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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 1,621 records · Page 90
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

The Mechanism of Fluorine Doping for the Enhanced Lithium Storage Behavior in Cation-Disordered Cathode Oxide

Li-rich cation-disordered rock-salt (DRX) materials have emerged as promising candidates for high-capacity oxide cathodes. Their fluorinated variants have shown improved cycling stability with effectively suppressed oxygen loss. However, a comprehensive understanding of how fluorination impacts the multiscale structure and lithium transportation in DRX remains elusive in experiments. In this study, the neutron total scattering technique in conjunction with the advanced reverse Monte Carlo (RMC) fitting method is employed to characterize the intricate structure of Li 1.16 Ti 0.37 Ni 0.37 Nb 0.1 O 2 (LTNNO) and the fluorinated Li 1.2 Ti 0.35 Ni 0.35 Nb 0.1 O 1.8 F 0.2 (LTNNOF). Through rigorous statistical analysis, the multiscale structural evolution upon fluorination is quantified from atomic (≤5 Å) to long-range scale (≈100 Å). The local Li-rich environments around F induce a modest 2.4% increment in the number of fast Li 0TM (transition metal) channels. Crucially, at a broader scale, the proportion of 0TM channels participating in percolation increases significantly from 2.9% in LTNNO to 8.7% in LTNNOF. Fluorination improves the capacity release mainly through merging isolated fast Li channels into the percolation network. This work experimentally unravels the multiscale mechanism of fluorination-induced performance improvement in DRX materials and highlights the necessity of adopting an advanced RMC fitting method to obtain a full view of the complex structural features in developing high-capacity DRX cathodes.

25 ENERGY STORAGE↗
DOE OSTI2024

Insight of Synthesis of Single Crystal Ni-Rich LiNi 1-x-y Co x Mn y O 2 Cathodes

Single-crystal Ni-rich LiNi 1-x-y Co x Mn y O 2 (NCM) cathodes have garnered widespread attention in the lithium-ion battery community due to their unique advantages in mechanical performance and their ability to minimize interfacial electrochemical side reactions. The synthesis of single-crystal materials with monodisperse and appropriate size, minimal lattice defects, and highly ordered structures is the key for high-performance batteries. However, achieving this goal poses challenges due to the lack of in-depth understanding regarding specific experimental parameters and the solid reaction mechanism during the synthesis process. Further, in this review, the aim is to provide an in-depth analysis of the critical process parameters involved in the synthesis and their impact on crystal morphology, structure, and electrochemical performance. Consequently, the first section focuses on the effect of the precursor morphology, lithium salt, atmosphere, and sintering procedure. In the second section, the study delves into an in-depth discussion of the solid reaction and crystal growth mechanism. Lastly, it is concluded by highlighting the prospects and challenges associated with the synthesis and application of single-crystal Ni-rich NCM cathodes.

25 ENERGY STORAGE↗
DOE OSTI2025

In Situ Diffraction and Ex Situ Transmission X‐Ray Microscopy Studies of Solid‐State Upcycling for NMC Cathodes

Upcycling of recycled LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622) cathodes offers an economical route to produce cathode materials with increased energy density (i.e., LiNi 0.8 Mn 0.1 Co 0.1 O 2 , NMC811) that meet the performance needs of present-day electric vehicles. In this work, solid-state upcycling of NMC622 via calcination with Ni(OH) 2 and LiOH was monitored using in situ synchrotron powder X-ray diffraction measurements. Sequential Rietveld refinements indicate that the calcination proceeds by initially converting Ni(OH) 2 to a rocksalt NiO phase followed by lithiation of NiO to form LiNiO 2 (LNO), with both NMC and LNO phases present in nearly equal proportions at the calcination endpoint. Variable-energy transmission X-ray microscopy tomograms of upcycled samples reveal that the NMC and LNO domains are intermixed at sub-micron length scales. Depth-dependent analysis of multi-elemental fitting maps matches the expected NMC811 composition at the secondary particle level and indicates that transition metal diffusion is not limited by the secondary particle size.

