Zinc negative electrode with amorphous high-entropy oxide protective layer and preparation method and application thereof

Abstract

The invention discloses a zinc negative electrode with an amorphous high-entropy oxide protective layer and a preparation method and application of the zinc negative electrode, and belongs to the technical field of aqueous zinc ion battery negative electrodes. A zinc ion battery zinc negative electrode material with the amorphous high-entropy oxide protective layer with long cycle life is prepared by utilizing an ALD (Atomic Layer Deposition) technology; the ALD modified high-entropy oxide protective layer inhibits zinc dendrites and by-products on the surface of the zinc negative electrode; due to the mixing effect of various elements, the high-entropy oxide electrode has rich zinc-loving sites and promotes uniform zinc deposition, and the high-entropy oxide modified electrode enhances migration kinetics of zinc ions, promotes a desolvation process of the zinc ions, reduces a zinc deposition energy barrier and obtains excellent and stable electrochemical performance of the zinc negative electrode.

Description

Technical Field

[0001] The invention belongs to the technical field of negative electrodes for aqueous zinc ion batteries, and in particular relates to a zinc negative electrode with an amorphous high entropy oxide protective layer, and a preparation method and application thereof. Background Art

[0002] Aqueous zinc-ion batteries (ZIBs) have attracted extensive attention in the field of future large-scale energy storage due to their high theoretical capacity (820 mAh / g and 5855 mAh / cm 3 ), lower reduction potential (-0.76 V), high safety and low cost. However, the uncontrollable zinc dendrite deposition during the zinc anode cycle seriously affects its cycle life. To address this problem, an effective method is to construct an artificial protective coating on the surface of the zinc anode. Atomic layer deposition (ALD) technology is expected to form a uniform ultra-thin coating on the zinc anode due to its advantages such as excellent three-dimensional conformality and simple and precise film control. For example, the patent application "A zinc metal anode for aqueous zinc ion batteries and its application" with application number 202410142287.5 discloses the use of atomic layer deposition (ALD) process to construct a single layer of aluminum oxide protective layer on the surface of the zinc metal anode, which inhibits the generation of zinc dendrites to a certain extent. The traditional single metal oxide coating material (Al2O3) is mainly prepared by atomic layer deposition (ALD) process. However, single, binary or ternary oxides are often not enough to solve the various challenges in zinc ion batteries.

[0003] In recent years, high entropy materials have become a hot topic in various research fields, and the application of high entropy oxides (HEOs) in zinc-ion batteries has also attracted more and more attention. However, the high temperature conditions required for the preparation of traditional high entropy oxides hinder their direct application on the surface of zinc metal. The research group of Academician Wang Weihua of the Chinese Academy of Sciences first proposed the concept of high entropy amorphous alloys in 2011, which immediately triggered a craze for amorphous high entropy materials in different research fields. However, there is no report on the use of amorphous high entropy oxides prepared by ALD for zinc negative electrode materials. Summary of the invention

[0004] The present invention provides a zinc negative electrode with an amorphous high entropy oxide protective layer, a preparation method and application thereof, and utilizes the ALD technology to prepare the zinc negative electrode with an amorphous high entropy oxide protective layer with a long cycle life. The ALD-modified high entropy oxide protective layer suppresses zinc dendrites and byproducts on the surface of the zinc negative electrode.

[0005] To achieve the above objectives, the present invention adopts the following technical solutions: A method for preparing a zinc negative electrode having an amorphous high entropy oxide protective layer comprises the following steps: (1) Preparation of zinc negative electrode: Process the zinc foil for later use; (2) ALD deposition of a high entropy protective layer: A 1-25 nm high entropy protective layer is deposited on the zinc negative electrode treated in step (1) to obtain a zinc negative electrode with an amorphous high entropy oxide protective layer.

