Frederick C. Krause

Solid State Multinuclear Magnetic Resonance Investigation of Electrolyte Decomposition Products on Lithium Ion Electrodes

Solid electrolyte interphase (SEI) formation in lithium ion cells prepared with advanced electrolytes is investigated by solid state multinuclear (7Li, 19F, 31P) magnetic resonance (NMR) measurements of electrode materials harvested from cycled cells subjected to an accelerated aging protocol. The electrolyte composition is varied to include the addition of fluorinated carbonates and triphenyl phosphate (TPP, a flame retardant). In addition to species associated with LiPF6 decomposition, cathode NMR spectra are characterized by the presence of compounds originating from the TPP additive. Substantial amounts of LiF are observed in the anodes as well as compounds originating from the fluorinated carbonates.

In Situ Polysulfide Detection in Lithium Sulfur Cells

Lithium sulfur batteries promise significant improvements in specific energy compared to Li-ion, but are limited by capacity fade upon cycling. Efforts to improve durability have focused on suppressing the solubility of intermediate polysulfides in the electrolyte. Here we describe an in situ electrochemical polysulfide detection method based on the cyclic volatmmetric response. The voltammetric peaks correlate with increased discharge, consistent with increased polysulfide species in the electrolyte as demonstrated by prior literature measurements using spectroscopic methods. We verified that adding metal sulfide species to the sulfur cathode and ceramic-coatings on the polyolefin separator result in reduced polysulfide concentration, consistent with improved cycle life reported earlier. Further, the use of highly concentrated electrolytes produces no detectable dissolved polysulfide species. Future advances in Li/S technology could utilize this method to determine the polysulfide contents in the electrolyte, and thus quantify the efficacy of the sulfur-sequestering strategies.