A Zn 3 V 3 O 8 / VO 2 Composite material and preparation method and application thereof
The Zn3V3O8/VO2 heterostructure composite material was synthesized by solid-phase ion pre-insertion method, which solved the problem of insufficient capacity durability and ionic conductivity of vanadium-based materials in zinc-ion batteries, and achieved the effects of high capacity, good conductivity and long cycle life.
Patent Information
- Application Number
- CN202211082016.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2022-09-06
- Publication Date
- 2025-06-06
- Estimated Expiration
- 2042-09-06
AI Technical Summary
Existing vanadium-based materials have problems in the application of zinc-ion battery, such as capacity durability and ionic conductivity, which require further optimization.
Using solid-phase ion pre-insert method, zinc acetate dihydrate and vanadium dioxide were mixed in a specific mass ratio, and the Zn3V3O8/VO2 heterostructure composite was calcined under a protective atmosphere to synthesize.
Through rich heterogeneous interfaces, the capacity of the positive electrode is increased and the ion mobility is enhanced, achieving high specific capacity, good conductivity and long cycle life.
Smart Images
Figure CN115275173B_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of battery materials and particularly relates to a Zn 3 V 3 O 8 / VO 2 Composite material and preparation method and application thereof. Background Art
[0002] In view of the growing environmental problems and limited fossil fuel resources, renewable energy has recently attracted worldwide attention. The effective utilization of renewable energy relies on the development of efficient, low-cost, and highly stable energy storage systems. Lithium-ion batteries (LIBs) are well-known secondary energy systems and are widely used in small mobile devices, electric vehicle batteries, and stationary grid storage due to their high energy density and technological maturity. Although the demand for energy consumption is expected to increase significantly, the widespread use of LIBs will also be limited by the lack of lithium-ion resources, high prices, and safety issues. Aqueous rechargeable batteries may become an alternative to LIBs and have great potential in grid storage applications.
[0003] In recent years, a lot of research has focused on the development of high-performance electrode materials for aqueous zinc-ion batteries (ZIBs) due to their environmental friendliness, low cost, high ionic conductivity, and high energy density. The main obstacles to the commercialization of aqueous zinc-ion batteries are the need for a suitable structurally stable cathode to ensure long-term cycle stability and a suitable crystal structure to store Zn 2+ , making the electrode material have the characteristics of high capacity and low price. So far, manganese-based oxides, zinc hexacyanoferrate, organic materials, Prussian blue analogs and vanadium-based materials have been explored as positive electrodes for reversible ZIBs. Among these materials, vanadium-based composites are more attractive due to their low cost and superior production capacity. However, capacity durability and ionic conductivity should be further optimized to achieve the goal of their practical application.
[0004] In view of this, the present invention proposes a new Zn 3 V 3 O 8 / VO 2 Heterogeneous structure composite material and preparation method and application thereof, based on solid phase ion pre-insertion method, zinc acetate dihydrate and vanadium dioxide are mixed in a certain mass ratio and calcined to synthesize Zn 3 V 3 O 8 / VO 2 Heterostructured composite materials can be used as positive electrode materials for zinc-ion batteries. Summary of the invention
[0005] The object of the present invention is to provide a Zn 3 V 3 O8 / VO 2 The preparation method of the composite material is based on the solid phase ion pre-insertion method, wherein zinc acetate dihydrate and vanadium dioxide are mixed in a certain mass ratio and calcined to synthesize Zn 3 V 3 O 8 / VO 2 Heterostructured composite materials.
[0006] In order to achieve the above purpose, the technical solution adopted is:
[0007] A Zn 3 V 3 O 8 / VO 2 The preparation method of the composite material is: based on the solid phase ion pre-insertion method, zinc acetate dihydrate and vanadium dioxide are mixed, and then calcined under a protective atmosphere to synthesize a heterogeneous structure Zn 3 V 3 O 8 / VO 2 Composite materials.
[0008] Furthermore, the mass ratio of zinc acetate dihydrate to vanadium dioxide is 3.5-1:1-1.2.
[0009] Furthermore, the protective atmosphere is a nitrogen atmosphere.
[0010] Furthermore, the calcination temperature is 350-500° C., and the calcination time is 3-12 hours.
[0011] Another object of the present invention is to provide a Zn 3 V 3 O 8 / VO 2 The composite material is prepared by the above-mentioned preparation method and has rich heterogeneous interfaces.
[0012] Another object of the present invention is to provide the above-mentioned Zn 3 V 3 O 8 / VO 2 Application of composite materials as positive electrode materials in zinc ion batteries, Zn 3 V 3 O 8 / VO 2 The heterointerface in the heterostructure can provide more locations for the storage of zinc ions, thereby effectively increasing the capacity of the positive electrode, while the heterointerface also enhances the ion mobility.
