Doping of Ni and Zn Elements in MnCO3: High‐Power Anode Material for Lithium–Ion Batteries

• Published in: Small (Weinheim an der Bergstrasse, Germany) Germany), 2018-02, Vol.14 (7), p.n/a
• Main Authors: Li, Qing, Liu, Zhengwang, Wang, Chao, Zhao, Yunhao, Che, Renchao
• Format: Article
• Language: English
• Subjects: Amorphization; Anodes; atomic mapping images; Carbonates; Chemical synthesis; Conversion; Cycles; doping; Electrical resistivity; Electrode materials; Fast Fourier transformations; Fourier transforms; Image transmission; Lithium; Lithium-ion batteries; Mapping; Nanotechnology; outstanding electrochemical performances; oxygen vacancies; Rechargeable batteries; Scanning transmission electron microscopy
• ISSN: 1613-6810; 1613-6829
• DOI: 10.1002/smll.201702574

Herein, Ni and Zn elements are doped simultaneously in MnCO3 and microspheric MnxNiyZnzCO3 is successfully obtained. Atomic mapping images reveal that the Ni and Zn elements have been successfully doped in MnCO3 and thus the prepared sample is not a mixture of MnCO3, NiCO3, and ZnCO3. It is the first time that the atomic mapping images of ternary transition metal carbonates have been demonstrated so far. The scanning transmission electron microscopy ‐ annular bright field (STEM‐ABF) image successfully confirms the formation of oxygen vacancies in MnxNiyZnzCO3, which is beneficial to improve the electrical conductivity. The evolution of the microstructure from crystal to amorphization during cycling process confirmed by the fast Fourier transform patterns effectively lowers the overpotential of the conversion reaction and accelerates the conversion between Mn2+ and much higher valence of Mn element, contributing to the superior capacity of MnxNiyZnzCO3 electrode. As anode material for lithium‐ion batteries, the prepared MnxNiyZnzCO3 exhibits excellent long‐term cycling stability and outstanding rate performance, delivering the superior reversible discharge capacities of 1066 mA h g−1 at 500 mA g−1 after 500 cycles and 760 mA h g−1 at 1 A g−1 after 1000 cycles. It is the first time that MnxNiyZnzCO3 has been synthesized and used as anode for lithium‐ion batteries so far. The ternary MnxNiyZnzCO3, MnxNiyCozCO3, and MnxNiyCuzCO3 corresponding to the standard rhodochrosite MnCO3 phase with microspheric structure are successfully synthesized as anode materials for lithium–ion batteries. The prepared MnxNiyZnzCO3 demonstrates the best electrochemical performances among the prepared three samples. The reasons for the superior electrochemical performances of MnxNiyZnzCO3 are reasonably explained.