La and Y ′ Zr result in a higher equilibrium concentration than the nominal dopant concentration and hence the nominal dopant concentration showing less destabilisation of V ′ Li . Furthermore, it is often assumed that the added dopants only will reside on the lowest energy sites. This, however, is not true and is especially important to keep in mind when investigating dopants that result in defects with relatively high and similar formation energies at the Fermi level such as Ga:LLZO. There will be a Boltzmann distribution over all available lattice sites, and for Ga, this means that the dopants will mainly be located at Li and Zr sites, but also at La sites. This type of non-convergent disordering of cations has for instance been studied in spinels, complex oxide LaSr 2 -x Ca x Cu 2 GaO 7 and more recently in tetragonal tungsten bronzes. 90