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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 343 records · Page 19

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↗

Concentration‐dependent Cycling of Phenothiazine‐based Electrolytes in Nonaqueous Redox Flow Cells

Increasing redox-active species concentrations can improve viability for organic redox flow batteries by enabling higher energy densities, but the required concentrated solutions can become viscous and less conductive, leading to inefficient electrochemical cycling and low material utilization at higher current densities. To better understand these tradeoffs in a model system, we study a highly soluble and stable redox-active couple, N-(2-(2-methoxyethoxy)ethyl)phenothiazine (MEEPT), and its bis(trifluoromethanesulfonyl)imide radical cation salt (MEEPT-TFSI). We measure the physicochemical properties of electrolytes containing 0.2–1 M active species and connect these to symmetric cell cycling behavior, achieving robust cycling performance. Specifically, for a 1 M electrolyte concentration, we demonstrate 94% materials utilization, 89% capacity retention, and 99.8% average coulombic efficiency over 435 h (100 full cycles). This demonstration helps to establish potential for high-performing, concentrated nonaqueous electrolytes and highlights possible failure modes in such systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A Comparative Review of Metal-Based Charge Carriers in Nonaqueous Flow Batteries

Energy storage is becoming the chief barrier to the utilization of more renewable energy sources on the grid. With independent service operators aiming to acquire gigawatts in the next 10–20 years, there is a large need to develop a suite of new storage technologies. Redox flow batteries (RFB) may be part of the solution if certain key barriers are overcome. This review focuses on a particular kind of RFB based on nonaqueous media that promises to meet the challenge through higher voltages than the organic and aqueous variants. This class of RFB is divided into three groups: molecular, macromolecular, and redox-targeted systems. The growing field of theoretical modeling is also reviewed and discussed.

25 ENERGY STORAGE↗

NASA Redox Storage System Development Project

The Redox Storage System Technology Project was jointly supported by the U.S. Department of Energy and NASA. The objectives of the project were to develop the Redox flow battery concept and to probe its technical and economic viability. The iron and chromium redox couples were selected as the reactants. Membranes and electrodes were developed for the original mode of operating at 25 C with the reactants separated by an ion-exchange membrane. Analytical capabilities and system-level operating concepts were developed and verified in a 1-kW, 13-kWh preprototype system. A subsequent change was made in operating mode, going to 65 C and using mixed reactants. New membranes and a new electrode catalyst were developed, resulting in single cell operation as high as 80 mA/sq cm with energy efficiencies greater than 80 percent. Studies indicate a likely system cost of about $75/kWh. Standard Oil of Ohio (Sohio) has undertaken further development of the Redox system. An exclusive patent license was obtained from NASA by Sohio. Transfer of Redox technology to Sohio is supported by the NASA Technology Utilization Office.

Hagedorn, N. H.↗

Field-Aging Test Bed for Behind-the-Meter PV + Energy Storage

Small DC-coupled battery test systems are deployed at the National Renewable Energy Laboratory to evaluate capacity fade models and report on performance parameters such as round-trip efficiency under indoor and outdoor deployment scenarios. Initial commercial battery products include LG Chem RESU lithium-ion (Li-ion) and Avalon vanadium redox flow batteries. Adapting indoor lab-scale test methods to outdoor systems has challenges, including maintaining constant temperature and fully controlling batteries through standard discharge curves. Initial measurements show the Li-ion battery systems performing within expectations, near 85% round-trip efficiency. Initial lifetime modeling and measurements indicate that battery capacity could degrade by 20%-35% over 10 years at current rates.

14 SOLAR ENERGY↗

Bismuth Electrocatalyst Enabling Reversible Redox Kinetics of a Chelated Chromium Flow Battery Anolyte

Metal electrocatalysts have been reported to improve the electron transfer kinetics of aqueous redox flow battery electrolytes on various types of carbon electrodes. In this work, we electrodeposited bismuth metal onto a carbon paper anode of a redox flow battery containing our previously reported polyaminocarboxylate-chelated chromium electrolyte. Depositing 0.58 mg cm –2 of bismuth metal enabled an electrochemically reversible electron transfer for the Cr(II)/Cr(III) couple, resulting in a 3.9% voltage efficiency increase over ten cycles at 100 mA cm –2 across an 80% state of charge window, while maintaining >99% current efficiency. The bismuth electrocatalyst provided other improvements, such as a 13% increase in average discharge power density when cycling at 80% energy efficiency, along with a 60% decrease in charge transfer resistance and 12% decrease in the full cell area specific resistance. A chelated bismuth complex was also utilized as a bismuth source for electrodeposition, providing an example of how polyaminocarboxylate ligands can be further implemented into efforts towards improving the energy efficiency of aqueous redox flow batteries.

