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Acta Physico-Chimica Sinca  2016, Vol. 32 Issue (6): 1489-1494    DOI: 10.3866/PKU.WHXB2016032802
ARTICLE     
Electron Microscopy Study of Surface Reconstruction and Its Evolution in P2-Type Na0.66Mn0.675Ni0.1625Co0.1625O2 for Sodium-Ion Batteries
Wei HUANG,Chun-Yang WU,Yue-Wu ZENG,Chuan-Hong JIN*(),Ze ZHANG
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Abstract  

We performed an aberration-corrected scanning transmission electron microscopy(STEM)andenergy-dispersive X-ray spectroscopy(EDS)study of Na0.66Mn0.675Ni0.1625Co0.1625O2,which was prepared via a solidstatereaction for sodium-ion battery applications.Powder X-ray diffraction(XRD)showed that the material hada well-crystallized P2-type layered structure(P63/mmc).Results from further STEM and EDS analyses showedthe presence of reconstructed surface layers of thickness about 1-2 nm,which contained a large amount ofantisite defects and obvious lattice distortions.Detailed chemical analysis showed an inhomogeneous elementaldistribution inside these reconstructed surface layers;they were cobalt rich and nickel deficient.These surfacelayers further evolved into thicker regions of width 5-10 nm,accompanied by a spinel(Fd3m)phase to rocksaltphase(Fm3m)transition.



Key wordsSodium ion battery      P2-type layer-structured cathode material      Surface reconstruction      Scanning transmission electron microscopy     
Received: 17 March 2016      Published: 28 March 2016
MSC2000:  O646  
Fund:  The project was supported by the National Natural Science Foundation of China(51222202)
Corresponding Authors: Chuan-Hong JIN     E-mail: chhjin@zju.edu.cn
Cite this article:

Wei HUANG,Chun-Yang WU,Yue-Wu ZENG,Chuan-Hong JIN,Ze ZHANG. Electron Microscopy Study of Surface Reconstruction and Its Evolution in P2-Type Na0.66Mn0.675Ni0.1625Co0.1625O2 for Sodium-Ion Batteries. Acta Physico-Chimica Sinca, 2016, 32(6): 1489-1494.

URL:

http://www.whxb.pku.edu.cn/10.3866/PKU.WHXB2016032802     OR     http://www.whxb.pku.edu.cn/Y2016/V32/I6/1489

Fig 1 (a) XRD patterns of Na0.66Mn0.675Ni0.1625Co0.1625O2 and (b) SEM image of as-prepared material The minor impurities are marked by the black arrows (a).
Fig 2 (a) Atomic model for the P2-Na0.66MO2 oriented along [110] direction (M represents the transition metal);(b, c) HAADF-STEM images of the bulk and the surface structures for a particle oriented along [110] direction; HAADF-STEM: high-angle annular dark field scanning transmission electron microscopy
Fig 3 (a-f) HAADF-STEM image of the surface layer for the particle in Fig.2and corresonding EDS maps;(g) quatification results of each rectangular area shown in Fig.3(a)
Fig 4 Expansion of surface reconstructed layer and sodium depletion caused by aging effect (a, b) HAADF-STEM imagesof an aged sample at different magnifications; (c) HAADF-STEM image of the surface reconstructed layer;(d, e) HAADF-STEM image of the surface reconstructed layer and corresponding EDS maps Spinel and rocksalt phases are present at the surface (c).
Fig 5 HAADF-STEM image of the upper-left part of the particle with exposed (001) facet in Fig.4(a) andcorresponding EDS maps
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