Solid-to-Solid Manufacturing Processes for High-Performance Li-Ion Solid-State Batteries.

Abstract

Batteries are used as energy storage devices in various equipment. Today, research is focused on solid-state batteries (SSBs), replacing the liquid electrolyte with a solid separator. The solid separators provide electrolyte stability, no leakage, and provide mechanical strength to the battery. Separators are mostly manufactured by either traditional processes or 3D printing technologies. These processes involve making a slurry of plastic, active and conductive material and usually adding a plasticizer when making thin films or filaments for 3D printing. This study investigates the additive manufacturing of solid-state electrolytes (SSEs) by employing fused deposition modeling (FDM) with recyclable, bio-derived polylactic acid (PLA) filaments. Precise control of macro-porosity is achieved by systematically varying key process parameters, including raster orientation, infill percentage, and interlayer adhesion conditions, thereby enabling the formation of tunable, interconnected pore networks within the polymer matrix. Following 3D printing, these engineered porous frameworks are infiltrated with lithium hexafluorophosphate (LiPF₆), which functions as the active ionic conductor. A tailored thermal sintering protocol is then applied to promote solid-phase fusion of the embedded salt throughout the macro-porous PLA scaffold, resulting in a mechanically robust and ionically conductive composite separator. The electrochemical ionic conductivity and structural integrity of the sintered SSEs are characterized through electrochemical impedance spectroscopy (EIS) and standardized mechanical testing to assess their suitability for integration into advanced solid-state battery architectures. The solid-state separator achieved an average ionic conductivity of 2.529 × 10^-5 S·cm^-1. The integrated FDM-sintering process enhances ion exchange at the electrode-electrolyte interface, minimizes material waste, and supports cost-efficient, fully recyclable component fabrication.