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At least 19 records

Machine learning-enabled discovery of ionic liquid–solvent electrolytes exhibiting high ionic conductivity

Ionic liquids (ILs), which are a class of materials with versatile nature and growing popularity, are facing impediments toward widespread usage as electrolytes due to various factors such as low ionic conductivity, high viscosity, high market price etc. One of the ways these limitations can be addressed is by mixing ILs with a molecular solvent. In a combinatorial sense, there exists an immense number of specific IL–solvent combinations. An exhaustive experimental or even simulation-based investigation of the chemical space spanned by such combinations can be extremely time-consuming, expensive, and nearly impossible. An alternative approach is to employ machine learning-based models developed from available databases. Although there exists prior literature that integrates machine learning to investigate mixtures of specific solvents with ILs, these models lack generalization necessitating development of a large number of ML models to handle various solvents. To remedy this shortcoming, as a part of designing green electrolytes with high ionic conductivity that can have potential applications in next-generation batteries and solar cells, this work aims to develop a unified machine learning model to predict ionic conductivity of any IL–solvent mixture system. In this regard, three models, namely, Random Forest, extreme gradient boosting (XGBoost), and artificial neural network (ANN) were formulated using the NIST ILThermo database. The dataset contained 549 unique ionic liquids from 16 cation families and 81 unique solvents, representing a total of 23 712 datapoints. SHAPLEY additive explanation (SHAP) method was used to assess the impact of various features on model prediction and their significance was compared with literature to gain physical insight about the model behavior. Finally, using the developed models, approximately 2.5 million IL–solvent mixtures at five different compositions were screened at room temperature. The high-throughput screening yielded nearly 19 000 IL–solvent mixtures for which ionic conductivity was found to exceed the ionic conductivity of conventional Li-ion battery electrolyte.

25 ENERGY STORAGE↗

Molecular-Level Control over Ionic Conduction and Ionic Current Direction by Designing Macrocycle-Based Ionomers

Poor ionic conductivity of the catalyst-binding, submicrometer- thick ionomer layers in energy conversion and storage devices is a huge challenge. However, ionomers are rarely designed keeping in mind the specific issues associated with nanoconfinement. Here, we designed nature-inspired ionomers (calix-2) having hollow, macrocyclic, calix[4]arene-based repeat units with precise, sub-nanometer diameter. In ≤100 nm-thick films, the in-plane proton conductivity of calix-2 was up to 8 times higher than the current benchmark ionomer Nafion at 85% relative humidity (RH), while it was 1-2 orders of magnitude higher than Nafion at 20-25% RH. Confocal laser scanning microscopy and other synthetic techniques allowed us to demonstrate the role of macrocyclic cavities in boosting the proton conductivity. The systematic self-assembly of calix-2 chains into ellipsoids in thin films was evidenced from atomic force microscopy and grazing incidence small-angle X-ray scattering measurements. Moreover, the likelihood of alignment and stacking of macrocyclic units, the presence of one-dimensional water wires across this macrocycle stacks, and thus the formation of long-range proton conduction pathways were suggested by atomistic simulations. We not only did see an unprecedented improvement in thin-film proton conductivity but also saw an improvement in proton conductivity of bulk membranes when calix-2 was added to the Nafion matrices. Nafion-calix-2 composite membranes also took advantage of the asymmetric charge distribution across calix[4]arene repeat units collectively and exhibited voltage-gating behavior. The inclusion of molecular macrocyclic cavities into the ionomer chemical structure can thus emerge as a promising design concept for highly efficient ion-conducting and ion-permselective materials for sustainable energy applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Identifying High Ionic Conductivity Compositions of Ionic Liquid Electrolytes Using Features of the Solvation Environment

