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At least 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Coupled Experimental–Theoretical Characterization of a Carbon Electrode in Vanadium Redox Flow Batteries using X-ray Absorption Spectroscopy

Vanadium redox flow batteries (VRFBs) have emerged as promising solutions for stationary grid energy storage due to their high efficiency, scalability, safety, near room-temperature operation conditions, and the ability to independently size power and energy capacities. The performance of VRFBs heavily relies on the redox couple reactions of V 2+ /V 3+ and VO 2+ /VO 2 + on carbon electrodes. Therefore, a thorough understanding of the surface functionality of carbon electrodes and their propensity for degradation during electrochemical cycles is crucial for designing VRFBs with extended lifespans. In this study, we present a coupled experimental–theoretical approach based on carbon K edge X-ray absorption spectroscopy (XAS) to characterize carbon electrodes prepared under different conditions and identify relevant functional groups that contribute to unique spectroscopic features. Atomic models were created to represent functional groups, such as hydroxyl, carboxyl, methyl, and aldehyde, bonded to carbon atoms in either sp 2 or sp 3 environments. The interactions between functionalized carbon and various solvated vanadium complexes were modeled using density functional theory. A library of carbon K-edge XAS spectra was generated for distinct carbon atoms in different functional groups, both before and after interacting with solvated vanadium complexes. Here we demonstrate how these simulated spectra can be used to deconvolve ex situ experimental spectra measured from carbon electrodes and to track changes in the electrode composition following immersion in different electrolytes or extended cycling within a functional VRFB. By doing so, we identify the active species present on the carbon electrodes, which play a crucial role in determining their electrochemical performance.

25 ENERGY STORAGE↗
DOE OSTI2026

Cation-Diffusive Carbon Interlayers Stabilize Na Metal and Double the Current in Na-S Redox-Flow Batteries for Grid-Scale Energy Storage

The sodium-sulfur nonaqueous redox-flow batteries (Na-S NARFBs) using earth-abundant elements are highly attractive due to the low material cost and improved energy density for grid-scale energy storage. However, the low current performance, poor Na0/Na+ redox kinetics, and Na dendrite growth pose severe challenges. We introduce cation-diffusive layers (CDLs): thin and Na+ affinitive interlayers at the Na anode that direct Na+ transport and stabilize Na deposition. Benchmarking three archetypal materials—carbon paper (CP), glass microfiber paper (GF), and foam—across Na-Na and Na-Cu, and Na-S cells identifies CP as the optimum. CP reduces symmetric cell overpotential by more than 70%, achieves 98% Na plating-stripping efficiency, and doubles the Na-S cell current density from 0.5 to 1.0 mA cm−2 without sacrificing capacity or efficiency. Ex situ electrochemical and SEM/XPS analysis, combined with molecular dynamics (MD) studies, reveal that electron-rich carbon fibers disperse supporting salt aggregates, enrich near-surface Na+ density, and create ion transport pathways for fast Na0/Na+ exchange while mitigating membrane degradation. Because of the ion-centric mechanism, CDLs can be generalized to other metal-anode designs. Further, this work establishes CDL design rules—cationic affinity and appropriate micro/nanostructure—as a simple, scalable route to high-current, durable metal-anode flow batteries.

Wu, Wenda [ORNL] (ORCID:000900033307687X)↗
DOE OSTI2024

Ionic Diffusion in Slurry Electrolytes for Redox Flow Batteries

Slurry electrodes have been proposed as a method to decouple the storage and power capacities of hybrid redox flow batteries by allowing the reduced metal to adhere to a flowing dispersion of electrically conductive particles rather than accumulate in the flow cell. In this work, the ionic mass transport through these slurry electrolytes is investigated via voltammetry at a rotating disc electrode and in a parallel channel flow cell. A modified Levich equation, i l = 0.6 2 nFC ω 1 / 2 ν − 1 / 6 ( D + r 2 Φ ω m ) 2 / 3 , is developed to describe limiting currents to a rotating disc electrode when using a particle filled electrolyte. Mass transfer is demonstrated to be enhanced by greater particle loading so long as there are sufficient particles such that their respective flow velocity boundary layers interact. In the flow cell, faradaic current in a carbon black slurry electrolyte was observed to decrease over time. This suggests that the carbon particles adhere and accumulate on the stationary electrode, impeding mass transport by imposing diffusion path tortuosity. This accumulation is undesirable in hybrid redox flow batteries as it encourages metal deposition in the cell, limiting the scalability of the technology.

