Leveraging High-Entropy Substitution to Achieve V4+/V5+ Redox Couple and Superior Na+ Storage in Na3V2(PO4)3-based Cathodes for Sodium-Ion Battery

IF 18.9 1区材料科学 Q1 CHEMISTRY, PHYSICAL

Energy Storage Materials Pub Date : 2025-03-09 DOI:10.1016/j.ensm.2025.104166

Xiangyue Liao, Xu Wu, Min Xie, Xiaoying Li, Yangjie Li, Zhaodan Fu, Gehong Su, Cuiqin Fang, Heng Zhang, Qiaoji Zheng, Jingxin Zhao, Bingang Xu, Dunmin Lin

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引用次数: 0

Abstract

Sodium super ionic conductor-structured Na₃V₂(PO₄)₃ (NVP) has garnered considerable attention owing to its excellent operational voltage and 3D framework, but the limited ionic conductivity and substantial volume fluctuation impede its practical application. In this work, high-performance Na₃V_1.45(Fe,Al,Cr,Mn,Ni)_0.5Mo_0.02Zr_0.03(PO₄)₃ (HE-NVP) is designed by the partial substitution of V³⁺ by seven metal ions in the NVP using high-entropy substitution. Due to the profound effect of high-entropy substitution, the M-O bond length in the HE-NVP is finely tuned, effectively reducing the distortion of MO6 octahedron. Simultaneously, high entropy substitution suppresses adverse phase transitions in the high voltage range above 4.0 V (vs Na⁺/Na) and enhances structural stability. The activated V^4+/5+ elevates energy density to an impressive 394.2 Wh kg^-1 at 0.5 C within the voltage range of 2.2-4.3 V, while the specific capacity remains 80.2 mAh g^-1 after 800 cycles at 5 C, exhibiting capacity attenuation per cycle at only 0.025 %. Ex-situ XRD reveals that the sodium storage process of HE-NVP undergoes a single solid solution phase reaction with a small volume change rate of 0.91 %. This study offers a promising avenue for the development of advanced polyanionic phosphate cathodes.

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来源期刊

Energy Storage Materials Materials Science-General Materials Science

CiteScore

33.00

自引率

5.90%

发文量

652

审稿时长

27 days

期刊介绍： Energy Storage Materials is a global interdisciplinary journal dedicated to sharing scientific and technological advancements in materials and devices for advanced energy storage and related energy conversion, such as in metal-O2 batteries. The journal features comprehensive research articles, including full papers and short communications, as well as authoritative feature articles and reviews by leading experts in the field. Energy Storage Materials covers a wide range of topics, including the synthesis, fabrication, structure, properties, performance, and technological applications of energy storage materials. Additionally, the journal explores strategies, policies, and developments in the field of energy storage materials and devices for sustainable energy. Published papers are selected based on their scientific and technological significance, their ability to provide valuable new knowledge, and their relevance to the international research community.