Binary mixtures of ionic liquids with molecular solvents are gaining interest in electrochemical applications due to the improvement in their performance over neat ionic liquids. Dilution with suitable molecular solvents can reduce the viscosity and facilitate faster diffusion of ions, thereby yielding substantially higher ionic conductivity than that for a pure ionic liquid. Although viscosity and diffusion coefficients typically behave as monotonic functions of concentration, ionic conductivity often passes through a peak value at an optimum molar ratio of the molecular solvent to the ionic liquid. The ionic conductivity maximum is generally explained in terms of a balance between the ease of charge transport and the concentration of the charge carriers. In this work, fluctuation in the local environment surrounding an ion is invoked as a plausible explanation for the ionic conductivity mechanism with a binary mixture of 1-ethyl-3-methylimidazolium tetrafluoroborate and ethylene glycol as an example. The magnitude of the dynamism in the local environment is captured by measuring the spatial and temporal features of the solvation environment. Standard deviation in the number of ions in the solvation environment serves as a spatial feature, while the cage correlation lifetimes for oppositely charged ions within the first solvation shell serve as a temporal feature. Large standard deviations in the cluster ion population and short cage correlation lifetimes are indicators of highly dynamic ionic environment at the molecular level and consequently yield high ionic conductivity. Such compositions were found to be in good agreement with the optimum ionic liquid mole fractions obtained through experimental measurement. Short cage correlation lifetimes enable the identification of optimum mixture compositions using simulation trajectories significantly shorter than those required to implement the Nernst–Einstein or Einstein formalisms for calculating ionic conductivity. We validated the applicability of this approach across force fields and in six ionic liquid-molecular solvent electrolytes formed with combination of cations, anions, and solvents. We offer a computationally efficient approach of screening ionic liquid-molecular solvent binary mixture electrolytes to identify molar ratios that yield high ionic conductivity.

25 ENERGY STORAGE↗

Fundamental Limitations of Ionic Conductivity in Polymerized Ionic Liquids

In this paper, we present detailed studies of ionic conductivity in several polymerized ionic liquids (PolyILs) with different size of mobile ions. Presented analysis revealed that charge diffusion in PolyILs is about 10 times slower than ion diffusion, suggesting strong ion–ion correlations that reduce ionic conductivity. The activation energy for the ion diffusion shows a nonmonotonous dependence on the mobile ion size, indicating a competition between Coulombic and elastic forces controlling ion transport in PolyILs. The former dominates mobility of small ions (e.g., Li), while the latter controls mobility of large ions (e.g., TFSI). We propose a simple qualitative model describing the activation energy for the ion diffusion. In conclusion, it suggests that an increase in dielectric constant of PolyILs should lead to a significant enhancement of conductivity of small ions (e.g., Li and Na).

36 MATERIALS SCIENCE↗

Enhancing grain boundary ionic conductivity in mixed ionic–electronic conductors

Mixed ionic–electronic conductors are widely used in devices for energy conversion and storage. Grain boundaries in these materials have nanoscale spatial dimensions, which can generate substantial resistance to ionic transport due to dopant segregation. Here, we report the concept of targeted phase formation in a Ce 0.8 Gd 0.2 O 2₋δ –CoFe 2 O 4 composite that serves to enhance the grain boundary ionic conductivity. Using transmission electron microscopy and spectroscopy approaches, we probe the grain boundary charge distribution and chemical environments altered by the phase reaction between the two constituents. The formation of an emergent phase successfully avoids segregation of the Gd dopant and depletion of oxygen vacancies at the Ce 0.8 Gd 0.2 O 2₋δ –Ce 0.8 Gd 0.2 O 2₋δ grain boundary. This results in superior grain boundary ionic conductivity as demonstrated by the enhanced oxygen permeation flux. Lastly, this work illustrates the control of mesoscale level transport properties in mixed ionic–electronic conductor composites through processing induced modifications of the grain boundary defect distribution.

36 MATERIALS SCIENCE↗

Poly(diallylmethylammonium) proton conducting membranes with high ionic conductivity at intermediate temperatures

High temperature proton exchange membrane fuel cells are being lately investigated because of their high energy efficiency, their superior heat/water management, CO tolerance, and electrode reaction kinetics. To further advance this technology, the polymer membrane portfolio and performance should be improved for intermediate or high temperature operation (>100 °C). In this work we present new poly(diallylmethylammonium) proton conducting membranes with high ionic conductivity at 120 °C. First, new protic ionic liquids, hereafter called DAMAH + X - , were synthesized leading to diallylmethylammonium monomers with different counter-anions. By radical cyclopolymerization through thermal and photoinitiation mechanisms, self-standing protic polymeric membranes of poly(diallylmethylammonium X - ) were obtained. Membranes showed good thermal stability (>250 °C) and mechanical properties without the need of additives such as (protic) ionic liquids, solvents or inorganic charges. Great attention was paid to understand the effect of the different counter-anions on the membrane properties. As a general trend, fluorinated anions coming from strong acids confer high ionic conductivity and allow to reduce the hygroscopic properties on the protic polymeric membranes. Proton structural and dynamical stability at different temperatures and humidification conditions were investigated by Neutron Scattering (QENS and NR). The optimized poly(diallylmethylammonium X - ) shows similar ionic conductivity values than Nafion 212 under varying relative humidity conditions at 80 °C. Furthermore, it shows a high ionic conductivity value of 1.9 × 10 -3 Scm -1 at 120 °C under dry conditions.

