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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 181 records · Page 10
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Unraveling transition-metal-mediated stability of spinel oxide via in situ neutron scattering

The energy materials performance is intrinsically determined by structures from the average lattice structure to the atom arrangement, valence, and distribution of the containing transition metal (TM) elements. Understanding the mechanism of the structure transition and atom rearrangement via synthesis or processing is key to expediting the exploration of excellent energy materials. In this work, in situ neutron scattering is employed to reveal the real-time structure evolution, including the TM-O bonds, lattice, TM valence and the migration of the high-voltage spinel cathode LiNi 0.5 Mn 1.5 O 4 . The transition-metal-mediated spinel destabilization under the annealing at the oxygen-deficient atmosphere is pinpointed. Additionally, the formation of Mn 3+ is correlated to the TM migration activation, TM disordered rearrangement in the spinel, and the transition to a layered-rocksalt phase. The further TM interdiffusion and Mn 2+ reduction are also revealed with multi-stage thermodynamics and kinetics. The mechanisms of phase transition and atom migrations as functions of temperature, time and atmosphere present important guidance on the synthesis in various-valence element containing oxides.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Halting Oxygen Evolution to Achieve Long Cycle Life in Sodium Layered Cathodes

Oxygen redox chemistries at high voltage have materialized as a revolutionary paradigm for cathodes with high-energy density; however, they are plagued by the challenges of labile oxygen loss and rapid degradations upon cycling, even after concerted endeavors from the research community. Here we propose a multi-concentration stratagem propelled by entropy reinforcement to enhance the electronic structure disorder (ESD) at high desodiation states for impeding undesired oxygen mobility and ensuring controlled oxygen activity, elucidated by density functional theory calculations. The increased disorder strengthens the reversible electrochemistry of lattice oxygen redox, leading to effectively suppressed P−O structural evolution and highly stable localized TMO 6 octahedral environments, as demonstrated by soft/hard X-ray absorption spectroscopy. Furthermore, through a comparative analysis of sodium-layered cathodes with different configuration entropy, we reveal that a high-entropy state induced by cationic disordering has the capacity to perturb cationic redox boundaries, significantly restraining the formation of detrimental O′3 phases. As a consequence, the high-voltage cycling stability has been greatly upgraded, up to 4.4 V versus Na + /Na, with an impressive 90.1 % capacity retention at 1 C over 100 cycles and 76.1 % capacity retention at 2 C over 300 cycles. In conclusion, the resilient oxygen redox, enabled through the control of ESD, broadens the horizons for entropy engineering and lays the foundation for advancements in high-energy, long-cycling, and safe batteries.

25 ENERGY STORAGE↗
DOE OSTI2024

Stabilizing Nickel‐Rich Cathodes in Aqueous Process through Nanocellulose as Water Barrier

Nickel-rich LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NMC 811) cathode offers high voltage and high specific capacity, making it promising for high energy density batteries. However, large-scale manufacturing of aqueous-processed NMC 811 electrodes remains challenging due to proton exchange causing material decomposition and capacity loss. This work addresses this issue by constructing an in situ nanocellulose protective layer for NMC 811 particles via electrostatic interactions during the slurry preparation. For the first time, the interatomic spacing between inter-chains of nanocellulose is measured through wide-angle X-ray scattering and demonstrate the ability to effectively confine interlayer water using atomistic simulations. Moreover, this nanocellulose coverage simultaneously minimizes Li + surface segregation and mitigates water infiltration. Owing to less material decomposition during the aqueous processing, nanocellulose-protected NMC electrodes exhibit higher initial coulombic efficiency (83% vs 62% at 0.1C) and capacity (133 vs 59 mAh g −1 at 6C) than unprotected electrodes. Additionally, optimized aqueous-processed NMC electrodes offer comparable or even superior electrochemical properties compared to the electrodes fabricated using the conventional toxic organic solvent, N-methyl-2-pyrrolidone. Consequently, the developed approach enables affordable, sustainable aqueous processing for Nickel-rich NMC 811 cathodes with excellent electrochemical performances.

