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

Abstract

The application discloses a zinc negative electrode with an amorphous high-entropy oxide protective layer and a preparation method and application thereof, and belongs to the technical field of negative electrodes of aqueous zinc ion batteries. The application uses an ALD technology to prepare a zinc ion battery zinc negative electrode material with an amorphous high-entropy oxide protective layer with long cycle life. The ALD modified high-entropy oxide protective layer inhibits zinc dendrites and by-products on the surface of the zinc negative electrode. The high-entropy oxide electrode has rich zincophilic sites due to the mixing effect of various elements, promotes uniform zinc deposition, and the high-entropy oxide modified electrode enhances the migration kinetics of zinc ions, promotes the desolvation process of the zinc ions, reduces the zinc deposition energy barrier, and achieves excellent and stable zinc negative electrode electrochemical performance.

Description

Technical Field

[0001] This invention belongs to the field of aqueous zinc-ion battery anode technology, specifically relating to a zinc anode with an amorphous high-entropy oxide protective layer, its preparation method, and its application. Background Technology

[0002] Aqueous zinc-ion batteries (ZIBs) have attracted widespread attention in the field of future large-scale energy storage due to their high theoretical capacity (820 mAh / g and 5855 mAh / cm³). 3 Zinc anodes offer advantages such as low reduction potential (-0.76 V), high safety, and low cost. However, uncontrollable zinc dendrite deposition during cycling severely impacts their cycle life. To address this issue, an effective method is to construct an artificial protective coating on the zinc anode surface. Atomic layer deposition (ALD) technology, with its excellent three-dimensional conformal properties and simple, precise thin-film control, holds promise for forming uniform, ultra-thin coatings on zinc anodes. For example, patent application No. 202410142287.5, entitled "A Zinc Metal Anode for Aqueous Zinc-Ion Batteries and Its Application Thereof," discloses the use of atomic layer deposition (ALD) to construct a single-layer alumina protective layer on the surface of a zinc metal anode. This, to some extent, suppresses the formation of zinc dendrites. It primarily utilizes the atomic layer deposition (ALD) process to prepare traditional single-metal oxide coating materials (Al2O3). However, single, binary, or ternary oxides are often insufficient 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 attracted increasing attention. However, the high-temperature conditions required for the preparation of traditional high-entropy oxides hinder their direct application on zinc metal surfaces. In 2011, Academician Wang Weihua's research group at the Chinese Academy of Sciences first proposed the concept of high-entropy amorphous alloys, which subsequently sparked a surge of interest in amorphous high-entropy materials across different research fields. However, there are currently no reports of using amorphous high-entropy oxides prepared by ALD (Alternating Layer Deposition) as zinc anode materials. Summary of the Invention

[0004] This invention provides a zinc anode with an amorphous high-entropy oxide protective layer, its preparation method, and its application. The zinc anode with a long cycle life and an amorphous high-entropy oxide protective layer is prepared using ALD technology. The ALD-modified high-entropy oxide protective layer suppresses zinc dendrites and by-products on the surface of the zinc anode.

[0005] To achieve the above objectives, the present invention adopts the following technical solution:

[0006] A method for preparing a zinc anode with an amorphous high-entropy oxide protective layer includes the following steps:

[0007] (1) Preparation of zinc negative electrode: Zinc foil is processed for later use;

[0008] (2) ALD deposition of high-entropy protective layer: A 1~25 nm high-entropy protective layer is deposited on the zinc anode treated in step (1) to obtain a zinc anode with an amorphous high-entropy oxide protective layer.

[0009] In the steps described above, the parameters for ALD deposition in step (2) are set as follows: reaction chamber temperature: 80-350℃; reaction source: selected according to the high-entropy oxide material; the reaction pulse sequence for 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 number of subcycles for each metal source reaction to generate oxides is 1-10, and the number of supercycles for growing quaternary or pentagonal high-entropy oxides is 1-50.

[0010] The high-entropy protective layer is a multi-element amorphous high-entropy oxide material, including quaternary or pentagonal high-entropy oxides, and the metal elements contained therein are four or five of Ti, Y, Zr, Al, Sn, Hf, Zn, Cu, In or Ce.