08 HYDROGEN↗

Mixed-Salt Effects on the Ionic Conductivity of Lithium-Doped PEO-Containing Block Copolymers

We demonstrate a simple, yet effective, mixed-salt method to increase the room temperature ionic conductivity of lithium-doped block copolymer electrolyte membranes by suppressing the crystalline phases in the conducting block. We examined a mixed-salt system of LiClO{sub 4} and LiN(SO{sub 2}CF{sub 3}){sub 2} (LiTFSI) doped into a lamellae-forming poly(styrene-b-ethylene oxide) (PS-PEO) diblock copolymer. The domain spacings, morphologies, thermal behavior, and crystalline phases of salt-doped PS-PEO samples were characterized, and the ionic conductivities of block copolymer electrolytes were obtained through ac impedance measurements. Comparing the ionic conductivity profiles of salt-doped PS-PEO samples at different mixed-salt ratios and total salt concentrations, we found that the ionic conductivity at room temperature can be improved by more than an order of magnitude when coinhibition of crystallite growth is promoted by the concerted behavior of the PEO:LiClO{sub 4} and PEO:LiTFSI phases. Additionally, we examined the influence of mixed-salt ratio and total salt concentration on copolymer energetics, and we found that the slope of the effective interaction parameter ({chi}{sub eff}) vs salt concentration in our lamellae-forming PS-PEO system was lower than that reported for a cylinder-forming PS-PEO system due to the balance between chain stretching and salt segregation in the PEO domains.

36 MATERIALS SCIENCE↗

Phase Behavior and Ionic Conductivity of Blended, Ion-Condensed Electrolytes with Ordered Morphologies

In this study, the amphiphilic salt lithium trifluoromethanesulfonylimide octadecane (C18LiTFSI) was used as a basis to investigate the effects of anion density and cation coordination sites within blended electrolytes with strong ionic aggregation. C18LiTFSI was previously reported as a single-component, ion-condensed electrolyte with a wide layered liquid crystalline phase regime. Three additive molecules with varyingly sized polar sulfonyl groups attached to an octodecane-tail were synthesized and mixed with C18LiTFSI. The thermal properties, morphology, and ionic conductivity of the blended electrolytes were characterized. It was found that the blended electrolytes exhibited layered liquid crystalline morphology over a narrower temperature range than the pure salt, and the ionic conductivity of the blended liquid crystalline electrolytes were generally lower than that of the pure salt. Surprising, the additives were found to have the greatest effect on the bulk ionic conductivity of the semicrystalline phase of the electrolytes. Addition of minor fractions of methylsulfonyloctadecane to C18LiTFSI resulted in increases in conductivity of over two orders of magnitude at room temperature, while addition of ethylsulfonyloctadecane or isopropylsulfonyloctadecane with the larger head group resulted in decreased ionic conductivity over the entire composition space and temperature range investigated.

Collins, Hannah (ORCID:0000000338858136)↗

Local Structural Investigations, Defect Formation, and Ionic Conductivity of the Lithium Ionic Conductor Li 4 P 2 S 6

Glassy, glass–ceramic, and crystalline lithium thiophosphates have attracted interest in their use as solid electrolytes in all-solid-state batteries. Despite similar structural motifs, including PS 4 3– , P 2 S 6 4– , and P 2 S 7 4– polyhedra, these materials exhibit a wide range of possible compositions, crystal structures, and ionic conductivities. Here, we present a combined approach of Bragg diffraction, pair distribution function analysis, Raman spectroscopy, and 31 P magic angle spinning nuclear magnetic resonance spectroscopy to study the underlying crystal structure of Li 4 P 2 S 6 . In this work, we show that the material crystallizes in a planar structural arrangement as a glass ceramic composite, explaining the observed relatively low ionic conductivity, depending on the fraction of glass content. Calculations based on density functional theory provide an understanding of occurring diffusion pathways and ionic conductivity of this Li + ionic conductor.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Enhanced ionic conductivity with Li 7 O 2 Br 3 phase in Li 3 OBr anti-perovskite solid electrolyte

Cubic anti-perovskites with general formula Li 3 OX (X = Cl, Br, I) were recently reported as superionic conductors with the potential for use as solid electrolytes in all-solid-state lithium ion batteries. These electrolytes are nonflammable, low-cost, and suitable for thermoplastic processing. However, the primary obstacle of its practical implementation is the relatively low ionic conductivity at room temperature. In this work, we synthesized a composite material consisting of two anti-perovskite phases, namely, cubic Li 3 OBr and layered Li 7 O 2 Br 3 , by solid state reaction routes. The results indicate that with the phase fraction of Li 7 O 2 Br 3 increasing to 44 wt. %, the ionic conductivity increased by more than one order of magnitude compared with pure phase Li 3 OBr. Formation energy calculations revealed the meta-stable nature of Li 7 O 2 Br 3 , which supports the great difficulty in producing phase-pure Li 7 O 2 Br 3 at ambient pressure. Here, methods of obtaining phase-pure Li 7 O 2 Br 3 will continue to be explored, including both high pressure and metathesis techniques.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

