Graphene Nanosheet-Wrapped Mesoporous La0.8Ce0.2Fe0.5Mn0.5O3 Perovskite Oxide Composite for Improved Oxygen Reaction Electro-Kinetics and Li-O2 Battery Application

Chelladurai Karuppiah; Chao-Nan Wei; Natarajan Karikalan; Zong-Han Wu; Balamurugan Thirumalraj; Li-Fan Hsu; Srinivasan Alagar; Shakkthivel Piraman; Tai-Feng Hung; Ying-Jeng Jame Li; Chun-Chen Yang

doi:10.3390/nano11041025

Graphene Nanosheet-Wrapped Mesoporous La_0.8Ce_0.2Fe_0.5Mn_0.5O₃ Perovskite Oxide Composite for Improved Oxygen Reaction Electro-Kinetics and Li-O₂ Battery Application

Nanomaterials (Basel). 2021 Apr 16;11(4):1025. doi: 10.3390/nano11041025.

Authors

Affiliations

¹ Battery Research Center of Green Energy, Ming Chi University of Technology, New Taipei City 24301, Taiwan.
² Department of Chemical Engineering, Ming Chi University of Technology, New Taipei City 24301, Taiwan.
³ Center of Precision Analysis and Material Research, National Taipei University of Technology, No. 1, Section 3, Chung-Hsiao East Road, Taipei 106, Taiwan.
⁴ Department of Energy & Mineral Resources Engineering, Sejong University, Seoul 05006, Korea.
⁵ Sustainable Energy and Smart Materials Research Lab, Department of Nanoscience and Technology, Alagappa University, Karaikudi 630002, India.
⁶ Department of Chemical and Materials Engineering, Chang Gung University, Kwei-Shan, Taoyuan 333, Taiwan.

Abstract

A novel design and synthesis methodology is the most important consideration in the development of a superior electrocatalyst for improving the kinetics of oxygen electrode reactions, such as the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) in Li-O₂ battery application. Herein, we demonstrate a glycine-assisted hydrothermal and probe sonication method for the synthesis of a mesoporous spherical La_0.8Ce_0.2Fe_0.5Mn_0.5O₃ perovskite particle and embedded graphene nanosheet (LCFM(8255)-gly/GNS) composite and evaluate its bifunctional ORR/OER kinetics in Li-O₂ battery application. The physicochemical characterization confirms that the as-formed LCFM(8255)-gly perovskite catalyst has a highly crystalline structure and mesoporous morphology with a large specific surface area. The LCFM(8255)-gly/GNS composite hybrid structure exhibits an improved onset potential and high current density toward ORR/OER in both aqueous and non-aqueous electrolytes. The LCFM(8255)-gly/GNS composite cathode (ca. 8475 mAh g^-1) delivers a higher discharge capacity than the La_0.5Ce_0.5Fe_0.5Mn_0.5O₃-gly/GNS cathode (ca. 5796 mAh g^-1) in a Li-O₂ battery at a current density of 100 mA g^-1. Our results revealed that the composite's high electrochemical activity comes from the synergism of highly abundant oxygen vacancies and redox-active sites due to the Ce and Fe dopant in LaMnO₃ and the excellent charge transfer characteristics of the graphene materials. The as-developed cathode catalyst performed appreciable cycle stability up to 55 cycles at a limited capacity of 1000 mAh g^-1 based on conventional glass fiber separators.

Keywords: Ce-doped LaMnO3 perovskite; XPS of LaMnO3; bifunctional activity; carbon-based composite; probe sonication.