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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

Achieving High Stability and Performance in P2-Type Mn-Based Layered Oxides with Tetravalent Cations for Sodium-Ion Batteries

We report P2-type sodium-manganese-based layered cathodes, owing to their high capacity from both cationic and anionic redox, are a potential candidate for Na-ion batteries to replace Li-ion technology in certain applications. Still, the structure instability originates from irreversible oxygen redox at high voltage remains a challenge. Here, a high sustainability cobalt-free P2- Na 0.72 Mn 0.75 Li 0.24 X 0.01 O 2 (X= Ti/Si) cathode is developed. The outstanding capacity retention and voltage retention after 150 cycles are obtained in Na half-cells. Our finding shows Ti locates on the surface while Si diffuses to the bulk of the particles. Thus, Ti can act as protective layer that alleviate side reactions in carbonate-based electrolyte. Meanwhile, Si can regulate the local electronic structure and suppress oxygen redox activities. Notably, full-cells with hard carbon (≈300-335 Whkg -1 based on the cathode mass) deliver the capacity retention of 83% for P2- Na 0.72 Mn 0.75 Li 0.24 Si 0.01 O 2 and 66% for P2-Na 0.72 Mn 0.75 Li 0.24 Ti 0.01 O 2 after 500 cycles; this electrochemical stability is the best compared to other reported cathodes based on oxygen redox at present. The superior cycle performance also stems from the ability to inhibit microcracking and planar gliding within the particles. Altogether, this finding offers new composition towards developing high performance low-cost cathodes for Na-ion batteries and highlights the unique role of Ti/Si ions.

25 ENERGY STORAGE↗

Physics-informed machine learning exploration of Na storage mechanisms in disordered carbon

Sodium-ion batteries are a cost-effective, sustainable alternative to lithium-ion systems for large-scale energy storage. However, optimizing sodium storage in carbon-based anodes with microstructural complexity and atomic disorder remains a major challenge. The intrinsic inhomogeneity of these materials produces diverse local environments, making it difficult for conventional methods to predict and control ion dynamics. Hard carbon (HC) anodes, composed of ranges of ordered-to-disordered graphitic and amorphous nanodomains, offer tunable ion storage and rate capacity, yet rationale design remains a challenge due to poorly understood correlation between local atomic feature and ion transport mechanism. Here, to address this challenge, we introduce a data-driven framework that integrates validated machine-learned interatomic potentials, large-scale molecular dynamics simulations, and machine learning to elucidate sodium transport mechanisms as a function of carbon and sodium loading densities. By computing per-ion structural descriptors and applying unsupervised learning, we identify distinct diffusion modes governed by microscopic features. Supervised analysis and correlation mapping then establish quantitative links between these transport regimes and processing variables such as bulk carbon density and sodium content. This physics-informed approach establishes quantitative structure–transport relationships and offers actionable design principles for engineering high-performance HC anodes.

Data-driven framework↗

A Continuous Action Space Tree search for INverse desiGn (CASTING) framework for materials discovery

Abstract Material properties share an intrinsic relationship with their structural attributes, making inverse design approaches crucial for discovering new materials with desired functionalities. Reinforcement Learning (RL) approaches are emerging as powerful inverse design tools, often functioning in discrete action spaces. This constrains their application in materials design problems, which involve continuous search spaces. Here, we introduce an RL-based framework CASTING (Continuous Action Space Tree Search for inverse design), that employs a decision tree-based Monte Carlo Tree Search (MCTS) algorithm with continuous space adaptation through modified policies and sampling. Using representative examples like Silver (Ag) for metals, Carbon (C) for covalent systems, and multicomponent systems such as graphane, boron nitride, and complex correlated oxides, we showcase its accuracy, convergence speed, and scalability in materials discovery and design. Furthermore, with the inverse design of super-hard Carbon phases, we demonstrate CASTING’s utility in discovering metastable phases tailored to user-defined target properties and preferences.

