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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 253 records · Page 14
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Redox Activity Modulation in Extended Fluorenone-Based Flow Battery Electrolytes with π-π Stacking Effect

Redox flow battery shows promise for grid-scale energy storage. Aqueous organic redox flow batteries are particularly popular due to their potentially low material cost and safe water-based electrolyte. Commonly, redox active molecules used in this field feature aromatic rings, and increasing π-aromatic conjugation has been a popular strategy to achieve high energy density, high power density, and reduced crossover in new material design. However, this approach can inadvertently hinder redox activity depending on redox mechanism. This study reveals the underlying π-π stacking effect in extended aromatic redox active compounds, where aromatic radical intermediates are involved in the redox process. We report a molecular design strategy to mitigate the negative effect of π-π stacking by altering solvation dynamics and introducing molecular steric hindrance.

25 ENERGY STORAGE↗
DOE OSTI2020

Measurement of Three Transport Coefficients and the Thermodynamic Factor in Block Copolymer Electrolytes with Different Morphologies

The design and engineering of composite materials is one strategy to satisfy the materials needs of systems with multiple orthogonal property requirements. In the case of rechargeable batteries with lithium metal anodes, the system requires a separator with fast lithium ion transport and good mechanical strength. In this work, we focus on the system polystyrene-block-poly(ethylene oxide) (SEO) with bis(trifluoromethane)sulfonimide lithium salt (LiTFSI). Ion transport occurs in the salt-containing poly(ethylene oxide)-rich domains. Mechanical rigidity arises due to the glassy nature of polystyrene (PS). If we assume that the salt does not interact with the PS-rich domains, we can describe ion transport in the electrolyte by three transport parameters (ionic conductivity, κ, salt diffusion coefficient, D, and cation transference number, t + 0 ) and a thermodynamic factor, T f . By systematically varying the volume fraction of the conducting phase, Φ c between 0.29 and 1.0, and chain length, N between 80 and 8000, we elucidate the role of morphology on ion transport. We find that κ is the strongest function of morphology, varying by three full orders of magnitude, while D is a weaker function of morphology. To calculate t + 0 and T f , we measure the current fraction, ρ + , and the open circuit potential, U, of concentration cells. We find that ρ + and U follow universal trends as a function of salt concentration, regardless of chain length, morphology, or Φ c , allowing us to calculate t + 0 for any SEO/LiTFSI or PEO/LiTFSI mixture when κ and D are known. Finally, the framework developed in this paper enables predicting the performance of any block copolymer electrolyte in a rechargeable battery.

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

Covalent Organic Framework as an Efficient Protection Layer for a Stable Lithium-Metal Anode

We report Lithium (Li) metal shows great potential for achieving high-energy-density rechargeable batteries. However, the practical applications of Li-metal batteries are still challenged by the formation of Li dendrites and unstable solid-electrolyte interphase (SEI) on metallic Li. Herein, a thin covalent organic framework layer is in situ fabricated on Li (COF-Li) to suppress Li dendrite growth and mitigate the side reaction on the Li anode. The COF has a periodic and uniform porosity, allowing for selectively sieving Li ions and guiding a uniform Li deposition. As a result, the COF-Li exhibits a non-dendrite morphology during repeated Li plating/stripping and demonstrates a remarkable cycle life over 13 200 h with an extremely low overpotential of only 16 mV at a high current density of 10 mA cm -2 and a high areal capacity of 10 mAh cm -2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

