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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 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

The Role of Electron Localization in Covalency and Electrochemical Properties of Lithium-Ion Battery Cathode Materials

Following the fundamental research conducted by J. B. Goodenough, the important role of electron localization induced by elemental substitution is studied. The size and electron negativity of host and substituting ions are two important factors in tuning material properties such as local structure and transition metal (TM) oxygen covalency. However, another factor, electron localization, which is widely studied in catalyst research but largely overlooked for battery materials, deserves systematic studies. A combined investigation using synchrotronbased X-ray spectroscopy and theoretical calculations is carried out on the Li-Co-Mn-O model system in which the substituting cation Mn 4+ , with its 3d 3 electronic structure, is used as a promoter for electron localization. Results indicate that electron localization greatly influences the Co - O bond by making it less covalent, which increases the delithiation voltage. It is also found that during charge/discharge, electron localization tends to make TM K-edge X-ray absorption near edge spectroscopy (XANES) spectra show a more “rigid shift” behavior while electron delocalization makes the XANES exhibit a “shape change.” It clearly explains why the K-edge XANES data of some TM oxides show no “rigid shift” while the nominal valence states changed. This work highlights the importance of electron localization with guidance for XANES interpretation.

25 ENERGY STORAGE↗
DOE OSTI2020

Probing Dopant Redistribution, Phase Propagation, and Local Chemical Changes in the Synthesis of Layered Oxide Battery Cathodes

Achieving the targeted control of layered oxide properties calls for more fundamental studies to mechanistically probe their evolution during their synthesis. Herein, dopant distribution, phase propagation, and local chemical changes as well as their interplay in multielement-doped LiNiO 2 materials are investigated using spectroscopic, imaging, and scattering techniques. It is shown that dopants undergo dynamic redistribution in the Ni(OH) 2 host lattice at the early stage of calcination (below 300 °C). Such redistribution behavior exhibits strong dopant-dependent characteristics, allowing for targeted surface and bulk doping control. The Ni oxidation process exhibits depth-dependent characteristics and the most rapid Ni oxidation takes place between 300 and 700 °C. Using Ni oxidation state as the proxy for the phase transformation, the buildup of heterogenous phase propagation in the early stage of calcination is shown, especially along the radial direction of secondary particles. Furthermore, the radial heterogenous phase distribution gradually decreases upon completing the calcination. However, a high degree of mosaic-like heterogeneity may still be present in the final product, departing from the perfect layered oxide. Overall, the present study offers fundamental insights into manipulating multiscale materials properties during calcination for obtaining stable, high-energy layered oxide cathodes.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Engineering lithium-ion battery cathodes for high-voltage applications using electromagnetic excitation

Microwave radiation (MWR), a type of electromagnetic excitation source, reduces the synthesis temperature and processing time for chemical reactions compared to traditional synthesis methods. Recently, we demonstrated that MWR can engineer ceramics with different crystal phases compared to traditional methods [ Journal of Materials Chemistry A 5 , 35 (2017)]. Here, we further apply the MWR-assisted technique to improve the electrochemical performance of LiCoO 2 cathodes by engineering TiO 2 and ZrO 2 ceramic coatings. Electrochemical tests suggest that the TiO 2 coating improves the rate capability of the LiCoO 2 electrode. Both TiO 2 and ZrO 2 coatings improve the high-voltage (4.5 V) cycling stability of LiCoO 2 . The capacity remaining is improved from 52.8 to 84.4% and 81.9% by the TiO 2 coating and the ZrO 2 coating, respectively, after 40 cycles. We compare these results with existing studies that apply traditional methods to engineer TiO 2 /ZrO 2 on LiCoO 2 , and find that the MWR-assisted method shows better performance improvement. X-ray photoelectron spectroscopy measurements suggest that the improved cycling stability arises from the formation of metal fluorides that protect the electrode from side reactions with electrolytes. This mechanism is further supported by the reduced Co dissolution from TiO 2 /ZrO 2 -coated LiCoO 2 electrode after cycling. This study provides a new toolbox facilitating the integration of many delicate, low melting point materials like polymers into battery electrodes.

25 ENERGY STORAGE↗
DOE OSTI2026

Chemo-Mechanics of α-V 2 O 5 During Lithiation and Implications for Rechargeable Battery Cathodes

Chemo-mechanical degradation of layered oxide electrodes is strongly influenced by crystallographic anisotropy, local stress evolution, and ion insertion, yet the intrinsic mechanical response of layered materials remains incompletely understood. Indeed, most prior studies have focused on polycrystalline materials but single crystals enable direct observation of coupling between anisotropic ion diffusion and mechanical response. This study aims to determine how crystallographic anisotropy and lithiation affect deformation, fracture, and mechanical properties in single-crystal V 2 O 5 , and compares this behavior with polycrystalline counterparts. Polycrystalline V 2 O 5 thin films and single-crystal α-V 2 O 5 were studied using nanoindentation, scanning electron microscopy, focused ion beam cross-sectioning, and Raman spectroscopy. Single crystals were tested in pristine and chemically lithiated states, including experiments in which crystals were first plastically deformed via nanoindentation and subsequently lithiated. Polycrystalline films exhibited significantly higher hardness and elastic modulus than single crystals. Single crystals indented normal to the exposed (001) basal plane exhibited pronounced anisotropic deformation, including directional slip, crystallographically-guided cracking, anisotropic crack propagation, interlayer separation, and shear localization. Lithiation caused substantial softening, reduced hardness and modulus, and suppressed displacement bursts during nanoindentation, while previously indented regions showed crack formation and growth upon lithiation. Mechanical behavior of α-V 2 O 5 is strongly governed by crystallographic anisotropy and further altered by lithiation, with pre-existing deformation serving as a strong driver of fracture during ion insertion. These findings illuminate the coupling among ion insertion, deformation, and fracture in layered oxides and provide a basis for understanding and mitigating mechanical failure in electrochemical energy-storage materials.

