CN117293299A - Composite material, preparation method and application thereof - Google Patents
Composite material, preparation method and application thereof Download PDFInfo
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- CN117293299A CN117293299A CN202311503641.4A CN202311503641A CN117293299A CN 117293299 A CN117293299 A CN 117293299A CN 202311503641 A CN202311503641 A CN 202311503641A CN 117293299 A CN117293299 A CN 117293299A
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- vanadium dioxide
- composite material
- magnesium acetate
- acetate tetrahydrate
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- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 claims abstract description 41
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 claims abstract description 41
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229940097364 magnesium acetate tetrahydrate Drugs 0.000 claims abstract description 30
- XKPKPGCRSHFTKM-UHFFFAOYSA-L magnesium;diacetate;tetrahydrate Chemical compound O.O.O.O.[Mg+2].CC([O-])=O.CC([O-])=O XKPKPGCRSHFTKM-UHFFFAOYSA-L 0.000 claims abstract description 30
- 239000011777 magnesium Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 6
- 239000002135 nanosheet Substances 0.000 claims description 5
- 239000007774 positive electrode material Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 abstract description 17
- 230000001965 increasing effect Effects 0.000 abstract description 9
- 238000003860 storage Methods 0.000 abstract description 7
- 230000002708 enhancing effect Effects 0.000 abstract description 2
- 239000012071 phase Substances 0.000 description 16
- 239000010406 cathode material Substances 0.000 description 10
- 239000011701 zinc Substances 0.000 description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- 238000004146 energy storage Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 239000007790 solid phase Substances 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 239000005486 organic electrolyte Substances 0.000 description 3
- 238000012975 pre-insertion method Methods 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010351 charge transfer process Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002060 nanoflake Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
-
- 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
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
-
- 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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a composite material, a preparation method and application thereof, relates to the technical field of battery materials, and mainly aims to provide a composite material capable of effectively increasing the capacity of a cathode and enhancing ion mobility. The main technical scheme of the invention is as follows: a composite material comprises vanadium dioxide and magnesium acetate tetrahydrate, wherein the mass ratio of the vanadium dioxide to the magnesium acetate tetrahydrate is in the range of 0.5-6:1, and the Mg is prepared by the method 2 VO 4 /VO 2 In the composite material, mg 2 VO 4 /VO 2 The hetero-interface in the heterostructure can provide more positions for the storage of zinc ions, so that the capacity of the positive electrode is effectively increased, and meanwhile, the phase boundary of the heterostructure also enhances the ion mobility.
Description
Technical Field
The invention relates to the technical field of battery materials, in particular to a composite material, a preparation method and application thereof.
Background
The Electrical Energy Storage (EES) technology has relatively high stability, flexibility and specific energy, which makes EES a key method for solving energy storage and release, and is a reasonable choice for realizing pursuit and utilization of low-cost, clean and reliable electrical energy in China. The development and development of novel energy storage technology are an important part of energy revolution and a key part of realizing energy cleanliness in China. Electrochemical energy storage is an important part of a novel power system, has the characteristics of being not influenced by geographical factors, being easy to store and release and being capable of being applied on a large scale, and is closely concerned by the scientific research field and the emerging market. The new energy industry is considering low-carbon, clean and sustainable as one of the directions of future energy development and application.
In recent years, unlike organic electrolytes and solid electrolytes with high interfacial resistance, which have potential safety hazards, aqueous electrolytes have high flame retardancy, can effectively avoid the problem of flammability and explosiveness of organic electrolytes, and have the characteristics of low cost, no toxicity, and environmental friendliness, and aqueous secondary batteries have relatively low requirements for assembly environments, further reduce the manufacturing cost, and in addition, the electrical conductivity of the aqueous electrolytes is far higher than that of organic electrolytes, so that rapid implementation can be achievedIs charged and discharged. Among various ion batteries studied at present, aqueous Zinc Ion Batteries (AZIBs) using zinc as a negative electrode are remarkable, and AZIBs have many advantages, such as abundant zinc ore resources and low price; the zinc metal material has high flexibility, is easy to produce, process and shape, and the recovery chain of the zinc metal is mature, so that the preparation cost is further reduced; zn (zinc) 2+ The redox reaction with ion participation is a double charge transfer process, which results in a negative electrode with 820mA h g -1 High theoretical capacity of (5) and 5851Ah L -1 Is a high volumetric energy density of (2); the aqueous electrolyte has high compatibility and stability; has excellent electron and ion conductivity, and can realize electron and Zn 2+ Rapid transport of ions and therefore excellent rate capability; the vanadium-based compound has good electrochemical performance due to various structures and rich valence states, but the advantages are often seriously affected by the problems of poor cycle stability, easy decomposition and the like.