25 ENERGY STORAGE↗
DOE OSTI2024

Amorphous Oxyhalide Matters for Achieving Lithium Superionic Conduction

The recently surged halide-based solid electrolytes (SEs) are great candidates for high-performance all-solid-state batteries (ASSBs), due to their decent ionic conductivity, wide electrochemical stability window, and good compatibility with high-voltage oxide cathodes. In contrast to the crystalline phases in halide SEs, amorphous components are rarely understood but play an important role in Li-ion conduction. Here, we reveal that the presence of amorphous component is common in halide-based SEs that are prepared via mechanochemical method. The fast Li-ion migration is found to be associated with the local chemistry of the amorphous proportion. Taking Zr-based halide SEs as an example, the amorphization process can be regulated by incorporating O, resulting in the formation of corner-sharing Zr–O/Cl polyhedrons. This structural configuration has been confirmed through X-ray absorption spectroscopy, pair distribution function analyses, and Reverse Monte Carlo modeling. The unique structure significantly reduces the energy barriers for Li-ion transport. As a result, an enhanced ionic conductivity of (1.35 ± 0.07) × 10 –3 S cm –1 at 25 °C can be achieved for amorphous Li 3 ZrCl 4 O 1.5 . In addition to the improved ionic conductivity, amorphization of Zr-based halide SEs via incorporation of O leads to good mechanical deformability and promising electrochemical performance. In conclusion, these findings provide deep insights into the rational design of desirable halide SEs for high-performance ASSBs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Asymmetric Lithium Extraction and Insertion in High Voltage Spinel at Fast Rate

Spinel-structured ordered-LiNi 0.5 Mn 1.5 O 4 (o-LNMO) has experienced a resurgence of interest in the context of reducing scarce elements such as cobalt from lithium-ion battery. O-LNMO undergoes two two-phase reaction at slow rates. However, it is not known if such phenomenon also applies at fast rates. Herein, we investigate the rate-dependent phase transition behavior of o-LNMO through in operando time-resolved X-ray diffraction. The results indicate that a narrow region of solid solution reaction exists for charge and discharge at both slow and fast rate. The overall phase transition is highly asymmetric at fast rates. During fast charge, it is a particle-by-particle mechanism resulting from asynchronized reaction among the particles. Finally, during fast discharge, it is likely a core-shell mechanism involving transition from Li 0+x Ni 0.5 Mn 1.5 O 4 to Li 1+x Ni 0.5 Mn 1.5 O 4 in the outer layer of particles. The Li 0.5 Ni 0.5 Mn 1.5 O 4 phase is suppressed during fast discharge and only appears through Li redistribution upon relaxation.

25 ENERGY STORAGE↗
DOE OSTI2024

Generalizable, tunable control of divalent cation solvation structure via mixed anion contact ion pair formation

Multivalent batteries are a promising new technology for energy storage, but they face challenges to developing suitable electrolytes that can support reversible deposition/dissolution at the metal anode and enable compatibility with high voltage oxide cathode materials. Here, in this work, we investigate the solvation behavior of Zn 2+ , Mg 2+ , Ca 2+ and Cu 2+ in mixed anion electrolytes containing TFSI - and Cl - . Raman and nuclear magnetic resonance spectroscopies are utilized to probe the bulk solvation structure of these electrolytes and demonstrate that mixed anion contact ion pairs (CIPs) are formed in all four systems, indicating this behavior is likely general to divalent cations. Furthermore, the relative population of mixed anion CIPs can be tuned by controlling the relative ratio of TFSI : Cl, with significant CIP populations observed even at low relative fractions of Cl - . These findings imply that modifying the anion chemistry can easily adjust the solvation structure of bulk cations, which has important implications for the development of next-generation electrolytes. By understanding the factors that influence the formation of mixed anion CIPs, we can design systems that promote the formation of electrochemically-active solvation structures that can enable multivalent batteries with improved performance and lifetimes.

