The influence of the initial Li/Co stoichiometry in LiCoO (LCO) (1.00 ≤ Li/Co ≤ 1.05) on the phase-transition mechanisms occurring at high voltage during lithium deintercalation ( V > 4.5 vs Li/Li) was investigated by in situ X-ray diffraction. Even if the excess Li in LiCoO does not hinder the formation of the H1-3 and O1 phases, the latter are obtained at higher voltages and exhibit larger c parameters compared with their analogues formed from LiCoO. We also showed that for the stoichiometric LiCoO the deintercalation process is more complex than already reported, with the formation of an intermediate structure between H1-3 and O1.

High-entropy ceramics are attracting large interest because of their unique materials properties. Nevertheless, the effect of entropy on the lithium transport remains largely elusive. Here, we report, for the first time, about medium- and high-entropy polyanionic lithium superionic conductors crystallizing in the F–43m space group and adopting the so-called argyrodite structure. The Li6PS5[Cl0.33Br0.33I0.33], Li6P­[S2.5Se2.5]­[Cl0.33Br0.33I0.33], and Li6.5[Ge0.5P0.5]­[S2.5Se2.5]­[Cl0.33Br0.33I0.33] materials were structurally characterized using complementary synchrotron and neutron scattering techniques in combination with 31P magic-angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy. We show that, in contrast to other high-entropy ceramics, an unequal distribution of elements over the respective crystallographic sites occurs in these materials. Using electrochemical impedance spectroscopy (EIS) and 7Li pulsed field gradient (PFG) NMR spectroscopy, we demonstrate that introducing entropy (compositional disorder) marginally affects the room-temperature ionic conductivity (∼10–3 S cm–1) but instead lowers the activation energy for conduction to 0.22 eV. Our results emphasize the possibility of increasing entropy in polyanionic materials, thereby opening up compositional space for the search of Li-ion conductors with unprecedented properties.