cathode upcycling↗
DOE OSTI2025

Mitigating Cyclable Li‐Ion Inventory Loss in Full Cells with Mn‐Rich Disordered Rocksalt Cathodes

Lithium (Li)- and manganese (Mn)-rich disordered rock salt (DRX) materials are promising cathode materials for next-generation Li-ion batteries. Although these cathode materials are Li-ions rich in their pristine state, their incorporation into full cells results in challenges with maintaining Li-ion inventory during cycling. Herein, the degradation mechanisms of DRX materials in different DRX||Graphite full cells are reported. It is found that DRX electrodes contain Li impurities, primarily due to the environmental sensitivity of mechanochemically synthesized DRX materials during sample transfer and storage. In addition, the structural instability of DRX triggers Mn dissolution. Dissolved Mn ions react with exposed Li x C y compounds and induce electrolyte decomposition on the anode, further depleting Li-ion inventory. Control experiments involving the pre-addition of Mn 2+ provide clear evidence of the impact of Mn dissolution on Li-ion inventory. The electrochemical activation process can stabilize DRX, alleviate Mn dissolution and thus mitigate the loss of Li-ion inventory. These mechanistic insights inform the development of chemical pre-lithiation and electrolyte additive strategies to collectively passivate interfaces, mitigate the effects of trace dissolved Mn ions, and preserve Li-ion inventory. Ultimately, the DRX||Graphite full cell achieves highly reversible electrochemical reactions with a high capacity retention. This study fills a research gap in DRX-based full cells and provides insights into degradation mechanisms and optimization strategies for their practical use.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Addressing Inherent Challenges to Chemical Relithiation of Cycled End‐of‐Life Cathode Materials

Recycling end‐of‐life (EOL) lithium‐ion batteries (LIBs) is important to retain valuable resources from critical materials present in EOL battery waste. Direct recycling methods offer an opportunity to recover intact valuable cathode materials with minimal re‐processing. An important step of the direct recycling process is relithiation which is used to restore lithium content to EOL cathode materials. However, little has been done to study how preprocessing steps such as washing or binder removal may affect relithiation methods in the direct recycling process. Here, the evolution of fluorine byproducts left over from preprocessing steps during a low‐temperature chemical redox mediator relithiation process is tracked. A facile washing step is presented as a solution for mediating adverse effects of surface contamination on the chemical relithiation performance. The structure, lithium content, and electrochemical performance of relithiated EOL NMC 622 material that underwent a pre‐relithiation washing step to remove fluorine byproducts is shown to match that of pristine NMC 622. In this work, it is showed that redox mediator relithiation as a part of a direct recycling process is a promising low energy method that can be applied to EOL material with inherent surface impurities if the proper pre‐relithiation processing steps are implemented.

25 ENERGY STORAGE↗
DOE OSTI2019

Stabilizing the Oxygen Lattice and Reversible Oxygen Redox Chemistry through Structural Dimensionality in Lithium-Rich Cathode Oxides

Lattice-oxygen redox (l-OR) has become an essential companion to the traditional transition-metal (TM) redox charge compensation to achieve high capacity in Li-rich cathode oxides. However, the understanding of l-OR chemistry remains elusive, and a critical question is the structural effect on the stability of l-OR reactions. As such, the coupling between l-OR and structure dimensionality is studied herein. We reveal that the evolution of the oxygen-lattice structure upon l-OR in Li-rich TM oxides which have a three-dimensional (3D)-disordered cation framework is relatively stable, which is in direct contrast to the clearly distorted oxygen-lattice framework in Li-rich oxides which have a two-dimensional (2D)/3D-ordered cation structure. Our results highlight the role of structure dimensionality in stabilizing the oxygen lattice in reversible l-OR, which broadens the horizon for designing high-energy-density Li-rich cathode oxides with stable l-OR chemistry.

