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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 1,747 records · Page 97
All sourcesNASA NTRSDOE OSTI
DOE OSTI2017

Atomic Insight into the Layered/Spinel Phase Transformation in Charged LiNi 0.80 Co 0.15 Al 0.05 O 2 Cathode Particles

Layered LiNi 0.80 Co 0.15 Al 0.05 O 2 (NCA) holds great promise as a potential cathode material for high energy density lithium ion batteries. However, its high capacity is heavily dependent on the stability of its layered structure, which suffers from a severe structure degradation resulting from a not fully understood layered → spinel phase transformation. Using high-resolution transmission electron microscopy and electron diffraction, we probe the atomic structure evolution induced by the layered → spinel phase transformation in the NCA cathode. We show that the phase transformation results in the development of a particle structure with the formation of complete spinel, spinel domains, and intermediate spinel from the surface to the subsurface region. The lattice planes of the complete and intermediate spinel phases are highly interwoven in the subsurface region. The layered → spinel transformation occurs via the migration of transition metal (TM) atoms from the TM layer into the lithium layer. Incomplete migration leads to the formation of the intermediate spinel phase, which is featured by tetrahedral occupancy of TM cations in the lithium layer. Finally, the crystallographic structure of the intermediate spinel is discussed and verified by the simulation of electron diffraction patterns.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Surface Characterization of Li-Substituted Compositionally Heterogeneous NaLi 0.045 Cu 0.185 Fe 0.265 Mn 0.505 O 2 Sodium-Ion Cathode Material

The understanding of surface chemical and structural processes can provide some insights into designing stable sodium cathode materials. Herein, Li-substituted and compositionally heterogeneous NaLi 0.045 Cu 0.185 Fe 0.265 Mn 0.505 O 2 is used as a platform to investigate the interplay between Li substitution, surface chemistry, and battery performance. Li substitution improves the initial discharge capacity and energy density. Yet, there is no noticeable benefit in the long-term cycling stability of this material. The Li substitution in the transition-metal (TM) layer also seems to influence the transition-metal (TM) 3d–oxygen (O) 2p hybridization. Upon desodiation, the surface of active particles undergoes significant transition-metal reduction, especially Mn. Furthermore, the presence of electrolyte drastically accelerates such surface degradation. In general, the Li-substituted material experiences severe surface degradation, which is partially responsible for the performance degradation upon long-term cycling. While some studies have introduced the benefits of Li substitution, the present study suggests that the effectiveness of the Li substitution strategy depends on the TM compositional distribution. More efforts are needed to improve the surface chemistry of Li-substituted sodium cathode materials.

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

Ca Cobaltites as Potential Cathode Materials for Rechargeable Ca-Ion Batteries: Theory and Experiment

Rechargeable Ca-based batteries can potentially achieve higher energy capacity than Li-ion batteries. The development of Ca-ion batteries, however, remains in its infancy, especially due to the challenge of finding cathode materials with high reversible capacity. In this work, we investigate properties of Ca cobaltites as Ca-ion intercalation cathodes, by means of density functional theory calculations validated by synthesis and electrochemical measurements. Computationally, we accessed thermodynamic, diffusion properties, energy capacity, and the voltage profiles for four Ca cobaltite compounds of different stoichiometry and Co oxidation states: Ca 3 Co 2 O 6 , CaCo 2 O 4 , Ca 2 Co 2 O 5 , and [Ca 2 CoO 3 ][CoO 2 ] 1.62 . We found good stability and relatively low migration barriers of some Ca cobaltites during cycling with the layered CaCo 2 O 4 having the lowest Ca migration barrier of 0.7 eV and the highest theoretical capacity. To validate our calculations, we synthesized Ca 3 Co 2 O 6 , CaCo 2 O 4 , and [Ca 2 CoO 3 ][CoO 2 ] 1.62 with the Pechini method and, subsequently, to test the electrochemical extraction of Ca.

