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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 1,405 records · Page 78
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Conditioning the Surface and Bulk of High-Nickel Cathodes with a Nb Coating: An In Situ X-ray Study

Surface coating is commonly employed by industries to improve the cycling and thermal stability of high-nickel (Ni) transition metal (TM) layered cathodes for their practical use in lithium-ion batteries. Niobium (Nb) coating or substitution has been shown to be effective in stabilizing LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) cathodes; in addition, the electrochemical performance of the final products varies depending on the postprocessing. In this follow-up study, we use in situ synchrotron X-ray diffraction to investigate the kinetic processes and the involved structural evolution in Nb-coated NMC811 upon heat treatment. Furthermore, quantitative structure analysis reveals thermally driven concurrent changes in the bulk and surface, in particular, the phase evolution of the coating layer and Nb/TM interdiffusion that facilitates penetration of Nb into the bulk and particle growth at the increased temperatures. Findings from this study highlight the new opportunities for the intended control of the structure and surface properties of high-Ni cathodes through surface coating in conjunction with postprocessing.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Understanding the Air-Exposure Degradation Chemistry at a Nanoscale of Layered Oxide Cathodes for Sodium-Ion Batteries

Undesired reactions between layered sodium transition-metal oxide cathodes and air impede their utilization in practical sodium-ion batteries. Consequently, a fundamental understanding of how layered oxide cathodes degrade in air is of paramount importance, but it has not been fully understood yet. Here a comprehensive study on a model material NaNi 0.7 Mn 0.15 Co 0.15 O 2 reveals its reaction chemistry with air and the dynamic evolution of the degradation species upon air exposure. In this work, we find that besides the extraction of Na + ions from the crystal lattice to form NaOH, Na 2 CO 3 , and Na 2 CO 3 ·H 2 O in contact with air, nickel ions gradually dissolve from the bulk to form NiO and accumulate on the particle surface as revealed by subnanometer surface-sensitive time-of-flight secondary ion mass spectroscopy. The degradation species on the surface are insulating, leading to an increase in interfacial resistance and declined electrochemical performance. We also demonstrate a feasible surface coating strategy for suppressing the unfavorable degradation process. Finally, understanding the degradation mechanism at a nanoscale can facilitate the future development of high-energy cathodes for sodium-ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2020

Understanding Reactivities of Ni-rich Li[NixMnyCo1-x-y]O2 Single-Crystal Cathode Materials

While Ni-rich Li[NixMnyCo1-x-y]O2 (NMC, x ? 0.8) compounds are considered the most promising cathode materials for high-energy lithium-ion batteries (LIBs), a significant challenge is the higher reactivities caused by the increased Ni content, especially under high-voltage operation conditions. In the present study, we synthesize three single-crystal NMC (SC-NMC) samples with the same particle size and morphology: LiNi0.8Mn0.1Co0.1O2 (NMC811), LiNi0.80Mn0.15Co0.05O2 (NMC80155) and LiNi0.85Mn0.10Co0.05O2 (NMC85105). By systematically varying the composition while controlling other properties, the role of each transition metal during air exposure, thermal treatment and long-term cycling is clearly demonstrated. We reveal that while higher Ni content leads to an overall increased reactivities, the presence of Mn provides a stabilizing effect on thermal, structural and chemical properties. In the absence of cycling-induced particle cracking, surface reconstruction is shown to be the dominating contributor to cathode capacity fade. Our study provides key insights needed for the development of better-performing Ni-rich NMC cathode materials.

Kim, Minkyung↗
DOE OSTI2025

Delineating the Factors Impacting the Electrochemical Behavior of Single-Crystal High-Nickel Layered Oxide Cathodes

High-nickel (Ni) (≥80%) single-crystal LiNi 1-x-y Mn x Co y O 2 (NMCs) have garnered recent interest as cathodes in lithium (Li)-ion batteries (LIBs). However, capacity fade at high voltages, particularly after the onset of the H2–H3 phase transition, hampers their viability. In this study, single-crystal LiNi 0.8 Mn x Co 0.2-x O 2 (x = 0.2, 0.1, 0) are synthesized and tested in LiPF 6 in ethyl methyl carbonate-based electrolytes, with and without monofluoroethylene carbonate and LiF 2 PO 2 additives, to clarify the effects of Co/Mn ratio and surface stabilization on high-voltage cycling degradation. By imposing a kinetic barrier to the accessible H2–H3 capacity, surface reconstruction is identified as the primary driver of high-voltage capacity loss, being greater in the Co-free cathode and in the absence of fluorinated electrolyte components. This is attributed to a synergy between increased mechanical stress due to worsened bulk and interfacial H2–H3 kinetics and decreased interfacial stability due to the poor passivating capability of the electrolyte. Here, the findings highlight the importance of limiting cathode impedance growth during high-voltage cycling, which can be achieved by tuning bulk dopants and electrolyte chemistry.

