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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 55 records · Page 3

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↗

In situ electrochemical recomposition of decomposed redox-active species in aqueous organic flow batteries

Aqueous organic redox flow batteries (AORFBs) offer a safe and potentially inexpensive solution to the problem of storing massive amounts of electricity produced from intermittent renewables. However, molecular decomposition is the major barrier preventing AORFBs from being commercialized. Structural modifications can improve molecular stability at the expense of increased synthetic cost and molecular weight. Utilizing 2,6-dihydroxy-anthraquinone (DHAQ), without further structural modification, we demonstrate that electrochemical regeneration could be a viable route to achieve low-cost, long-lifetime AORFBs. In situ (online) NMR and EPR and complementary electrochemical analyses reveal that decomposition compounds i.e., 2,6-dihydroxy-anthrone (DHA) and its tautomer, 2,6-dihydroxy-anthranol (DHAL), can be converted back to DHAQ in two steps: first DHA(L) 2- are oxidized to the dimer (DHA) 2 4- at - 0.32 V vs. SHE by one-electron transfer; subsequently, the (DHA) 2 4- is oxidized to DHAQ 2- at +0.57 V vs. SHE by three-electron transfer. Electrochemical regeneration rejuvenates not only DHAQ 2- , but also the positive electrolyte – rebalancing the states of charge of both electrolytes without introducing extra ions. We demonstrate the repeated capacity recovery with DHAQ | potassium ferro-/ferricyanide flow battery in basic conditions, and show the approach is also effective for anthraquinone-2,7-disulfonate in acid. Electrochemical regeneration strategies may extend the useful lifetime of many water-soluble organic molecules with anthraquinone core structures in electrochemical cells.

25 ENERGY STORAGE↗

Probing and Tuning Spatiotemporal pH Evolution in Aqueous Zinc Ion Batteries

Aqueous zinc-ion batteries (AZIBs) offer a combination of safety and low cost, but they suffer from dynamic pH fluctuations that drive parasitic reactions and capacity fading. In this review, we report the current mechanistic understanding of the dynamic pH evolution across the electrolyte-electrode interface and its role in triggering interphase instability. We summarize advanced strategies to regulate pH, including electrolyte engineering, electrode surface modification, and interphase construction. We further discuss current methods for probing pH dynamics and outline potential future approaches for gaining deeper mechanistic and design insights.

Zheng, Xueli [SLAC]↗

Structural, Dynamic, and Chemical Complexities in Zinc Anode of an Operating Aqueous Zn-Ion Battery

Aqueous Zn-ion battery is a promising technology for electrochemical energy storage. The formation of Zn dendrites, however, can jeopardize the cell cycle life and thus, hinders the industrial adoption of this technology. A fundamental understanding of the kinetic mechanisms is crucial for improving the Zn-ion battery. Here, in situ and operando X-ray microscopy methods are utilized to visualize the Zn plating and stripping behaviors under different electrochemical conditions. It is demonstrated that the substrate curvature, local morphology, electrochemical protocols, and the surface chemistry can collectively affect the Zn plating behavior. Furthermore, these results provide new insights for developing the next-generation dendrite-free and long-span aqueous Zn-ion battery.

25 ENERGY STORAGE↗

Revealing the Fast and Durable Na + Insertion Reactions in a Layered Na 3 Fe 3 (PO 4 ) 4 Anode for Aqueous Na-Ion Batteries

Aqueous sodium-ion batteries represent a promising approach for stationary energy storage; however, the lack of appropriate anode materials has substantially retarded their development. Herein, we demonstrated an iron-based phosphate material of Na 3 Fe 3 (PO 4 ) 4 as an inexpensive and efficacious anode alternative. While the Fe 3+ /Fe 2+ redox couple renders a two-Na-insertion reaction with desirable potentials, its unique layered structure further facilitates the Na-insertion kinetics and reversibility. Consequently, this electrode exhibits an appealing Na-insertion performance, with a reversible capacity of ~83 mAh g –1 , suitable anode potential of -0.4 V vs Ag/AgCl, excellent rate capability of 200 C, and outstanding cycling of 6000 cycles. Utilizing operando synchrotron X-ray diffraction and X-ray absorption spectroscopy, we revealed the structural evolution of the Na 3 Fe 3 (PO 4 ) 4 anode during the two-electron reaction, where the extremely small volume expansion (~3%) enables its fast-charging and long-cycling capability. Our work suggests new considerations of developing versatile iron phosphate compounds as appealing anode materials for energy storage in aqueous electrolytes.