Disclosure of Invention
In view of the above, the embodiment of the invention provides a composite material, a preparation method and an application thereof, and mainly aims to provide a composite material capable of effectively increasing the capacity of a cathode and enhancing the ion mobility.
In order to achieve the above purpose, the present invention mainly provides the following technical solutions:
in one aspect, embodiments of the present invention provide a composite material comprising:
vanadium dioxide and magnesium acetate tetrahydrate, wherein the mass ratio of the vanadium dioxide to the magnesium acetate tetrahydrate is in the range of 0.5-6:1.
On the other hand, the embodiment of the invention also provides a preparation method of the composite material, which comprises the following steps:
fully mixing vanadium dioxide and magnesium acetate tetrahydrate in the air according to the mass ratio ranging from 0.5 to 6:1;
calcining a mixture of vanadium dioxide and magnesium acetate tetrahydrate in a protective gas environment to obtain Mg 2 VO 4 /VO 2 A composite material.
Further, before the vanadium dioxide and the magnesium acetate tetrahydrate are fully mixed in the air in the mass ratio ranging from 0.5 to 6:1, the method further comprises the following steps:
a method of making vanadium dioxide comprising the steps of:
the volume ratio of adding vanadium pentoxide into ethylene glycol and deionized water is 2:3 in the solution of 3;
heating for 5 hours after stirring to obtain a dark blue vanadium dioxide nano sheet;
washing the vanadium dioxide nano-sheet by deionized water, and then drying for 24 hours to obtain vanadium dioxide powder.
Further, the calcination temperature is 350-500 ℃ and the calcination time is 3-12 h.
Further, the heating temperature ranges from 170 ℃ to 180 ℃.
On the other hand, the embodiment of the invention also provides application of the composite material, and the prepared load material is applied to a positive electrode material of a zinc ion battery and is used for being arranged at the positive electrode of the zinc ion battery.
Compared with the prior art, the invention has the following technical effects:
1. mg of the invention 2 VO 4 /VO 2 In the composite material, mg 2 VO 4 /VO 2 The heterogeneous interface in the heterostructure can provide more positions for the storage of zinc ions, so that the capacity of the anode is effectively increased, and meanwhile, the phase boundary of the heterostructure also enhances the ion mobility;
2. mixing vanadium dioxide and magnesium acetate tetrahydrate by adopting a solid-phase ion pre-insertion method, heating and calcining to form Mg 2 VO 4 /VO 2 Heterostructure composite material, mg with rich phase boundaries 2 VO 4 /VO 2 Heterostructure material as cathode material of zinc ion battery, mg 2 VO 4 /VO 2 The phase boundary in the heterostructure can provide more positions for the storage of zinc ions, so that the capacity of a cathode is effectively increased, and meanwhile, the ion transition dynamics is enhanced by the phase boundary of the heterostructure;
3. the inventionMing prepared Mg 2 VO 4 /VO 2 The composite material can be used as a positive electrode material of a zinc ion battery, and has high specific capacity, good electric conductivity and long cycle life.
