Nb18W8O69 (9Nb2O5×8WO3) is the tungsten-rich end-member of the Wadsley–Roth crystallographic shear (cs) structures within the Nb2O5–WO3 series. It has the largest block size of any known, stable Wadsley–Roth phase, comprising 5 ´ 5 units of corner-shared MO6 octahedra between the shear planes, giving rise to 2 nm ´ 2 nm blocks. Rapid lithium intercalation is observed in this new candidate battery material and 7Li pulsed field gradient nuclear magnetic resonance spectroscopy – measured in a battery electrode for the first time at room temperature – reveals superionic lithium conductivity. In addition to its promising rate capability, Nb18W8O69 adds a piece to the larger picture of our understanding of high-performance Wadsley–Roth complex metal oxides.
