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DOE OSTI2025

Designing the Nanoconfined Environment for Energy-Efficient Metal Nanoparticle/Ligand-Based Electrocatalysts

Nanoconfined electrocatalysts demonstrate enhanced selectivity and activity owing to new phenomena emerging from chemical species confined at the interface. Creating these nanoconfined pockets at the interface is not trivial. We need highly negative potentials to create the pockets in metal/ligand catalysts like Ag-nanoparticle/ordered ligand interlayer catalysts. Lowering this activation potential can make the electrocatalysis more energy-efficient, and changes in the environment can impact this potential. We used Density Functional Theory (DFT) to evaluate the impact of ligand length and density, interfacial protons, and surface defects like Ag vacancies and Cu and Au dopants. The nanoconfined configuration is stabilized when the ligands are longer and more densely packed, leading to better agglomeration. It is also stabilized when the ligands adsorb protons and when the ligands detach from the surface easily owing to lower charge transfer. Au-doped surfaces displayed the lowest charge transfer and decreased the activation potential.

Jana, Asmita↗

DOE OSTI2023

Insights into Acetic Acid Binding and Ketene Formation on Anatase TiO 2 (101)

Understanding the adsorption and reactivity of carboxylic acids on oxide surfaces is of great interest in catalysis for biomass upgrading via ketonization, a carbon–carbon coupling reaction. Herein, we investigate the adsorption and reaction of acetic acid on anatase TiO 2 (101) using scanning tunneling microscopy, infrared spectroscopy, temperature programmed reaction, and density functional theory calculations. We demonstrate the adsorption of acetic acid can form two intermediates: (1) dissociated, bidentate acetate with an associated bridging hydroxyl, and (2) molecular, monodentate acetic acid. The coexistence of ordered phases with increasing monolayer (ML) saturation coverages consisting of (1) pure acetate (0.5 ML), (2) mixed acetate/acetic acid (0.67 ML), (3) mixed acetate/acetic acid (1.0 ML) and (4) pure acetic acid demonstrates similar energetics for both acetate and acetic acid species. Under ultra-high vacuum conditions, the presence of both monodentate acetic acid and bidentate acetate was observed below room temperature, while solely bidentate acetate was observed up to 575 K. The deprotonation of acetic acid produces water at 280 K, while the thermal decomposition of bidentate acetate produces ketene and acetic acid at 645 K. In conclusion, this model study provides detailed insight into the stability and reactivity of carboxylic acid surface-bound intermediates, which could participate during ketonization reactions for biomass upgrading.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2016

Photo-stability and time-resolved photoluminescence study of colloidal CdSe/ZnS quantum dots passivated in Al{sub 2}O{sub 3} using atomic layer deposition

We report photo-stability enhancement of colloidal CdSe/ZnS quantum dots (QDs) passivated in Al{sub 2}O{sub 3} thin film using the atomic layer deposition (ALD) technique. 62% of the original peak photoluminescence (PL) intensity remained after ALD. The photo-oxidation and photo-induced fluorescence enhancement effects of both the unpassivated and passivated QDs were studied under various conditions, including different excitation sources, power densities, and environment. The unpassivated QDs showed rapid PL degradation under high excitation due to strong photo-oxidation in air while the PL intensity of Al{sub 2}O{sub 3} passivated QDs was found to remain stable. Furthermore, recombination dynamics of the unpassivated and passivated QDs were investigated by time-resolved measurements. The average lifetime of the unpassivated QDs decreases with laser irradiation time due to photo-oxidation. Photo-oxidation creates surface defects which reduces the QD emission intensity and enhances the non-radiative recombination rate. From the comparison of PL decay profiles of the unpassivated and passivated QDs, photo-oxidation-induced surface defects unexpectedly also reduce the radiative recombination rate. The ALD passivation of Al{sub 2}O{sub 3} protects QDs from photo-oxidation and therefore avoids the reduction of radiative recombination rate. Our experimental results demonstrated that passivation of colloidal QDs by ALD is a promising method to well encapsulate QDs to prevent gas permeation and to enhance photo-stability, including the PL intensity and carrier lifetime in air. This is essential for the applications of colloidal QDs in light-emitting devices.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