60 Years of Betaine 30–From Solvatochromic Discovery to Future Frontiers

Betaine-30 (B30) was reported by Karl Dimroth and Christian Reichardt et al. in 1963 as a solvatochromic probe that can be easily synthesized, shows good solubility, and remains stable in various organic solvents and solutions. Its strongly negatively solvatochromic behavior arises from differential solvation between its electronic ground and excited states, making it a valuable tool for assessing solvent polarity using the E T (30) polarity scale, also devised by Dimroth and Reichardt. In addition, advancements in femtosecond laser spectroscopy in the 1990s greatly improved the understanding of B30’s relaxation dynamics following photoexcitation. In solvents capable of hydrogen bonding, such as alcohols, intermolecular hydrogen-bond rearrangement contributes to the multiple relaxation components observed. Since the 1990s, the applications of B30 have expanded beyond simple organic solvents to include complex solvent mixtures, such as electrolyte solutions for battery technologies and eutectic solvent mixtures. Furthermore, given the growing importance of these complex solvent mixtures, B30 is becoming an increasingly valuable tool for studying previously unexplored solvation properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Combination of Counterion Size and Doping Concentration Determines the Electronic and Thermoelectric Properties of Semiconducting Polymers

In both chemical and electrochemical doping of organic semiconductors (OSCs), a counterion, either from the electrolyte or ionized dopant, balances the charge introduced to the OSC. Despite the large influence of this counterion on OSC optical and electronic response, there remains substantial debate on how a fundamental parameter, ion size, impacts these properties. Here, this work resolves much of this debate by accounting for two doping regimes. In the low-doping regime, the Coulomb binding energies between charge carriers on the OSC and the counterions are significant, and larger counterions lead to decreased Coulomb interactions, more delocalized charge carriers, and higher electrical conductivities. In the high-doping regime, the Coulomb binding energies become negligible due to the increased dielectric constant of the films and a smoothing of the energy landscape; thereby, the electrical conductivities depend primarily on the extent of morphological disorder in the OSC. Moreover, in regioregular poly(3-hexylthiophene), rr-P3HT, smaller counterions lead to greater bipolaron concentrations in the low-doping regime due to the increased Coulomb interactions. Emphasizing the impact of the counterion size, it is shown that larger counterions can lead to increased thermoelectric power factors for rr-P3HT.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Effect of temperature on capacity fade in silicon-rich anodes

Coin half-cells containing 80 wt% silicon electrodes are assembled and cycled at the similar to C/10 rate in the temperature range of 25-55 degrees C. To the best of our knowledge, this is the first time that the effect of temperature is reported for such high-silicon-containing cells. Two different electrolytes are used in this study, a baseline electrolyte and the baseline electrolyte +10 wt% fluoroethylene carbonate (FEC). Analysis of the capacity vs. cycle count data by curve fitting reveals that the addition of FEC markedly affects the capacity loss mechanism. Without FEC, the kinetic rate law for the capacity loss mechanism can be described as the sum of two logistic growth models. With the addition of FEC, the rate law depends on ln(t). Clearly, the addition of FEC has a profound effect on the mechanism of capacity loss. Interestingly, X-ray photoelectron spectroscopy (XPS) shows that the composition of the solid electrolyte interphase (SEI) layer changes markedly from mostly organic to mostly inorganic in the presence of FEC and how it varies at the different temperatures tested, especially in the absence of FEC.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

The Solid Electrolyte Interphase Dispersion Can Predict Cycle and Calendar Lifetimes in Silicon Anodes for Lithium-Ion Batteries

The solid electrolyte interphase (SEI) plays a critical role in lithium-ion battery (LIB) anodes. It is responsible for passivating the reactive surface of lithiated anodes against degradation of the electrolyte which enables long cycle and calendar lifetimes for LIBs. This role is especially important in high energy density anodes like silicon, that undergo massive volumetric changes during electrochemical cycling. The mechanism by which the SEI performs this role, however, is not clear which makes designing an SEI to passivate silicon anodes impossible. Through decades of research, dozens of chemical species have been identified within the SEI ranging from inorganic solids to polymeric coatings all of which simultaneously exist in a 'mosaic' composition at the anode surface. This mosaic creates a highly dispersive environment in which electrostatic screening of the anode surface from the electrolyte is not always complete. Here, we present an electrochemical technique to directly test the dispersion at the anode surface. We use this technique to screen more than 20 different electrolytes against silicon anodes and find correlations between both the cycle life and calendar life. The insights from this study offer a new framework to think about the SEI and a rapid screening method to test novel electrode/electrolyte combinations.

