CN115124080A - 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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- 239000002135 nanosheet Substances 0.000 title claims abstract description 61
- 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
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 27
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 22
- 238000006722 reduction reaction Methods 0.000 claims abstract description 20
- 230000009467 reduction Effects 0.000 claims abstract description 9
- 239000007774 positive electrode material Substances 0.000 claims abstract description 8
- 239000012429 reaction media Substances 0.000 claims abstract description 6
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 11
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- 229960005070 ascorbic acid Drugs 0.000 claims description 8
- 239000011668 ascorbic acid Substances 0.000 claims description 8
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
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- 239000011229 interlayer Substances 0.000 claims description 3
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- 239000011230 binding agent Substances 0.000 claims description 2
- 239000002055 nanoplate Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 230000008569 process Effects 0.000 abstract description 10
- 239000011701 zinc Substances 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 8
- 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
- 239000002243 precursor Substances 0.000 abstract description 7
- 239000003792 electrolyte Substances 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000001994 activation Methods 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
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- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 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
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
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- 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
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
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- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
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- 230000033116 oxidation-reduction process Effects 0.000 description 1
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- 229910052710 silicon Inorganic materials 0.000 description 1
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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Images
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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
-
- 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
-
- 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
-
- 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 provides a vanadium oxide nanosheet array and a preparation method and application thereof, wherein the preparation method comprises the step of mixing V 2 O 5 And a reducing agent is subjected to reduction reaction in a reaction medium to prepare the vanadium oxide nanosheet array. The invention is realized by the way that the precursor is commercialized 2 O 5 The vanadium oxide nanosheet array is prepared by reduction under mild reaction conditions, and the phase structure and the microscopic morphology of the vanadium oxide nanosheet array are changed, so that the electrochemical performance of the vanadium oxide nanosheet array is integrally improved; the one-step reduction method has simple process, convenient operation and easy industrialization; the vanadium oxide nanosheet array obtained by the preparation method has the advantages of large specific surface area, clear and uniform layers,the material has a stable structure and excellent electrochemical performance, can be used as a positive active material to be applied to a zinc ion battery, can be more fully contacted with electrolyte to provide more active sites, and can store more zinc ions by a larger lattice spacing, so that the zinc storage performance of the material is integrally improved.
Description
Technical Field
The invention relates to the technical field of electrode materials, in particular to a vanadium oxide nanosheet array and a preparation method and application thereof.
Background
With the continuous development of human society, the demand of people for renewable energy sources is more urgent. In order to improve the utilization rate of renewable energy, electrochemical energy storage systems have attracted the attention of researchers and are rapidly developed. Among them, Lithium Ion Batteries (LIBs) have been widely used in our lives because of their advantages such as high energy density. However, the further application of the lithium metal is greatly limited by the defects of limited resources, high cost, high toxicity, flammability and explosiveness of the used organic electrolyte and the like. Water-based zinc ion batteries (AZIBs) have high theoretical capacity (820mAh g) due to low oxidation-reduction potential (-0.76V vs. SHE) of metal zinc -1 ) And the advantages of abundant reserves, low cost, high safety and the like are expected to be widely used in large-scale energy storage equipment, and the development of a high-performance positive electrode material becomes a key for developing a water-system zinc ion battery.
Vanadium has multiple valence states (+5, +4, +3, +2), can realize the transfer of many electrons in the electrochemical process, thus obtain higher reversible capacity, simultaneously, vanadium oxide has laminated structure or tunnel structure, can provide the diffusion channel for zinc ion in the electrochemical process, shorten its diffusion route, so vanadium oxide is regarded as very promising zinc ion battery positive electrode material.
