3D printing of a high-performance composite solid-state electrolyte with enhanced interface stabilityOA

Polymer-ceramic composite electrolytes hold great promise for high-performance,flexible all-solid-state lithium(Li)metal batteries.However,limited ionic conductivity and high interfacial impedance remain major obstacles to their commercial deployment.Herein,a dual-composite solid electrolyte was fabricated using a simple and innovative 3D printing approach,incorporating a polyvinylidene fluoride(PVDF)-Li_(6.4)La_(3)Zr_(1.4)Ta_(0.6)O_(12)(LLZTO)structural layer and a polyethylene oxide(PEO)-LLZTO interfacial modification layer.In this design,the PVDF matrix serves as a robust structural framework,while the LLZTO filler synergistically enhances ionic conductivity by promoting Li-salt dissociation and suppresses dendrite formation through improved mechanical strength,particularly at the Li-metal interface.The dense PEO-LLZTO layer on the opposing side ensures intimate contact with the cathode,minimizes interfacial side reactions,and optimizes interfa-cial electrochemical properties,thereby enabling stable and high-performance all-solid-state Li batteries.At 25℃,the dual-composite solid electrolyte exhibits a high ionic conductivity of 4.87×10^(−4) S·cm^(−1) and a wide electrochemical stability window of 5.01 V.Leveraging this advanced electrolyte,LiLi symmetric cells demonstrate stable Li plating and stripping for over 1200 h at 0.1 mA·cm^(−2) without dendrite formation or short-circuiting.Correspondingly,LiFePO4/Li full cells deliver excellent electrochemical performance,maintaining 98.2%capacity retention after 200 cycles.These results highlight that employing a dual-composite solid electrolyte is an effective strategy for mitigating interfacial challenges,thereby enabling the development of high-performance solid-state Li-metal batteries.