Lin Yuda, Chen Yiheng, Qiu Liting, Zheng Shenghui
School of Electromechanical and Information Engineering, PuTian University, Putian, Fujian 351100, China.
Department of Physics, Xiamen University, Xiamen 361005, China.
J Chem Phys. 2024 Mar 7;160(9). doi: 10.1063/5.0193437.
In view of the inherent pseudocapacitance, rich redox pairs (Nb5+/Nb4+ and Nb4+/Nb3+), and high lithiation potential (1.0-3.0 V vs Li/Li+), Nb2O5 is considered a promising anode material. However, the inherent low electronic conductivity of Nb2O5 limits its lithium storage performance, and the rate performance after carbon modification is still unsatisfactory because the intrinsic conductivity of Nb2O5 has not been substantially improved. In this experiment, taking the improvement of the intrinsic electrical conductivity of Nb2O5 as the guiding ideology, we prepared F-doped Nb2O5@fluorocarbon composites (F-Nb2O5@FC) with a large number of oxygen vacancies by one-step annealing. As the anode electrode of lithium-ion batteries, the reversible specific capacity of F-Nb2O5@FC reaches 150 mA g-1 at 5 A g-1 after 1100 cycles, and the rate performance is particularly outstanding, with a capacity up to 130 mA g-1 at 16 A g-1, which is far superior to other Nb2O5@carbon-based anode electrodes. Compared with other single conductivity sources of Nb2O5@carbon-based composites, the electrical conductivity of F-Nb2O5@FC composites is greatly improved in many aspects, including the introduction of free electrons by F- doping, the generation of oxygen vacancies, and the provision of a three-dimensional conductive network by FC. Through analytical chemistry (work function, UV-Vis diffuse reflectance spectroscopy, and EIS) and theoretical calculations, it is proved that F-Nb2O5@FC has high electrical conductivity and realizes rapid electron transfer.
鉴于五氧化二铌具有本征赝电容、丰富的氧化还原对(Nb5+/Nb4+和Nb4+/Nb3+)以及较高的锂化电位(相对于Li/Li+为1.0 - 3.0 V),五氧化二铌被认为是一种很有前景的负极材料。然而,五氧化二铌固有的低电子电导率限制了其储锂性能,并且碳改性后的倍率性能仍不令人满意,因为五氧化二铌的本征电导率并未得到实质性改善。在本实验中,以提高五氧化二铌的本征电导率为指导思想,我们通过一步退火制备了具有大量氧空位的氟掺杂五氧化二铌@氟碳复合材料(F-Nb2O5@FC)。作为锂离子电池的负极,F-Nb2O5@FC在1100次循环后,5 A g-1时的可逆比容量达到150 mA g-1,倍率性能尤为突出,在16 A g-1时容量高达130 mA g-1,远远优于其他五氧化二铌@碳基负极。与其他五氧化二铌@碳基复合材料的单一导电源相比,F-Nb2O5@FC复合材料的电导率在多个方面得到了极大提高,包括通过F-掺杂引入自由电子、产生氧空位以及由FC提供三维导电网络。通过分析化学(功函数、紫外-可见漫反射光谱和电化学阻抗谱)和理论计算,证明了F-Nb2O5@FC具有高电导率并实现了快速电子转移。