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通过相协同工程和铜掺杂提高铌氧化物负极的锂存储性能

Enhancing the Lithium Storage Performance of the NbO Anode via Synergistic Engineering of Phase and Cu Doping.

作者信息

Dong Hao, Yao Tianhao, Ji Xin, Zhang Qingmiao, Lin Xiongfeng, Zhang Binglin, Ma Chuansheng, Meng Lingjie, Chen Yu, Wang Hongkang

机构信息

State Key Lab of Electrical Insulation and Power Equipment, Center of Nanomaterials for Renewable Energy (CNRE), School of Electrical Engineering, Xi'an Jiaotong University, Xi'an 710049, PR China.

School of Chemistry & Instrumental Analysis Center, Xi'an Jiaotong University, Xi'an 710049, P. R. China.

出版信息

ACS Appl Mater Interfaces. 2024 May 1;16(17):22055-22065. doi: 10.1021/acsami.4c03044. Epub 2024 Apr 18.

DOI:10.1021/acsami.4c03044
PMID:38636080
Abstract

NbO has been viewed as a promising anode material for lithium-ion batteries by virtue of its appropriate redox potential and high theoretical capacity. However, it suffers from poor electric conductivity and low ion diffusivity. Herein, we demonstrate the controllable fabrication of Cu-doped NbO with orthorhombic (T-NbO) and monoclinic (H-NbO) phases through annealing the solvothermally presynthesized NbO precursor under different temperatures in air, and the Cu doping amount can be readily controlled by the concentration of the precursor solution, whose effect on the lithium storage behaviors of the Cu-doped NbO is thoroughly investigated. H-NbO shows obvious redox peaks (Nb/Nb and Nb/Nb) with much higher capacity and better cycling stability than those for the widely investigated T-NbO. When introducing appropriate Cu doping, the optimized H-Cu-NbO electrode shows greatly enhanced conductivity and lower diffusion barrier as revealed by the theoretical calculations and electrochemical characterizations, delivering a high reversible capacity of 203.6 mAh g and a high capacity retention of 140.8 mAh g after 5000 cycles at 1 A g, with a high initial Coulombic efficiency of 91% and a high rate capacity of 144.2 mAh g at 4 A g. As a demonstration for full-cell application, the H-Cu-NbO||LiFePO cell displays good cycling performance, exhibiting a reversible capacity of 135 mAh g after 200 cycles at 0.2 A g. More importantly, this work offers a new synthesis protocol of the monoclinic NbO phase with high capacity retention and improved reaction kinetics.

摘要

由于其合适的氧化还原电位和高理论容量,NbO被视为一种有前景的锂离子电池负极材料。然而,它存在电导率差和离子扩散率低的问题。在此,我们通过在空气中不同温度下对溶剂热预合成的NbO前驱体进行退火,展示了具有正交相(T-NbO)和单斜相(H-NbO)的Cu掺杂NbO的可控制备,并且Cu掺杂量可以通过前驱体溶液的浓度轻松控制,全面研究了其对Cu掺杂NbO储锂行为的影响。H-NbO显示出明显的氧化还原峰(Nb/Nb和Nb/Nb),与广泛研究的T-NbO相比,具有更高的容量和更好的循环稳定性。当引入适当的Cu掺杂时,优化后的H-Cu-NbO电极通过理论计算和电化学表征显示出大大增强的电导率和更低的扩散势垒,在1 A g下5000次循环后具有203.6 mAh g的高可逆容量和140.8 mAh g的高容量保持率,在4 A g下具有91%的高初始库仑效率和144.2 mAh g的高倍率容量。作为全电池应用的示范,H-Cu-NbO||LiFePO电池显示出良好的循环性能,在0.2 A g下200次循环后具有135 mAh g的可逆容量。更重要的是,这项工作提供了一种具有高容量保持率和改善反应动力学的单斜相NbO的新合成方案。

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