Preparation method of fluorinated zinc oxide metal composite foil anode Zn@F-ZnO and energy storage application thereof

Abstract

The application discloses a preparation method of fluorinated zinc oxide metal composite foil anode Zn@F-ZnO and energy storage application thereof, and constructs a fluorinated zinc oxide interface phase on the surface of zinc metal through a hydrothermal method to inhibit zinc dendrites of a water-based zinc ion battery anode. The preparation method is as follows: sodium fluoride is dissolved in 200 mL deionized water, and then 2M NaOH is added until the overall pH of the solution is close to 10. Then the mixed solution is transferred to a hydrothermal kettle, and a 100 mu m thick commercial zinc foil is placed in the kettle to react for 36 h at 120 DEG C. Then the metal foil is dried in a vacuum drying box at 60 DEG C for 12 h to obtain the final composite zinc foil Zn@F-ZnO. The hydrothermal method is used to prepare the high-performance Zn@F-ZnO composite foil in one step. The preparation method has the advantages of simple process, low cost and large-scale preparation, and provides a novel electrode material for the research and application of a long-life anode of the water-based zinc ion battery.

Description

Technical Field

[0001] This invention belongs to the field of nanomaterial preparation technology, specifically relating to a method for preparing fluorinated zinc oxide metal composite foil and its energy storage application. Background Technology

[0002] The extensive use of fossil fuels in the industrial sector has exacerbated global environmental pollution. The application scenarios for most renewable energy sources, such as solar, wind, and tidal power, are subject to numerous limitations. Therefore, exploring efficient and low-cost energy storage technologies is crucial for sustainable industrial development. Thanks to its high energy density and excellent operating potential range, lithium-ion batteries are currently the most widely used large-scale energy storage devices and are extensively applied in electric vehicles and portable electronic devices.

[0003] However, lithium resources in the Earth's crust are finite and unevenly distributed, which not only affects the efficiency of lithium resource extraction but also severely hinders the long-term sustainable development of lithium-ion batteries. Sodium-ion, potassium-ion, aluminum-ion, and zinc-ion batteries, among many other rechargeable batteries, are being researched as potential alternatives to lithium-ion batteries. Among these, aqueous zinc-ion batteries have emerged as a strong contender due to their low cost, high safety, and environmental friendliness. The cost of zinc metal is less than one-twentieth that of lithium metal. Furthermore, zinc metal possesses a suitable redox potential (-0.76V vs. SHE) and an ultra-high volumetric energy density (5855 mAh cm⁻¹). -3 It also boasts excellent electroplating / stripping reversibility. Notably, zinc metal can be used directly as the anode in aqueous zinc-ion batteries due to its relative stability in water.

[0004] However, during long-cycle operation, aqueous zinc-ion batteries experience hydrogen evolution and zinc dendrite formation at the metal anode. Uncontrolled zinc dendrite growth caused by uneven zinc stripping / deposition not only severely reduces the battery's energy storage efficiency but can even puncture the separator, leading to short circuits, significantly impairing the battery's lifespan. Therefore, controlling zinc deposition behavior at the anode interface is essential for stabilizing the metal anode in zinc-ion batteries. Constructing an artificial interface layer on the zinc metal anode surface is one of the most common optimization strategies currently employed.

[0005] CN115799512A discloses the preparation and application of an aqueous zinc-ion battery anode material that can suppress dendrite growth, comprising the following steps: zinc nitrate and sodium selenite are added sequentially to deionized water, stirred, and then hydrazine hydrate is added to obtain a mixed solution; the mixed solution undergoes a hydrothermal reaction, and the product is washed, centrifuged, and vacuum dried to obtain ZnSe powder; ZnSe powder and polyvinylidene fluoride are added to an organic solvent and stirred at room temperature to obtain a zinc anode modification slurry; the zinc anode modification slurry is coated onto zinc foil and vacuum dried to obtain a ZnSe@Zn electrode sheet. This invention forms a protective coating of a certain thickness by coating the surface of the zinc electrode with a modified slurry. The modified anode surface has increased specific surface area, uniform electric field distribution, and induces zinc ion redistribution to achieve homogenization. This coating effectively solves the problems of easy corrosion and dendrite growth of zinc anodes during charging and discharging, significantly improving the electrochemical performance of the battery. Summary of the Invention

