Transport Properties Of Electrolytes Research Articles

Structure and transport properties of LiTFSI-based deep eutectic electrolytes from machine-learned interatomic potential simulations.

Deep eutectic solvents have recently gained significant attention as versatile and inexpensive materials with many desirable properties and a wide range of applications. In particular, their characteristics, similar to those of ionic liquids, make them a promising class of liquid electrolytes for electrochemical applications. In this study, we utilized a local equivariant neural network interatomic potential model to study a series of deep eutectic electrolytes based on lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) using molecular dynamics (MD) simulations. The use of equivariant features combined with strict locality results in highly accurate, data-efficient, and scalable interatomic potentials, enabling large-scale MD simulations of these liquids with first-principles accuracy. Comparing the structure of the liquids to the reported results from classical force field (FF) simulations indicates that ion-ion interactions are not accurately characterized by FFs. Furthermore, close contacts between lithium ions, bridged by oxygen atoms of two amide molecules, are observed. The computed cationic transport numbers (t+) and the estimated ratios of Li+-amide lifetime (τLi-amide) to the amide's rotational relaxation time (τR), combined with the ionic conductivity trend, suggest a more structural Li+ transport mechanism in the LiTFSI:urea mixture through the exchange of amide molecules. However, a vehicular mechanism could have a larger contribution to Li+ ion transport in the LiTFSI:N-methylacetamide electrolyte. Moreover, comparable diffusivities of Li+ cation and TFSI- anion and a τLi-amide/τR close to unity indicate that vehicular and solvent-exchange mechanisms have rather equal contributions to Li+ ion transport in the LiTFSI:acetamide system.

Characterisation and modelling of potassium-ion batteries

Potassium-ion batteries (KIBs) are emerging as a promising alternative technology to lithium-ion batteries (LIBs) due to their significantly reduced dependency on critical minerals. KIBs may also present an opportunity for superior fast-charging compared to LIBs, with significantly faster K-ion electrolyte transport properties already demonstrated. In the absence of a viable K-ion electrolyte, a full-cell KIB rate model in commercial cell formats is required to determine the fast-charging potential for KIBs. However, a thorough and accurate characterisation of the critical electrode material properties determining rate performance—the solid state diffusivity and exchange current density—has not yet been conducted for the leading KIB electrode materials. Here, we accurately characterise the effective solid state diffusivities and exchange current densities of the graphite negative electrode and potassium manganese hexacyanoferrate K2Mn[Fe(CN)6]\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${{{{\\rm{K}}}}}_{2}{{{\\rm{Mn}}}}[{{{\\rm{Fe}}}}{({{{\\rm{CN}}}})}_{6}]$$\\end{document} (KMF) positive electrode, through a combination of optimised material design and state-of-the-art analysis. Finally, we present a Doyle-Fuller-Newman model of a KIB full cell with realistic geometry and loadings, identifying the critical materials properties that limit their rate capability.

Thermal and Transport Properties of Ionic Electrolytes with Tailored Guanidinium and Pyrrolidinium-Based Cation Structures for Na-Ion Batteries

Thermal and Transport Properties of Ionic Electrolytes with Tailored Guanidinium and Pyrrolidinium-Based Cation Structures for Na-Ion Batteries

Computational Analysis of Ion Clustering Statistics in Liquid Battery Electrolytes

The transport properties of liquid battery electrolytes critically depend on molecular-level solvation structures of ions. In contrast to the dilute regime where the majority of counterions are sufficiently separated spatially, in global or localized high-concentrated electrolytes (HCEs) counterions tend to form superstructures such as contact-ion pairs (CIPs) or aggregates (AGGs). The presence and relative population of such superstructures can drastically change the ionic transport behavior in liquid electrolytes. We have developed a computer program [1] that can efficiently perform analysis of ion clustering statistics from molecular dynamics simulations, complementary to experimental measurements. We have successfully applied our method to various systems, including (1) a prototypical concentrated liquid electrolyte (Li:EC:DEC) [2], and (2) a series of newly developed high-entropy liquid electrolytes [3]. In both cases, we find consistent agreements between our prediction and experimentally measured nanostructures and solvation strengths. We envision that our method would be widely applicable to generic structurally disordered systems.[1] Cohen et al., Journal of Open Source Software 8, 84 (2023)[2] Xie and Wang et al., Science Advances 9, eadc9721 (2023)[3] Kim and Wang et al. Nature Energy 8, 814–826 (2023)