[0006] In the above steps, the parameters of ALD deposition in step (2) are set as follows: reaction chamber temperature: 80-350°C; reaction source: selected according to the high entropy oxide material; the reaction pulse sequence of each oxide is: metal pulse 0.1-5 s-nitrogen (argon) cleaning pulse 2-10 s-water pulse (or plasma oxygen) 0.1-25 s-nitrogen (argon) cleaning pulse 2-10 s; the sub-cycle number of each metal source reaction to generate oxide is 1-10, and the super-cycle number of the growth of quaternary or quinary high entropy oxide is 1-50; The high entropy protective layer is a multi-element amorphous high entropy oxide material, including a quaternary or quinary high entropy oxide, wherein the metal elements contained in the material are four or five of Ti, Y, Zr, Al, Sn, Hf, Zn, Cu, In or Ce; The zinc negative electrode prepared as above can be used in soft-pack batteries, square batteries, cylindrical batteries; it can also be used in battery packs, which can be parallel combinations, series combinations, or series-parallel combinations of zinc metal batteries; it can also be used in battery packs, which are composed of zinc metal batteries or zinc metal battery packs.

[0007] Beneficial effects: The present invention provides a zinc negative electrode with an amorphous high-entropy oxide protective layer, a preparation method and application thereof, and uses the ALD technology to prepare a zinc negative electrode with an amorphous high-entropy oxide protective layer having a long cycle life. The present invention is oriented to the field of zinc ion battery materials and nano-preparation technology, and develops a novel amorphous high-entropy oxide-modified zinc negative electrode. The obtained zinc negative electrode has the following advantages: (1) The high-entropy oxide electrode has a cocktail effect produced by mixing various zinc-philic elements (Ti, Sn, Zn, In and Ce) with various corrosion-resistant elements (Y, Zr, Al, Hf and Cu), which has abundant zinc-philic sites, promotes uniform zinc deposition, and inhibits zinc dendrites and byproducts on the surface of the zinc negative electrode; (2) The high-entropy oxide electrode enhances the migration kinetics of zinc ions, promotes the desolvation process of zinc ions, and reduces the zinc deposition energy barrier; (3) The high-entropy oxide can effectively inhibit the hydrogen evolution reaction and reduce the generation of byproducts; (4) The high-entropy oxide can significantly improve the coulombic efficiency of zinc ion batteries and greatly improve the cycle stability of the zinc negative electrode. Therefore, the amorphous high entropy oxide protective layer can inhibit zinc dendrites and byproducts on the surface of the zinc negative electrode, effectively improving the cycle life of the electrode material. BRIEF DESCRIPTION OF THE DRAWINGS

[0008] Figure 1 It is a schematic diagram of the modification of the zinc negative electrode material of the zinc ion battery with an amorphous high entropy oxide protective layer of the present invention; Figure 2 (a) is the five-element high entropy TiYZrAlSnO in the embodiment of the present invention. x (a) is the SEM image of the zinc metal anode modified with TYZAS after 50 constant current cycles, and (b) is the SEM image of the bare zinc metal anode after 50 constant current cycles; Figure 3 (a) is a graph showing the cycling data of a zinc|zinc symmetric battery of a zinc metal negative electrode modified with TYZAS in an embodiment of the present invention, (b) is a graph showing the cycling data of a zinc|zinc symmetric battery of a zinc metal negative electrode modified with TiO2, (c) is a graph showing the cycling data of a zinc|zinc symmetric battery of a zinc metal negative electrode modified with Y2O3, (d) is a graph showing the cycling data of a zinc|zinc symmetric battery of a zinc metal negative electrode modified with ZrO2, (e) is a graph showing the cycling data of a zinc|zinc symmetric battery of a zinc metal negative electrode modified with Al2O3, and (f) is a graph showing the cycling data of a zinc|zinc symmetric battery of a zinc metal negative electrode modified with SnO2; Figure 4 The quaternary high entropy TiYAlSnO in the embodiment of the present invention x (abbreviated as TYAS) modified zinc metal anode zinc|zinc symmetric battery cycle data diagram; Figure 5 The ternary intermediate entropy TiZrSnO x (abbreviated as TZS) modified zinc metal anode zinc|zinc symmetric battery cycling data diagram. DETAILED DESCRIPTION

[0009] The present invention is described in detail below with reference to the accompanying drawings and specific embodiments: Example 1

