Ketkar, Priyanka M.Epps, Thomas H. III2023-12-052023-12-052021-12-07Ketkar, Priyanka M., and Thomas H. III Epps. “Nanostructured Block Polymer Electrolytes: Tailoring Self-Assembly to Unlock the Potential in Lithium-Ion Batteries.” Accounts of Chemical Research 54, no. 23 (December 7, 2021): 4342–53. https://doi.org/10.1021/acs.accounts.1c00468.1520-4898https://udspace.udel.edu/handle/19716/33649This article was originally published in Accounts of Chemical Research. The version of record is available at: https://doi.org/10.1021/acs.accounts.1c00468. Copyright © 2021 The Authors. Published by American Chemical Society.Conspectus Ion-containing solid block polymer (BP) electrolytes can self-assemble into microphase-separated domains to facilitate the independent optimization of ion conduction and mechanical stability; this assembly behavior has the potential to improve the functionality and safety of lithium-ion batteries over liquid electrolytes to meet future demands (e.g., large capacities and long lifetimes) in various applications. However, significant enhancements in the ionic conductivity and processability of BPs must be realized for BP-based electrolytes to become robust alternatives in commercial devices. Toward this end, the controlled modification of BP electrolytes’ intra-domain (nanometer-scale) and multi-grain (micrometer-scale) structure is one viable approach; intra-domain ion transport and segmental compatibility (related to the effective Flory–Huggins parameter, χeff) can be increased by tuning the ion and monomer-segment distributions, and the morphology can be selected such that the multi-grain transport is less sensitive to grain size and orientation. To highlight the characteristics of intra-domain structure that promote efficient ion transport, this Account begins by describing the relationship between BP thermodynamics (namely, χeff and the statistical segment length, b, which is indicative of chain stiffness) and local ion concentration. These thermodynamic insights are vital because they inform the selection of synthesis and formulation variables, such as polymer and ion chemistry, polymer molecular weight and composition, and ion concentration, which boost electrolyte performance. In addition to its relationship with local ion transport, χeff is also an important factor with respect to electrolyte processability. For example, a reduced χeff can allow BP electrolytes to be processed at lower temperatures (i.e., lower energy input), with less solvent (i.e., reduced waste), and/or for shorter times (i.e., higher throughput) yet still form desired nanostructures. This Account also examines the impact of electrolyte preparation and processing on the ion transport across nanostructured grains because of grain size and orientation. As morphologies with a 3D-connected versus 2D-connected conducting phase show different sensitivities to conductivity losses that can occur because of the fabrication methods, it is necessary to account for electrolyte processing effects when probing ion transport. The intra-domain and micrometer-scale structure also can be tuned using either tapered BPs (macromolecules with modified monomer-segment composition profiles between two homogeneous blocks) or blends of BPs and homopolymers, independent of the BP molecular weight and composition, as detailed herein. The application of TBPs or BP/HP blends as ion-conducting materials leads to improved ion transport, reduced χeff, and greater availability of morphologies with 3D connectivity relative to traditional (non-tapered and unblended) BP electrolytes. This feature results from the fact that ion transport is related more closely to the monomer-segment distributions within a domain than the overall nanoscale morphology or average polymer/ion mobilities. Taken together, this Account describes how ion transport and processability are influenced by BP architecture and nanostructural features, and it provides avenues to tune nanoassemblies that can contribute to improved lithium-ion battery technologies to meet future demands.en-USAttribution-NonCommercial-NoDerivatives 4.0 Internationalcharge transportelectrolytesionic conductivityionspolymersaffordable and clean energyArticle