Ultrathin Aramid/COF Heterolayered Membrane for Solid-State Li-Metal Batteries.

Ultrathin, ultrastrong, and highly conductive solid-state polymer-based composite electrolytes have long been exploited for the next-generation lithium-based batteries. In particular, the lightweight membranes that are less than tens of microns are strongly desired, aiming to maximize the energy densities of solid-state batteries. However, building such ideal membranes are challenging when using traditional materials and fabrication technologies. Here we reported a 7.1 µm thick heterolayered Kevlar/covalent organic framework (COF) composite membrane fabricated via a bottom-up spin layer-by-layer assembly technology that allows for precise control over the structure and thickness of the obtained membrane. Much stronger chemical/mechanical interactions between cross-linked Kevlar and conductive 2D-COF building blocks were designed, resulting in a highly strong and Li+ conductive (1.62 × 10-4 S cm-1 at 30 °C and 4.6 × 10-4 S cm-1 at 70 °C) electrolyte membrane that can prevent solid-state batteries from short-circuiting after over 500 h of cycling. All-solid-state lithium batteries using this membrane enable a significantly improved energy density.

Simple Transformation of Covalent Organic Frameworks to Highly Proton-Conductive Electrolytes.

We report the rational design and implementation of a new class of gel guest-assisted, ionic covalent organic framework (COF) membranes that exhibit superior H+ conduction. The as-synthesized COFs are postmodified via a lithiation (or sodiation) treatment. The hydrophilic Li or Na ions in the COFs form a dense and extensive hydrogen-bonding network of H2O molecules with mobile H+ at the periphery, thereby transforming COFs into H+ conductors. Then, the ionic COFs are assembled into a flexible H+ conductor membrane via a gelation process, where the organic gel provides both mechanical strength and additional H+ carriers for fast H+ conduction. The final COF-based membrane exhibits an excellent H+ conductivity of 1.3 × 10-1 S cm-1 at 313 K and 98% relative humidity, which are the highest values of the COF-based H+ conductors reported until now and are even comparable with those of the typical commercial Nafion membrane. We anticipate that the two-in-one strategy would open up a porous COF-driven new molecular framework and membrane architectural design/opportunity for development of next-generation ionic conductors.