TY - JOUR
T1 - Exceptionally highly stable cycling performance and facile oxygen-redox of manganese-based cathode materials for rechargeable sodium batteries
AU - Konarov, Aishuak
AU - Jo, Jae Hyeon
AU - Choi, Ji Ung
AU - Bakenov, Zhumabay
AU - Yashiro, Hitoshi
AU - Kim, Jongsoon
AU - Myung, Seung Taek
N1 - Funding Information:
This research was supported by the International Research & Development Program of the National Research Foundation of Korea (NRF) funded by the Ministry of Science and ICT of Korea ( NRF-2017K1A3A1A30084795, NRF-2015M3D1A1069713 and NRF-2017R1A2A2A05069634 ).
PY - 2019/5/1
Y1 - 2019/5/1
N2 -
In this study, the effect of Zn doping on the electrochemical properties of P2-Na
2/3
[Mn
1−x
Zn
x
]O
2
(x = 0.0, 0.1, 0.2, 0.3) is investigated for the first time. The P2-Na
2/3
[Mn
0.7
Zn
0.3
]O
2
electrode deliveres a specific discharge capacity of approximately 190 mAh g
−1
based on the oxygen-redox reaction (O
2−
/O
1−
), after which the Mn
4+
/Mn
3+
redox reaction contributes to the capacity. The cycling performance of the P2-Na
2/3
[Mn
0.7
Zn
0.3
]O
2
electrode is also greatly enhanced compared with that of the P2-Na
2/3
MnO
2
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 Zn
2+
ions. First-principle calculations and experimental analysis, including X-ray photoelectron spectroscopy and X-ray absorption near edge structure spectroscopy, clearly confirms that the Zn
2+
substitution in P2-Na
2/3
MnO
2
enables the O
2−
/O
1−
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.
AB -
In this study, the effect of Zn doping on the electrochemical properties of P2-Na
2/3
[Mn
1−x
Zn
x
]O
2
(x = 0.0, 0.1, 0.2, 0.3) is investigated for the first time. The P2-Na
2/3
[Mn
0.7
Zn
0.3
]O
2
electrode deliveres a specific discharge capacity of approximately 190 mAh g
−1
based on the oxygen-redox reaction (O
2−
/O
1−
), after which the Mn
4+
/Mn
3+
redox reaction contributes to the capacity. The cycling performance of the P2-Na
2/3
[Mn
0.7
Zn
0.3
]O
2
electrode is also greatly enhanced compared with that of the P2-Na
2/3
MnO
2
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 Zn
2+
ions. First-principle calculations and experimental analysis, including X-ray photoelectron spectroscopy and X-ray absorption near edge structure spectroscopy, clearly confirms that the Zn
2+
substitution in P2-Na
2/3
MnO
2
enables the O
2−
/O
1−
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.
KW - Cathode
KW - First-principle calculation
KW - Mn rich
KW - Oxygen-redox
KW - Sodium ion battery
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UR - http://www.scopus.com/inward/citedby.url?scp=85061809146&partnerID=8YFLogxK
U2 - 10.1016/j.nanoen.2019.02.042
DO - 10.1016/j.nanoen.2019.02.042
M3 - Article
AN - SCOPUS:85061809146
SN - 2211-2855
VL - 59
SP - 197
EP - 206
JO - Nano Energy
JF - Nano Energy
ER -