25 ENERGY STORAGE↗
DOE OSTI2020

How Bulk Sensitive is Hard X-ray Photoelectron Spectroscopy: Accounting for the Cathode–Electrolyte Interface when Addressing Oxygen Redox

Sensitivity to the `bulk' oxygen core orbital makes hard X-ray photoelectron spectroscopy (HAXPES) an appealing technique for studying oxygen redox candidates. Various studies have reported an additional O 1s peak (530-531 eV) at high voltages, which has been considered a direct signature of the bulk oxygen redox process. Here, we find the emergence of a 530.4 eV O 1s HAXPES peak for three model cathodes, Li 2 MnO 3 , Li-rich NMC, and NMC 442, that shows no clear link to oxygen redox. Instead, the 530.4 eV peak for these three systems is attributed to transition metal reduction and electrolyte decomposition in the near-surface region. Claims of oxygen redox relying on photoelectron spectroscopy must explicitly account for the surface sensitivity of this technique and the extent of the cathode degradation layer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Nanostructured metal carbides for aprotic Li-O 2 batteries. New insights into interfacial reactions and cathode stability

The development of nonaqueous Li–oxygen batteries, which relies on the reversible reaction of Li + O 2 to give lithium peroxide (Li 2 O 2 ), is challenged by several factors, not the least being the high charging voltage that results when carbon is typically employed as the cathode host. We report here on the remarkably low 3.2 V potential for Li 2 O 2 oxidation on a passivated nanostructured metallic carbide (Mo 2 C), carbon-free cathode host. Furthermore, online mass spectrometry coupled with X-ray photoelectron spectroscopy unequivocally demonstrates that lithium peroxide is simultaneously oxidized together with the Li x MoO 3 -passivated conductive interface formed on the carbide, owing to their close redox potentials. We found that the process rejuvenates the surface on each cycle upon electrochemical charge by releasing Li x MoO 3 into the electrolyte, explaining the low charging potential.

25 ENERGY STORAGE↗
DOE OSTI2018

Mechanism of Exact Transition between Cationic and Anionic Redox Activities in Cathode Material Li 2 FeSiO 4

The discovery of anion redox activity is promising for boosting the capacity of lithium ion battery (LIB) cathodes. However, fundamental understanding of the mechanisms that trigger the anionic redox is still lacking. In this study, using hybrid density functional study combined with experimental soft X-ray absorption spectroscopy (sXAS) measurements, we unambiguously proved that Li (2-x) FeSiO 4 performs sequent cationic and anionic redox activity through delithiation. Specifically, Fe 2+ is oxidized to Fe 3+ during the first Li ion extraction per formula unit (f.u.), while the second Li ion extraction triggered the oxygen redox exclusively. Cationic and anionic redox result in electron and hole polaron states, respectively, explaining the poor conductivity of Li (2-x) FeSiO 4 noted by previous experiments. In contrast, other cathode materials in this family exhibit diversity of the redox process. Li 2 MnSiO 4 shows double cationic redox (Mn 2+ -Mn 4+ ) during the whole delithiation, while Li 2 CoSiO 4 shows simultaneous cationic and anionic redox. The present finding not only provides new insights into the oxygen redox activity in polyanionic compounds for rechargeable batteries but also sheds light on the future design of high-capacity rechargeable batteries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Metal–Organic Framework-derived Atomic Metal Sites Promoting Sulfur Cathode for All-Solid-State Lithium–Sulfur Batteries

All-solid-state lithium–sulfur batteries (ASSLSBs) offer high energy density and intrinsic safety; however, they still face major challenges, including sluggish redox kinetics and poor sulfur utilization. Incorporating conductive materials into sulfur cathodes is an effective strategy to mitigate these limitations. Here, a highly conductive cobalt–nitrogen–doped carbon (Co–NC) derived from a metal–organic framework (MOF) is introduced to accelerate charge transfer and promote reversible sulfur conversion. Co−NC provides atomically dispersed Co–N sites and conductive carbon pathways that correlate with improved charge transfer, sulfur utilization, and rate capability. Co–NC@S cathode delivers 1499 mAh g–1 at C/20 with a high sulfur loading (5 mg cm–2) and retains 1292 mAh g–1 after five cycles (vs 443 mAh g–1 without Co–NC). Moreover, Co–NC derived ASSLSB achieves 903 mAh g–1 at 5C at 60 °C. This work provides a practical and effective approach to develop high energy, high-rate ASSLSBs.

25 ENERGY STORAGE↗
DOE OSTI2020

All-Sputtered, Superior Power Density Thin-Film Solid Oxide Fuel Cells with a Novel Nanofibrous Ceramic Cathode

