Engineering Na 3 V 2 (PO 4 ) 3 Cathodes via High-Entropy Substitution for Enhanced Pseudocapacitive Sodium Storage and Extended Cycle Life

作者：Xiangyue Liao, S. Yi, Min Xie, Xiaoying Li, Binshan Lin, Yu‐Fan Chen, Yangjie Li, Xuemei He, Qiaoji Zheng, Kwok Ho Lam, Dunmin Lin · 发表于：ACS Sustainable Chemistry & Engineering · 年份：2025 · DOI：10.1021/acssuschemeng.5c08014 · 被引用次数：7 · 研究领域：Advancements in Battery Materials、Supercapacitor Materials and Fabrication、Advanced Battery Materials and Technologies

High Resolution Image Download MS PowerPoint Slide Na 3 V 2 (PO 4 ) 3 (NVP) is regarded as a promising cathode for sodium-ion batteries (SIBs) owing to its high operating voltage and robust NASICON-type framework. However, its practical application is hindered by poor rate capability and limited long-term cycling stability. In this work, a high-entropy substituted cathode, Na 3 V 1.75 (Ca, Zr, Al, Mn, Mg) 0.25 (PO 4 ) 3 (denoted as HE-NVP), is successfully synthesized via a conventional solid-state method. The introduction of multiple aliovalent cations leads to local structural regulation, where elongation of Na(1)–O bonds and contraction of Na(2)–O bonds enhance structural stability and facilitate fast Na + migration. Simultaneously, the V 4+ /V 5+ redox couple is activated at ∼4.0 V, significantly boosting energy density and cycling stability. High-entropy substitution also promotes pseudocapacitive behavior through the modulation of the local chemical environment and vanadium redox chemistry. As a result, HE-NVP delivers excellent rate performance with a high specific capacity of 93.2 mAh g –1 at 50 C and outstanding long-term durability, retaining 81.8% of its initial capacity after 2,000 cycles at 20 C. Even under harsh conditions of 50 C, it maintains 78% capacity retention after 4,000 cycles, with an ultralow capacity decay rate of 0.006% per cycle after 6,000 cycles. Ex-situ XRD analysis confirms a single-phase solid-solution reaction mechanism with a minimal volume ...