25 ENERGY STORAGE↗
DOE OSTI2023

Study of dielectric breakdown in liquid xenon with XeBrA: The xenon breakdown apparatus

Maintaining the electric fields necessary for the current generation of noble liquid time projection chambers (TPCs), with drift lengths exceeding 1 m, requires a large negative voltage applied to their cathode. Delivering such high voltage is associated with an elevated risk of electrostatic discharge and electroluminescence, which would be detrimental to the performance of the experiment. The Xenon Breakdown Apparatus (XeBrA) is a 5-l, high voltage test chamber built to investigate the contributing factors to electrical breakdown in noble liquids. Here, in this work, we present the main findings after conducting scans over stressed electrode areas, surface finish, pressure, and high voltage ramp speed in the medium of liquid xenon. Area scaling and surface finish were observed to be the dominant factors affecting breakdown, whereas no significant changes were observed with varying pressure or ramp speed. A general rise in both the anode current and photon rate was observed in the last 30 s, leading up to a breakdown, with a marked increase in the last couple of seconds. In addition, the position of breakdowns was reconstructed with a system of high-speed cameras and a moderate correlation with the Fowler–Nordheim field emission model was found. Tentative evidence for bubble nucleation being the originating mechanism of breakdown in the liquid was also observed. We deem the results presented in this work to be of particular interest for the design of future, large TPCs, and practical recommendations are provided.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2025

DUNE Photon Detection System

The Deep Underground Neutrino Experiment (DUNE) aims to provide a broad physics program primarily addressed to probing CP violation in the neutrino sector and identifying the neutrino mass hierarchy. The search for proton decay, the observation of supernova neutrino bursts, and the investigation of solar neutrinos represent other additional goals of DUNE experiment, which can be enhanced by the use and the high performances of the Photon Detection System (PDS). Using the technology based on liquid argon Time Projection Chamber (LArTPC), the experiment plans to observe neutrino interactions inside detectors located 1300 km away from the Long Baseline Neutrino Facility (LBNF) at Fermi National Accelerator Laboratory (FNAL), where the neutrinos are produced. The experiment consists of two main parts, respectively the far and near detectors. The far site will comprise four detector modules. The first module is constituted by a vertical drift single-phase LArTPC, while the second module provides a horizontal drift single-phase LArTPC. The configurations of the other modules are still under definition. Neutrino detection in LArTPCs is achieved by identifying the charge and light generated from its interactions with liquid argon. The wire planes of the instrumented anode and the PDS detect these signals, respectively. The PDS in the first two modules, detailed in the present document, uses a modified version of the so-called ARAPUCA technology, named X-ARAPUCA. This system consisting of a highly reflecting box with an entrance window made by dichroic filters and wavelength shifters, creates a trap to detect the VUV (128 nm) scintillation photons. The X-ARAPUCA of the first module is called Supercell, and it has dimensions of 488×100 mm 2 , while Megacell is the second module version, with an active area of 60×60 cm 2 . This latter configuration also represents a significant technological advancement. Since half of the modules are placed on the cathode at high voltage, they are powered and read out using innovative power-over-fiber (PoF) and signal-over-fiber (SoF) technologies. Meanwhile, the other half are installed in a membrane behind the field cage, with a total transparency of around 70%.

Neutrino detectors↗
DOE OSTI2008

Vehicle Technologies Program: Energy Storage R&D (2008 Annual Progress Report)

One of the primary objectives of the Energy Storage effort is the development of durable and affordable advanced batteries (and ultracapacitors) for use in a full range of vehicle applications, from start/stop to full-power HEVs, EVs, and PHEVs. The battery technology development activity spans three areas: system development of full battery systems; benchmark testing of emerging technologies in order to remain abreast of the latest industry developments; and Small Business Innovative Research (SBIR) to fund early-stage R&D for small businesses/entrepreneurs.