Anisotropy↗
DOE OSTI2021

A Polymer-Assisted Spinodal Decomposition Strategy toward Interconnected Porous Sodium Super Ionic Conductor-Structured Polyanion-Type Materials and Their Application as a High-Power Sodium-Ion Battery Cathode

A general polymer-assisted spinodal decomposition strategy is used to prepare hierarchically porous sodium super ionic conductor (NASICON)-structured polyanion-type materials (e.g., Na 3 V 2 (PO 4 ) 3 , Li 3 V 2 (PO 4 ) 3 , K 3 V 2 (PO 4 ) 3 , Na 4 MnV(PO 4 ) 3 , and Na 2 TiV(PO 4 ) 3 ) in a tetrahydrofuran/ethanol/H 2 O synthesis system. Depending on the boiling point of solvents, the selective evaporation of the solvents induces both macrophase separation via spinodal decomposition and mesophase separation via self-assembly of inorganic precursors and amphiphilic block copolymers, leading to the formation of hierarchically porous structures. We find that the resulting hierarchically porous Na 3 V 2 (PO 4 ) 3 possessing large specific surface area (≈77 m 2 g -1 ) and pore volume (≈0.272 cm 3 g -1 ) shows a high specific capacity of 117.6 mAh g -1 at 0.1 C achieving the theoretical value and a long cycling life with 77% capacity retention over 1000 cycles at 5 C. This method presented here can open a facile avenue to synthesize other hierarchically porous polyanion-type materials.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Cobalt Dissolution from Metal Oxides and Battery Cathode Materials with Acetic Acid-Based Deep Eutectic Solvents

Recovery of critical metals with alternative solvents beyond those in traditional pyrometallurgy and hydrometallurgy is needed in consideration of environmental challenges and the growing demand for metals in energy technologies. Deep eutectic solvents (DESs) have emerged as sustainable alternatives for solvometallurgy in metal separation and recovery. In this study, DESs based on hydrogen bond acceptors (HBAs) including choline chloride (ChCl), acetylcholine chloride (AChCl), and betaine (Bet) were investigated for their effectiveness when paired with acetic acid (AA) as the hydrogen bond donor (HBD) for the dissolution of cobalt from cobalt oxide (CoO), lithium cobalt oxide (LiCoO 2 ), and lithium nickel manganese cobalt oxide (LNMC). Based on the spectroscopic analysis of the metal dissolution and coordination, Bet:AA was found to provide the highest solubility for CoO (0.33 M) in the form of an octahedral complex. On the other hand, ChCl:AA solvent was more effective at dissolving LiCoO 2 with 0.04 M Co 2+ corresponding to 17% dissolution efficiency and LNMC with 0.06 M Co 2+ corresponding to 72% dissolution efficiency at 50 °C, compared to Bet:AA (9% for LiCoO 2 and 31% for LNMC). Although the solubilities of LiCoO 2 and LNMC have not significantly improved in ChCl:AA, this difference in effectiveness between the solvents clearly reveals the role of the HBA in solubilization. The coordination synergy between the chloride and the –OH moiety facilitates the breakdown of the LiCoO 2 driven by the alteration of the solvent polarity. Cobalt in these solutions was found dominantly as a tetrahedral [CoCl 4 ] 2– complex. A chemical separation of cobalt oxalate from a mixed-metal oxide system based on Co, Fe, and Ni was also demonstrated, confirming the potential of these solvents for practical metal recovery.

Cobalt separation↗
DOE OSTI2020

High Voltage Mg-Ion Battery Cathode via a Solid Solution Cr–Mn Spinel Oxide

We discuss how lattice Mg 2+ in a tailored solid solution spinel, MgCrMnO 4 , is electrochemically utilized at high Mn-redox potentials in a nonaqueous electrolyte. Complementary evidence from experimental and theoretical analyses supports bulk Mg 2+ (de)intercalation throughout the designed oxide frame where strong electrostatic interaction between Mg 2+ and O 2- exists. Mg/Mn antisite inversion in the spinel is lowered to similar to 10% via postannealing at 350 degrees C to further improve Mg 2+ mobility. Spinel lattice is preserved upon removal of Mg 2+ without any phase transformations, denoting structural stability at the charged state at a high potential similar to 3.0 V (vs Mg/Mel. Clear remagnesiation upon first discharge, harvesting up to similar to 180 Wh/kg at 60 degrees C is shown. In the remagnesiated state, insertion of Mg 2+ into interstitial sites in the spinel is detected, possibly resulting in partial reversibility which needs to be addressed for structural stability. The observations constitute a first clear path to the development of a practical high voltage Mg-ion cathode using a spinel oxide.

25 ENERGY STORAGE↗
DOE OSTI2021

Stabilizing NMC 811 Li-Ion Battery Cathode through a Rapid Coprecipitation Process

Improving the capacity of LiNi x Mn y Co 1-x-y O 2 (NMC) by increasing the Ni content results in materials with poor cycling performance and reduced thermal stability. These problems can be alleviated by creating concentration gradients in the materials, but this requires more expensive batch processing. Herein, a simple process is described that can create a coating that penetrates into the precursor particles, creating unique gradients in the precursor material. The coated material demonstrates improved cycling performance and thermal stability as compared to uncoated materials. Additionally, rapid heating to simulate a thermal runaway event while observing these materials with X-rays gives a deeper understanding of how the coating affects the decomposition process.

25 ENERGY STORAGE↗