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Solid electrolytes with sufficiently high conductivities and stabilities are the elusive answer to the inherent shortcomings of organic liquid electrolytes prevalent in today's rechargeable batteries. We recently revealed a novel fast-ion-conducting sodium salt, Na 2 B 12 H 12 , which contains large, icosahedral, divalent B 12 H 12  2- anions that enable impressive superionic conductivity, albeit only above its 529 K phase transition. Its lithium congener, Li 2 B 12 H 12 , possesses an even more technologically prohibitive transition temperature above 600 K. Here we show that the chemically related LiCB 11 H 12 and NaCB 11 H 12 salts, which contain icosahedral, monovalent CB 11 H 12  - anions, both exhibit much lower transition temperatures near 400 K and 380 K, respectively, and truly stellar ionic conductivities (&gt; 0.1 S cm -1 ) unmatched by any other known polycrystalline materials at these temperatures. With proper modifications, we are confident that room-temperature-stabilized superionic salts incorporating such large polyhedral anion building blocks are attainable, thus enhancing their future prospects as practical electrolyte materials in next-generation, all-solid-state batteries.

Unparalleled lithium and sodium superionic conduction in solid electrolytes with large monovalent cage-like anions