Synergy of F− doping and fluorocarbon coating on elevating high-voltage cycling stability of NCM811 for lithium-ion batteries

IF 11 1区材料科学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY Rare Metals Pub Date : 2024-10-22 DOI:10.1007/s12598-024-02951-y

Gao-Xing Sun, Bin Zhu, Rui He, Qi-Dong Liang, Sheng-Yu Jiang, Yan Ren, Xiao-Xiao Pan, Yu-Qing Sun, Mi Lu, Wen-Xian Zhang, Cheng-Huan Huang, Shu-Xin Zhuang

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Abstract

Although lithium-ion batteries are widely recognized as a new generation of energy storage devices, their large-scale application is severely hampered by their low energy density and restricted cyclic stability. Herein, an ingenious dual-modified interface, where the F-doping and fluorocarbon coating co-existed on Li[Ni_0.8Co_0.1Mn_0.1]O₂ surface, is rationally constructed to elevate its energy density and structural stability attributed to F⁻ grafting between the bulk material and the coating utilizing a robust super-conformal fluorocarbon coating structural framework and more stable F-doped system under high charge/discharge cut-off voltage. In comparison with a single carbon-coated modified Li[Ni_0.8Co_0.1Mn_0.1]O₂, the dual-modified sample overcomes the fatal disadvantage of carbon coating stripping during long-period cycles ascribed to the “TM-F-multifunctional coating” connector which firmly combines the bulk material with the coating with a strong interaction force, exhibiting a more stable-reversible structure and excellent comprehensive electrochemical performance under high cut-off voltage. Concomitantly, the F-transition metal bonds with stronger bond energies improve its structural reversibility during the processes of charge/discharge under high voltage. Furthermore, the fluorocarbon coating enhances its charge transfer ability and effectively restrains the interfacial side reactions. Additionally, the climbing nudged elastic band methodology is used to calculate the diffusion energy barrier of lithium-ions in the matrix material, which confirms the fundamental reason for its superior lithium-ion diffusion ability. The high pseudocapacitance contribution ratio is perfectly explained by calculating the adsorption capacity on the surface of the dual-modified sample. Consequently, experiments and theoretical calculations unequivocally confirm its distinguished electrochemical properties under high cut-off voltage.

Graphical Abstract

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掺杂 F 和碳氟化合物涂层对提高锂离子电池 NCM811 高电压循环稳定性的协同作用

虽然锂离子电池作为新一代储能设备被广泛认可，但其能量密度低、循环稳定性受限等问题严重阻碍了其大规模应用。本文巧妙地构建了F掺杂和氟碳涂层在Li[Ni0.8Co0.1Mn0.1]O2表面共存的双修饰界面，利用强大的超共形氟碳涂层结构框架和高充放电截止电压下更稳定的F掺杂体系，提高了本体材料与涂层之间F−接枝的能量密度和结构稳定性。与单一碳包覆改性Li[Ni0.8Co0.1Mn0.1]O2相比，双改性样品克服了“tm - f多功能涂层”连接器在长周期循环中碳涂层剥离的致命缺点，该连接器将本体材料与涂层牢固地结合在一起，相互作用力强，具有更稳定的可逆结构和高截止电压下优异的综合电化学性能。同时，具有较强键能的f -过渡金属键提高了其在高压充放电过程中的结构可逆性。此外，氟碳涂层增强了其电荷转移能力，有效地抑制了界面副反应。此外，采用爬升微推弹性带方法计算了锂离子在基体材料中的扩散能垒，证实了其优越的锂离子扩散能力的根本原因。通过计算双改性样品表面的吸附容量，可以很好地解释高赝电容贡献比。因此，实验和理论计算明确地证实了它在高截止电压下的优异电化学性能。图形抽象

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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文献相关原料

公司名称

产品信息

阿拉丁

LiOH·H2O

阿拉丁

MnSO4·4H2O

阿拉丁

NiSO4·7H2O

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.