Electrochemistry↗
DOE OSTI2025

Stress Corrosion Cracking of NaSICON Membranes in Aqueous Electrolytes for Redox-Flow Batteries

The sodium super-ionic conductor (NaSICON) has versatile applications as a ceramic electrolyte for energy storage, where it can serve as an impermeable separator in solid-state batteries and redox flow systems. In particular, NaSICON systems have been proposed to be relatively stable in contact with water, making them compatible with aqueous battery chemistries. However, owing to their brittle nature and metal oxide constituents, stress-corrosion cracking (SCC) is an important failure mechanism that has not been previously explored. In this study, we assess the fracture toughness of NaSICON membranes in contact with aqueous solutions that are relevant to redox flow systems. Microindentation was performed to generate visible surface cracks and residual stress, which were observed to grow in length after exposure to aqueous solutions. This allows for a quantitative measurement of fracture toughness, which decreases after exposure to water. To contextualize these results, we develop a simplified model of the fracture behavior in aqueous redox-flow batteries that incorporate NaSICON membranes, illustrating the importance of SCC in cell design. This work provides quantitative insights into SCC as a failure mode in NaSICON, enhancing our understanding of the chemo-mechanical behavior of ceramic electrolytes in contact with aqueous solutions.

Zhang, Mengyao↗
DOE OSTI2022

A three-dimensional pore-scale model for redox flow battery electrode design analysis

A three-dimensional (3-D) pore-scale model has been developed to construct multiscale fibrous electrodes for redox flow batteries (RFB). New designs, such as biporous electrodes modify electrode structures by creating secondary pores on single carbon fiber to reduce internal battery resistance. Existing pore-scale models only resolve electrodes to the single carbon fiber scale and cannot incorporate recent multiscale electrode designs into numerical models. Our new model aims to bridge this gap and provide a tool to rapidly screen new electrode configurations. Two multiscale electrodes, laser-perforated and biporous electrodes, were investigated at varying operation conditions with the proposed 3-D pore-scale models. The laser-perforated electrode exhibits a reduced pressure drop, but follows the same permeability correlation compared to the corresponding pristine electrode. For the biporous electrode, the added specific surface area and faster reaction kinetics from the secondary pores are the most influential factors leading to improved battery efficiency. However, operating the biporous electrode in limiting current density conditions should be avoided due to the decreased mass transfer efficiency and a more significant voltage loss. Finally, we believe that our 3-D pore-scale model can accelerate the flow battery electrode design process and provide new insights into electrode geometry optimizations.

25 ENERGY STORAGE↗
DOE OSTI2020

Electrolyte Lifetime in Aqueous Organic Redox Flow Batteries: A Critical Review

Aqueous organic redox flow batteries (RFBs) could enable widespread integration of renewable energy, but only if costs are sufficiently low. Because the levelized cost of storage for an RFB is a function of electrolyte lifetime, understanding and improving the chemical stability of active reactants in RFBs is a critical research challenge. We review known or hypothesized molecular decomposition mechanisms for all five classes of aqueous redox-active organics and organometallics for which cycling lifetime results have been reported: quinones, viologens, aza-aromatics, iron coordination complexes, and nitroxide radicals. We collect, analyze, and compare capacity fade rates from all aqueous organic electrolytes that have been utilized in the capacity-limiting side of flow or hybrid flow/nonflow cells, noting also their redox potentials and demonstrated concentrations of transferrable electrons. We categorize capacity fade rates as being “high” (>1%/day), “moderate” (0.1–1%/day), “low” (0.02–0.1%/day), and “extremely low” (≤0.02%/day) and discuss the degree to which the fade rates have been linked to decomposition mechanisms. Capacity fade is observed to be time-denominated rather than cycle-denominated, with a temporal rate that can depend on molecular concentrations and electrolyte state of charge through, e.g., bimolecular decomposition mechanisms. We then review measurement methods for capacity fade rate and find that simple galvanostatic charge–discharge cycling is inadequate for assessing capacity fade when fade rates are low or extremely low and recommend refining methods to include potential holds for accurately assessing molecular lifetimes under such circumstances. We consider separately symmetric cell cycling results, the interpretation of which is simplified by the absence of a different counter-electrolyte. We point out the chemistries with low or extremely low established fade rates that also exhibit open circuit potentials of 1.0 V or higher and transferrable electron concentrations of 1.0 M or higher, which are promising performance characteristics for RFB commercialization. We indicate important directions for future research.

