ACS Appl Mater Interfaces. 2018 May 16;10(19):16561-16571. doi: 10.1021/acsami.8b03608. Epub 2018 May 7.
Li-rich layered oxides (LLOs) with high specific capacities are favorable cathode materials with high-energy density. Unfortunately, the drawbacks of LLOs such as oxygen release, low conductivity, and depressed kinetics for lithium ion transport during cycling can affect the safety and rate capability. Moreover, they suffer severe capacity and voltage fading, which are major challenges for the commercializing development. To cure these issues, herein, the synthesis of high-performance antimony-doped LLO nanofibers by an electrospinning process is put forward. On the basis of the combination of theoretical analyses and experimental approaches, it can be found that the one-dimensional porous micro-/nanomorphology is in favor of lithium-ion diffusion, and the antimony doping can expand the layered phase lattice and further improve the lithium ion diffusion coefficient. Moreover, the antimony doping can decrease the band gap and contribute extra electrons to O within the LiMnO phase, thereby enhancing electronic conductivity and stabilizing lattice oxygen. Benefitting from the unique architecture, reformative electronic structure, and enhanced kinetics, the antimony-doped LLO nanofibers possess a high reversible capacity (272.8 mA h g) and initial coulombic efficiency (87.8%) at 0.1 C. Moreover, the antimony-doped LLO nanofibers show excellent cycling performance, rate capability, and suppressed voltage fading. The capacity retention can reach 86.9% after 200 cycles at 1 C, and even cycling at a high rate of 10 C, a capacity of 172.3 mA h g can still be obtained. The favorable results can assist in developing the LLO material with outstanding electrochemical properties.
富含锂的层状氧化物(LLO)具有高比容量,是高能密度的理想正极材料。然而,LLO 存在一些缺点,例如在循环过程中氧气释放、导电性低以及锂离子传输动力学受阻,这些问题会影响电池的安全性和倍率性能。此外,LLO 还存在严重的容量和电压衰减问题,这是其商业化发展的主要挑战。为了解决这些问题,本文提出了一种通过静电纺丝工艺合成高性能掺锑 LLO 纳米纤维的方法。通过理论分析和实验方法的结合,可以发现一维多孔微/纳米形态有利于锂离子扩散,而锑掺杂可以扩展层状相晶格,进一步提高锂离子扩散系数。此外,锑掺杂可以降低带隙并向 LiMnO 相中 O 贡献额外电子,从而提高电子电导率并稳定晶格氧。得益于独特的结构、改良的电子结构和增强的动力学,掺锑 LLO 纳米纤维具有高可逆容量(272.8 mA h g)和初始库仑效率(87.8%),在 0.1 C 时。此外,掺锑 LLO 纳米纤维还表现出优异的循环性能、倍率性能和抑制的电压衰减。在 1 C 下循环 200 次后,容量保持率可达 86.9%,即使在 10 C 的高倍率下循环,仍可获得 172.3 mA h g 的容量。这些有利的结果有助于开发具有优异电化学性能的 LLO 材料。