Multi-Scale Development and Integration of Granular Activated Carbon Electrodes in Multiphase Electrochemical Systems

Providing clean water remains a significant challenge in underserved areas that lack access to public water systems or are affected by extreme natural events like hurricanes. Electrochemical technologies show promise for developing affordable and effective water treatment systems due to their ability to efficiently oxidize contaminants. Particularly, the electrochemical synthesis of in-situ reagents, such as H2O2, systems can oxidize contaminants over the full range of pH with high oxidation potential, leaving only water and oxygen at the end of process, making it a safe and effective method for water treatment. This study is focused on integrating carbon-based electrodes into electrochemical water treatment systems emphasizing their scalability, cost effectiveness, and the efficient generation of reactive oxygen species (ROS). By employing multiscale computational approaches, we develop a comprehensive mechanistic understanding and optimization of ROS generation at the surface of granular activated carbon (GAC) electrodes. Using reactive molecular dynamics simulations, the thermodynamic and transport properties of water-based electrolyte (e.g., adsorption, viscosity, and diffusion) are investigated as a function of the GAC particle size and chemistry. The obtained results show that tuning the GAC particle structure at nanoscale can improve the local diffusion rates by three times. Subsequently, multiphase continuum simulations are used to integrate the GAC electrodes in full electrochemical systems through optimizing the dispersion and the solid-liquid-gas interactions in a reactive environment. The computational findings reveal that higher production of H2O2 and are observed at optimized electrode porosity values when the GAC electrodes are integrated at the system level. These observations are linked to the complex reactive solid-fluid interactions. Specifically, the electrochemical oxygen bubble splitting and coalescence are minimized by optimizing the electrode porosity, which improves the dispersion mass transfer processes by at least one order of magnitude. This leads to higher generation rates of ROS and enhanced degradation of water contaminants. These mechanistic observations will help in designing and scaling up carbon-based electrodes for developing efficient and cost-effective electrochemical water treatment reactors.

Refractive Laser Beam Measuring Diffusion Coefficient of Concentrated Battery Electrolytes

A thorough understanding of electrolyte transport properties is crucial in the development of alternative battery technology. As a key parameter, the diffusion coefficient offers important insights into the behavior of electrolytes, especially for fast charge of high-energy batteries. Existing methods of measurement are often limited by redox species or offer questionable accuracy due to side reactions and/or disruption of the diffusion profile. A highly sensitive optical method was developed using a refractive laser beam through triangular diffusion column to measure the diffusion coefficient of concentrated battery electrolytes. The method based on Snell’s law can be applied to all liquid phase electrolytes since the refractive index is concentration dependent for all liquid electrolytes. This universal method relies on the deflection of a refractive laser beam passing through an electrolyte of a minor concentration gradient in a triangular diffusion column (Figure 1). A polarized HeNe laser was arranged to pass the beam through a right-angled triangular quartz precision cell, slightly rotated to the normal. The exact position of the refracted beam was located by a silicon photodiode-based position detector. Deflection calibration curves made simple conversion of beam position to concentration, and during the diffusion of two layered solutions, data points were collected every minute to produce a concentration profile descriptive of the 48-hour diffusion. Diffusion coefficients were calculated using a model based on OSM theory, accounting for multi-component concentrated systems in a restricted diffusion column.1 The measured diffusion coefficients are between 4.12x10-10 m2/s for 0.15 mol/kg ZnSO4 and 0.681x10-10 m2/s for 2.5 mol/kg ZnSO4 at 22.4 °C. The profile of concentration-dependent diffusion coefficients follows a non-linear inverse relationship described by the function D=4.943(1+m)-1.564 (Figure 2).Several other physicochemical properties of the same electrolytes were studied to correlate to the concentration-dependent diffusion coefficients, including refractive index, viscosity, conductivity, and microstructure analysis based on vibrational spectroscopy (Infrared and Raman). High concentration electrolytes with more ion pairs show increased viscosity which ultimately leads to smaller diffusion coefficients. A QCM-I instrument standard flow cell were used to determine the viscosity of ZnSO4 electrolyte and the concentration-dependent viscosity was fitted to the function η=1.06-0.476m+2.13m2-1.01m3+0.204m4. Interionic interactions also led to reduced conductivity at concentrations beyond 1.5mol/kg, despite the increased charge density of concentrated solutions. FT-IR spectrums allowed analyzation of increased charge density, which increased intensity of the O-H stretching peak in concentrated electrolytes, despite the decrease in the ratio of water. Competition between charge density and viscosity continues to challenge the efficiency of concentrated electrolytes.Lastly, we demonstrate the prototype in situ triangular cell to characterize the electrolyte in working batteries. The cell responds to short, low-voltage pulses with beam deflection and relaxation, and offers an opportunity as a novel in situ spectroscopic tool to characterize the battery electrolyte. Acknowledgments This work is supported by a grant from NSF (CBET-2243098).

