Microporous Metal–Organic Framework (MOF)-Based Composite Polymer Electrolyte (CPE) Mitigating Lithium Dendrite Formation in All-Solid-State-Lithium Batteries

[Image: see text] Poly(ethylene oxide) (PEO)-based composite polymer electrolytes (CPEs) containing the amine-functionalized, zirconium-based metal–organic framework @silica (UiO-66-NH(2)@SiO(2)) and lithium, LiN(CF(3)SO(2))(2) salt (LiTFSI) are prepared using a simple hot press method. The electrochemical properties such as compatibility of the electrolyte with the Li metal anode, Li transference number, and ionic conductivity are investigated for the different systems containing different relative concentrations of the additives. The incorporation of UiO-66-NH(2)@SiO(2) in the PEO-LiTFSI matrix not only enhanced ionic conductivity by one order of magnitude but also offered better compatibility and suppressed the formation of lithium dendrites appreciably. X-ray photoelectron spectroscopy studies on post-cycled materials revealed the formation of lithium alkoxide (RO–Li) on the cathode and Li(2)O on the anode. The coin cell (2032-type) consisting of LiFePO(4)/CPE/Li with UiO-66-NH(2)@SiO(2) as filler provided a discharge capacity of 151 mA h g(–1) at 0.1 C-rate at 60 °C, measurably higher than control experiments utilizing SiO(2) and UiO-66-NH(2). The notable enhancement of electrochemical properties when incorporating the UiO-66-NH(2)@SiO(2) at the CPE was attributed to formation of more uniform ion conduction pockets and channels within the PEO matrix, facilitated by the presence of the microporous UiO-66-NH(2)@SiO(2). The enhanced distribution of microporous channels, where Li ions are assumed to percolate through within the matrix, is assumed to desirably reduce formation of Li dendrites by increasing diffusion channels and therefore reducing crystallization and growth of dendrites at the electrode surface.