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Sodiation Kinetics of Metal Oxide Conversion Electrodes: A Comparative Study with Lithiation
被引:113
作者:
He, Kai
[1
]
Lin, Feng
[2
]
Zhu, Yizhou
[3
]
Yu, Xiqan
[4
]
Li, Jing
[1
]
Lin, Ruoqian
[1
]
Nordlund, Dennis
[5
]
Weng, Tsu-Chien
[5
]
Richards, Ryan M.
[6
]
Yang, Xiao-Qing
[4
]
Doeff, Marca M.
[2
]
Stach, Eric A.
[1
]
Mo, Yifei
[3
]
Xin, Huolin L.
[1
]
Su, Dong
[1
]
机构:
[1] Brookhaven Natl Lab, Ctr Funct Nanomat, Upton, NY 11973 USA
[2] Univ Calif Berkeley, Lawrence Berkeley Natl Lab, Energy Storage & Distributed Resources Div, Berkeley, CA 94720 USA
[3] Univ Maryland, Dept Mat Sci & Engn, College Pk, MD 20742 USA
[4] Brookhaven Natl Lab, Dept Chem, Upton, NY 11973 USA
[5] SLAC Natl Accelerator Lab, Stanford Synchrotron Radiat Lightsource, Menlo Pk, CA 94025 USA
[6] Colorado Sch Mines, Mat Sci Program, Dept Chem & Geochem, Golden, CO 80401 USA
基金:
美国国家科学基金会;
关键词:
Sodiation;
kinetics;
nickel oxides;
reaction pathways;
conversion electrodes;
in situ TEM;
SODIUM-ION BATTERIES;
IN-SITU OBSERVATION;
ELECTROCHEMICAL LITHIATION;
NEGATIVE-ELECTRODE;
LITHIUM;
STORAGE;
NANOWIRES;
SURFACE;
CHALLENGES;
MICROSCOPY;
D O I:
10.1021/acs.nanolett.5b01709
中图分类号:
O6 [化学];
学科分类号:
0703 ;
摘要:
The development of sodium ion batteries (NIBs) can provide an alternative to lithium ion batteries (LIBs) for sustainable, low-cost energy storage. However, due to the larger size and higher m/e ratio of the sodium ion compared to lithium, sodiation reactions of candidate electrodes are expected to differ in significant ways from the corresponding lithium ones. In this work, we investigated the sodiation mechanism of a typical transition metal-oxide, NiO, through a set of correlated techniques, including electrochemical and synchrotron studies, real-time electron microscopy observation, and ab initio molecular dynamics (MD) simulations. We found that a crystalline Na2O reaction layer that was formed at the beginning of sodiation plays an important role in blocking the further transport of sodium ions. In addition, sodiation in NiO exhibits a "shrinking-core" mode that results from a layer-by-layer reaction, as identified by ab initio MD simulations. For lithiation, however, the formation of Li antisite defects significantly distorts the local NiO lattice that facilitates Li insertion, thus enhancing the overall reaction rate. These observations delineate the mechanistic difference between sodiation and lithiation in metal-oxide conversion materials. More importantly, our findings identify the importance of understanding the role of reaction layers on the functioning of electrodes and thus provide critical insights into further optimizing NIB materials through surface engineering.
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页码:5755 / 5763
页数:9
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