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J Phys Chem Lett ; 11(6): 2046-2052, 2020 Mar 19.
Artigo em Inglês | MEDLINE | ID: mdl-32079402


Detailed speciation of electrolytes as a function of chemical system and concentration provides the foundation for understanding bulk transport as well as possible decomposition mechanisms. In particular, multivalent electrolytes have shown a strong coupling between anodic stability and solvation structure. Furthermore, solvents that are found to exhibit reasonable stability against alkaline-earth metals generally exhibit low permittivity, which typically increases the complexity of the electrolyte species. To improve our understanding of ionic population and associated transport in these important classes of electrolytes, the speciation of Mg(TFSI)2 in monoglyme and diglyme systems is studied via a multiscale thermodynamic model using first-principles calculations for ion association and molecular dynamics simulations for dielectric properties. The results are then compared to Raman and dielectric relaxation spectroscopies, which independently confirm the modeling insights. We find that the significant presence of free ions in the low-permittivity glymes in the concentration range from 0.02 to 0.6 M is well-explained by the low-permittivity redissociation hypothesis. Here, salt speciation is largely dictated by long-range electrostatics, which includes permittivity increases due to polar contact ion pairs. The present results suggest that other low-permittivity multivalent electrolytes may also reach high conductivities as a result of redissociation.

ACS Cent Sci ; 5(7): 1250-1260, 2019 Jul 24.
Artigo em Inglês | MEDLINE | ID: mdl-31403073


Nonaqueous polyelectrolyte solutions have been recently proposed as high Li+ transference number electrolytes for lithium ion batteries. However, the atomistic phenomena governing ion diffusion and migration in polyelectrolytes are poorly understood, particularly in nonaqueous solvents. Here, the structural and transport properties of a model polyelectrolyte solution, poly(allyl glycidyl ether-lithium sulfonate) in dimethyl sulfoxide, are studied using all-atom molecular dynamics simulations. We find that the static structural analysis of Li+ ion pairing is insufficient to fully explain the overall conductivity trend, necessitating a dynamic analysis of the diffusion mechanism, in which we observe a shift from largely vehicular transport to more structural diffusion as the Li+ concentration increases. Furthermore, we demonstrate that despite the significantly higher diffusion coefficient of the lithium ion, the negatively charged polyion is responsible for the majority of the solution conductivity at all concentrations, corresponding to Li+ transference numbers much lower than previously estimated experimentally. We quantify the ion-ion correlations unique to polyelectrolyte systems that are responsible for this surprising behavior. These results highlight the need to reconsider the approximations typically made for transport in polyelectrolyte solutions.