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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 235 records · Page 13
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Symmetry-Breaking Design of an Organic Iron Complex Catholyte for a Long Cyclability Aqueous Organic Redox Flow Battery

The limited availability of a high-performance catholyte has hindered development of aqueous organic redox flow batteries (AORFB) that are environmentally benign, have tunable structures, and are safer than their traditional transition metal ion-based counterparts for large-scale energy storage. In this paper, a symmetry-breaking design of iron complexes with 2,2’-bipyridine-4,4’-dicarboxylic (Dcbpy) acid and cyanide ligands is described. By introducing two ligands to the metal center, the complex compounds (M4[FeII(Dcbpy)2(CN)2], M = Na, K) exhibited 4.2 times higher solubility (1.22 M, 33 Ah/L) and a 50% increase in potential compared with the widely used ferrocyanide. The symmetry-breaking, iron complex catholyte-based AORFBs were demonstrated at a concentration near the solubility limit (1.02 M Na4[FeII(Dcbpy)2(CN)2]) with a 1:1 catholyte:anolyte electron ratio. The AORFBs achieved a cell voltage of 1.2 V and a demonstrated energy density of 12.5 Wh/L. This symmetry-breaking design paves the way for development of metal complexes for high-energy-density AORFBs.

Li, Xiang↗
DOE OSTI2024

Surfactant Effects in Porous Electrodes for Microemulsion Redox Flow Batteries

The effect of surfactant additives on electrochemical behavior in porous electrodes was investigated using vanadium redox flow battery half-cells and the dependence of volumetric kinetics and mass transport on electrolyte, surfactant, and electrode type was explored. Without surfactant added, carbon paper electrodes demonstrated greater kinetics and transport compared to carbon felt, for a given electrolyte. Additionally, posolyte kinetics are greater than negolyte kinetics by one to three orders of magnitude, depending on the electrode type. Addition of surfactant increased electrode wettability and possibly electrochemical surface area. However, this was accompanied by a decrease in volumetric mass transport, due to stronger electrolyte-electrode interactions. The presence of sodium dodecyl sulfate (SDS) influenced posolyte and negolyte kinetics differently. Kinetics showed a dependence on electrode type and surfactant. On carbon felt, volumetric kinetics decreased for both posolyte and negolyte with SDS addition. On carbon paper, SDS decreased volumetric kinetics for the posolyte but increased (>2X) kinetics for the negolyte! This kinetic enhancement depends on surfactant chemistry: cetyltrimethylammonium bromide, a cationic surfactant, failed to increase kinetics. Furthermore, SDS did not increase areal specific resistance. Furthermore, these findings show the superior performance of carbon paper compared to carbon felt and suggest SDS as a possible VRFB negolyte additive.

25 ENERGY STORAGE↗
DOE OSTI2024

Titanium-Cerium Electrode-Decoupled Redox Flow Batteries Integrated With Fossil Fuel Assets For Load-Following, Long-Duration Energy Storage

Operation of fossil plants at partial capacity with frequent cycling results in decreased efficiency, increased emissions and increased wear and maintenance. The objective of this project is to advance the integration of a titanium-cerium electrode-decoupled redox flow battery (RFB) system with conventional fossil-fueled power plants through technical and economic system-level studies and component scale-up and R&D. The Ti-Ce chemistry has a pathway to meet the DOE cost targets of $\$$100/kWh and $\$$0.05/kWh-cycle owing to the use of low-cost, earth abundant elemental actives and incorporation of inexpensive carbon felt electrodes and non-fluorinated anion exchange membrane (AEM) separators. The initial unit cell design was scaled up, with some modifications made to improve ease of manufacturing, from 25 cm 2 cell area to 400 cm 2 . Electrochemical tests demonstrated operation at a current density up to 50 mA/cm 2 , which is on par with other commercial RFB offerings. Furthermore, the Ti-Ce technology developed by WashU was evaluated and tested by industrial team partner, Giner, Inc., in their modular 3-cell stack. Several cell design modifications and alternate component material selections were successfully implemented to accommodate this chemistry while reducing polarization and leakage. Results from stack testing show high columbic efficiency and indicate that further optimization of cell compression and components will lead to successful operation of the Ti-Ce ED-RFB over longer duration at the multi-cell stack level. Engineering and cost analysis showed that an RFB system with power output on the order of 100 MW and with a charge/discharge duration of approx. 12 hours is the most cost effective for integration with fossil plants. At this scale, projected cycling of fossil fuel power plants can be significantly reduced. The use of a storage system is shown to reduce the fossil plant standalone cost of electricity by $\$$7/MWh, through increased capacity factor and improved average efficiency, in the scenario of high penetration of renewable power.

