The LiV₃O₈ Superlattice Cathode with Optimized Zinc Ion Insertion Chemistry for High Mass‐Loading Aqueous Zinc‐Ion Batteries

Abstract Resolving the sluggish transport kinetics of divalent Zn²⁺ in the cathode lattice and improving mass‐loading performance are crucial for advancing the zinc‐ion batteries (AZIBs) application. Herein, PEO‐LiV₃O₈ superlattice nanosheets (PEO‐LVO) with expanded interlayer spacing (1.16 nm) are fabricated to provide a high‐rate, stable lifetime, and large mass‐loading cathode. The steady in‐plane expansion without shrinkage after the first cycle, but reversible H⁺/Zn²⁺ co‐insertion in PEO‐LVO are demonstrated by operando synchrotron X‐ray diffraction and ex situ characterizations. Moreover, the large capacity of PEO‐LVO is traced back to the optimized Zn²⁺ insertion chemistry with increased Zn²⁺ storage ratio, which is facilitated by the interlayer PEO in lowering the Zn²⁺ diffusion barrier and increased number of active sites from additional interfaces, as anticipated by density functional theory. Due to the optimized ion insertion resulting in stalled interfacial byproducts and rapid kinetics, PEO‐LVO achieves excellent high mass‐loading performance (areal capacity up to 6.18 mAh cm⁻² for freestanding electrode with 24 mg cm⁻² mass‐loading and 2.8 mAh cm⁻² at 130 mA cm⁻² for conventional electrode with 27 mg cm⁻² mass‐loading). As a proof‐of‐concept, the flexible all‐solid‐state fiber‐shaped AZIBs with high mass‐loading woven into a fabric can power an electronic watch, highlighting the application potential of PEO‐LVO cathode.