CN-117174839-B - Zinc cathode material for water-based zinc ion battery and preparation method thereof

Abstract

The invention provides a zinc negative electrode material for a water-based zinc ion battery, which is Te@Zn negative electrode material prepared by loading an antimony layer material on a zinc layer material. The invention also provides a preparation method of the zinc anode material for the water-based zinc ion battery. The invention relates to a Te@Zn material with excellent stability, high conductivity and high cycle performance applied to a water-based zinc ion battery and a preparation method thereof, wherein the preparation of a zinc anode material with a nano flaky Te surface modification layer is realized by utilizing an electrochemical deposition method and high-temperature calcination.

Inventors

• HUANG FUQIANG
• BI HUI
• LIU NING

Assignees

• 中国科学院上海硅酸盐研究所

Dates

Publication Date

20260512

Application Date

20220525

Claims (10)

1. 1. A preparation method of a zinc negative electrode material for a water-based zinc ion battery is characterized in that the zinc negative electrode material is a Te@Zn negative electrode material formed by loading Te materials on a zinc electrode material, an electrochemical deposition method is adopted, zn is taken as a substrate, the Te materials are electrochemically deposited in electrolyte under certain voltage and temperature conditions, and the prepared Te@Zn materials are subjected to high-temperature treatment in an inert atmosphere, so that the Te@Zn negative electrode material is finally obtained.
2. 2. The method of claim 1, wherein the zinc electrode material is zinc flakes.
3. 3. The method of claim 1, wherein the zinc electrode material is zinc foil.
4. 4. The method of claim 1, wherein the zinc electrode material is porous zinc.
5. 5. The method of claim 1, wherein the Te material is a one-dimensional nanostructured material comprising nanowires, nanorods, nanotubes.
6. 6. The preparation method of claim 1, wherein the Te material is a nano-sheet structure material, the thickness of a sheet of the nano-sheet structure material is 3 nm-100 nm, and the diameter of the sheet is 20 nm-2 μm.
7. 7. The preparation method of claim 1, wherein the zinc anode material has a cycle life of 100-3000 circles under the test conditions of a current density of 0.2-10 mA/cm 2 and a capacity of 0.2-10 mAh/cm 2 .
8. 8. The preparation method of claim 1, wherein the electrolyte is an aqueous electrolyte prepared from TeO 2 、NaTeO 3 or a mixture thereof, the electrolyte concentration is 0.1-10 mg/ml, and the pH value of the electrolyte is 1-11.
9. 9. The preparation method according to claim 1, wherein the electrochemical deposition voltage is-1.1 to-0.8V, the deposition temperature is 30-95 ℃, and the deposition time is 30 s-300 min.
10. 10. The production method according to any one of claims 1 to 9, wherein the high temperature treatment is performed at 100 to 400 ℃ in a protective atmosphere of N 2 , ar or a mixed atmosphere thereof, the high temperature treatment time is 10 to 600 min, and the gas flow rate of the protective atmosphere is 50 to 500 sccm.

Description

Zinc cathode material for water-based zinc ion battery and preparation method thereof Technical Field The invention belongs to the technical field of zinc batteries, and particularly relates to a zinc anode material for a water-based zinc ion battery and a preparation method thereof. Background Electrochemical energy storage devices, such as rechargeable batteries, are critical to overcoming global energy challenges. Nonaqueous Lithium Ion Batteries (LIBs) are currently considered as a possible choice for future electric vehicles and power grid energy storage systems due to their high energy density and long cycle life, leading to the field of portable electronics and emerging electric/hybrid vehicles. However, the growing concern over limited lithium resources, high cost and safety issues has severely limited the development of further large scale applications. Sodium Ion Batteries (SIBs) and potassium ion batteries (KIBs) are a reasonable replacement for LIBs because these devices are based on relatively abundant and inexpensive sodium (potassium) elements and their similar chemistry to lithium, but their energy density is low, use highly toxic and flammable electrolytes, high operating costs, and serious safety issues. The drawbacks of these organic-based systems have prompted us to explore alternative battery chemistries that are low cost, high safety, and long cycle life. The water charging battery has the advantages of low cost, high operation safety, environmental protection and the like, and is a promising electrochemical energy storage battery. The current research efforts have focused on exploring ZIBs high-performance cathode materials, such as manganese-based materials, vanadium-based materials, prussian blue, and the like. Through a series of mechanism researches and various structural optimizations, the electrochemical performance, particularly the cycling stability, of the cathode is greatly improved, and the development of water ZIB is greatly promoted, so that the cathode has high feasibility in practical application. However, industrialization of zinc anodes is an immature technology, which prevents improvement of performance due to limited and insufficient knowledge of its mechanism. In most of the current studies on AZIB, zinc foil is used directly as a negative electrode, but its electrochemical behavior cannot meet the production requirements of industrially scalable devices. The zinc cathode has strong electrochemical activity when being exposed in an aqueous electrolyte, so that the battery inevitably suffers from serious problems of dendrite, hydrogen evolution, corrosion and the like in the charge-discharge cycle process. Chinese patent document CN114243019A discloses a zinc cathode material with double modification layers on the surface, and the problems of dendrite, hydrogen evolution, corrosion and the like of the cathode of the water-based zinc ion battery are solved by modifying the surface of zinc foil with the double modification layers of simple substance bismuth and bismuth oxide. However, the process for obtaining the dual modification layers of the simple substance bismuth and the bismuth oxide on the surface of the zinc foil is complex, and is not beneficial to large-scale production. Disclosure of Invention Aiming at the problems, the invention aims to provide a zinc anode material with excellent stability, high conductivity and high cycle performance, which is applied to a water-based zinc ion battery, and a preparation method thereof, so as to prepare the anode material which has simple and feasible process and can realize AZIBs stable long cycle performance of the zinc anode. In order to achieve the above purpose, the invention adopts the following technical scheme: In a first aspect, the invention provides a zinc anode material for an aqueous zinc ion battery, wherein the zinc anode material is Te@Zn anode material formed by loading Te materials on the zinc electrode material. Preferably, the zinc electrode material is zinc sheet, zinc foil or porous zinc. Preferably, the Te material is a one-dimensional nano-structure material, comprising nanowires, nanorods, nanotubes and nano-sheet structure materials, preferably nano-sheet structure materials, wherein the thickness of a sheet layer of the nano-sheet structure is 3 nm-100 nm, and the diameter of the sheet layer is 20 nm-2 mu m. Preferably, the cycle life of the zinc anode material is 100-3000 circles under the test conditions that the current density is 0.2-10 mA/cm 2 and the capacity is 0.2-10 mAh/cm 2. In a second aspect, the invention also provides a preparation method of the zinc anode material for the water-based zinc ion battery, which adopts an electrochemical deposition method, takes Zn as a substrate, and electrochemically deposits Te material in electrolyte under certain voltage and temperature conditions, and the prepared Te@Zn material is subjected to high temperature treatment in inert atmosphere, s