25 ENERGY STORAGE↗

Ball Milling-Enabled Fe 2.4+ to Fe 3+ Redox Reaction in Prussian Blue Materials for Long-Life Aqueous Sodium-Ion Batteries

Aqueous Na-ion batteries using Prussian blue materials have inherent advantages on safety, material sustainability, and economic cost. However, it is challenging to obtain long term cycling stability because many redox reactions have poor intrinsic stability in water. In this report we demonstrate reversible Fe 2.4+ to Fe 3+ redox reaction of Prussian blue electrodes cycled in 17 m NaClO 4 water-in-salt electrolyte. The cubic phase c-Na 1.17 Fe[Fe(CN) 6 ]·0.35H 2 O) derived from monoclinic Prussian blue (m-Na 1.88 Fe[Fe(CN) 6 ]·0.7H 2 O) through ball milling delivers excellent cycling stability of >18,000 cycles with >90% capacity retention at 10C rate. The specific capacity is ~75 mAh/g and ~67 mAh/g at 1C and 10C rate, respectively. Systematic characterizations including electron microscopy, X-ray diffraction, Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy have verified the phase transition and iron oxidation state evolution, revealing the mechanism that enables the material’s high rate and long durability as the battery cathode.

25 ENERGY STORAGE↗

A hybrid numerical and machine learning framework for evaluating the performance of a 780 cm 2 aqueous organic redox flow battery

Aqueous organic redox flow battery (AORFB) is a promising cost-competitive technology for large-scale energy storage. Among existing work, the dihydroxyphenazine (DHP)-based AORFB has demonstrated high energy density and low capacity degradation in 10 cm2 cells during lab tests. However, its commercial-scale performance in more complex environments remains unknown, posing a barrier for commercialization. To address this gap, this work presents a comprehensive performance evaluation of a 780 cm 2 DHP-based AORFB by combining physics-based numerical model, machine learning (ML)-based surrogate models, and ML-derived sensitivity quantification. Specifically, we first select 12 key battery parameters that include 10 physicochemical quantities and 2 operation quantities, then select 6 performance metrics that include energy efficiency (EE), discharging capacity, charging energy, and power losses due to concentration, activation, and ohmic over-potentials. With such selection, 12800 combinations of the 12 parameters are subsequently generated using the Latin Hypercube Sampling method. These combinations, together with 38 pre-defined State of Charge, are then integrated to a validated AORFB model developed in COMSOL to compute the performance metrics. With both input parameters and performance metrics, 60 deep neural network (DNN) surrogate models are then trained to approximate the relationship between the 10 physicochemical quantities and 6 performance metrics at each flow rate and current density. Sensitivity scores are then calculated based on the DNN models. Two additional sensitivity analysis tools, i.e., MARS, and SHAP, are also used to cross-validate the sensitivity scores from the DNN. The results demonstrate that 1) the standard potential ranks the first in controlling EE and charging energy, 2) the membrane conductivity is most critical for power loss and EE, and 3) specific area and reaction rate control activation power loss.

25 ENERGY STORAGE↗

Architecting a Stable High-Energy Aqueous Al-Ion Battery

Aqueous Al-ion batteries (AAIBs) are the subject of great interest due to the inherent safety and high theoretical capacity of aluminum. The high abundancy and easy accessibility of aluminum raw materials further make AAIBs appealing for grid-scale energy storage. However, the passivating oxide film formation and hydrogen side reactions at the aluminum anode as well as limited availability of the cathode lead to low discharge voltage and poor cycling stability. Here, we proposed a new AAIB system consisting of an Al x MnO 2 cathode, a zinc substrate-supported Zn-Al alloy anode, and an Al(OTF) 3 aqueous electrolyte. Through the in situ electrochemical activation of MnO, the cathode was synthesized to incorporate a two-electron reaction, thus enabling its high theoretical capacity. The anode was realized by a simple deposition process of Al 3+ onto Zn foil substrate. The featured alloy interface layer can effectively alleviate the passivation and suppress the dendrite growth, ensuring ultralong-term stable aluminum stripping/plating. The architected cell delivers a record-high discharge voltage plateau near 1.6 V and specific capacity of 460 mAh g -1 for over 80 cycles. Finally, this work provides new opportunities for the development of high-performance and low-cost AAIBs for practical applications.