Investigating Li-Ion Depletion during Fast Charging with Operando FTIR

Lithium-ion concentration polarization and slow ionic transport in the electrolyte phase hinder fast charging of electric vehicle batteries and can cause cell degradation. Although pseudo-2D (P2D) models capture concentration polarization phenomena during fast charging, experimental measurements of Li-ion concentration in the electrolyte phase have been limited. In this research, Fourier transform infrared spectroscopy (FTIR) and attenuated total reflection (ATR) were used to collect operando optical measurements of Li-ion concentration in a high-loading graphite/NMC811 full cell with 1.2M LiPF6 in 3/7 (wt./wt.) ethylene carbonate (EC)/ethyl methyl carbonate (EMC). For this research, an optically accessible operando battery was developed that enables real-time measurements of Li-ion concentration at the back of the graphite anode near the current collector. Significant Li-ion concentration changes up to 0.5M were observed during charging at 1C, 2C, and 3C, as well as discharging at C/2, and compared with a P2D model. Both the model and the experiments showed Li-ion depletion and sinuous fluctuations at the graphite/current collector interface that indicate non-ideal behavior. These gradients likely develop due to insufficient electrolyte transport properties. This research enables novel Li-ion concentration measurements with FTIR. This research also validates P2D model physics for measuring and analyzing Li-ion concentration polarization at fast charging rates.

Phase-Field Modeling of Electrolyte Transport Properties and Elasticity Modulus in Suppression of Dendrite Growth in Solid-State-Lithium-Ion-Batteries

Dendrite formation in batteries is a critical issue that affects battery performance and lifespan. Solid-state electrolytes have gained attention due to their advantages such as compactness, higher energy density, and enhanced safety. This study investigates dendrite growth in batteries via phase field simulations utilizing a grand potential-based phase field model. The simulations are executed using the MOOSE (Multiphysics Object-Oriented Simulation Environment) framework, a Finite Element Method (FEM) based solver known for its modular approach and proficiency in handling complex multi-physics problems. Initially, the study considers a pure lithium anode and a 1M LiPF6 electrolyte for the liquid case. To explore the benefits of solid electrolytes, a fictitious solid electrolyte with transport properties similar to the liquid electrolyte but having different mechanical properties is considered. The mechanical impact resulting from the volume changes due to lithium deposition is not accounted for in the liquid electrolyte model. However, the solid electrolyte model addresses this by modifying the Butler-Volmer kinetics and incorporating the influence of stresses on the localized lithium deposition. Sensitivity analysis is performed for various parameters in both the liquid and solid electrolytes. The results indicate that dendrite growth is reduced with decreased applied over-potential and interfacial energies. For solid electrolytes, an additional parameter, increased Young’s modulus, contributes to reduced dendrite growth. The evaluation of dendrite growth involves quantifying surface roughness using the root mean square (RMS) approach. The elasticity modulus significantly influences dendrite formation, with higher values in materials like LLZO, and glass Li3PS4 exhibiting lower dendrite growth, while lower values in polymer-based materials like P(VDF-HFP) and PVDF/CAB/PE exhibit higher dendrite growth. The solid electrolyte acts as a crucial mechanical barrier, influencing the dendrite tip growth rate and ensuring uniform electrodeposition throughout the dendritic structure. Furthermore, the work investigates the impact of the cathode on dendrite growth. The contraction of the cathode provides additional space for dendrites to move, leading to reduced compressive stresses and increased dendrite growth. Conversely, higher compressive stresses suppress dendrite growth.