Thin film solid oxide fuel cells (TF-SOFCs) are attracting attention due to their ability to operate at comparatively lower temperatures (400–650 °C) that are unattainable for conventional anode-supported SOFCs (650–800 °C). However, limited cathode performance and cell scalability remain persistent issues. Here, we report a new approach of fabricating yttria-stabilized zirconia (YSZ)-based TF-SOFCs via a scalable magnetron sputtering process. Notable is the development and deposition of a porous La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 2.95 (LSCF)-based cathode with a unique fibrous nanostructure. This all-sputtered cell shows an open-circuit voltage of ~1.0 V and peak power densities of ~1.7 and ~2.5 W/cm 2 at 600 and 650 °C, respectively, under hydrogen fuel and air along with showing stable performance in short-term testing. The power densities obtained in this work are the highest among YSZ-based SOFCs at these low temperatures, which demonstrate the feasibility of fabricating exceptionally high-performance TF-SOFC cells with distinctive dense or porous nanostructures for each layer, as desired, by a sputtering process. This work illustrates a new, potentially low-cost, and scalable platform for the fabrication of next-generation TF-SOFCs with excellent power output and stability.

25 ENERGY STORAGE↗
DOE OSTI2020

Systematic Study of Different Anion Doping on the Electrochemical Performance of Cobalt-Free Lithium–Manganese-Rich Layered Cathode

Regardless of the appealingly high energy density (1000 Wh kg –1 ) of the lithium–manganese-rich layered oxide cathode (LMR-NMO), this material still suffers from rapid capacity and voltage decay after continuous cycling. LMR-NMO involves the redox reaction of both transition metals and oxygen to gain additional capacity in comparison with a conventional NMC cathode. Due to the use of a high voltage range (beyond 4.4 V), the oxygen release from the structure initiates and in turn generates intergranular cracks and spinel formation, consequently, into rock-salt structure. Here, LMR-NMO with different doping ranges (1–5 mol %) of F, S, and Cl are being examined to summarize the benefits and drawbacks of each anion. This study shows that F is the best candidate as it increases average voltage (voltage retention 96–97% after 200 cycles at 0.5 C), improves ionic conductivity (nearly two times higher than pristine), reduces cation mixing, minimizes oxygen release, and offers high stability during high temperature cycle. However, for S and Cl, the results are conflicted. An optimal amount of anion dopants should be considered as the side effects might overcome the benefits when the doping amount is excessive.

25 ENERGY STORAGE↗
DOE OSTI2023

Suppressing the Shuttle Effects with FeCo/SPAN Cathodes and High-Concentration Electrolytes for High-Performance Lithium–Sulfur Batteries

The shuttle effects and the sluggish redox kinetics are two of the main challenges in lithium–sulfur (Li–S) batteries, which significantly reduce the capacity of the batteries and restrict their commercialization. Herein, FeCo/sulfurized polyacrylonitrile (SPAN) is synthesized as a cathode material via the electrospinning technique and a further heat treatment. Synchrotron X-ray absorption spectroscopy confirmed the existence of Fe–S/Fe and Co–S bonds in FeCo/SPAN, which benefit the adsorptive and catalytic activities toward lithium polysulfides (LiPSs). Here, we further investigated the effect of electrolyte concentration in inhibiting the shuttle of LiPSs in Li–S batteries. Small-angle X-ray scattering (SAXS) reveals that more contact ion pairs are formed and fewer free solvent molecules exist with the increase of the electrolyte concentration, which can inhibit the dissolution and shuttle of LiPSs. Finally, the batteries assembled with high-concentration electrolytes (3 M LiTFSI in DOL/DME) exhibit a higher specific capacity retention compared to those assembled with low-concentration electrolytes. This work enriches the route to prepare Li–S batteries with the rational design of cathode materials and electrolytes.

25 ENERGY STORAGE↗
DOE OSTI2026

4D-STEM Coupled with Unsupervised Machine Learning to Reveal at Large-Scale the Microstructural Evolution in Li- and Mn-Rich Cathodes

Li- and Mn-rich (LMR) layered oxides are known to exhibit a thin surface reconstruction layer, which grows during electrochemical cycling in a manner that depends on exposed crystallographic facets, cycling conditions, and electrolyte chemistry. Direct characterization of this layer has traditionally relied on high-resolution electron microscopy, which is inherently limited to small fields of view. Here, we employ four-dimensional scanning transmission electron microscopy (4D-STEM) combined with unsupervised machine-learning clustering to quantitatively map phase distributions over large areas and track their evolution in LMR cathodes during electrochemical aging. Our results show that the surface reconstruction layer consists predominantly of a rocksalt phase, whose thickness varies across different facets following activation cycling and becomes substantially thicker and more uniform during calendar aging. In contrast, a spinel-like phase is observed within the particle bulk. Large-area phase mapping and correlative high-resolution imaging reveal that this spinel-like phase preferentially nucleates at bulk crystallographic defects, including boundaries between 60°-rotated layered domains and associated mixed-phase regions, rather than exclusively at the particle surface. Our findings establish a mechanistic distinction between surface-driven rocksalt formation and bulk-defect-mediated spinel nucleation while demonstrating the unique capability of 4D-STEM to provide statistically robust, mesoscale insight into complex phase-evolution processes in LMR cathodes.