36 MATERIALS SCIENCE↗

A Green, Fire–Retarding Ether Solvent for Sustainable High–Voltage Li–Ion Batteries at Standard Salt Concentration

Lithium-ion batteries (LIBs) are increasingly encouraged to enhance their environmental friendliness and safety while maintaining optimal energy density and cost-effectiveness. Although various electrolytes using greener and safer glyme solvents have been reported, the low charge voltage (usually lower than 4.0 V vs Li/Li + ) restricts the energy density of LIBs. Herein, tetraglyme, a less-toxic, non-volatile, and non-flammable ether solvent, is exploited to build safer and greener LIBs. It is demonstrated that ether electrolytes, at a standard salt concentration (1 m), can be reversibly cycled to 4.5 V vs Li/Li + . Anchored with Boron-rich cathode-electrolyte interphase (CEI) and mitigated current collector corrosion, the LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) cathode delivers competitive cyclability versus commercial carbonate electrolytes when charged to 4.5 V. Synchrotron spectroscopic and imaging analyses show that the tetraglyme electrolyte can sufficiently suppress the overcharge behavior associated with the high-voltage electrolyte decomposition, which is advantageous over previously reported glyme electrolytes. The new electrolyte also enables minimal transition metal dissolution and deposition. NMC811||hard carbon full cell delivers excellent cycling stability at C/3 with a high average Coulombic efficiency of 99.77%. In conclusion, this work reports an oxidation-resilient tetraglyme electrolyte with record-high 4.5 V stability and enlightens further applications of glyme solvents for sustainable LIBs by designing Boron-rich interphases.

36 MATERIALS SCIENCE↗

A 3D porous honeycomb carbon as Na-ion battery anode material with high capacity, excellent rate performance, and robust stability

Motivated by the synthesis of three-dimensional (3D) honeycomb carbon structures and the subsequent theoretical prediction of an energetically more favorable hexagonal carbon phase composed of 28 carbon atoms in the unit cell (hC28) with ordered pores, excellent mechanical properties, and metallic feature, we explore its potential for a Na-ion battery (NIB) anode material. Using density functional theory based calculations, we find that hC28 is a promising candidate whose specific capacity of 717 mAh/g is almost three times larger than that of hard carbon (~250 mAh/g). In addition, migration barrier of Na ions along the honeycomb channel is only 0.08 eV and the volume change during the charging/discharging process is merely 2.30%, which are much less than those of other carbon-based NIB anode materials. The average voltage is also low (0.36 eV) which can provide high operating voltage when connected to the cathode. Finally, these encouraging results would pave the way towards the development of hC28 as NIB anode with high capacity, excellent rate performance, low open-circuit voltage, and long-term cycle life.

36 MATERIALS SCIENCE↗

Multiple Functional Bonds Integrated Interphases for Long Cycle Sodium-Ion Batteries

Sodium-ion batteries (SIBs) have garnered significant interest as one of the most promising energy suppliers for power grid energy storage. However, the poor electrode/electrolyte interfacial stability leads to continual electrolyte decomposition and transition metal dissolution, resulting in rapid performance degradation of SIBs. In this work, we propose a strategy integrating multiple functional bonds to regulate electrode/electrolyte interphase by triple-coupling of succinonitrile (SN), sodium hexafluorophosphate (NaPF 6 ) and fluorinated ethylene carbonate (FEC). Theoretical calculation and experiment results show that the solvation structure of Na + and ClO 4 – is effectively reconfigured by the solvated FEC, SN and PF 6 – in PC-based carbonate electrolyte. The newly developed electrolyte demonstrates increased Na + -FEC coordination, weakened interaction of Na + -PC and participation of SN and PF 6 – anions in solvation, resulting in the formation of a conformal interfacial layer comprising of sodium oxynitrides (NaN x O y ), sodium fluoride (NaF) and phosphorus oxide compounds (NaP x O y ). Consequently, a 3 Ah pouch full cell of hard carbon//NaNi 1/3 Fe 1/3 Mn 1/3 O 2 exhibits an excellent capacity retention of 90.4 % after 1000 cycles. Detailed postmortem analysis of interface chemistry is further illustrated by multiple characterization methods. Finally, this study provides a new avenue for developing electrolyte formulations with multiple functional bonds integrated interphases to significantly improve the long-term cycling stability of SIBs.

