Stereolithography Three-Dimensional Printing Solid Polymer Electrolytes for All-Solid-State Lithium Metal Batteries

Liquid-free all-solid-state lithium metal batteries (ASSLMBs) are promising candidates to meet the requirements of safety and high energy density for energy storages. However, poor interfacial contact is a major obstacle limiting their applications. Herein, we report a solid polymer electrolyte (SPE), originally prepared by stereolithography (SLA) three-dimensional (3D) printing for ASSLMBs. A 3D-Archimedean spiral structured SPE is rationally designed, which can shorten the Li-ion transport pathway from the electrolyte into the electrode, reinforce the interfacial adhesion, and improve the mass loading of active materials. The SLA printed SPE exhibits a high ionic conductivity of 3.7 × 10^-4 S cm^-1 at 25 °C. Furthermore, Li|3D-SPE|LFP cells achieve reduced interfacial impedance and higher specific capacity of 128 mAh g^-1 after 250 cycles than those using structure-free SPE of 32 mAh g^-1. This work opens the great promise of SLA 3D printing technology to fabricate high-performance SPEs in ASSLMBs for next-generation energy storages.