25 ENERGY STORAGE↗
DOE OSTI2016

Resolving Electrode Morphology’s Impact on Platinum Group Metal-Free Cathode Performance Using Nano-CT of 3D Hierarchical Pore and Ionomer Distribution

This paper reports on the characterization of polymer electrolyte fuel cell (PEFC) cathodes featuring a platinum group metal-free (PGM-free) catalyst using nano-scale resolution X-ray computed tomography (nano-CT) and morphological analysis. PGM-free PEFC cathodes have gained significant interest in the past decade since they have the potential to dramatically reduce PEFC costs by eliminating the large platinum (Pt) raw material cost. However, several challenges remain before they are commercially viable. Since these catalysts have lower volumetric activity, the PGM-free cathodes are thicker and are subject to increased gas and proton transport resistances that reduce the performance. To better understand the efficacy of the catalyst and improve electrode performance, a detailed understanding the correlation between electrode fabrication, morphology, and performance is crucial. In this work, the pore/solid structure and the ionomer distribution was resolved in three dimensions (3D) using nano-CT for three PGM-free electrodes of varying Nafion® loading. The associated transport properties were evaluated from pore/particlescale simulations within the nano-CT imaged structure. These characterizations are then used to elucidate the microstructural origins of the dramatic changes in fuel cell performance with varying Nafion® ionomer loading. We show that this is primarily a result of distinct changes in ionomer’s spatial distribution. The significant impact of electrode morphology on performance highlights the importance of PGM-free electrode development in concert with efforts to improve catalyst activity and durability.

42 ENGINEERING↗
DOE OSTI2017

Mesoscale Elucidation of Surface Passivation in the Li–Sulfur Battery Cathode

We report the cathode surface passivation caused by Li 2 S precipitation adversely affects the performance of lithium-sulfur (Li-S) batteries. Li 2 S precipitation is a complicated mesoscale process involving adsorption, desorption and diffusion kinetics, which are affected profoundly by the reactant concentration and operating temperature. In this work, a mesoscale interfacial model is presented to study the growth of Li 2 S film on carbon cathode surface. Li 2 S film growth experiences nucleation, isolated Li 2 S island growth and island coalescence. The slow adsorption rate at small S 2- concentration inhibits the formation of nucleation seeds and the lateral growth of Li 2 S islands, which deters surface passivation. An appropriate operating temperature, especially in the medium-to-high temperature range, can also defer surface passivation. Fewer Li 2 S nucleation seeds form in such an operating temperature range, which facilitates heterogeneous growth and thereby inhibits the lateral growth of the Li 2 S film, which may also result in reduced surface passivation. Finally, the high specific surface area of the cathode microstructure is expected to mitigate the surface passivation.

25 ENERGY STORAGE↗
DOE OSTI2018

Solution-Processed n-Type Graphene Doping for Cathode in Inverted Polymer Light-Emitting Diodes

n-Type doping with (4-(1,3-dimethyl-2,3-dihydro-1H-benzoimidazol-2-yl)phenyl) dimethylamine (N-DMBI) reduces a work function (WF) of graphene by ~0.45 eV without significant reduction of optical transmittance. Solution process of N-DMBI on graphene provides effective n-type doping effect and air-stability at the same time. Although neutral N-DMBI act as an electron receptor leaving the graphene p-doped, radical N-DMBI acts as an electron donator leaving the graphene n-doped, which is demonstrated by density functional theory. We also verify the suitability of N-DMBI-doped n-type graphene for use as a cathode in inverted polymer light-emitting diodes (PLEDs) by using various analytical methods. Inverted PLEDs using a graphene cathode doped with N-DMBI radical showed dramatically improved device efficiency (~13.8 cd/A) than did inverted PLEDs with pristine graphene (~2.74 cd/A). Finally, N-DMBI-doped graphene can provide a practical way to produce graphene cathodes with low WF in various organic optoelectronics.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Mechanistic Study of Electrolyte Additives to Stabilize High-Voltage Cathode–Electrolyte Interface in Lithium-Ion Batteries