25 ENERGY STORAGE↗

Novel Q-Carbon Anodes for Sodium-Ion Batteries

The lack of a standard anode for sodium-ion batteries (SIBs) has greatly hindered their applications. Herein, we show that a novel phase of carbon, namely Q-carbon, is an effective anode material for sodium-ion batteries. The Q-carbon, which is a metastable phase of carbon consisting of about 80% sp 3 - and 20% sp 2 -bonded carbon, is synthesized by nonequilibrium pulsed laser annealing and arc-discharge methods. Two types of Q-carbons, Q1 and Q2, were evaluated as anode material for SIBs. Q1 had a slow quench and was used as the control, whereas Q2 was Q-carbon with a rapid quenching. Q1 exhibits a high initial columbic efficiency of 81% and a low-capacity retention of less than 60%, whereas Q2 has a low initial columbic efficiency of 58% and a high-capacity retention of 81%. Q2 exhibits a stable capacity of 168 mAh·g −1 at a cycling rate of C/3 (124 mA·g −1 ), which is comparable to other hard carbon anodes reported in the literature. This unique synthesis method opens a pathway for the further tuning of Q-carbon with higher trapping/charging of Na + ions in improved SIBs.

25 ENERGY STORAGE↗

Sucrose‐Based Dense, Pure, and Highly‐Crystalline Graphitic Materials for Lithium‐Ion Batteries

At present, most synthetic graphite materials commonly used as anode active ingredients in lithium-ion cells are produced by graphitization of petroleum cokes. The carbon footprint associated with synthetic graphite production is significant. Thus, bio-derived and cheap precursors, such as saccharides, would be an attractive alternative for the sustainable production of graphitic carbons. However, they are non-graphitizing at temperatures as high as 3000 °C, preserving the curved, fullerene-like structure of graphene layers and microporosity. Consequently, many lithium ions are consumed during the formation of solid electrolyte interphase films and passivated in the nanovoids. Here, a method for the production of pure, crystalline, graphitic materials based on sucrose disposed of microporosity is presented, which also works with a variety of saccharides and other organic precursors of hard carbons—generally considered incapable of such transformation. This process employs catalytic graphitization by Si particles at high temperatures. Finally, the electrochemical response of such derived sucrose-based graphite in Li-ion half-cells demonstrated its feasibility to serve as an anode active material for rechargeable Li-ion batteries.

Si particles↗

Temperature-dependent Battery Performance of a Na 3 V 2 (PO 4 ) 2 F 3 @MWCNT Cathode and In-situ Heat Generation on Cycling

Excellent structural stability, high operating voltage, and high capacity have made Na 3 V 2 (PO 4 ) 2 F 3 a promising cathode material for sodium-ion batteries. However, high-temperature battery performances and heat generation measurements have not been systematically reported yet. Carbon-coated Na 3 V 2 (PO 4 ) 2 F 3 @MWCNT (multi-walled carbon nanotube) samples are fabricated by a hydrothermal-assisted sol-gel method and the electrochemical performances are evaluated at three different temperatures (25, 45, and 55 °C). Furthermore, the well-crystallized Na 3 V 2 (PO 4 ) 2 F 3 @MWCNT samples exhibit good cycling stability at both low and high temperatures; they deliver an initial discharge capacity of 120–125 mAhg -1 at a 1 C rate with a retention of 53 % capacity after 1,400 cycles with 99 % columbic efficiency. The half-cell delivers a capacity of 100 mAhg -1 even at a high rate of 10 C at room temperature. Furthermore, the Na 3 V 2 (PO 4 ) 2 F 3 @MWCNT samples show good long-term durability; the capacity loss is an average of 0.05 % per cycle at a 1 C rate at 55 °C. Additionally, ionic diffusivity and charge transfer resistance are evaluated as functions of state of charge, and they explain the high electrochemical performance of the Na 3 V 2 (PO 4 ) 2 F 3 @MWCNT samples. In-situ heat generation measurements reveal reversible results upon cycling owing to the high structural stability of the material. Excellent electrochemical performances are also demonstrated in the full-cell configuration with hard carbon as well as antimony Sb/C anodes.

