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−O₂) 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−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 (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.