[0013] Compared with the prior art, the advantages of the present invention are:
[0014] 1. Zn of the present invention 3 V 3 O 8 / VO 2 In heterogeneous materials, Zn 3 V 3 O 8 / VO 2 The heterointerface in the heterostructure can provide more sites for the storage of zinc ions, thereby effectively increasing the capacity of the positive electrode, while the phase boundary of the heterostructure also enhances the ion mobility.
[0015] 2. The present invention uses a two-step synthesis method: first, a hydrothermal method is used to synthesize vanadium dioxide nanosheets as a precursor of the heterostructure. In the second step, based on the solid phase ion pre-insertion method, zinc acetate dihydrate and vanadium dioxide are mixed in a mass ratio within the range of 3.5:1-1:1.2. The mixture is heated and calcined in a tubular furnace under a nitrogen atmosphere to synthesize Zn 3 V 3 O 8 / VO 2 Heterostructured composites. Zn with abundant phase boundaries 3 V 3 O 8 / VO 2 Heterostructured materials as positive electrode materials for zinc-ion batteries, Zn 3 V 3 O 8 / VO 2 The phase boundaries in the heterostructure can provide more locations for the storage of zinc ions, thereby effectively increasing the capacity of the positive electrode. At the same time, the phase boundaries of the heterostructure also enhance the ion mobility.
[0016] 3. Zn prepared by the present invention 3 V 3 O 8 / VO 2 The composite material can be used as a positive electrode material for zinc ion batteries with high specific capacity, good conductivity, and long cycle life. When used as a positive electrode for zinc ion batteries, the -1 The current density can reach 386.0mA hg -1 The specific capacity of 3A g -1 The specific capacity retention rate after 1000 cycles at the current density is 90.5%. BRIEF DESCRIPTION OF THE DRAWINGS
[0017] Figure 1 The Zn obtained in Example 1 3 V 3 O 8 / VO 2 X-ray diffraction spectra of heterogeneous materials;
[0018] Figure 2 The Zn obtained in Example 1 3 V 3 O 8 / VO 2 Transmission electron microscope images and high magnification transmission electron microscope images;
[0019] Figure 3 The Zn prepared in Example 1 3 V 3 O 8 / VO 2 EDS diagram of .
[0020] Figure 4 The Zn prepared in Example 1 3 V 3 O 8 / VO 2 Cyclic voltammetry curve of zinc-ion battery positive electrode material.
[0021] Figure 5 The figure is a cycle performance diagram of a zinc ion battery assembled from the sample prepared in Example 1.
[0022] Figure 6 This is a cycle performance diagram of a zinc ion battery assembled from the sample prepared in Comparative Example 1.
[0023] Figure 7 This is a cycle performance diagram of a zinc ion battery assembled from the sample prepared in Comparative Example 2. DETAILED DESCRIPTION
[0024] In order to further illustrate the present invention, a Zn 3 V 3 O 8 / VO 2 Composite material and preparation method and application thereof, to achieve the expected purpose of the invention, the following is combined with preferred embodiments of the present invention to provide a Zn 3 V 3 O 8 / VO 2 The composite material and its preparation method, application, specific implementation, structure, characteristics and efficacy are described in detail below. In the following description, different "one embodiment" or "embodiment" do not necessarily refer to the same embodiment. In addition, specific features, structures or characteristics in one or more embodiments may be combined in any suitable form.
[0025] The following will be combined with specific embodiments to describe a Zn 3 V 3 O 8 / VO 2 The composite material, its preparation method and application are further introduced in detail:
[0026] In order to solve the problems existing in the application of existing vanadium-based materials in zinc ion batteries, the present invention aims to provide a Zn 3 V 3 O 8 / VO 2 Composite material and preparation method and application thereof, Zn with rich heterogeneous interface 3 V 3 O 8 / VO 2 Heterostructured materials as positive electrode materials for zinc-ion batteries, Zn 3 V 3 O 8 / VO 2 The heterointerface in the heterostructure can provide more locations for the storage of zinc ions, thereby effectively increasing the capacity of the positive electrode, while the heterointerface also enhances the ion mobility.
[0027] The technical solution of the present invention is:
[0028] A Zn 3 V 3 O 8 / VO 2 The preparation method of the composite material is: based on the solid phase ion pre-insertion method, zinc acetate dihydrate and vanadium dioxide are mixed, and then calcined under a protective atmosphere to synthesize a heterogeneous structure Zn 3 V 3 O 8 / VO 2 Composite materials.
