The rapid expansion of flexible and wearable electronics has necessitated a focus on ensuring their safety and operational reliability. Gel polymer electrolytes (GPEs) have become preferred alternatives to traditional liquid electrolytes, offering enhanced safety features and adaptability to the design requirements of flexible lithium-ion batteries. This review provides a comprehensive and critical overview of recent advancements in GPE technology, highlighting significant improvements in its physicochemical properties, which contribute to superior long-term cycling stability and high-rate capacity compared with traditional organic liquid electrolytes. Special attention is given to the development of smart GPEs endowed with advanced functionalities such as self-protection, thermotolerance, and self-healing properties, which further enhance battery safety and reliability. This review also critically examines the application of GPEs in high-energy cathode materials, including lithium nickel cobalt manganese (NCM), lithium nickel cobalt aluminum (NCA), and thermally stable lithium iron phosphate (LiFePO₄). Despite the advancements, several challenges in GPE development remain unresolved, such as improving ionic conductivity at low temperatures and ensuring mechanical integrity and interfacial compatibility. This review concludes by outlining future research directions and the remaining technical hurdles, providing valuable insights to guide ongoing and future efforts in the field of GPEs for lithium-ion batteries, with a particular emphasis on applications in high-energy and thermally stable cathodes.

The rapid expansion of flexible and wearable electronics has necessitated a focus on ensuring their safety and operational reliability. Gel Polymer Electrolytes (GPEs) have become preferred alternatives to traditional liquid electrolytes, offering enhanced safety features and adaptability to the design requirements of flexible lithium-ion batteries. This review provides a comprehensive and critical overview of recent advancements in GPEs technology, highlighting significant improvements in their physicochemical properties, which contribute to superior long-term cycling stability and high-rate capacity compared to traditional organic liquid electrolytes. Special attention is given to the development of smart GPEs endowed with advanced functionalities such as self-protection, thermotolerance, and self-healing properties, which further enhance battery safety and reliability. The review also critically examines the application of GPEs in high-energy cathode materials, including Lithium Nickel Cobalt Manganese (NCM), Lithium Nickel Cobalt Aluminum (NCA), and thermally stable Lithium Iron Phosphate (LiFePO4). Despite the advancements, several challenges in GPE development remain unresolved, such as improving ionic conductivity at low temperatures and ensuring mechanical integrity and interfacial compatibility. The review concludes by outlining future research directions and the remaining technical hurdles, providing valuable insights to guide ongoing and future efforts in the field of GPEs for lithium-ion batteries, with a particular emphasis on applications in high-energy and thermally stable cathodes.