20 FOSSIL-FUELED POWER PLANTS↗
DOE OSTI2023

Size and Charge Effects on Crossover of Flow Battery Reactants Evaluated by Quinone Permeabilities Through Nafion

Organic reactants are promising candidates for long-lifetime redox flow batteries, and synthetic chemistry unlocks a wide design space for new molecules. Minimizing crossover of these molecules through ion exchange membranes is one important design consideration, but the ways in which the crossover rate depends on the structure of the crossing species remain unclear. Here, we contribute a systematic evaluation of size- and charge-based effects on dilute-solution small molecule permeability through the Nafion NR212 cation exchange membrane. We found that increasing the magnitude of charge number z with the same sign as membrane fixed charges, achieved here by successive sulfonation of quinone redox cores, results in more than an order of magnitude permeability reduction per sulfonate. Size-based effects, understood by comparing the Stokes radii of the quinones studied, also reduces permeability with increasing effective molecule size, but doubling the effective size of the redox reactants resulted in a permeability decrease of less than a factor of three.

25 ENERGY STORAGE↗
DOE OSTI2023

Fluorenone/fluorenol derivatives for aqueous redox flow batteries

Aqueous electrolytes comprising fluorenone/fluorenol derivatives are disclosed. The electrolyte may be an anolyte for an aqueous redox flow battery. In some embodiments, the compound, or salt thereof, has a structure according to any one of formulas I-III where Q 1 -Q 4 independently are CH, C(R 1 ) or N, wherein 0, 1, or 2 of Q 1 -Q 4 are N; Q 5 -Q 8 independently are CH, C(R 2 ), or N, wherein 0, 1, or 2 of Q 5 -Q 8 are N; Y is C=O or C(H)OH; R 1 and R 2 independently are an electron withdrawing group; n is an integer >1; and x and y independently are 0, 1, 2, 3, or 4, where at least one of x and y is not 0.

Wang, Wei↗
DOE OSTI2024

Aqueous redox flow battery electrolytes with high chemical and electrochemical stability, high water solubility, low membrane permeability

The invention features redox flow batteries and compound useful therein as negolytes or posolytes. The batteries and compounds are advantageous in terms of being useable in water solutions at neutral pH and have extremely high capacity retention. Suitable negolytes are diquaternized bipyridines, suitable posolytes are water-soluble ferrocene derivatives.

Gordon, Roy G.↗
DOE OSTI2024

Mild pH-decoupling aqueous flow battery with practical pH recovery

Establishing a pH difference between the two electrolytes (pH decoupling) of an aqueous redox flow battery (ARFB) enables cell voltages exceeding the 1.23 V thermodynamic water-splitting window, but acid–base crossover penalizes efficiency and lifetime. Here we employ mildly acidic and mildly alkaline electrolytes to mitigate crossover, achieving high round-trip energy efficiency with open circuit voltage >1.7 V. We implemented an acid–base regeneration system to periodically restore electrolytes to their initial pH values. The combined system exhibited capacity fade rate <0.07% per day, round-trip energy efficiency >85% and approximately 99% Coulombic efficiency during stable operation for over a week. Cost analysis shows that the tolerance of acid–base crossover could be increased if the pH-decoupling ARFB achieved a higher voltage output and lower resistance. Finally, this work demonstrates principles for improving lifespan, rate capability and energy efficiency in high-voltage pH-decoupling ARFBs and pH recovery concepts applicable for pH-decoupling systems.