battery↗
DOE OSTI2020

A Fireproof, Lightweight, Polymer–Polymer Solid-State Electrolyte for Safe Lithium Batteries

Safety issues in lithium-ion batteries have raised serious concerns due to their ubiquitous utilization and close contact with the human body. Replacing flammable liquid electrolytes, solid-state electrolytes (SSEs) is thought to address this issue as well as provide unmatched energy densities in Li-based batteries. However, among the most intensively studied SSEs, polymeric solid electrolyte and polymer/ceramic composites are usually flammable, leaving the safety issue unattended. Here, we report the first design of a fireproof, ultralightweight polymer–polymer SSE. The SSE is composed of a porous mechanic enforcer (polyimide, PI), a fire-retardant additive (decabromodiphenyl ethane, DBDPE), and a ionic conductive polymer electrolyte (poly(ethylene oxide)/lithium bis(trifluoromethanesulfonyl)imide). The whole SSE is made from organic materials, with a thin, tunable thickness (10–25 μm), which endorse the energy density comparable to conventional separator/liquid electrolytes. The PI/DBDPE film is thermally stable, nonflammable, and mechanically strong, preventing Li–Li symmetrical cells from short-circuiting after more than 300 h of cycling. LiFePO 4 /Li half cells with our SSE show a high rate performance (131 mAh g –1 at 1 C) as well as cycling performance (300 cycles at C/2 rate) at 60 °C. Most intriguingly, pouch cells made with our polymer–polymer SSE still functioned well even under flame abuse tests.

25 ENERGY STORAGE↗
DOE OSTI2023

Bioderived Radical Polymers for Sustainable Energy Storage Materials

Organic mixed ionic and electronic conductors have emerged as promising materials for next-generation energy applications, and a variety of molecular designs have been implemented to push performance to higher levels. Importantly, nonconjugated redox-active radical polymers capable of charge transport offer benefits such as ready synthesis in large quantities and the capability to separate thermomechanical and electrochemical behaviors. This affords more freedom with respect to macromolecular backbone design; thus, the resultant materials properties make this class of polymers appealing alternatives for energy storage. However, these radical polymers often still rely on petrochemically derived polymer backbones. Here, we demonstrate the polymerization of the bioderived terpene β-myrcene and its functionalization by attaching stable radical pendant groups capable of mixed electronic and ionic conduction. The electrochemical enhancement of these materials was substantial as the addition of carbon black and doping of lithium salts electronic conductivities of ~60 S cm -1 were achieved for the composite systems. The addition of the lithium salts proved fruitful as the electric and ionic conductivities of the radical polymers surpassed 10 -4 S cm -1 at elevated temperatures when both lithium hexafluorophosphate and lithium chloride, a more bio and environmentally friendly material, where introduced to the system. Finally, these findings demonstrate a bioderived alternative for an organic mixed conductor serving as both potential cathode and polymer electrolyte for a more sustainable alternative for energy storage applications.

25 ENERGY STORAGE↗
DOE OSTI2024

Colloidal Stability of PFSA-Ionomer Dispersions. Part I. Single-Ion Electrostatic Interaction Potential Energies