25 ENERGY STORAGE↗

High Energy Density Aqueous Flow Battery Utilizing Extremely Stable, Branching-Induced High-Solubility Anthraquinone near Neutral pH

An anthraquinone featuring a chiral carboxylate-capped methyl-branched side chain with an ether linkage, 2,2'-((9,10-dioxo-9,10-dihydroanthracene-2,6-diyl)bis(oxy))dipropionic acid (2,6-D2PEAQ), was synthesized and evaluated for use in aqueous redox flow batteries. It was found to have an extraordinary solubility of 2 M (4 M electrons), corresponding to a theoretical volumetric capacity of 107.2 Ah/L for the negative electrolyte, which is 10 times that of its unbranched counterpart. The 2,6-D2PEAQ molecule demonstrated stability against thermal 2 decomposition and was extremely stable under cell cycling conditions. Here, a capacity fade rate of 0.02% day over 14 days was demonstrated in a 1.1 M 2,6-D2PEAQ nearly capacity-balanced cell when paired with a ferro-/ferricyanide posolyte at pH 7. Compared to other aqueous redoxactive organic molecules, its demonstrated fade rate is lower than that of any molecule with a demonstrated volumetric capacity of ≥55 Ah/L, and its volumetric capacity is greater than that of any molecule with a demonstrated fade rate of ≤0.5%/day.

25 ENERGY STORAGE↗

Dual Modification of MOFs Improves Dispersion and Ionic Conductivity of Mixed Matrix Membranes

Nonaqueous redox flow batteries (NARFBs) are a promising class of energy storage devices, but the lack of a chemically stable, conductive membrane that exhibits size-selectivity over redox-active species prevents their broader implementation. Recently, metal–organic frameworks (MOFs) have been implemented into mixed-matrix membranes (MMMs) for NARFBs, but the effects of the MOF linker functionality on membrane properties are not well-understood. In this work, we develop a series of MOF-based MMMs by blending postsynthetically modified variants of UiO-66-NH2 with poly(ethylene-co-vinyl acetate). The modification of UiO-66-NH2 with sulfate groups initially resulted in poor dispersion throughout the MMMs, but when dual-modified with poly(N-isopropylacrylamide), MOF dispersion throughout the MMM was improved, and ionic conductivity was significantly higher than the UiO-66-NH2 MMMs. Furthermore, the dual-modified MMMs demonstrated excellent size-selectivity by blocking redox active species transport. This work demonstrates a synergy between the MOF functional groups to improve MMM properties critical for the development of practical NARFBs.

Carey, Cassidy A.↗

Untapped Potential of Fluoride Ions in Maximizing the Electrochemical Stability of Deep Eutectic Solvents

Advancing the batteries is pivotal to propelling our society toward a sustainable, electrified future. The stability of electrolytes forms the backbone of energy storage systems. This is particularly the case for redox flow batteries (RFBs). Their deployability depends on their longevity and dependability. The presence of unstable electrolytes can trigger undesirable reactions, degrade performance, and lead to battery failure. Aqueous electrolytes, with limited electrochemical stability window (ESW), are prone to hydrogen and oxygen evolution. Conversely, non-aqueous electrolytes offer enhanced stability. In this study, we unveil the ESW of a non-aqueous eutectic solvent, comprising choline fluoride and ethylene glycol—a composition that has eluded experimental investigation until now. Our findings show that the stability window, reduction and oxidation potential limits of deep eutectic solvents, are sensitive to variations in the halide component of the ammonium salt. Furthermore, this work not only highlights the benefits of novel deep eutectic solvents but also sets the stage for their strategic use in future battery electrolytes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structuring, stochastic behavior, and charge storage capacity of redox-active microemulsions formulated with mixtures of toluene and ionic liquid as oil phase