In recent years, a great deal of research has been done to develop a series of efforts and materials for positive electrodes of vanadium oxides, including V 2 O 5 ，VO 2 And Na 2 V 6 O 16 ·3H 2 O and Zn 0.25 V 2 O 5 ·nH 2 And vanadium oxide doped with a metal such as O. However, since vanadium oxides have problems of vanadium dissolution, structural collapse and retarded kinetics in aqueous electrolytes, they greatly reduce their zinc storage properties. For example, commercial vanadium pentoxide typically exhibits longer activation processes, low electrical conductivity, low diffusion efficiency, and cycling stability. In general terms,the two-dimensional material (nanosheet, nanobelt and the like) has a very high specific surface area, is beneficial to the diffusion of zinc ions and the promotion of electrochemical reaction kinetics, but can easily cause stacking and agglomeration phenomena due to the high specific surface area, and can embed active sites and hinder substance transmission.
Disclosure of Invention
In view of the defects of the prior art, the 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 an electrochemical process.
In order to achieve the above objects and other related objects, the present invention provides a method for preparing a vanadium oxide nanosheet array, comprising the steps of: will V 2 O 5 And a reducing agent in a reaction medium to perform a reduction reaction to prepare the vanadium oxide nanosheet array.
The invention is realized by the commercialization of a precursor V 2 O 5 The vanadium oxide nanosheet array is prepared by reduction under mild reaction conditions, and the phase structure and the microscopic morphology of the vanadium oxide nanosheet array are changed, so that the electrochemical performance of the vanadium oxide nanosheet array is integrally improved; the one-step reduction method has simple process, 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 bisulfite and hydrogen peroxide.
In the invention, the selection of the reducing agent is critical, if the selected reducing agent is too strong in acidity, excessive corrosion can cause collapse of the whole structure of the vanadium oxide in the conversion process, and formed V 10 O 24 ·12H 2 O will also react further with acid; if the acidity of the selected reducing agent is too weak, the reduced V 10 O 24 ·12H 2 Morphology of O and precursor V 2 O 5 Similarly, in the shape of a block; if the reducibility is too weak, V cannot be reduced 2 O 5 Reduction to V 10 O 24 ·12H 2 O; if the reducibility is too strong，V 2 O 5 Vanadium oxides which are reduced to lower valences, e.g. V 2 O 3 And so on.
Preferably, said V 2 O 5 The mass ratio of the reducing agent to the reducing agent is (1-10) to 1, and the mass ratio is (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 has a structure in which enol or hydroxyl is easily dissociated to release H + This is advantageous in commercial V 2 O 5 The interlayer position of the silicon wafer is subjected to slow weak etching reaction, so that the formation of an accordion structure is facilitated. In addition, the ascorbic acid feed was too low, commercial V 2 O 5 Is not sufficiently converted into V 10 O 24 ·12H 2 High feed of O, ascorbic acid, commercial V 2 O 5 To a mixture of other vanadium oxides. Thus, ascorbic acid is commercially available from V 2 O 5 The optimal feeding mass ratio of 1: 5.
preferably, the temperature of the reduction reaction is 60-120 ℃, and the time of the reduction reaction is 0.5-10 h, more preferably 5 h. Too short of reduction reaction time, commercial precursor V 2 O 5 Insufficient to convert into a nanosheet array structure (accordion structure), thereby greatly reducing the number of active sites thereof; the reduction reaction time is too long, which can lead to the disintegration of the nano-sheet 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 the steps of impurity removal and drying. The impurity removal can be centrifugal washing by adopting deionized water and ethanol respectively; the drying temperature can be 60-80 ℃.
The second purpose of the invention is to provide a vanadium oxide nanosheet array prepared by the preparation method.
Preferably, the molecular formula of the vanadium oxide nanosheet array is V 10 O 24 ·12H 2 O。
Preferably, the vanadium oxide nanosheet arrayThe specific surface area of the rows is 6-10 m 2 /g。
Preferably, in the vanadium oxide nanosheet array, the thickness of the nanosheet is 10-20 nm, and the interlayer spacing of the nanosheet is 50-200 nm.