4D-STEM↗
DOE OSTI2020

Optimized Al Doping Improves Both Interphase Stability and Bulk Structural Integrity of Ni-Rich NMC Cathode Materials

Ni-rich layered transition metal oxide (NMC, LiNi1-x-yMxCoyO2, 1 – x – y = 0.6) is promising for high-energy-density lithium-ion batteries, but its large-scale application is still hindered by several technical challenges, including secondary particle cracking, interfacial instability, and cell degassing during cycling. Here, we report a facile wet-chemical method to modify both the surface and the bulk of the LiNi0.76Mn0.14Co0.10O2 (NMC76) cathode with Al doping to effectively improve the structural/interfacial stability of the cathode, and hence its long-term cycling capability. With only 1 mol% Al doping, the Al-NMC76 electrode delivers a good capacity retention of 79.2% after 500 cycles at a high voltage limit of 4.5 V, which is far better than those of undoped NMC76 under the similar condition. The enhanced performance can be attributed to the Al doping in the NMC76, which not only strengthens the bulk structural stability through doping into the lattice, but also suppresses acidic attack from the electrolyte through altered surface structure of NMC76.

Al doping, capacity retention, high voltage, elect↗
DOE OSTI2021

High-Capacity Aqueous Storage in Vanadate Cathodes Promoted by the Zn-Ion and Proton Intercalation and Conversion–Intercalation of Vanadyl Ions

Aqueous Zn-ion batteries (AZIBs) are promising alternatives to lithium-ion batteries in stationary storage. However, limited storage capacity and cyclic life impede their large-scale implementation. In this study, we report reversible electrochemical insertion of multi-ions into sodium vanadate (NaV 3 O 8 ) cathode materials for AZIBs, achieving a maximum storage capacity of 450 mAh g –1 at 0.05 A g –1 and a capacity retention of 82% after 500 cycles at 0.4 A g –1 . In addition to Zn 2+ and H + insertion, in situ X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS) collectively provide explicit evidence on vanadyl ions (VO 2+ ) conversion–intercalation at the NaV 3 O 8 cathode, showing the deintercalation of VO 2+ from NaV 3 O 8 and the consequent conversion of VO 2+ into V 2 O 5 on charging, and vice versa on discharging. Our study is the first to report on the cation conversion–intercalation mechanism in AZIBs. This reversible multi-ion storage mechanism provides a design principle for developing high-capacity aqueous electrode materials by engaging both the intercalation and conversion of charge carriers.

25 ENERGY STORAGE↗
DOE OSTI2024

Electro-Chemo-Mechanical Evolution at the Garnet Solid Electrolyte–Cathode Interface

Solid-state batteries promise higher energy density and improved safety compared with lithium-ion batteries. However, electro-chemomechanical instabilities at the solid electrolyte interface with the cathode and the anode hinder their large scale implementation. Here, in this study, we focus on resolving electro-chemo-mechanical instability mechanisms and their onset conditions between a state-of-the-art cathode, LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622), and the garnet Li 7 La 3 Zr 2 O 12 (LLZO) solid electrolyte. We used thin-film NMC622 on LLZO pellets to place the interfacial region within the detection depth of the X-ray characterization techniques. The experimental probes of the near-interface region included in operando X-ray absorption spectroscopy and ex situ focused ion beam scanning electron microscopy. Electrochemical degradation was not observable during cycling at room temperature with 4.3 V versus Li/Li + charge voltage cutoff, or with stepwise potentiostatic hold up to 4.1 V versus Li/Li + . In contrast, secondary phases including reduced transition metal species (Ni 2+ , Co 2+ ) were found after cycling up to 4.3 V versus Li/Li + at 80 °C and during potentiostatic hold at 4.3 V versus Li/Li + (Ni 2+ ). Intergranular cracks between NMC622 grains and delamination at the NMC622|LLZO interface occurred readily after the first charge. These interface reaction products and mechanical failure lowered the capacity and cell efficiency due to partial loss of the NMC622 phase, partial loss of contact at the interface, and a higher polarization resistance. Electrochemical instability between delithiated NMC622 and LLZO could be mitigated by using a low charge voltage cutoff or cycling at lower temperature. Ways to engineer the mechanical properties to avoid crack deflection and delamination at the interface are also discussed for enhancing mechanical stability.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Nanostructured Anatase Titania as a Cathode Catalyst for Li–CO 2 Batteries