DOE OSTI2018

Crystal Orientation-Dependent Reactivity of Oxide Surfaces in Contact with Lithium Metal

Understanding ionic transport across interfaces between dissimilar materials and the intrinsic chemical stability of such interfaces is a fundamental challenge spanning many disciplines and is of particular importance for designing conductive and stable solid electrolytes for solid-state Li-ion batteries. In this work, we establish a surface science-based approach for assessing the intrinsic stability of oxide materials in contact with Li metal. Through a combination of experimental and computational insights, using Nb-doped SrTiO3 (Nb/STO) single crystals as a model system, we were able to understand the impact of crystallographic orientation and surface morphology on the extent of the chemical reactions that take place between surface Nb, Ti, and Sr upon reaction with Li. By expanding our approach to investigate the intrinsic stability of the technologically relevant, polycrystalline Nb-doped lithium lanthanum zirconium oxide (Li6.5La3Zr1.5Nb0.5O12) system, we found that this material reacts with Li metal through the reduction of Nb, similar to that observed for Nb/STO. These results clearly demonstrate the feasibility of our approach to assess the intrinsic (in)stability of oxide materials for solid-state batteries and point to new strategies for understanding the performance of such systems.

36 MATERIALS SCIENCE↗

DOE OSTI2025

Probing Alkylpolyglycoside Hydrogen Bonding and Its Destabilization by Sulfonate Hydrotropes with X‑ray and Vibrational Spectroscopy

It has been proposed that intersurfactant H-bonding networks can produce highly stable foams, specifically those generated from solutions containing alkylpolyglycoside surfactants. In this work, we aim to characterize the presence and destabilization of these networks by introducing a hydrotrope (sodium p-toluene sulfate) at various concentrations into an alkylpolyglycoside (Glucopon 225 DK) surfactant containing solution. Solution surface properties are probed by using aerosol velocity map imaging X-ray photoelectron spectroscopy (A-VMI-XPS) and tensiometer measurements. Bulk properties below the surface are probed using Fourier transform infrared spectroscopy (FTIR) and C-edge near-edge X-ray fine structure spectroscopy (NEXAFS). The surface measurements provide the framework to describe the destabilization of the solution H-bonding network, while the bulk solution measurements provide hints about the disruption of the hydrogen bonding network upon hydrotrope addition. The collected data support the hypothesis that the destabilization of the intersurfactant H-bonding network frees surfactant molecules from the bulk, increasing surfactant population at the air/water interface. This was quantified through an increase in peak area and width in XPS measurements as well as a decrease in surfactant critical micelle concentration. Three regimes with increasing amounts of hydrotrope addition are suggested, described as (1) a hydrotrope affecting only surfactant surface properties, (2) a hydrotrope affecting surfactant surface and bulk properties, and (3) hydrotrope-dominated surface and bulk properties. Future studies will characterize foam stability across the hydrotrope concentration regimes to better define correlations between intersurfactant H-bonding networks and foam stability.

Molecules↗

DOE OSTI2024

CO 2 Uptake and Stability Enhancement in Vinyltrimethoxysilane‐Treated SBA‐15 Solid Amine‐Based Sorbents