Quantifying Electrolyte Variation through Coupled Molecular Dynamics and Porous Electrode Modeling of Lithium-Ion Battery Cells

Lithium-ion battery cell modeling using physics-based approaches such as porous electrode theory is a powerful tool for battery design and performance analysis both at the beginning and end of life[1]. Cell metrics such as resistance and thermal performance[2-6] can be quickly calculated in a pseudo-two-dimensional (P2D) framework. For engineering of electric vehicle batteries, speed and fidelity of electrochemical models is paramount in a competitive landscape. Physics-based models[7, 8] allow for high fidelity but require detailed knowledge of the cell component material properties. Acquiring these material characteristics typically requires time-consuming and expensive experiments limiting the ability to quickly screen through cell designs. One approach to circumvent costly experiments is to use molecular dynamics[9, 10] to calculate electrolyte transport properties. We demonstrate how cell modeling using simulated transport properties enables predictions of cell level metrics, allowing for experiment-free component screening. We also show how the variation in transport property predictions from molecular dynamics affects the final cell level performance predictions.

Electrolytes for solid state lithium batteries in the [N13pip]ClO4-LiClO4-Al2O3 system for solid state lithium batteries

The transport, electrochemical, structural, and thermal properties of electrolytes in the ternary system [N13pip]ClO4-LiClO4-γ-Al2O3 (N13pip is N-methyl-N-ethyl-piperidinium cation) were investigated at the molar ratio [N13pip]ClO4:LiClO4 = 0.82:0.18. The addition of alumina leads to a change in the thermodynamic properties of the [N13pip]ClO4-LiClO4 system that can be explained by a partial transfer of lithium perchlorate from the organic phase to the surface of γ-Al2O3. The highest ionic conductivity of 6.2∙10–4 S/cm at 110 °C was observed for the composition containing the volume fraction (f) of γ-Al2O3 equal to 0.5. The increase in conductivity compared to the binary system 0.82[N13pip]ClO4-0.18LiClO4 is achieved due to the amorphization of the organic salt near the salt/LiClO4/oxide interfaces. Galvanostatic cycling with Li electrodes shows that composites with f = 0.5 are stable at 110 °C for at least 68 charge/discharge cycles, and the electrolyte is shown to be electrochemically stable up to 5 V. This system can be used as a solid-state electrolyte in lithium-ion current sources.

To Pair or not to Pair? Machine-Learned Explicitly-Correlated Electronic Structure for NaCl in Water.

The extent of ion pairing in solution is an important phenomenon to rationalize transport and thermodynamic properties of electrolytes. A fundamental measure of this pairing is the potential of mean force (PMF) between solvated ions. The relative stabilities of the paired and solvent shared states in the PMF and the barrier between them are highly sensitive to the underlying potential energy surface. However, direct application of accurate electronic structure methods is challenging, since long simulations are required. We develop wave function based machine learning potentials with the random phase approximation (RPA) and second order Møller-Plesset (MP2) perturbation theory for the prototypical system of Na and Cl ions in water. We show both methods in agreement, predicting the paired and solvent shared states to have similar energies (within 0.2 kcal/mol). We also provide the same benchmarks for different DFT functionals as well as insight into the PMF based on simple analyses of the interactions in the system.