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

In Situ Reliability Investigation of All-Vanadium Redox Flow Batteries by a Stable Reference Electrode

Redox flow batteries (RFBs) have been studied over the past several decades as a promising candidate for stationary energy storage applications. It is therefore important to understand the reliability of RFBs and the mechanisms that cause degradation with time. Contributions from individual electrodes (cathode or anode) are difficult to separate especially for long-term cycle testing, due to the lack of a stable reference electrode. In our work, the reliability and degradation mechanisms of an all-vanadium RFB were investigated by a stable reference electrode based on the dynamic hydrogen electrode (DHE). With factor exploration and design optimization, the newly developed DHE reference electrode demonstrated high accuracy and long-term stability that enables in-situ monitoring of individual electrode signals (potentials and impedances) over hundreds of cycles in a vanadium RFB. This approach enables the full cell degradation to be separated and the degradation attributed to contributions from the cathode and anode. The cathode and anode were found to play quite different roles in the increase in overpotential of the vanadium RFB during long-term cycling. The anode reaction limited both the charge and discharge capacity over 100 cycles. In addition, the negative side also appeared to be the rate limiting factor throughout cycling as determined by EIS measurement. The cathode contributed to the performance degradation as cycling exceeded 50 cycles.

Huang, Qian↗
DOE OSTI2021

Polysulfide-Permanganate Flow Battery Using Abundant Active Materials

A new flow battery is presented using the abundant and inexpensive active material pairs permanganate/manganate and disulfide/tetrasulfide. A wetted material set is identified for compatibility with the strongly oxidizing manganese couple at ambient and elevated temperatures. Both solutions allow high active material solubility, with cells tested at theoretical energy densities up to 43 Wh l −1 for the ∼1.2 V cell. Full cells built with nickel foam electrodes and sodium-exchanged Nafion 115 membranes deliver a baseline area-specific resistance of 2.7 Ω-cm 2 . Incorporation of high-surface-area cobalt-coated carbon paper and high-surface-area stainless steel mesh electrodes, and an expanded Nafion 115 membrane delivers cells with 44% lower resistance at 1.6 Ω-cm 2 . All cells show performance decay over the course of cycling. The Co-decorated carbon paper electrodes provide significant kinetic improvements, shifting electrode performance from non-linear with Ni-foam to linear with a volume-normalized exchange current density value of 3.2 A cm −3 . The expanded membrane provides increased conductivity over the 13 mS cm −1 conductivity observed in as-received, sodium-exchanged Nafion 115. Although boiled membranes provide improved conductivity, it is at the cost of decreased Coulombic efficiency and poorer manufacturability. Full cell models suggest that similar cell resistances (1.7 Ω-cm 2 ) should be feasible with as-received Nafion 115 and advanced electrodes.

25 ENERGY STORAGE↗
DOE OSTI2020

Aqueous Na-ion redox flow battery with ceramic NaSICON membrane

A redox flow battery is described herein that has a sodium-super-ionic-conductor NaSICON barrier disposed between an anolyte chamber of the battery and the catholyte chamber of the battery. The NaSICON barrier prevents crossover of solvents or active redox species between the anolyte chamber and the catholyte chamber, while permitting transport of sodium ions between the chambers. In exemplary embodiments, the anolyte chamber includes an anolyte solution that comprises a first active redox species dissolved in a first solvent, while the catholyte chamber includes a catholyte solution that comprises a second active redox species dissolved in a second solvent.

25 ENERGY STORAGE↗
DOE OSTI2020

All-vanadium sulfate acid redox flow battery system

All-vanadium sulfate redox flow battery systems have a catholyte and an anolyte comprising an aqueous supporting solution including chloride ions and phosphate ions. The aqueous supporting solution stabilizes and increases the solubility of vanadium species in the electrolyte, allowing an increased vanadium concentration over a desired operating temperature range. According to one example, the chloride ions are provided by MgCl2, and the phosphate ions are provided by (NH4)2HPO4.

25 ENERGY STORAGE↗
DOE OSTI2022

Organic redox molecules for flow batteries

The present invention provides a redox flow battery comprising a negative electrode (also referred to herein as an “anode”) immersed in a first liquid electrolyte (also referred to herein as a “negative electrolyte” or “anolyte”), a positive electrode (also referred to herein as a “cathode”) immersed in a second liquid electrolyte (also referred to herein as a “positive electrolyte” or “catholyte”), and a cation-permeable separator (e.g., a membrane or other cation-permeable material) partitioning the negative electrode/anolyte from the positive electrode/catholyte. The redox reactant of the catholyte comprises a compound of Formula (I) as described herein.