25 ENERGY STORAGE↗

Fast Oxygen Redox Kinetics Induced by CoO 6 Octahedron With π –Interaction in P2–Type Sodium Oxides

Enhancing the kinetics of lattice oxygen redox (LOR) in P2-type layered sodium oxide cathodes is crucial for the advancement of sodium-ion batteries (SIBs) with superior energy and power densities. Electronic structure regulation stands out as a highly effective approach to address the inherent limitations of P2-type layered oxides with LOR, including sluggish kinetics, phase transitions, voltage hysteresis, and local structural distortion. In this work, a strategy involving the introduction of CoO 6 octahedra with π-interaction into Na 0.6 Li 0.1 Fe 0.3–x Co x Mn 0.6 O 2 (x = 0, 0.15, 0.3) cathodes to facilitate Na-ion transport is proposed. Furthermore, the impact of FeO 6 octahedra with σ-interaction in P2-type cathodes on electrochemical performance is comprehensively investigated. Through multimodal in-situ and ex-situ characterization techniques, it is revealed that Co–O with π-interaction effectively mitigates P2-OP4 phase transitions by strengthening Na–O, reduces voltage hysteresis, and stabilizes the local structure. Consequently, Na 0.6 Li 0.1 Co 0.3 Mn 0.6 O 2 demonstrates enhanced Na-ion diffusion kinetics, leading to improved rate performance and a reversible capacity of 55 mAh g –1 at 10 C, significantly outperforming cathodes with Fe–O σ-interaction. Moreover, when coupled with hard carbon, the full cell achieves a remarkable energy density of 395 Wh kg –1 (on cathode) at 0.1 C, with a capacity retention of 75% over 100 cycles at 1 C.

25 ENERGY STORAGE↗

Insight Into Sulfur‐Containing Additive to Boost Anti‐Oxidation Ability of the Ether‐Based Electrolyte for Sodium‐Ion Full Batteries

Ether-based electrolytes are considered as promising candidates for sodium-ion batteries (SIBs) due to their high ionic conductivity and good compatibility with hard carbon (HC) anode. However, they suffer from poor anti-oxidative ability with unstable cathode electrolyte interface, inducing successive electrolyte decomposition and rapid capacity fading. Herein, the sulfur-containing additive (1,3-propanediol cyclic sulfate, PCS) is introduced to boost the stability of the electrode-electrolyte interface (EEI) in ether-based electrolyte. PCS largely participates in the inner Na + sheath, causing more diglyme (G2) molecules and fewer PF 6 - anions to occupy the inner Na + solvation sheath, avoiding the decomposition of G2 molecules at high operation voltage. Moreover, PCS is beneficial for simultaneously constructing thin and robust sulfur-containing EEI on both Prussian blue (PB) cathode and HC anode, maintaining the structural stability of PB and alleviating the dissolution of transition metals. These enable PB||HC pouch cells to deliver a capacity retention of 60.3% after 400 cycles, significantly higher than the 32.1% in PCS-free electrolytes. In conclusion, this work discloses the underlying mechanism of PCS to evoke the anti-oxidation ability of ether-based electrolyte and provides a promising method for realizing advanced sodium-ion full cells.

anti-oxidation ability↗

Na 3 Zr 2 Si 2 PO 12 Solid Electrolyte Membrane for High‐Performance Seawater Battery

Abstract Seawater batteries (SWBs) have gained tremendous interest in the electrochemical energy storage research field because of their low cost, natural abundance, and potential use for long‐duration energy storage. Advancing a SWB to demonstration projects is plagued by the poor electrochemical performance stemming from the poor interfaces of the solid electrolyte (SE), as well as the structural and chemical instabilities and sluggish ionic transport properties. In this study, the anode compartment of a surrogate SWB is constructed with a Na | SE | hard carbon configuration, and tailored dopants are introduced into the Nasicon‐type Na 3 Zr 2 Si 2 PO 12 (NZSP) SE membrane. After doping with TiO 2 , a much more densely packed pellet with uniformly distributed porous structure is obtained. Changes in surface chemistry and local structure in the bulk are observed, which are believed to contribute to the improved ionic conductivity and higher critical current density of the TiO 2 ‐doped NZSP. Stable cycling performance with reversible capacities based on different Na storage mechanisms are also demonstrated.