Abstract Silica‐supported amine absorbents, including materials produced by tethering aminosilanes or infusion of poly(ethyleneimine), represent a promising class of materials for CO 2 capture applications, including direct air and point source capture. Various silica surface treatments and functionalization strategies are explored to enhance stability and CO 2 uptake in amine‐based solid sorbent systems. Here, the synthesis and characterization of novel vinyltrimethoxysilane‐treated Santa Barbara Amorphous‐15 (SBA‐15) supports and the corresponding enhancement in CO 2 uptake compared to various SBA‐15‐based control supports are presented. The relationship between CO 2 diffusion and amine efficiency in these systems is explored using a previously reported kinetic model. The synthesized materials are characterized with CO 2 and H 2 O isotherms, diffuse reflectance infrared Fourier transform spectroscopy, 1 H T 1 – T 2 relaxation correlation NMR, and rapid thermal cycling experiments. The novel support materials are shown to enable high amine efficiencies, approaching a fourfold improvement over standard SBA‐15‐supported amines, while simultaneously exhibiting excellent stability when cycled rapidly under humid conditions. As the poly(ethyleneimine) loadings are held constant across the various samples, enhancements in CO 2 uptake are attributed to differences in the way the poly(ethyleneimine) interacts with the support surface.

Vallace, Anthony↗

DOE OSTI2017

Excess Li-Ion Storage on Reconstructed Surfaces of Nanocrystals To Boost Battery Performance

Abstract. Due to the enhanced kinetic properties, nanocrystallites have received much attention as potential electrode materials for energy storage. However, because of the large specific surface areas of nanocrystallites, they usually suffer from decreased energy density, reduced cycling stability and total electrode capacity. In this work, we report a size-dependent excess capacity beyond the theoretical value of 170 mAhg-1 in a special carbon coated LiFePO4 composite cathode material, which delivers capacities of 191.2 and 213.5 mAhg-1 with the mean particle sizes of 83 nm and 42 nm, respectively. Moreover, this LiFePO4 composite also shows excellent cycling stability and high rate performance. Our further experimental tests and ab initio calculations reveal that the excess capacity comes from the charge passivation for which the C-O-Fe bonds would lead to charge redistribution on the surface of LiFePO4 and hence to enhance the bonding interaction between surface O atoms and Li-ions. The surface reconstruction for excess Li-ion storage makes full use of the large specific surface area for the nanocrystallites, which can maintain the fast Li-ion transport and enhance the capacity greatly that the nanocrystallites usually suffers.

Duan, Yandong↗

NASA NTRS2001

Hydrodynamic Stability of Liquid-Propellant Combustion: Landau's Problem Revisited

Hydrodynamic, or Landau, instability in combustion is typically associated with the onset of wrinkling of a flame surface, corresponding to the formation of steady cellular structures as the stability threshold is crossed. As its name suggests, it stems from hydrodynamic effects connected with thermal expansion across the reaction region. In the context of liquid-propellant combustion, the classical models that originally predicted this phenomenon have been extended to include the important effects that arise from a dynamic dependence of the burning rate on the local pressure and temperature fields. Thus, the onset of Landau instability has now been shown to occur for sufficiently small negative values of the pressure sensitivity of the burning rate, significantly generalizing previous classical results for this problem that assumed a constant normal burning rate. It has also been shown that the onset of instability occurs for decreasing values of the disturbance wave number as the gravitational-acceleration parameter decreases. Consequently, in an appropriate weak-gravity limit, Landau instability becomes a long-wave phenomena associated with the formation of large cells on the liquid-propellant surface. Additionally, a pulsating form of hydrodynamic instability has been shown to occur as well, corresponding to the onset of temporal oscillations in the location of the liquid/gas interface. This instability occurs for sufficiently large negative values of the pressure sensitivity, and is enhanced by increasing values of the burning-rate temperature sensitivity. It is further shown that for sufficiently small values of this parameter, there exists a stable range of pressure sensitivities for steady, planar burning such that the classical cellular form of hydrodynamic instability and the more recent pulsating form of hydrodynamic instability can each occur as the corresponding stability threshold is crossed. For larger thermal sensitivities, however, the pulsating stability boundary evolves into a C-shaped curve in the (disturbance-wave number, pressure-sensitivity) plane, indicating loss of stability to pulsating perturbations for all sufficiently large disturbance wavelengths. It is thus concluded, based on characteristic parameter values that an equally likely form of hydrodynamic instability in liquid-propellant combustion is of a nonsteady, long-wave nature, distinct from the steady, cellular form originally predicted by Landau.

