Relation between microscopic structure and macroscopic properties in polyacrylonitrile-based lithium-ion polymer gel electrolytes.

Polymer gel electrolytes (PGE) have seen a renewed interest in their development because they have high ionic conductivities but low electrochemical degradation and flammability. PGEs are formed by mixing a liquid lithium-ion electrolyte with a polymer at a sufficiently large concentration to form a gel. PGEs have been extensively studied, but the direct connection between their microscopic structure and macroscopic properties remains controversial. For example, it is still unknown whether the polymer in the PGE acts as an inert, stabilizing scaffold for the electrolyte or it interacts with the ionic components. Here, a PGE composed of a prototypical lithium-carbonate electrolyte and polyacrylonitrile (PAN) is pursued at both microscopic and macroscopic levels. Specifically, this study focused on describing the microscopic and macroscopic changes in the PGE at different polymer concentrations. The results indicated that the polymer-ion and polymer-polymer interactions are strongly dependent on the concentration of the polymer and the lithium salt. In particular, the polymer interacts with itself at very high PAN concentrations (10% weight) resulting in a viscous gel. However, the conductivity and dynamics of the electrolyte liquid components are significantly less affected by the addition of the polymer. The observations are explained in terms of the PGE structure, which transitions from a polymer solution to a gel, containing a polymer matrix and disperse electrolyte, at low and high PAN concentrations, respectively. The results highlight the critical role that the polymer concentration plays in determining both the macroscopic properties of the system and the molecular structure of the PGE.

Tale of a "Non-interacting" Additive in a Lithium-Ion Electrolyte: Effect on Ionic Speciation and Electrochemical Properties.

New lithium electrolytes compatible with high energy density cells are critical for lithium metal battery applications, but dendrite formation associated with the use of dilute organic electrolytes complicates their realization. High-concentration electrolytes mitigate some of the issues of the electrolytes but introduce additional problems, such as low conductivity and high cost. Hence, pseudo-concentrated electrolytes, wherein a co-solvent is added to a dilute electrolyte, have been presented as a possible alternative to both dilute and concentrated electrolytes. However, the effect that the co-solvent has on the electrolyte properties at both macroscopic and microscopic levels is unknown. Here, a study of the structure and electrochemical properties of two electrolytes as a function of co-solvent concentration is presented using an array of spectroscopies (FTIR, ATR-FTIR, and nuclear magnetic resonance) and computational methods (density functional theory calculations). The chosen electrolytes comprised two different lithium salts (LiPF6 and LiTFSI) in a mixture of dimethyl carbonate (DMC) with 1,1,1,3,3-pentafluorobutane (PFB) as the co-solvent. Our results show that in the case of the LiPF6/DMC electrolyte, the addition of a co-solvent (PFB) with a larger dielectric constant results in the strengthening of the lithium-anion interaction and the formation of aggregate species since PFB does not interact with the anion. Conversely, in the LiTFSI/DMC electrolyte, the co-solvent appears to interact with the anion via hydrogen bonds, which leads to the dissociation of contact ion pairs. The change in ionic speciation of the electrolytes upon addition of PFB provides a reasonable framework to explain the different trends in both the bulk and interfacial macroscopic properties, such as conductivity, viscosity, and electrochemical stability. Overall, our findings demonstrate that the interactions between the anion and the co-solvent must be taken into consideration when adding a co-solvent because they play a major role in determining the final electrolyte properties.

Structural and dynamical changes observed when transitioning from an ionic liquid to a deep eutectic solvent.

The microscopic molecular structure and dynamics of a new deep eutectic solvent (DES) composed of an ionic liquid (1-hexyl-3-methylimidazolium chloride) and an amide (trifluoroacetamide) at various molar ratios were investigated using linear and non-linear infrared spectroscopy with a vibrational probe. The use of the ionic liquid allows us to investigate the changes that the system undergoes with the addition of the amide or, equivalently, the changes from an ionic liquid to a DES. Our studies revealed that the vibrational probe in the DES senses a very similar local environment irrespective of the cation chemical structure. In addition, the amide also appears to perceive the same molecular environment. The concentration dependence studies also showed that the amide changes from being isolated from other amides in the ionic liquid environment to an environment where the amide-amide interactions are favored. In the case of the vibrational probe, the addition of the amide produced significant changes in the slow dynamics associated with the making and breaking of the ionic cages but did not affect the rattling-in-cage motions perceived by it. Furthermore, the concentration dependence of slow dynamics showed two regimes which are linked to the changes in the overall structure of the solution. These observations are interpreted in the context of a nanoscopic heterogeneous environment in the DES which, according to the observed dynamical regimes, appears at very large concentrations of the amide (molar ratio of greater than 1:1) since for lower amide molar ratios, the amide appears to be not segregated from the ionic liquid. This proposed molecular picture is supported by small angle x-ray scattering experiments.

Molecularly Heterogeneous Structure of a Nonionic Deep Eutectic Solvent Composed of N-Methylacetamide and Lauric Acid.

Deep eutectic solvents (DES) are a new class of designer solvents with a wide range of possible applications. DESs are typically made from an ionic compound and a hydrogen bond donor, but lately DESs made of nonionic compounds with interesting properties have started to appear. This study focuses on describing the structure, dynamics, and interactions of a nonionic DES composed of  N-methylacetamide (NMA) and lauric acid (LA). Linear IR and time-resolved IR experiments show that LA-NMA DES is the result of hydrogen bond interaction between the two molecular components, though the interaction energy is only favored by ∼1 kJ/mol with respect to the pure components. The IR experiments also reveal the presence of molecular heterogeneities produced by the nanosegregation of polar and nonpolar domains formed by N-methylacetamide and lauric acid, respectively. In addition, it is observed that the hydrogen bond interaction between components occurs at the interface of the two distinct polarity domains. The proposed molecular picture is also supported by the observation of nanodomains with the approximate size of two lauric acids via small-angle X-ray scattering.