Unlocking Advanced Sodium Storage Performance: High-Entropy Modulates Crystallographic Sites with Reversible Multi-Electron Reaction

IF 18.9 1区材料科学 Q1 CHEMISTRY, PHYSICAL

Energy Storage Materials Pub Date : 2024-11-20 DOI:10.1016/j.ensm.2024.103920

Xiangyue Liao, Yangjie Li, Bin Xie, Min Xie, Xin Tan, Qiaoji Zheng, Lin Li, Xin-Xin Zhao, Zhen-Yi Gu, Sean C. Smith, Jingxin Zhao, Dunmin Lin, Xing-Long Wu

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Abstract

Poor migration dynamics and low energy density are the main challenges of Na₃V₂(PO₄)₃ as a cathode material for sodium ion batteries. Herein, a nanoscale polyhedron high-entropy cathode of Na₃V_1.47(Fe,Al,Ga,Mg,Mn)_0.5Mo_0.01Nb_0.02(PO₄)₃ is designed to modify the crystal structure and enhance the electrons transfer. Distributed nanoparticles improve the electrolyte interface, promoting rapid migration of Na⁺, while the abundant specific surface area offers extra sites for Na⁺ storage. High entropy and multi-metal synergistic effects increase the number of occupied Na(1) and Na(2) sites, maintaining multiple redox couples (V^3+/4+/5+ and Mn^2+/3+/4+) and obtaining a reversible 2.18-electron reaction. Consequently, the high-entropy cathode of Na₃V_1.47(Fe,Al,Ga,Mg,Mn)_0.5Mo_0.01Nb_0.02(PO₄)₃ delivers excellent specific capacity of 130.2 mAh g⁻¹ at 0.5 C, achieving high energy density of 448.3 Wh kg⁻¹, and exhibiting the capacity retention of 95% after 500 cycles at 5 C and 86.5% after 1000 cycles at 15 C, respectively. In situ XRD, ex situ XAS and DFT calculations reveal the influence of structural evolution, valence changes, and high-entropy effects on chemical kinetics. This study provides a guideline for designing advanced polyanionic phosphate cathode materials for sodium ion batteries.

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开启先进的钠存储性能：高熵通过可逆多电子反应调节晶体学位点

Na3V2(PO4)3作为钠离子电池阴极材料面临的主要挑战是迁移动力学差和能量密度低。本文设计了一种纳米级多面体高熵阴极 Na3V1.47(Fe,Al,Ga,Mg,Mn)0.5Mo0.01Nb0.02(PO4)3，以改变晶体结构并增强电子转移。分布式纳米粒子改善了电解质界面，促进了 Na+ 的快速迁移，而丰富的比表面积则为 Na+ 的储存提供了额外的场所。高熵和多金属协同效应增加了所占据的 Na(1) 和 Na(2) 位点的数量，维持了多个氧化还原偶（V3+/4+/5+ 和 Mn2+/3+/4+），并获得了可逆的 2.18 电子反应。因此，Na3V1.47(Fe,Al,Ga,Mg,Mn)0.5Mo0.01Nb0.02(PO4)3 的高熵阴极在 0.5 C 时的比容量为 130.2 mAh g-1，能量密度高达 448.3 Wh kg-1，在 5 C 下循环 500 次后的容量保持率为 95%，在 15 C 下循环 1000 次后的容量保持率为 86.5%。原位 XRD、原位 XAS 和 DFT 计算揭示了结构演化、价态变化和高熵效应对化学动力学的影响。这项研究为设计用于钠离子电池的先进聚阴离子磷酸盐阴极材料提供了指导。

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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.