Medium-entropy configuration enabling reversible P2-OP4 phase transition in layered oxides for high-rate sodium-ion batteries

IF 9.6 1区材料科学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY

Rare Metals Pub Date : 2025-02-14 DOI:10.1007/s12598-024-03196-5

Fei-Fei Hong, Xin Zhou, Hao Liu, Gui-Lin Feng, Xiao-Hong Liu, Heng Zhang, Wei-Feng Fan, Bin Zhang, Mei-Hua Zuo, Wang-Yan Xing, Ping Zhang, Wei Xiang

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引用次数: 0

Abstract

Layered transition metal oxides have emerged as promising cathode materials for sodium ion batteries. However, irreversible phase transitions cause structural distortion and cation rearrangement, leading to sluggish Na⁺ dynamics and rapid capacity decay. In this study, we propose a medium-entropy cathode by simultaneously introducing Fe, Mg, and Li dopants into a typical P2-type Na_0.75Ni_0.25Mn_0.75O₂ cathode. The modified Na_0.75Ni_0.2125Mn_0.6375Fe_0.05Mg_0.05Li_0.05O₂ cathode predominantly exhibits a main P2 phase (93.5%) with a minor O3 phase (6.5%). Through spectroscopy techniques and electrochemical investigations, we elucidate the redox mechanisms of Ni^2+/3+/4+, Mn^3+/4+, Fe^3+/4+, and O²⁻/O₂ⁿ⁻ during charging/discharging. The medium-entropy doping mitigates the detrimental P2-O2 phase transition at high-voltage, replacing it with a moderate and reversible structural evolution (P2-OP4), thereby enhancing structural stability. Consequently, the modified cathode exhibits a remarkable rate capacity of 108.4 mAh·g⁻¹ at 10C, with a capacity retention of 99.0% after 200 cycles at 1C, 82.5% after 500 cycles at 5C, and 76.7% after 600 cycles at 10C. Furthermore, it also demonstrates superior electrochemical performance at high cutoff voltage of 4.5 V and extreme temperature (55 and 0 °C). This work offers solutions to critical challenges in sodium ion batteries cathode materials.

Graphic abstract

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高倍率钠离子电池层状氧化物中实现可逆P2-OP4相变的中熵配置

层状过渡金属氧化物已成为钠离子电池极具前景的正极材料。然而，不可逆相变引起结构畸变和阳离子重排，导致Na+动力学缓慢，容量衰减迅速。在本研究中，我们提出了一种中熵阴极，通过在典型的p2型Na0.75Ni0.25Mn0.75O2阴极中同时引入Fe、Mg和Li掺杂剂。改性后的Na0.75Ni0.2125Mn0.6375Fe0.05Mg0.05Li0.05O2阴极主要为P2相（93.5%）和少量O3相（6.5%）。通过光谱技术和电化学研究，我们阐明了Ni2+/3+/4+、Mn3+/4+、Fe3+/4+和O2−/O2n−在充放电过程中的氧化还原机理。中熵掺杂减轻了高压下有害的P2-O2相变，取而代之的是温和可逆的结构演变（P2-OP4），从而提高了结构的稳定性。结果表明，改性后的阴极在10C下的倍率容量为108.4 mAh·g−1，在1C下循环200次后容量保持率为99.0%，在5C下循环500次后容量保持率为82.5%，在10C下循环600次后容量保持率为76.7%。此外，在4.5 V的高截止电压和55°C和0°C的极端温度下，它也表现出优异的电化学性能。这项工作为钠离子电池正极材料的关键挑战提供了解决方案。图形抽象

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来源期刊

Rare Metals 工程技术-材料科学：综合

CiteScore

12.10

自引率

12.50%

发文量

2919

审稿时长

2.7 months

期刊介绍： Rare Metals is a monthly peer-reviewed journal published by the Nonferrous Metals Society of China. It serves as a platform for engineers and scientists to communicate and disseminate original research articles in the field of rare metals. The journal focuses on a wide range of topics including metallurgy, processing, and determination of rare metals. Additionally, it showcases the application of rare metals in advanced materials such as superconductors, semiconductors, composites, and ceramics.