[0010] like Figure 1 As shown, a method for preparing a zinc negative electrode material for a zinc ion battery having an amorphous high entropy oxide protective layer comprises the following steps: (1) Ultrasonic cleaning of zinc foil in anhydrous ethanol and deionized water for 5 min, and then drying the water stains on the surface of zinc foil with a nitrogen gun; (2) A 10 nm thick five-element high entropy TiYZrAlSnO was deposited on the zinc anode treated in step (1) by ALD. x(abbreviated as TYZAS) protective layer to obtain a high entropy oxide modified zinc metal anode, wherein the parameters of ALD deposition of TYZAS are as follows: reaction chamber temperature: 300°C; reaction source: titanium tetrachloride, yttrium dimethylacetonate, zirconium tetramethylamino, trimethylaluminum and tin tetrachloride; source temperature: titanium tetrachloride, trimethylaluminum and tin tetrachloride are room temperature, yttrium dimethylacetonate is 180°C, and zirconium tetramethylamino is 115°C; pulse and cleaning time: TiCl4 pulse 0.1 s-nitrogen cleaning pulse 4 s-water pulse 0.1 s-nitrogen cleaning pulse 4 s, Y(thd)3 pulse 5 s-nitrogen cleaning pulse 8 s-plasma oxygen pulse 25 s-nitrogen cleaning pulse 6 s, TDMAZr pulse 0.1 s-nitrogen cleaning pulse 4 s-water pulse 0.1 s-nitrogen cleaning pulse 4 s, TMA pulse 0.1 s-nitrogen cleaning pulse 6 s-water pulse 0.1 s-nitrogen purge pulse 6 s, SnCl4 pulse 0.3 s-nitrogen purge pulse 6 s-water pulse 0.1 s-nitrogen purge pulse 4 s; the sub-cycle ratio of each metal source reaction to generate oxide is set to 1:1:1:1:1, and the super cycle number for growing pentacyclic high entropy oxide is 30.

[0011] To study the practical effect, the zinc metal anode modified with TYZAS protective layer and 2 M zinc sulfate electrolyte were assembled into a zinc metal symmetric battery. In order to study the enhancement effect of TYZAS protective layer on the electrochemical performance of zinc metal anode, several comparative examples were made. Take commercial zinc foil (thickness 100μm) and ultrasonically clean it in anhydrous ethanol and deionized water for 5 min, then use a nitrogen gun to blow dry the water stains on the surface of the zinc foil, cut it into a circular electrode with a diameter of 12 mm, and directly use it as a zinc anode. In addition, ALD was used to deposit 10 nanometers thick unit metal oxide coatings (TiO2, Y2O3, ZrO2, Al2O3 and SnO2) directly on the zinc anode.

[0012] The SEM image of the zinc metal negative electrode modified with the TYZAS protective layer prepared in this example after 50 constant current cycles is as follows: Figure 2 As shown in (a), the surface of the zinc metal anode modified with the TYZAS protective layer remained smooth and flat after 50 constant current cycles, while a large number of uneven moss-like byproducts appeared on the surface of the bare zinc metal anode after 50 constant current cycles ( Figure 2 (b)), which shows that the TYZAS protective layer prepared by ALD in this embodiment can effectively inhibit the formation of zinc dendrites on the surface of zinc metal negative electrode.

[0013] When the zinc negative electrode modified with the TYZAS protective layer obtained in this example is used to assemble a zinc|zinc symmetric battery, the current density is 5 mA cm -2 , with a capacity of 1 mAh cm -2Under the condition of , the battery can run stably for 4000 hours, while the potential of the symmetrical battery with bare zinc negative electrode increases sharply after 180 hours of cycling ( Figure 3 (a)). The cycle life of zinc metal anodes protected by various pure metal oxide coatings (TiO2, Y2O3, ZrO2, Al2O3 and SnO2) is longer than that of bare zinc ( Figure 3 (b), (c), (d), (e) and (f)), but are significantly inferior to the high-entropy TYZAS protective layer, which indicates that the high-entropy TYZAS protective layer can significantly improve the cycling performance of zinc-ion batteries and extend the service life of the zinc metal anode. Example 2

