Stabilizing Cobalt-Free Li-Rich Layered Oxide Cathodes By Site-Specific Doping
Authors: Fan Yameng , Pang Wei Kong , Cai Qiong , Guo Zaiping 
Published: February 2024

The limited theoretical capacity of traditional cathode materials solely based on transition metal (TM) redox has been a primary factor for the ceiling placed on the energy density of LIBs. In this regard, Li-rich layered oxides (LLOs) have received a great deal of attention, due to their high reversible capacity (> 250 mAh g-1) and high energy density (900 Wh kg-1), courtesy of the TM redox and the additional high-voltage O2- redox.1, 2 Although the electrochemical performance of Co-free LLOs is significantly less satisfactory, developing Co-free cathodes is inevitably a holy grail owing to cobalt’s economic, ethical, and political issues caused by high-cost toxicity. Therefore, studies on Co-free LLOs are necessary for creating long-term benefits for the cathode industry.

Unfortunately, Co-free LLOs suffer from capacity and voltage decay on cycling, which for now obviously limits the materials use outside the academics laboratory. It is well accepted that that performance decay is primarily attributed to the irreversible anionic redox and structural degradation in LLOs. The doping strategy has been widely used to address the voltage decay of LLOs.3 While the dopant is typically introduced to the layered R
m component, the lithium-rich component (C2/c) in the LLOs, which is the source of anionic redox, has always been ignored.

Our team comprehensively investigates the structural involution of LLOs based on a Co-free Li-rich Mn-based Li1.2Ni0.2Mn0.6O2 (LNMO) cathode using in-operando and ex-situ synchrotron-based characterizations. We learned through mechanistic characterization that the transition from the monoclinic (C2/c) to the hexagonal (R-3m) behaviour is an intrinsic behaviour of LLOs for the first time. According to this structure-function relationship, we introduced a small quantity of one electrochemically active metal, ruthenium, into both R-3m and C2/c components in LNMO and found that the oxygen lattice and structural stability can be significantly improved by the site-specific doping against lithiation and delithiation processes.4

Additionally, reducing the irreversible TM migration is key to advancing the performance of layered oxide cathode materials. Contrary to many previous studies that emphasize suppressing cation migration, our team proposed that reversible tetrahedral-octahedral TM migration helps inhibit the formation of undesirable structural changes and phase transformation. The oxidation state of TM, such as Ni, Mn, and Co, are easily trapped into the octahedral sites in the Li layer due to their high octahedral-site splitting energy when a large amount of Li has extracted from the structure. By introducing Cr into LNMO, we found that Cr can migrate reversibly between the tetrahedral and octahedral sites, which makes Cr-doped LNMO possess significantly enhanced structural stability and thus achieve higher electrochemical performance than LNMO.

In all, our research focuses on the site-specific doping of the Co-free LLOs and understanding the structure- and chemistry-function relationship of the LLOs. The findings in our work might provide possible pathways for the future design of high-performance cathode materials for lithium-ion batteries and may also apply to developing cathode materials for other energy storage systems.

Reference

S. Hu, A. S. Pillai, G. Liang, W. K. Pang, H. Wang, Q. Li and Z. Guo, Electrochem. Energy Rev., 2019, 2, 277-311.

M. Han, J. Jiao, Z. Liu, X. Shen, Q. Zhang, H.-J. Lin, C.-T. Chen, Q. Kong, W. K. Pang, Z. Guo, R. Yu, L. Gu, Z. Hu, Z. Wang and L. Chen, Adv. Energy Mater., 2020, 10, 1903634.

Y. Fan, W. Zhang, Y. Zhao, Z. Guo and Q. Cai, Energy Stor. Mater., 2021, 40, 51-71.

Y. Fan, E. Olsson, G. Liang, Z. Wang, A. M. D'Angelo, B. Johannessen, L. Thomsen, B. Cowie, J. Li, F. Zhang, Y. Zhao, W. K. Pang, Q. Cai and Z. Guo, Angew. Chem. Int. Ed., 2022, DOI: 10.1002/anie.202213806.