An Investigation of the Ionic Conductivity and Species Crossover of Lithiated Nafion 117 in Nonaqueous Electrolytes

Nonaqueous redox flow batteries are a fast-growing area of research and development motivated by the need to develop lowcost energy storage systems. The identification of a highly conductive, yet selective membrane, is of paramount importance to enabling such a technology. We report the swelling behavior, ionic conductivity, and species crossover of lithiated Nafion 117 membranes immersed in three nonaqueous electrolytes (PC, PC : EC, and DMSO). Our results show that solvent volume fraction within the membrane has the greatest effect on both conductivity and crossover. An approximate linear relationship between diffusive crossover of neutral redox species (ferrocene) and the ionic conductivity of membrane was observed. As a secondary effect, the charge on redox species modifies crossover rates in accordance with Donnan exclusion. The selectivity of membrane is derived mathematically and compared to experimental results reported here. The relatively low selectivity for lithiated Nafion 117 in nonaqueous conditions suggests that new membranes are required for competitive nonaqueous redox flow batteries to be realized. Potential design rules are suggested for the future membrane engineering work.

25 ENERGY STORAGE↗

Grain boundary blocking of ionic conductivity in nanocrystalline yttria-doped ceria thin films

Nanocrystalline YDC thin films with grain-sizes ranging from 38 to 93-nm were prepared using pulsed laser deposition followed by thermal annealing. Ionic conductivity decreased up to four orders of magnitude as the grain size increased. Using energy-dispersive X-ray spectroscopy, we showed that the counter-intuitive reduction in conductivity with grain-size is likely due to dopant and impurity segregation near grain-boundaries. Spectroscopic evidence suggests that the blocking effect due to defect segregation is more dominant on ionic conductivity than the grain-sizes.

36 MATERIALS SCIENCE↗

The Relationship between Ionic Conductivity and Solvation Structures of Localized High-Concentration Fluorinated Electrolytes for Lithium-Ion Batteries

Localized high concentration electrolyte (LHCE) combines a diluent with high concentration electrolyte (HCE), offering promising properties. The ions, solvent, and diluent interact to form a complex heterogenous liquid structure, where high salt concentration clusters are embedded in diluent. Optimizing LHCE for desired electrolyte properties like high ionic conductivity, low viscosity, effective solid electrolyte interphase (SEI) formability, within the vast chemical and compositional design space requires deeper understanding and theoretical guidance. For this work, we investigated the structures and conductivity of LHCEs based on a fluorinated solvent with two different diluents at varying concentrations. The 2,2,3,3-tetrafluoropropyl trifluoroacetate (TFPTFA) enters the solvation cluster due to its stronger Li-ion interactions, whereas 1,1,2,2-tetrafuoroethyl 2,2,2-trifuoroethyl ether (TFETFE) enters only at extremely high diluent concentrations. The ionic conductivity increases with decreasing diluent concentrations, with a slope change during cluster percolation. Overall, TFETFE demonstrates higher effectiveness than TFPTFA, forming higher local salt concentration clusters, and resulting in higher ionic conductivity.

cluster chemistry↗

Measurement of Ionic Conductivity and Electrode Polarization at Low Temperatures on 8YSZ by a DC Technique

Measurement of ionic conductivity and electrode polarization resistance on a 8YSZ sample with platinum paste electrodes was conducted using a DC method with high input impedance meters over a temperature range from 119°C to 589°C. Over the entire temperature range, the meter resistance was much larger than the sample resistance including the polarization resistance. At lower temperatures, a faraday cage was used to minimize noise. The measured polarization resistance was also verified using electrochemical impedance spectroscopy. Ionic conductivity of 8YSZ exhibited Arrhenius behavior with an activation energy of ~1.1 eV, in good agreement with the literature. In the low current regime, electrode kinetics could be described by the linearized form of the Butler-Volmer equation. At higher current densities, electrode kinetics exhibited Tafel behavior. The polarization resistance exhibited Arrhenius behavior with the activation energy ranging between 1.05 and 1.27 eV. The present work shows that electrode polarizations can be investigated using a DC method. The approach may allow study of different electrodes in various atmospheres using one sample.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