agent is different, 30mg of sodium bisulphite is used and the rest of the process is exactly the same.
Example 4
Example 4 differs from example 1 in that the conditions of the reduction reaction are different, the reduction reaction temperature is 120 ℃, the time is 0.5h, and the rest of the process is identical.
The methods and results of the vanadium oxide nanosheet arrays prepared in examples 2 to 4 are equivalent to those of example 1, and are not described in detail herein.
Comparative example 1
Comparative example 1 differs from example 1 in that the reducing agent was different, hydrazine hydrate was used, and the rest of the process was identical.
The comparative example did not form a V 10O24·12H2 O nanoplatelet array, but rather produced a bulk of low-valent vanadium oxide.
The above examples are provided to illustrate the disclosed embodiments of the invention and are not to be construed as limiting the invention. In addition, many modifications and variations of the methods and compositions of the invention set forth herein will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the invention. While the invention has been specifically described in connection with various specific preferred embodiments thereof, it should be understood that the invention should not be unduly limited to such specific embodiments. Indeed, various modifications of the described modes for carrying out the invention which are obvious to those skilled in the art are intended to be within the scope of the present invention.
Claims (4)
1. The preparation method of the vanadium oxide nano-sheet array is characterized by comprising the following steps of:
Carrying out reduction reaction on V 2O5 and a reducing agent in a reaction medium, removing impurities and drying to obtain the vanadium oxide nano-sheet array; the reducing agent is a weak acid strong reducing agent, and the weak acid strong reducing agent is selected from one of ascorbic acid and sodium bisulphite; the mass ratio of V 2O5 to the reducing agent is (1-10): 1; the reaction medium is selected from one or more of N, N-dimethylformamide, dimethyl sulfoxide and acetonitrile; the temperature of the reduction reaction is 60-120 ℃, and the time of the reduction reaction is 0.5-10 h; the molecular formula of the vanadium oxide nano-sheet array is V 10O24·12H2 O; the specific surface area of the vanadium oxide nano sheet array is 6-10 m/g; in the vanadium oxide nano-sheet array, the thickness of the nano-sheet is 10-20 nm, and the interlayer spacing of the nano-sheet is 50-200 nm.
2. A vanadium oxide nanoplatelet array produced by the production process of claim 1.
3. Use of the vanadium oxide nanoplatelet array of claim 2 as a positive electrode active material in a zinc ion battery.
4. A zinc ion battery characterized in that: comprising a positive electrode comprising conductive carbon black, a binder, and the vanadium oxide nanoplatelet array of claim 2, a negative electrode, and a separator.
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| CN101565205A (en) * | 2009-05-26 | 2009-10-28 | 同济大学 | Method for preparing novel nano-material V10O24.12H2O |
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| CN110707299A (en) * | 2019-04-17 | 2020-01-17 | 中南大学 | Vanadium oxide/carbon/clay composite positive electrode material, preparation method thereof and application thereof in water-based battery |
| CN111056571A (en) * | 2020-01-19 | 2020-04-24 | 兰州大学 | Simple method for preparing low-crystallinity vanadium oxide in batches and doping modification thereof |
| CN114039044A (en) * | 2021-11-16 | 2022-02-11 | 安阳工学院 | Three-dimensional electrode material composed of carbon-coated nanosheets and preparation method thereof |
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| CN101565205A (en) * | 2009-05-26 | 2009-10-28 | 同济大学 | Method for preparing novel nano-material V10O24.12H2O |
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