Ultrafast Preparation of High‐Entropy NASICON Cathode Enables Stabilized Multielectron Redox and Wide‐Temperature (−50–60 °C) Workability in Sodium‐Ion Batteries

• Published in: Advanced materials (Weinheim) Vol. 37; no. 9; pp. e2418219 - n/a
• Main Authors: Du, Miao, Li, Kai, Yu, Ning, Hao, Ze‐Lin, Guo, Jin‐Zhi, Liang, Hao‐Jie, Gu, Zhen‐Yi, Zhang, Xiao‐Hua, Zhang, Kai‐Yang, Liu, Yan, Yang, Jia‐Lin, Liu, Yi‐Tong, Wu, Xing‐Long
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 01.03.2025
• Subjects: Batteries; Cathodes; Density functional theory; Electrode materials; Entropy; multielectron redox; NASICON cathode; Phase separation; Phase transitions; Reaction kinetics; Redox reactions; Sodium; Sodium-ion batteries; Solid solutions; ultrafast preparation; wide‐temperature workability; Workability; wide‐temperature workability; ultrafast preparation; NASICON cathode; sodium‐ion batteries; multielectron redox
• ISSN: 0935-9648; 1521-4095; 1521-4095
• DOI: 10.1002/adma.202418219

Avoiding severe structural distortion, irreversible phase transition, and realizing the stabilized multielectron redox are vital for promoting the development of high‐performance NASICON‐type cathode materials for sodium‐ion batteries (SIBs). Herein, a high‐entropy Na3.45V0.4Fe0.4Ti0.4Mn0.45Cr0.35(PO4)3 (HE‐Na3.45TMP) cathode material is prepared by ultrafast high‐temperature shock, which inhibits the possibility of phase separation and achieves reversible and stable multielectron transfer of 2.4/2.8 e− at voltage range of 2.0–4.45/1.5–4.45 V versus Na+/Na (the capacity of 137.2/162.0 mAh g−1). The galvanostatic charge/discharge and in‐situ X‐ray diffraction tests indicate the sequential redox reactions and approximate solid solution phase transition behavior of HE‐Na3.45TMP. Density functional theory calculations analyze the migration pathways and energy barriers, further confirming the superior reaction kinetics of HE‐Na3.45TMP. Accordingly, the HE‐Na3.45TMP exhibits outstanding wide temperature applicability and can operate stably in the temperature range of −50–60 °C, accompanied by a capacity retention of 92.8% after 400 cycles at −40 °C and a capacity of 73.7 mAh g−1 even at −50 °C. The assembled hard carbon//HE‐Na3.45TMP full‐cell offers an energy density of ≈301 Wh kg−1 based on total cathode and anode active mass, verifying the application feasibility of HE‐Na3.45TMP. This work provides an innovative and ultrafast pathway to rationally fabricate high‐performance cathodes for SIBs. The high‐entropy Na3.45V0.4Fe0.4Ti0.4Mn0.45Cr0.35(PO4)3 cathode material prepared by ultrafast high temperature shock inhibits the possibility of phase separation and achieves the reversible and stable multielectron transfer, fabulous cycling stability and excellent wide‐temperature range operation from −50 to 60 °C. The ultrafast sintering strategy provides a broad platform for the development of polyanionic materials for long‐lifespan and all‐climate sodium‐ion batteries.