Scalable Synthesis of Selenide Solid-State Electrolytes for Sodium-Ion Batteries.

Solid-state sodium-ion batteries employing superionic solid-state electrolytes (SSEs) offer low manufacturing costs and improved safety and are considered to be a promising alternative to current Li-ion batteries. Solid-state electrolytes must have high chemical/electrochemical stability and superior ionic conductivity. In this work, we employed precursor and solvent engineering to design scalable and cost-efficient solution routes to produce air-stable sodium selenoantimonate (Na3SbSe4). First, a simple metathesis route is demonstrated for the production of the Sb2Se3 precursor that is subsequently used to form ternary Na3SbSe4 through two different routes: alcohol-mediated redox and alkahest amine-thiol approaches. In the former, the electrolyte was successfully synthesized in EtOH by using a similar redox solution coupled with Sb2Se3, Se, and NaOH as a basic reagent. In the alkahest approach, an amine-thiol solvent mixture is utilized for the dissolution of elemental Se and Na and further reaction with the binary precursor to obtain Na3SbSe4. Both routes produced electrolytes with room temperature ionic conductivity (∼0.2 mS cm-1) on par with reported performance from other conventional thermo-mechanical routes. These novel solution-phase approaches showcase the diversity and application of wet chemistry in producing selenide-based electrolytes for all-solid-state sodium batteries.