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At least 145 records · Page 8

Analyzing the effect of pressure on the properties of point defects in $\gamma\mathrm{U–Mo}$ through atomistic simulations

Uranium–molybdenum (U–Mo) alloys in monolithic fuel foil are the primary candidate for the conversion of high-performance research reactors in the USA. Monolithic fuel is utilized in a plate-type design with a zirconium diffusion barrier and aluminum cladding. These fuel types are unique in that they contain no plenum for the release of fission gases, which, in conjunction with the aluminum cladding, can lead to large stress states within the fuel. The nature of how fundamental processes of radiation damage, including the evolution of point defects, under such stresses occur is unknown. In this work, we present molecular dynamics simulations of the formation energy of point defects under applied stress. We report this work will allow for the implementation of stress-dependent microstructural evolution models of nuclear fuels, including those for both fission gas bubble growth and creep, which are critical to ensure the stable and predictable behavior of research reactor fuels.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

High Throughput In-Line Coating Metrology Development for Solid Oxide Fuel Cell Manufacturing

Coatings play key roles in solid oxide fuel cell (SOFC) stack durability. For example, diffusion barrier coatings on Cr-containing interconnect and balance of plant (BOP) components protect electrodes from Cr poisoning over the long operational lifetimes (>10,000 hours) of the fuel cell stack. Common defects in coatings, such as cracks, pinholes, and porosity, result in a failure to protect the electrodes, resulting in shorter operational lifetime and thus higher cost. It is very unlikely, even in the best coating process, that all these defects can be mitigated, hence identifying critical defects in parts, and removing defective parts from production before they can damage the stack, becomes paramount. Furthermore, these quality control techniques must be operational in the production/assembly line (in-line), i.e., high throughput and non-destructive, and cost effective. Redox Power Systems, LLC (Redox) together with the National Renewable Energy Laboratory (NREL) developed much needed high throughput, in-line metrology techniques for protective coatings. The overall goal of the project is to lower cost while increasing robustness, reliability, and endurance of SOFC stacks. To accomplish this, we had several objectives, including: to identify key coating and substrate defects that lead to coating failure through the use of detailed characterization methods (e.g., microscopy, XRD, EDS, electrochemistry); to assess capabilities of in-line metrology techniques, e.g., optical profilometry (Redox) and thermography (NREL), to probe these defects, or evidence thereof; demonstrate long-term performance of “defect-free” protective coatings, as identified by in-line metrology, in solid oxide fuel cell (SOFC) stack operation. In the first part of this project, the ability to identify key defects expected to lead to coating and SOFC degradation using in-line metrology tools were evaluated. Coated interconnect samples with controlled defect types and populations were tested under conditions similar to SOFC operation, followed by detailed post-test analysis to reveal the defects responsible for observed degradation. In the second part of the project, the optimal in-line metrology techniques and methodologies were used to map the defect distribution in full-size interconnects with critical defects intentionally allowed to exist in some cases. These interconnects underwent SOFC testing for extended periods (up to ~3,000 hours) followed by post-test analysis to evaluate the effectiveness of in-line metrology techniques in mitigating MCO coating related degradation. Key accomplishments in this project included the following: Demonstrated ASR of < 0.05 ohm-cm 2 at 650 °C for 1,000 hours with low defect (determined by in-line metrology) interconnect samples (average ASR=37 milliohms-cm 2 after over 1,000 hours). Demonstrated that low defect coatings on interconnects (as screened using in-line metrology) have low volatilization of chromium at ~650 °C for 1,000 hours as detected using Cr-getter material (< 5 at% increase above baseline); 1022 hour duration tests under humidified, elevated temperature (750 °C rather than 650 °C) compared a base case against different coating thicknesses. Demonstrated capability to identify initial key defects of interest with in-line metrology techniques using up to 8 cm by 10 cm having coatings with and without intentional defects of interest using thermal imaging and optical profilometry. Correlated key defects identified using metrology techniques with observed coating performance (e.g., ASR and Cr volatility). Conducted several 4 cm by 4 cm cell tests using MCO-interconnects that were pre-screened using some of the metrology techniques developed in the project (e.g., optical profilometry). An analysis of ASR measurements were able to show that defect-free coatings resulted in the anticipated performance in the cell tests.

