Dual-Site Doping Strategy for Enhancing the Structural Stability of Lithium-Rich Layered Oxides

ACS Appl Mater Interfaces. 2021 Apr 14;13(14):16407-16417. doi: 10.1021/acsami.1c02020. Epub 2021 Mar 31.

Abstract

Lithium-rich layered oxide (LLO) cathode materials are considered to be one of the most promising next-generation candidates of cathode materials for lithium-ion batteries due to their high specific capacity. However, some inherent defects of LLOs hinder their practical application due to the oxygen loss and structure collapse resulting from intrinsic anion and cation redox reactions, such as poor cycle stability, sluggish Li+ kinetics, and voltage decay. Herein, we put forward a facile synergistic strategy to respond to these shortcomings of LLOs via dual-site doping with cerium (Ce) and boron (B) ions. The doped Ce ions occupy the octahedral sites, which not only enlarge the cell volume but also stabilize the layered framework and introduce abundant oxygen vacancies for LLOs, while B ions occupy the tetrahedral sites in the lattice, which block the migration path of transition metal (TM) ions and reduce the oxygen loss using the strong B-O bond. Based on this dual-site doping effect, after 100 cycles at 1 C, the dual-site doped materials exhibit excellent structural stability with a capacity retention of 91.15% (vs 75.12%) and also greatly suppress the voltage decay in LLOs with a voltage retention of 93.60% (vs 87.83%).

Keywords: Li-rich layered oxides; dual-site doping; lithium-ion batteries; oxygen loss; voltage decay.