[0006] To address the problems existing in the prior art, this invention provides a method for preparing a fluorinated zinc oxide metal composite foil Zn@F-ZnO anode and its energy storage application. This invention uses a hydrothermal method for preparation, which is simple, low-cost, scalable, and has good electrochemical energy storage performance. It provides a novel nanomaterial for the research and application of electrode materials for aqueous zinc-ion batteries.

[0007] To solve the above-mentioned technical problems, the present invention adopts the following technical solution:

[0008] A method for preparing a fluorinated zinc oxide metal composite foil anode Zn@F-ZnO, comprising the following steps:

[0009] (1) First, dissolve sodium fluoride in deionized water and stir magnetically for a period of time to obtain a sodium fluoride solution;

[0010] (2) Add NaOH solution dropwise to the sodium fluoride solution under low-speed magnetic stirring until the overall pH of the mixed solution is 10, and continue stirring for a period of time;

[0011] (3) Transfer the solution obtained in step (2) to a hydrothermal reactor and place a piece of commercial zinc foil in it, and then place it in a drying oven for hydrothermal reaction;

[0012] (4) After the hydrothermal reaction is completed, the obtained sample is placed in a vacuum drying oven for vacuum drying to obtain fluorinated zinc oxide metal composite foil anode Zn@F-ZnO.

[0013] Furthermore, in step (1), taking 200 mL of deionized water as an example, the required mass of sodium fluoride is 0.85 g.

[0014] Furthermore, in step (1), the magnetic stirring time is 30 to 60 minutes.

[0015] Furthermore, in step (2), the speed of the low-speed magnetic stirring is 1000 rpm, and the concentration of the NaOH solution is 2M.

[0016] Furthermore, the stirring time in step (2) is 30 to 60 minutes.

[0017] Furthermore, in step (3), the thickness of the commercial zinc foil is 100 μm and the size is 4 cm × 10 cm.

[0018] Furthermore, in step (3), the hydrothermal reaction temperature is 120–180°C, and the heat preservation time is 12–36 h.

[0019] Furthermore, in step (4), the vacuum drying temperature is 60-80°C and the vacuum drying time is 12-24 hours.

[0020] The present invention also provides a fluorinated zinc oxide metal composite foil anode Zn@F-ZnO prepared by the preparation method described above.

[0021] The present invention also provides the energy storage application of the fluorinated zinc oxide metal composite foil anode Zn@F-ZnO in the anode of an aqueous zinc-ion battery, wherein the fluorinated zinc oxide metal composite foil anode Zn@F-ZnO can suppress zinc dendrites in the anode of an aqueous zinc-ion battery.

[0022] The beneficial effects of this invention are as follows: This invention synthesizes a one-step metal composite foil Zn@F-ZnO with a fluorinated zinc oxide sieve-like interface for use as an anode in aqueous zinc-ion batteries via a hydrothermal method. The sieve-like interface composed of ZnO can orderly regulate the zinc plating process and homogenize the surface electron density of the deposition interface, thereby limiting the growth of zinc dendrites. The fluorinated surface reduces the contact between water molecules and the metal anode, thus suppressing electrode side reactions. Under the protection of this sieve-like interface, the electrochemical performance of the zinc anode is significantly optimized. Therefore, the use of fluorinated zinc oxide metal composite foil Zn@F-ZnO can effectively suppress the formation of zinc dendrites at the anode of aqueous zinc-ion batteries, promoting the large-scale application of aqueous zinc-ion batteries and other related fields. This preparation method has advantages such as simple process, low cost, environmental friendliness, high reproducibility, large-scale production capability, and good long-term stability. Attached Figure Description

[0023] Figure 1 This is a process flow diagram for preparing the fluorinated zinc oxide metal composite foil anode Zn@F-ZnO of the present invention.