Oil/water microemulsions (µEs) are promising electrolytes for redox flow batteries (RFBs) as they simultaneously improve charge capacity and ionic conductivity. Here, we report the successful formulation of bicontinuous µEs where the oil phase is a solution of trihexyltetradecylphosphonium bis(trifluoromethylsulfonyl)amide ionic liquid in toluene with redox-active ferrocene. We examined the effect of supporting electrolyte anion (NO 3 – , Cl – , ClO 4 – ) on the structure, reactivity, transport, and electrolytic performance of redox-active µEs. Neutron scattering and nuclear magnetic resonance showed that the domain size increased as Cl – > NO 3 – > ClO 4 – while the ferrocene diffusion coefficient increased as NO 3 – > Cl – > ClO 4 – . Scanning electrochemical microscopy indicated anion-dependent current fluctuations during electrolysis, with ClO 4 – exhibiting the least high-frequency oscillations, which correlate to the highest charge and discharge capacity and reversibility. All ionic liquid containing systems improved the performance of toluene-based µEs, highlighting new design principles for these electrolytes.

diffusion↗

CHARACTERIZATION AND DEVELOPMENT OF THE ALL–AQUEOUS COPPER THERMALLY REGENERATIVE AMMONIA BATTERY

Low temperature thermal energy is an abundant and untapped energy source for large scale electrical power and energy production around the world. Many different stationary sources such as industrial and thermal power plants produce significant amounts of low temperature heat that goes unused. The primary reason for the energy loss is because the temperature of the heat is often too low for traditional systems to economically generate power from this waste heat. Many different technologies are being researched to produce grid–scale power from low temperature heat to increase grid efficiency, advance decarbonization efforts, and progress electrical power production to a more distributed system. A thermally regenerative battery (TRB) is one promising technology in this space, as it has large power and energy densities relative to competitive technologies and therefore has the potential to disrupt the current power generation mix. TRBs combine two unit operations (a redox flow battery and a distillation column) which are easily scalable and mature, meaning that if a viable TRB chemistry can be identified, its development to pilot and commercial scale can be streamlined. The all–aqueous, copper thermally regenerative ammonia battery (Cuaq–TRAB) was the first TRB that did not use an electrodeposition/dissolution reaction by stabilizing Cu(I) and Cu(II) in the electrolyte, allowing all electroactive species to be stable in an aqueous phase. Through these electrolyte modifications, coulombic efficiency, open circuit potential, and copper solubility all increased, resulting in large gains to power density, energy density, and energy efficiency.

Cross, Nicholas↗

Expanding the potential of redox carriers for flow battery applications

Here, using theoretical modeling to guide our approach, substituents were selected to improve the negative and positive potentials associated with a representative metal-based redox carrier, a phenyl spaced nickel bispicolinamide complex, [Ni(bpb)], 1. To broaden the cell potential, electron donating groups were selected and installed on the pyridyl moieties, [Ni(bpb-(NMe 2 ) 2 )], 2, while electron withdrawing groups were incorporated on the phenyl linker, [Ni(bpb-R)] (R = –F, –CF 3 , and –NO 2 ), 3–5. Our model predicts an increase of ~300 mV and ~500 mV for the first and second negative waves of Ni(bpb-NMe 2 ), 2, and up to ~330 mV and ~210 mV increase to the first and second positive waves in 3–5. The modeled complexes were synthesized in good yields using a modification of the literature procedure. Due to limited solubility, the differential pulse voltammetry was measured on complexes 2–5 using a drop cast technique. Comparison of the observed and predicted potentials is discussed in acetonitrile (MeCN) and dimethylformamide (DMF) solvents.