Margolis, S. B.↗

DOE OSTI2025

Co‐Doping Approach for Enhanced Electron Extraction to TiO 2 for Stable Inorganic Perovskite Solar Cells

Inorganic perovskite CsPbI 3 solar cells hold great potential for improving the operational stability of perovskite photovoltaics. However, electron extraction is limited by the low conductivity of TiO 2 , representing a bottleneck for achieving stable performance. In this study, a co‐doping strategy for TiO 2 using Nb(V) and Sn(IV), which reduces the material's work function by 80 meV compared to Nb(V) mono‐doped TiO 2 , is introduced. To gain fundamental understanding of the processes at the interfaces between the perovskite and charge‐selective layer, transient surface photovoltage measurements are applied, revealing the beneficial effect of the energetic and structural modification on electron extraction across the CsPbI 3 /TiO 2 interface. Using 2D drift‐diffusion simulations, it is found that co‐doping reduces the interface hole recombination velocity by two orders of magnitude, increasing the concentration of extracted electrons by 20%. When integrated into n–i–p solar cells, co‐doped TiO 2 enhances the projected T S80 lifetimes under continuous AM1.5G illumination by a factor of 25 compared to mono‐doped TiO 2 . This study provides fundamental insights into interfacial charge extraction and its correlation with operational stability of perovskite solar cells, offering potential applications for other charge‐selective contacts.

14 SOLAR ENERGY↗

DOE OSTI2025

Colloidal Behavior of Plutonium Oxide in Concentrated Electrolyte Solutions

The Hanford Site in Washington State manages legacy high-level radioactive waste streams that display major chemistry and engineering challenges, including the high salt levels and pH values that correspond to conditions under which many classical concepts describing chemical reactivity cannot be applied. One particular challenge that needs to be tackled at Hanford is that Pu concentrations, [Pu], in the soluble phases of the tank wastes are higher than expected based on the solubility of crystalline PuO2, which is widely accepted to be caused by the formation of PuO2 colloid, consisting of nano- to submicron-sized particles (PuO2 NPs). Fundamental research underpinning the behavior of PuO2 NPs under conditions not only relevant to the Hanford tank waste but at high ionic strength in general is needed to reliably predict the chemical reactivity of PuO2 NPs and develop engineering solutions to safely and efficiently process high-level radioactive waste into forms suitable for long-term storage. In this work, we study the behavior of PuO2 NPs (particle size ~100 nm) under high ionic strength conditions by reacting it with highly concentrated (up to 5 M) salt solutions. We explore different electrolyte compositions to elucidate the impact of different anions (NO3-, Cl-, ClO4-, SO42-, C2O42-, CO32-) on the stability of PuO2 NP in the acidic and alkaline pH regime. PuO2 NP aggregation and precipitation as function electrolyte concentration is tracked by a combination of liquid scintillation counting, dynamic light scattering for determination of particle size distributions, and zeta potentials as a proxy for particle charge. At acidic pH, electrolytes containing non-coordinating anions, such as NaNO3, NaCl, and NaClO4 mostly stabilize PuO2 NPs over a large electrolyte concentration range, showing only subtle differences in their reactivity. Other electrolyte anions show a more pronounced effect on the PuO2 NP stability: SO42-, binds directly to the particles’ surface, reverses the particle charge, and precipitates the PuO2 NPs efficiently even at intermediate sulfate concentrations (>0.1 M). In contrast, C2O42- is found to lead to high [Pu] in solution, in the milli-molar range, even at mildly acidic pH (~4). Thermodynamic modeling of the dissolved Pu concentrations using PHREEQC is unable to predict the observed [Pu] in the acidic pH regime, supporting the influence of colloids in maintaining elevated [Pu]. It is noteworthy that the current thermodynamic databases do not include constants for colloidal Pu phases and cannot accurately predict many of the high ionic strength solutions relevant to this work. The mechanisms and models responsible for these observations will need further investigation in the future. At high pH values (~12), PuO2 NPs exhibits classical sol-gel chemistry, meaning that upon destabilization of the colloidal sol, for example by addition of concentrated NaOH, highly porous and viscid PuO2 coagulates are formed that consist of a three-dimensional network likely held together by physical interactions. The PuO2 NP coagulate shows no significant reversibility of the aggregation when contacted with concentrated brines; however, PuO2 NPs can be efficiently resuspended in solution by addition of diluted electrolytes, alkaline solutions containing high amounts of carbonate, or simple addition of water. Especially carbonate is shown to stabilize PuO2 NPs in solution at high pH, characterized by stable colloidal suspensions that are resistant against sedimentation during centrifugation. Thermodynamic modeling of the carbonate system was able to predict an increasing dissolved Pu concentration with increasing carbonate concentration. However, the model was profoundly sensitive to the fixed redox potential and does not include any thermodynamic constants for colloidal Pu species.

