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Updated: Jun 17, 2026

Protocol of Electrochemical Test and Characterization of Aprotic Li-O2 Battery
Published on: July 12, 2016
Thermodynamic Control of Oxygen Vacancies for Li-Rich Cathode Materials
Yongqi Sun1,2, Gui Chu3, Xiaobo Zhu3
1School of Metallurgy and Environment and National Center for International Research of Clean Metallurgy, Central South University, Changsha, 410083, China.
Abstract:
Oxygen vacancies (OVs) play a critical role in tuning the properties of oxides, yet their rational control remains challenging. We present a meticulous engineering approach to modulate OVs in lithium-rich layered oxides (LRLOs), a promising cathode material for next-generation lithium-ion batteries. Guided by a Mn-O2 binary phase diagram, our method achieves accurate and broad tuning of the oxygen partial pressure (PO2) during calcination using a pyrometallurgical CO/CO2 gas pair. Using an ultra-high-Mn LRLO model, we quantify a thermodynamic equilibrium between OV concentration and a wide PO2 range (10-0.7-10-10.0 atm). Structural characterizations reveal progressive lattice expansion and an unprecedented enhancement of Li@Mn6 superstructures. An optimized LRLO with 3.8 mol % OVs shows a sixfold improvement in initial discharge capacity (175.9 mAh g-1) over a reference sample (28.5 mAh g-1) at 0.1C, achieving a maximum capacity of 287.9 mAh g-1. Theoretical calculations clarify the role of OVs in modifying the electronic structure of LRLOs, which enables ideal conditioning for facile and reversible anion redox. This study provides a generalizable and facile strategy for OV engineering, which accelerates the commercial viability of LRLOs and offers a new framework for the rational design of other modern materials.
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