[0011] The zinc anode prepared above can be used in pouch cells, prismatic cells, and cylindrical cells; it can also be used in battery packs, which can be parallel, series, or series-parallel combinations of zinc metal batteries; or it can be used in battery packs, which are composed of zinc metal batteries or zinc metal battery packs.

[0012] Beneficial effects: This invention provides a zinc anode with an amorphous high-entropy oxide protective layer, its preparation method and application. A zinc anode with a long cycle life and an amorphous high-entropy oxide protective layer is prepared using ALD technology. This invention is aimed at the field of zinc-ion battery materials and nanotechnology, and develops a novel type of zinc anode modified with amorphous high-entropy oxide. The obtained zinc anode has the following advantages: (1) Due to the cocktail effect generated by the mixing of various zinc-loving elements (Ti, Sn, Zn, In and Ce) and various corrosion-resistant elements (Y, Zr, Al, Hf and Cu), the high-entropy oxide electrode has abundant zinc-loving sites, which promotes uniform zinc deposition and inhibits zinc dendrites and by-products on the surface of the zinc anode; (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 by-products; (4) The high-entropy oxide can significantly improve the coulombic efficiency of zinc-ion batteries and greatly improve the cycle stability of zinc anodes. Therefore, the amorphous high-entropy oxide protective layer can suppress zinc dendrites and by-products on the zinc anode surface, effectively improving the cycle life of the electrode material. Attached Figure Description

[0013] Figure 1 This is a schematic diagram illustrating the modification of the zinc anode material for zinc-ion batteries with an amorphous high-entropy oxide protective layer according to the present invention.

[0014] Figure 2 (a) is a pentagonal high-entropy TiYZrAlSnO in an embodiment of the present invention. x (a) SEM image of zinc metal anode modified with TYZAS after 50 constant current cycles, and (b) SEM image of bare zinc metal anode after 50 constant current cycles.

[0015] Figure 3 (a) is a cycle data diagram of zinc-zinc symmetric cells of zinc metal anode modified with TYZAS in the embodiments of the present invention; (b) is a cycle data diagram of zinc-zinc symmetric cells of zinc metal anode modified with TiO2; (c) is a cycle data diagram of zinc-zinc symmetric cells of zinc metal anode modified with Y2O3; (d) is a cycle data diagram of zinc-zinc symmetric cells of zinc metal anode modified with ZrO2; (e) is a cycle data diagram of zinc-zinc symmetric cells of zinc metal anode modified with Al2O3; and (f) is a cycle data diagram of zinc-zinc symmetric cells of zinc metal anode modified with SnO2.

[0016] Figure 4 The quaternary high-entropy TiYAlSnO in this embodiment of the invention x Zinc-zinc symmetric cell cycle data of zinc metal anode modified with (abbreviated as TYAS);

[0017] Figure 5Ternary mesoentropy TiZrSnO x Zinc-zinc symmetric cell cycle data of zinc metal anode modified with TZS (abbreviated as TZS). Detailed Implementation

[0018] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments: Example 1

[0019] like Figure 1 As shown, a method for preparing a zinc anode material for a zinc-ion battery with an amorphous high-entropy oxide protective layer includes the following steps:

[0020] (1) Clean the zinc foil in anhydrous ethanol and deionized water by ultrasonic cleaning for 5 min in sequence, and then dry the water stains on the surface of the zinc foil with a nitrogen gun.

[0021] (2) A 10-nanometer-thick pentagonal high-entropy TiYZrAlSnO was deposited on the zinc anode treated in step (1) using ALD. x A high-entropy oxide modified zinc metal anode was obtained by using a TYZAS (Taiwanese Oxide-Based Alternating Layer) protective layer. The parameters for ALD deposition of TYZAS were as follows: reaction chamber temperature: 300℃; reaction source: titanium tetrachloride, yttrium dimethyl acetone, tetradimethylaminozirconium, trimethylaluminum, and tin tetrachloride; source temperature: titanium tetrachloride, trimethylaluminum, and tin tetrachloride at room temperature; yttrium dimethyl acetone at 180℃; tetradimethylaminozirconium at 115℃; 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 purging pulse 6 s, SnCl4 pulse 0.3 s - nitrogen purging pulse 6 s - water pulse 0.1 s - nitrogen purging pulse 4 s; the subcycle ratio of oxides generated by each metal source reaction is set to 1:1:1:1:1, and the supercycle number for growing pentagonal high-entropy oxides is 30.