01 COAL, LIGNITE, AND PEAT↗

Preliminary results from Low Pressure Steam Oxidation Testing of ALD ZrN and ZrO2 Coating Deposited over UCN Fuel Kernels

Steam oxidation testing was used to investigate as-developed 100 nm ALD ZrN and 1000 nm ZrO 2 coatings deposited over UC1-xNx fuel kernels. The results of these tests were compared against oxidation of uncoated kernels. This work was performed to support development of coatings which both provide high temperature Zr metal diffusion barrier and also provide resistance against oxidation, especially against high temperature steam and/or air. This work was performed in collaboration with Oak Ridge National Laboratory (ORNL), using ORNL-provided samples. The oxidation tests yielded valuable information, including relative differences in performance of different coating materials and coating thicknesses.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Versatile Heat Transfer Module

Development of micro-reactors that can be easily transported to remote areas for civilian or military applications is an immediate focus of U.S. nuclear industry and therefore is being pursued by multiple reactor vendors (e.g. HolosGen LLC, Westinghouse, Ultra Safe Nuclear Corporation, URENCO, etc.) and actively supported by DOE-NE, DOE-ARPA-E and by the Department Of Defense (DoD). Very-high-temperature gas-cooled (VHTR) and heat pipe cooled reactor technologies are regarded as promising concepts for microreactors applications since they enable compact power conversion systems and display beneficial inherent safety features. Development of microreactors with enhanced performance must be supported by innovations in nuclear technologies. Several technologies being developed by the microreactor industry are being revisited with material technologies developed at the Argonne National Laboratory (ANL). Innovative high-temperature compatible solutions are developed to enable advanced thermal-spectrum microreactor designs featuring improved neutronics performance at high-temperature operating conditions to enable high thermal efficiency and economic competitiveness. This report focuses on the Versatile Heat Transfer Module (VHTM) technology that is developed at ANL for heat-transfer in thermal-spectrum microreactors. This technology is built on a liquid alkali metal heat pipe concept while leveraging advanced nuclear material technologies for high-temperature applications at reduced neutronic penalty with potential improvement in inherent safety behavior. The VHTM can be applied to design high-temperature thermal-spectrum microreactor systems with reduced size, weight, uranium enrichment, or increased lifetime. The INFINIT technology deriving from the VHTM enables design of a highly compact long-life microreactor concept for fission surface power (FSP). Demonstration of multiphysics modeling capability was also completed to showcase the added inherent safety benefits obtained with this concept. The VHTM technology remain at an early development stage with low Technology Readiness Level and Manufacturing Readiness Level. The current demonstration of these technologies has focused on manufacturing capability, on performance of the hydrogen diffusion barrier under thermal cycling, while radiation tolerance demonstration is planned. The next step of the demonstration plan will be the assembly of miniature VHTM for high-temperature testing, which can be used as a prototype for future pilot scale demonstration. Such research is critical to pursue development of these technologies that have the clear potential to significantly improve the performance of currently investigated micro-reactors systems.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Arbitrary Low-Dimensional Film Transfer Enabled by GeO 2 Release Layer

Low-dimensional materials show great promise for enhanced computing and sensing performance in mission-relevant environments. However, integrating low-dimensional materials into conventional electronics remains a challenge. Here, we demonstrate a novel transfer method by which low-dimensional materials and their heterostructures can be transferred onto any arbitrary substrate. Our method relies on a water soluble GeO 2 substrate from which lowdimensional materials are transferred without significant perturbation. We apply the method to transfer a working electronic device based on a low-dimensional material. Process developments are achieved to enable the fabrication and transfer of a working electronic device, including the growth of high-k dielectric on GeO 2 by atomic layer deposition and inserting an indium diffusion barrier into the device gate stack. This work supports Sandia’s heterogeneous integration strategy to broaden the implementation of low-dimensional films and their devices.