The invention also aims to provide application of the vanadium oxide nanosheet array as a positive electrode active material in a zinc ion battery.
The vanadium oxide nanosheet array obtained by the preparation method has the advantages of large specific surface area, clear and uniform layers, stable material structure and excellent electrochemical performance. When the zinc ion battery cathode material is used as a positive electrode active material in a zinc ion battery, the zinc ion battery cathode material can be in more sufficient contact with an electrolyte to provide more active sites, and meanwhile, the larger lattice spacing of the zinc ion battery cathode material can store more zinc ions so as to integrally improve the zinc storage performance of the zinc ion battery cathode material.
The invention also aims to provide a zinc ion battery, which comprises a positive electrode, a negative electrode and a diaphragm, wherein the positive electrode comprises conductive carbon black, a binder and a vanadium oxide nanosheet array.
As described above, the vanadium oxide nanosheet array, the preparation method and the application thereof of the invention have the following beneficial effects: the invention is realized by the commercialization of a precursor V 2 O 5 The vanadium oxide nanosheet array is prepared by reduction under mild reaction conditions, and the phase structure and the microscopic morphology of the vanadium oxide nanosheet array are changed, so that the electrochemical performance of the vanadium oxide nanosheet array is integrally improved; the one-step reduction method has simple working procedures, is convenient to operate and is easy to industrialize; the vanadium oxide nanosheet array obtained by the preparation method has the advantages of large specific surface area, distinct and uniform layers, stable material structure and excellent electrochemical performance, can be used as a positive electrode active material applied to a zinc ion battery, can be in more full contact with an electrolyte to provide more active sites, and can store more zinc ions by virtue of large lattice spacing, so that the zinc storage performance of the vanadium oxide nanosheet array is integrally improved.
Drawings
FIG. 1 shows vanadium oxide nanosheet arrays (a, b) and commercial V made in example 1 2 O 5 (c, d) SEM image.
FIG. 2 shows vanadium oxide nanosheet array produced for example 1 and commercial V 2 O 5 The isothermal curve was taken up and taken off with nitrogen.
FIG. 3 shows vanadium oxide nanosheet array produced for example 1 and commercial V 2 O 5 XRD spectrum of (a).
FIG. 4 shows vanadium oxide nanosheet arrays prepared for example 1 and commercial V 2 O 5 At 2A g -1 Current density of (a) and (b) are compared.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
It is to be understood that the processing equipment or apparatus not specifically identified in the following examples is conventional in the art.
Furthermore, it is to be understood that one or more method steps mentioned in the present invention does not exclude that other method steps may also be present before or after the combined steps or that other method steps may also be inserted between these explicitly mentioned steps, unless otherwise indicated; it is also to be understood that a combined connection between one or more devices/apparatus as referred to in the present application does not exclude that further devices/apparatus may be present before or after the combined device/apparatus or that further devices/apparatus may be interposed between two devices/apparatus explicitly referred to, unless otherwise indicated. Moreover, unless otherwise indicated, the numbering of the various method steps is merely a convenient tool for identifying the various method steps, and is not intended to limit the order in which the method steps are arranged or the scope of the invention in which the invention may be practiced, and changes or modifications in the relative relationship may be made without substantially changing the technical content.
In the following examples of the present application, said V 2 O 5 Using commercial V 2 O 5 Purchased from welfare technologies, 99% pure, product number 972308.
Example 1
The embodiment provides a preparation method of a vanadium oxide nanosheet array, which comprises the following steps:
100mg of commercial V 2 O 5 Dispersing in 40mL deionized water, continuously stirring for 30min under the condition of oil bath at 90 ℃, then adding 20mg ascorbic acid, continuously stirring for 5h, finally respectively centrifugally washing with deionized water and ethanol once, and then drying in a vacuum oven at 60 ℃ for 12h to obtain the vanadium oxide nanosheet array.
