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Results for “Organic liquid electrolyte”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 217 records · Page 12
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Energy efficient supercritical water desalination using a high-temperature heat pump: A zero liquid discharge desalination

Supercritical water desalination (SCWD) is zero liquid discharge technology that can potentially control the solubility of different electrolytes. However, SCWD is an energy-intensive process and requires high-quality thermal heat (> 450 °C). This study proposes the integration of a high-temperature heat pump to reduce the SCWD energy requirement. The integrated system energy consumption improves by 36% for 3.5% feed concentration and 14% for 20% feed, and the distillate cost reduces by 15% and 10%. Another benefit of the proposed integration is the system can be operated using only electricity as a heat source, as is the case with commonly used high-recovery thermal desalination technology. The integrated SCWD-heat pump system shows superior performance compared to the commercially used brine concentrator and crystallizer system. It is approximately 20% more energy-efficient for 25% feed concentration and 8% cheaper. Hence, the integrated SCWD-heat pump has the potential to outperform the pre-existing high-recovery desalination technology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Compressive Creep of Polymer Electrolyte Membranes: A Case Study for Electrolyzers

For proton-exchange membrane (PEM) water electrolyzers to be commercially feasible, PEMs must perform over long lifetimes in liquid environments under compression while maintaining mechanical stability. A hydrated environment, while inherent for operation and conductivity, undermines PEM stability. Mechanical stability of PEMs is commonly characterized in tension, which is not applicable to electrolyzers, wherein PEMs could undergo high pressures. In this study, a compression creep procedure is developed using a custom-designed setup to monitor creep response of hydrated PEMs. Furthermore, our results show that PEMs exhibit continuous creep response under compression over 24 h, with a dependence on the applied pressure and hydration state.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

The early-stage growth and reversibility of Li electrodeposition in Br-rich electrolytes

Significance Spatial variations in chemical composition and transport properties of the material phases (interphases) formed on reactive metals in liquid electrolytes are thought to be responsible for the propensity of metal battery electrodes to electrodeposit in irregular, nonplanar morphologies. Equilibrium theoretical calculations using joint density functional analysis in vacuum and generic liquid media indicate that in-plane transport at such interphases is enhanced substantially if LiX (X = Br > Cl > F) species predominate. This study employs optical visualization experiments and nucleation theory to experimentally investigate nucleation and early-stage growth dynamics of metallic lithium in electrolytes enriched with LiBr. It is shown that the Li-Br–rich interphases formed profoundly alter the morphology of Li electrodeposits by enhancing Li-ion surface diffusion.

25 ENERGY STORAGE↗
DOE OSTI2020

Real-time mass spectrometric characterization of the solid–electrolyte interphase of a lithium-ion battery

Solid-electrolyte interphase (SEI) is a key component that dictates the performance of most electrochemical devices, but the understanding of its chemistry and structure has been limited by the lack of in-situ tools. In this work, we report SEI live-formation in Li-ion battery under operando condition with liquid secondary ion mass spectrometry (SIMS), which, in combination with molecular dynamics (MD) simulation, presents the first dynamic picture with molecular-accuracy about this key component. Before any interphasial chemistry occurs during the initial charging, an electric double layer forms at the electrode-electrolyte interface via the self-assembly of solvent molecules directed by both Li+ and potential of the electrified surface. Such double layer structure predicts the eventual interphasial chemistries formed from the electrolytes, where the negatively-charged electrode surface repels salt anions from the inner-Helmholtz layer and results in an inner SEI that is thin, dense and inorganic in nature but LiF-depleted. It was this dense layer that exercises the major functions of an interphase, i.e., conducting Li+ but insulating electrons. An outer layer that is electrolyte-permeable and organic-rich appears after formation of the inner SEI. In highly-concentrated electrolyte, the presence of LiF in the inner-SEI is raised due to the high population of salt anions in the double layer. These real-time observations at nano-scale reveal in general sense how an interphase inherits chemistry from inner-Helmholtz layer structure, and establish guidelines in engineering desirable interphases for the future battery chemistries.