36 MATERIALS SCIENCE↗

Computationally Accelerated Discovery and Experimental Demonstration of High-Performance Materials for Advanced Solar Thermochemical Hydrogen Production

This project achieved its overarching goal of accelerating the discovery and validation of solar thermochemical hydrogen (STCH) materials through a tightly integrated approach that combined high-throughput computational screening, advanced machine learning (ML), and experimental testing. Guided by the objectives outlined in the Statement of Project Objectives (SOPO), our work fulfilled all major milestones across four technical tasks and delivered scientific breakthroughs and practical tools that significantly exceeded the original scope of the project. We began by addressing the challenge of predicting material phase stability through machine learning. A novel Python module was developed to generate thousands of meaningful features from composition, structure, and electronic properties, enabling rapid and reproducible ML model development. Using these tools, we trained a model to predict temperature-dependent Gibbs energies (G(T)) for inorganic crystalline materials with near-chemical accuracy—roughly 40 meV/atom—marking the first such descriptor of its kind. We also introduced a new machine-learned tolerance factor, τ, that accurately predicted perovskite formability with over 90% success, outperforming traditional heuristic models, such as the Goldschmidt tolerance factor. These capabilities allowed for rapid and accurate predictions of phase stability across a vast oxide composition space, setting the stage for high-throughput thermodynamic screening. Building on this foundation, we conducted an extensive computational screening of candidate STCH oxide materials. Over 1.1 million perovskite compositions were evaluated using the τ descriptor, leading to the identification of more than 27,000 predicted stable structures. Using density functional theory (DFT), we refined over 68,000 multinary perovskite structures and computed oxygen vacancy formation energies for over 1,300 ternary and double perovskites. These calculations enabled us to isolate compounds with redox behavior consistent with STCH requirements and resulted in a public dataset now hosted on the Materials Project. Recognizing that thermodynamic screening alone is insufficient, we addressed kinetic limitations by developing a suite of tools to estimate transition state (TS) energies for key redox reactions. We implemented a novel bounding approach that provides lower and upper estimates of TS energies with dramatically reduced computational cost, requiring less than 10% of the CPU time of a full nudged elastic band (NEB) calculation while maintaining high accuracy. This enabled rapid evaluation of over 200 reaction pathways across 90 materials. To further accelerate screening, we developed a SISSO-based ML model to predict diffusion barriers with a 96.7% success rate in classifying fast vs. slow materials, supporting a robust, data-driven framework for assessing redox kinetics. Experimental validation was critical to confirming the predictive power of our models. We synthesized and tested a wide array of candidate materials, including Mn-doped hercynite and several Gd- and La-based perovskites. Notably, Sr 0.4 Gd 0.6 Mn 0.6 Al 0.4 O 3 (SGMA) and Gd 0.5 La 0.5 Co 0.5 Fe 0.5 O 3 (GLCF) emerged as leading STCH materials, exhibiting robust redox cycling and high hydrogen yields exceeding 150 µmol H 2 /g per cycle. These materials also retained over 50% of their hydrogen productivity under high-conversion conditions (H 2 O:H 2 = 1333:1), demonstrating strong thermodynamic favorability and promising performance under industrially relevant scenarios. Additional candidates, such as La 2 MnNiO 6 (L2MN), were found to produce even higher yields than ceria under standard STCH conditions. Our collaborators at Sandia National Laboratories confirmed these findings using high-temperature X-ray diffraction and thermogravimetric analysis, observing stable phase evolution and reversible redox activity. In several respects, the project went beyond the goals initially outlined in the SOPO. We published 17 peer-reviewed articles, including a large dataset of over 66,000 theoretical perovskites and a new structure prediction method (SPuDS-DFT) that accurately identifies ground-state structures at a fraction of the cost of traditional DFT. We demonstrated that our machine-learned G(T) model offers accuracy rivaling quasiharmonic calculations while being orders of magnitude faster. In partnership with the Materials Project, we made our datasets openly available, providing a powerful new resource for the broader materials science community. The combined computational and experimental advances of this project represent a significant advance in STCH materials discovery. By creating a robust, generalizable, and open workflow for thermodynamic and kinetic screening, and validating key findings through synthesis and reactor testing, we have provided a practical and scalable pathway for the rapid identification of new redox-active materials. The tools, data, and materials developed under this project are already supporting ongoing research and have laid the groundwork for the next generation of solar fuel technologies.

