Electrochemical lithium ion intercalation in Li0.5Ni0.25TiOPO4 examined by in situ X-ray diffraction

Abstract

The complex structural transformations of Li0.5Ni0.25TiOPO4 during electrochemical lithiation have been examined by in situ X-ray diffraction. During the first lithiation two structural changes take place: first a transition to a second monoclinic phase (a=9.085(4), b=8.414(5), c=6.886(5), β=99.85(4)) and secondly a transition to a third phase with limited long-range order. The third phase is held together by a network of corner sharing Ti–O octahedra and phosphate ions with disordered Ni–Li channels. During delithiation the third phase is partially transformed back to a slightly disordered original phase, Li0.5Ni0.25TiOPO4 without formation of the second intermediate phase. These phase transitions correspond well to the different voltage plateaus that this material shows during electrochemical cycling.