Electrolyte design is critical for enabling next-generation batteries with higher energy densities. Hydrofluoroether (HFE) solvents have drawn a lot of attention as the electrolytes based on HFEs showed great promise to deliver highly desired properties, including high oxidative stability, ionic conductivity, as well as enhanced lithium metal compatibility. However, the structure-dynamics-properties relationships and design principles for high-performance HFE solvents are still poorly understood. Herein, we proposed four novel asymmetric HFE designs by systematically varying polyether and fluorocarbon structural building blocks. By leveraging molecular dynamics (MD) modeling to analyze the solvation structures and predict the properties of the corresponding 1 M lithium bis(fluorosulfonyl)imide (LiTFSI) solutions, we downselected the most promising candidate based on high conductivity, solvation species distribution, and oxidative stability for extensive electrochemical characterizations. The formulated electrolyte demonstrated properties consistent with the predictions from the simulations and showed muchimproved capacity retention as well as Coulombic efficiency compared to the baseline electrolytes when cycled in lithium metal cells. This work exemplifies the construction of candidate electrolytes from building block functional moieties to engineer fundamental solvation structures for desired electrolyte properties and guide the discovery and rational design of new solvent materials.

Water confined in mesoporous silica plays a central role in its many uses ranging from gas sorption to nanoconfined chemical reactions. Here, the influence of pore diameter (2.5–5.4 nm) on water hydrogen bond (H-bond) dynamics in MCM41 and SBA15 mesoporous silicas is investigated using femtosecond infrared vibrational spectroscopy and molecular dynamics simulations on selenocyanate (SeCN−) anions dissolved in the pores. As shown recently, SeCN− spectral diffusion is a reliable probe of surrounding water H-bond structural motions. Additionally, the long CN stretch vibrational lifetime facilitates measurement of the full range of confined dynamics, which are much slower than in bulk water. The simulations shed light on quantitative details that are inaccessible from the spatially averaged observables. The dependence of SeCN− orientational relaxation and that of spectral diffusion on the distance from the silica interface are quantitatively described with an exponential decay and a smoothed step-function, respectively. The distance-dependence of both quantities is found to be independent of the diameter of the pores, and the spatial distribution of SeCN− is markedly non-uniform, reaching a maximum between the interface and the pore center. The results indicate that the commonly invoked two-state, or core–shell, model is a more appropriate description of spectral diffusion. Using these insights, we model the full time-dependence of the measured dynamics for all pore sizes and extract the “core” and “shell” dynamical correlation functions and SeCN− spatial probability distributions. The results are critically compared to those for water confined in reverse micelles.

Enhancement of processes ranging from gas sorption to ion conduction in a liquid can be substantial upon nanoconfinement. Here, the dynamics of a polar aprotic solvent, 1methylimidazole (MeIm), in mesoporous silica (2.8, 5.4, and 8.3 nm pore diameters) were examined using femtosecond infrared vibrational spectroscopy and molecular dynamics simulations of a dilute probe, the selenocyanate (SeCN − ) anion. The long vibrational lifetime and sensitivity of the CN stretch enabled a comprehensive investigation of the relatively slow time scales and subnanometer distance dependences of the confined dynamics. Because MeIm does not readily donate hydrogen bonds, its interactions in the hydrophilic silanol pores differ more from the bulk than those of water confined in the same mesopores, resulting in greater structural order and more dramatic slowing of dynamics. The extent of surface effects was quantified by modified two-state models used to fit three spatially averaged experimental observables: vibrational lifetime, orientational relaxation, and spectral diffusion. The length scales and the models (smoothed step, exponential decay, and simple step) describing the transitions between the distinctive shell behavior at the surface and the bulk-like behavior at the pore interior were compared to those of water. The highly nonuniform distributions of the SeCN − probe and antiparallel layering of MeIm revealed by the simulations guided the interpretation of the results and development of the analytical models. The results illustrate the importance of electrostatic effects and H-bonding interactions in the behavior of confined liquids.

A significant enhancement in the Menshutkin S N 2 reaction between 1-methylimidazole (MeIm) and methyl thiocyanate (MeSCN) is observed when the reaction is confined in the nanoscale silica pores of MCM41 and SBA15. The experiments in the silica pores are conducted without the surrounding bulk reaction mixture. The influences of temperature, pore radius, and surface chemistry on the kinetics of the confined reaction are analyzed with time-dependent infrared spectroscopy, molecular dynamics simulations, and ab initio calculations. The rate constant of the pseudofirst order reaction increases with decreasing pore size, and the activation energy is found to decrease by 5.6 kJ/mol in the smallest pore studied (2.8 nm) relative to the bulk reaction. The rate constant dependence on pore size is accurately described by a twostate model in which molecules within the 4.6 Å interfacial layer experience a 2.4-fold rate constant increase relative to those reacting at the bulk rate further away from the interface. The removal of polar silanol groups from the silica surface via passivation with trimethylsilyl chloride results in bulk-like kinetics despite a reduction in the pore diameter, demonstrating the role of silanols as catalytic sites. Electronic structure calculations of the energy profile on a model silica surface confirm that silanol groups, particularly those of the vicinal type, can reduce the activation energy and reaction endothermicity through the donation of hydrogen bonds to the reactant, transition state, and product complexes.

The dynamics of imidazole (IM) and 1-methylimidazole (1-MeIM) in the liquid phase at 95 °C were studied by IR polarization selective pump–probe and two-dimensional IR (2D IR) spectroscopies. The two molecules are very similar structurally except that IM can be simultaneously a hydrogen bond donor and acceptor and therefore forms extended hydrogen-bonded networks. The broader IR absorption spectrum and a shorter vibrational lifetime of the vibrational probe, selenocyanate anion (SeCN–), in IM vs 1-MeIM indicate that stronger hydrogen bonding exists between SeCN– and IM. Molecular dynamics (MD) simulations support the strong hydrogen bond formation between SeCN– and IM via the HN moiety. SeCN– makes two H-bonds with IM; it is inserted in the IM H-bonded chains rather than being a chain terminator. The strong hydrogen bonding influenced the reorientation dynamics of SeCN– in IM, leading to a more restricted short time angular sampling (wobbling-in-a-cone). The complete orientational diffusion time in IM is 1.7 times slower than in 1-MeIM, but the slow down is less than expected, considering the 3-fold larger viscosity of IM. The jump reorientation mechanism accounts for the anomalously fast orientational relaxation in IM, and the MD simulations determined the average jump angle of the probe between hydrogen bonding sites. Spectral diffusion time constants obtained from the 2D IR experiments are only modestly slower in IM than in 1-MeIM in spite of the significant increase in viscosity. The results indicate that the spectral diffusion sensed by the SeCN– has IM hydrogen bond dynamics contributions not present in 1-MeIM.