Covalent organic frameworks (COFs) are an emerging material family having several potential applications. Their porous framework and redox-active centers enable gas/ion adsorption, allowing them to function as safe, cheap, and tunable electrode materials in next-generation batteries, as well as CO₂ adsorption materials for carbon-capture applications. Herein, we develop four polyimide COFs by combining aromatic triamines with aromatic dianhydrides and provide detailed structural and electrochemical characterization. Through density functional theory (DFT) calculations and powder X-ray diffraction, we achieve a detailed structural characterization, where DFT calculations reveal that the imide bonds prefer to form at an angle with one another, breaking the 2D symmetry, which shrinks the pore width and elongates the pore walls. The eclipsed perpendicular stacking is preferable, while sliding of the COF sheets is energetically accessible in a relatively flat energy landscape with a few metastable regions. We investigate the potential use of these COFs in CO₂ adsorption and electrochemical applications. The adsorption and electrochemical properties are related to the structural and chemical characteristics of each COF, giving new insights for advanced material designs. For CO₂ adsorption specifically, the two best performing COFs originated from the same triamine building block, which—in combination with force-field calculations—revealed unexpected structure–property relationships. Specific geometries provide a useful framework for Na-ion intercalation with retainable capacities and stable cycle life at a relatively high working potential (>1.5 V vs Na/Na⁺). Although this capacity is low compared to conventional inorganic Li-ion materials, we show as a proof of principle that these COFs are especially promising for sustainable, safe, and stable Na-aqueous batteries due to the combination of their working potentials and their insoluble nature in water.

Characteristics of COFs and their proton conducting mechanisms.

Graphene, being a two-dimensional all-aromatic sheet bonded with sp² carbon atoms, has attracted much attention due to its excellent physicochemical properties like a large surface area, good electrical conductivity, and high thermal and chemical stability.

All-solid-state batteries (ASSBs) are promising to be next-generation battery that provides high energy density and intrinsic safety. Research in the field of ASSBs has so far focused on the development of highly conductive solid electrolytes (SEs). The commercialization of ASSBs requires well-established large-scale manufacturing for sulfide SEs with high ionic conductivity. However, the synthesis for sulfide SEs remains at the laboratory scale with limited scalability owing to their air sensitivity. The liquid-phase synthesis would be an economically viable manufacturing technology for sulfide SEs. Herein, we review a chemical perspective in liquid-phase synthesis that offers high scalability, low cost, and high reaction kinetics. This review provides a guideline for desirable solvent selection based on the solubility and polarity characterized by the donor number and dielectric permittivity of solvents. Additionally, we offer a deeper understanding of the recent works on scalable liquid-phase synthesis using solubilizers and reactant agents. We present an outlook on a universal liquid-phase synthesis of sulfide SEs toward the commercialization of sulfide-based ASSBs.