[0022] To investigate practical effects, a zinc metal anode modified with a TYZAS protective layer and a 2 M zinc sulfate electrolyte were assembled into a zinc metal symmetric battery. Several comparative examples were conducted to study the enhancing effect of the TYZAS protective layer on the electrochemical performance of the zinc metal anode. Commercial zinc foil (100 μm thick) was ultrasonically cleaned in anhydrous ethanol and deionized water for 5 min, then dried with a nitrogen gun, and cut into 12 mm diameter circular electrode sheets, which were directly used as zinc anodes. Additionally, 10 nm thick single-unit metal oxide coatings (TiO2, Y2O3, ZrO2, Al2O3, and SnO2) were deposited directly on the zinc anode using ALD.

[0023] The SEM image of the zinc metal anode modified with the TYZAS protective layer prepared in this embodiment after 50 constant current cycles is shown below. Figure 2 As shown in (a), the zinc metal anode modified with the TYZAS protective layer maintained a smooth and flat surface after 50 constant current cycles, while the bare zinc metal anode showed a large number of uneven moss-like byproducts on its surface after 50 constant current cycles. Figure 2 (b) This shows that the TYZAS protective layer prepared by ALD in this embodiment can effectively suppress the formation of zinc dendrites on the surface of zinc metal anode.

[0024] When assembling a zinc / zinc symmetric cell using the zinc anode modified with the TYZAS protective layer obtained in this embodiment, at a current density of 5 mA cm⁻¹ -2 The capacity is 1 mAh cm -2 Under these conditions, the battery can operate stably for 4000 hours, while the potential of a symmetrical battery with a bare zinc negative electrode increases sharply after 180 cycles. Figure 3 (a) The cycle life of zinc metal anodes protected by various pure metal oxide coatings (TiO2, Y2O3, ZrO2, Al2O3, and SnO2) is increased compared to that of bare zinc. Figure 3 (b), (c), (d), (e) and (f)), but significantly inferior to the high-entropy TYZAS protective layer, indicating that the high-entropy TYZAS protective layer can significantly improve the cycle performance of zinc-ion batteries and extend the service life of zinc metal anodes. Example 2

[0025] A method for preparing a zinc anode with an amorphous high-entropy oxide protective layer includes the following steps:

[0026] (1) Clean the zinc foil in anhydrous ethanol and deionized water by ultrasonic cleaning for 5 min in sequence, and then dry the water stains on the surface of the zinc foil with a nitrogen gun.

[0027] (2) A 10-nanometer-thick quaternary high-entropy TiYAlSnO was deposited on the zinc anode treated in step (1) using ALD. xA TYAS (Type Atom Removal) protective layer was used to obtain a zinc metal anode modified with high entropy oxide. Parameters for ALD deposition of TYAS: Reaction chamber temperature: 300℃; Reaction source: Titanium tetrachloride, yttrium dimethyl acetone, trimethylaluminum, and tin tetrachloride; Source temperature: Titanium tetrachloride, trimethylaluminum, and tin tetrachloride at room temperature; yttrium dimethyl acetone at 180℃; 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 subcycle ratio of oxides generated by the reactions of each metal source was set to 1:1:1:1, and the supercycle number for growing quaternary high-entropy oxides was 42.

[0028] To investigate practical effects, a zinc metal anode modified with a TYAS protective layer and a 2 M zinc sulfate electrolyte were assembled into a zinc metal symmetric battery. To study the enhancing effect of the TYAS protective layer on the electrochemical performance of the zinc metal anode, a ternary medium-entropy TiZrSnO4 was prepared. x A TZS (Temporal-Entropy Saturated Gas) protective layer was used as a comparative example. A 10 nm thick medium-entropy TZS protective layer was deposited on the zinc anode using ALD. The subcycle ratio of oxides generated by the reactions of each metal source was set to 4:8:3, and the supercycle number for growing the ternary medium-entropy oxide was 8.