25 ENERGY STORAGE↗

Sodium Rich Vanadium Oxy‐Fluorophosphate – Na 3.2 Ni 0.2 V 1.8 (PO 4 ) 2 F 2 O – as Advanced Cathode for Sodium Ion Batteries

Abstract Conventional sodium‐based layered oxide cathodes are extremely air sensitive and possess poor electrochemical performance along with safety concerns when operating at high voltage. The polyanion phosphate, Na 3 V 2 (PO 4 ) 3 stands out as an excellent candidate due to its high nominal voltage, ambient air stability, and long cycle life. The caveat is that Na 3 V 2 (PO 4 ) 3 can only exhibit reversible capacities in the range of 100 mAh g −1 , 20% below its theoretical capacity. Here, the synthesis and characterizations are reported for the first time of the sodium‐rich vanadium oxyfluorophosphate, Na 3.2 Ni 0.2 V 1.8 (PO 4 ) 2 F 2 O, a tailored derivative compound of Na 3 V 2 (PO 4 ) 3 , with extensive electrochemical and structural analyses. Na 3.2 Ni 0.2 V 1.8 (PO 4 ) 2 F 2 O delivers an initial reversible capacity of 117 mAh g −1 between 2.5 and 4.5 V under the 1C rate at room temperature, with 85% capacity retention after 900 cycles. The cycling stability is further improved when the material is cycled at 50 °C within 2.8–4.3 V for 100 cycles. When paired with a presodiated hard carbon, Na 3.2 Ni 0.2 V 1.8 (PO 4 ) 2 F 2 O cycled with a capacity retention of 85% after 500 cycles. Cosubstitution of the transition metal and fluorine in Na 3.2 Ni 0.2 V 1.8 (PO 4 ) 2 F 2 O as well as the sodium‐rich structure are the major factors behind the improvement of specific capacity and cycling stability, which paves the way for this cathode in sodium‐ion batteries.

25 ENERGY STORAGE↗

Stable Cycling of Sodium All‐Solid‐State Batteries with High‐Capacity Cathode Presodiation

Sodium all-solid-state batteries (NaSSBs) with an alloy-type anode (e.g., Sn and Sb) offer superior capacity and energy density compared to hard carbon anode. However, the irreversible loss of Na + at the alloy anode during the initial cycle results in diminished capacity and stability, impairing full-cell performance. Here, this study presents an easy-to-implement cathode presodiation strategy by employing a Na-rich material to address these challenges. Leveraging the high theoretical capacity and suitable voltage window, Na 2 S is chosen as the Na donor, which is activated by creating a mixed electron-ion conducting network, delivering a high capacity of 511.7 mAh g −1 . By adding a small amount (i.e., 3 wt.%) of Na 2 S to the cathode composite, a NaCrO 2 || Sn full cell demonstrated capacity improvement from 90.8 to 118.2 mAh g −1 (based on cathode mass). The capacity-balanced full cell can thus cycle to more than 300 times with >90% capacity retention. This work provides a practical solution to enhance the full-cell performance and advance the transformation from half-cell to full-cell applications of NaSSBs.

25 - ENERGY STORAGE↗

Hypochlorite Redox Chemistry Enables High-Voltage and High-Power Saltwater Batteries

Saltwater batteries (SWBs) are promising alternatives to lithium-ion batteries for large-scale stationary energy storage. However, the performance of conventional oxygen redox-based saltwater battery systems is often constrained by sluggish oxygen evolution and reduction reactions (OER/ORR) at the cathode, leading to low voltage efficiency and limited power density. Here, OER and ORR are replaced by hypochlorite-based redox reactions through the introduction of sodium hypochlorite into saltwater. Operando pH and dissolved oxygen measurements confirm that OER and ORR are minimized and that hypochlorite redox reactions dominate the cathode behavior. Owing to the higher operating potential and faster reaction kinetics, the hypochlorite-redox-based SWBs delivers a higher discharge voltage of 3.3 V and reduced charge-discharge voltage polarization to 0.66 V. Further improvement is achieved by adjusting the saltwater pH to near-neutral conditions, increasing the discharge voltage to 3.5 V and more than doubling the peak power. The hypochlorite redox environment also exhibits chemical stability with key cell components, including the solid electrolyte and cathode current collectors. Operation of series-connected cells and cells employing hard carbon anodes demonstrates scalability and compatibility with alternative anode materials. These results provide a strong foundation for next-generation SWBs targeting large-scale stationary energy storage applications.

