Solid-state electrolytes are widely expected to enhance the performance of lithium-ion batteries, providing higher energy density and improved safety. However, challenges still need to be solved in their practical application due to low ionic conductivity and high interfacial resistance at room temperature. In this study, we successfully developed a high-performance gel polymer electrolyte (GPEs) by blending poly(vinylidene fluoride-co-hexafluoropropylene)(PVDF-HFP) and polyacrylonitrile (PAN) through UV curing, cross-linking with ethoxylated trimethylolpropane triacrylate (ETPTA), and incorporating Li_6.4La₃Zr_1.4Ta_0.6O₁₂ (LLZTO). At room temperature, the ionic conductivity of the GPEs was 2.8 × 10⁻⁴ S/cm, with a lithium-ion transference number of 0.6. Moreover, during lithium plating/stripping tests, the assembled Li/PPEL/Li symmetric cell exhibited stable cycling for up to 600 h at a current density of 0.1 mA/cm². Notably, the GPEs enabled the LiFePO₄/GPEs/Li battery to achieve excellent performance, delivering high discharge capacities at room temperature (164.3 mAh g⁻¹ at 0.1 C and 88.8 mAh g⁻¹ at 1 C), with a capacity retention of 89.4% after 200 cycles at 0.5 C. Therefore, solid-state batteries using this electrolyte exhibit excellent performance, including adequate capacity and cycling stability.

Solid-state electrolytes (SSEs) have emerged as a promising solution for next-generation lithium-ion batteries due to their excellent safety and high energy density. However, their practical application is still hindered by critical challenges such as their low ionic conductivity and high interfacial resistance at room temperature. The innovative application of 3D printing in the field of electrochemistry, particularly in solid-state electrolytes, endows energy storage devices with attractive characteristics. In this study, ceramic-in-gel polymer electrolytes (GPEs) based on PVDF-HFP/PAN@LLZTO were fabricated using a direct ink writing (DIW) 3D printing technique. Under the optimal printing conditions (printing speed of 40 mm/s and fill density of 70%), the printed electrolyte exhibited a uniform and dense sponge-like porous structure, achieving a high ionic conductivity of 5.77 × 10⁻⁴ S·cm⁻¹, which effectively facilitated lithium-ion transport. A structural analysis indicated that the LLZTO fillers were uniformly dispersed within the polymer matrix, significantly enhancing the electrochemical stability of the electrolyte. When applied in a LiFePO₄|GPEs|Li cell configuration, the electrolyte delivered excellent electrochemical performance, with high initial discharge capacities of 168 mAh·g⁻¹ at 0.1 C and 166 mAh·g⁻¹ at 0.2 C, and retained 92.8% of its capacity after 100 cycles at 0.2 C. This work demonstrates the great potential of 3D printing technology in fabricating high-performance GPEs. It provides a novel strategy for the structural design and industrial scalability of lithium-ion batteries.