[0024] Figure 2 The images show the XRD patterns of pure Zn and Zn@F-ZnO in Embodiment 1 of the present invention.

[0025] Figure 3This is a SEM image of the pure Zn surface in Embodiment 1 of the present invention.

[0026] Figure 4 This is a SEM image of the Zn@F-ZnO surface in Embodiment 1 of the present invention.

[0027] Figure 5 The image shows the XRD patterns of pure Zn and Zn@F-ZnO after soaking in 2M ZnSO4 electrolyte solution for 15 days in Example 1 of this invention.

[0028] Figure 6 This is a surface SEM image of pure Zn after being soaked in 2M ZnSO4 electrolyte solution for 15 days in Example 1 of the present invention.

[0029] Figure 7 This is a surface SEM image of Zn@F-ZnO after being immersed in 2M ZnSO4 electrolyte solution for 15 days in Example 1 of the present invention.

[0030] Figure 8 The Zn||Zn and Zn@F-ZnO||Zn@F-ZnO symmetrical cells in Embodiment 1 of the present invention are at 1 mA cm -2 Current density and 1mAh cm -2 Electrochemical tests at capacitance density.

[0031] Figure 9 The Zn||Zn and Zn@F-ZnO||Zn@F-ZnO symmetrical cells in Embodiment 1 of the present invention are at 4 mA cm⁻¹ -2 Current density and 1mAh cm -2 Electrochemical tests at capacitance density.

[0032] Figure 10 The Zn||Cu and Zn@F-ZnO||Cu asymmetric cells in Example 1 of this invention are used at 4 mA cm⁻¹ -2 Current density and 1mAh cm -2 Electrochemical tests at capacitance density.

[0033] Figure 11 The Zn||VO2 and Zn@F-ZnO||VO2 full cell in Example 1 of this invention is at 0.5 mV s -1 Cyclic voltammetry test at the scan rate.

[0034] Figure 12 This is an AC impedance test of the Zn||VO2 and Zn@F-ZnO||VO2 full cells in Example 1 of the present invention.

[0035] Figure 13This is a rate performance test of the Zn||VO2 and Zn@F-ZnO||VO2 full cells in Example 1 of the present invention. Figure 14 The Zn||VO2 and Zn@F-ZnO||VO2 full cells in Example 1 of this invention are in a 0.1 A g... -1 Long-cycle testing at current density. Detailed Implementation

[0036] The following examples, in conjunction with the accompanying drawings, further illustrate the present invention. These embodiments are implemented based on the technical solution of the present invention, providing detailed implementation methods and processes. However, the scope of protection of the present invention is not limited to the following embodiments. Experimental methods in the following embodiments, unless otherwise specified, are generally performed under conventional conditions or according to the manufacturer's recommendations.

[0037] A method for preparing a fluorinated zinc oxide metal composite foil anode Zn@F-ZnO, comprising the following steps:

[0038] (1) First, dissolve sodium fluoride in deionized water and stir magnetically for a period of time to obtain a sodium fluoride solution;

[0039] (2) Add NaOH solution dropwise to the sodium fluoride solution under low-speed magnetic stirring until the overall pH of the mixed solution is 10, and continue stirring for a period of time;

[0040] (3) Transfer the solution obtained in step (2) to a hydrothermal reactor and place a piece of commercial zinc foil in it, and then place it in a drying oven for hydrothermal reaction;

[0041] (4) After the hydrothermal reaction is completed, the obtained sample is placed in a vacuum drying oven for vacuum drying to obtain fluorinated zinc oxide metal composite foil anode Zn@F-ZnO.

[0042] Furthermore, in step (1), taking 200 mL of deionized water as an example, the required mass of sodium fluoride is 0.85 g.