Upgrading Gel Electrolytes Through Electrostatic-Induced Dual-Salt Paradigm for Superior Zn-Ion Battery Performance.

Gel electrolytes are gaining attention for rechargeable Zn-ion batteries because of their high safety, high flexibility, and excellent comprehensive electrochemical performances. However, current gel electrolytes still perform at mediocre levels due to incomplete Zn salts dissociation and side reactions. Herein, an electrostatic-induced dual-salt strategy is proposed to upgrade gel electrolytes to tackle intrinsic issues of Zn metal anodes. The competitive coordination mechanism driven by electrostatic repulsion and steric hindrance of dual anions promotes zinc salt dissociation at low lithium salt addition levels, improving ion transport and mechanical properties of gel electrolytes. Li+ ions and gel components coordinate with H2O, reducing active H2O molecules and inhibiting associated side reactions. The dual-salt gel electrolyte enables excellent reversibility of Zn anodes at both room and low temperatures. Zn||Polyaniline cells using the dual-salt gel electrolyte exhibit a high discharge capacity of 180mAhg-1 and long-term cycling stability over 180 cycles at -20°C. The dual-salt strategy offers a cost-effective approach to improving gel electrolytes for high-performance flexible Zn-ion batteries.

Insight of transport properties of glassy solid electrolytes for energy storage applications

The goal of developing battery systems has attracted researchers' attention for about 30 years, almost since the development of primary electrochemical systems with a lithium anode. To realize the benefits of lithium ion batteries (LIBs) and lithium metal anode batteries, several important issues need to be addressed. The use of liquid non-aqueous electrolytes based on aprotic solvents in lithium battery systems certainly offers advantages over traditional battery systems. However, due to the relatively low evaporation temperatures and high flammability of solvents, liquid electrolytes significantly limit the operating range of battery systems in the high-temperature range. Special measures are required to ensure the safe operation of a lithium-ion battery system. The use of inorganic solid electrolytes (SEs) is one of the most promising directions for improving lithium-ion and solid-state battery systems. The use of SEs will enable the safe cycling of battery systems with both lithium electrodes and intercalation anodes, significantly extend the temperature range of battery operation towards high temperatures and enable the creation of battery systems of new sizes and designs. The development of new solid oxide salt materials and technologies to produce battery systems with electrolytes based on them is an urgent task to solve the above problems.

Refractive Laser Beam Measuring Diffusion Coefficient of Concentrated Battery Electrolytes

A thorough understanding of electrolyte transport properties is crucial in the development of alternative battery technology. As a key parameter, the diffusion coefficient offers important insights into the behavior of electrolytes, especially for fast charge of high-energy batteries. Existing methods of measurement are often limited by redox species or offer questionable accuracy due to side reactions and/or disruption of the diffusion profile. This work provides a novel optical method for measuring diffusion coefficients of liquid-phase concentrated battery electrolytes without electrochemical reactions. The method relies on the deflection of a refractive laser beam passing through an electrolyte of a minor concentration gradient in a triangular diffusion column. The diffusion coefficient, D, for a range of zinc sulfate electrolytes was successfully extracted by correlating the position of the laser beam to its concentration. Several other physicochemical properties of the same electrolytes are studied to correlate to the concentration-dependent diffusion coefficients, including viscosity, conductivity, and microstructure analysis based on vibrational spectroscopy (Infrared and Raman). Also included is the future application of the triangular column for in situ electrochemical measurements.

Micro Area Interface Wetting Structure with Tailored Li+-Solvation and Fast Transport Properties in Composite Polymer Electrolytes for Enhanced Performance in Solid-State Lithium Batteries.