25 ENERGY STORAGE↗
DOE OSTI2020

Direct observation of defect-aided structural evolution in Ni-rich layered cathode

Ni-rich LiNi 1-x-y Mn x Co y O 2 (NMC) layered compounds have become the dominated cathode for lithium ion batteries. The role of crystallographic defects on their structure evolution and consequent performance degradation during electrochemical cycling is not yet fully understood. In this work, we investigated the structural evolution of Ni-rich NMC cathode in a solid-state cell via in-situ transmission electron microscopy. We identified antiphase boundary (APB) and twin boundary (TB) separating layered phases played an important role on phase change. Upon the lithium depletion, the APB extends across the layered structure, while Li/transition metal (TM) ion mixing in the layered phases is detected to induce the rock-salt phase formation along the coherent TB. According to DFT calculations, Li/TM mixing and phase transition are aided by the low diffusion barriers of TM ions at planar defects. Finally, this work reveals the dynamical scenario of secondary phase evolution, which helps to unveil the origin of performance fading in Ni-rich NMC.

25 ENERGY STORAGE↗
DOE OSTI2023

Implanting Transition Metal into Li 2 O-Based Cathode Prelithiation Agent for High-Energy-Density and Long-Life Li-Ion Batteries

Compensating the irreversible loss of limited active lithium (Li) is essentially important for improving the energy-density and cycle-life of practical Li-ion battery full-cell, especially after employing high-capacity but low initial coulombic efficiency anode candidates. Introducing prelithiation agent can provide additional Li source for such compensation. Herein, we precisely implant trace Co (extracted from transition metal oxide) into the Li site of Li 2 O, obtaining (Li 0.66 Co 0.11$\square$0.23 ) 2 O (CLO) cathode prelithiation agent. Further, the synergistic formation of Li vacancies and Co-derived catalysis efficiently enhance the inherent conductivity and weaken the Li-O interaction of Li 2 O, which facilitates its anionic oxidation to peroxo/superoxo species and gaseous O 2 , achieving 1642.7 mAh/g ~Li2O prelithiation capacity (≈980 mAh/g for prelithiation agent). Coupled 6.5 wt % CLO-based prelithiation agent with LiCoO 2 cathode, substantial additional Li source stored within CLO is efficiently released to compensate the Li consumption on the SiO/C anode, achieving 270 Wh/kg pouch-type full-cell with 92 % capacity retention after 1000 cycles.

25 ENERGY STORAGE↗
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 OSTI2021

Synthesis and Processing by Design of High-Nickel Cathode Materials

The high demand of lightweight, high energy density batteries for energy storage promotes new materials discovery and development. Despite the large number of battery materials being discovered, very few of them have been commercially deployed, mostly bottlenecked by synthesis and processing – namely, making certain phases with the desired structure and properties to meet the multifaceted performance requirements. Alternative to the traditional trial and error, we present here an in situ study aided synthesis- and processing-by-design approach. With specific examples, we illustrate how to use the approach to identify reaction pathways in synthesis and processing of high-Nickel (Ni) cathode materials for next-generation lithium-ion batteries, thereby ensuring precise control of their structure, morphology, and surface properties. Furthermore, perspectives are provided on the wide applicability of the approach to solving critical issues inherent to high-Ni cathodes and the new directions and opportunities in the area.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Li 3 BN 2 as a Transition Metal Free, High Capacity Cathode for Li-ion Batteries

Li 3 BN 2 is investigated for the first time as a transition metal free, high capacity cathode material for Li-ion batteries. It is shown that α-Li 3 BN 2 can exhibit a specific capacity of 890 mA h g -1 with the charge storage mechanism associated with the valence state change of N ions in the BN 2 anion. The particular capacity demonstrated in this study is the highest one ever reported in literature for an intercalation-type cathode material. Moreover, using the valence state change of N ions as a charge storage mechanism opens the door for designing additional high performance, transition metal free electrodes in the future.

