Journal
NANO ENERGY
Volume 59, Issue -, Pages 197-206Publisher
ELSEVIER
DOI: 10.1016/j.nanoen.2019.02.042
Keywords
Oxygen-redox; Mn rich; First-principle calculation; Cathode; Sodium ion battery
Categories
Funding
- International Research & Development Program of the National Research Foundation of Korea (NRF) - Ministry of Science and ICT of Korea [NRF-2017K1A3A1A30084795, NRF-2015M3D1A1069713, NRF-2017R1A2A2A05069634]
- National Research Foundation of Korea [2017K1A3A1A30084795] Funding Source: Korea Institute of Science & Technology Information (KISTI), National Science & Technology Information Service (NTIS)
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In this study, the effect of Zn doping on the electrochemical properties of P2-Na-2/3[Mn1-xZnx]O-2 (x = 0.0, 0.1, 0.2, 0.3) is investigated for the first time. The P2-Na-2/3[Mn0.7Zn0.3]O-2 electrode deliveres a specific discharge capacity of approximately 190 mAh g(-1) based on the oxygen-redox reaction (O2-/O1-), after which the Mn-4/Mn3+ redox reaction contributes to the capacity. The cycling performance of the P2-Na-2/3[Mn0.7Zn0.3]O-2 electrode is also greatly enhanced compared with that of the P2-Na2/3MnO2 electrode (capacity retention of 80% vs. 30% after 200 cycles). This improved cyclability is due to the suppression of cooperative Jahn-Teller distortion as well as stabilization of the structure by the electrochemically inactive Zn2+ ions. First-principle calculations and experimental analysis, including X-ray photoelectron spectroscopy and X-ray absorption near edge structure spectroscopy, clearly confirms that the Zn2+ substitution in P2-Na2/3MnO2 enables the O2-/O1- redox reaction. In addition, time-of-flight secondary ion mass spectroscopy analysis reveals that no sodium carbonates forms on the electrode surface. Our findings provide a potential new path to utilize cost-effective Mn-rich cathode materials for sodium-ion batteries via not only cationic redox but also anodic redox.
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