Hydrogen‐Bonded Organic Frameworks‐based Electrolytes with Controllable Hydrogen Bonding Networks for Solid‐State Lithium Batteries

Abstract The lack of stable solid‐state electrolytes (SSEs) with high‐ionic conductivity and the rational design of electrode/electrolyte interfaces remains challenging for solid‐state lithium batteries. Here, for the first time, a high‐performance solid‐state lithium‐oxygen (Li−O 2 ) battery is developed based on the Li‐ion‐conducted hydrogen‐bonded organic framework (LHOF) electrolyte and the HOF‐DAT@CNT composite cathode. Benefiting from the abundant dynamic hydrogen bonding network in the backbone of LHOF‐DAT SSEs, fast Li + ion transport (2.2×10 −4 S cm −1 ), a high Li + transference number (0.88), and a wide electrochemical window of 5.05 V are achieved. Symmetric batteries constructed with LHOF‐DAT SSEs exhibit a stably cycled duration of over 1400 h with uniform deposition, which mainly stems from the jumping sites that promote a uniformly high rate of Li + flux and the hydrogen‐bonding network structure that can relieve the structural changes during Li + transport. LHOF‐DAT SSEs‐based Li−O 2 batteries exhibit high specific capacity (10335 mAh g −1 ), and stable cycling life up to 150 cycles. Moreover, the solid‐state lithium metal battery with LHOF‐DAT SSEs endow good rate capability (129.6 mAh g −1 at 0.5 C), long‐term discharge/charge stability (210 cycles). The design of LHOF‐DAT SSEs opens an avenue for the development of novel SSEs‐based solid‐state lithium batteries.