Cointercalation of Polyaniline and Alkali-Earth Cations into V₂O₅ to Boost Aqueous Zinc-Ion Storage Performance with Superior Cycling Stability

Abstract

Aqueous zinc-ion batteries (AZIBs) are considered as an attractive alternative to lithium-ion batteries. Although the vanadium pentoxide (V 2 O 5 ) cathode exhibits high theoretical capacity of 589 mA h g −1 for zinc-storage, it suffers from capacity decay and sluggish Zn 2+ diffusion kinetics due to the strong electrostatic interactions with Zn 2+ , slight dissolution in aqueous electrolytes, and low electronic conductivity. Herein, the polyaniline and alkali-earth cation (Mg 2+ , Ca 2+ ) cointercalated V 2 O 5 composites (PVO-Mg, PVO-Ca) are fabricated to boost the zinc ion storage performance of vanadium oxide cathodes. PVO-Mg exhibits an enlarged interlayer distance of 14.15 Å and a tremelliform nanoarchitecture composed of nanosheets. The intercalated polyaniline and alkali-earth cations not only expand the Zn 2+ diffusion channels but also form a pillar net which can improve the structural stability and electronic conductivity of the layered structure, contributing to superior electrochemical kinetics, interfacial kinetics, and Zn 2+ diffusion kinetics. Moreover, ex situ X-ray diffraction results of PVO-Mg show a nearly constant interlayer distance during the insertion and extraction of Zn 2+ , which indicates that polyaniline and Mg 2+ firmly support the layered framework and prevent the expansion and contraction of the interlayer distance. Ex situ X-ray photoelectron spectroscopy results of PVO-Mg reveal the highly reversible formations of Zn x (CF 3 SO 3 ) y (OH) 2x−y •nH 2 O on the electrode surface and Zn 2+ inserted PVO-Mg inside the electrode, as well as a H + and Zn 2+ insertion/extraction process during which the polyaniline serves as a H + reservoir and a capacity contributor. Consequently, the PVO-Mg electrode exhibits high capacity (387.0 mA h g −1 at 0.5 A g −1 ), ultrafast rate capability (199.3 mA h g −1 at 30 A g −1 ), improved cycling stability, and high reversibility and would be a promising cathode for high performance AZIBs.

Electrolyte Additive Strategies for Safe and High-Performance Aqueous Zinc-Ion Batteries: A Mini-Review

“…With the intensification of environmental pollution and the energy crisis, the development of sustainable energy storage systems has become a priority in energy conversion. − Recognized for high energy density and long cycle stability (250–400 Wh kg –1 ), lithium-ion batteries (LIBs) have played a crucial role in portable electronics and electric vehicles. − However, the scarcity of lithium resources and flammability of organic electrolytes hinder the specific applications of LIBs. − Therefore, it is significant to explore advanced energy storage systems to replace LIBs. Aqueous zinc-ion batteries (ZIBs), including a stable Zn metal anode, an electrolyte with high Zn 2+ ions transmission, and structurally adjustable cathode materials, have emerged as potent contenders for the forthcoming advanced energy storage system. − …”