Zhou, Yufan↗
DOE OSTI2021

Helical Covalent Polymers with Unidirectional Ion Channels as Single Lithium-Ion Conducting Electrolytes

Single-ion conducting polymer electrolytes have attracted great attention as safe alternatives to liquid electrolytes in high energy density lithium-ion batteries. Herein, we report the first example of a crystalline anionic helical polymer as a single lithium-ion conducting solid polymer electrolyte (SPE). Single-crystal X-ray analysis shows that the polymer folds into densely packed double helices, with bundles of unidirectional negatively charged channels formed that can facilitate lithium-ion transportation. Such a helical covalent polymer ( HCP) exhibits excellent room temperature lithium-ion conductivity (1.2 x 10 -3 S cm -1 ) in the absence of external lithium salts, a high transference number (0.84), low activation energy (0.14 eV), and a wide electrochemical stability window (0.2-5 V). We found that nonflammable, nonvolatile ionic liquid can serve as a solvating medium and excellent conductivity enhancer (>1000 times increase). These ion-conducting properties are comparable to the best polyethylene oxide-based polymer electrolytes mixed with lithium salts. Finally, we show that the solvated HCP SPE enables the reversible cycling of an all-solid-state cell prepared with a high-voltage NMC 811 cathode. Our study opens up new possibilities for developing next-generation high-performance solid-state electrolytes.

25 ENERGY STORAGE↗
DOE OSTI2020

Examination of Solvent- Room Temperature Ionic Liquid Interactions using 2D NMR and Computational Chemistry

Rare earth metals (REMs) are the key functioning material found in microelectronics, advanced batteries, and high-efficiency electrical motors. Current methods for producing REMs require high temperatures (i.e. energy intensive) and produce an abundance of hazardous fluoride waste. Room temperature ionic liquids (RTILs) are an ideal alternative electrolyte because they allow for a low-temperature, energy-efficient electrochemical process. RTIL properties such as viscosity and conductivity determine how effective they can be in this process. Since viscosity is directly related to both intra and intermolecular forces, this study sets out to investigate two RTILs-Trihexyltetradecylphosphonium dicyanamide (Cyphos 105) and Trihexyltetradecylphosphonium bistrifimide (Cyphos 109) and their interactions. Results from 2-dimensional nuclear magnetic resonance (2D NMR) spectroscopy show that there is an interaction between the tetradecyl tail and the phosphorus atom of the Cyphos RTIL. In order to establish whether this is an intra or an inter-molecular interaction, DFT-based computational calculations were performed to determine the optimized geometry. Calculations were done both in the gas phase and with propylene carbonate as an augmenting solvent. Preliminary results show that there is minimal intramolecular interaction between the tetradecyl tail and the phosphorus atom of the RTILs, and that the interaction seen in the 2D NMR experiment is likely of an intermolecular nature instead.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Solid Electrolytes in the Spotlight

This virtual issue is targeted to students and researchers, and highlights 32 research articles published over the past 5 years (from July 2016 to July 2021) in Chemistry of Materials (CM). Here, the compilation of papers summarizes the latest advances in the field of solid-state electrolytes for lithium (Li)-, sodium (Na)-, and multivalent-ion (not among the 32 articles discussed) all-solid-state batteries (ASSBs), with a focus on inorganic materials and excluding hybrid systems, e.g., polymer/ceramic composites or systems including liquid media. A total of 125 articles reporting exciting experimental and/or theoretical findings on solid electrolytes were considered for this issue. During 2017–2019, there were about 25–30 papers published per year on this topic, but 2020 and 2021 saw a significant increase, with 26 publications in the first half of 2021 alone. Submissions came from many countries around the world, as shown in Figure 1. While most papers were led by research groups located in the United States, Germany and Japan follow closely, and Austria, the United Kingdom, Canada, and China are also well represented.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Anion Coordination Improves High-Temperature Performance and Stability of NaPF 6 -Based Electrolytes for Supercapacitors