To satisfy the demand for high safety and energy density in energy storage devices, all-solid-state lithium metal batteries with solid polymer electrolytes (SPE) replacing traditional liquid electrolytes and separators have been proposed and are increasingly regarded as one of the most promising candidates as next-generation energy storage systems. In this study, poly(vinylidene fluoride)-hexafluoropropylene/lignosulfonic acid (PVDF-HFP/LSA) composite polymer electrolyte (CPE) membranes with a micro area interface wetting structure were successfully prepared by incorporating LSA into the PVDF-HFP polymer matrix. The enhanced interaction between the polar functional group in LSA and the C═O in N-methylpyrrolidone (NMP) hinders the evaporation of solvent NMP, thus creating a micro area wetting structure, which offers a flexible region for the chain segment movement and enlarging the area of the amorphous zone in PVDF-HFP. From the results of IR and Raman spectroscopy, it was found that the presence of LSA induced unique ion transport channels created by the massive aggregated ion pair (AGG) and contact ion pair (CIP) of ion cluster structures composed of Li+ and multiple TFSI- and, at the same time, effectively reduced the crystallinity of the polymer electrolyte, hence further contributing to the Li+ diffusion. As a result, at a rate of 2 C, the Li|CPE-15|LiFePO4 solid-state battery delivers an initial discharge-specific capacity of 134.9 mAh g-1 and maintains stability with a retention of 84% during 400 charge-discharge cycles while the Li|CPE-0|LiFePO4 battery fails after only a few cycles at the same rate.

Linear ether-based highly concentrated electrolytes for Li-sulfur batteries.

Li-S batteries have attracted attention as next-generation rechargeable batteries owing to their high theoretical capacity and cost-effectiveness. Sparingly solvating electrolytes hold promise because they suppress the dissolution and shuttling of polysulfide intermediates to increase the coulombic efficiency and extend the cycle life. This study investigated the solubility of polysulfide (Li2S8) in a range of liquid electrolytes, including organic electrolytes, highly concentrated electrolytes, and ionic liquids. The Li2S8 solubility was well correlated with the donor number (DNNMR), estimated via23Na-NMR, and was lower than 100 mM_(elemental sulfur) in electrolytes with DNNMR < 14, regardless of the type of electrolyte. Highly concentrated electrolytes comprising lithium bis(trifluoromethanesulfonyl)amide (LiTFSA) and linear chain dialkyl ethers such as methyl propyl ether (MPE), n-butyl methyl ether (BME), and ethyl propyl ether (EPE) were studied as sparingly solvating electrolytes for Li-S batteries. Monomethyl ethers, such as BME, showed more pronounced Li-ion coordination and higher ionic conductivity, whereas the steric hindrance of the longer alkyl chains in EPE lowered the solvation number, enhanced ion association, and lowered the ionic conductivity despite the solvents having similar dielectric constants. The charge-discharge rate capabilities of Li-S cells with dialkyl ether-based electrolytes were more impressive than those of cells with a localized high-concentration electrolyte using sulfolane (SL) and hydrofluoroether (HFE), [Li(SL)2][TFSA]-2HFE. The higher rate performance was attributed to the superior Li-ion transport properties of the dialkyl ether-based electrolytes. A pouch-type cell using lightweight [Li(BME)3][TFSA] demonstrated an energy density exceeding 300 W h kg-1 under lean electrolyte conditions.

Structural and transport properties of battery electrolytes at sub-zero temperatures

Formulating and establishing design principles to improve low-temperature performance of battery electrolytes.

Error Analysis for Transport Properties of Lithium-Ion Battery Electrolytes

Accurate determination of electrolyte transport properties in lithium-ion batteries (LIBs) is pivotal for understanding battery performance and optimizing their design. Electrolyte transport properties, encompassing ionic conductivity, diffusion coefficients, and transference numbers, are critical parameters that influence charge and discharge rates, ion mobility, and energy efficiency.[1,2] However, experimental measurements are inevitably accompanied by uncertainties stemming from experimental conditions, instrument calibration, and data analysis methods. Error propagation in electrolyte transport properties has substantial ramifications for battery research and development. Inaccurate measurements can lead to flawed conclusions about battery behavior and hinder the design of optimal electrolyte formulations.[3] Based on the literature, measurements of concentration cells for the determination of electrolyte properties were conducted at different temperatures and concentrations to study its impact on transport properties, and the Gaussian error propagation method was used to analyze the data. The concentration cell experiment is essential to determine the transport factor a. [4] The equation to determine the transport factor is shown in Figure 1a and the exemplary results are represented in Figure 1b. The results show that the error bars are significantly higher at certain concentration pairs.The main aim of this research is to identify the sources that contribute to the prominent difference in the error bars across different concentrations and temperatures. It also discusses the significance of systematic errors, which arise due to calibration issues or instrumental biases, and random errors stemming from variations in experimental conditions.[5] Recognizing the nature of these errors is critical for accurate interpretation of experimental data. To determine the electrolyte transport properties and the corresponding error or uncertainty, experimental datasets from the literatureare studied and repeated in our laboratories.

