Entropy Driving “Quasi‐Zero Strain” Stepwise Multicationic Redox Chemistry Toward a High‐Performance NASICON‐Cathode for Na‐Ion Batteries

作者：Can Jin, Yao Wang, Xudong Zhao, Junteng Jin, Zhenyou Li, Xuanhui Qu, Lifang Jiao, Yongchang Liu · 发表于：Advanced Functional Materials · 年份：2025 · DOI：10.1002/adfm.202422101 · 被引用次数：31 · 研究领域：Advancements in Battery Materials、Advanced battery technologies research、Advanced Battery Technologies Research

Abstract Achieving multicationic redox reactions with low lattice strain accumulation upon repeated sodiation/desodiation processes is pivotal for developing high‐energy and long‐durability Na superionic conductor (NASICON)‐type cathodes but still a formidable task. Herein, a novel NASICON‐structured high‐entropy Na 3.4 VMn 0.2 Fe 0.2 Al 0.3 Cr 0.3 (PO 4 ) 3 (HE‐NVMFACP) cathode is delicately devised, where the entropy‐driving stepwise Fe 2+ /Fe 3+ , V 3+ /V 4+ /V 5+ , Mn 2+ /Mn 3+ /Mn 4+ , and Cr 3+ /Cr 4+ redox couples not only trigger the multielectron transfer chemistry, but also alleviate the lattice strain accumulation. Consequently, the HE‐NVMFACP cathode exhibits a high reversible capacity of 151.3 mAh g −1 with an admirable energy density of 520.5 Wh kg −1 , and an impressive “quasi‐zero strain” behavior (1.33% cell volume change) during the whole charge‐discharge process. Meanwhile, an excellent rate capability of 90.4 mAh g −1 at 50 C and an ultralong cycling life of 91.9% capacity retention after 5000 cycles are demonstrated. Advanced in situ/ex situ techniques reveal the complete solid‐solution behavior and highly reversible stepwise multicationic redox mechanism of HE‐NVMFACP upon Na + uptake/release, and the rapid electrode process kinetics of HE‐NVMFACP are confirmed by systematic electrochemical measurements and theoretical computations. Furthermore, the HE‐NVMFACP||hard carbon Na‐ion full batteries are assembled in both coin and pouch configurations, manifes...