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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 307 records · Page 17
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Diamond and methane formation from the chemical decomposition of polyethylene at high pressures and temperatures

Abstract Polyethylene (C 2 H 4 ) n was compressed to pressures between 10 and 30 GPa in a diamond anvil cell (DAC) and laser heated above 2500 K for approximately one second. This resulted in the chemical decomposition of the polymer into carbon and hydrocarbon reaction products. After quenching to ambient temperature, the decomposition products were measured in the DAC at pressures ranging from ambient to 29 GPa using a combination of x-ray diffraction (XRD) and small angle x-ray scattering (SAXS). XRD identified cubic diamond and methane as the predominant product species with their pressure–volume relationships exhibiting strong correlations to the diamond and methane equations of state. Length scales associated with the diamond products, obtained from SAXS measurements, indicate the formation of nanodiamonds with a radius of gyration between 12 and 35 nm consistent with 32–90 nm diameter spherical particles. These results are in good agreement with the predicted product composition under thermodynamic and chemical equilibrium.

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

Evolution of micro-pores in Ni–Cr alloys via molten salt dealloying

Porous materials with high specific surface area, high porosity, and high electrical conductivity are promising materials for functional applications, including catalysis, sensing, and energy storage. Molten salt dealloying was recently demonstrated in microwires as an alternative method to fabricate porous structures. The method takes advantage of the selective dissolution process introduced by impurities often observed in molten salt corrosion. This work further investigates molten salt dealloying in bulk Ni–20Cr alloy in both KCl–MgCl 2 and KCl–NaCl salts at 700 °C, using scanning electron microscopy, energy dispersive spectroscopy, and X-ray diffraction (XRD), as well as synchrotron X-ray nano-tomography. Micro-sized pores with irregular shapes and sizes ranging from sub-micron to several microns and ligaments formed during the process, while the molten salt dealloying was found to progress several microns into the bulk materials within 1–16 h, a relatively short reaction time, enhancing the practicality of using the method for synthesis. The ligament size increased from ~ 0.7 μm to ~ 1.3 μm in KCl–MgCl 2 from 1 to 16 h due to coarsening, while remaining ~ 0.4 μm in KCl–NaCl during 16 h of exposure. The XRD analysis shows that the corrosion occurred primarily near the surface of the bulk sample, and Cr 2 O 3 was identified as a corrosion product when the reaction was conducted in an air environment (controlled amount sealed in capillaries); thus surface oxides are likely to slow the morphological coarsening rate by hindering the surface diffusion in the dealloyed structure. 3D-connected pores and grain boundary corrosion were visualized by synchrotron X-ray nano-tomography. This study provides insights into the morphological and chemical evolution of molten salt dealloying in bulk materials, with a connection to molten salt corrosion concerns in the design of next-generation nuclear and solar energy power plants.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Synthesis of a novel multifunctional organic–inorganic nanocomposite for metal ions and organic dye removals

In this study, we used solvent assisted mechano-synthesis strategies to form multifunctional organic–inorganic nanocomposites capable of removing both organic and inorganic contaminants. A zeolite X (Ze) and activated carbon (AC) composite was synthesized via state-of-the-art mechanical mixing in the presence of few drops of water to form Ze/AC. The second composite (Ze/L/AC) was synthesized in a similar fashion, however this composite had the addition of disodium terephthalate as a linker. Both materials, Ze/AC and Ze/L/AC, were characterized using scanning electron microscope (SEM), energy-dispersive X-ray spectroscopy (EDS), Powdered X-ray diffraction (P-XRD), Fourier-transform infrared spectrometry (FTIR), Accelerated Surface Area and Porosimetry System (ASAP), and thermal gravimetric analysis (TGA). The SEM–EDS displayed the surface structure and composition of each material. The sodium, oxygen and carbon contents increased after linker connected Ze and AC. The P-XRD confirmed the crystallinity of each material as well as the composites, while FTIR indicated the function groups (C=C, O–H) in Ze/L/AC. The contaminant adsorption experiments investigated the effects of pH, temperature, and ionic strength on the adsorption of methylene blue (MB) and Co(II) for each material. In MB adsorption, the first-order reaction rate of Ze/L/AC (0.02 h -1 ) was double that of Ze/AC (0.01 h -1 ). The reaction rate of Ze/L/AC (4.8 h -1 ) was also extraordinarily higher than that of Ze/AC (0.6 h -1 ) in the adsorption of Co(II). Ze/L/AC composite achieved a maximum adsorption capacity of 44.8 mg/g for MB and 66.6 mg/g for Co(II) ions. The MB adsorption of Ze/AC and Ze/L/AC was best fit in Freundlich model with R 2 of 0.96 and 0.97, respectively, which indicated the multilayer adsorption. In the Co(II) adsorption, the data was highly fit in Langmuir model with R 2 of 0.94 and 0.92 which indicated the monolayer adsorption. These results indicated both materials exhibited chemisorption. The activation energy of Ze/L/AC in MB adsorption (34.9 kJ mol -1 ) was higher than that of Ze/L/AC in Co (II) adsorption (26 kJ mol -1 ).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Carbon mineralization pathways in interfacial adsorbed water nanofilms

