title: New insight into the atomic structure of electrochemically delithiated O3-Li(₁-x)CoO₂ (0 ≤ x ≤ 0.5) nanoparticles.
abstract: Direct observation of delithiated structures of LiCoO(2) at atomic scale has been achieved using spherical aberration-corrected scanning transmission electron microscopy (STEM) with high-angle annular-dark-field (HAADF) and annular-bright-field (ABF) techniques. The ordered Li, Co, and O columns for LiCoO(2) nanoparticles are clearly identified in ABF micrographs. Upon the Li ions extraction from LiCoO(2), the Co-contained (003) planes distort from the bulk to the surface region and the c-axis is expanded significantly. Ordering of lithium ions and lithium vacancies has been observed directly and explained by first-principles simulation. On the basis of HAADF micrographs, it is found that the phase irreversibly changes from O3-type in pristine LiCoO(2) to O1-type Li(x)CoO(2) (x ≈ 0.50) after the first electrochemical Li extraction and back to O2-type Li(x)CoO(2) (x ≈ 0.93) rather than to O3-stacking after the first electrochemical lithiation. This is the first report of finding O2-Li(x)CoO(2) in the phase diagram of O3-LiCoO(2), through which the two previously separated LiCoO(2) phases, i.e. O2 and O3 systems, are connected. These new investigations shed new insight into the lithium storage mechanism in this important cathode material for Li-ion batteries.
authors.affiliation: Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China.
authors.forename: Xia
authors.initials: X
authors.lastname: Lu
authors.forename: Yang
authors.initials: Y
authors.lastname: Sun
authors.forename: Zelang
authors.initials: Z
authors.lastname: Jian
authors.forename: Xiaoqing
authors.initials: X
authors.lastname: He
authors.forename: Lin
authors.initials: L
authors.lastname: Gu
authors.forename: Yong-Sheng
authors.initials: YS
authors.lastname: Hu
authors.forename: Hong
authors.initials: H
authors.lastname: Li
authors.forename: Zhaoxiang
authors.initials: Z
authors.lastname: Wang
authors.forename: Wen
authors.initials: W
authors.lastname: Chen
authors.forename: Xiaofeng
authors.initials: X
authors.lastname: Duan
authors.forename: Liquan
authors.initials: L
authors.lastname: Chen
authors.forename: Joachim
authors.initials: J
authors.lastname: Maier
authors.forename: Susumu
authors.initials: S
authors.lastname: Tsukimoto
authors.forename: Yuichi
authors.initials: Y
authors.lastname: Ikuhara