08 HYDROGEN↗

Rapid Alloy Surface Engineering through Closed-Vessel Reagent Pyrolysis

For rapid surface engineering of Cr-containing alloys by low-temperature nitrocarburization, we introduce a process based on pyrolysis of solid reagents, e.g., urea, performed in an evacuated closed vessel. Upon heating to temperatures high enough for rapid diffusion of interstitial solute, but low enough to avoid second-phase precipitation, the reagent is pyrolyzed to a gas atmosphere containing molecules that (i) activate the alloy surface by stripping away the passivating Cr 2 O 3 -rich surface film (diffusion barrier) and (ii) rapidly infuse carbon and nitrogen into the alloy. We demonstrate quantitatively that this method can generate a subsurface zone with concentrated carbon and nitrogen comparable to what can be accomplished by established (e.g., gas-phase- or plasma-based) methods, but with significantly reduced processing time. As another important difference to established gas-phase processing, the interaction of gas molecules with the alloy surface can have auto-catalytic effects by altering the gas composition in a way that accelerates solute infusion by providing a high activity of HNCO. The new method lends itself to rapid experimentation with a minimum of laboratory equipment.

36 MATERIALS SCIENCE↗

Measurement techniques of thermoelectric devices and modules

Thermoelectric (TE) energy conversion devices are designed based on measured material transport properties. Although an ideal device efficiency can be calculated using the figure of merit, zT, the actual efficiency of a thermoelectric module is smaller and must be measured. TE device performance testing techniques and procedures are reviewed with a focus on energy conversion efficiency. One of the areas that attract less attention in the literature is the transition from basic thermoelectric materials research to the production of modules and devices. The effects of interface layers, diffusion barriers, thermal insulations, and heat sinks are reviewed. Finally, device performance from single couples to standard modules and long-term reliability are discussed.

Wang, Hsin↗

Assessment of Cladding-Cladding Delamination Failures in U-Mo Fuel Plates

Monolithic fuel is a candidate fuel form for the conversion of high-performance research reactors. This plate-type fuel consists of a high-density, U-Mo alloy-based fuel in a monolithic form that is sandwiched between zirconium diffusion barriers and encapsulated in an aluminum cladding. To qualify this fuel system, the program must demonstrate that the fuel meets the safety standards, has a predictable behavior, and performs well in a reactor. Although many plates have shown satisfactory thermo-mechanical performance in reactor, a small number of experimental plates exhibited failures, rendering performance of these plates unacceptable. Post-irradiation examinations of failed plates have revealed that various failures modes are present, including pillowing, blistering, buckling, warping, delamination, fracture, rupture, oxide spallation, etc. Previous studies have implied that such various operational and loading conditions could generate a complex stress-strain state, facilitating distinct failure modes that could impact the structural integrity. To understand such various failure modes, a comprehensive set of studies focusing on failure modes is being performed. As a part of these studies, this work studies the cladding-cladding separation failures that were observed in some of previous irradiation tests. To understand the root cause of cladding separation failures, selected plates from previous irradiation experiments were simulated under comparable operational conditions. Stress-strain state of the plates at the interface were examined. The results were comparatively evaluated to understand possible effects of stress state of the bond-line on delamination failures. This paper presents these findings, discusses such failure modes, and examines the influence of various factors on previously observed cladding delamination failures.