[0014] A method for preparing a zinc negative electrode having an amorphous high entropy oxide protective layer comprises the following steps: (1) Ultrasonic cleaning of zinc foil in anhydrous ethanol and deionized water for 5 min, and then drying the water stains on the surface of zinc foil with a nitrogen gun; (2) A 10 nm thick quaternary high entropy TiYAlSnO was deposited on the zinc anode treated in step (1) by ALD. x (abbreviated as TYAS) protective layer, and a high entropy oxide modified zinc metal anode was obtained. The parameters of ALD deposition of TYAS are as follows: reaction chamber temperature: 300 °C; reaction source: titanium tetrachloride, yttrium dimethylacetonate, trimethylaluminum and tin tetrachloride; source temperature: titanium tetrachloride, trimethylaluminum and tin tetrachloride are at room temperature, and yttrium dimethylacetonate is 180 °C; pulse and cleaning time: TiCl4 pulse 0.1 s-nitrogen cleaning pulse 4 s-water pulse 0.1 s-nitrogen cleaning pulse 4 s, Y(thd)3 pulse 5 s-nitrogen cleaning pulse 8 s-plasma oxygen pulse 25 s-nitrogen cleaning pulse 6 s, TMA pulse 0.1 s-nitrogen cleaning pulse 6 s-water pulse 0.1 s-nitrogen cleaning pulse 6 s, SnCl4 pulse 0.3 s-nitrogen cleaning pulse 6 s-water pulse 0.1 s-nitrogen cleaning pulse 4 s. The sub-cycle ratio of each metal source reaction to generate oxides was set to 1:1:1:1, and the super-cycle number for growing quaternary high-entropy oxides was 42; In order to study the practical effect, the zinc metal anode modified with TYAS protective layer and 2 M zinc sulfate electrolyte were assembled into a zinc metal symmetric battery. In order to study the enhancement effect of TYAS protective layer on the electrochemical performance of zinc metal anode, a ternary intermediate entropy TiZrSnO x A 10-nanometer-thick medium-entropy TZS protective layer was deposited on the zinc anode by ALD, and the sub-cycle ratio of each metal source reaction to generate oxide was set to 4:8:3, and the super-cycle number of the growth of the ternary medium-entropy oxide was 8.

[0015] When the zinc negative electrode modified with the TYAS protective layer obtained in this example is used to assemble a zinc|zinc symmetric battery, the current density is 5 mA cm -2 , with a capacity of 1 mAh cm -2 Under the condition of Figure 4 ), far exceeding the cycle life of the zinc metal anode modified with the TZS protective layer ( Figure 5 ), which indicates that the TYAS protective layer can significantly improve the cycling performance of Zn-ion batteries and extend the service life of the Zn metal anode. Example 3

[0016] A method for preparing a zinc negative electrode having an amorphous high entropy oxide protective layer comprises the following steps: (1) Ultrasonic cleaning of zinc foil in anhydrous ethanol and deionized water for 5 min, and then drying the water stains on the surface of zinc foil with a nitrogen gun; (2) A 25 nm thick five-element high entropy TiHfZrAlSnO was deposited on the zinc anode treated in step (1) by ALD. x (abbreviated as THZAS) protective layer to obtain a high-entropy oxide-modified zinc metal anode. Parameters of ALD deposition of THZAS: reaction chamber temperature: 350°C; reaction sources: titanium tetrachloride, hafnium tetra(methylethylamino), zirconium tetra(dimethylamino), trimethylaluminum and tin tetrachloride; source temperature: room temperature for titanium tetrachloride, trimethylaluminum and tin tetrachloride, 155°C for hafnium tetra(methylethylamino) and 115°C for zirconium tetra(dimethylamino); pulse and cleaning time: TiCl4 pulse 0.1 s-nitrogen cleaning pulse 4 s-water pulse 0.1 s-nitrogen cleaning pulse 4 s, TEMAH pulse 0.1 s-nitrogen cleaning pulse 4 s-water pulse 0.1 s-nitrogen cleaning pulse 4 s, TDMAZr pulse 0.1 s-nitrogen cleaning pulse 4 s-water pulse 0.1 s-nitrogen cleaning pulse 4 s, TMA pulse 0.1 s-nitrogen cleaning pulse 6 s-water pulse 0.1 s-nitrogen cleaning pulse 6 s, SnCl4 pulse 0.3 s-nitrogen purge pulse 6 s-water pulse 0.1 s-nitrogen purge pulse 4 s. The sub-cycle ratio of each metal source reaction to generate oxides is set to 1:2:1:2:1, and the number of super cycles for growing five-element high entropy oxides is 40. Example 4