25 ENERGY STORAGE↗
DOE OSTI2019

Defect Control in the Synthesis of 2 D MoS 2 Nanosheets: Polysulfide Trapping in Composite Sulfur Cathodes for Li–S Batteries

One of the inherent challenges with Li–S batteries is polysulfide dissolution, in which soluble polysulfide species can contribute to the active material loss from the cathode and undergo shuttling reactions inhibiting the ability to effectively charge the battery. Prior theoretical studies have proposed the possible benefit of defective 2 D MoS 2 materials as polysulfide trapping agents. Herein the synthesis and thorough characterization of hydrothermally prepared MoS 2 nanosheets that vary in layer number, morphology, lateral size, and defect content are reported. Here, the materials were incorporated into composite sulfur–based cathodes and studied in Li–S batteries with environmentally benign ether–based electrolytes. Through directed synthesis of the MoS 2 additive, the relationship between synthetically induced defects in 2 D MoS 2 materials and resultant electrochemistry was elucidated and described.

25 ENERGY STORAGE↗
DOE OSTI2023

Electron energy levels determining cathode electrolyte interphase formation

Cathode electrolyte interphase (CEI) has a significant impact on the performance of rechargeable batteries and is gaining increasing attention. Understanding the fundamental and detailed CEI formation mechanism is of critical importance for battery chemistry. Herein, a diverse of characterization tools are utilized to comprehensively analyze the composition of the CEI layer as well as its formation mechanism by LiCoO 2 (LCO) cathode. We reveal that CEI is mainly composed of the reduction products of electrolyte and it only parasitizes the degraded LCO surface which has transformed into a disordered spinel structure due to oxygen loss and lithium depletion. Based on the energy diagram and the chemical potential analysis, the CEI formation process has been well explained, and the proposed CEI formation mechanism is further experimentally validated. This work highlights that the CEI formation process is nearly identical to that of the anode-electrolyte-interphase, both of which are generated due to the electrolyte directly in contact with the low chemical potential electrode material. This work can deepen and refresh our understanding of CEI.

LiCoO2↗
DOE OSTI2024

Rational optimization of substituted α–MnO 2 cathode for aqueous zinc–ion battery

Density functional theory (DFT) is utilized to explore the effects of increasing concentrations of vanadium (V) and chromium (Cr) substitution on the discharge of α-MnO 2 cathode in hydrated zinc-ion batteries (ZIBs). During H + -intercalation and Zn 2+ -intercalation, Cr-substitution proves to be more effective than V-substitution in promoting discharge behaviors. Transitioning from Mn 0.875 Cr 0.125 O 2 , Mn 0.75 Cr 0.25 O 2 to Mn 0.625 Cr 0.375 O 2 is found to consistently enhance the discharge voltage, along with improved tunnel structure retention and volume expansion suppression. In comparison, the promoting effect of increasing V-substitution is relatively small at initial discharge stages and leads to degradation at later stages, primarily due to an increased concentration of unstable Mn 2+ ion. The superior effect of Cr-substitution is attributed to the unique atomic and electronic structures of substituted Cr 4+ and reduced Cr 3+ ions during discharge. These ions serve as active electron acceptors to limit the formation of Mn 3+ and Mn 2+ ions, and as anchors to stabilize the α-MnO 2 framework and intercalated H + /Zn 2+ ions, respectively. Finally, our study highlights fine-tuning through substitution to enhance the performance of α-MnO 2 -based cathode materials in ZIBs.

