For LiMO2 (M=Co, Ni, Mn) cathode materials, lattice parameters, a(b), contract during charge. Here we report such changes in opposite directions for lithium molybdenum trioxide (Li2MoO3). A 'unit cell breathing' mechanism is proposed based on crystal and electronic structural changes of transition metal oxides during charge-discharge. Metal-metal bonding is used to explain such 'abnormal' behaviour and a generalized hypothesis is developed. The expansion of the metal-metal bond becomes the controlling factor for a(b) evolution during charge, in contrast to the shrinking metal-oxygen bond as controlling factor in 'normal' materials. The cation mixing caused by migration of molybdenum ions at higher oxidation state provides the benefits of reducing the c expansion range in the early stage of charging and suppressing the structure collapse at high voltage charge. These results may open a new strategy for designing layered cathode materials for high energy density lithium-ion batteries.