Electrolyte stability can be improved by incorporating complexing agents that bind key decomposition intermediates and slow down decomposition. We show that hexamethyl-phosphoramide (HMPA) extends both the thermal stability threshold of sodium hexafluorophosphate (NaPF 6 ) in dimethoxyethane (DME) electrolyte and the cycle life of double-layer capacitors. HMPA forms a stable complex with PF 5 , an intermediate in PF 6 anion thermal degradation. Unbound, this intermediate leads to autocatalytic degradation of the electrolyte solution. The results of electrochemical impedance spectroscopy (EIS) and galvanostatic cycling measurements show large changes in the cell without the presence of HMPA at higher temperatures (≥60 °C). Fourier transform infrared spectroscopy (FTIR) on the liquid and gas phase of the electrolyte shows without HMPA the formation of measurable amounts of PF 5 and HF. The complimentary results of these measurements proved the usefulness of using Lewis bases such as HMPA to inhibit the degradation of the electrolyte solution at elevated temperatures and potentially lead to improve cycle life of a nonaqueous capacitor. The results showed a large increase in capacitance retention during cycling (72% retention after 750,000 cycles). The results also provide evidence of major decomposition processes (0% capacitance retention after 100,000 cycles) that take place at higher temperatures without the additive of a thermal stability additive such as HMPA.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Improving the Accuracy of Atomistic Simulations of the Electrochemical Interface

Atomistic simulation of the electrochemical double layer is an ambitious undertaking, requiring quantum mechanical description of electrons, phase space sampling of liquid electrolytes, and equilibration of electrolytes over nanosecond time scales. All models of electrochemistry make different trade-offs in the approximation of electrons and atomic configurations, from the extremes of classical molecular dynamics of a complete interface with point-charge atoms to correlated electronic structure methods of a single electrode configuration with no dynamics or electrolyte. Here, we review the spectrum of simulation techniques suitable for electrochemistry, focusing on the key approximations and accuracy considerations for each technique. Additionally, we discuss promising approaches, such as enhanced sampling techniques for atomic configurations and computationally efficient beyond density functional theory (DFT) electronic methods, that will push electrochemical simulations beyond the present frontier.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Electrolysis on a Chip with Tunable Thin Film Nanostructured PGM Electrocatalysts Generated from Self-Assembled Block Copolymer Templates

Self-assembled block copolymers are promising templates for fabricating thin film materials with tuned periodic feature sizes and geometry at the nanoscale. Here, a series of nanostructured platinum and iridium oxide electrocatalysts templated from poly(styrene)-block-poly(vinyl pyridine) (PSbPVP) block copolymers via an incipient wetness impregnation (IWI) pathway is reported. Both nanowire and nanocylinder electrocatalysts of varying feature sizes are assessed and higher catalyst loadings are achieved by the alkylation of the pyridine moieties in the PVP block prior to IWI. Electrocatalyst evaluations featuring hydrogen pump and water electrolysis demonstrations are carried out on interdigitated electrode (IDE) chips flexible with liquid supporting electrolytes and thin film polymer electrolytes. Notably, the mass activities of the nanostructured electrocatalysts from alkylated block copolymer templates are 35%–94% higher than electrocatalysts from non-alkylated block copolymer templates. Standing cylinder nanostructures lead to higher mass activities than lamellar variants despite their not having the largest surface area per unit catalyst loading demonstrating that mesostructure architectures have a profound impact on reactivity. Overall, IDE chips with model thin film electrocatalysts prepared from self-assembled block copolymers offer a high-throughput experimental method for correlating electrocatalyst nanostructure and composition to electrochemical reactivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Molecular Functionalization of Semiconductor Surfaces