25 ENERGY STORAGE↗
DOE OSTI2023

A04-0491 - Reduced Electrolyte Reactivity of Pitch-Carbon Coated Si Nanoparticles for Li-Ion Battery Anodes

Silicon-based anodes for Li-ion batteries (LIB) have the potential to increase the energy density over graphite-based LIB anodes. However, silicon anodes exhibit poor cycle and calendar lifetimes due to mechanical instabilities and high chemical reactivity with the carbonate-based electrolytes that are typically used in LIBs. In this work, we synthesize a pitch-carbon coated silicon nanoparticle composite active material for LIB anodes that exhibits reduced chemical reactivity with the carbonate electrolyte compared to an uncoated silicon anode. Silicon primary particle sizes <10 nm minimize micro-scale mechanical degradation of the anode composite, while conformal coatings of pitch-carbon minimized the parasitic reactions between the silicon and the electrolyte. When matched with a high voltage NMC622 cathode, the pitch-carbon coated Si anode retains -75% of its initial capacity over 1000 cycles. Efforts to increase the areal loading of the pitch-carbon coated silicon anodes to realize real energy density improvements over graphite anodes results in severe mechanical degradation on the electrode level. Developing procedures to engineer the architecture of the composite silicon anode may be a solution to this mechanical challenge.

DIRECT ENERGY CONVERSION,ENERGY STORAGE↗
DOE OSTI2021

Formation of LiF Surface Layer During Direct Fluorination of High-Capacity Co-Free Disordered Rocksalt Cathodes

Disordered rocksalt (DRX) cathodes have attracted interest due to their high capacity and compositional flexibility (e.g., Co-free chemistries). However, the sloping voltage profile and gradual capacity fade during cycling have hindered widespread adoption of these materials. Simulations predict that fluorine substitution in DRX cathodes will improve their capacity, rate performance and cyclability. In this study we use a fluidized bed reactor to fluorinate a model Lirich DRX composition (Li1.15Ni0.375Ti0.375Mo0.1O2, NTMO) to investigate how fluorine content impacts the cathode’s structure and electrochemical performance. Instead of substituting O with F to form oxyfluoride phases, direct fluorination of DRX cathodes leads to formation of LiF surface films which improves the specific energy and capacity retention. This study demonstrates the feasibility of direct fluorination to improve the electrochemical performance of high voltage cathodes by tuning the material’s surface chemistry.

Co-free disordered rock-salt cathode, direct fluor↗
DOE OSTI2021

Operando X-ray Diffraction Studies of the Mg-Ion Migration Mechanisms in Spinel Cathodes for Rechargeable Mg-Ion Batteries

A promising high-voltage spinel oxide cathode material MgCrMnO 4 with 18% Mg/Mn inversion was synthesized successfully. A new custom operando battery device was designed to study the cation migration mechanisms of the MgCrMnO 4 cathode using 0.1 M Mg(TPFA) 2 electrolyte dissolved in triglyme and activated carbon as the anode. For the first time in multivalent batteries, high-quality operando diffraction data enabled the accurate quantification of cation contents in the host structure. Besides the exceptional reversibility of 12% Mg 2+ insertion in Mg 1- x CrMnO 4 ( x ≤ 1), a partially reversible insertion of excess Mg 2+ during overdischarging was also observed. Moreover, the insertion/extraction reaction was experimentally shown to be accompanied by a series of cation redistributions in the spinel framework, which were further supported by density functional theory calculations. Furthermore, the inverted Mn is believed to be directly involved in the cation migrations, which would cause voltage hysteresis and irreversible structural evolution after overdischarging. Tuning the Mg/Mn inversion rate could provide a direct path to further optimize spinel oxide cathodes for Mg-ion batteries, and more generally, the operando techniques developed in this work should play a key role in understanding the complex mechanisms involved in multivalent ion insertion systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Unblocking Oxygen Charge Compensation for Stabilized High‐Voltage Structure in P2‐Type Sodium‐Ion Cathode