42 ENGINEERING↗

Thermo-physical Properties of U-10Mo Monolithic Fuel

Monolithic fuel is a candidate fuel form that is being considered for the conversion of high-performance research reactors. This plate-type fuel consists of a high-density, U-Mo fuel in a monolithic form that is sandwiched between zirconium diffusion barriers and encapsulated in an aluminum cladding. To date, many plates were irradiated with a satisfactory irradiation performance, demonstrating that the conceptual design works. The program is now moving to the qualification phase, a predecessor to the timely conversion of the target reactors. To qualify this fuel system, the program must show that the fuel plates have predictable behavior, meet the safety standards, and perform well in reactors. The requirement of a satisfactory irradiation performance under normal operating conditions is primarily demonstrated by a successful testing. To demonstrate that the fuel system has a predictable behavior, the several key material properties should be quantified accurately since these properties are needed to estimate the thermal and mechanical behavior of the fuel system. Although, there is a large set of thermophysical property data available for unirradiated material, the property data for irradiated fuel is scarce. Since irradiation causes drastic effects in material, a significant change in material properties occurs. Consequently, using representative degradation models becomes essential for accurate performance assessments. This work examines thermal conductivity of U-10Mo, by evaluating recent experimental data from the literature and available theoretical models. The study has discovered inconsistencies in the literature data, revealing that previously developed theoretical models fail to predict the thermal conductivity of irradiated fuel.

42 ENGINEERING↗

Overview of Base Model in Parametric Studies Specific to Performance of U-Mo Plates

This paper provides an overview of the base model specifically developed to perform parametric sensitivity studies on the U-10Mo monolithic fuel system. U-Mo monolithic fuels are being considered for the conversion of test reactors into high-performance research reactors that operate using proliferation-resistant, low-enriched uranium (LEU) fuels. These plate-type fuels contain a high-density, low-enrichment fuel sandwiched between zirconium diffusion barriers and encapsulated in aluminum claddings. All U.S. high-performance research reactors have released the designs of their LEU monolithic fuel reactor cores. These designs include nearly 50 distinct fuel plate geometries with different operational parameters. Consequently, a single generic plate geometry representing all the extreme points in this design matrix is unrealistic. To evaluate the performance for various parameters, a set of sensitivity studies was performed. These studies considered various input parameters (i.e., geometric, operational, and material property-related). The results revealed valuable information about plate performance and the sensitivity of this performance to various modeling inputs. To establish a reference state for comparing these result, base model featuring representative irradiation conditions was developed. To capture in-reactor behavior accurately, incorporation of representative constitutive models capable of evolving properties with respect to temperature, irradiation time, and burnup was needed. The behavioral models considered burnup-dependent properties, swelling, creep, and degradation. This paper introduces the base model created for the parametric sensitivity studies. The detailed description of the procedure includes the model geometry, model discretization, thermo-mechanical coupling, material properties and behavioral models. This paper also provides selected results and assesses the performance of the base model.

42 ENGINEERING↗

Heat transfer module

A heat transfer module can include an envelope sealed to define an internal volume that contains a working fluid and a wick disposed on an internal surface of the envelope. The wick and envelope each has a first portion extending through an evaporator region and a second portion extending through adiabatic and condenser regions. The first portion of the wick is a metal hydride. The first portion of the envelope includes a metal liner surrounding the first portion of the wick, a first diffusion barrier layer disposed between the first portion of the wick and the metal liner, and a ceramic matrix composite cladding surrounding the metal liner. The second portions of the wick and envelope each includes a refractory metal and/or stainless steel.

Stauff, Nicolas E.↗

Evaluating the Performance and Reliability of Screen-Printable Fire-Through Copper Paste on PERC Solar Cells

A bifacial silicon heterojunction solar cell demands approximately 210 mg usage of silver paste (9 busbars, 24.5%, bifacial, M6 size wafer). Copper is an excellent alternative to silver: 100x cheaper, similar elecvtrical resistivities, and 1000x more abundant. Successful demonstration of large area selective emitter PERC solar cells using Cu fire-through paste with FF approximately 75% and approximately 19%. Paste chemistry results in oxide-based Cu diffusion barrier, leading to good reliability of the devices: 1000h DHT giving a 3.5% efficiency drop. The additional series resistance still needs to be lowered. Printed and fired cell performance is governed mostly by pFF, especially J02 ; same for DHT degradation. Further improvement in printing and firing optimization for lower series resistance and higher FF.

