Quantitative Mapping of Molecular Substituents to Macroscopic Properties Enables Predictive Design of Oligoethylene Glycol-Based Lithium Electrolytes
Name
acscentsci.0c00475.pdf
Description
Published version
Size
5.37 MB
Format
Adobe PDF
Checksum (MD5)
a201f44c836609d64f3b8591538bf66a
Author(s)
Qiao, Bo
Mohapatra, Somesh
Lopez, Jeffrey Frank
Leverick, Graham M.
Tatara, Ryoichi
Shibuya, Yoshiki
Jiang, Yivan
France-Lanord, Arthur
Grossman, Jeffrey C.
Gómez-Bombarelli, Rafael
Date Issued
June 2020
Journal
ACS Central Science
Publisher
American Chemical Society (ACS)
Citation
Qiao, Bo et al. "Quantitative Mapping of Molecular Substituents to Macroscopic Properties Enables Predictive Design of Oligoethylene Glycol-Based Lithium Electrolytes." ACS Central Science 6, 7 (June 2020): 1115–1128 © 2020 American Chemical Society
Version
Final published version
Abstract
Molecular details often dictate the macroscopic properties of materials, yet due to their vastly different length scales, relationships between molecular structure and bulk properties can be difficult to predict a priori, requiring Edisonian optimizations and preventing rational design. Here, we introduce an easy-to-execute strategy based on linear free energy relationships (LFERs) that enables quantitative correlation and prediction of how molecular modifications, i.e., substituents, impact the ensemble properties of materials. First, we developed substituent parameters based on inexpensive, DFT-computed energetics of elementary pairwise interactions between a given substituent and other constant components of the material. These substituent parameters were then used as inputs to regression analyses of experimentally measured bulk properties, generating a predictive statistical model. We applied this approach to a widely studied class of electrolyte materials: oligo-ethylene glycol (OEG)-LiTFSI mixtures; the resulting model enables elucidation of fundamental physical principles that govern the properties of these electrolytes and also enables prediction of the properties of novel, improved OEG-LiTFSI-based electrolytes. The framework presented here for using context-specific substituent parameters will potentially enhance the throughput of screening new molecular designs for next-generation energy storage devices and other materials-oriented contexts where classical substituent parameters (e.g., Hammett parameters) may not be available or effective.
MIT Department
Massachusetts Institute of Technology. Department of Chemical Engineering
Massachusetts Institute of Technology. Department of Materials Science and Engineering
Massachusetts Institute of Technology. Research Laboratory of Electronics
Terms of Use
Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use.
Persistent DSpace Link
DOI of Published Version
https://doi.org/10.1021/acscentsci.0c00475
