Enabling All-Solid-State Lithium–Carbon Dioxide Battery Operation in a Wide Temperature Range

Flexible all-solid-state lithium–carbon dioxide batteries (FASSLCBs) are recognized as a next-generation energy storage technology by solving safety and shuttle effect problems. However, the present FASSLCBs rely heavily on high-temperature operation due to sluggish solid–solid–gas multiphase mass transfer and unclear capacity degradation mechanism. Herein, we designed bicontinuous hierarchical porous structures (BCHPSs) for both solid polymer electrolyte and cathode for FASSLCBs to facilitate the mass transfer in all connected directions. The formed large Lewis acidic surface effectively promotes the lithium salt dissociation and the CO2 conversion. Furthermore, it is unraveled that the battery capacity degradation originates from the "dead Li2CO3" formation, which is inhibited by the fast decomposition of Li2CO3. Accordingly, the assembled FASSLCBs exhibit an excellent cycling stability of 133 cycles at 60 °C, which is 2.7 times longer than that without BCHPSs, and the FASSLCBs can be operated repeatedly even at room temperature. This BCHPS method and fundamental deactivation mechanism provide a perspective for designing FASSLCBs with long cycling life.