The vanadium oxide nanosheet array produced in this example was characterized and tested as follows:
(1) and (3) morphology characterization:
SEM characterization was performed on a HITACHI S-4700 scanning electron microscope using the following sample preparation methods: the dried accordion structure V 10 O 24 ·12H 2 The O nanosheet array is placed on the surface of a support table pasted with conductive glue, and then the support table is placed into an SEM chamber for testing.
Nitrogen adsorption and desorption isothermal curve test conditions: the sample is pretreated for 10 hours under the vacuum condition of 300 ℃, and then is subjected to a nitrogen desorption test under the condition of 77k liquid nitrogen, wherein the degassing temperature is 300 ℃, and the degassing time is 8 hours.
SEM of the vanadium oxide nanosheet array prepared in example 1 is shown in FIG. 1, and V can be observed from FIGS. 1a and b 10 O 24 ·12H 2 The O nano-sheet array presents a unique accordion structure shape, and the nano-sheet retains a precursor V 2 O 5 The length and width of the nano-sheet are about 15nm, and the distance between nano-sheet layers is 50-200 nm. As shown in FIG. 2, the morphology has a large specific surface area (9.1764 m) 2 Per g), higher than the precursor commercial V 2 O 5 (4.1611m 2 /g) and thus has a large number of active sites, the kinetics of the electrochemical reaction can be significantly enhanced. And FIGS. 1c, d are commercial V 2 O 5 In the above-mentioned SEM of (1),it exhibits larger blocky irregularities than V 10 O 24 ·12H 2 O exhibits retarded reaction kinetics.
(2) And (3) component characterization:
the XRD test was performed on an X' Pert Pro X-ray diffractometer, and the samples to be tested were prepared as follows: the dried accordion structure V 10 O 24 ·12H 2 And placing the O nanosheet array in the square frosted groove on the quartz plate for testing.
FIG. 3 is each V 10 O 24 ·12H 2 O and commercial V 2 O 5 The XRD spectrum of the compound is known from a blue curve, and all diffraction peaks of the compound are similar to V of monoclinic system 10 O 24 ·12H 2 O (JCPDS 25-1006) is matched, and the material is proved to be successfully prepared by us. And a very clear diffraction peak is positioned at the position of 6.22 degrees of 2 theta, the corresponding crystal face is (002), and the lattice spacing is
The large lattice spacing is beneficial to the intercalation and deintercalation of zinc ions, and promotes the reaction kinetics.
(3) Electrochemical performance testing of zinc ion batteries
V prepared in this example 10 O 24 ·12H 2 O and commercial V 2 O 5 Respectively mixing with conductive carbon black and PVDF to prepare a positive electrode, a zinc sheet as a negative electrode, Whatman GF/D type glass fiber as a diaphragm, and 3M Zn (CF) 3 SO 3 ) 2 The solution was used as an electrolyte to assemble a CR 2032 type cell. The battery performance tests were all performed on the nova battery tester. All assembly and testing was performed at room temperature.
FIG. 4 shows the V prepared in this example 10 O 24 ·12H 2 O-nanoplate array and commercial V 2 O 5 In 2Ag -1 Comparison of electrochemical cycling stability at current density of (1), it can be seen that V 10 O 24 ·12H 2 O can reach 370.3mAh g after short circulation -1 Has the highest specific capacity, anAfter 650 cycles of circulation, the specific capacity still reaches 274.1mAh g -1 Capacity retention of 74.0%, vs. commercial V 2 O 5 After a longer electrochemical activation process, the specific capacity can reach 307.2mAh g -1 It is worth noting that when commercial V 2 O 5 When the electrode is cycled to 325 circles, short circuit occurs and the battery is damaged, and the specific capacity is 186.8mAh g -1 And the capacity retention rate is only 60.8 percent and is obviously lower than V 10 O 24 ·12H 2 And O. We theorize that this may be due to commercial V 2 O 5 The irreversible destruction of the material structure, which is caused during the longer electrochemical activation process, leads to a decline in the cycling stability and ultimately to a short circuit of the battery.
