TY - JOUR
T1 - Scalable Screening of Soft Matter
T2 - A Case Study of Mixtures of Ionic Liquids and Organic Solvents
AU - Thompson, Matthew W.
AU - Matsumoto, Ray
AU - Sacci, Robert L.
AU - Sanders, Nicolette C.
AU - Cummings, Peter T.
N1 - Publisher Copyright:
Copyright © 2019 American Chemical Society.
PY - 2019/2/14
Y1 - 2019/2/14
N2 - Room-temperature ionic liquids (RTILs) are a class of organic salts that are liquid at room temperature. Their physiochemical properties, including low vapor pressure and wide electrochemical stability window, have driven their use as electrolytes in many electrochemical applications; however, the slow transport properties of many RTILs have limited their utility in some applications. This issue is often mitigated by solvating ionic liquids in neutral organic solvents. To date, however, solvent interactions have only been explored for a small number of solvents, particularly acetonitrile and propylene carbonate, at only a few compositions. In this work, we use molecular dynamics simulations in the context of a computational screening approach to study mixtures of ionic liquids in many different solvents at a range of concentrations. Building on prior work, we again find that ionic liquid diffusivity increases monotonically with greater solvent concentration. In contrast to prior work, we find that pure solvent diffusivity, not polarity, is the most influential solvent property on mixture behavior. We also explore the concentration dependence of ionic conductivity and find maxima at intermediate concentrations. Experimental conductivity measurements, inspired by the computational screening study, support this observation with qualitatively consistent results. These results can further guide the selection of solvents for electrochemical applications of RTILs.
AB - Room-temperature ionic liquids (RTILs) are a class of organic salts that are liquid at room temperature. Their physiochemical properties, including low vapor pressure and wide electrochemical stability window, have driven their use as electrolytes in many electrochemical applications; however, the slow transport properties of many RTILs have limited their utility in some applications. This issue is often mitigated by solvating ionic liquids in neutral organic solvents. To date, however, solvent interactions have only been explored for a small number of solvents, particularly acetonitrile and propylene carbonate, at only a few compositions. In this work, we use molecular dynamics simulations in the context of a computational screening approach to study mixtures of ionic liquids in many different solvents at a range of concentrations. Building on prior work, we again find that ionic liquid diffusivity increases monotonically with greater solvent concentration. In contrast to prior work, we find that pure solvent diffusivity, not polarity, is the most influential solvent property on mixture behavior. We also explore the concentration dependence of ionic conductivity and find maxima at intermediate concentrations. Experimental conductivity measurements, inspired by the computational screening study, support this observation with qualitatively consistent results. These results can further guide the selection of solvents for electrochemical applications of RTILs.
UR - http://www.scopus.com/inward/record.url?scp=85061755794&partnerID=8YFLogxK
U2 - 10.1021/acs.jpcb.8b11527
DO - 10.1021/acs.jpcb.8b11527
M3 - Article
C2 - 30652873
AN - SCOPUS:85061755794
SN - 1520-6106
VL - 123
SP - 1340
EP - 1347
JO - Journal of Physical Chemistry B
JF - Journal of Physical Chemistry B
IS - 6
ER -