The presence of molecules on semiconductor surfaces can have a profound impact on their properties and applications in solar energy conversion. In this chapter we discuss the methods used to effect functionalization of semiconductor surfaces with molecular dipoles and catalysts. A major focus is the energetic impacts such molecules have to the fields at the semiconductor|contact interface. These field modulations are strongly dependent on the nature of the surface-bound molecule including its dipole moment and orientation as well as the distance of the dipole from the semiconductor surface. The contacting phase also has a strong impact on the energetics, since ions in the liquid electrolytes relevant to inorganic photochemistry partially screen dipolar effects at the surface. In addition to detailed description of these fundamentals, we present the history of this field as well as state-of-the-art chemistries that leverage the preceding decades of knowledge to impart the molecular interfacial layer with dynamic properties such as light absorption and catalysis. The challenges of establishing stable molecular attachment schemes at semiconductor|electrolyte interfaces are interwoven throughout the chapter. We conclude with a prognosis and future outlook that we hope will be a useful guide to those interested in developing the next generation of molecular chemistries at photoelectrode interfaces.

CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS,I↗
DOE OSTI2022

Unraveling Ion Transport in Trifluoromethanesulfonimide Pentablock Copolymer Membranes in Nonaqueous Electrolytes

Cation exchange membranes provide a key function in various nonaqueous energy storage technologies. As such, understanding the role of a nonaqueous liquid electrolyte on ion transport through a membrane is imperative. This study unravels relationships between membrane ion transport and electrolyte salt concentration utilizing a trifluoromethanesulfonimide-based pentablock copolymer membrane with polar and nonpolar nonaqueous electrolyte solutions. Here, the membrane plasticized with propylene carbonate (PC) exhibits a single-ion conductivity of 9.3 × 10 –6 S/cm at 25 °C. Tailoring the nonaqueous electrolyte and electrolyte salt concentration enables the single-ion conducting membrane to maintain a high cation transport number, >0.75, and boost ion conductivity more than 10 times to 1.3 × 10 –4 S/cm at 25 °C for the PC-based electrolyte solution. The findings provide critically important design parameters for energy storage systems utilizing nonaqueous electrolytes, such as Li- and Na-ion batteries and nonaqueous flow battery technologies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Polar liquids at charged interfaces: A dipolar shell theory

The structure of polar liquids and electrolytic solutions, such as water and aqueous electrolytes, at interfaces underlies numerous phenomena in physics, chemistry, biology, and engineering. In this work, we develop a continuum theory that captures the essential features of dielectric screening by polar liquids at charged interfaces, including decaying spatial oscillations in charge and mass, starting from the molecular properties of the solvent. The theory predicts an anisotropic dielectric tensor of interfacial polar liquids previously studied in molecular dynamics simulations. We explore the effect of the interfacial polar liquid properties on the capacitance of the electrode/electrolyte interface and on hydration forces between two plane-parallel polarized surfaces. In the linear response approximation, we obtain simple formulas for the characteristic decay lengths of molecular and ionic profiles at the interface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Fast estimation of ion-pairing for screening electrolytes: A cluster can approximate a bulk liquid

The propensity for ion-pairing can often dictate the thermodynamic and kinetic properties of electrolyte solutions. Fast and accurate estimates of ion-pairing can thus be extremely valuable for supplementing design and screening efforts for novel electrolytes. We introduce an efficient cluster model to estimate the local ion-pair potential-of-mean-force between ionic solutes in electrolytes. The model incorporates an ion-pair and a few layers of explicit solvent in a gas-phase cluster and leverages an enhanced sampling approach to achieve high efficiency and accuracy. We employ harmonic restraints to prevent solvent escape from the cluster and restrict sampling of large inter-ion distances. We develop a cluster ion-pair sampling tool that implements our cluster model and demonstrate its potential utility for screening simple and poly-electrolyte systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Enhancing ion transport in charged block copolymers by stabilizing low symmetry morphology: Electrostatic control of interfaces