Current developments of electrolyte additives to stabilize electrode-electrolyte interface in Li-ion batteries highly rely on a trial-and-error search, which involves repetitive testing and intensive amount of resources. The lack of understandings on the fundamental protection mechanisms of the additives significantly increases the difficulty for the transformational development of new additives. In this study, we investigated two types of individual protection routes to build a robust cathode-electrolyte interphase at high potentials: (i) a direct reduction in the catalytic decomposition of the electrolyte solvent; and (ii) formation of a “corrosion inhibitor film” that prevents severely attack and passivation from protons that generated from the solvent oxidation, even the decomposition of solvent cannot not mitigated. Effect of three exemplary electrolyte additives: (i) lithium difluoro(oxalato)borate (LiDFOB); (ii) 3-hexylthiophene (3HT); and (iii) tris(hexafluoro-iso-propyl)phosphate (HFiP), on LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC 622) cathode were investigated to validate our hypothesis. It is demonstrated that understandings of both electrolyte additives and solvent are essential and careful balance between the cathode protection mechanism of additives and their side effects is critical to obtain optimum results. In conclusion, more importantly, this study opens up new directions of rational design of functional electrolyte additives for the next generation high-energy density lithium-ion chemistries.

25 ENERGY STORAGE↗
DOE OSTI2022

A New Cathode Material for a Li–O 2 Battery Based on Lithium Superoxide

Li–O 2 batteries suffer from large charge overpotentials due to the high charge transfer resistance of Li 2 O 2 discharge products. A potential solution to this problem is the development of LiO 2 -based batteries that possess low charge overpotentials due to the lower charge transfer resistance of LiO 2 . In this report, IrLi nanoparticles were synthesized and implemented for the first time as a LiO 2 battery cathode material. The IrLi nanoparticle synthesis was achieved by a temperature- and time-optimized thermal reaction between a precise ratio of iridium nanoparticles and lithium metal. Li–O 2 batteries employing the IrLi-rGO cathodes were cycled up to 100 cycles at moderate current densities with sustained low cell charge potentials (<3.5 V). Further, various characterization techniques, including SEM, DEMS, TEM, Raman, and titration, were used to demonstrate the LiO 2 discharge product and the absence of Li 2 O 2 . On the basis of first-principles calculations, it was concluded that the formation of crystalline LiO 2 can be stabilized by epitaxial growth on the (111) facets of IrLi nanoparticles present on the cathode surface. These findings demonstrate that, in addition to the previously studied Ir 3 Li intermetallic, the IrLi intermetallic also provides a means by which LiO 2 discharge products can be stabilized and confirms the importance of templating for the formation process.

25 ENERGY STORAGE↗
DOE OSTI2023

Stabilizing a Li–Mn–O Cathode by Blocking Lattice O Migration through a Nanoscale Phase Complex

Among all intercalation cathodes for Li-ion batteries, Li–Mn–O layered oxides offer the highest initial energy density at the lowest cost, due to the joint contribution from cationic and anionic redox chemistry. However, the poor cycling capability, resulting from the continuous lattice O loss at high potentials (>4.5 V), hinders practical applications. Herein, we employed phase complex engineering to obtain a new Li–Mn–O nanohybrid cathode featuring the uniform and coherent integration of layered nanodomains and spinel nanodomains. The combination of DFT calculations, synchrotron-based transmission X-ray microscopy, in situ differential electrochemical mass spectrometry, in situ synchrotron XRD, and electrochemical tests demonstrated that the O migration path in layered nanodomains was blocked by the neighboring spinel nanodomains with a higher oxygen vacancy migration energy, thus effectively suppressing the irreversible lattice O loss at high potentials and enhancing the cycling stability in both capacity and average voltage. Finally, the strategy is experimentally demonstrated to be effective and it leads to a new path for developing stable high-energy-density cathode materials.

25 ENERGY STORAGE↗
DOE OSTI2024

Importance of High Valence Element Nb in Ni-Rich Layered Cathodes for High-Voltage Lithium-Metal Batteries

Ni-rich layered cathode materials have attracted extensive attention due to their higher energy density and technological maturity in commercialization. As the nickel content is raised, especially surpassing 80%, the increased energy density comes with the tradeoff of diminished thermal stability and increased electrochemical structural instability of the cathode. Compared with Co, Al, B, and Ta, the introduction of high valence element Nb significantly improved the electrochemical cycling, delivering a capacity of 202 mAh/g, corresponding to a capacity retention of 92% after 200 cycles tested at 45 °C. Further, the ex situ differential scanning calorimetry and in situ isothermal microcalorimetry demonstrate that the Nb-modified cathode has the potential to enhance the safety of ultrahigh nickel (Ni) NMCs and displays remarkable resilience to extensive cycling by inhibiting high-temperature decomposition reactions and exhibiting a lower heat flow during electrochemical cycling.