Drawings
FIG. 1 shows the Mg prepared in example 1 provided by the present invention 2 VO 4 /VO 2 An X-ray diffraction pattern of the heterogeneous material;
FIG. 2 shows the Mg obtained in example 1 provided by the present invention 2 VO 4 /VO 2 Transmission electron microscopy pictures and high magnification transmission electron microscopy pictures;
FIG. 3 shows the Mg obtained in example 1 provided by the present invention 2 VO 4 /VO 2 Cyclic voltammograms as cathode materials for zinc ion batteries;
FIG. 4 is a graph showing the cycle performance of the sample prepared in example 1 according to the present invention assembled into a zinc ion battery;
FIG. 5 is a graph showing the cycle performance of a sample prepared in comparative example 1 according to the present invention assembled into a zinc ion battery;
FIG. 6 is a graph showing the cycle performance of a sample prepared in comparative example 2 according to the present invention assembled into a zinc ion battery;
fig. 7 is a flowchart of a method for preparing a composite material according to the present invention.
Detailed Description
The invention is described in further detail below with reference to the drawings and examples.
In one aspect, embodiments of the present invention provide a composite material comprising:
vanadium dioxide and magnesium acetate tetrahydrate, wherein the mass ratio of the vanadium dioxide to the magnesium acetate tetrahydrate is in the range of 0.5-6:1.
Compared with the prior art, the invention has the following technical effects:
mg of the invention 2 VO 4 /VO 2 In heterogeneous materials, mg 2 VO 4 /VO 2 The hetero interface in the hetero structure can provide more positions for the storage of zinc ions, thereby effectively increasing the anodeWhile the phase boundaries of the heterostructure also enhance ion mobility.
On the other hand, as shown in fig. 7, the embodiment of the invention also provides a preparation method of the composite material, which comprises the following steps:
fully mixing vanadium dioxide and magnesium acetate tetrahydrate in the air according to the mass ratio ranging from 0.5 to 6:1;
calcining a mixture of vanadium dioxide and magnesium acetate tetrahydrate in a protective gas environment to obtain Mg 2 VO 4 /VO 2 A composite material.
Mixing vanadium dioxide and magnesium acetate tetrahydrate by adopting a solid-phase ion pre-insertion method, heating and calcining to form Mg 2 VO 4 /VO 2 Heterostructure composite material, mg with rich phase boundaries 2 VO 4 /VO 2 Heterostructure material as cathode material of zinc ion battery, mg 2 VO 4 /VO 2 The phase boundaries in the heterostructure can provide more locations for storage of zinc ions, effectively increasing the capacity of the cathode, while the phase boundaries of the heterostructure also enhance ion transition kinetics.
Example 1
The embodiment of the invention also provides a preparation method of the composite material, which comprises the following steps:
101. 1g of vanadium pentoxide is added into ethylene glycol and deionized water, wherein the volume ratio of the ethylene glycol to the deionized water is 2:3 in 30mL of solution.
102. The solution was stirred for 2h, transferred to an autoclave and heated at 180 ℃ for 5h to give deep blue vanadium dioxide nanoflakes.
103. Washing the vanadium dioxide nano-sheet by deionized water, and then drying for 24 hours at 60 ℃ to obtain vanadium dioxide powder.
104. Vanadium dioxide and magnesium acetate tetrahydrate are fully mixed in the air in a mass ratio of 2:1.
105. The mixture of vanadium dioxide and magnesium acetate tetrahydrate was calcined at 400 ℃ for 9 hours in a nitrogen atmosphere to obtain a composite material.
As shown in FIG. 1The composite material is shown as code MVO/VO-S2, diffraction peaks at 30.1, 35.5, 43.1, 56.9 and 62.5, corresponding to cubic Mg 2 VO 4 The characteristic peaks of (PDF #50-0532, fd-3m space group) at 15.3, 25.3, 33.9, 45.1, 49.5 and 59.6 diffraction peaks corresponding to VO 2 Characteristic peaks of (PDF # 31-1438).
As shown in FIG. 2, it can be seen from FIG. 2 that the morphology of the material is in the range of 0.5-5 μm in particle size, stacked agglomerated nanoparticulates, and the heterogeneous interface can be observed in high resolution TEM.
