X-ray/Neutron Diffraction and Electrochemical Studies of Lithium De/Re-Intercalation in Li₁₋xCo1/₃Ni1/3Mn1/3O₂ (x = 0 → 1)

X-ray and neutron diffraction studies were carried out on highly ordered (2−3% Li/Ni exchange) layered Li 1 - x Co 1/3 Ni 1/3 Mn 1/3 O 2 [(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 3̄ m phase (O3) is maintained up to extraction of 0.70−0.75 Li and exhibits only ∼1% change in volume over the range of composition. Additional extraction of Li results in the appearance of the O1 phase (trigonal; P 3̄ m 1), 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 O3 and O1 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 O3 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.