Abstract Layered transition‐metal (TM) oxides are ideal hosts for Li + charge carriers largely due to the occurrence of oxygen charge compensation that stabilizes the layered structure at high voltage. Hence, enabling charge compensation in sodium layered oxides is a fascinating task for extending the cycle life of sodium‐ion batteries. Herein a Ti/Mg co‐doping strategy for a model P2‐Na 2/3 Ni 1/3 Mn 2/3 O 2 cathode material is put forward to activate charge compensation through highly hybridized O 2 p TM 3 d covalent bonds. In this way, the interlayer OO electrostatic repulsion is weakened upon deeply charging, which strongly affects the systematic total energy that transforms the striking P2–O2 interlayer contraction into a moderate solid‐solution‐type evolution. Accordingly, the cycling stability of the codoped cathode material is improved superiorly over the pristine sample. This study starts a perspective way of optimizing the sodium layered cathodes by rational structural design coupling electrochemical reactions, which can be extended to widespread battery researches.

25 ENERGY STORAGE↗
DOE OSTI2022

Tailoring Disordered/Ordered Phases to Revisit the Degradation Mechanism of High‐Voltage LiNi 0.5 Mn 1.5 O 4 Spinel Cathode Materials

Abstract In the spinel oxide cathode family, LiNi 0.5 Mn 1.5 O 4 (LNMO) shows a high operating voltage (≈4.7 V vs Li/Li + ) and excellent Li‐ion mobility with stable 3D conducting channels. Ni/Mn cation disordered and ordered phases usually coexist in LNMO materials, and they have distinct structural and electrochemical properties, resulting in different battery performances for LNMO materials with different phase compositions. Identifying the correlation between phase compositions and electrochemical properties is of significance to the improvement of battery performance and understanding of degradation mechanisms. Herein, the disordered/ordered phase compositions in LNMO materials are tailored by post‐annealing strategies and their impacts on electrochemical performance and degradation mechanisms from the surface to the bulk are systematically investigated. The ordered phase increases rapidly as Mn 3+ is oxidized to Mn 4+ through a post‐annealing process. LNMO with an intermediate fraction of disordered and ordered phases gives rise to improved cycling stability. This article further reports that a high ordered phase fraction can preferentially protect Ni from dissolution during cycling. However, these results suggest that the transition metal dissolution and surface structural change of LNMO do not exhibit a direct correlation with cycling stability. These results indicate the capacity fading mainly correlates with the bulk structural distortion, leading to decreased Li‐ion kinetics.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Exploring the Basic Physical Mechanisms of Cathode- and Anode-Initiated High-Voltage Surface Flashover

Surface flashover in vacuum imposes a substantial physical limit on modern, large-scale pulsed power. One of the ramifications is a minimum size requirement for new machines, which in itself becomes a hard barrier to the modernization and improvement of existing infrastructure. Pulsed power topologies require the physical mechanisms of both anode- and cathode-initiated flashover to be considered. Originally, the geometrical implications of field emission at the cathode triple junction (CTJ) motivated the usage of configurations that avoid electrons impinging on the insulating material. This will largely suppress the cathode-initiated flashover, which is best described by the secondary electron avalanche mechanism, gas desorption, and final breakdown in the desorbed gas. It depends on the cascade growth of a conducting plasma along the length of the insulator from the cathode. Mitigating the cathode-initiated flashover typically comes at the cost of a significant field enhancement at the anode triple junction (ATJ). In a typical implementation, the anode field may be three times higher than the cathode field for a given voltage, making the corresponding anode-initiated flashover much more common than otherwise. In the case of pulsed, anode-initiated flashover, experimental evidence suggests that charge is directly extracted from the insulator resulting in the insulator taking on a net positive charge advancing the anode potential. Furthermore, along with accompanying gas desorption from the surface, the potential will then propagate from the anode toward the cathode until the effective length of the gap is sufficiently reduced to support flashover. The underlying physical mechanisms of cathode- and anode-directed flashover are discussed in light of previously gathered experimental data and recent experiments with pulsed, high-gradient, anode-initiated flashover.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2020

Research advances on cobalt-free cathodes for Li-ion batteries - The high voltage LiMn 1.5 Ni 0.5 O 4 as an example