The electrochemical performance of the material was tested using a CR2032 type coin cell. An electrode was prepared by mixing 70% active material, 20% super P and 10% polyvinylidene fluoride (PVDF). The mixture was dispersed in N-methylpyrrolidone (NMP) to form a uniform slurry, which was then coated on a titanium foil. Drying at 80deg.C under vacuum for 10 hr to obtain powder with mass load of-1.5 mg cm -2 Is provided. Zinc ion battery, with glass fiber as diaphragm, with 3M Zn (CF 3 SO 3 ) 2 As an electrolyte, CR2032 type ZIBs were assembled in air with zinc foil as a counter electrode. The cyclic voltammetry performance is shown in figure 3, and the battery is 300mAg -1 The specific capacity reaches 393.6mAh g after 20 circles of current density circulation -1 As shown in fig. 4.
In this example, a solid phase ion pre-intercalation method is used to mix vanadium dioxide and magnesium acetate tetrahydrate and heat and calcine to form Mg 2 VO 4 /VO 2 Heterostructure composite material, mg with rich phase boundaries 2 VO 4 /VO 2 Heterostructure material as cathode material of zinc ion battery, mg 2 VO 4 /VO 2 The phase boundaries in the heterostructure can provide more locations for storage of zinc ions, effectively increasing the capacity of the cathode, while the phase boundaries of the heterostructure also enhance ion transition kinetics.
Example 2
201. Vanadium dioxide and magnesium acetate tetrahydrate are fully mixed in the air in a mass ratio of 5:1.
202. The mixture of vanadium dioxide and magnesium acetate tetrahydrate was calcined at 350℃for 12 hours in a nitrogen atmosphere, and the obtained composite material was represented by the code MVO/VO-S1.
The diffraction peak of MVO/VO-S1 is very similar to that of MVO/VO-S2, and the diffraction peak of MVO/VO-S1 is weaker than that of MVO/VO-S2. Zinc ion battery is assembled as cathode material, and the battery is 300mAg -1 After 50 circles of operation under the current density, the specific capacity reaches 286.9mAh g -1 The method comprises the steps of carrying out a first treatment on the surface of the After 80 cycles, the capacity retention was about 80.2% relative to the first cycle.
Example 3
301. Vanadium dioxide and magnesium acetate tetrahydrate are fully mixed in the air in a mass ratio of 6:1.
302. The mixture of vanadium dioxide and magnesium acetate tetrahydrate was calcined at 500℃for 3 hours in a nitrogen atmosphere, and the obtained composite material was represented by the code MVO/VO-S3.
As a cathode material, a zinc ion battery was assembled at 300mAg -1 After 50 circles of operation under the current density, the specific capacity reaches 69.3mAh g -1 The method comprises the steps of carrying out a first treatment on the surface of the After 100 cycles of operation, the capacity retention was about 68.7% relative to the first cycle.
Example 4
401. Vanadium dioxide and magnesium acetate tetrahydrate were thoroughly mixed in air in a mass ratio of 0.5:1.
402. The mixture of vanadium dioxide and magnesium acetate tetrahydrate was calcined at 400℃for 9 hours in a nitrogen atmosphere, and the obtained composite material was represented by the code MVO/VO-S4.
As a cathode material, a zinc ion battery was assembled at 300mAg -1 After 50 circles of operation under the current density, the specific capacity reaches 375.0mAh g -1 The method comprises the steps of carrying out a first treatment on the surface of the After 60 cycles of operation, the capacity retention was about 90% with respect to the first cycle.
Comparative example 1
The only difference from example 1 is that in step (1), the ratio of vanadium dioxide to magnesium acetate tetrahydrate is 7:1. The obtained composite material is denoted by the code VO-S2.
As shown in FIG. 5, VO-S2 was located at diffraction peaks at 15.3, 25.3, 33.9, 45.1, 49.5 and 59.6, corresponding toAt VO 2 Characteristic peaks of (PDF # 31-1438). The 3 diffraction peaks existing near 15.3 °, 30.2 °,45.1 ° in 2θ correspond to VO, respectively 2 (200) (-401) (-511) crystal plane; and VO (VO) 2 The peak of VO-S2 shifts to a low angle compared to (PDF # 31-1438), indicating an expansion of the interplanar spacing. This result may be due to VO in the VO-S2 sample 2 Zinc ions are inserted into the crystal structure of the matrix. In addition, the absence of other hetero peaks confirms that VO-S2 is converted from VO 2 Single phase composition. As a cathode material, a zinc ion battery was assembled, and as shown in fig. 5, the battery was at 300mAg -1 After 15 circles of operation under the current density, the specific capacity reaches 245.0mAh g -1 The method comprises the steps of carrying out a first treatment on the surface of the After 100 runs, the capacity retention was about 85% relative to the first cycle. Its specific capacity and capacity retention were significantly lower than in example 1.
