Trapped O2and the origin of voltage fade in layered Li-rich cathodes

Oxygen redox cathodes, such as Li1.2Ni0.13Co0.13Mn0.54O2, deliver higher energy densities than those based on transition metal redox alone. However, they commonly exhibit voltage fade, a gradually diminishing discharge voltage on extended cycling. Recent research has shown that, on the first charge, oxidation of O2−ions forms O2molecules trapped in nano-sized voids within the structure, which can be fully reduced to O2−on the subsequent discharge. Here we show that the loss of O-redox capacity on cycling and therefore voltage fade arises from a combination of a reduction in the reversibility of the O2−/O2redox process and O2loss. The closed voids that trap O2grow on cycling, rendering more of the trapped O2electrochemically inactive. The size and density of voids leads to cracking of the particles and open voids at the surfaces, releasing O2. Our findings implicate the thermodynamic driving force to form O2as the root cause of transition metal migration, void formation and consequently voltage fade in Li-rich cathodes.