[0029] When assembling a zinc / zinc symmetric cell using the zinc anode modified with the TYAS protective layer obtained in this embodiment, at a current density of 5 mA cm⁻¹ -2 The capacity is 1 mAh cm -2 Under these conditions, the battery can operate stably for 2500 hours ( Figure 4 ), far exceeding the cycle life of zinc metal anodes modified with TZS protective layer ( Figure 5 This indicates that the TYAS protective layer can significantly improve the cycle performance of zinc-ion batteries and extend the service life of the zinc metal anode. Example 3

[0030] A method for preparing a zinc anode with an amorphous high-entropy oxide protective layer includes the following steps:

[0031] (1) Clean the zinc foil in anhydrous ethanol and deionized water by ultrasonic cleaning for 5 min in sequence, and then dry the water stains on the surface of the zinc foil with a nitrogen gun.

[0032] (2) A 25 nm thick pentagonal high-entropy TiHfZrAlSnO was deposited on the zinc anode treated in step (1) using ALD. xA THZAS (Thin-Oxide-Semiconductor) protective layer is used to obtain a zinc metal anode modified with high-entropy oxides. Parameters for ALD deposition of THZAS: Reaction chamber temperature: 350℃; Reaction source: Titanium tetrachloride, tetra(methylethylamino)hafnium, tetra(dimethylamino)zirconium, trimethylaluminum, and tin tetrachloride; Source temperature: Titanium tetrachloride, trimethylaluminum, and tin tetrachloride at room temperature; tetra(methylethylamino)hafnium at 155℃; tetra(dimethylamino)zirconium at 115℃; Pulse and cleaning time: TiCl4 pulse 0.1 s - nitrogen cleaning pulse 4 s - water pulse 0.1 s - nitrogen cleaning pulse 4 s; TMAH 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. The nitrogen purge pulse duration is 6 s, the water purge pulse duration is 0.1 s, and the nitrogen purge pulse duration is 4 s. The subcycle ratio of oxides generated by the reactions of each metal source is set to 1:2:1:2:1, and the supercycle number for growing the pentagonal high-entropy oxide is 40. Example 4

[0033] A method for preparing a zinc anode with an amorphous high-entropy oxide protective layer includes the following steps:

[0034] (1) Clean the zinc foil in anhydrous ethanol and deionized water by ultrasonic cleaning for 5 min in sequence, and then dry the water stains on the surface of the zinc foil with a nitrogen gun.

[0035] (2) A 1-nanometer thick pentagonal high-entropy TiZnZrAlSnO is deposited on the zinc anode treated in step (1) using ALD. xA protective layer (abbreviated as TZZAS) is used to obtain a zinc metal anode modified with high entropy oxide. Parameters for ALD deposition of TZZAS: Reaction chamber temperature: 200℃; Reaction source: Titanium tetrachloride, diethylzinc, tetradimethylaminozirconium, trimethylaluminum, and tin tetrachloride; Source temperature: Titanium tetrachloride, diethylzinc, trimethylaluminum, and tin tetrachloride at room temperature, tetradimethylaminozirconium at 115℃; 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 4 s. The subcycle ratio of oxides generated by the reactions of each metal source is set to 3:1:2:2:3, and the supercycle number for growing the pentagonal high-entropy oxide is 1. Example 5

[0036] A method for preparing a zinc anode with an amorphous high-entropy oxide protective layer includes the following steps:

[0037] (1) Clean the zinc foil in anhydrous ethanol and deionized water by ultrasonic cleaning for 5 min in sequence, and then dry the water stains on the surface of the zinc foil with a nitrogen gun.