25 ENERGY STORAGE↗

Unraveling the Dissolution-Mediated Reaction Mechanism of α-MnO 2 Cathodes for Aqueous Zn-Ion Batteries

Aqueous Zn/α-MnO 2 batteries have attracted immense interest owing to their high energy density, low cost, and safety, making them desirable for future large-scale energy application. Despite these merits, the comprehensive understanding of their reaction mechanism has been elusive due to the limitations of standard bulk characterization. Here, via transmission electron microscopy, the dissolution-mediated reaction mechanism of a Zn/α-MnO 2 system is discovered and explored in full scope to involve reversible formation of Zn 4 SO 4 (OH) 6 · x H 2 O and “birnessite-like” Zn-MnO x phase upon cycling. Overall, α-MnO 2 acts primarily as a source for cell activation through dissolution and thus is not directly involved in the Zn redox chemistry. Overall, this microscopic study offers a unique knowledge on the unconventional reaction chemistry of Zn/α-MnO 2 batteries.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Highly Stable, Low Redox Potential Quinone for Aqueous Flow Batteries**

Abstract Aqueous organic redox flow batteries are promising candidates for large‐scale energy storage. However, the design of stable and inexpensive electrolytes is challenging. Here, we report a highly stable, low redox potential, and potentially inexpensive negolyte species, sodium 3,3′,3′′,3′′′‐((9,10‐anthraquinone‐2,6‐diyl)bis(azanetriyl))tetrakis(propane‐1‐sulfonate) (2,6‐N‐TSAQ), which is synthesized in a single step from inexpensive precursors. Pairing 2,6‐N‐TSAQ with potassium ferrocyanide at pH=14 yielded a battery with the highest open‐circuit voltage, 1.14 V, of any anthraquinone‐based cell with a capacity fade rate <10 %/yr. When 2,6‐N‐TSAQ was cycled at neutral pH, it exhibited two orders of magnitude higher capacity fade rate. The great difference in anthraquinone cycling stability at different pH is interpreted in terms of the thermodynamics of the anthrone formation reaction. This work shows the great potential of organic synthetic chemistry for the development of viable flow battery electrolytes and demonstrates the remarkable performance improvements achievable with an understanding of decomposition mechanisms.

Wu, Min↗

An Overview of Challenges and Strategies for Stabilizing Zinc Anodes in Aqueous Rechargeable Zn-Ion Batteries

Aqueous rechargeable zinc ion batteries (ZIBs) have been revived and are considered a promising candidate for scalable electrochemical energy storage systems due to their intrinsic safety, low cost, large abundance, mature recyclability, competitive electrochemical performance, and sustainability. However, the deployment of aqueous rechargeable ZIBs is still hampered by the poor electrochemical stability and reversibility of Zn anodes, which is a common, inherent issue for most metal-based anodes. This review presents a comprehensive and timely overview of the challenges and strategies of Zn anodes toward durable ZIBs. First, several challenges that significantly reduce the Coulombic efficiency and cycling stability of Zn anodes are briefly discussed including dendrite formation, hydrogen evolution, and corrosion. Then, the mitigation strategies are summarized in terms of modifying the electrode/electrolyte interfaces, designing electrode structures, and optimizing electrolytes and separators. Further, we comprehensively discuss the mechanisms behind these issues and improvement strategies with respect to the anodes, electrolytes, and separators. Lastly, we provide perspectives and critical analyses of remaining challenges, outlook, and future direction for accelerating the practical application of aqueous rechargeable ZIBs.