25 ENERGY STORAGE↗

Decoding the Effect of Anion Identity on the Solubility of N -(2-(2-Methoxyethoxy)ethyl)phenothiazine (MEEPT)

Variations in the solubility of redox-active organic molecules (ROM) of interest for nonaqueous redox flow batteries (RFB), especially as the ROM state-of-charge changes during charge-discharge cycling, present significant molecular design challenges. The situation is further complicated as ROM solubility can be regulated by the choice of electrolyte salt and solvent that together with the ROM comprise the catholyte or anolyte (redox electrolyte) formulation, presenting materials design challenges. The ROM N-(2-(2-methoxyethoxy)ethyl)phenothiazine (MEEPT) is a viscous liquid at room temperature and is miscible in several organic solvents, including acetonitrile and propylene carbonate. The MEEPT radical cation (MEEPT +· ) paired with tetrafluoroborate (BF 4 - ) in acetonitrile presents a 0.5 M solubility, a dramatic decrease when compared to the viscous liquid of neutral MEEPT. Here, in this study, we present a joint experimental, regression modeling, and molecular dynamics (MD) simulations investigation to explore MEEPT-X (where X represents the counteranion) salt solubility variability as a function of concentration and counteranion chemistry in acetonitrile. We find a strong dependence of the salt solubility on the counteranion and relate these findings to explicit intermolecular interactions between MEEPT +· and the counteranion in the electrolyte solution.

Perera, Anton S. [Univ. of Kentucky, Lexington, KY↗

Electro–Oxidation of Nitroxide Radicals: Adsorption–Mediated Charge Transfer Probed Using SERS and Potentiometry

Organic compounds containing nitroxide radicals such as 4–hydroxy–2,2,6,6–tetramethylpiperidine–1–oxyl (4–hydroxy–TEMPO) are redox–active and are of interest for potential applications in redox flow batteries. The mechanisms governing charge–transfer reactions of such compounds are not well understood. Specifically, the anodic charge transfer coefficient (αa) corresponding to the electro–oxidation of 4–hydroxy–TEMPO in an aqueous medium is ~0.9, i.e., αa deviates considerably from the expected value (0.5) for a symmetric single–step one–electron transfer redox reaction. In a previous publication (J. Electrochem. Soc., 2020, 167, 143505), we have proposed a reaction mechanism to explain such asymmetric behavior by invoking adsorption–desorption processes. In the proposed mechanism, reversible oxidation of 4–hydroxy–TEMPO leads to the adsorption of the oxidation product, which then undergoes slow rate–limiting desorption from the electrode surface. In the present contribution, supporting evidence is provided for this mechanism. In situ surface–enhanced Raman spectroscopy combined with density functional theory simulations are employed to confirm the presence of surface–adsorbed species at a Au electrode during electro–oxidation of 4–hydroxy–TEMPO. Furthermore, we employ chronopotentiometry to track the gradual re–equilibration of the electrode–electrolyte interface following the electro–oxidation of 4–hydroxy–TEMPO. Analysis of the chronopotentiometry data further suggests the presence of adsorbed species, which were previously proposed and are now confirmed by direct spectroscopic evidence.

25 ENERGY STORAGE↗

Discovery of Energy Storage Molecular Materials Using Quantum Chemistry-Guided Multiobjective Bayesian Optimization

Redox flow batteries (RFBs) are a promising technology for stationary energy storage applications due to their flexible design, scalability, and low cost. In RFBs, energy is carried in flowable redoxactive materials (redoxmers) which are stored externally and pumped to the cell during operation. Further improvements in the energy density of RFBs necessitates redoxmer designs with wider redox potential windows and higher solubility. Additionally, designing redoxmers with a fluorescence-enabled self-reporting functionality allows monitoring of the state of health of RFBs. To accelerate the discovery of redoxmers with desired properties, state-of-the- art machine learning ( ML) methods, such as multiobjective Bayesian optimization (MBO), are useful. Here, we first employed density functional theory calculations to generate a database of reduction potentials, solvation free energies, and absorption wavelengths for 1400 redoxmer molecules based on a 2,1,3-benzothiadiazole (BzNSN) core structure. From the computed properties, we identified 22 Pareto-optimal molecules that represent best trade-off among all of the desired properties. We further utilized these data to develop and benchmark an MBO approach to identify candidates quickly and efficiently with multiple targeted properties. With MBO, optimal candidates from the 1400-molecule data set can be identified at least 15 times more efficiently compared to the brute force or random selection approach. Importantly, we utilized this approach for discovering promising redoxmers from an unseen database of 1 million BzNSN-based molecules, where we discovered 16 new Pareto-optimal molecules with significant improvements in properties over the initial 1400 molecules. Furthermore, we anticipate that this active learning technique is general and can be utilized for the discovery of any class of functional materials that satisfies multiple desired property criteria.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mesolytic cleavage of homobenzylic ethers for programmable end-of-life function in redoxmers

