Zinc negative electrode material for aqueous zinc-ion batteries and preparation method thereof

Abstract

The application provides a zinc negative electrode material for a water-based zinc ion battery, the zinc negative electrode material being a Te@Zn negative electrode material in which an antimony layer material is loaded on a zinc layer material. The application also provides a preparation method of the zinc negative electrode material for the water-based zinc ion battery. The application relates to a Te@Zn material with excellent stability, high conductivity and high cycle performance and a preparation method applied in a water-based zinc ion battery, and the preparation of the zinc negative electrode material with a nanosheet-shaped Te surface modification layer is realized by using an electrochemical deposition method and high-temperature calcination. The preparation method has the advantages of simple process, easy process control, short preparation time, high single yield and the like, and is beneficial to large-scale production.

Description

Technical Field

[0001] This invention belongs to the field of zinc battery technology, and particularly relates to a zinc anode material for aqueous zinc-ion batteries and its preparation method. Background Technology

[0002] Electrochemical energy storage devices, such as rechargeable batteries, are key to overcoming global energy challenges. Non-aqueous lithium-ion batteries (LIBs), due to their high energy density and long cycle life, dominate the portable electronics and emerging electric / hybrid vehicle sectors and are currently considered a potential option for future electric vehicles and grid energy storage systems. However, growing concerns about limited lithium resources, high cost, and safety issues strongly limit their further large-scale application. Sodium-ion batteries (SIBs) and potassium-ion batteries (KIBs) are reasonable alternatives to LIBs because these devices are based on the relatively abundant and inexpensive sodium (potassium) elements and their similar chemistry to lithium, but they suffer from low energy density, use highly toxic and flammable electrolytes, have high operating costs, and pose serious safety concerns. The drawbacks of these organic-based systems have prompted the exploration of alternative battery chemistry that offers low cost, high safety, and long cycle life. Aqueous rechargeable batteries, with their advantages of low cost, high operational safety, and environmental friendliness, are a promising electrochemical energy storage option.

[0003] Current research primarily focuses on exploring high-performance cathode materials for zinc-based anodes (ZIBs), such as manganese-based materials, vanadium-based materials, and Prussian blue. Through a series of mechanistic studies and various structural optimizations, the electrochemical performance of these cathodes, especially their cycle stability, has been greatly improved, significantly promoting the development of aqueous ZIBs and making their practical application highly feasible. However, the industrialization of zinc anodes is an immature technology, and the limited and insufficient understanding of their mechanisms hinders performance improvement.

[0004] In most current studies on AZIB, zinc foil is used directly as the negative electrode, but its electrochemical behavior does not meet the requirements for the production of industrially scalable devices. Zinc negative electrodes exhibit strong electrochemical activity when exposed to aqueous electrolytes, inevitably leading to severe problems such as dendrite formation, hydrogen evolution, and corrosion during charge-discharge cycles.

[0005] Chinese patent document CN114243019A discloses a zinc anode material with a dual-modification layer on its surface. This material addresses the problems of dendrite formation, hydrogen evolution, and corrosion present in aqueous zinc-ion battery anodes by modifying the zinc foil surface with a dual-modification layer of elemental bismuth and bismuth oxide. However, the process for obtaining the dual-modification layer of elemental bismuth and bismuth oxide on the zinc foil surface is complex and not conducive to large-scale production. Summary of the Invention

[0006] To address the aforementioned problems, the present invention aims to provide a zinc anode material with excellent stability, high conductivity, and high cycle performance for use in aqueous zinc-ion batteries, as well as a method for preparing the same. This method provides a simple and feasible anode material capable of achieving long cycle performance of stable AZIBs zinc anodes.

[0007] To achieve the above objectives, the present invention adopts the following technical solution:

[0008] In a first aspect, the present invention provides a zinc anode material for aqueous zinc-ion batteries, wherein the zinc anode material is a Te@Zn anode material on which Te material is loaded onto a zinc electrode material.

[0009] Preferably, the zinc electrode material is zinc sheet, zinc foil, or porous zinc.