25 ENERGY STORAGE↗
DOE OSTI2025

Ni-Rich Li[Ni x MnyCo 1– x – y ]O 2 Single Crystals as Superior Fast Charge Cathodes for Lithium-Ion Batteries

The utilization of single-crystal (SC) Li[Ni x MnyCo 1-x-y ]O 2 (NMC) cathodes has facilitated unparalleled performance in commercial high-energy lithium-ion batteries (LIBs). In the current study, we evaluate the application of SC cathodes in fast charge (FC)-LIBs where particle cracking is a predominant failure mechanism. Ni-rich SC-NMC samples with various compositions, sizes, and shapes are synthesized and investigated for their influence on FC performance. We reveal the necessity of utilizing smaller SCs (<1 μm) as larger sizes (>2 μm) experience significant particle-level lithium concentration gradients under FC conditions. To improve lithium transport and minimize side reactivities, we strategically expose the (104) crystal facets on the surface. Exceptional performance was observed on an optimized SC-LiNi 0.80 Mn 0.05 Co 0.15 O 2 , delivering a discharge capacity of 165 mAh/g even after 150 cycles at 6C charge. Our study not only demonstrates the promise of SC-NMC but also provides the key insights for the design and optimization of advanced cathodes for FC-LIBs.

25 ENERGY STORAGE↗
DOE OSTI2026

Cathode-Confined Polysulfide Retention-Release Reprograms Li 2 S Deposition in High-Loading Li–S Batteries

High-loading lithium-sulfur (Li-S) cells operated with lean electrolyte are limited by polysulfide crossover to Li metal and by transport-limited liquid-solid conversion that forms passivating Li 2 S films. Here, we show that a cathode-facing separator coating of carboxylated multiwalled carbon nanotubes acts as a cathode-confined polysulfide reservoir with intermediate binding. Early in discharge it captures newly generated polysulfides at the separator interface, suppressing shuttle reactions. As polysulfides are consumed, the reservoir buffers concentration gradients and feeds reactants back to the cathode, shifting Li 2 S deposition from burst-like film growth to progressive, three-dimensional, porous formation. Synchrotron XRD and S K-edge XANES, together with Scharifker–Hills nucleation analysis and depth-of-discharge EIS/DRT, substantiate this coupled transport–reaction control. With 4.3 mg S cm -2 and E/S = 5, cells reach 4.2 mAh cm -2 and retain 90% capacity over 100 cycles at 20 °C.

25 ENERGY STORAGE↗
DOE OSTI2026

Coupling Redox Compensation and Interfacial Stabilization in Low-Ni O3-Type Sodium Layered Oxide Cathodes

Low-Ni O3-type sodium layered oxides are attractive cathodes for cost-robust sodium-ion batteries, yet high-voltage cycling is often limited by Fe-driven degradation, including cation migration/dissolution, irreversible slab gliding with large strain, particle cracking, and accelerated interfacial parasitic reactions. Here, in this study, we introduce a redox-interface codesign strategy using stoichiometric, charge-balanced Cu 2+ /Ti 4+ cosubstitution while preserving full Na stoichiometry, transitioning from NaNi 1/4 Fe 1/2 Mn 1/4 O 2 to NaNi 1/4 Fe 1/5 Mn 1/4 Cu 3/20 Ti 3/20 O 2 . With the cosubstitution, Cu and Ti suppress Fe migration and dissolution and facilitate sustained Fe oxidation at high voltage. Meanwhile, Cu is also shown to be redox-active, providing reversible cationic charge compensation that mitigates the capacity penalty typically associated with reducing Fe participation. Operando diffraction and spectroscopy collectively indicate a more reversible high-voltage structural evolution with suppressed Fe-related irreversibility. Particularly, spontaneous Ti enrichment at surface/grain-boundary regions stabilizes the cathode−electrolyte interface and promotes a more NaF-rich interphase signature. This work establishes a generalizable route to reconcile stability and capacity in low-Ni, Fe-containing O3 sodium layered oxide cathodes via compositionally encoded bulk-interfacial coupling.