Ag↗

Interfacial Analysis of Blister Formation in U-10Mo Mini-Plates

A thorough investigation of potential failure mechanisms builds confidence in the performance of monolithic U-10wt%Mo (U-10Mo) fuel plates. The lowenriched uranium (LEU) fuel system is currently undergoing qualification as a high U-density fuel that can be used to convert United States high-performance research reactors from high-enriched uranium (HEU) operation. This will require establishing fuel operational limits such that fission products and a coolable geometry are retained, even during off-normal reactor operation conditions [1]. Such off-normal conditions can subject the fuel plates to temperatures where the internal pressure of precipitated fission gasses result in a permanent deformed, raised area of the cladding, referred to as a blister. These blisters can reduce the local coolability of a fuel plate and can even close coolant channels of a fuel assembly, so blistered plates are considered failed regardless of whether the fuel is truly breached. Historically, a marginto- failure is established through out-of-pile blister threshold testing of irradiated fuel plates. This is accomplished by incrementally heating irradiated fuel plates until blisters are observed. This reveals the temperature threshold that would have resulted in a blister if a plate experienced them at those irradiation conditions [2]. While the blister testing itself reveals the temperatures at which the cladding mechanical integrity was exceeded, a more thorough investigation of the interface evolution in proximity to formed blisters may reveal mechanisms as to the blister formation and retention of fission gases. Previous studies have explored potential underlying mechanisms in historical plates that may have been close to blistering [3]; however, this work is the first exploration of blister tested irradiated plates, fabricated by a commercial vendor—another requirement for qualification of the fuel system [1]. The Mini-plate 1 (MP-1) experiment was the first in a series of irradiation and post-irradiation examination (PIE) campaigns to qualify the U-10Mo monolithic fuel system. It consisted of commercially fabricated 25.4×101.5 mm Al-clad mini-plates with a monolithic U-10Mo foil coated in a Zr diffusion barrier. The primary MP-1 PIE campaign was previously completed. Among the suit of examinations was a blister testing campaign, where plates were incrementally annealed in 25°C increments until blisters were observed or a maximum temperature of 550°C was reached [4]. The previously blistered plates from this campaign were revisited in this work.

25228↗

Evolving radon diffusion through earthen barriers at uranium waste disposal sites

Field measurements of Rn-222 fluxes from the tops and bottoms of compacted clay radon barriers were used to calculate effective Rn diffusion coefficients (D Rn ) at four uranium waste disposal sites in the western United States to assess cover performance after more than 20 years of service. Values of D Rn ranged from 7.4 × 10 -7 to 6.0 × 10 -9 m 2 /s, averaging 1.42 × 10 -7 . Water saturation (S W ) from soil cores indicated that there was relatively little control of D Rn by S W , especially at higher moisture levels, in contrast to estimates from most steady-state diffusion models. Further, this is attributed to preferential pathways intrinsic to construction of the barriers or to natural process that have developed over time including desiccation cracks, root channels, and insect burrows in the engineered earthen barriers. A modification to some models in which fast and slow pathway D Rn values are partitioned appears to give a good representation of the data; 4% of the fast pathway was needed to fit the data regression. For locations with high S w and highest D Rn (and fluxes) at each site, the proportion of fast pathway ranged from 1.7% to 34%, but for many locations with lower fluxes, little if any fast pathway was needed.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

First principles density functional theory study of tritium species adsorption on Ni(111) surface and diffusion in nickel-sublayer for tritium storage