[0010] Preferably, the Te material is a one-dimensional nanostructure material, including nanowires, nanorods, nanotubes and nanosheets, and is preferably a nanosheet material, wherein the thickness of the nanosheets is 3 nm to 100 nm and the diameter of the nanosheets is 20 nm to 2 μm.

[0011] Preferably, the zinc anode material is used when the current density is 0.2–10 mA / cm². 2 Capacity is 0.2~10mAh / cm³ 2 Under test conditions, the cycle life is 100–3000 cycles.

[0012] Secondly, the present invention also provides a method for preparing zinc anode material for aqueous zinc-ion batteries as described above. The method employs electrochemical deposition, using Zn as a substrate, and electrochemically deposits Te material in an electrolyte under certain voltage and temperature conditions. The prepared Te@Zn material is then subjected to high-temperature treatment under an inert atmosphere to finally obtain the Te@Zn anode material.

[0013] Preferably, the electrolyte is an aqueous electrolyte prepared using TeO2, NaTeO3, or a mixture thereof, with an electrolyte concentration of 0.1–10 mg / ml and a pH value of 1–11.

[0014] In this invention, an aqueous electrolyte prepared from TeO2, NaTeO3 and mixtures thereof is used to provide the Te source for the Te@Zn anode material of this invention, and a modified electrolyte suitable for the Te@Zn anode material of this invention is prepared.

[0015] Preferably, the electrodeposition voltage is -1.1 to -0.8V, the deposition temperature is 30 to 95℃, and the deposition time is 30s to 300min.

[0016] Preferably, in a protective atmosphere of N2, Ar, or a mixture thereof, the high-temperature treatment temperature is 100–400°C, the high-temperature treatment time is 10–600 min, and the gas flow rate of the protective atmosphere is 50–500 sccm (ml / min).

[0017] In this invention, by loading Te material onto the zinc electrode material for interface modification and electrolyte modification, the Te material can isolate the zinc electrode material from the zinc sulfate electrolyte used in the battery, reducing the solvation effect. This can prevent problems such as dendrite formation, hydrogen evolution, and corrosion of the zinc anode, thereby achieving long-cycle stability of the AZIBs zinc anode.

[0018] Compared with the prior art, the present invention has the following beneficial effects:

[0019] This invention relates to a Te@Zn material and its preparation method, exhibiting excellent stability, high conductivity, and high cycle performance for use in aqueous zinc-ion batteries. The method utilizes electrochemical deposition and high-temperature calcination to prepare a zinc anode material with a nanosheet-like Te surface modification layer. The Te@Zn anode material prepared by this method exhibits excellent stability, high conductivity, and high cycle performance at current densities ranging from 0.2 to 10 mA / cm². 2 Capacity is 0.2~10mAh / cm³ 2 Under the tested conditions, the cycle life can reach 3000 cycles, making it suitable for electrochemical energy storage. Furthermore, the preparation method is simple, easy to control, and has a short preparation time, enabling high single-batch yields and facilitating large-scale production. Attached Figure Description

[0020] Figure 1 The X-ray electron diffraction pattern of the Te@Zn anode material prepared in Example 4 of this invention is shown. The vertical axis represents the intensity of the acquired signal (individual dimensionless), and the horizontal axis represents twice the incident angle of the X-ray (2Theta) (in degrees).

[0021] Figure 2 The image shows the SEM morphology of the Te@Zn anode material prepared in Example 4 of this invention.

[0022] Figure 3 The impedance comparison diagram shows the symmetrical cells assembled using bare zinc and the Te@Zn electrode prepared in Example 4 of this invention. The vertical axis represents the negative number of the imaginary part of the impedance (-Z”), in Ohm, and the horizontal axis represents the real part of the impedance (Z'), in Ohm.

[0023] Figure 4 The graphs show the cycling performance of a symmetrical battery assembled using the Te@Zn electrode prepared in Example 4 of this invention at different rates. The vertical axis represents voltage (V) and the horizontal axis represents cycling time (h).