[0043] Furthermore, in step (1), the magnetic stirring time is 30 to 60 minutes.

[0044] Furthermore, in step (2), the speed of the low-speed magnetic stirring is 1000 rpm, and the concentration of the NaOH solution is 2M.

[0045] Furthermore, the stirring time in step (2) is 30 to 60 minutes.

[0046] Furthermore, in step (3), the thickness of the commercial zinc foil is 100 μm and the size is 4 cm × 10 cm.

[0047] Furthermore, in step (3), the hydrothermal reaction temperature is 120–180°C, and the heat preservation time is 12–36 h.

[0048] Furthermore, in step (4), the vacuum drying temperature is 60-80°C and the vacuum drying time is 12-24 hours.

[0049] Example 1

[0050] The preparation method of the fluorinated zinc oxide metal composite foil anode Zn@F-ZnO in this embodiment is as follows:

[0051] (1) First, dissolve 0.85g of sodium fluoride in 200mL of deionized water and stir magnetically for 30min;

[0052] (2) Add 2M NaOH dropwise to the solution under low-speed magnetic stirring at 100rpm until the overall pH of the mixed solution is 10, and continue stirring for 30min;

[0053] (3) Transfer the solution obtained in step (2) to a hydrothermal reactor and place a 100μm thick commercial zinc foil (4cm×10cm) in it. Then place it in a drying oven and keep it at 180℃ for 16h.

[0054] (4) The obtained sample was then placed in a vacuum drying oven and vacuum dried at 60°C for 12 hours to obtain the final zinc composite foil Zn@F-ZnO.

[0055] The SEM and XRD patterns of the prepared product are as follows: Figure 2-7 As shown, the electrochemical energy storage performance is as follows: Figure 8-14 As shown.

[0056] The obtained fluorinated zinc oxide metal composite foil Zn@F-ZnO was cut into metal discs with a diameter of 12 mm for use as battery anodes. In an electrolyte immersion test with 2M ZnSO4, Zn@F-ZnO exhibited excellent corrosion inhibition performance. Figure 5-7 Then, a coin cell was assembled using 2M ZnSO4 as the electrolyte for electrochemical testing, based on a zinc-zinc symmetric cell assembled with Zn@F-ZnO. Figure 8-9 ) and zinc-copper asymmetric cells ( Figure 10 It also exhibits superior cycle life compared to pure Zn, and the full cell assembled based on Zn@F-ZnO anode and VO2 cathode also has superior specific capacity and service life.

[0057] Example 2

[0058] The preparation method of the fluorinated zinc oxide metal composite foil anode Zn@F-ZnO in this embodiment is as follows:

[0059] (1) First, dissolve 0.85g of sodium fluoride in 200mL of deionized water and stir magnetically for 40min;

[0060] (2) Add 2M NaOH dropwise to the solution under low-speed magnetic stirring until the overall pH of the mixed solution is 10, and continue stirring for 40 minutes;

[0061] (3) Transfer the solution obtained in step (2) to a hydrothermal reactor and place a 100μm thick commercial zinc foil (4cm×10cm) in it. Then place it in a drying oven and keep it at 120℃ for 36h.

[0062] (4) The obtained sample was then placed in a vacuum drying oven and vacuum dried at 60°C for 24 hours to obtain the final zinc composite foil Zn@F-ZnO.

[0063] Example 3

[0064] The preparation method of the fluorinated zinc oxide metal composite foil anode Zn@F-ZnO in this embodiment is as follows:

[0065] (1) First, dissolve 0.85g of sodium fluoride in 200mL of deionized water and stir magnetically for 50min;

[0066] (2) Add 2M NaOH dropwise to the solution under low-speed magnetic stirring until the overall pH of the mixed solution is 10, and continue stirring for 50 min;

[0067] (3) Transfer the solution obtained in step (2) to a hydrothermal reactor and place a 100μm thick commercial zinc foil (4cm×10cm) in it. Then place it in a drying oven and keep it at 180℃ for 12h.

