Computationally Guided Discovery of the Sulfide Li(3)AlS(3) in the Li–Al–S Phase Field: Structure and Lithium Conductivity

[Image: see text] With the goal of finding new lithium solid electrolytes by a combined computational–experimental method, the exploration of the Li–Al–O–S phase field resulted in the discovery of a new sulfide Li(3)AlS(3). The structure of the new phase was determined through an approach combining synchrotron X-ray and neutron diffraction with (6)Li and (27)Al magic-angle spinning nuclear magnetic resonance spectroscopy and revealed to be a highly ordered cationic polyhedral network within a sulfide anion hcp-type sublattice. The originality of the structure relies on the presence of Al(2)S(6) repeating dimer units consisting of two edge-shared Al tetrahedra. We find that, in this structure type consisting of alternating tetrahedral layers with Li-only polyhedra layers, the formation of these dimers is constrained by the Al/S ratio of 1/3. Moreover, by comparing this structure to similar phases such as Li(5)AlS(4) and Li(4.4)Al(0.2)Ge(0.3)S(4) ((Al + Ge)/S = 1/4), we discovered that the AlS(4) dimers not only influence atomic displacements and Li polyhedral distortions but also determine the overall Li polyhedral arrangement within the hcp lattice, leading to the presence of highly ordered vacancies in both the tetrahedral and Li-only layer. AC impedance measurements revealed a low lithium mobility, which is strongly impacted by the presence of ordered vacancies. Finally, a composition–structure–property relationship understanding was developed to explain the extent of lithium mobility in this structure type.