[0017] A method for preparing a zinc negative electrode having an amorphous high entropy oxide protective layer comprises the following steps: (1) Ultrasonic cleaning of zinc foil in anhydrous ethanol and deionized water for 5 min, and then drying the water stains on the surface of zinc foil with a nitrogen gun; (2) A 1 nm thick five-element high entropy TiZnZrAlSnO was deposited on the zinc anode treated in step (1) by ALD. x(abbreviated as TZZAS) protective layer to obtain a high-entropy oxide-modified zinc metal anode. Parameters of ALD deposition of TZZAS: reaction chamber temperature: 200℃; reaction sources: titanium tetrachloride, diethyl zinc, tetramethylamino zirconium, trimethyl aluminum and tin tetrachloride; source temperature: room temperature for titanium tetrachloride, diethyl zinc, trimethyl aluminum and tin tetrachloride, 115℃ for tetramethylamino zirconium; pulse and cleaning time: TiCl4 pulse 0.1 s-nitrogen cleaning pulse 4 s-water pulse 0.1 s-nitrogen cleaning pulse 4 s, DEZ pulse 0.1 s-nitrogen cleaning pulse 4 s-water pulse 0.1 s-nitrogen cleaning pulse 4 s, TDMAZr pulse 0.1 s-nitrogen cleaning pulse 4 s-water pulse 0.1 s-nitrogen cleaning pulse 4 s, TMA pulse 0.1 s-nitrogen cleaning pulse 6 s-water pulse 0.1 s-nitrogen cleaning pulse 6 s, SnCl4 pulse 0.3 s-nitrogen cleaning pulse 6 s-water pulse 0.1 s-nitrogen purge pulse for 4 s. The sub-cycle ratio of each metal source reaction to generate oxides was set to 3:1:2:2:3, and the super-cycle number for growing five-element high entropy oxides was 1. Example 5

[0018] A method for preparing a zinc negative electrode having an amorphous high entropy oxide protective layer comprises the following steps: (1) Ultrasonic cleaning of zinc foil in anhydrous ethanol and deionized water for 5 min, and then drying the water stains on the surface of zinc foil with a nitrogen gun; (2) A 15 nm thick quaternary high entropy TiHfAlSnO was deposited on the zinc anode treated in step (1) by ALD. x (abbreviated as THAS) protective layer, and a high entropy oxide modified zinc metal anode was obtained. The parameters of ALD deposition of THAS are as follows: reaction chamber temperature: 120°C; reaction sources: titanium tetrachloride, tetra(methylethylamino)hafnium, trimethylaluminum and tin tetrachloride; source temperature: titanium tetrachloride, trimethylaluminum and tin tetrachloride are room temperature, tetra(dimethylamino)hafnium is 80°C; pulse and cleaning time: TiCl4 pulse 0.1 s-nitrogen cleaning pulse 4 s-water pulse 0.1 s-nitrogen cleaning pulse 4 s, TEMAH pulse 0.1 s-nitrogen cleaning pulse 4 s-water pulse 0.1 s-nitrogen cleaning pulse 4 s, TMA pulse 0.1 s-nitrogen cleaning pulse 6 s-water pulse 0.1 s-nitrogen cleaning pulse 6 s, SnCl4 pulse 0.3 s-nitrogen cleaning pulse 6 s-water pulse 0.1 s-nitrogen cleaning pulse 4 s. The sub-cycle ratio of each metal source reaction to generate oxide is set to 1:2:1:2, and the super-cycle number for growing quaternary high-entropy oxide is 28. Example 6

