One-Pot Structure Direction of Large-Pore Co-Continuous Carbon Monoliths from Ultralarge Linear Diblock Copolymers

Carbon materials have found ubiquitous use in the fields of electrochemical energy storage (EES) and conversion, due to their electrical and thermal transport properties, typically high specific surface areas, low densities, and stability in a variety of systems. As the demand in particular for increasingly efficient EES devices grows, three-dimensionally (3D) continuous nanostructured electrode materials have gained interest, as they present a pathway to high interfacial areas between electrodes while the overall device has a low areal footprint. Therefore, the development of nanostructured carbon materials with 3D network architectures suited for routes to 3D functional composite materials, e.g., via straightforward backfilling approaches, is an appealing challenge. In this work, two ultralarge pore-size carbons with nonperiodically ordered co-continuous network structures and average pore sizes of 125 nm and 94 nm, respectively, were synthesized using two ultralarge molar mass poly(styrene-block-2-dimethylaminoethyl methacrylate) (PS-b-PDMAEMA, or simply SA) diblock copolymers as structure-directing agents for carbon precursors based on phenol-formaldehyde resols. Careful tuning of a binary solvent system allowed for the avoidance of micellization during evaporation-induced self-assembly of the SA and resols and yielded continuous porous 3D network structures in both carbon and pore spaces upon pyrolysis at higher temperatures of up to 1600 degrees C, as well as subsequent carbon activation processes. The resulting materials were monolithic and their macroscopic shape and thickness were controllable. These large-pore carbon monoliths may be promising candidates for electrode materials in the future design in particular of 3D continuous EES devices.