TY - JOUR
T1 - Manganese based layered oxides with modulated electronic and thermodynamic properties for sodium ion batteries
AU - Zhang, Kai
AU - Kim, Duho
AU - Hu, Zhe
AU - Park, Mihui
AU - Noh, Gahee
AU - Yang, Yujeong
AU - Zhang, Jing
AU - Lau, Vincent Wing hei
AU - Chou, Shu Lei
AU - Cho, Maenghyo
AU - Choi, Si Young
AU - Kang, Yong Mook
N1 - Funding Information:
Y.-M. Kang and M. Cho would like to thank the National Research Foundation of Korea (NRF) grants through the Korean government (MSIP) for funding this work. The grant numbers are NRF-2017R1A2B3004383, NRF-2017M3D1A1039553, NRF-2017R1A5A1015365 and 2012R1A3A2048841. Y. -M. Kang would also like to thank the Korea Institute of Energy Technology Evaluation and Planning (KETEP) and the Ministry of Trade, Industry and Energy (MOTIE) in South Korea; the number for the grant is 20152020105420. Additionally, the authors are grateful for the assistance of PAL, the Australian Synchrotron, and Dr. Qinfen Gu regarding synchrotron XAS and XRD data for the samples. Finally, K. Zhang would like to thank the Korea Research Fellowship Program of the NRF, which was funded by the Ministry of Science and ICT; the number for this grant is 2016H1D3A1906790.
Publisher Copyright:
© 2019, The Author(s).
PY - 2019/12/1
Y1 - 2019/12/1
N2 - Manganese based layered oxides have received increasing attention as cathode materials for sodium ion batteries due to their high theoretical capacities and good sodium ion conductivities. However, the Jahn–Teller distortion arising from the manganese (III) centers destabilizes the host structure and deteriorates the cycling life. Herein, we report that zinc-doped Na 0.833 [Li 0.25 Mn 0.75 ]O 2 can not only suppress the Jahn–Teller effect but also reduce the inherent phase separations. The reduction of manganese (III) amount in the zinc-doped sample, as predicted by first-principles calculations, has been confirmed by its high binding energies and the reduced octahedral structural variations. In the viewpoint of thermodynamics, the zinc-doped sample has lower formation energy, more stable ground states, and fewer spinodal decomposition regions than those of the undoped sample, all of which make it charge or discharge without any phase transition. Hence, the zinc-doped sample shows superior cycling performance, demonstrating that zinc doping is an effective strategy for developing high-performance layered cathode materials.
AB - Manganese based layered oxides have received increasing attention as cathode materials for sodium ion batteries due to their high theoretical capacities and good sodium ion conductivities. However, the Jahn–Teller distortion arising from the manganese (III) centers destabilizes the host structure and deteriorates the cycling life. Herein, we report that zinc-doped Na 0.833 [Li 0.25 Mn 0.75 ]O 2 can not only suppress the Jahn–Teller effect but also reduce the inherent phase separations. The reduction of manganese (III) amount in the zinc-doped sample, as predicted by first-principles calculations, has been confirmed by its high binding energies and the reduced octahedral structural variations. In the viewpoint of thermodynamics, the zinc-doped sample has lower formation energy, more stable ground states, and fewer spinodal decomposition regions than those of the undoped sample, all of which make it charge or discharge without any phase transition. Hence, the zinc-doped sample shows superior cycling performance, demonstrating that zinc doping is an effective strategy for developing high-performance layered cathode materials.
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U2 - 10.1038/s41467-018-07646-4
DO - 10.1038/s41467-018-07646-4
M3 - Article
C2 - 30617270
AN - SCOPUS:85059742639
SN - 2041-1723
VL - 10
JO - Nature communications
JF - Nature communications
IS - 1
M1 - 5203
ER -