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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 361 records · Page 20

Defect-mediated ripening of core-shell nanostructures

Abstract Understanding nanostructure ripening mechanisms is desirable for gaining insight on the growth and potential applications of nanoscale materials. However, the atomic pathways of nanostructure ripening in solution have rarely been observed directly. Here, we report defect-mediated ripening of Cd-CdCl 2 core-shell nanoparticles (CSN) revealed by in-situ atomic resolution imaging with liquid cell transmission electron microscopy. We find that ripening is initiated by dissolution of the nanoparticle with an incomplete CdCl 2 shell, and that the areas of the Cd core that are exposed to the solution are etched first. The growth of the other nanoparticles is achieved by generating crack defects in the shell, followed by ion diffusion through the cracks. Subsequent healing of crack defects leads to a highly crystalline CSN. The formation and annihilation of crack defects in the CdCl 2 shell, accompanied by disordering and crystallization of the shell structure, mediate the ripening of Cd-CdCl 2 CSN in the solution.

36 MATERIALS SCIENCE↗

Gas nitriding behavior of refractory metals and implications for multi-principal element alloy design

Multi-principal element alloys (MPEAs) comprise a large, flexible compositional space that enables tuning of their chemistry, structure, and properties. Here, to facilitate the development of nitriding-based surface-enhancement strategies that harness a broad compositional space, this study examined the gas nitriding behavior of Hf, Mo, Nb, Ta, Ti, and Zr as a function of time, temperature (750 and 1000 °C), and nitriding potential (i.e. ammonia-to-hydrogen ratio). These metals were selected because they have a strong driving force to form nitrides, and appear in many promising refractory MPEA compositions. The nitriding temperatures were selected based on the phase transformation temperature of Ti and Zr, and the nitriding potentials were chosen such that all elements are expected to form nitrides. Mass gain measurements indicate that all six elements follow parabolic kinetics. The microstructure observations and quantitative microchemical analysis show formation of dense and well-adhered compound layers for Mo, Nb, and Ta. Thick diffusion zones appear in Hf, Ta, Ti, and Zr, and diffusion coefficients were fit to the composition profiles. Partial delamination of the compound layer occurred for Ti and Zr. Peak hardness values above 30 GPa are obtained in the dense compound layers, and the solute hardening of the underlying alloy is correlated with the nitrogen content. The results provide insight into the dynamics of nitride compound formation relative to interstitial dissolution of nitrogen, and are discussed in the context of MPEA composition and processing design.

36 MATERIALS SCIENCE↗

Corrosion mechanism of cold forged 316 stainless steel in molten FLiNaK salt

This study examined how cold forging (CF) affects the corrosion of 316 stainless steel (SS) in molten FLiNaK salt at 700 °C for 48 h. CF samples had two corrosion areas: one near the top and another displaying intergranular corrosion (IGC). Samples with lower CF (5–30 %) showed more IGC, while the 50 % CF sample had less IGC but the shallowest corrosion depth. This was due to the increased number of grain boundaries, which raised the potential corrosion initiation sites, and certain grain boundaries promoting chromium dissolution, thus enhancing IGC.

FLiNaK↗

Evaluation of Degradation Mechanisms for Solid Secondary Waste Grout Waste Forms

The overall objective of this work is to provide defensibility for the long-term performance of grouted Hanford SSW streams when disposed in a near surface disposal facility, IDF, on the Hanford Site. Providing defensibly for the long-term performance of the grouted waste forms is consistent with the research and development activities identified in the Performance Assessment Maintenance Plan, (Westcott et al. 2019), that are necessary to address the assumptions made in the PA. Specifically, this work addresses two areas identified for further research and development activities in the plan: (1) “Evaluate ongoing research on transport characteristics of cementitious materials using accelerated tests to approximate the effects of aging/alteration/weathering”; and (2) “Evaluate ongoing research on microbial effects on transport processes in cementitious materials.” The assembled subject matter expert team evaluated a list of degradation mechanisms and supporting processes and provided rankings of areas where further research and development (R&D) are needed. From this assessment, high priority R&D areas include: (1) the effects of carbonation, Ca leaching, and SSW dimensional change in grout waste forms; (2) updated model representations of grouted waste forms; and (3) scaled testing demonstrations. Moderate priority items including a paper study on possible microbial influence, reoxidation rates, radionuclide/contaminant dissolution from SSW in the grout and freeze thaw behavior. Other processes evaluated were either deemed unlikely to occur, to have little impact on the SSW waste forms, or to occur at time frames beyond those considered (>10,000 years). The assessments and proposed R&D approaches are expected to support an update to the WRPS SSW roadmap.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Rechargeable Manganese Dioxide||Hard Carbon Lithium Batteries in an Ether Electrolyte

Earth-abundant, cost-effective electrode materials are essential for sustainable rechargeable batteries and global decarbonization. Manganese dioxide (MnO 2 ) and hard carbon both exhibit high structural and chemical tunability, making them excellent electrode candidates for batteries. Herein, we elucidate the impact of electrolytes on the cycling performance of commercial electrolytic manganese dioxide in Li chemistry. We leverage synchrotron X-ray analysis to discern the chemical state and local structural characteristics of Mn during cycling, as well as to quantify the Mn deposition on the counter electrode. By using an ether-based electrolyte instead of conventional carbonate electrolytes, we circumvent the formation of a surface Mn(II)-layer and Mn dissolution from Li x MnO 2 . Consequently, we achieved an impressive ~100% capacity retention for MnO 2 after 300 cycles at C/3. To create a lithium metal-lean full cell, we introduce hard carbon as the anode which is compatible with ether-based electrolytes. Commercial hard carbon delivers a specific capacity of ~230 mAh g -1 at 0.1 A g -1 without plateau, indicating a surface-adsorption mechanism. The resulting manganese dioxide||hard carbon full cell exhibits stable cycling and high Coulombic efficiency. Our research provides a promising solution to develop cost-effective, scalable, and safe energy storage solutions using widely available manganese oxide and hard carbon materials.