(Invited) Ion Transport in Solid-State Electrolytes Based on TTF - TCNQ Charge-Transfer Complexes

Current research on solid-state organic electrolytes mainly focuses on polymer electrolytes where ion transport is facilitated by chain segmental motion. The ionic conductivity of these polymer electrolytes at room temperature in too low for many practical applications. A limited number of prior reports suggest that solid-state electrolytes including organic crystalline charge-transfer complexes can have surprisingly high ionic conductivity. We report1 that processing and environmental conditions drastically impact electron and ion charge transport properties of charge-transfer complex electrolytes based on tetrathiafulvalene-tetracyanoquinodimethane (TTF-TCNQ) mixed with lithium bis(trifluoromethylsulfonylimide) (LiTFSI). Thermal annealing and water vapor treatment decrease electronic conductivity and increase ionic conductivity. The electrolyte with 1-1-2-0.45 molar ratio of TTF-TCNQ-LiTFSI-H2O has an ionic conductivity of 2 × 10-3 S/cm at 25 °C with electronic conductivity of order 10-7 S/cm. Thermal annealing helps reduce connectivity of the charge-transfer complexes and expose more surfaces to interact with LiTFSI, thereby decreasing electronic conductivity. Exposure of the sample to water vapor then causes a substantial increase in ionic conductivity, even when the material remains in the solid state. In this presentation, we will also report on additional experimental studies of solid-state electrolytes incorporating TTF-TCNQ.Reference 1. L. Yang and J. L. Schaefer, “Water-Assisted Ion Conduction in Solid-State Charge-Transfer Complex Electrolytes for Lithium Batteries,” ChemRxiv, 2023. https://doi.org/10.26434/chemrxiv-2023-9k024

Impact of fluorination on Li+ solvation and dynamics in ionic liquid-hydrofluoroether locally concentrated electrolytes

The thermal, physical, structural, and transport properties of ionic liquid (IL) electrolytes based on n-methyl-n-butylpyrrolidinium bis(trifluoromethanesulfonyl)imide [PYR14][TFSI] and Li-salts of lithium (nonafluorobutane)(trifluoromethanesulfonyl)imide [Li][IM14] and [Li][TFSI] (0 ≤ xLi ≤ 0.3), with addition of 1,1,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether (TTE) (0 ≤ xTTE ≤ 0.45) were studied. While [IM14] increases glass transition, TTE improves conductivity over a wider liquidus range. Li+ is solvated primarily by [TFSI] with some contribution by [IM14]. However, both 7Li- 19F HOESY NMR and spatial distribution functions (SDFs) derived from molecular dynamics (MD) indicate short contacts between the fluorines of TTE and Li+. This is a result of tighter anion-solvated Li+ without aggregation of the Li+ solvates, consistent with Raman measurements, thus confirming the existence of fluorous domains in the bulk which leads to improved fluidity and a Li+ diffusivity of 1.26 × 10−12 m2/s at 0 °C (xLi = 0.20) with a Li+ transference of 0.16. Improved transport properties translated to a higher capacity of the TTE/IL electrolyte in a Li||LiFePO4 half-cell with 95mAh/g at 0.1C, compared to the IL electrolyte without TTE (60 mAh/g). This study demonstrates the tunability of solvation and transport properties in IL electrolytes by asymmetric fluorinated anions and hydrofluoroether co-solvents for low temperature Li-ion batteries.