The Assembly of a High-Efficiency Tris-benzotriazolate-Based Metal–Organic Framework Solid-State Electrolyte

Metal–organic frameworks (MOFs) with tunable ion transport pathways are considered promising solid-state electrolyte (SSE) candidates for developing lithium or sodium metal batteries. However, their low ionic conductivity and inferior stability with metal anodes limit practical applications. Herein we synthesized a high-stability tris-benzotriazolate-based MOFCu-TTBTwith ordered pore channels for SSE applications via a network-directed approach. Cu-TTBT, overcoming the synthetic challenge of tritopic benzotriazolate-based linkers, greatly advances the field of azolate-based MOFs. The resultant framework displays fast ion transport pathways with a high ionic conductivity of 1.83 × 10–4 S cm–1 and 1.1 × 10–4 S cm–1 at 298 K for Cu-TTBT-Li and Cu-TTBT-Na, respectively, among the highest in azolate-based MOFs. The Li|SSE|LiFePO4 and Na|SSE|Na3V2(PO4)3 coin cells exhibit stable cycling performances over 200 cycles at 1.0 C and 298 K. This research advances the synthetic chemistry of azolate-based MOFs and paves the way for the development of robust frameworks with high-efficiency SSE performances.