[0019] A method for preparing a zinc negative electrode having an amorphous high entropy oxide protective layer comprises the following steps: (1) Ultrasonic cleaning of zinc foil in anhydrous ethanol and deionized water for 5 min, and then drying the water stains on the surface of zinc foil with a nitrogen gun; (2) A 10 nm thick quaternary high entropy TiZnAlSnO was deposited on the zinc anode treated in step (1) by ALD. x (TZAS for short) protective layer is formed to obtain a high entropy oxide modified zinc metal anode. The parameters of ALD deposition of TZAS are as follows: reaction chamber temperature: 80 °C; reaction source: titanium tetrachloride, diethyl zinc, trimethyl aluminum and tin tetrachloride; source temperature: titanium tetrachloride, diethyl zinc, trimethyl aluminum and tin tetrachloride are at room temperature; pulse and cleaning time: TiCl4 pulse 0.1 s-argon cleaning pulse 4 s-plasma oxygen pulse 15 s-argon cleaning pulse 4 s, DEZ pulse 0.1 s-argon cleaning pulse 4 s-plasma oxygen pulse 15 s-argon cleaning pulse 4 s, TMA pulse 0.1 s-argon cleaning pulse 6 s-plasma oxygen pulse 15 s-argon cleaning pulse 6 s, SnCl4 pulse 0.3 s-argon cleaning pulse 4 s-plasma oxygen pulse 15 s-argon cleaning pulse 4 s. The sub-cycle ratio of each metal source reaction to generate oxides is set to 5:1:1:1, and the super-cycle number for growing quaternary high-entropy oxides is 20.

[0020] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the technical solutions described in the aforementioned embodiments can be modified, or some of the technical features can be replaced by equivalents. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for preparing a zinc negative electrode having an amorphous high entropy oxide protective layer, characterized in that: The following steps are involved: (1) Preparation of zinc negative electrode: Process the zinc foil for later use; (2) ALD deposition of high entropy protective layer: A multi-element amorphous high entropy protective layer is deposited on the zinc foil treated in step (1) using ALD technology to obtain a zinc negative electrode with an amorphous high entropy oxide protective layer.

2. The method for preparing a zinc negative electrode having an amorphous high entropy oxide protective layer according to claim 1, characterized in that: The reaction chamber temperature of ALD deposition is 80-350°C; the reaction source temperature is selected according to the high entropy oxide material.

3. The method for preparing a zinc negative electrode having an amorphous high entropy oxide protective layer according to claim 1 or 2, characterized in that: The pulse sequence for each oxide reaction in ALD deposition is: metal pulse 0.1~5 s-nitrogen or argon cleaning pulse 2~10 s-water pulse or plasma oxygen 0.1~25 s-nitrogen or argon cleaning pulse 2~10 s.

4. The method for preparing a zinc negative electrode having an amorphous high entropy oxide protective layer according to claim 1 or 2, characterized in that: The multi-component amorphous high entropy oxide is a quaternary or quinary amorphous high entropy oxide.

5. The method for preparing a zinc negative electrode having an amorphous high entropy oxide protective layer according to claim 4, characterized in that: The metal elements contained in the high entropy oxide are four or five of Ti, Y, Zr, Al, Sn, Hf, Zn, Cu, In or Ce.

6. The method for preparing a zinc negative electrode having an amorphous high entropy oxide protective layer according to claim 3, characterized in that: The number of sub-cycles for each metal source to generate oxides is 1-10, and the number of super-cycles for growing multi-component high-entropy oxides is 1-50.

7. The method for preparing a zinc negative electrode having an amorphous high entropy oxide protective layer according to claim 1, characterized in that: The thickness of the high entropy oxide protective layer is 1-25 nm.

8. A zinc negative electrode having an amorphous high entropy oxide protective layer prepared by the method according to any one of claims 1 to 7, characterized in that: The amorphous high entropy oxide is a quaternary or quinary amorphous high entropy oxide, in which a cocktail effect is produced by mixing zinc-philic elements and corrosion-resistant elements, and the oxide has abundant zinc-philic sites.

9. The use of the zinc negative electrode with an amorphous high entropy oxide protective layer as claimed in claim 8, characterized in that: The zinc negative electrode is used for soft-pack batteries, square batteries, cylindrical batteries, battery packs or battery packs.

10. The use of the zinc negative electrode with an amorphous high entropy oxide protective layer according to claim 9, characterized in that: The battery group is a parallel combination, a series combination or a series-parallel combination of zinc metal batteries; the battery pack is composed of zinc metal batteries or zinc metal battery groups.

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