Neumann, Julia↗

DOE OSTI2018

FY18 Status Report: SNL Research into Stress Corrosion Cracking of SNF Interim Storage Canisters

This progress report describes work done in FY18 at Sandia National Laboratories (SNL) to assess the localized corrosion performance of container/cask materials used in the interim storage of spent nuclear fuel (SNF). The work focuses on stress corrosion cracking (SCC), the only mechanism by which a through-wall crack could potentially form in a canister outer wall over time intervals that are shorter than possible dry storage times. Work in FY18 continued several studies initiated in FY17 that are aimed at refining the understanding of the chemical and physical environment on canister surfaces, and evaluating the relationship between chemical and physical environment and the form and extent of corrosion that occurs. The SNL canister environment work focused on evaluating the stability of sea-salt deliquescent brines on the heated canister surface; an additional opportunity to analyze dusts sampled from an inservice spent nuclear fuel storage canister also arose. The SNL corrosion work focused predominantly on pitting corrosion, a necessary precursor for SCC, and process of pit-to-crack transition. SNL is collaborating with several university partners to investigate SCC crack growth experimentally, providing guidance for design and interpretation of experiments. The scope of these efforts targets near-marine Independent Spent Fuel Storage Installation environments which are generally considered to be most aggressive for pitting and SCC. Work to define the chemical and physical environment that could develop on storage canister surfaces in near-marine environments included experiments to evaluate the thermal stability of magnesium chloride brines, representative of the first brines to form when sea-salts deliquesce, with the specific goal of understanding and interpreting results of sea-salt and magnesium chloride corrosion experiments carried out under accelerated conditions. The experiments showed that magnesium chloride brines, and by extension, low RH sea-salt deliquescent brines, are not stable at elevated temperatures, losing chloride via degassing of HC1 and conversion to Mg-hydroxychlorides and carbonates. The experiments were carried out on an inert substrate to eliminate the effects of corrosion reactions, simulating brine stabilities in the absence of, or prior to, corrosion. Moreover, analysis of salts recovered from actively corroding metal samples shows that corrosion also supports or drives conversion of magnesium chloride or sea-salt brines to less deliquescent salts. This process has significant implications on corrosion, as the secondary phases are less deliquescent than magnesium chloride; the conversion reaction results in decreases in brine volume, and potentially results in brine dry-out. The deliquescence properties of these reaction products will be a topic of active research in FY19.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

NASA NTRS1960

Aerodynamic Characteristics at Low Speed of a Reentry Configuration Having Rigid Retractable Conical Lifting Surfaces

