Oxygen Vacancies and Stacking Faults Introduced by Low-Temperature Reduction Improve the Electrochemical Properties of Li2MnO3 Nanobelts as Lithium-Ion Battery Cathodes

Among the Li-rich layered oxides Li2MnO3 has significant theoretical capacity as a cathode material for Li-ion batteries. Pristine Li2MnO3 generally has to be electrochemically activated in the first charge-discharge cycle which causes very low Coulombic efficiency and thus deteriorates its electrochemical properties. In this work, we show that low-temperature reduction can produce a large amount of structural defects such as oxygen vacancies, stacking faults, and orthorhombic LiMnO2 in Li2MnO3. The Rietveld refinement analysis shows that, after a reduction reaction with stearic acid at 340 °C for 8 h, pristine Li2MnO3 changes into a Li2MnO3-LiMnO2 (0.71/0.29) composite, and the monoclinic Li2MnO3 changes from Li2.04Mn0.96O3 in the pristine Li2MnO3 (P-Li2MnO3) to Li2.1Mn0.9O2.79 in the reduced Li2MnO3 (R-Li2MnO3), indicating the production of a large amount of oxygen vacancies in the R-Li2MnO3. High-resolution transmission electron microscope images show that a high density of stacking faults is also introduced by the low-temperature reduction. When measured as a cathode material for Li-ion batteries, R-Li2MnO3 shows much better electrochemical properties than P-Li2MnO3. For example, when charged-discharged galvanostatically at 20 mA·g-1 in a voltage window of 2.0-4.8 V, R-Li2MnO3 has Coulombic efficiency of 77.1% in the first charge-discharge cycle, with discharge capacities of 213.8 and 200.5 mA·h·g-1 in the 20th and 30th cycles, respectively. In contrast, under the same charge-discharge conditions, P-Li2MnO3 has Coulombic efficiency of 33.6% in the first charge-discharge cycle, with small discharge capacities of 80.5 and 69.8 mA·h·g-1 in the 20th and 30th cycles, respectively. These materials characterizations, and electrochemical measurements show that low-temperature reduction is one of the effective ways to enhance the performances of Li2MnO3 as a cathode material for Li-ion batteries.