The lithium – carbon dioxide (Li-CO 2 ) battery previously garnered significant interest over the past five years as a next-generation energy storage device. In this letter, we report a nanocomposite of anatase titania nanoparticles (TiO 2 -NP), carbon nanotubes (CNT), and carbon nanofibers (CNF) as a freestanding gas diffusion cathode (GDC) for Li-CO 2 batteries. Nanostructured anatase TiO 2 is demonstrated as a low-cost, easy-to-synthesize catalyst for CO 2 capture and utilization. With the developed composite electrode, we confirm the successful reversibility of the carbon dioxide reduction reaction (CDRR) and evolution reaction (CDER) at the cathode, and demonstrate improved Li-CO 2 cell performance, through a variety of materials and electrochemical characterization techniques.

25 ENERGY STORAGE↗
DOE OSTI2020

Surpassing the Organic Cathode Performance for Lithium-Ion Batteries with Robust Fluorinated Covalent Quinazoline Networks

Organic electrode materials have promising application prospects in energy storage, but issues including rapid capacity fading and poor power capacity restrict their practical applications. In this study, nanoporous fluorinated covalent quinazoline networks (F-CQNs) were constructed by condensation of fluorinated aromatic aminonitrile precursors via an ionothermal pathway. Precise control of the reaction parameters afforded F-CQN-1-600 material featuring high surface area, permanent porosity, high nitrogen content (23.49 wt %), extended π-conjugated architecture, layered structure, and bipolar combination of benzene and tricycloquinazoline. Synergy among these unique properties leads to a good performance as a cathode source for lithium-ion batteries (LIBs) in terms of high capacity (250 mA h g –1 at 0.1 A g –1 ), high rate capability (105 mA h g –1 at 5.0 A g –1 ), and impressive cycling stability (95.8% retention rate after 2000 cycles at 2.0 A g –1 together with a high Coulombic efficiency of 99.95%), surpassing most of the previous organic cathode counterparts.

25 ENERGY STORAGE↗
DOE OSTI2020

Enabling Facile Anionic Kinetics through Cationic Redox Mediator in Li-Rich Layered Cathodes

Anionic oxygen redox has aroused great interests in developing high-capacity Li-ion battery cathode materials. The fundamental understanding of this concept, compared to cationic redox, has promoted extensive studies on lithium transition metal oxides including those of 4d and 5d transition metals. Lithium ruthenium oxide has been found to exhibit a reversible anionic redox upon cycling. However, lithium-rich layered oxide with anionic redox is still facing great challenges such as sluggish kinetics. Here we investigate the effect of cationic redox on the kinetics of anionic reaction when they are strongly coupled. We report the cobalt substituted lithium ruthenium oxide, where all Ru, Co and O redox participate in the charge compensation mechanism in relatively defined voltage regions. Additionally, the improved anionic kinetics is attributed to the fast cationic Co redox process that serves as a redox mediator. Our work sheds light into the potential direction to address the commonly believed sluggish anionic kinetics in high-capacity oxygen-redox cathode materials.

25 ENERGY STORAGE↗
DOE OSTI2021

Chemical Modulation of Local Transition Metal Environment Enables Reversible Oxygen Redox in Mn-Based Layered Cathodes

Oxygen redox plays a prominent role in enhancing the energy density of Mn-based layered cathodes. However, understanding the factors affecting the reversibility of oxygen redox is nontrivial due to complicated structural and chemical transformations. Here in this paper, we show that local Mn–O symmetry induced structural/chemical evolutions majorly dictate the reversibility of oxygen redox of Na x Li y Mn 1–y O 2 in Na cells. Na x Li y Mn 1–y O 2 with Jahn–Teller distorted MnO 6 octahedra undergoes severe Mn dissolution during cycling, which destabilizes the transition metal layer resulting in poor Li retention and irreversible oxygen redox. Jahn–Teller distortion of MnO 6 octahedra can be suppressed by modulating the local charge of Mn and Mn–O distance through Mg/Ti dual doping. This leads to reduced Mn dissolution and more reversible oxygen redox. Such stabilization significantly improves the electrochemical performance of Mg/Ti dual doped Na x Li y Mn 1–y O 2 . Through this work, we show that local structural stabilization through local chemical environment modification can promote reversible oxygen redox in layered cathodes.

25 ENERGY STORAGE↗