[0068] (4) The obtained sample was then placed in a vacuum drying oven and vacuum dried at 80°C for 12 hours to obtain the final zinc composite foil Zn@F-ZnO.

[0069] Example 4

[0070] The preparation method of the fluorinated zinc oxide metal composite foil anode Zn@F-ZnO in this embodiment is as follows:

[0071] (1) First, dissolve 0.85g of sodium fluoride in 200mL of deionized water and stir magnetically for 60min;

[0072] (2) Add 2M NaOH dropwise to the solution under low-speed magnetic stirring until the overall pH of the mixed solution is 10, and continue stirring for 60 min;

[0073] (3) Transfer the solution obtained in step (2) to a hydrothermal reactor and place a 100μm thick commercial zinc foil (4cm×10cm) in it. Then place it in a drying oven and keep it at 150℃ for 24h.

[0074] (4) The obtained sample was then placed in a vacuum drying oven and vacuum dried at 70°C for 20 hours to obtain the final zinc composite foil Zn@F-ZnO.

[0075] The foregoing has shown and described the basic principles and main features of the present invention, as well as its advantages. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely illustrative of the principles of the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the present invention as claimed. The scope of protection of this invention is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a fluorinated zinc oxide metal composite foil anode Zn@F-ZnO, characterized in that... The steps are as follows: (1) First, dissolve sodium fluoride in deionized water and stir magnetically for a period of time to obtain a sodium fluoride solution; (2) Add NaOH solution dropwise to the sodium fluoride solution under low-speed magnetic stirring until the overall pH of the mixed solution is 10, and continue stirring for a period of time; (3) Transfer the solution obtained in step (2) to a hydrothermal reactor and place a piece of commercial zinc foil in it, and then place it in a drying oven for hydrothermal reaction; (4) After the hydrothermal reaction is completed, the obtained sample is placed in a vacuum drying oven for vacuum drying to obtain fluorinated zinc oxide metal composite foil anode Zn@F-ZnO; In step (3), the hydrothermal reaction temperature is 120 ~ 180℃ and the heat preservation time is 12 ~ 36 h.

2. The method for preparing the fluorinated zinc oxide metal composite foil anode Zn@F-ZnO according to claim 1, characterized in that: In step (1), taking 200 mL of deionized water as an example, the required mass of sodium fluoride is 0.85 g.

3. The method for preparing the fluorinated zinc oxide metal composite foil anode Zn@F-ZnO according to claim 1, characterized in that: In step (1), the magnetic stirring time is 30 to 60 minutes.

4. The method for preparing the fluorinated zinc oxide metal composite foil anode Zn@F-ZnO according to claim 1, characterized in that: In step (2), the speed of the low-speed magnetic stirring is 1000 rpm, and the concentration of the NaOH solution is 2M.

5. The method for preparing the fluorinated zinc oxide metal composite foil anode Zn@F-ZnO according to claim 1, characterized in that: The stirring time in step (2) is 30 to 60 minutes.

6. The method for preparing the fluorinated zinc oxide metal composite foil anode Zn@F-ZnO according to claim 1, characterized in that: In step (3), the commercial zinc foil has a thickness of 100 μm and a size of 4 cm × 10 cm.

7. The method for preparing the fluorinated zinc oxide metal composite foil anode Zn@F-ZnO according to claim 1, characterized in that: In step (4), the vacuum drying temperature is 60 ~ 80℃ and the vacuum drying time is 12 ~ 24 h.

8. Fluorinated zinc oxide metal composite foil anode Zn@F-ZnO prepared by any one of the preparation methods described in claims 1-7.

9. The energy storage application of the fluorinated zinc oxide metal composite foil anode Zn@F-ZnO according to claim 8 in the anode of an aqueous zinc-ion battery, characterized in that: The fluorinated zinc oxide metal composite foil anode Zn@F-ZnO can suppress zinc dendrites in the anode of aqueous zinc-ion batteries.

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