[0024] Figure 5 This is a comparison graph showing the long-cycle performance of symmetrical batteries assembled using bare zinc and the Te@Zn electrode prepared in Example 4 of this invention under test conditions of current density of 1 mA / cm2 and capacity of 1 mAh / cm2. The vertical axis represents voltage (V) and the horizontal axis represents cycle time (h). Detailed Implementation

[0025] The present invention will be further illustrated by the following embodiments. It should be understood that the following embodiments are for illustrative purposes only and are not intended to limit the present invention.

[0026] This invention discloses a zinc anode material for aqueous zinc-ion batteries, wherein the zinc anode material is a Te@Zn anode material with Te material loaded on a zinc electrode material. The zinc electrode material is a zinc sheet, zinc foil, or porous zinc; the Te material is a one-dimensional nanostructure material, including nanowires, nanorods, nanotubes, and nanosheet structures, preferably a nanosheet structure material, wherein the thickness of the nanosheet structure is 3 nm to 100 nm, and the sheet diameter is 20 nm to 2 μm.

[0027] In this invention, a Te material with a nanosheet structure is loaded onto a zinc layer. Te is an important narrow bandgap (Eg = 0.35 eV) semiconductor material with properties such as photoconductivity, high voltage and thermoelectric properties, nonlinear optical response, and catalytic activity for hydration and oxidation reactions. It also has high reactivity, especially one-dimensional Te nanostructure materials, including nanowires, nanorods, nanotubes, and nanosheets, which can react with zinc.

[0028] In this invention, the preparation methods of Te one-dimensional nanostructure materials mainly include reflux polyol method, hydrothermal method, surfactant-assisted solution method, visible light-assisted solution method, microwave-assisted ionic liquid method, and thermal evaporation method.

[0029] In this invention, the Te@Zn anode material for aqueous zinc-ion batteries is prepared by electrochemical deposition. Using Zn as a substrate, Te material is electrochemically deposited in an electrolyte under specific voltage and temperature conditions. The prepared Te@Zn material is then subjected to high-temperature treatment under an inert atmosphere to finally obtain the Te@Zn anode material. In a preferred embodiment of the preparation method of the Te@Zn anode material for aqueous zinc-ion batteries of this invention, the following steps are included:

[0030] Step (1), preparation of electrolyte solution: Prepare electrolyte in container. In this invention, the electrolyte is an aqueous electrolyte prepared with TeO2, NaTeO3 or a mixture thereof, with an electrolyte concentration of 0.1 to 10 mg / ml and a pH value of 1 to 11; pour the electrolyte solution into the electrolytic cell;

[0031] Step (2), electrochemical deposition: The electrodeposition process is carried out in a standard three-electrode system with a zinc electrode, a counter electrode and a reference electrode. The temperature of the electrolyte in step (1) is maintained at 30 to 95°C (i.e., deposition temperature) by a water bath. A potential of -1.1 to -0.8V relative to the reference electrode is applied to the working electrode by an electrochemical analyzer to carry out the reaction. The deposition time can be 30s to 300min. Te@Zn material with Te nanosheet structure is deposited on the zinc electrode.

[0032] Step (3), high-temperature calcination: The Te@Zn material with Te nanosheet structure obtained in step (2) is calcined at high temperature in a protective atmosphere of N2, Ar and their mixture. The high-temperature calcination temperature can be 100-400℃, the high-temperature calcination time can be 10-600min, and the gas flow rate of the protective atmosphere can be 50-500sccm (ml / min).

[0033] This invention achieves the preparation of zinc anode materials with nanosheet-like Te surface modification layers through electrochemical deposition and high-temperature calcination. The preparation method is simple, easy to control, and has a short preparation time, and can achieve high single-batch yield, which is conducive to large-scale production.

