Advances in electrospun nanofiber engineering for solid-state electrolytes: Pioneering technologies, diversified indicators, and extensive applications

Conventional liquid lithium-ion batteries (LIBs) face inherent safety risks and limited energy density. In contrast, solid-state batteries (SSBs) incorporating solid-state electrolytes (SSEs) have emerged as promising alternatives. Their appeal arises from the superior attributes of SSEs, which suppress lithium dendrite growth, enable long-term cycling stability, and operate across wide temperature ranges, properties demonstrating immense potential for electronics, electric vehicles, smart grids, and biomedical devices. However, practical deployment of SSBs is hindered by critical challenges, including low ionic conductivity and inadequate mechanical integrity of SSEs. Nano-structural engineering, particularly via electrospun nanofiber engineering, offers an efficient strategy to tailor SSEs architecture and composition, enhancing both ionic transport and mechanical robustness. Capitalizing on its simplicity, cost-effectiveness, and compatibility with diverse technical integrations, electrospinning represents a compelling nanomanufacturing platform for next-generation SSEs. This review first delineates electrospinning fundamentals and applications, followed by a systematic summary of synergistic methodologies integrating electrospinning with complementary fabrication techniques. We then critically analyze how electrospun nanofibrous frameworks modulate SSEs performance and discuss mechanistic roles of these structures in SSEs. Finally, we outline innovative refinements in electrospinning technology and emphasize future prospects for electrospun nanofiber-based SSEs, highlighting scalable manufacturing, interfacial engineering, and sustainability-driven design.