From the above tests and characterization, it is clear that V prepared in this example 10 O 24 ·12H 2 The O nanosheet array has more excellent electrochemical performance, can be used as a positive electrode active material to be applied to a zinc ion battery, can be in more sufficient contact with electrolyte to provide more active sites, and can store more zinc ions due to larger lattice spacing, so that the zinc storage performance of the O nanosheet array is integrally improved.
Example 2
Example 2 differs from example 1 in that the reaction medium is different and N, N-Dimethylformamide (DMF) is used, the rest of the process being identical.
Example 3
Example 3 differs from example 1 in that the reducing agent is different, 30mg of sodium bisulfite is used, and the rest of the process is exactly the same.
Example 4
Example 4 is different from example 1 in that the reduction reaction conditions are different, the reduction reaction temperature is 120 ℃, the time is 0.5h, and the rest processes are completely the same.
The demonstration method and the result of the vanadium oxide nanosheet array prepared in the embodiments 2-4 are equivalent to those in the embodiment 1, and are not repeated herein.
Comparative example 1
Comparative example 1 differs from example 1 in that the reducing agent is different and hydrazine hydrate is used, and the rest of the process is exactly the same.
V not formed by this comparative example 10 O 24 ·12H 2 An O nanosheet array, but rather a bulk of the subvanadium oxide is produced.
The above examples are intended to illustrate the disclosed embodiments of the invention and are not to be construed as limiting the invention. In addition, various modifications of the methods and compositions set forth herein, as well as variations of the methods and compositions of the present invention, will be apparent to those skilled 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 above-described embodiments which are obvious to those skilled in the art to which the invention pertains are intended to be covered by the scope of the present invention.
Claims (10)
1. A preparation method of a vanadium oxide nanosheet array is characterized by comprising the following steps: will V 2 O 5 And a reducing agent is subjected to reduction reaction in a reaction medium to prepare the vanadium oxide nanosheet array.
2. The method of claim 1, wherein: the reducing agent is an acidic reducing agent.
3. The production method according to claim 1, characterized in that: the reducing agent is a weak acid strong reducing agent, and the weak acid strong reducing agent is one selected from ascorbic acid, sodium bisulfite and hydrogen peroxide.
4. The production method according to claim 1, characterized in that: the V is 2 O 5 The mass ratio of the reducing agent to the reducing agent is (1-10): 1.
5. The method of claim 1, wherein: the temperature of the reduction reaction is 60-120 ℃, and the time of the reduction reaction is 0.5-10 h.
6. The production method according to claim 1, characterized in that: the reaction medium is selected from one or more of N, N-dimethylformamide, dimethyl sulfoxide, acetonitrile and water; and/or after reduction, impurity removal and drying processes are also included.
7. A vanadium oxide nanosheet array produced by the production method as recited in any one of claims 1 to 6.
8. An array of vanadium oxide nanoplates according to claim 7, wherein: the molecular formula of the vanadium oxide nanosheet array is V 10 O 24 ·12H 2 O；
And/or the specific surface area of the vanadium oxide nanosheet array is 6-10 m 2/g;
and/or in the vanadium oxide nanosheet array, the thickness of the nanosheets is 10-20 nm, and the interlayer spacing of the nanosheets is 50-200 nm.
9. Use of the vanadium oxide nanosheet array of claim 7 as a positive electrode active material in a zinc-ion battery.
10. A zinc-ion battery, characterized by: comprising a positive electrode, a negative electrode, and a separator, the positive electrode comprising conductive carbon black, a binder, and the vanadium oxide nanosheet array of claim 7.
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| CN116282156A (en) * | 2023-04-13 | 2023-06-23 | 重庆大学 | Magnesium ion pre-intercalated hydrated vanadium oxide positive electrode material, preparation method and application |
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