25 ENERGY STORAGE↗
DOE OSTI2022

All-vanadium sulfate acid redox flow battery system

All-vanadium sulfate redox flow battery systems have a catholyte and an anolyte comprising an aqueous supporting solution including chloride ions and phosphate ions. The aqueous supporting solution stabilizes and increases the solubility of vanadium species in the electrolyte, allowing an increased vanadium concentration over a desired operating temperature range. According to one example, the chloride ions are provided by MgCl 2 , and the phosphate ions are provided by (NH 4 ) 2 HPO 4 .

Nie, Zimin↗
DOE OSTI2025

Conformational Control as a Design Strategy to Tune the Redox Behavior of Benzotriazole Negolytes for Nonaqueous Flow Batteries

Here, we present a molecular engineering strategy to tune the reduction potentials of benzotriazole derivatives as high-energy-density negolytes in nonaqueous redox flow batteries. Within nonaqueous electrolytes, these derivatives, notably 2-(o-tolyl)-2H-benzo[d][1,2,3]triazole (1), demonstrate a theoretical capacity of up to 93.8 Ah L⁻¹ and a reduction potential of –2.35 V vs ferrocene/ferrocenium (Fc/Fc⁺). Introducing dimethyl substitution (i.e., 2-(2,6-dimethylphenyl)-2H-benzo[d][1,2,3]triazole (4)) shifts the reduction potential even more negatively to –2.55 V vs Fc/Fc⁺. We ascribe the nonlinear effect of dimethyl substitution on reduction potential to ground-state conformational effects. Flow battery tests with negolyte 1 and ferrocene posolyte demonstrated >90% Coulombic efficiency at 6.7 mA cm⁻² with improved cyclability in the presence of lithium bis(trifluoromethylsuylfonyl)imide supporting salt.

25 ENERGY STORAGE↗
DOE OSTI2021

Durable and Highly Selective Ion Transport of a Sulfonated Diels Alder Poly(phenylene) for Vanadium Redox Flow Batteries

In order to improve the durability and ion selectivity of a hydrocarbon membrane for vanadium redox flow batteries (VRFBs) a polymer was rationally designed with an external hydrophobic shell and internal hydrophilic core. The polymer was designed to prevent hydrophilic polymer chain aggregation by functionalizing the external polymer shell with hydrophobic side chains and attaching acid moieties onto the polymer backbone. The hydrophobic shell is the result of pentafluorobenzoyl group functionalization on the pendent aryl rings in a Diels Alder poly(phenylene) backbone. The internal polymer chain contains sulfonic acid moieties to impart hydrophilic character. The physical and electrochemical characteristics of the membrane were systematically studied and compared with widely used Nafion-212. The synthesized membranes were found to be superior to Nafion-212 not only in terms of lower vanadium ion permeability (4.25 x 10 -8 vs. Nafion-212: 6.0 x 10 -6 cm 2 min -1 ) but also in higher VRFB performance (EE = 89% and vs. Nafion-212: 85.5% at 40 mA/cm 2 ). The membrane also showed over three times higher capacity retention than Nafion-212 (0.075 % vs. 0.25 % capacity loss per cycle respectively) and excellent ex situ and in situ chemical stability.

25 ENERGY STORAGE↗
DOE OSTI2022

Nafion Inhibits Polysulfide Crossover in Hybrid Nonaqueous Redox Flow Batteries

Here, we report on the effectiveness of sodium-exchanged Nafion membranes for inhibiting polysulfide crossover during redox flow battery operation. The solubility of polysulfides allows them to be used as a high-capacity catholyte for nonaqueous redox flow batteries (NARFB). The NARFB cathode capacity is controlled by the total tank catholyte volume and polysulfide concentration and, as such, is independent of polysulfide adsorption sites on carbon fibers or nanotubes as found within traditional Na or Li–S batteries. However, one of the major barriers to the realization of polysulfide NARFBs is associated with developing a robust membrane that has minimal polysulfide crossover under the operating conditions. We found that sodium-exchanged Nafion membrane separators effectively inhibit polysulfide crossover within a Na–sulfur NARFB. These membranes significantly improve both capacity retention (70%) and Coulombic efficiencies (99%) after 50 cycles. Commercial porous membranes showed a large crossover as detected by UV–vis spectroscopy and resulted in low capacity retention (20%) and Coulombic efficiency (74%) after 45 cycles. Electrochemical impedance spectroscopy (EIS) measurements highlighted the trade-off between innate reactivity and ionic conduction of the membranes. The results show that dense, single ion conducting Nafion enables a long cycle life; however, it reacts with Na metal to form a resistive passivation layer and increases the cell resistance. On the contrary, the open pore structure of Celgard allows for higher current charge/discharge, and its chemical nature is compatible with Na; however, it has a high degree of polysulfide crossover.

