Stacking Faults in an O2-type Cobalt-Free Lithium-Rich Layered Oxide: Mechanisms of the Ion Exchange Reaction and Lithium Electrochemical (De)Intercalation
Valentin Saïbi, Laurent Castro, Issei Sugiyama, Stéphanie Belin, Claude Delmas, Marie Guignard
Abstract
The metastable, O2-type cobalt-free lithium-rich layered oxide Li 0.84 Ni 0.14 Mn 0.72 O 2 was successfully prepared by a new all-solid-state ion-exchange reaction from the P2-type sodium layered oxide precursor Na 0.7 [Li 0.14 Ni 0.14 Mn 0.72 ]O 2 using lithium chloride at moderate temperature. The particular oxygen stacking in the resulting O2-type structure is assumed to suppress the detrimental layer-to-spinel phase transition usually observed upon cycling in conventional O3-type lithium-rich layered oxides due to the irreversible migration of transition metal cations, causing substantial voltage decay and capacity fading. Despite the existence of stacking faults originating from the P2-to-O2 topotactic reaction during the Na + -to-Li + exchange, as evidenced by X-ray diffraction simulation and high-resolution microscopy, the electrochemical tests conducted on the faulted O2-type positive electrode material revealed a greatly improved reversible (de)intercalation mechanism along with high specific capacity values. An operando X-ray diffraction study indicated that there are only small structural changes upon cycling and that they are stable and reversible. Moreover, operando X-ray absorption spectroscopy experiments showed that a large part of the capacity relies on the oxygen redox, which is also reversible upon cycling.