Wang Zhenbo, Yin Yanfeng, He Guanjie, Zhao Huiling, Bai Ying
International Joint Research Laboratory of New Energy Materials and Devices of Henan Province, School of Physics and Electronics, Henan University, Kaifeng, 475004, China.
Academy for Advanced Interdisciplinary Studies, Henan University, Kaifeng, 475004, China.
Nanoscale. 2023 Jan 5;15(2):588-598. doi: 10.1039/d2nr04074c.
With large specific capacity, wide voltage window, and high energy density, Li-rich layered oxides have been considered as a promising cathode candidate for advanced lithium-ion batteries (LIBs). However, their commercial application is challenging due to severe capacity degradation and voltage fading caused by irreversible oxygen evolution and phase transition upon repeated cycling. This work proposes an effective strategy to improve the long-term electrochemical performances of LiMnNiCoO (LMNCO) by constructing multifunctional nanolayers composed of element-doping, layered-spinel heterostructural connection, and fast ion conductor shell a facile method. The LiBPO (LBPO) coating shell acts as a fast ion carrier and physical screen to promote Li diffusion and isolate side reactions at the cathode-electrolyte interface; moreover, two-phase transitional region provides three-dimensional channel to facilitate Li transport and inhibit phase transition. Besides, B and PO-doping collaborates with oxygen vacancies to stabilize lattice oxygen and restrain oxygen evolution from the bulk active cathode. The optimized LMNCO@LBPO material exhibits a superior capacity retention of 78.6%, higher than that of the pristine sample (49.3%), with the mitigated voltage fading of 0.73 mV per cycle after 500 cycles at 1 C. This study opens up an avenue for the surface modification to the electrochemical properties and perspective application of Li-rich cathodes in high-performance LIBs.
富锂层状氧化物具有比容量大、电压窗口宽和能量密度高的特点,被认为是先进锂离子电池(LIBs)中一种很有前景的正极材料。然而,由于在反复循环过程中不可逆的析氧和相变导致严重的容量衰减和电压衰减,其商业应用面临挑战。这项工作提出了一种有效的策略,通过构建由元素掺杂、层状-尖晶石异质结构连接和快速离子导体壳组成的多功能纳米层(一种简便方法)来提高LiMnNiCoO(LMNCO)的长期电化学性能。LiBPO(LBPO)涂层壳作为快速离子载体和物理屏障,促进锂扩散并隔离阴极-电解质界面处的副反应;此外,两相过渡区域提供三维通道,促进锂传输并抑制相变。此外,B和PO掺杂与氧空位协同作用,稳定晶格氧并抑制本体活性阴极的析氧。优化后的LMNCO@LBPO材料在1 C下循环500次后,具有78.6%的优异容量保持率,高于原始样品(49.3%),且每循环的电压衰减减轻至0.73 mV。这项研究为富锂正极在高性能LIBs中的电化学性能表面改性和应用前景开辟了一条途径。