We studied the changes in the electronic structure of LiCoO2 induced by Li
deintercalation using Co 2p and O 1s X-ray absorption spectroscopy. The mea
n probing depth of this technique is similar to 50 Angstrom. The results we
re analyzed using atomic multiplet and band structure calculations. The Co
2p spectrum shows that the Co ions in LiCoO2 are in a trivalent Co3+ low-sp
in state. The Co 2p spectra of deintercalated LiCoO2 show only minor change
s as a function of Li concentration. The absence of changes indicates that
the Co ions remain mostly unaffected by Li deintercalation. In particular,
the Co ions in deintercalated LiCoO2 are not oxidized to a tetravalent Co4 state as normally assumed. The O 1s spectra of deintercalated LiCoO2 show
an increase in the absorption intensity below threshold; this absorption in
crease indicates that the O ions in LixCoO2 are reduced upon Li deintercala
tion. (C) 2000 The Electrochemical Society. S1099-0062(00)05-077-X. All rig
hts reserved.