25 ENERGY STORAGE↗

Challenges and Opportunities for Rechargeable Aqueous Sn Metal Batteries

Rechargeable aqueous batteries based on metallic anodes hold tremendous potential of high energy density enabled by the combination of relatively low working potential and large capacity while retaining the intrinsic safety nature and economical value of aqueous systems; However, the realization of these promised advantages relies on the identification of an ideal metal anode chemistry with all these merits. In this review, the emerging Sn metal anode chemistry is examined as such an anode candidate in both acidic and alkaline media, where the inertness of Sn toward hydrogen evolution, flat low voltage profile, and low polarization make it a unique metal anode for aqueous batteries. From a panoramic viewpoint, the key challenges and detrimental issues of Sn metal batteries are discussed, including dead Sn formation, self‐discharge, and electrolyte degradation, as well as strategies for mitigating these issues by constructing robust Sn anodes. New design approaches for more durable and reliable Sn metal batteries are also discussed, with the aim of fully realizing the potential of Sn anode chemistry.

Sn metal↗

Tuning the Solvation Structure in Aqueous Zinc Batteries to Maximize Zn-Ion Intercalation and Optimize Dendrite-Free Zinc Plating

Aqueous zinc batteries are recognized to suffer from H + /Zn 2+ coinsertion in the cathode, but few approaches have been reported to suppress deleterious H + intercalation. We realize this goal by tuning the solvation structure, using LiV 2 (PO 4 ) 3 (LVP) as a model cathode. Phase conversion of LVP induced by H + intercalation is observed in 4 m Zn(OTf) 2 , whereas dominant Zn 2+ insertion is confirmed in a ZnCl 2 water-in-salt electrolyte (WiSE). This disparity is ascribed to the complete absence of free water and a strong Zn 2+ –H 2 O interaction in the latter that interrupts the H 2 O hydrogen bonding network, thus suppressing H + intercalation. On the basis of this strategy, a novel PEG-based hybrid electrolyte is designed to replace the corrosive ZnCl2 WiSE. This system exhibits an optimized Zn 2+ solvation sheath with a similar low free water content, showing not only much better suppression of H + intercalation but also highly reversible Zn plating/stripping with a CE of ~99.7% over 150 cycles.

25 ENERGY STORAGE↗

Microemulsions: Breakthrough Electrolytes for Redox Flow Batteries

Aqueous and non-aqueous redox flow batteries (RFBs) have limited energy and current densities, respectively, due to the nature of the electrolytes. New approaches to electrolyte design are needed to improve the performance of RFBs. In this work, we combined a highly conductive aqueous phase and an organic redox-active phase in a microemulsion to formulate a novel RFB electrolyte. As a proof-of-concept, we demonstrate an RFB using this microemulsion electrolyte with maximum current density of 17.5 mA·cm −2 with a 0.19 M posolyte and 0.09 M negolyte at a flow rate of only ∼2.5 ml·min −1 , comparable to early vanadium electrolyte RFBs at similar flow rates on a per molar basis. The novel active negolyte component is an inexpensive oil-soluble vitamin (K 3 ). By combining aqueous and organic phases, the solvent potential window and energy density may be increased without sacrificing current density and new redox couples may be accessed. Microemulsion electrolytes show great promise for improved performance and increased energy densities in aqueous RFBs but the path forward is complex. We end with discussion of areas that need work to achieve the potential of these electrolytes.

25 ENERGY STORAGE↗

An Anode-Free Zn–MnO 2 Battery

Aqueous Zn-based batteries are attractive because of the low cost and high theoretical capacity of the Zn metal anode. However, the Zn-based batteries developed so far utilize an excess amount of Zn (i.e., thick Zn metal anode), which decreases the energy density of the whole battery. In this study, we demonstrate an anode-free design (i.e., zero-excess Zn), which is enabled by employing a nanocarbon nucleation layer. Electrochemical studies show that this design allows for uniform Zn electrodeposition with high efficiency and stability over a range of current densities and plating capacities. Using this anode-free configuration, we showcase a Zn–MnO 2 battery prototype, showing 68.2% capacity retention after 80 cycles. Our anode-free design opens a new direction for implementing aqueous Zn-based batteries in energy storage systems.

25 ENERGY STORAGE↗