Organic cathode materials have attracted widespread attention due to their diverse structures, abundant raw materials, low cost, and eco-friendliness. However, their practical applications are restricted because of the poor cycling stability and lifespan owing to the dissolution and shuttle effect of the organic cathode in the liquid electrolyte. In this work, a novel all-solid-state Li-organic battery with ultralong lifespan is developed by using perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) as the organic cathode, composite solid polymer electrolyte (hybrid polymer-LiTFSI-LLZTO, HLL) as the electrolyte, and Li metal as the anode. The as-prepared HLL electrolyte exhibits high ionic conductivity (1.46 × 10^-4 S cm⁻¹ at 30 °C), superior thermal stability (~202 °C), outstanding electrode/electrolyte interfacial compatibility, and significant suppression to the dissolution/shuttle of PTCDA and the growth of Li dendrite. Ascribing to these advantages, the solid-state PTCDA|HLL|Li battery delivers a reversible capacity of 60 mAh g⁻¹ after 1000 cycles at a high current density of 500 mA g⁻¹, corresponding to an outstanding capacity retention of 91%. Moreover, the solid-state PTCDA|Li battery presents an elevated thermal stable window (178 °C) and less heat release (430 J g⁻¹) compared with the analogous battery using liquid electrolyte (151 °C and 486 J g⁻¹). Furthermore, the solid-state battery exhibits desirable flexibility and satisfactory safety under various abuse conditions (bending, cutting, and punching), demonstrating its outstanding safety in practical environments. This work offers a new pathway toward safer, longer lifespan solid-state Li-organic batteries.

有机阴极材料因其结构多样，原料丰富，成本低廉和环保而受到广泛关注。然而，由于有机阴极在液体电解质中的溶解和穿梭效应，循环稳定性和寿命差，限制了它们的实际应用。在这项工作中，通过使用per 3,4,9,10-四羧酸二酐（PTCDA）作为有机阴极，复合固体聚合物电解质（混合聚合物- LiTFSI-LLZTO（HLL）作为电解质，Li金属作为阳极。所制备的HLL电解质具有高离子电导率（1.46×10 ^-4 S cm ^-1在30°C下），优异的热稳定性（〜202°C），出色的电极/电解质界面相容性以及对PTCDA溶解/穿梭和Li树枝状晶体生长的显着抑制作用。归因于这些优点，固态PTCDA | HLL | Li电池在1000次循环后以500 mA g ^-1的高电流密度提供了60 mAh g ^-1的可逆容量，相当于91％的出色容量保持率。此外，与使用液体电解质的类似电池（151°C和486 J g ^-1）相比，固态PTCDA | Li电池具有更高的热稳定窗口（178°C）和更少的热释放（430 J g ^-1）。）。此外，固态电池在各种滥用条件（弯曲，切割和打孔）下表现出理想的柔韧性和令人满意的安全性，证明了其在实际环境中的出色安全性。这项工作提供了一条通往更安全，更长寿命的固态锂有机电池的新途径。