25 ENERGY STORAGE↗
DOE OSTI2022

Oxygen Vacancy Introduction to Increase the Capacity and Voltage Retention in Li‐Excess Cathode Materials

Li‐rich rocksalt oxides are promising cathode materials for lithium‐ion batteries due to their large capacity and energy density, and their ability to use earth‐abundant elements. The excess Li in the rocksalt, needed to achieve good Li transport, reduces the theoretical transition metal redox capacity and introduces a labile oxygen state, both of which lead to increased oxygen oxidation and concomitant capacity loss with cycling. Herein, it is demonstrated that substituting the labile oxygen in Li‐rich cation‐disordered rocksalt materials with a vacancy is an effective strategy to inhibit oxygen oxidation. It is found that the oxygen vacancy in cation‐disordered lithium manganese oxide favors high Li coordination thereby reducing the concentration of unhybridized oxygen states, while increasing the theoretical Mn capacity. It is shown that in the vacancy‐containing compound, synthesized by ball milling, the Mn valence is lowered to less than +3, providing access to more than 300 mAh g −1 capacity from the Mn 2+ /Mn 4+ redox reservoir. The increased transition metal redox and decreased O oxidation are found to improve the capacity and voltage retention, indicating that oxygen vacancy creation to remove the most vulnerable oxygen ions and reduce transition metal valence provides a new opportunity for the design of high‐performance Li‐rich rocksalt cathodes.

25 ENERGY STORAGE↗
DOE OSTI2023

A Self‐Healing Chemistry‐Enabled Organic Cathode for Sustainable and Stable Sodium‐Ion Batteries

Sodium‐on batteries (SIBs) are promising alternatives to lithium‐ion batteries (LIBs) because of the low cost, abundance, and high sustainability of sodium resources. Analogous to LIBs, the high‐capacity electrodes in SIBs always suffer from rapid capacity decay upon long‐term cycling due to the particle pulverization induced by a large volume change. Circumventing particle pulverization plays a critical role in developing high‐energy and long‐life SIBs. Herein, tetrahydroxy‐1,4‐benzoquinone disodium salt (TBDS) that can self‐heal the cracks by hydrogen bonding between hydroxyl group and carbonyl group is employed as a cathode for sustainable and stable SIBs. The self‐healing TBDS exhibits long cycle life of 1000 cycles with a high rate capability up to 2 A g −1 due to the fast Na‐ion diffusion reaction in the TBDS cathode. The intermolecular hydrogen bonding has been comprehensively characterized to understand the self‐healing mechanism. The hydrogen bonding‐enabled self‐healing organic materials are promising for developing high‐energy and long‐cycle‐life SIBs.

25 ENERGY STORAGE↗
DOE OSTI2017

Formation and Transportation of an Intense Sub-Millisecond Electron Beam in a Longitudinal Magnetic Field in the Source with a Mesh Plasma Cathode

The limiting parameters of an intense sub-millisecond electron beam generated in the source with a plasma cathode on the basis of a low-pressure multi-arc discharge with mesh stabilization of the cathode (emission) plasma boundary and mobile anode (beam) plasma boundary are investigated. It is demonstrated that the limiting parameters of the electron beam in the examined electrode system are limited by its energy content on a level of about 4 kJ the excess of which leads to an electric breakdown of the accelerating gap. The optimal pressures are determined at which the beam during its transportation in the longitudinal magnetic field with a preset configuration has maximal parameters for the given electrode system. Different mechanisms of electric breakdown initiation and methods for increasing the electric strength of the high-voltage accelerating gap in this electrode system are discussed.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2018

Pulsed Electron Source with Grid Plasma Cathode and Longitudinal Magnetic Field for Modification of Material and Product Surfaces

The description and the main characteristics of the pulsed electron source “SOLO” developed on the basis of the plasma cathode with grid stabilization of the emission plasma boundary are presented. Тhe emission plasma is generated by a low-pressure arc discharge, and that allows to form the dense low-energy electron beam with a wide range of independently adjustable parameters of beam current pulses (pulse duration of 20–250 μs, pulse repetition rate of 1–10 s{sup –1}, amplitude of beam current pulses of 20–300 A, and energy of beam electrons of 5–25 keV). Тhe special features of generation of emission plasma by constricted low-pressure arc discharge in the grid plasma cathode partially dipped into a non-uniform magnetic field and of formation and transportation of the electron beam in a longitudinal magnetic field are considered. The application area of the electron source and technologies realized with its help are specified.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