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 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 battery is developed based on the Li‐ion‐conducted hydrogen‐bonded organic framework (LHOF) electrolyte and the core‐shell HOF‐DAT@CNT cathode with a few layers of HOF‐DAT on surface of carbon nanotubes. Benefiting from the abundant dynamic hydrogen bonding network in LHOF‐DAT SSEs, fast Li+ ion transport (2.2 × 10–4 S cm–1), a high Li+ transfer 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, 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–O2 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 (128.8 mAh g–1 at 1 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.