25 ENERGY STORAGE↗
DOE OSTI2020

Fluorescence-Enabled Self-Reporting for Redox Flow Batteries

Monitoring battery health is challenging. Self-reporting enables the rapid health assessment of redox flow batteries (RFBs) and provides insight into degradation mechanisms of electrochemically active molecules (redoxmers). In this study, we introduce fluorescence as an orthogonal property to probe this chemistry in situ. An established anolyte redoxmer, 2,1,3-benzothiadiazole, is rendered an efficient blue-green fluorophore through minimalistic derivatization. One of the derivatives is electrochemically reversible with a long lifetime and cycling stability in the charged state. Spectroscopic measurements on this new redoxmer reveal strong effects of the electrolyte cation on the fluorescence that are useful for probing the solvent microenvironment. Using this probe, we demonstrate proof-of-concept in situ crossover sensing and characterize the effects of electrolyte composition on this crossover. In this way, real-time tracing of redoxmers in a flow cell is demonstrated, paving the way to include still more self-reporting functions into the redoxmers.

25 ENERGY STORAGE↗
DOE OSTI2023

Impact of Pendent Ammonium Groups on Solubility and Cycling Charge Carrier Performance in Nonaqueous Redox Flow Batteries

The synthesis, characterization, electrochemical performance, and theoretical modeling of two base-metal charge carrier complexes incorporating a pendent quaternary ammonium group, [Ni(bppn-Me3)][BF4], 3′, and [Fe(PyTRENMe)][OTf]3, 4’, are described. Both complexes were produced in high yield and fully characterized using NMR, IR, and UV–vis spectroscopies as well as elemental analysis and single-crystal X-ray crystallography. The solubility of 3′ in acetonitrile showed a 283% improvement over its neutral precursor, whereas the solubility of complex 4’ was effectively unchanged. Cyclic voltammetry indicates an ∼0.1 V positive shift for all waves, with some changes in reversibility depending on the wave. Bulk electrochemical cycling demonstrates that both 3′ and 4’ can utilize the second more negative wave to a degree, whereas 4’ ceases to have a reversible positive wave. Flow cell testing of 3′ and 4’ with Fc as the posolyte reveals little improvement to the cycling performance of 3′ compared with its parent complex, whereas 4’ exhibits reductions in capacity decay when cycling either negative wave. Postcycling CVs indicate that crossover is the likely source of capacity loss in complexes 3, 3′, and 4’ because there is little change in the CV trace. Density functional theory calculations indicate that the ammonium group lowers the HOMO energy in 3′ and 4’, which may impart stability to cycling negative waves while making positive waves less accessible. The incorporation of a positively charged species can improve solubility, stored electron density, and capacity decay depending on the complex, features critical to high energy density redox flow battery performance.

25 ENERGY STORAGE↗
DOE OSTI2023

Electrochemical Performance of Mixed Redox-Active Organic Molecules in Redox Flow Batteries

Designing electrolytes based on mixture of different organic redox active molecules brings the opportunity of enhancing the volumetric energy density of flow batteries and removes the requirement of high solubility for individual organic species in the mixture. Here, in the present work, we conduct computational and experimental analysis to investigate the electrochemical performance of mixed redox-active organic molecules. A zero-dimensional transient model is employed to investigate the changes in the half-cell potential and the concentrations and partial currents of individual redox reactions in a mixture of organic molecules over time. The model demonstrates the effects of individual properties of species such as kinetic rate constants, mass transfer coefficients, concentration ratios and standard redox potentials and reports the effect of energy-losing homogenous chemical redox reaction on the voltage efficiency and concentration ratios of the mixed species. Pairs of anthraquinone negolyte species were selected for an experimental case study. A mixture of 2,6-N-TSAQ and 2,6-DHAQ showed 40% increase in the volumetric energy density compared to the performance of 2,6-DHAQ alone. Based on the results of the experimental and computational analysis, we propose guidelines for the design of suitable mixed redox-active organic species.

25 ENERGY STORAGE↗
DOE OSTI2020

Redox Flow Battery Having Metal-Ligand Complex

Researchers at Los Alamos National Laboratory have developed new non-aqueous electrolyte materials for redox flow batteries (RFB). These batteries are a viable technology for scalable energy storage beyond lithium ion batteries. Cost is currently limiting deployment, with poor energy density being the primary culprit. One way to improve energy density is by increasing the cell potential beyond the current limit in aqueous media. The higher cell potential and additional electrons stored per molecule will increase the energy density of the RFB medium, overcoming a critical limitation to the current RFBs. Like lithium ion batteries, RFB's can span from the kW to multi MW power storage systems. The nickel complexes described herein have demonstrated redox potentials >3 V which is at least twice the aqueous limit. We are interested in partnering with battery developers to further advance this technology to the product prototype stage.

