Proton Ion Exchange Reaction in Li3IrO_4: A Way to New H_(3+x)IrO_4 Phases Electrochemically Active in Both Aqueous and Nonaqueous Electrolytes

摘要

Progress over the past decade in Li-insertion compounds has led to a new class of Li-rich layered oxide electrodes cumulating both cationic and anionic redox processes. Pertaining to this new class of materials are the Li/Na iridate phases, which present a rich crystal chemistry. This work reports on a new protonic iridate phase H3+xIrO4 having a layered structure obtained by room temperature acid-leaching of Li3IrO4. This new phase shows reversible charge storage properties of 1.5 e(-) per Ir atom with high rate capabilities in both nonaqueous (vs Li+/Li) and aqueous (vs capacitive carbon) media. It is demonstrated that Li-insertion in carbonate LiPF6-based electrolyte occurs through a classical reduction process (Ir5+ Ir3+), which is accompanied by a well-defined structural transition. In concentrated H2SO4 electrolyte, this work provides evidence that the overall capacity of 1.7 H+ per Ir results from two additive redox processes with the low potential one showing ohmic limitations. Altogether, the room temperature protonation approach, which can be generalized to various Li-rich phases containing either 3d, 4d or 5d metals, offers great opportunities for the judicious design of attractive electrode materials.