Charged colloidal particles neutralized by a single counterion are increasingly important for many emerging technologies. Attention here is paid specifically to hydrogen fuel cells and water electrolyzers whose catalyst layers are manufactured from a perfluorinated sulfonic acid polymer (PFSA) suspended in aqueous/alcohol solutions. Partially dissolved PFSA aggregates, known collectively as ionomers, are stabilized by the electrostatic repulsion of overlapping diffuse double layers consisting of only protons dissociated from the suspended polymer. We denote such double layers containing no added electrolyte as "single ion". Size-distribution predictions build upon interparticle interaction potential energies from the Derjaguin-Landau-Verwey-Overbeek (DLVO) formalism. However, when only a single counterion is present in solution, classical DLVO electrostatic potential energies no longer apply. Accordingly, here a new formulation is proposed to describe how single-counterion diffuse double layers interact in colloidal suspensions. Part II (Srivastav, H.; Weber, A. Z.; Radke, C. J. Langmuir 2024 DOI: 10.1021/acs.langmuir.3c03904) of this contribution uses the new single-ion interaction energies to predict aggregated size distributions and the resulting solution pH of PFSA in mixtures of n-propanol and water. A single-counterion diffuse layer cannot reach an electrically neutral concentration far from a charged particle. Consequently, nowhere in the dispersion is the solvent neutral, and the diffuse layer emanating from one particle always experiences the presence of other particles (or walls). Thus, in addition to an intervening interparticle repulsive force, a backside osmotic force is always present. With this new construction, we establish that single-ion repulsive pair interaction energies are much larger than those of classical DLVO electrostatic potentials. The proposed single-ion electrostatic pair potential governs dramatic new dispersion behavior, including dispersions that are stable at a low volume fraction but unstable at a high volume fraction and finite volume-fraction dispersions that are unstable with fine particles but stable with coarse particles. Finally, the proposed single-counterion electrostatic pair potential provides a general expression for predicting colloidal behavior for any charged particle dispersion in ionizing solvents with no added electrolyte.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Prediction and Experimental Verification of Electrolyte Solvation Structure from an OMol25-Trained Interatomic Potential

A molecular-level understanding of electrolyte solvation structure and ion–ion correlations is critical to developing next-generation battery chemistries. Atomistic simulation capabilities with sufficient accuracy, speed, and transferability to deliver reliable structural insights while avoiding arduous system-specific reparameterization are thus highly desirable. Machine learning interatomic potentials (MLIPs) trained on large, chemically diverse data sets are revolutionizing computational chemistry, enabling molecular dynamics simulations of battery electrolytes with near-DFT accuracy over 10,000× faster than DFT. While previous MLIP training data sets with suitable elemental coverage for electrolytes have been based on inorganic materials, the Open Molecules 2025 (OMol25) data set provides large-scale molecular DFT MLIP training data with broad elemental coverage and specifically samples tens of millions of electrolyte configurations. Here, we integrate computational modeling with experimental validation to systematically assess the ability of large-scale MLIPs pretrained on materials data or on OMol25 to accurately resolve nanoscale structural organization and ion-solvation characteristics in Na-ion battery electrolytes across diverse physicochemical conditions and compositional regimes. We find that the OMol25-trained Universal Model of Atoms (UMA-OMol) predicts experimentally measured densities and X-ray structure factors in substantially better agreement compared to state-of-the-art models trained only on inorganic materials data. Using UMA-OMol, we further analyze systematic trends in solvation structure as a function of cation identity, anion chemistry, salt concentration, and solvent topology. We observe that increasing system temperature amplifies the heterogeneity within the solvation environment, perturbing cation–solvent interactions and promoting the formation of contact ion pairs (CIPs). Moreover, subtle variations in the solvent topology of glyme-based electrolytes cause pronounced changes in ion correlations and solvation structure. The experimental agreement and microscopic insights shown here position OMol25-trained MLIPs as a practical route to predictive, high-throughput electrolyte simulations beyond the limits of classical force fields and direct DFT molecular dynamics, serving as a powerful tool for accelerating the design of next-generation Na-ion battery electrolytes and beyond.