An exploratory investigation has been made in the Langley 300 MPH 7 by 10 foot tunnel to study the low-speed static longitudinal and lateral stability characteristics of a reentry configuration having rigid retractable conical lifting surfaces that unfolded from the surface of a conical fuselage. The model also had curved tail surfaces that unfolded from a cylindrical aft section attached to the cone. Longitudinal tests were made through an angle-of-attack range from -4 deg to 90 deg and limited lateral tests were made through an angle-of-sideslip range from -12 deg to 32 deg at an angle of attack of 0 deg. The tail surface provided longitudinal trim to maximum lift and beyond and up to an angle of attack of 51 deg for a center-of-moment location of 42.9 percent mean aerodynamic chord. For this center-of-moment position the model had a static margin of 12 percent mean aerodynamic chord at the lower lift coefficients and was longitudinally stable up to a lift coefficient between 1.0 and 1.2. Neutral stability occurred from lift coefficient of 1.0 up to near maximum lift coefficient. The maximum value of trimmed lift-drag ratio was 4.85 at a lift coefficient of approximately 0.3 and a trimmed angle of attack of approximately 10 deg. The configuration was directionally stable throughout the test angle of sideslip range for an angle of attack of 0 deg.

Fournier, Paul G.↗

DOE OSTI2023

Multifunctional Effect of Fe Substitution in Na Layered Cathode Materials for Enhanced Storage Stability

In this study, developing stable cathode materials that are resistant to storage degradation is essential for practical development and industrial processing of Na-ion batteries, as many sodium layered oxide materials are susceptible to hygroscopicity and instability when exposed to ambient air. Among the various layered compounds, Fe-substituted O 3 -type Na(Ni 1/2 Mn 1/2 ) 1-x Fe x O 2 materials have emerged as a promising option for high-performance and low-cost cathodes. While previous reports have noted the decent air-storage stability of these materials, the role and origin of Fe substitution in improving storage stability remain unclear. In this study, we investigate the air resistant effect of Fe substitution in O 3 -Na(Ni 1/2 Mn 1/2 ) 1-x Fe x O 2 cathode materials by performing systematic surface and structural characterizations. We find that the improved storage stability can be attributed to the multifunctional effect of Fe substitution, which forms a surface protective layer containing an Fe-incorporated spinel phase and decreases the thermodynamical driving force for bulk chemical sodium extraction. With these mechanisms, the Fe-containing cathodes can suppress the cascades of cathode degradation processes and better retain the electrochemical performance after air storage.

25 ENERGY STORAGE↗

DOE OSTI2018

Facile synthesis of high surface area nanostructured ceria-zirconia-yttria-lanthana solid solutions with the assistance of lauric acid and dodecylamine

Highlights: • High surface area nanostructured ceria-zirconia-yttria-lanthana solid solutions are synthesized by a facile method. • Hydrophobic surfaces are obtained with the addition of lauric acid and dodecylamine in the synthesis. • The introduced lauric acid and dodecylamine are chemically adsorbed onto the surface of materials through a coordination effect. • Excellent thermal stability are obtained in lauric acid and dodecylamine assisted materials. - Abstract: Co-precipitation combined with the assistance of lauric acid and dodecylamine was used to synthesize high surface area nanostructured ceria-zirconia-yttria-lanthana solid solutions (CZ-L and CZ-D). The promotion effects of lauric acid and dodecylamine were studied systematically by N{sub 2} adsorption-desorption, scanning electron microscopy (SEM), transmission electron microscopy (TEM), FT-IR and Raman analysis. After being thermal aged at 1100 °C for 4 h in air, CZ-L and CZ-D present high surface areas of 26 m{sup 2}/g and 16 m{sup 2}/g, respectively. The results indicate that the added lauric acid and dodecylamine are chemically adsorbed onto the surface of materials through coordination effect. The obtained hydrophobic surface could greatly decrease the amount of superficial adsorbed water on the material and significantly reduce the surface tension. The addition of lauric acid and dodecylamine could also effectively support the network structures of the material and resist the collapse of pores upon drying and calcination.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

NASA NTRS1994

Characteristics of finite amplitude stationary gravity waves in the atmosphere of Venus