[0034] The following examples further illustrate the present invention in detail. It should also be understood that the following examples are only for further explanation of the present invention and should not be construed as limiting the scope of protection of the present invention. Any non-essential improvements and adjustments made by those skilled in the art based on the above description of the present invention are within the scope of protection of the present invention. The specific process parameters, etc., in the following examples are merely examples within a suitable range; that is, those skilled in the art can make appropriate selections within the appropriate range based on the description herein, and are not intended to be limited to the specific values ​​in the examples below.

[0035] Example 1

[0036] Zinc sheets were used as the substrate, and TeO2 was used to prepare the electrolyte with a concentration of 0.8 mg / ml and a pH of 1. The deposition voltage was -0.95 V, the deposition temperature was 90 °C, and the deposition time was 180 s. A protective atmosphere of Ar was introduced at a flow rate of 200 sccm, and the high-temperature treatment was performed at 300 °C for 60 min. After natural cooling, the stable zinc anode material Te@Zn was obtained. The surface of the material showed high crystallinity and exhibited all the major diffraction peaks of Te@Zn. The Te@Zn material was cut into electrode sheets with a diameter of 12 mm and assembled into a button cell using a CR2016 battery case. The current density was 1 mA / cm². 2 The capacity is 1mAh / cm 2 Under the test conditions, the cycle life is 800 cycles.

[0037] Example 2

[0038] A zinc plate was used as the substrate, and NaTeO3 was used to prepare the electrolyte with a concentration of 0.2 mg / ml and a pH of 10.5. The deposition voltage was -1.0 V, the deposition temperature was 30 °C, and the deposition time was 10 min. An Ar protective atmosphere was introduced at a flow rate of 50 sccm, and the high-temperature treatment was performed at 200 °C for 500 min. After natural cooling, the stable zinc anode material Te@Zn was obtained. The surface of the material showed high crystallinity and exhibited all the major diffraction peaks of Te@Zn. The Te@Zn material was cut into 12 mm diameter electrode sheets and assembled into a button cell using a CR2016 battery case. The current density was 5 mA / cm². 2 The capacity is 1mAh / cm 2 Under the test conditions, the cycle life is 2000 cycles.

[0039] Example 3

[0040] Porous zinc was used as the substrate, and TeO2 was used to prepare the electrolyte with a concentration of 5 mg / ml and a pH of 3.7. The deposition voltage was -0.80 V, the deposition temperature was 80 °C, and the deposition time was 200 min. A protective atmosphere of N2 was introduced at a flow rate of 300 sccm, and the high-temperature treatment temperature was 150 °C for 60 min. After natural cooling, the stable zinc anode material Te@Zn was obtained. The surface of the material showed high crystallinity and all the main diffraction peaks of Te@Zn were observed. The Te@Zn material was cut into electrode sheets with a diameter of 12 mm and assembled into a button cell using a CR2016 battery case. The current density was 0.2 mA / cm². 2 The capacity is 0.2mAh / cm³. 2 Under the test conditions, the cycle life is 100 cycles.

[0041] Example 4

[0042] Zinc sheets were used as the substrate, and an electrolyte was prepared using TeO2 and NaTeO3 with an electrolyte concentration of 2 mg / ml and a pH of 11. The deposition voltage was -0.90 V, the deposition temperature was 80 °C, and the deposition time was 300 s. A protective atmosphere of Ar and N2 was introduced at a gas flow rate of 500 sccm, and the high-temperature treatment temperature was 400 °C for 150 min. After natural cooling, the stable zinc anode material Te@Zn was obtained. The surface of the material showed high crystallinity and all the major diffraction peaks of Te@Zn were observed. The Te@Zn material was cut into electrode sheets with a diameter of 12 mm and assembled into a button cell using a CR2016 battery case. The current density was 10 mA / cm². 2 , with a capacity of 10mAh / cm 2 Under the test conditions, the cycle life is 3000 cycles.

[0043] Figure 1 The X-ray electron diffraction pattern of the Te@Zn anode material prepared in Example 4 of this invention is shown. The vertical axis represents the intensity of the acquired signal (individual dimensionless), and the horizontal axis represents twice the incident angle of the X-ray (2Theta) (in degrees). Figure 2 This is a SEM image of the Te@Zn anode material prepared in Example 4 of this invention. From... Figure 1 As can be seen, the XRD pattern of the Te@Zn material shows peaks corresponding to Zn and Te, indicating that the material has good crystallinity and is free of impurities.