Carbon mineralization in humidified carbon dioxide offers a promising route to mitigate anthropogenic emissions in a world stressed by water security. Despite its technological importance, our understanding of carbonation in water-poor environments lags, as traditional dissolution-precipitation pathways struggle to explain the adsorbed water nanofilm-mediated reactivity. Here, we utilize in operando X-ray diffraction (XRD) and advanced molecular simulations to investigate nanoconfined reactions driving forsterite carbonation, the magnesium-rich olivine. By examining magnesium ion dissolution and transport in atomistic simulations of the forsterite-water-carbon dioxide interface and comparing these with the in operando XRD activation energies, we identify both processes as rate-limiting at saturation. Our simulations reveal a mechanistic view of interfacial carbonation, where dissolution and precipitation are mediated by anomalous quasi two-dimensional diffusion. The transport process involves intermittent diffusive hopping in the desorbed state, separated by crawling events that are spatially short but temporally long. This understanding transcends carbon mineralization, with implications for understanding the transport of contaminants in geosystems, the design of multifunctional materials, water desalination, and molecular recognition systems.

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

Hydration of α-UO 3 following storage under controlled conditions of temperature and relative humidity

Changes in chemical speciation of uranium oxides following storage under varied conditions of temperature and relative humidity are valuable for characterizing material provenance. In this study, subsamples of high purity α-UO 3 were stored under four sets of controlled conditions of temperature and relative humidity over several years, and then measured periodically for chemical speciation. Powder X-ray diffraction (XRD) analysis and extended X-ray absorption fine structure spectroscopy confirm hydration of α-UO 3 to a schoepite-like end product following storage under each of the varied storage conditions, but the species formed during exposure to the lower relative humidity and lower temperature condition follows different trends from those formed under the other three storage conditions (high relative humidity with high or low temperatures, and low relative humidity with a high temperature). Thermogravimetry coupled with XRD analysis was carried out to distinguish desorption pathways of water from the hydrated end products. Density functional theory calculations discern changes in the structure of α-UO 3 following incorporation of 1, 2 or 3 H 2 O molecules or 1, 2 or 3 OH groups into the orthorhombic lattice, revealing differences in lattice constants, U–O bond lengths, and U–U distances. The collective results from this analysis are in contrast to analogous studies that report that U 3 O 8 is oxidized and hydrated in air during storage under high relative humidity conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Mechanochemical synthesis and structural analysis of trivalent lanthanide and uranium diphenylphosphinodiboranates

Phosphinodiboranates (H 3 BPR 2 BH 3 – ) are a class of borohydrides that have merited a reputation as weakly coordinating anions, which is attributed in part to the dearth of coordination complexes known with transition metals, lanthanides, and actinides. We recently reported how K(H 3 BP t Bu 2 BH 3 ) exhibits sluggish salt elimination reactivity with f-metal halides in organic solvents such as Et 2 O and THF. Here we report how this reactivity appears to be further attenuated in solution when the t Bu groups attached to phosphorus are exchanged for R = Ph or H, and we describe how mechanochemistry was used to overcome limited solution reactivity with K(H 3 BPPh 2 BH 3 ). Grinding three equivalents of K(H 3 BPPh 2 BH 3 ) with UI 3 (THF) 4 or LnI 3 (Ln = Ce, Pr, Nd) allowed homoleptic complexes with the empirical formulas U(H 3 BPPh 2 BH 3 ) 3 (1), Ce(H 3 BPPh 2 BH 3 ) 3 (2), Pr(H 3 BPPh 2 BH 3 ) 3 (3), and Nd(H 3 BPPh 2 BH 3 ) 3 (4) to be prepared and subsequently crystallized in good yields (50–80%). Single-crystal XRD studies revealed that all four complexes exist as dimers or coordination polymers in the solid-state, whereas 1 H and 11 B NMR spectra showed that they exist as a mixture of monomers and dimers in solution. Treating 4 with THF breaks up the dimer to yield the monomeric complex Nd(H 3 BPPh 2 BH 3 ) 3 (THF) 3 (4-THF). XRD studies revealed that 4-THF has one chelating and two dangling H 3 BPPh 2 BH 3 – ligands bound to the metal to accommodate binding of THF. In contrast to the results with K(H 3 BPPh 2 BH 3 ), attempting the same mechanochemical reactions with Na(H 3 BPH 2 BH 3 ) containing the simplest phosphinodiboranate were unsuccessful; only the partial metathesis product U(H 3 BPH 2 BH 3 )I 2 (THF) 3 (5) was isolated in poor yields. Here, despite these limitations, our results offer new examples showing how mechanochemistry can be used to rapidly synthesize molecular coordination complexes that are otherwise difficult to prepare using more traditional solution methods.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Cluster defects in gibbsite nanoplates grown at acidic to neutral pH

