Dual Substitution Strategy to Enhance Li⁺ Ionic Conductivity in Li₇La₃Zr₂O₁₂ Solid Electrolyte

Solid state electrolytes could address the current safety concerns of lithium-ion batteries as well as provide higher electrochemical stability and energy density. Among solid electrolyte contenders, garnet-structured Li 7 La 3 Zr 2 O 12 appears as a particularly promising material owing to its wide electrochemical stability window; however, its ionic conductivity remains an order of magnitude below that of ubiquitous liquid electrolytes. Here, we present an innovative dual substitution strategy developed to enhance Li-ion mobility in garnet-structured solid electrolytes. A first dopant cation, Ga 3+, is introduced on the Li sites to stabilize the fast-conducting cubic phase. Simultaneously, a second cation, Sc 3+, is used to partially populate the Zr sites, which consequently increases the concentration of Li ions by charge compensation. This aliovalent dual substitution strategy allows fine-tuning of the number of charge carriers in the cubic Li 7 La 3 Zr 2 O 12 according to the resulting stoichiometry, Li 7–3 x +y Ga x La 3 Zr 2– y Sc y O 12 . The coexistence of Ga and Sc cations in the garnet structure is confirmed by a set of simulation and experimental techniques: DFT calculations, XRD, ICP, SEM, STEM, EDS, solid state NMR, and EIS. This thorough characterization highlights a particular cationic distribution in Li 6.65 Ga 0.15 La 3 Zr 1.90 Sc 0.10 O 12, with preferential Ga 3+ occupation of tetrahedral Li 24 d sites over the distorted octahedral Li 96 h sites. 7 Li NMR reveals a heterogeneous distribution of Li charge carriers with distinct mobilities. This unique Li local structure has a beneficial effect on the transport properties of the garnet, enhancing the ionic conductivity and lowering the activation energy, with values of 1.8 × 10 –3 S cm –1 at 300 K and 0.29 eV in the temperature range of 180 to 340 K, respectively.