[0029] The vanadium dioxide precursor in the present invention is prepared by a typical hydrothermal method. Specifically, 1 g of vanadium pentoxide is added to 30 ml of ethylene glycol solution (ethylene glycol and deionized water volume ratio 2:3). After stirring the solution for 2 hours, it is transferred to a 50 mL autoclave and then heated at 180°C for 5 hours. After the reaction, the product is rinsed with deionized water and dried at 60°C for 24 hours to obtain vanadium dioxide powder.
[0030] Preferably, the mass ratio of zinc acetate dihydrate to vanadium dioxide is 3.5:1-1:1.2.
[0031] Preferably, the protective atmosphere is a nitrogen atmosphere.
[0032] Preferably, the calcination temperature is 350-500° C., and the calcination time is 3-12 hours.
[0033] The Zn of the present invention 3 V 3 O 8 / VO 2The composite material is prepared by the above-mentioned preparation method. 3 V 3 O 8 / VO 2 In composite materials, Zn 3 V 3 O 8 / VO 2 The phase boundaries in the heterostructure can provide more locations for the storage of zinc ions, thereby effectively increasing the capacity of the positive electrode. At the same time, the phase boundaries of the heterostructure also enhance the ion mobility.
[0034] The above Zn 3 V 3 O 8 / VO 2 Application of heterogeneous materials as positive electrode materials for zinc-ion batteries.
[0035] The present invention uses a two-step synthesis method. First, a hydrothermal method is used to synthesize vanadium dioxide nanosheets as a precursor of a heterostructure. In the second step, zinc acetate dihydrate and vanadium dioxide are mixed in a mass ratio within a range of 3.5:1-1:1.2 based on a solid pre-insertion method. The mixture is calcined in a tubular furnace under a nitrogen atmosphere to synthesize Zn 3 V 3 O 8 / VO 2 Heterostructured composites. Zn with rich heterogeneous interfaces 3 V 3 O 8 / VO 2 As the positive electrode material of zinc ion battery, Zn 3 V 3 O 8 / VO 2 The heterointerface in the heterostructure can provide more locations for the storage of zinc ions, thereby effectively increasing the capacity of the positive electrode. At the same time, the interface of the heterostructure also enhances the ion mobility.
[0036] The vanadium dioxide of the present invention is prepared by the following method:
[0037] (1) Add 1 g of vanadium pentoxide into 30 mL of a solution containing ethylene glycol and deionized water in a volume ratio of 2:3;
[0038] (2) The solution was stirred for 2 h, transferred into a 50 mL autoclave, and then heated at 180 °C for 5 h.
[0039] (3) The dark blue vanadium dioxide nanosheets are rinsed with deionized water, and then dried at 60° C. for 24 h to obtain vanadium dioxide powder.
[0040] Example 1.
[0041] (1) In air, zinc acetate dihydrate and vanadium dioxide are uniformly mixed in a mass ratio of 2:1;
[0042] (2) The mixture was calcined at 400 °C for 9 h under nitrogen atmosphere.
[0043] like Figure 1 As shown, the diffraction peaks at 30.1°, 35.5°, 43.1°, 56.9°, and 62.5° correspond to cubic Zn 3 V 3 O 8 The characteristic peaks of (PDF#31-1477, Fd-3m space group) are located at 15.3°, 25.3°, 33.9°, 45.1°, 49.5° and 59.6°, corresponding to VO 2 (PDF#31-1438) characteristic peaks.
[0044] like Figure 2 As shown by Figure 2 The material morphology is a rough nanosheet with a width of about 100-220nm. The heterogeneous interface can be observed in high-resolution TEM.
[0045] like Figure 3 As shown, the element distribution diagram shows that the sample is composed of Zn, V, and O.
[0046] Zn 3 V 3 O 8 / VO 2 As the positive electrode material of zinc ion battery, the cyclic voltammetry curve is as follows Figure 4 As shown, the oxidation peak of the positive electrode sample is located at 0.53 V, while the reduction peak is located at 0.74 V and 1.01 V (the 2nd and 3rd cycles). The reduction peak at 1.38 V in the 1st cycle disappears in the 2nd and 3rd cycles.
[0047] The electrochemical properties of the material were tested using a CR2032 coin cell. The electrode was prepared by mixing 70% active material, 20% SuperP 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. After drying at 80 °C under vacuum for 10 h, a mass loading of 1.5 mg cm -2 The zinc ion battery uses glass fiber as the separator and 3M Zn(CF 3 SO 3 ) 2 As electrolyte, zinc foil was used as counter electrode to assemble CR2032 type ZIBs in air. Figure 5As shown, the battery is at 300mA g -1 After 20 cycles at the current density, the specific capacity reaches 386.0 mA h g -1 .
[0048] Example 2.