Recently, the interest in charged polymers has been rapidly growing due to their uses in energy storage and transfer devices. Yet, polymer electrolyte-based devices are not on the immediate horizon because of the low ionic conductivity. In the present study, we developed a methodology to enhance the ionic conductivity of charged block copolymers comprising ionic liquids through the electrostatic control of the interfacial layers. Unprecedented reentrant phase transitions between lamellar and A15 structures were seen, which cannot be explained by well-established thermodynamic factors. X-ray scattering experiments and molecular dynamics simulations revealed the formation of fascinating, thin ionic shell layers composed of ionic complexes. The ionic liquid cations of these complexes predominantly presented near the micellar interfaces if they had strong binding affinity with the charged polymer chains. Therefore, the interfacial properties and concentration fluctuations of the A15 structures were crucially dependent on the type of tethered acid groups in the polymers. Overall, the stabilization energies of the A15 structures were greater when enriched, attractive electrostatic interactions were present at the micellar interfaces. Contrary to the conventional wisdom that block copolymer interfaces act as “dead zone” to significantly deteriorate ion transport, this study establishes a prospective avenue for advanced polymer electrolyte having tailor-made interfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Nanostructured Block Polymer Electrolytes: Tailoring Self-Assembly to Unlock the Potential in Lithium-Ion Batteries

Ion-containing solid block polymer (BP) electrolytes can self-assemble into microphase-separated domains to facilitate the independent optimization of ion conduction and mechanical stability; this assembly behavior has the potential to improve the functionality and safety of lithium-ion batteries over liquid electrolytes to meet future demands (e.g., large capacities and long lifetimes) in various applications. However, significant enhancements in the ionic conductivity and processability of BPs must be realized for BP-based electrolytes to become robust alternatives in commercial devices. Toward this end, the controlled modification of BP electrolytes’ intra-domain (nanometer-scale) and multi-grain (micrometer-scale) structure is one viable approach; intra-domain ion transport and segmental compatibility (related to the effective Flory–Huggins parameter, χ eff ) can be increased by tuning the ion and monomer-segment distributions, and the morphology can be selected such that the multi-grain transport is less sensitive to grain size and orientation.

25 ENERGY STORAGE↗
DOE OSTI2020

Electrochemical Characterization of Bromine Reduction to Tribromide in Individual Nitrobenzene-in-Water Emulsion Droplets

We report an electrochemical study of bromine reduction to tribromide in a single nitrobenzene (NB) droplet during a single collision event. The feasibility of this study is based on the favorable distribution of Br 2 in NB rather than in water, which was demonstrated by voltammetry at the NB/water interface. The NB-in-water emulsions containing the ionic liquids trihexyltetradecylphosphonium bis(trifluoromethylsulfonyl)amide (ILPA) as the supporting electrolyte and sodium dodecyl sulfate (SDS) as the surfactant were prepared by a high-power ultrasonication. Its single droplet as an attoliter reactor, colliding on a 25 μm Pt UME, was monitored by chronoamperometry. The spike-type current transients of Br 2 reduction can elucidate the size and size distribution of NB, and measure the diffusion in the droplet as analyzed by a bulk electrolysis model. The frequency of collisions can provide diffusion coefficient of the droplets to the UME. Moreover, the i-t decay behavior can be simulated, which fits well with the experimental one.

25 ENERGY STORAGE↗
DOE OSTI2023

Transition Metal Dissolution in Lithium-Ion Cells: A Piece of the Puzzle

Static leaching tests were performed using the chemically delithiated positive electrode materials, LiFePO 4 , LiCoO 2 , LiMn 2 O 4 , LiNiO 2 , and LiNi 0.8 Mn 0.1 Co 0.1 O 2 . Instead of the common electrolyte, which contains LiPF 6 , the solvent consisted of only ethylene carbonate (EC) and ethyl methyl carbonate (EMC), limiting the possible reactions to only those that depend on the solvent. The product liquids from these experiments showed that there were lithium-bearing species in common, such as Li(EC) + and Li(EMC) + . Interestingly, we found evidence of electrolyte degradation products in both the positive-and negative-ion mass spectral results. The positive-ion results showed that the products tended to coordinate to lithium. In conclusion, the negative-ion results showed that most of the products tended to complex with transition metals. It was difficult to discern which positive ion was associated with which negative ion.

25 ENERGY STORAGE↗