25 ENERGY STORAGE↗
DOE OSTI2021

Accessing a high‐voltage nonaqueous hybrid flow battery with a sodium‐methylphenothiazine chemistry and a sodium‐ion solid electrolyte

Abstract The development of redox flow batteries (RFBs) with nonaqueous electrolytes offers the possibility of accessing a high cell‐operation voltage (no restrain of hydrogen evolution and oxygen evolution potentials) and a low operation temperature (can be operated below the freezing point of water). Therefore, nonaqueous RFBs have recently garnered increasing attention. However, the cross‐mixing of liquid electrode/electrolyte materials has been plaguing the progress of the nonaqueous RFBs. Herein, we present a crossover‐free, high voltage nonaqueous hybrid flow battery (HFB) with a novel sodium‐methylphenothiazine (MPT) chemistry and a single‐ion solid‐electrolyte separator. The Na‐MPT redox couple delivers a high voltage of ~2.6 V when the cell was operated at a medium current density. A NASICON‐type solid electrolyte membrane (Na 3 Zr 2 Si 2 PO 12 ) could circumvent the crossover of the liquids between the positive and negative electrodes, and meanwhile could maintain a single‐ion (Na + ‐ion) conduction between the two electrodes to sustain the electrochemical reactions. Under such an electrochemical mechanism, the nonaqueous Na‐MPT HFB shows remarkable cycling performance.

Yu, Xingwen↗
DOE OSTI2025

A polysulfide/ferricyanide redox flow battery with extended cycling

The inexpensive sulfur raw material is promising to enable cost-effective redox flow batteries for long duration energy storage. But the catastrophic through-membrane crossover of polysulfides remains a severe challenge resulting in irreversible performance degradation and short cycle life. In this work, we demonstrate that use of a permselective cation exchange membrane yields a two orders of magnitude enhancement in polysulfide retention compared to the benchmark Nafion membrane. Combined physico-chemical, spectroscopic, and microscopic analyses suggest more disordered sidechain structures, which lead to the more hydrophobic nature and smaller hydrophilic domains in the membrane. The microstructural features contribute to the effective mitigation of polysulfide crossover. As a result, the cycle life of polysulfide/ferricyanide flow cells is boosted over a substantially extended test time. This finding sheds light on the fundamental membrane factors that cause polysulfide permeation and can provide feasible directions in the development of permselective membranes for polysulfide flow batteries.

36 MATERIALS SCIENCE↗
DOE OSTI2022

A Comparative Study of Compressive Effects on the Morphology and Performance of Carbon Paper and Cloth Electrodes in Redox Flow Batteries

Compressing porous carbon electrodes is a common approach to improve flow battery performance, but the resulting impact on electrode structure, fluid dynamics, and cell performance is not well understood. Herein, microtomographic imaging, load cell testing, and flow cell diagnostics are employed to characterize how compression‐induced changes impact pressure drop, polarization, and mass‐transfer scaling. Five different compressions are tested, spanning ranges typically used in literature, for AvCarb 1071 cloth (0%, 9%, 20%, 25%, 32%) and Freudenberg H23 paper (0%, 8%, 12%, 17%, 22%). It is found that the two electrode structures have distinct responses to compression, resulting in differing optimal conditions identified for each material; specifically, the Freudenberg H23 exhibits lower combined ohmic, charge‐transfer, and mass‐transport values at 8% compression, resulting in improved electrochemical performance across all compressive values, as compared to the optimal AvCarb 1071 compression (20%). Overall, Freudenberg H23 exhibits a greater sensitivity to compression with peak electrochemical activity correlating with increased permeability, whereas AvCarb 1071 is insensitive to compressive loads but produces lower electrochemical performance. Herein, the trade‐offs of mechanical robustness on fluid‐dynamic and electrochemical performance between the two electrodes are demonstrated by the aforementioned findings, suggesting each could be used for specific operating environments.

25 ENERGY STORAGE↗