In situ synchrotron diffraction revealed a stepwise appearance of two new phases upon electrochemical lithium extraction from LiCoPO 4 . These phases were demonstrated to have the same olivine-like structure as the pristine compound. The lithium-deficient phases were proposed to be Li 0.7 CoPO 4 and CoPO 4 . The completely delithiated phase appears to be unstable in air and undergoes amorphization. The phase transitions are reversible, but a slow kinetics of the initial delithiation was identified by in situ synchrotron diffraction and the potentiostatic intermittent titration technique. We demonstrated that the electrochemical extraction of lithium is accompanied by significant electrolyte decomposition, contributing to the capacity loss upon cycling. The galvanostatic intermittent titration technique combined with impedance spectroscopy revealed self-discharge of the cell in the charged state. This study argues different mechanisms of lithium extraction from LiCoPO 4 in comparison with LiFePO 4 and LiMnPO 4 .

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Li(x)CoO(2) and Li(x)NiO(2) (0.5 < x < 1) are used as prototype cathode materials in lithium ion batteries. Both systems show degradation and fatigue when used as cathode material during electrochemical cycling. In order to analyze the change of the structure and the electronic structure of Li(x)CoO(2) and Li(x)NiO(2) as a function of Li content x in detail, we have performed X-ray diffraction studies, photoelectron spectroscopy (PES) investigations and band structure calculations for a series of compounds Li(x)(Co,Ni)O(2) (0 < x < or = 1). The calculated density of states (DOS) are weighted by theoretical photoionization cross sections and compared with the DOS gained from the PES experiments. Consistently, the experimental and calculated DOS show a broadening of the Co/Ni 3d states upon lithium de-intercalation. The change of the shape of the experimental PES curves with decreasing lithium concentration can be interpreted from the calculated partial DOS as an increasing energetic overlap of the Co/Ni 3d and O 2p states and a change in the orbital overlap of Co/Ni and O wave functions.