Scalable Dry-Pressed Electrodes Based on Holey Graphene

ConspectusHoley graphene (hG) is a structural derivative of graphene with arrays of through-thickness holes of a few to tens of nanometers in diameter, randomly distributed across the nanosheet surfaces. In most bulk preparation methods, the holes on hG sheets are preferentially generated from the pre-existing defects on graphene. Therefore, contrary to intuitive belief, hG is not necessarily more defective than the intact graphene. Instead, it retains essential parent properties, including high electrical conductivity, high surface area, mechanical robustness, and chemical inertness. Furthermore, the added holey structural motif imparts unique properties that are not present in unmodified graphene, making hG advantageous in numerous applications such as sensing, membranes, reinforcements, and electrochemical energy storage. In particular, the presence of holes enhances the mass transport through the nanosheet plane and thus significantly reduces tortuosity. This difference is a key advantage for using hG in energy storage applications where the transport of ions through the thickness becomes more hindered as the electrode thickness increases to meet practical energy density requirements.An unexpected discovery is that the holes of the hG sheets enable the dry hG powder to be directly compressed into robust monoliths. hG not only can be pressed into monoliths by itself but also can host other electrochemically active materials as a compressible matrix. This important yet unique property, which is not available for other carbon materials including intact graphene, significantly broadens the application horizon in energy storage applications. With the dry compressibility, electrodes with ultrahigh mass loading and thus ultrahigh areal capacity may be conveniently fabricated without toxic solvents or parasitic binders, which are required in conventional slurry-based approaches for electrode fabrication. The dry-press electrode preparation process can be completed within minutes regardless of mass loading. In comparison, high-mass-loading electrodes for advanced battery chemistries using conventional fabrication methods often need stringent and time-consuming process control. hG can also be combined with electrochemically active battery materials while maintaining dry compressibility. This has allowed the unprecedented, convenient manipulation of a wide variety of thick electrode compositions and architectures, which provides not only outstanding performance but also new physical insights for various battery chemistries.In this Account, we first present some basic observations on the dry compressibility of hG as well as the mechanistic investigations from atomistic modeling rationalizing this unique property. We then showcase the applications of neat and composite dry-pressed hG electrodes for various energy storage platforms including supercapacitors, lithium (Li) ion batteries, Li-O₂ batteries, and Li-S/Se batteries. The preparation and performance of thick electrodes with practical mass loadings and unique electrode architecture manipulation, both enabled by the dry compressibility of hG, are highlighted and discussed.