Irreparable chemical damage to redox-active monomers, oligomers, and polymers (i.e. redoxmers) limits the lifetime of energy storage devices (e.g. redox flow batteries) by causing electrode and membrane fouling, as well as irreversible capacity loss. To predictably restore device and materials performance, it is desirable to add programmed destruction capabilities into these damage-prone materials. Here, we report the use of triggerable retrograde reactions to achieve programmable end-of-life function in redoxmers. Retrograde reactions are intended to break up damaged redoxmer materials into more soluble small-molecule constituents to prevent irreparably fouling battery interfaces. We investigated the redox-triggered mesolytic cleavage of homobenzylic ethers (HBEs) for this purpose. Combining experimental methods with simulations, we probed the influence of ring substituents on the programmable bond-scission behavior of HBEs. Variation of para-substituents on the HBEs allowed us to modify the oxidation potential, degradation pathway, and electrochemical mechanisms of the generated products. Given its ideal oxidation potential, we selected the para-methoxy-based HBE as the cleavage scaffold and integrated it with dialkoxybenzene, TEMPO, viologen, and para-nitrobenzene redox centers for compatibility, bulk deconstruction, and electrode defouling tests. Upon applying a high oxidation potential, the redox-active pendant is cleaved from the backbone via HBE bonds; of the four redox centers tested, three of them remained fully redox active. Viologen-appended redox active polymers with HBE linkers were cleaved to fully separate the redox centers from the backbone. Polymer-filmed electrodes were partially restored following HBE oxidation defouling. Here these studies highlight the co-design of new materials functions for developing sustainable energy storage materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Cross-Platform Classifier of Chemical Stability for Charged Redoxmers

The development of new redox flow battery chemistries is hampered by time-consuming organic syntheses and electrochemical characterization of candidate redoxmer molecules. Here, we use Sure Independence Screening and Sparsifying Operator (SISSO) to demonstrate a cross-platform classifier for chemical stability of charged redoxmers in electrolyte solutions. This SISSO model yields a single formula to separate positively charged dialkoxyarene catholytes and negatively charged pyridinium anolytes into stable and unstable species in acetonitrile-based electrolytes as probed through cyclic voltammetry measurements. Using such classifiers, the stability of new compounds across different synthetic platforms can be rapidly assessed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Scanning Electrochemical Microscopy for Kinetic Investigations in Viscous Deep Eutectic Solvents: Identifying Practical Approach Curves and Deviations from Electron Transfer Models

Determining heterogeneous electrochemical electron transfer (ET) kinetics in electrolytes with a wide range of physical properties is of great interest for achieving high-performance redox flow batteries. Among such electrolytes, concentrated hydrogen-bonded electrolytes (CoHBEs), including deep eutectic solvents (DESs), have recently garnered significant attention. Unfortunately, traditional Tafel analysis using macroelectrodes often encounters issues with mass transfer limitations in CoHBEs with high viscosities, thereby restricting kinetic analysis to a narrow potential window. Here, in this work, we introduce a methodology for evaluating ET kinetics in viscous DES using the scanning electrochemical microscopy (SECM). We first determined practical solutions to SECM tip positioning in ethaline DES, which yield pseudopositive feedback responses. Lattice Boltzmann method (LBM) simulations helped us rationalize the impact of the fluid and concentration fields, as well as tip geometry, tip approach velocity v, and the solvent viscosity ηs, on the shape of the approach curves. In addition to successfully recreating approach curves over a variety of conditions, we found that approaching a conductor ensured a practical point where the normalized tip response (Ni T = 2) converged at L = 0.7 within ∼10% error regardless of tip velocity. With positioning capabilities at hand, we investigated the kinetics of Fe 3+ /Fe 2+ redox couple in aqueous and the ethaline media. The experimental kinetic results were interpreted using the Butler–Volmer (BV) and Marcus–Hush–Chidsey (MHC) models. For ethaline, a nonideal kinetic behavior was observed, potentially attributed to solvent dynamics within DESs or to the interplay of chloride anions in the charge transfer process.

electrodes↗