X-ray/neutron diffraction and electrochemical studies of lithium De/Re-intercalation in Li1-xCo1/3Ni1/3Mn1/3O2 (x=0→1)

被引:263
作者
Yin, SC
Rho, YH
Swainson, I
Nazar, LF [1 ]
机构
[1] Univ Waterloo, Dept Chem, Waterloo, ON N2L 3G1, Canada
[2] AECL Res, Chalk River Labs, Chalk River, ON K0J 1J0, Canada
关键词
D O I
10.1021/cm0511769
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
X-ray and neutron diffraction studies were carried out on highly ordered (2-3% Li/Ni exchange) layered Li1-xCo1/3Ni1/3Mn1/3O2 [(1 - x) = 1.0; 0.8, 0.6, 0.45, 0.30, 0.04] prepared by chemical delithiation and relithiation. The studies reveal that the initial R(3) over bar m phase (O3) is maintained up to extraction of 0.70-0.75 Li and exhibits only similar to 1% change in volume over the range of composition. Additional extraction of Li results in the appearance of the 01 phase (trigonal; P3m1), which displays a strong contraction in the c axis by 5.3% and a volume decrease of 7.2%. Oxygen vacancies were not evident in the completely delithiated material. Re-intercalation of lithium in this phase was relatively irreversible, however, resulting in poorly defined mixtures of the 03 and 01 structures that exhibited a large fraction of stacking faults. In contrast, materials that were not delithiated beyond x = 0.30 resulted in fully reversible reformation of the original crystalline 03 phase on re-intercalation. Electrochemical cycling under different cutoff voltages were in accord with these observations and suggest an optimum upper cutoff voltage of 4.3-4.4 V.
引用
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页码:1901 / 1910
页数:10
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