Zheng Hao-Wen, Liu Zhi-Chao, Chen Yao-Zhong, Gao Xue-Ping
Institute of New Energy Material Chemistry, School of Materials Science and Engineering, Nankai University, Tianjin 300350, China.
Tianjin B&M Science and Technology Co. Ltd, Tianjin 300384, China.
ACS Appl Mater Interfaces. 2023 Jul 26;15(29):35043-35051. doi: 10.1021/acsami.3c06472. Epub 2023 Jul 16.
Currently, ultrahigh-nickel layered oxide is one of the most promising cathodes for lithium-ion batteries, with the advantages of high theoretical capacity and low cost. However, some problems in ultrahigh-nickel layered oxides are more serious, such as irreversible structural transformation, particle cracking, and side reactions at the electrode/electrolyte interface, resulting in the fast decay of the discharge capacity and midpoint potential. In this work, La doping is introduced into ultrahigh-nickel layered LiNiCoO oxide to improve the cycle stability on both discharge capacity and midpoint potential. As demonstrated, La can be doped successfully into the subsurface of LiNiCoO oxide, and the morphology of the oxide microspheres is not changed obviously by La doping. Compared with the pristine sample, the La-doped sample presents improved electrochemical performance, especially good cycle stabilization on both discharge capacity and midpoint potential. In addition, after a long-term cycle, the La-doped sample still maintains a relatively complete spherical morphology. It means that the pillaring effect of La with a large radius is helpful in accommodating the volume change caused by the insertion/extraction of Li ions, thus easing the anisotropic stress accumulation and microcrack growth inside the microspheres of the La-doped sample.
目前,超高镍层状氧化物是锂离子电池中最具潜力的正极材料之一,具有理论容量高和成本低的优点。然而,超高镍层状氧化物存在一些更为严重的问题,如不可逆的结构转变、颗粒开裂以及电极/电解质界面处的副反应,导致放电容量和中点电位快速衰减。在这项工作中,将La掺杂引入超高镍层状LiNiCoO氧化物中,以提高其在放电容量和中点电位方面的循环稳定性。结果表明,La能够成功掺杂到LiNiCoO氧化物的次表面,并且La掺杂后氧化物微球的形貌没有明显变化。与原始样品相比,La掺杂样品具有更好的电化学性能,尤其是在放电容量和中点电位方面具有良好的循环稳定性。此外,经过长期循环后,La掺杂样品仍保持相对完整的球形形貌。这意味着大半径的La的支撑作用有助于容纳由锂离子嵌入/脱出引起的体积变化,从而缓解La掺杂样品微球内部的各向异性应力积累和微裂纹生长。