Highly Conductive Imidazolate Covalent Organic Frameworks with Ether Chains as Solid Electrolytes for Lithium Metal Batteries.

Poly(ethylene oxide) (PEO)-based electrolytes are often used for Li+ conduction as they can dissociate the Li salts efficiently. However, high entanglement of the chains and lack of pathways for rapid ion diffusion limit their applications in advanced batteries. Recent developments in ionic covalent organic frameworks (iCOFs) showed that their highly ordered structures provide efficient pathways for Li+ transport, solving the limitations of traditional PEO-based electrolytes. Here, we present imidazolate COFs, PI-TMEFB-COFs, having methoxyethoxy chains, synthesized by Debus-Radziszewski multicomponent reactions and their ionized form, Li+@PI-TMEFB-COFs, showing a high Li+ conductivity of 8.81 mS cm-1 and a transference number of 0.974. The mechanism for such excellent electrochemical properties is that methoxyethoxy chains dissociate LiClO4, making free Li+, then those Li+ are transported through the imidazolate COFs' pores. The synthesized Li+@PI-TMEFB-COFs formed a stable interface with Li metal. Thus, employing Li+@PI-TMEFB-COFs as the solid electrolyte to assemble LiFePO4 batteries showed an initial discharge capacity of 119.2 mAh g-1 at 0.5 C, and 82.0 % capacity and 99.9 % Coulombic efficiency were maintained after 400 cycles. These results show that iCOFs with ether chains synthesized via multicomponent reactions can create a new chapter for making solid electrolytes for advanced rechargeable batteries.

Mechanically Interlocked Macrocycles on Covalent Networks for Energy and Environmental Applications.

Macrocycles' unique properties of interacting with guest molecules have been an intriguing scientific endeavor for many decades. They are potentially practically useful for engineering applications, especially in energy and environmental applications. These applications are usually demanding, involving a high temperature, pH, voltage, etc., thus, finding suitable substrates that can endure working environments and sustain macrocycles' properties is highly desirable. In that sense, covalent networks are ideal as they are chemically/electrochemically/thermally stable and can be porous by design. Emerging porous materials, especially covalent organic frameworks (COFs), could be suitable as their porous spaces allow macrocycles to interact with guest species. In the past seven years, we have seen the rise of mechanically interlocked macrocycles on covalent networks (MIMc-CNs) that translate macrocycles' properties into macroscale materials. In this conceptual review, we first describe the idea of integrating MIMcs into COFs or conventional amorphous polymers. Next, we review the reported representative MIMc-CNs used in energy and environmental applications. We also provide a brief outlook for the future directions for the MIMc-CNs research.