Gibbsite [α-Al(OH) 3 ] is the solubility limiting phase for aluminum across a wide pH range, and it is a common mineral phase with many industrial applications. The growth mechanism of this layered-structure material, however, remains incompletely understood. Synthesis of gibbsite at low to circumneutral pH yields nanoplates with substantial interlayer disorder. Here we examine defects in this material in detail, and the effects of recrystallization in highly alkaline sodium hydroxide solution at 80 °C. We employed a multimodal approach, including scanning electron microscopy, magic-angle spinning nuclear magnetic resonance (MAS-NMR), Raman and infrared spectroscopies, X-ray diffraction (XRD), and X-ray total scattering pair distribution function (XPDF) analysis to characterize the ageing of the nanoplates over several days. Additionally, XRD and XPDF indicate that gibbsite nanoplates precipitated at circumneutral pH contain dense, truncated sheets imparting a local difference in interlayer distance. These interlayer defects appear well described by flat Al 13 aluminum hydroxide nanoclusters nearly isostructural with gibbsite sheets present under synthesis conditions and trapped as interlayer inclusions during growth. Ageing at elevated temperature in alkaline solutions gradually improves crystallinity, showing a gradual increase in H-bonding between interlayer OH groups. Between 7 to 8 vol% of the initial gibbsite nanoparticles exhibit this defect, with the majority of differences disappearing after 2–4 hours of recrystallization in alkaline solution. The results not only identify the source of disorder in gibbsite formed under acidic/neutral conditions but also point to a possible cluster-mediated growth mechanism evident through inclusion of relict oligomers with gibbsite-like topology trapped in the interlayer spaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Importance of multimodal characterization and influence of residual Li 2 S impurity in amorphous Li 3 PS 4 inorganic electrolytes

Amorphous Li 3 PS 4 (LPS) solid-state electrolytes are promising for energy-dense lithium metal batteries. LPS glass, synthesized from a 3:1 mol ratio of Li 2 S and P 2 S 5 , has high ionic conductivity and can be synthesized by ball milling or solution processing. Ball milling has been attractive because it provides the easiest route to access amorphous LPS with a conductivity of 3.5 × 10 –4 S cm –1 (20 °C). However, achieving the complete reaction of precursors via ball milling can be difficult, and most literature reports use X-ray diffraction (XRD) or Raman spectroscopy to confirm sample purity, both of which have limitations. Furthermore, the effect of residual precursors on ionic conductivity and lithium metal cycling is unknown. In this work, we illustrate the importance of multimodal characterization to determine LPS phase and chemical purity. To determine the residual Li 2 S content in LPS, we show that (1) XRD and 31 P solid state nuclear magnetic resonance (ssNMR) are insufficient and (2) Raman loses sensitivity at concentrations below 12 mol% Li 2 S. Most importantly, we show that 7 Li ssNMR is highly sensitive. Using 7 Li ssNMR, we investigate the effect of ball milling parameters and develop a robust and highly reproducible procedure for pure LPS synthesis. We find that as the residual Li 2 S precursor content increases, LPS conductivity decreases and lithium metal batteries exhibit higher overpotentials and poor cycle life. Furthermore, our work reveals the importance of multimodal characterization techniques for amorphous solid-state electrolyte characterization and will enable better synthetic strategies for highly conductive electrolytes for efficient energy-dense solid-state lithium metal batteries.

