Trapped O2 and the orgin of voltage fade in layered Li-rich cathodes

5um magnification of a detail of the sample

A team of researchers from this department, the Faraday Institution and Diamond Light Source investigated 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 O2 molecules trapped in nano-sized voids within the structure, which can be fully reduced to O2- on the subsequent discharge. 


In this paper* the authors demonstrate 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-/O2 redox process and O2 loss.   The closed voids that trap O2 grow on cycling, rendering more of the trapped O2 electrochemically inactive.  The size and density of voids leads to cracking of the particles and open voids at the surfaces, releasing O2.


The findings implicate the thermodynamic driving force to form O2 as the root cause of transition metal migration, void formation and consequently voltage fade in Li-rich cathodes.


*'Trapped O2 and the origin of voltage fade in layered Li-rich cathodes' published in Nature Materials.