Engineering topics

Suarez, Sophia N.

Publications and source records attributed to Suarez, Sophia N..

5 records

DOE OSTI2023

Nuclear Magnetic Resonance Relaxation Pathways in Electrolytes for Energy Storage

Nuclear Magnetic Resonance (NMR) spin relaxation times have been an instrumental tool in deciphering the local environment of ionic species, the various interactions they engender and the effect of these interactions on their dynamics in conducting media. Of particular importance has been their application in studying the wide range of electrolytes for energy storage, on which this review is based. Here we highlight some of the research carried out on electrolytes in recent years using NMR relaxometry techniques. Specifically, we highlight studies on liquid electrolytes, such as ionic liquids and organic solvents; on semi-solid-state electrolytes, such as ionogels and polymer gels; and on solid electrolytes such as glasses, glass ceramics and polymers. Although this review focuses on a small selection of materials, we believe they demonstrate the breadth of application and the invaluable nature of NMR relaxometry.

25 ENERGY STORAGE↗

DOE OSTI2017

Investigation of Dynamics in BMIM TFSA Ionic Liquid through Variable Temperature and Pressure NMR Relaxometry and Diffusometry

A comprehensive variable temperature, pressure and frequency multinuclear ( 1 H, 2 H, and 19 F) magnetic resonance study was undertaken on selectively deuterated 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide (BMIM TFSA) ionic liquid isotopologues. This study builds on our earlier investigation of the effects of increasing alkyl chain length on diffusion and dynamics in imidazolium-based TFSA ionic liquids. Fast field cycling 1 H T 1 data revealed multiple modes of motion. Through calculation of diffusion coefficient (D) values and activation energies, the low- and high-field regimes were assigned to the translational and reorientation dynamics respectively. Variable-pressure 2 H T 1 measurements reveal site-dependent interactions in the cation with strengths in the order MD 3 > CD 3 > CD 2 , indicating dissimilarities in the electric field gradients along the alkyl chain, with the CD 2 sites having the largest gradient. Additionally, the α saturation effect in T 1 vs. P was observed for all three sites, suggesting significant reduction of the short-range rapid reorientational dynamics. This reduction was also deduced from the variable pressure 1 H T 1 data, which showed an approach to saturation for both the methyl and butyl group terminal methyl sites. Pressure-dependent D measurements show independent motions for both cations and anions, with the cations having greater D values over the entire pressure range.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2017

Exploring the Use of Ionic Liquid Mixtures to Enhance the Performance of Dicationic Ionic Liquids

Dicationic ionic liquids (DILs) of diverse structural architectures (including symmetrical and asymmetrical ammonium, phosphonium and heterodications and the bis(trifluoromethylsulfonyl)amide (NTf 2 - ) anion) have been prepared and used as additives to N-methyl-N-ethoxyethylpyrrolidinium (P 1 EOE) NTf 2 , a relatively high-performing IL in terms of its transport properties (viscosity 53 mPa s). The three-ion, binary IL mixtures were characterized for their thermal and transport properties using differential scanning calorimetry, temperature dependent viscosity, conductivity and Pulsed Gradient Spin Echo (PGSE) NMR. Variable temperature 1 H, 19 F and 31 P self-diffusion coefficients were determined at 25, 60 and 75°C. The order of the diffusion coefficients was D(P 1 EOE + ) > D(anion) > D(dication), and the composition of the dication had a strong effect on the degree to which diffusion of all three species is more or less coupled. IL mixtures containing about 30 mol % of the dicationic NTf 2 and 70 mol % of P 1 EOE NTf 2 resulted in a significant decrease in glass transition temperatures and viscosities compared to the pure DIL. The mixtures extended the liquid range and potential for practical applications significantly. Finally, the data obtained here provides insight into the future design of dicationic salts tailored to exhibit lower viscosity and higher conductivities.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2015

Do TFSA anions slither? Pressure exposes the role of TFSA conformational exchange in self-diffusion

Multi-nuclear ( 1 H, 2 H, and 19 F) magnetic resonance spectroscopy techniques as functions of temperature and pressure were applied to the study of selectively deuterated 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide (EMIM TFSA) ionic liquid isotopologues and related ionic liquids. For EMIM TFSA, temperature-dependent 2 H T 1 data indicate stronger electric field gradients in the alkyl chain region compared to the imidazolium ring. Most significantly, the pressure dependences of the EMIM and TFSA self-diffusion coefficients revealed that the displacements of the cations and anions are independent, with diffusion of the TFSA anions being slowed much more by increasing pressure than for the EMIM cations, as shown by their respective activation volumes (28.8 ± 2.5 cm³/mol for TFSA vs. 14.6 ± 1.3 cm³/mol for EMIM). Increasing pressure may lower the mobility of the TFSA anion by hindering its interconversion between trans and cis conformers, a process that is coupled to diffusion according to published molecular dynamics simulations. Measured activation volumes (ΔV ‡ ) for ion self-diffusion in EMIM bis(fluoromethylsulfonyl)amide and EMIM tetrafluoroborate support this hypothesis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2014

Cyclic phosphonium ionic liquids

Ionic liquids (ILs) incorporating cyclic phosphonium cations are a novel category of materials. We report here on the synthesis and characterization of four new cyclic phosphonium bis(trifluoromethylsulfonyl)amide ILs with aliphatic and aromatic pendant groups. In addition to the syntheses of these novel materials, we report on a comparison of their properties with their ammonium congeners. These exemplars are slightly less conductive and have slightly smaller self-diffusion coefficients than their cyclic ammonium congeners.

phospholanium↗