25 ENERGY STORAGE↗
DOE OSTI2021

Multi-scale investigation of heterogeneous swift heavy ion tracks in stannate pyrochlore

Er 2 Sn 2 O 7 pyrochlore was irradiated with swift heavy Au ions (2.2 GeV), and the induced structural modifications were systematically examined using complementary characterization techniques including transmission electron microscopy (TEM), X-ray diffraction (XRD), and neutron total scattering with pair distribution function (PDF) analysis. Each technique probes different aspects and length scales of the transformed material regions. TEM revealed a core–shell ion track structure—an amorphous core surrounded by a disordered, anion-deficient fluorite shell—which was confirmed by XRD. Neutron total scattering, with sensitivity to the oxygen sublattice, provided relative fractions of amorphous and disordered fluorite phases and confirmed the presence of a defective pyrochlore phase, which largely maintains its structural ordering but is clearly distinct from the pristine pyrochlore matrix. This defect-rich pyrochlore phase forms a halo extending radially beyond the well-characterized core–shell track morphology observed in electron micrographs. Despite their differing long-range periodicity, the short-range structures of the amorphous, disordered, and defective pyrochlore phases are all modeled well with a weberite-type configuration. Evolution of the phase fractions with increasing ion fluence was examined to ascertain the phase-to-phase pathways that occur during primary and secondary ion impact. Furthermore, this approach extends knowledge about the multi-scale response of stannate pyrochlores to swift heavy ion irradiation in the electronic energy loss regime and improves existing track-overlap models.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Ce stabilized Ni–SrO as a catalytic phase transition sorbent for integrated CO 2 capture and CH 4 reforming

Integration of carbon dioxide capture from flue gas with dry reforming of CH 4 represents an attractive approach for CO 2 utilization. The selection of a suitable bifunctional material serving as a catalyst/sorbent is the key. This paper reports Ni decorated and CeO x -stabilized SrO (SrCe 0.5 Ni 0.5 ) as a multi-functional, phase transition catalytic sorbent material. The effect of CeO x on the morphology, structure, decarbonation reactivity, and cycling stability of the catalytic sorbent was determined with TEM-EDX, XRD, in situ XRD, CH 4 -TPR and TGA. Here, cyclic process tests were conducted in a packed bed reactor. The results indicate that large Ni clusters were present on the surface of the SrNi sorbent, and the addition of CeO 2 promoted even distribution of Ni on the surface. Moreover, the Ce–Sr interaction promoted a complex carbonation/decarbonation phase-transition, i.e. SrCO 3 + CeO 2 ↔ Sr 2 CeO 4 + CO 2 as opposed to the conventional, simple carbonation/decarbonation cycles (e.g. SrCO 3 ↔ SrO + CO 2 ). This double replacement crystalline phase transition mechanism not only adjusts the carbonation/calcination thermodynamics to facilitate SrCO 3 decomposition at relatively low temperatures but also inhibits sorbent sintering. As a result, excellent activity and stability were observed with up to 91% CH 4 conversion, >72% CO 2 capture efficiency and ~100% residual O 2 capture efficiency from flue gas by utilizing the CeO 2 ↔ Ce 2 O 3 redox transition. This renders an intensified process with zero coke deposition. Moreover, the SLDRM with SrCe 0.5 Ni 0.5 has the flexibility to produce concentrated CO via CO 2 -splitting while co-producing a syngas with tunable H 2 /CO ratios.

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

The diversity of aluminum-based drinking water treatment residuals for use in environmental remediation

Drinking water treatment residuals (DWTRs) are complex mixtures of organic and inorganic phases generally disposed of as waste materials. However, their strong sorptive properties could be further exploited to immobilize contaminants. To characterize these materials, we applied a range of analytical techniques to a set of aluminum-based DWTRs. Here we determined surface areas, elemental compositions using CHNS analysis and X-ray fluorescence (XRF), performed thermogravimetric analyses paired with mass spectrometry (TGA-MS), and used synchrotron-based methods: X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS). Elemental analyses and specific surface area measurements – that vary between 7.23 ± 0.03 and 197.6 ± 0.9 m 2 g –1 – indicate that non-coagulant additives must play an important role in controlling sorption. High resolution powder XRD reveals the presence of only a few crystalline minerals mostly derived from source waters or additives. Fe was detected by XRF in all samples, whereas Mn was present in significant levels in samples with potassium permanganate as additive. The chemical speciation of these elements was characterized by performing spectral decompositions of XAS spectra. The spectral features of Fe are consistent with iron(III) oxides/hydroxides and structural iron in clays. On the other hand, Mn is predominantly present under its reduced form, Mn(II).