[0038] (2) A 15-nanometer-thick quaternary high-entropy TiHfAlSnO was deposited on the zinc anode treated in step (1) using ALD. x A high-entropy oxide modified zinc metal anode was obtained by using a THAS (Thin-Alternating Layer) protective layer. The parameters for ALD deposition of THAS were as follows: reaction chamber temperature: 120℃; reaction source: titanium tetrachloride, tetra(dimethylamino)hafnium, trimethylaluminum, and tin tetrachloride; source temperature: titanium tetrachloride, trimethylaluminum, and tin tetrachloride at room temperature, tetra(dimethylamino)hafnium at 80℃; pulse and cleaning time: TiCl4 pulse 0.1 s - nitrogen cleaning pulse 4 s - water pulse 0.1 s - nitrogen cleaning pulse 4 s, TMAH 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 subcycle ratio of oxides generated by the reactions of various metal sources was set to 1:2:1:2, and the supercycle number for growing quaternary high-entropy oxides was 28. Example 6

[0039] A method for preparing a zinc anode with an amorphous high-entropy oxide protective layer includes the following steps:

[0040] (1) Clean the zinc foil in anhydrous ethanol and deionized water by ultrasonic cleaning for 5 min in sequence, and then dry the water stains on the surface of the zinc foil with a nitrogen gun.

[0041] (2) A 10-nanometer-thick quaternary high-entropy TiZnAlSnO is deposited on the zinc anode treated in step (1) using ALD. x A high-entropy oxide modified zinc metal anode was obtained by using a TZAS (Temperature-Zinc Assay) protective layer. The parameters for ALD deposition of TZAS were as follows: reaction chamber temperature: 80℃; reaction source: titanium tetrachloride, diethylzinc, trimethylaluminum, and tin tetrachloride; source temperature: titanium tetrachloride, diethylzinc, trimethylaluminum, and tin tetrachloride were 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 subcycle ratio of oxides generated by the reactions of various metal sources was set to 5:1:1:1, and the supercycle number for growing quaternary high-entropy oxides was 20.

[0042] 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, modifications can be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for producing a zinc anode having an amorphous high-entropy oxide protective layer, characterized by, The method comprises the following steps: (1) Preparation of zinc negative electrode: treating zinc foil for standby; (2) ALD deposition of high-entropy protective layer: depositing a multi-element amorphous high-entropy protective layer on the zinc foil treated in step (1) by using ALD technology to obtain a zinc negative electrode with an amorphous high-entropy oxide protective layer; the amorphous high-entropy oxide is a quaternary or quinary amorphous high-entropy oxide; the metal elements contained in the amorphous high-entropy oxide are four or five of Ti, Y, Zr, Al, Sn, Hf, Zn, Cu, In or Ce; the cocktail effect is produced by mixing the zincophilic elements and the corrosion-resistant elements in the amorphous high-entropy oxide, the zincophilic elements are selected from at least one of Ti, Sn, Zn, In and Ce; the corrosion-resistant elements are selected from at least one of Y, Zr, Al, Hf and Cu.

2. The method of claim 1, wherein the method is characterized by: The reaction cavity temperature for ALD deposition is 80-350℃; the reaction source temperature is selected according to the high-entropy oxide material.

3. The method of producing a zinc negative electrode with an amorphous high-entropy oxide protective layer according to claim 1 or 2, characterized in that, The reaction pulse sequence of each oxide 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 of claim 3, wherein the method further comprises: The sub-cycle number of each metal source reaction to generate oxide is 1-10, and the supercycle number of growing multi-element high-entropy oxide is 1-50.

5. The method of claim 1, wherein the method further comprises: The thickness of the high-entropy oxide protective layer is 1-25 nm.

6. The zinc anode with an amorphous high-entropy oxide protective layer prepared by the method of any one of claims 1-5, characterized in that, The amorphous high-entropy oxide is a quaternary or quinary amorphous high-entropy oxide, the cocktail effect is produced by mixing the zincophilic elements and the corrosion-resistant elements in the amorphous high-entropy oxide, and there are abundant zincophilic sites.

7. Use of the zinc anode with an amorphous high-entropy oxide protective layer according to claim 6, characterized in that, The zinc negative electrode is used for soft-packaged batteries, square batteries, cylindrical batteries, battery packs or battery packages.

8. Use of a zinc anode with a protective layer of amorphous high-entropy oxide according to claim 7, characterized in that, The battery pack is a parallel combination, series combination or series-parallel combination of zinc metal batteries; the battery package is composed of zinc metal batteries or zinc metal battery packs.

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