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Single‐Phase Mixed Transition Metal Carbonate Encapsulated by Graphene: Facile Synthesis and Improved Lithium Storage Properties
Authors:Rui Zhang  Xiaoxiao Huang  Dong Wang  Tuan K A Hoang  Yang Yang  Xiaoming Duan  Pu Chen  Lu‐Chang Qin  Guangwu Wen
Affiliation:1. School of Materials Science and Engineering, Harbin Institute of Technology, Harbin, China;2. Department of Physics and Astronomy, University of North Carolina at Chapel Hill, Chapel Hill, NC, USA;3. Key Laboratory of Advanced Structural‐Functional Integration Materials and Green Manufacturing Technology, Harbin Institute of Technology, Harbin, China;4. Department of Chemical Engineering and Waterloo Institute of Nanotechnology, University of Waterloo, Waterloo, ON, Canada;5. School of Chemistry and Chemical Engineering, Shandong University of Technology, Zibo, China;6. School of Materials Science and Engineering, Shandong University of Technology, Zibo, China;7. Shandong Industrial Ceramics Research and Design Institute Co. Ltd., Zibo, China
Abstract:Transition metal carbonates (TMCs) with complex composition and robust hybrid structure hold great potential as high‐performance electrode materials for lithium‐ion batteries (LIBs). However, poor ionic/electronic conductivities and large volume changes of TMCs during lithiation/delithiation processes have hindered their applications. Herein, single‐phase Mn? Co mixed carbonate composites encapsulated by reduced graphene oxide (MnxCo1?xCO3/RGO), in which Mn and Co species are distributed randomly in one crystal structure, are successfully synthesized through a facial liquid‐state method. When evaluated as LIB anodes, the MnxCo1?xCO3/RGO composites exhibit enhanced electrochemical performance compared with the reference CoCO3/RGO and MnCO3/RGO. Specifically, the Mn0.7Co0.3CO3/RGO delivers an ultrahigh capacity of 1454 mA h g?1 after 130 cycles at 100 mA g?1 and exhibits an ultralong cycling stability (901 mA h g?1 after 1500 cycles at 2000 mA g?1). This is the best lithium storage performance among carbonate‐based anodes reported up to date. Such superb performance is attributed to the hybrid structure and enhanced electroconductivity due to the integration of Co and Mn into one crystal structure, which is complemented by electrochemical impedance spectroscopy and density functional theory calculations. The facile synthesis, promising electrochemical results, and scientific understanding of the MnxCo1?xCO3/RGO provides a design principle and encourages more research on TMCs‐based electrodes.
Keywords:hybrids  lithium‐ion batteries  mixed transition metal carbonates  nanostructures
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