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

XANES analysis of phosphate glasses melted with Tb 4 O 7 and SnO: evaluating the impact of valence states on structural, thermal, and luminescent properties

Barium phosphate glasses were prepared with 0.5 mol% Tb 4 O 7 added alongside SnO up to 5 mol% with the purpose of evaluating the resulting terbium and tin oxidation states and their impact on glass structural, thermal, and luminescent properties. In this work, following material synthesis by melt-quenching, the composition-structure–property investigation was pursued encompassing measurements by X-ray diffraction (XRD), X-ray absorption near-edge spectroscopy (XANES), Raman spectroscopy, differential scanning calorimetry (DSC), dilatometry, and photoluminescence (PL) spectroscopy. While XRD confirmed the amorphous nature of the glasses, results from XANES indicated that terbium occurs as terbium(III) with a predisposition for tin to exist as tin(IV) which decreased at high SnO content. The structural as well as the thermal properties appeared to be mostly impacted by the presence of tin(IV). Specifically, glass depolymerization was indicated to be induced by Sn 4+ ions, and their concentration was observed to correlate with glass transition and softening temperatures. On the other hand, the tin(II) remnants were observed to exert an impact on the luminescent properties shifting light emission from the green towards the blue-green (cyan). It is indicated that Tb 4 O 7 reacting to produce Tb 2 O 3 supports the oxidation of tin(II) to tin(IV) which in turn dominates the physical properties. However, this was somewhat circumvented at the highest SnO content wherein tin(IV) appeared to be lower.

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

Investigation into the crystal structure–dielectric property correlation in barium titanate nanocrystals of different sizes

For high capacitance multilayer ceramic capacitors, high dielectric constant and lead-free ceramic nanoparticles are highly desired. However, as the particle size decreases to a few tens of nanometers, their dielectric constant significantly decreases, and the underlying mechanism has yet to be fully elucidated. Herein, we report a systematic investigation into the crystal structure–dielectric property relationship of combustion-made BaTiO 3 (BTO) nanocrystals. When the nanocrystal size was 100 nm and below, a metastable paraelectric cubic phase was found in the as-received BTO (denoted as arBTO) nanocrystals based on an X-ray diffraction (XRD) study. A stable ferroelectric tetragonal phase was present when the nanocrystal size was above 200 nm. Notably, the cubic arBTO (particle size ≤100 nm) exhibited tetragonal fluctuations as revealed by Raman spectroscopy, whereas the tetragonal arBTO (particle size ≥200 nm) contained ~10% cubic fraction according to the Rietveld fitting of the XRD profiles. Thermal annealing of the multi-grain tetragonal arBTO at 950 °C yielded single crystals of annealed BTO (denoted as anBTO), whose dielectric constants were higher than those of arBTO. However, the single crystalline anBTO prevented the formation of 90° domains; therefore, they exhibited a low dielectric constant of ~300. Although X-ray photoelectron spectroscopy and high-resolution transmission electron microscopy could not identify the exact structural defects, our study revealed that surface and bulk defects formed during synthesis affect the final crystal structures and thus the dielectric properties of BTO nanocrystals with different sizes. Finally, the understanding obtained from this study will help us design high dielectric constant perovskite nanocrystals for next-generation multilayer ceramic capacitor applications.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Chemical and spectroscopic characterization of plutonium tetrafluoride

Anhydrous plutonium tetrafluoride is an important intermediate in the production of metallic Pu. This historically important compound is also known to exist in at least two distinct, yet understudied hydrate forms, PuF 4 ·xH 2 O(s) (0.5 ≤ x ≤ 2) and PuF 4 ·2.5H 2 O(s). X-ray diffraction (XRD), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM) are the most common tools used to characterize these materials, often in a context for studying structural and morphological changes that arise from aging or calcination. However, fundamental electronic and vibrational spectroscopic information is rather scarce. Here, in this study, we measured the visible and shortwave infrared (SWIR) diffuse reflectance, Fourier transform infrared (FTIR), fluorescence and Raman spectra of PuF 4 (s) and PuF 4 ·xH 2 O(s) to obtain a better electronic and vibrational fingerprint. Our work provides clear indication of the polymeric structure of anhydrous PuF 4 , consistent with the Raman spectrum of UF 4 (s) and its hydrates. This is supplemented with XRD, TGA and SEM analysis. Findings in this study indicate that the spectra are modified by particle size, which in turn is influenced by synthetic technique.

