Vanadium-Based Cathodes for Aqueous Zinc-Ion Batteries: Mechanisms, Challenges, and Strategies

Abstract

Zinc-ion batteries (ZIBs) are highly promising for large-scale energy storage because of their safety, high energy/power density, low cost, and eco-friendliness. Vanadium-based compounds are attractive cathodes because of their versatile structures and multielectron redox processes (+5 to +3), leading to high capacity. Layered structures or 3-dimensional open tunnel frameworks allow easy movement of zinc-ions without breaking the structure apart, offering superior rate-performance. However, challenges such as dissolution and phase transformation hinder the long-term stability of vanadium-based cathodes in ZIBs. Although significant research has been dedicated to understanding the mechanisms and developing high-performance vanadium-based cathodes, uncertainties still exist regarding the critical mechanisms of energy storage and dissolution, the actual active phase and the specific optimization strategy. For example, it is unclear whether materials such as α-V₂O₅, VO₂, and V₂O₃ serve as the active phase or undergo phase transformations during cycling. Additionally, the root cause of V-dissolution and the role of byproducts such as Zn₃(OH)₂V₂O₇·2H₂O in ZIBs are debated.

In this account, we aim to outline a clear and comprehensive roadmap for V-based cathodes in ZIBs. On the basis of our studies, we analyzed intrinsic crystal structures and their correlation with performance to guide the design of V-based materials with high-capacity and high-stability for ZIBs. Then, we revealed the underlying mechanisms of energy storage and instability, enabling more effective design and optimization of V-based cathodes. After identifying the key challenges, we proposed effective design principles to achieve high cycling performance of V-based cathodes and outlined future development directions toward their practical application. Vanadium-based compounds include [VO₄] tetrahedrons, [VO₅] square pyramids, and [VO₆] octahedra, which are connected through a cocorner, coedge and coplane. The [VO₄] tetrahedron is inactive, and the [VO₅] square pyramid is unstable in aqueous solutions because water attacks the exposed vanadium, whereas stable [VO₆] octahedra are desirable because of their ability to reduce from +5 to +3 with minimal structural distortion. Therefore, high-performance vanadium-based oxides in ZIBs should maintain intact [VO₆] octahedra while avoiding [VO₄] tetrahedra or [VO₅] square pyramids. The energy storage mechanism involves H₂O/H⁺/Zn²⁺ coinsertion. The existence of interlayer water in V-based cathodes significantly improves the rate and cycling performance by expanding galleries, screening Zn²⁺ electrostatically via solvation, reducing ion diffusion energy barriers, and increasing layer flexibility. The insertion of H⁺/Zn²⁺ and the instability of V-based cathodes lead to the formation of byproducts such as basic zinc salts (i.e., Zn₄SO₄(OH)₆·nH₂O) and dead vanadium (Zn₃(OH)₂V₂O₇·2H₂O), whose reversibility strongly affects long-term stability. To increase the cycling stability of vanadium-based cathodes, strategies such as electrolyte modulation and coating have been proposed to decrease water attack on the surface of V-oxides, thereby affecting the formation of byproducts. Additionally, in situ electrochemical transformation, ion preintercalation, and ion exchange were explored to prepare intrinsically stable V-based cathodes with enhanced performance. Furthermore, future research should focus on revealing atomic-scale mechanisms through advanced in situ characterization and theoretical calculations, enhancing rate-performance by facilitating ion/electron diffusion, promoting cycling stability by developing highly stable cathodes and refining interface engineering, and scaling up vanadium-based cathodes for practical ZIB applications.