MLIPs↗
DOE OSTI2023

Trimer Quinoxalines as Organic Cathode Materials for Lithium-Ion Batteries

Due to synthetic ease, high redox potentials, low solubility in polar electrolytes, and good electric conductivity of their semiconducting crystals, discotic quinoxaline trimers (3Q) have been considered as possible candidates for 4 V organic cathodes in lithium-ion batteries. To assess their feasibility as such materials, several 3Q derivatives have been synthesized and tested in half-cells. In voltage limited cycling tests at 1.2–3.9 V vs Li/Li + , the specific discharge capacities of 40–180 mAh g -1 were obtained at a rate of 1 C, and multiple lithiation of 3Q and its derivatives was observed during discharge. However, the obtained discharge capacity was only a fraction of the theoretical capacity expected for reversible six-electron reduction; there was also rapid capacity fade. Our spectroscopic studies indicate the reversible three-electron lithiation at 2 V vs Li/Li + , but suggest instability of more highly discharged states. Finally, our conclusion is that while the 3Q derivatives combine several traits that are desirable in an organic cathode material (including negligible solubility, capacity for multiple charging, and near-100% coulombic efficiency), these materials are still impractical to use.

25 ENERGY STORAGE↗
DOE OSTI2021

Exploring the Ion Solvation Environments in Solid-State Polymer Electrolytes through Free-Energy Sampling

The success of poly(ethylene oxide) (PEO) in solid-state polymer electrolytes for lithium-ion batteries is well established. Recently, in order to understand this success and to explore possible alternatives, we studied polyacetal electrolytes to deepen the understanding of the effect of the local chemical structure on ion transport. Advanced molecular dynamics techniques using newly developed, tailored interaction potentials have helped elucidate the various coordination environments of ions in these systems. In particular, the competition between cation-Anion pairing and coordination by the polymer has been explored using free-energy sampling (metadynamics). At equivalent reduced temperatures, with respect to the polymer-specific glass-Transition temperature, two-dimensional free-energy plots reveal the existence of multiple coordination environments for the lithium (Li) ions in these systems and their relative stabilities. Furthermore, we observe that the Li-ion movement in PEO follows a serial, stepwise pathway when moving from one coordination state to another, whereas this happens in a more continuous and concerted fashion in a polyacetal such as poly(1,3-dioxalane) [P(EO-MO)]. The implication is that interconversion between coordination states of the Li ions may be easier in P(EO-MO). However, the overarching observation from our free-energy analysis is that Li-ion coordination is dominated by the polymer (in either case) and contact-ion pairs are rare. We rationalize the observed higher increase in glass-Transition temperature (Tg) with salt loading in polyacetals as due to intermolecular Li-ion coordination involving multiple polymer chains, rather than just one chain for PEO-based electrolytes. This interchain coupling in the polyacetals, resulting in the higher Tg, works against any gains due to variations in Li-ion coordination that might enhance transport processes over PEO. Further research is required to overcome the interdependence between local coordination and macroscopic properties to compete with PEO electrolytes at the same absolute working temperature.

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 OSTI2020

NMR-Guided High-Temperature Electrolyte Design Using a Novel PF 5 Marker

The thermal degradation of electrolytes containing lithium hexafluorophosphate (LiPF 6 ) is a well-studied subject. However, practical application of the knowledge is difficult since the effects of the degradation process on battery performance are not well known. In this work, we propose a novel NMR experimental setup allowing direct observation of the effects of various perturbations on the electrolyte thermal degradation process, which guides the design and synthesis of new additives that improve lithium-ion battery performance at elevated temperatures.

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

Multielectron Organic Redoxmers for Energy-Dense Redox Flow Batteries

Redox flow battery is a highly promising stationary energy storage method but the limited energy density and high chemical cost are among the main barriers for commercialization. Multi-electron organic redoxmers represent a family of structurally tailorable candidates that can achieve multiplied energy density with decreased materials consumption, potentially resulting in a viable solution to address these challenges. In this work, the recent development of organic molecules with reversible multi-redox activities in both aqueous and nonaqueous electrolytes is reviewed. The major focus is on the fundamental correlation between the chemical structures and the functional properties of reported multi-electron organic molecules. Valuable insights are offered on rational structural design strategies for improving the relevant physico- and electro-chemical properties. Finally, the current challenges are discussed to suggest future research needs along the avenue of using the multi-electron approach to achieve energy-dense, stable, cost-effective redox flow batteries.

25 ENERGY STORAGE↗