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

A study of silver acetate under extreme conditions

With the aim of exploring chemical systems that may undergo metallization when irradiated with hard X-rays, we selected silver acetate (AgC 2 H 3 O 2 ) for the subject of this study. X-ray-induced decomposition of silver acetate under ambient and high-pressure conditions was observed in a diamond anvil cell (DAC), leading to the formation of metallic nanograins of silver at ambient pressure and 1.65 GPa. At 4 GPa, no decomposition was observed. The Avrami kinetics equation also provides information about novel structural formation at ambient pressure and 1.65 GPa. By modeling of the XRD data, it was found that the size of the silver nanocrystallites formed at 1.65 GPa pressure steadily increased to ∼5 nm after 600 min of X-ray irradiation as determined by applying the Scherrer equation to the diffraction peak widths. Time-resolved X-ray diffraction (XRD) revealed pressure-dependent kinetics, demonstrating that coupling pressure with irradiation enables controlled photochemical pathways in this model system. Concurrent with previous studies, the application of high pressure (HP) can be considered as a means of controlling X-ray synthetic photochemistry.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Effects of heteroatom doping on hydrogen uptake in tungsten oxide

Redox-active transition metal oxides (TMOs) that can undergo proton-insertion coupled electron transfer (PICET) are promising candidates for catalyzing molecular conversion reactions which require the transfer of hydrogen atoms (or the thermochemical equivalent, H + , e − ). Herein, we studied the effects of isovalent (Mo 6+ ) and aliovalent (V 5+ and Nb 5+ ) heteroatom doping on the electrochemical PICET behavior of monoclinic tungsten oxide (WO 3 ). Cyclic voltammetry in aqueous acidic electrolytes shows that the addition of redox-active heteroatoms (Mo 6+ and V 5+ ) leads to systematic shifts in redox couple half-wave potentials (E 1/2 ), broadening, and an overall decrease in the current response. Conversely, the non-redox active heteroatom (Nb 5+ ) only reduces the current response with no observable peak-current broadening. This broadening is attributed to changes in the proton binding affinities of oxygen in different chemical environments, i.e., bridging different pairs of redox-active transition metal cations. We determined the hydrogen bond dissociation free energy (H BDFE) values to elucidate the thermodynamic effect of heteroatom substitution. Density functional theory calculations reveal a differentiation in the hydrogen binding and oxygen vacancy formation energies between heteroatom doped structures. The PICET-induced structural phase transitions of the pristine and doped samples were further probed with operando electrochemical X-ray diffraction (EC-XRD) and with ex situ chemical reduction. The broadening of the potential-dependent current response with increased heteroatom doping manifests in the operando EC-XRD results as prolonged structural regions where multiple hydrogen bronze phases exist and the appearance of cubic bronze phases at lower degrees of reduction compared to pristine WO 3 .

Holzapfel, Noah P. [North Carolina State Universit↗
DOE OSTI2025

Understanding the structure and mechanism of Na + diffusion in NASICON solid-state electrolytes and the effect of Sc- and Al/Y-substitution

NASICON (sodium superionic conductor) based ceramics are one of the most promising classes of solid-state electrolytes for all-solid-state batteries. However, the mechanism of sodium ion diffusion is not understood in great detail since there is still a discrepancy between reported average structure models, local structures, and the number and position of sodium sites. To close this gap, we investigate the underlying diffusion mechanism and structural changes governing the Na + transport in Na 3.4 Zr 2 Si 2.4 P 0.6 O 12 using quasielastic neutron scattering (QENS) and powder X-ray diffraction (XRD). In the temperature range from 298 K to 640 K, the correlations between structural changes of a monoclinic C2/c to rhombohedral R $\bar{3}$c phase transition and the result of ion diffusion are investigated. The analysis of the quasielastic neutron scattering data reveals two quasielastic components corresponding to the Chudley-Elliott jump-diffusion model. It clearly shows two different Na + diffusion processes, local and long-range, on two different time and length scales and allows calculations of their corresponding activation energies. Additionally, the effects of Sc 3+ and Al 3+ /Y 3+ aliovalent substitution of Zr 4+ ions on the crystal structure and Na + diffusion are also studied. We can distinguish a local, chain, and cross-chain diffusion mechanism based on correlated QENS and XRD comparison of relevant nearest crystallographic Na–Na distances. The results reveal that the Na + diffusion in these NASICONs is three-dimensional and can provide guidelines on how dopants and changes in the crystal structure can affect the Na + conductivity.

25 ENERGY STORAGE↗