25 ENERGY STORAGE↗
DOE OSTI2026

Pressure Heterogeneity and Material Utilization in Thin-Film Solid-State Cathodes

Intimate interfacial contact between the solid electrolyte and the cathode active material is critical for maximizing cathode utilization in solid-state batteries. However, volume changes during electrochemical cycling induce internal stresses that drive interfacial degradation, particularly under nonuniform stack pressure. In this study, we employ in situ energy-dispersive X-ray diffraction tomography to visualize and quantify reaction heterogeneities across a 3 mm-diameter solid-state cathode with a well-defined interface. Our results reveal that regions under a lower stack pressure exhibit reduced material utilization and reversibility, which negatively affect the high-pressure regions. Interfacial degradation further impedes lithium-ion transport and amplifies microscale reaction heterogeneity. These findings highlight the critical role of stack pressure distribution in governing interfacial stability and electrochemical performance, offering important design insights into practical solid-state battery systems.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Honeycomb-Ordered Na 3 Ni 1.5 M 0.5 BiO 6 (M = Ni, Cu, Mg, Zn) as High-Voltage Layered Cathodes for Sodium-Ion Batteries

Developing high-voltage layered cathodes for sodium-ion batteries (SIBs) has always been a severe challenge. Herein, a new family of honeycomb-layered Na 3 Ni 1.5 M 0.5 BiO 6 (M = Ni, Cu, Mg, Zn) with a monoclinic superstructure has been shown to combine good Na + (de)intercalation activity with a competitive 3.3 V high voltage. By coupling the electrochemical process with ex situ X-ray absorption spectroscopy as well as in situ X-ray diffraction, the charge compensation mechanism and structural evolution of these new cathodes are clearly investigated. Interestingly, both Ni 2+ /Ni 3+ and Cu 2+ /Cu 3+ participate in the redox reaction upon cycling, and the succession of single-phase, two-phase, or three-phase regions upon Na+ extraction/insertion were identified with rather good accuracy. Furthermore, this research strategy could provide insights into the structure–function–property relationships on a new series of honeycomb-ordered materials with the general formula Na 3 Ni 1.5 M 0.5 BiO 6 and also serve as a bridge to guide future design of high-performance cathodes for SIBs.

25 ENERGY STORAGE↗
DOE OSTI2018

TiS 2 –Polysulfide Hybrid Cathode with High Sulfur Loading and Low Electrolyte Consumption for Lithium–Sulfur Batteries

Sulfur cathodes have a high theoretical capacity of 1675 mAh g –1 , making the lithium–sulfur batteries a promising technology for future energy-storage devices. However, their commercial viability is faced with challenges arising from intrinsic electrochemical instabilities and inappropriate cell fabrication parameters. We report here the feasibility of employing TiS 2 as a conductive polysulfide adsorbent, which allows the use of a high amount of electrochemically active polysulfides in building a TiS 2 –polysulfide hybrid cathode. The hybrid cathode exhibits long cycle stability at a C/5 rate over 200 cycles with a high areal capacity and energy density of, respectively, 10 mAh cm –2 and 20 mWh cm –2 , exceeding those of commercial LiCoO 2 . Furthermore, such an enhanced electrochemical performance is obtained in cells with a high sulfur content (65 wt %), high sulfur loading (12 mg cm –2 ), high sulfur mass (12 mg/cathode), and a low electrolyte/sulfur ratio of just 5 μL mg –1 .

25 ENERGY STORAGE↗
DOE OSTI2019

Artificial Solid Electrolyte Interphase for Suppressing Surface Reactions and Cathode Dissolution in Aqueous Zinc Ion Batteries

Vanadium-based compounds have been widely used as electrode materials in aqueous zinc ion batteries (ZIBs) due to the multiple oxidation states of vanadium and their open framework structure. However, the solubility of vanadium in aqueous electrolytes and the formation of byproducts during the charge/discharge process cause severe capacity fading and limit cycle life. Here in this paper, we report an ultrathin HfO 2 film as an artificial solid electrolyte interphase (SEI) that is uniformly and conformally deposited by atomic layer deposition (ALD). The inactive hafnium(IV) oxide (HfO 2 ) film not only decreases byproduct (Zn 4 SO 4 (OH) 6 ·xH 2 O) formation on the surface of Zn 3 V 2 O 7 (OH) 2 ·2H 2 O (ZVO) but also suppresses the ZVO cathode dissolution in the electrolyte. As a result, the obtained HfO 2 -coated ZVO cathodes deliver higher capacity and better cycle life (227 mAh g –1 @100 mA g –1 , 90% retention over 100 cycles) compared with pristine ZVO (170 mAh g –1 @100 mA g –1 , 45% retention over 100 cycles). A mechanistic investigation of the role of HfO 2 is presented, along with data showing that our method constitutes a general strategy for other cathodes to enhance their performance in aqueous ZIBs.

25 ENERGY STORAGE↗