This paper extends the study of stationary gravity waves generated near the surface of Venus reported previously by Young et al. to include finite amplitude effects associated with large amplitude waves. Waves are forced near the surface of Venus by periodic forcing. The height-dependent profiles of static stability and mean wind in the Venus atmosphere play a very important role in the evolution of the nonlinear behavior of the waves, just as they do in the linear wave solutions. Certain wave properties are qualitatively consistent with linear wave theory, such as wave trapping, resonance, and wave evanescence for short horizontal wavelenghts. However, the finite amplitude solutions also exhibit many other interesting features. In particular, for forcing amplitudes representative of those that could be expected in mountainous regions such as Aphrodite Terra, waves generated near the surface can reach large amplitudes at and above cloud levels, with clear signatures in the circulation pattern. At still higher levels, the waves can reach large enough amplitude to break, unless damping rates above the clouds are sufficient to limit wave amplitude growth. Well below cloud levels the waves develop complex flow patterns as the result of finite amplitude wave-wave interactions, and waves are generated having considerably shorter horizontal wavelenghts than that associated with the forcing near the surface. Nonlinear interactions can excite waves that are resonant with the background wind and static stability fields even when the primary surface forcing does not, and these waves can dominate the wave spectrum near cloud levels. A global map of Venus topographic slopes derived from Magellan altimetry data shows that slopes of magnitude comparable to or exceeding that used to force the model are ubiquitous over the surface.

Young, Richard E.↗

DOE OSTI2016

Final Report: “Energetics of Nanomaterials”

Nanomaterials, solids with very small particle size, form the basis of new technologies that are revolutionizing fields such as energy, lighting, electronics, medical diagnostics, and drug delivery. These nanoparticles are different from conventional bulk materials in many ways we do not yet fully understand. This project focused on their structure and thermodynamics and emphasized the role of water in nanoparticle surfaces. Using a unique and synergistic combination of high-tech techniques—namely oxide melt solution calorimetry, cryogenic heat capacity measurements, and inelastic neutron scattering—this work has identified differences in structure, thermodynamic stability, and water behavior on nanoparticles as a function of composition and particle size. The systematics obtained increase the fundamental understanding needed to synthesize, retain, and apply these technologically important nanomaterials and to predict and tailor new materials for enhanced functionality, eventually leading to a more sustainable way of life. Highlights are reported on the following topics: surface energies, thermochemistry of nanoparticles, and changes in stability at the nanoscale; heat capacity models and the gapped phonon spectrum; control of pore structure, acid sites, and thermal stability in synthetic γ-aluminas; the lattice contribution is the same for bulk and nanomaterials; and inelastic neutron scattering studies of water on nanoparticle surfaces.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2016

Final Report: “Energetics of Nanomaterials”

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2020

Potassium Prussian blue-coated Li-rich cathode with enhanced lithium ion storage property

With high specific capacity, the layered Li-rich Mn-based oxide (LRMO) is a promising candidate cathode material for Li-ion batteries. However, the irreversible release of Li-ions during the first charging process, instability of LRMO/electrolyte interface and relatively low ion conductivity of LRMO result in low initial Coulombic efficiency (ICE), poor cycle stability and rate performance, which prohibit its further application. Furthermore, interface engineering via additive coating is expected to effectively address these issues. Herein, we rely on potassium Prussian blue (KPB), a Li + acceptor with good ion conductivity, as a new coating material on LRMO particles. The KPB coating not only forms a protective layer on the surface of LRMO against electrolyte corrosion, but also functions as a host for Li + transport and accommodation, leading to enhanced ion conductivity and ICE of LRMO cathode. Consequently, 2 wt% KPB coated LRMO cathode achieved an initial discharge capacity of up to 281.7 mA h g -1 with an ICE of 85.69% compared to an ICE of 79.52% for the LRMO cathode without coating. The cycling and rate performance are also greatly improved as evidenced by the well maintained capacity of up to 176.8 mA h g -1 after 100 cycles at a current density of 0.5 C, compared to the limited capacity of only 135.3 mA h g -1 for the LRMO cathode without coating. Overall, this work pioneers the use of potassium Prussian blue as additive coating material to enhance performance of LRMO cathode, and we expect it to inspire the battery community with new strategies of material engineering/design toward practical application in high-energy lithium-ion batteries.

25 ENERGY STORAGE↗