[0049] (1) In air, zinc acetate dihydrate and vanadium dioxide are uniformly mixed in a mass ratio of 3.5:1;
[0050] (2) The mixture was calcined at 350 °C for 12 h under nitrogen atmosphere.
[0051] As the positive electrode material, the zinc-ion battery is assembled at 300mA g -1 After running 50 cycles at the current density, the specific capacity reached 301.0 mA hg -1 After running 100 cycles, the capacity retention rate relative to the 50th cycle is about 92%.
[0052] Example 3.
[0053] (1) In air, zinc acetate dihydrate and vanadium dioxide are uniformly mixed in a mass ratio of 1:1.2;
[0054] (2) The mixture was calcined at 500°C for 3 h under nitrogen atmosphere. The zinc ion battery was assembled as the positive electrode material. The battery was charged at 300 mA g -1 After running for 15 cycles at the current density, the specific capacity reached 342.0 mA hg -1 ; After running 60 cycles, the capacity retention rate relative to the first cycle is about 91%.
[0055] Example 4.
[0056] (1) In air, zinc acetate dihydrate and vanadium dioxide are uniformly mixed in a mass ratio of 1:1;
[0057] (2) The mixture was calcined at 400°C for 9 h under nitrogen atmosphere. The positive electrode material was used to assemble a zinc ion battery. The battery was operated at 300 mA g -1 After running for 15 cycles at the current density, the specific capacity reached 375.0 mA hg -1 ; After running 60 cycles, the capacity retention rate is about 90% relative to the first cycle.
[0058] Comparative Example 1.
[0059] The same as Example 1, except that in step (1), the mass ratio of zinc acetate dihydrate to vanadium dioxide is 4:1.
[0060] The diffraction peaks at 15.3°, 25.3°, 33.9°, 45.1°, 49.5°, and 59.6° correspond to VO2 The three diffraction peaks at 2θ of 15.3°, 30.2°, and 45.1° correspond to VO 2 (200)(-401)(-511) crystal plane; and VO 2 (PDF#31-1438), the peak of this sample shifts to a lower angle, indicating an increase in the interplanar spacing. This result may be due to the presence of VO in this sample. 2 The zinc ions were inserted into the crystal structure of the matrix. In addition, the absence of other impurity peaks confirmed that the sample was composed of VO 2 Single-phase composition. As a positive electrode material for assembling zinc-ion batteries, such as Figure 6 As shown, the battery is at 300mA g -1 After running for 15 cycles at the current density, the specific capacity reached 275.0 mA hg -1 After running 100 cycles, the capacity retention rate relative to the first cycle is about 85%. Its specific capacity and capacity retention rate are significantly lower than those of Example 1.
[0061] Comparative Example 2.
[0062] The same as Example 1, except that in step (1), the mass ratio of zinc acetate dihydrate to vanadium dioxide is 1:1.5.
[0063] There are only diffraction peaks located at 30.1°, 35.5°, 43.1°, 56.9°, and 62.5°, corresponding to the cubic phase Zn 3 V 3 O 8 (PDF#31-1477, Fd-3m space group). As positive electrode material for zinc ion batteries, such as Figure 7 As shown, the battery is at 300mA g -1 After running for 4 cycles at the current density, the specific capacity reached 329.4 mA hg -1 After running 80 cycles, its specific capacity decreased significantly, and its specific capacity and capacity retention rate were much lower than those in Example 1.
[0064] The above is only a preferred embodiment of the embodiment of the present invention, and does not impose any form of limitation on the embodiment of the present invention. Any simple modification, equivalent changes and modifications made to the above embodiment based on the technical essence of the embodiment of the present invention are still within the scope of the technical solution of the embodiment of the present invention.
Claims
1. A Zn 3 V 3 O 8 / VO 2 A method for preparing a composite material, It is characterized in that The preparation method is: based on the solid phase ion pre-insertion method, zinc acetate dihydrate and vanadium dioxide are mixed and calcined under a protective atmosphere to synthesize a heterogeneous structure of Zn 3 V 3 O 8 / VO 2 Composite materials; The mass ratio of zinc acetate dihydrate to vanadium dioxide is 1:1-1.
2.
2. The preparation method according to claim 1, It is characterized in that The protective atmosphere is a nitrogen atmosphere.
3. The preparation method according to claim 1, It is characterized in that The calcination temperature is 350-500°C, and the calcination time is 3-12h.
4. A Zn 3 V 3 O 8 / VO 2 Composite materials, It is characterized in that The Zn 3 V 3 O 8 / VO 2 The composite material is prepared by the preparation method described in any one of claims 1 to 3.
5. Zn according to claim 4 3 V 3 O 8 / VO 2 Application of composite materials in positive electrode materials of zinc-ion batteries.