LiMn 1.5 Ni 0.5 O 4 is one of the most promising cathode materials for use in either next generation lithium-ion batteries or all solid-state batteries. However, despite the significant Research and Development (R&D) carried out throughout the last two decades the material has not made serious inroads into market. One of the major reasons is the lack of consistency in the reported intrinsic properties and electrochemical performance owing to major controversies in synthesis, crystal structure and bulk and interfacial properties of LiMn 1.5 Ni 0.5 O 4 , notably in contact with electrolytes. This paper is a compelling review providing an assessment on the mainstream R&D dealing with the various crystal structures of LiMn 1.5 Ni 0.5 O 4 and their evolutions observed during synthesis and cycling in correlation with their electrochemical performance. Influence of electrolytes and additives along with modifications through doping and surface treatments are interrelated, and the electronic and ionic transport properties of the ordered and disordered LiMn 1.5 Ni 0.5 O 4 phases are discussed. Overall, this review provides a detailed assessment on LiMn1.5Ni0.5O4 and the underlying mechanisms governing its electrochemical performance broadly providing a focused framework for further advancement towards commercialization.

25 ENERGY STORAGE↗
DOE OSTI2020

Universal chemomechanical design rules for solid-ion conductors to prevent dendrite formation in lithium metal batteries

Dendrite formation during electrodeposition while charging lithium metal batteries compromises their safety. Although high-shear-modulus ( G s ) solid-ion conductors (SICs) have been prioritized to resolve the pressure-driven instabilities that lead to dendrite propagation and cell shorting, it is unclear whether these or alternatives are needed to guide uniform lithium electrodeposition, which is intrinsically density-driven. Here, we show that SICs can be designed within a universal chemomechanical paradigm to access either pressure-driven dendrite-blocking or density-driven dendrite-suppressing properties, but not both. This dichotomy reflects the competing influence of the SIC’s mechanical properties and the partial molar volume of Li + $(V_{\mathrm{Li}^+})$ relative to those of the lithium anode ( G Li and V Li ) on plating outcomes. Within this paradigm, we explore SICs in a previously unrecognized dendrite-suppressing regime that are concomitantly ‘soft’, as is typical of polymer electrolytes, but feature an atypically low $(V_{\mathrm{Li}^+})$ that is more reminiscent of ‘hard’ ceramics. Li plating (1 mA cm -2 ; T = 20 °C) mediated by these SICs is uniform, as revealed using synchrotron hard X-ray microtomography. As a result, cell cycle life is extended, even when assembled with thin Li anodes (~30 µm) and either high-voltage NMC-622 cathodes (1.44 mAh cm -2 ) or high-capacity sulfur cathodes (3.02 mAh cm -2 ).

25 ENERGY STORAGE↗
DOE OSTI2022

Towards extreme fast charging of 4.6V LiCoO 2 via mitigating high-voltage kinetic hindrance

High-voltage LiCoO 2 (LCO) is an attractive cathode for ultra-high energy density lithium-ion batteries (LIBs) in the 3C markets. However, the sluggish lithium-ion diffusion at high voltage significantly hampers its rate capability. Herein, combining experiments with density functional theory (DFT) calculations, we demonstrate that the kinetic limitations can be mitigated by a facial Mg 2+ +Gd 3+ co-doping method. The as-prepared LCO shows significantly enhanced Li-ion diffusion mobility at high voltage, making more homogenous Li-ion de/intercalation at a high-rate charge/discharge process. The homogeneity enables the structural stability of LCO at a high-rate current density, inhibiting stress accumulation and irreversible phase transition. When used in combination with a Li metal anode, the doped LCO shows an extreme fast charging (XFC) capability, with a superior high capacity of 193.1 mAhg -1 even at the current density of 20C and high-rate capacity retention of 91.3% after 100 cycles at 5C. In conclusion, this work provides a new insight to prepare XFC high-voltage LCO cathode materials.

25 ENERGY STORAGE↗