[0044] Figure 3 This is a comparison graph of the impedance of symmetrical cells assembled using bare zinc and the Te@Zn electrode prepared in Example 4 of this invention. The vertical axis represents the negative of the imaginary part of the impedance (-Z”), in Ohms, and the horizontal axis represents the real part of the impedance (Z'), in Ohms. Figure 3 It can be seen that the impedance of the symmetrical cell assembled with Te@Zn electrodes is significantly reduced compared with that assembled with bare zinc electrodes, and the conductivity of the surface Te@Zn electrode is higher than that of the bare zinc electrode.

[0045] Figure 4 The graphs show the cycling performance of a symmetrical battery assembled using the Te@Zn electrode prepared in Example 4 of this invention at different rates. The vertical axis represents voltage (V) and the horizontal axis represents cycling time (h).

[0046] Figure 5This is a comparison graph showing the long-cycle performance of a symmetrical battery assembled using bare zinc and the Te@Zn electrode prepared in Example 4 of this invention under test conditions of a current density of 1 mA / cm² and a capacity of 1 mAh / cm². The vertical axis represents voltage (V), and the horizontal axis represents cycle time (h). Figure 5 It can be seen that the cycle life of the Te@Zn symmetric cell can reach 1200h, while the cycle life of the bare zinc symmetric cell is only 80h, indicating that the Te@Zn material can reduce side reactions and greatly extend the cell life.

[0047] Finally, it is necessary to state that the above embodiments are only used to further illustrate the technical solution of the present invention in detail, and should not be construed as limiting the scope of protection of the present invention. Any non-essential improvements and adjustments made by those skilled in the art based on the above content of the present invention shall fall within the scope of protection of the present invention.

Claims

1. A method for preparing a zinc anode material for an aqueous zinc-ion battery, characterized in that, The zinc anode material is a Te@Zn anode material loaded with Te material on a zinc electrode material. It is prepared by electrochemical deposition, using Zn as a substrate, and electrochemically depositing Te material in an electrolyte under certain voltage and temperature conditions. The prepared Te@Zn material is then subjected to high-temperature treatment in an inert atmosphere to finally obtain the Te@Zn anode material.

2. The preparation method according to claim 1, characterized in that, The zinc electrode material is zinc sheet.

3. The preparation method according to claim 1, characterized in that, The zinc electrode material is zinc foil.

4. The preparation method according to claim 1, characterized in that, The zinc electrode material is porous zinc.

5. The preparation method according to claim 1, characterized in that, The Te material is a one-dimensional nanostructure material, including nanowires, nanorods, and nanotubes.

6. The preparation method according to claim 1, characterized in that, The Te material is a nanosheet structure material with a sheet thickness of 3 nm to 100 nm and a sheet diameter of 20 nm to 2 μm.

7. The preparation method according to claim 1, characterized in that, The zinc anode material operates at current densities of 0.2~10 mA / cm². 2 Capacity is 0.2~10mAh / cm³ 2 Under test conditions, the cycle life is 100~3000 cycles.

8. The preparation method according to claim 1, characterized in that, The electrolyte is an aqueous electrolyte prepared using TeO2, NaTeO3, or a mixture thereof, with an electrolyte concentration of 0.1~10 mg / ml and a pH value of 1~11.

9. The preparation method according to claim 1, characterized in that, The electrochemical deposition voltage is -1.1 to -0.8V, the deposition temperature is 30 to 95 ℃, and the deposition time is 30s to 300min.

10. The preparation method according to any one of claims 1-9, characterized in that, In a protective atmosphere of N2, Ar, or a mixture thereof, the high-temperature treatment temperature is 100~400℃, the high-temperature treatment time is 10~600 min, and the gas flow rate of the protective atmosphere is 50~500 sccm.

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