title: In situ XAS study of LixNi0.7Fe0.15Co0.15O2 cathode material.
abstract: We have examined the oxidation states and local atomic structures of Ni, Fe, and Co in Li(x)Ni0.7Fe0.15Co0.15O2 as a function of Li content during the first charge in a Li/Li(x)Ni0.7Fe0.15Co0.15O2 nonaqueous cell. We show that the composition of the material in the pristine state is more accurately described by Li0.95Ni(II)0.09Ni(III)0.66Fe(III)0.15Co(III)0.25O2 Half of the Ni(II) resides in Li-vacant sites. Both Fe and Co substitute for Ni within the NiO2 slabs with no significant amounts of Fe or Co that can be attributed to Li-vacant sites. The local structure parameters are consistent with oxidation states observed on the basis of the XANES data. The Ni K-edge energy continuously shifts to a higher energy with decrease in Li content due to oxidation of Ni(II) to Ni(II) and Ni(III) to Ni(IV). After the complete oxidation of Ni(III) to Ni(IV), the Fe K-edge energy begins to increase with further decrease in Li content indicating the oxidation of Fe(III) to Fe(IV). The Co K-edge energy at half-height, on the other hand, is unchanged during the whole range of Li deintercalation indicating that no significant change in the oxidation state of Co occurs upon the complete removal of Li.
authors.affiliation: Naval Surface Warfare Center, Carderock Division, West Bethesda, MD 20817-5700, USA. MansourAN@nswccd.navy.mil
authors.forename: A N
authors.initials: AN
authors.lastname: Mansour
authors.forename: L
authors.initials: L
authors.lastname: Croguennec
authors.forename: G
authors.initials: G
authors.lastname: Prado
authors.forename: C
authors.initials: C
authors.lastname: Delmas