Go, Wooseok [ORNL]↗

Anionic‐Based Layered Oxide Cathodes with High Electrochemical Performance through Dual‐Site Substitutions for Sodium‐Ion Batteries

Mn-rich layered oxide cathodes with anionic redox promise high energy density for sodium-ion batteries (SIBs) due to ultra-high capacity derived from both Mn and O redox couples. Nevertheless, instability of the reactions that lead to poor electrochemical stability hinders the cathodes from practical applications. Here, the Al and Zn dual-site substitution strategy is proposed to enhance electrochemical performance. Here, the designed cathode, Na 0.73 Zn 0.03 Li 0.25 Mn 0.76 Al 0.01 O 2 (AlZn), delivers a high discharge capacity of 242 mAh g −1 with an impressive rate capability (162 mAh g −1 at 1000 mA g −1 ) and excellent capacity retention (89.69% over 150 cycles). In addition, full-cell SIB based on AlZn coupled with hard carbon exhibits a high energy density of 317 Wh kg −1 (based on both cathode and anode mass) and a reasonable capacity retention of 80.8% after 250 cycles. Revealed by advanced investigations, the synergy of robust Al–O in TM layers and O–Zn–O pillars in Na layers helps alleviate severe inactive spinel/rock-salt phase transformation and intragranular cracks in the AlZn cathode. This consequently leads to greatly enhanced electrochemical performance over the pristine cathode. This work provides insight into improving electrochemical properties of anionic-redox-based layered oxides by Al/Zn co-substitutions toward high-energy SIBs.

25 ENERGY STORAGE↗

Controlling Surface Phase Transition and Chemical Reactivity of O3-Layered Metal Oxide Cathodes for High-Performance Na-Ion Batteries

O3-layered metal oxides are promising cathode materials for high-energy Na-ion batteries (SIBs); however, they suffer from fast capacity fade. In this work, we develop a high-performance O3-NaNi 0.68 Mn 0.22 Co 0.10 O 2 cathode for SIBs toward practical applications by suppressing the formation of a rock salt layer at the cathode surface with an advanced electrolyte. The cathode can deliver a high specific capacity of ~196 mAh g –1 and demonstrates >80% capacity retention over 1000 cycles. NaNi 0.68 Mn 0.22 Co 0.10 O 2 –hard carbon full-cells with practical loading (>2.5 mAh cm –2 ) and lean electrolyte (~40 μL) demonstrate ~82% capacity retention after 450 cycles. A 60 mAh single-layer pouch cell has also been fabricated and demonstrated stable performance. This work represents a significant leap in SIB development and brings new insights to the development of advanced layered metal oxide cathodes for alkaline-ion batteries.

25 ENERGY STORAGE↗

Highly Reversible Sodium Ion Batteries Enabled by Stable Electrolyte-Electrode Interphases

Sodium (Na) ion battery is a very promising technology for the alternative energy storage systems because of the abundance and low cost of Na element in the Earth’s crust. However, the limited cycle life and safety concerns still hinder its large-scale applications. Here, we report a nonflammable localized high concentration electrolyte (sodium bis(fluorosulfonyl)imide - triethyl phosphate/1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (1:1.5:2 in molar ratio)), which enables a very high initial Coulombic efficiency (CE) of 97.8% for Na||Na-CNFM (O3-NaCu1/9Ni2/9Fe1/3Mn1/3O2) cells and stable cycling of Na||hard carbon (HC) cells with a capacity retention of 95.4% after 500 cycles. The HC||Na-CNFM full cells using this electrolyte retain 82.5% capacity after 200 cycles with a CE of ~99.9% compared to 48.4% capacity retention in the carbonate electrolyte (1 M NaPF6/EC+DMC (1:1 in weight)). The extremely high CE and stability of HC||Na-CNFM cells in this electrolyte can be attributed to the stable interphase layers formed on both HC anode and Na-CNFM cathode. These layers minimize undesirable reaction between HC and electrolyte, and block the dissolution of transition metal from cathode. The insight obtained in this work can be used to further improve cycling stability and safety of rechargeable batteries.

Jin, Yan↗