The nickel-plated zircaloy-4 is used as a tritium ( 3 H) getter in the tritium-producing burnable absorber rods (TPBARs) to capture 3 H produced in the 6 Li-riched annular γ-LiAlO 2 pellet under neutron irradiation. The experimental data and our previous theoretical results showed that the 3 H species produced from the γ-LiAlO 2 pellet were mainly 3 H 2 and 3 H 2 O. These 3 H species diffuse from the surface of the LiAlO 2 pellet across vacuum to the nickel-plated zircaloy-4 getter and then further diffuse into the getter to chemically form metal hydrides. While a number of studies show that oxygen binds strongly as compared to 3 H on the nickel (Ni) layer, the detailed mechanism of 3 H species absorption and diffusion across the Ni plate and Ni/Zr interface are still unclear. By employing density functional theory calculations, here we explored the 3 H 2 and 3 H 2 O species adsorption and dissociation on the Ni(111) surface and diffusion into the Ni sublayer. Our results indicated that the 3 H 2 and 3 H 2 O dissociate on the Ni(111) surface. The NiO x and Ni(O 3 H) x could be formed in the Ni layer due to the higher oxygen (O) diffusion energy barrier and formation of Ni vacancy defects. The oxygen was found to be retained in the Ni layer from diffusing across the Ni–Zr interface. This was revealed by comparing the diffusion barriers for 3 H with O. 3 H was found to have nearly three times smaller diffusion barrier than for O, making 3 H comparatively easier to diffuse through the Ni layer. In conclusion, the obtained results provide guidelines for experimental measurements on 3 H retention behavior in TPBARs and may open further avenues to explore the impurity effects on 3 H diffusion and storage at the Ni/zircaloy interfaces.

Tafen, De Nyago [National Energy Technology Lab. (↗

Aggregation of Size-Selected Oxide Clusters Deposited onto Au(111)

Kinetic Monte Carlo (kMC) simulations along with density functional theory (DFT) calculations were used to investigate the aggregation of size-selected Nb 3 O y (y = 5, 6, 7) clusters deposited onto the Au(111) surface. Recent STM experiments showed that the cluster binding sites and sizes of the cluster assemblies on the Nb 3 O y /Au(111) surfaces strongly depend on the stoichiometry of the clusters, i.e., the oxygen-to-niobium ratio. To better understand the origins of these differences, kMC simulations of the nucleation and growth of cluster assemblies were performed using energy barriers for diffusion and intercluster interactions estimated from DFT calculations of cluster binding and dimerization energies, respectively. Comparisons of the kMC simulations with STM images of the as-deposited Nb 3 O y /Au(111) surfaces at RT and after high temperature annealing were used to further optimize the energetics and gauge the importance of nearest neighbor interactions. The kMC simulations demonstrate that the assembly of Nb 3 O y clusters on Au(111) are largely controlled by the magnitude of the barriers for diffusion and interparticle-bond formation, while changes at higher temperatures are sensitive to the binding energies between nearest neighbors. Simulations for the Nb 3 O 5 and Nb 3 O 6 clusters, which exhibit smaller cluster assembly sizes in STM, required larger diffusion barriers as well as different barriers for interparticle binding, which reflected differences in DFT calculated dimerization energies. Furthermore, the results demonstrate the effectiveness of combined DFT and kMC calculations for understanding how the stoichiometry affects the aggregation of small oxide clusters on a metal surface.

36 MATERIALS SCIENCE↗

Mixed Ionic–Electronic Conductor of Perovskite Li x La y MO 3-δ toward Carbon-Free Cathode for Reversible Lithium–Air Batteries

Mixed ionic–electronic conductors (MIECs) can play a pivotal role in achieving high energies and power densities in rechargeable batteries owing to their ability to simultaneously conduct ions and electrons. In our study, a new strategy is proposed wherein late 3d transition metals (TMs) are substituted into a perovskite Li-ion conductor to transform it into a Li-containing MIEC. First-principles calculations show that perovskite Li x La y MO 3 with late 3d TMs have a low oxygen vacancy formation energy, implying high electron carrier concentrations corresponding to high electronic conductivity. The activation barriers for Li diffusion in Li x La y MO 3 (M = Ti, Cr, Mn, Fe, and Co) are below 0.411 eV, resulting in high Li-ion conductivity. The designed perovskites of Li0.34La 0.55 MnO 3-δ experimentally prove to have high electronic (2.04 × 10 -3 S cm -1 ) and Li-ion (8.53 × 10 -5 S cm -1 ) conductivities, and when applied in a carbon-free cathode of a Li–air cell, they deliver superior reversibility at 0.21 mAh cm -2 over 100 charge/discharge cycles while avoiding the degradation associated with carbonaceous materials. Finally, this strategy enables the effective design of Li-conducting MIEC and reversible Li–air batteries.

36 MATERIALS SCIENCE↗