25 ENERGY STORAGE↗
DOE OSTI2021

Critical role of structural order in bipolar redox-active molecules for organic redox flow batteries

Bipolar redox-active molecules (BRMs) have been suggested as a means to address crossover related issues in all-organic redox flow batteries (RFBs). In such species, electron donors (anolytes) and electron acceptors (catholytes) are linked by a chain, and the same chemical composition is used in both anode and cathode compartments to reduce chemical gradients and unbalanced ion transport. The resultant RFBs resemble the aqueous vanadium RFBs, but offer greater design flexibility and potentially more favorable electrochemical and physicochemical properties. Yet the complex trade-offs in these properties have been a complication. Here we developed a fundamental rubric to uncover the likely origins in the performance metrics of these BRMs that are salient for their use in RFBs. Methylene linked phenothiazine and phthalimide moieties were employed as model BRMs and variations in their properties and molecular conformations were evaluated by systematically varying the methylene linker. Our results revealed that even minimalistic changes in the linker length resulted in dramatic oscillations in the solubility and stability. Using crystallography, quantum chemistry, and molecular dynamics, we clarify that the seemingly fluctuating behavior is due to (1) the inter- and intra-molecular charge transfer between the donor and acceptor through bond or/and through space; (2) the formation of distinctive packing/clustering motifs. Both interactions are strongly dependent on the molecular conformation. As these structural factors modify the electronic structure of both electroactive functional groups and do not change monotonically, the structure–property response in BRMs is often complex. Finally, accordingly, these behaviors need to be taken into account in developing BRMs and knowledge of these structural factors will allow the more rational design of BRMs for grid-scale energy storage.

25 ENERGY STORAGE↗
DOE OSTI2020

In situ electrosynthesis of anthraquinone electrolytes in aqueous flow batteries

In this work, we demonstrate the electrochemical oxidation of an anthracene derivative to a redox-active anthraquinone at room temperature in a flow cell without the use of hazardous oxidants or noble metal catalysts. The anthraquinone, generated in situ, was used as the active species in a flow battery electrolyte without further modification or purification. This potentially scalable, safe, green, and economical electrosynthetic method is also applied to another anthracene-based derivative and may be extended to other redox-active aromatics.

25 ENERGY STORAGE↗
DOE OSTI2025

Proton Selective Nanoporous Atomically Thin Graphene Membranes for Vanadium Redox Flow Batteries

Angstrom-scale proton-selective pores in atomically thin 2D materials present fundamentally new opportunities for advancing proton exchange membranes (PEMs). Vanadium Redox Flow Batteries (VRFBs) for grid-scale energy storage require PEMs with high areal proton conductance (>1 S cm −2 ) and minimal vanadium ion (VO 2+ ) crossover. However, state-of-the-art Nafion 212 membranes (N212 ≈50 µm thick), suffer from persistent VO 2+ crossover reducing performance and efficiency. Here, a layered PEM is demonstrated, comprising monolayer CVD graphene with Angstrom-scale proton-selective pores introduced via Ar plasma, integrated with an ultra-thin ≈300 nm polybenzimidazole (PBI) layer and sandwiched between two Nafion 211 (25 µm thick) layers. The layered architecture facilitates scalable membrane fabrication by mitigating defects while processing and facile stacking of graphene layers allows stochastic non-selective defect isolation enabling exceptionally low VO 2+ crossover (selectivity (H + areal conductance / VO 2+ permeability) ≈6709 × 10 6 S min cm −4 ), with proton conductance >8 S cm −2 . Systematic transport experiments supported by resistance-based transport modelling elucidate the role of defect size, defect isolation, and sealing, as well as layering/stacking, to enable orders of magnitude (>671× over N212) improvements in selectivity, along with areal proton conductance >8 S cm −2 . This work highlights the potential of atomic-scale proton-selective defect engineering in 2D materials, in conjunction with facile stacking and layering of materials as strategies for scalable, high-performance advances in PEMs for energy, electrochemical, and separation applications beyond VRFBs.

Chaturvedi, Pavan [Vanderbilt Univ., Nashville, TN↗