Comparative example 2
The difference from example 1 is only that in step (1), the ratio of vanadium dioxide to magnesium acetate tetrahydrate is 0.33:1. the composite obtained is denoted by the code MVO.
As shown in fig. 6, MVO has only diffraction peaks at 30.1 °,35.5 °,43.1 °,56.9 °, and 62.5 °, corresponding to cubic Mg phase 2 VO 4 Characteristic peaks of (PDF #50-0532, fd-3m space group). As a cathode material, a zinc ion battery was assembled, and as shown in fig. 6, the battery was at 300mAg -1 After 4 circles of operation under the current density, the specific capacity reaches 319.4mAh g -1 The method comprises the steps of carrying out a first treatment on the surface of the The specific capacity was significantly reduced after 80 runs, and the specific capacity and capacity retention were much lower than in example 1.
As can be seen from the above examples 1 to 4, comparative example 1 and comparative example 2, the MVO/VO-S2 of example 1 produced a battery at 300mAg -1 The specific capacity reaches 393.6mAh g after 20 circles of current density circulation -1 Mixing vanadium dioxide and magnesium acetate tetrahydrate by adopting a solid-phase ion pre-insertion method, heating and calcining to form Mg 2 VO 4 /VO 2 Heterostructure composite material, mg with rich phase boundaries 2 VO 4 /VO 2 Heterostructure material as cathode material of zinc ion battery, mg 2 VO 4 /VO 2 The phase boundaries in the heterostructure may be zinc ionsThe storage provides more sites, effectively increasing the capacity of the cathode, while the phase boundaries of the heterostructure also enhance ion transition kinetics.
On the other hand, the embodiment of the invention also provides application of the composite material, and the prepared load material is applied to a positive electrode material of a zinc ion battery and is used for being arranged at the positive electrode of the zinc ion battery.
Mg prepared by the invention 2 VO 4 /VO 2 The composite material can be used as a positive electrode material of a zinc ion battery, and has high specific capacity, good electric conductivity and long cycle life.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any person skilled in the art will readily recognize that variations or substitutions are within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (6)
1. A composite material, comprising:
vanadium dioxide and magnesium acetate tetrahydrate, wherein the mass ratio of the vanadium dioxide to the magnesium acetate tetrahydrate is in the range of 0.5-6:1.
2. A method of preparing a composite material, comprising the steps of:
fully mixing vanadium dioxide and magnesium acetate tetrahydrate in the air according to the mass ratio ranging from 0.5 to 6:1;
calcining a mixture of vanadium dioxide and magnesium acetate tetrahydrate in a protective gas environment to obtain Mg 2 VO 4 /VO 2 A composite material.
3. The preparation method according to claim 2, further comprising, before said thoroughly mixing in air vanadium dioxide and magnesium acetate tetrahydrate in a mass ratio ranging from 0.5 to 6:1:
a method of making vanadium dioxide comprising the steps of:
the volume ratio of adding vanadium pentoxide into ethylene glycol and deionized water is 2:3 in the solution of 3;
heating for 5 hours after stirring to obtain a dark blue vanadium dioxide nano sheet;
washing the vanadium dioxide nano-sheet by deionized water, and then drying for 24 hours to obtain vanadium dioxide powder.
4. The method according to claim 2, wherein,
the calcination temperature is 350-500 ℃ and the calcination time is 3-12 h.
5. A method of preparation according to claim 3, wherein the heating is at a temperature in the range 170 ℃ to 180 ℃.
6. The application of the composite material is characterized in that the prepared load material is applied to a positive electrode material of a zinc ion battery and is used for being arranged on the positive electrode of the zinc ion battery.
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