25 ENERGY STORAGE↗

Recent developments in catalyst-related PEM fuel cell durability

Cost and durability remain the two major barriers to the widespread commercialization of polymer electrolyte membrane fuel cell (PEMFC)-based power systems, especially for the most impactful but challenging fuel cell electric vehicle (FCEV) application. Commercial FCEVs are now on the road; however, their PEMFC systems do not meet the cost targets established by the U.S. Department of Energy, primarily due to the high platinum loading needed on the cathode to achieve the requisite performance and lifetime. Furthermore, while the activities of a number of commercial Pt-based alloy cathode catalysts exceed the beginning-of-life (BOL) targets, these activities, and the overall cathode performance, degrade via a variety of mechanisms described herein. Degradation is mitigated in current FCEVs by utilizing a cathode catalyst with a lower BOL activity (e.g., much lower transition metal alloy content and larger BOL nanoparticle size), necessitating higher catalyst loadings, and through the utilization of system controls that avoid conditions known to exacerbate degradation processes, such as limiting the fuel cell stack voltage range. The design and development of active and robust materials and eliminating the need for vehicle mitigation strategies would greatly simplify the operating system, allowing for greater transient operation, avoiding large hybridization, and curtailing of fuel cell power. Although system mitigation strategies have provided the near-term pathway for FCEV commercialization, material-specific solutions are required to further reduce costs and improve operability and efficiency. Future material developments should focus on stabilization of the electrode structure and minimization of the catalyst particle susceptibility to dissolution caused by oxide formation and reduction over PEMFC cathode-relevant operating potentials plus minimization of support corrosion. Ex situ accelerated stress tests have provided insight into the processes responsible for material and performance degradation and will continue to provide useful information on the relative stability of materials and benchmarks for robust and stable materials-based solutions not requiring system mitigation strategies to achieve adequate lifetime.

25 ENERGY STORAGE↗

Synthesis of results for Brine Availability Test in Salt (BATS) DECOVALEX-2023 Task E

In the 2023 phase of the international collaborative DECOVALEX modeling project, Task E focused on understanding thermal, hydrological, and mechanical (THM) processes related to predicting brine migration in the excavation damaged zone around a heated excavation in salt. Salt is attractive as a disposal medium for radioactive waste because it is self-healing and is essentially impermeable and non-porous in the far field. Investigation of the short-term, near-field behavior is important for radioactive waste disposal because this early period strongly controls the amount of inflowing brine. Brine leads to corrosion of waste forms and waste packages, and possible dissolution of radionuclides with brine transport being a potential transport vector to the accessible environment.The Task was divided into steps. Step 0 included matching unheated brine inflow data from boreholes at the Waste Isolation Pilot Plant (WIPP) and matching temperature observations during a Brine Availability Test in Salt (BATS) heater test. Step 1 included validation of models against a thermo-poroelastic analytical solution, and two-phase flow around an excavation. Finally, Step 2 required all the individual components covered in steps 0 and 1 to come together to match observed brine inflow behavior during the same BATS heater test.There were a range of approaches from the teams, from mechanistic to prescriptive. Given the uncertainties in the problem, some teams used one- or two-dimensional models of the processes, while other teams included more geometrical complexity in three-dimensional models. Task E was a learning experience for the teams involved, and feedback from the modeling teams has led to changes in follow-on BATS experiments at WIPP. The primary Task E lessons learned were the impact of hydrologic initialization methods (wetting up vs. drying down), the difference between confined and unconfined thermal expansion, and the large changes in permeability associated with heating and cooling.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

A space-time adaptive finite element method with exponential time integrator for the phase field model of pitting corrosion

In this paper we propose a space-time adaptive finite element method for the phase field model of pitting corrosion, which is a parabolic partial differential equation system consisting of a phase variable and a concentration variable. A major challenge in solving this phase field model is that the problem is very stiff, which makes the time step size extremely small for standard temporal discretizations. Another difficulty is that a high spatial resolution is required to capture the steep gradients within the diffused interface, which results in very large number of degrees of freedom for uniform meshes. To overcome the stiffness of this model, we combine the Rosenbrock–Euler exponential integrator with Crank–Nicolson scheme for the temporal discretization. Moreover, by exploiting the fact that the speed of the corroding interface decreases with time, we derive an adaptive time stepping formula. For the spatial approximation, we propose a simple and efficient strategy to generate adaptive meshes that reduces the computational cost significantly. Thus, the proposed method utilizes local adaptivity and mesh refinement for efficient simulation of the corrosive dissolution over long times in heterogeneous media with complex microstructures. We also present an extensive set of numerical experiments in both two and three dimensional spaces to demonstrate efficiency and robustness of the proposed method.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Increasing the Pressure‐Free Stripping Capacity of the Lithium Metal Anode in Solid‐State‐Batteries by Carbon Nanotubes

Abstract Lithium metal is the key anode material for solid‐state‐batteries as its successful implementation will drastically increase their energy and power densities. However, anode contact loss during stripping leads to dendrites upon plating and subsequent cell failure. Design strategies to mitigate these issues are crucial to enable the use of lithium metal anodes. This paper reports the dissolution kinetics of composite anodes made of lithium metal and carbon nanotubes (CNTs) with a garnet‐type solid electrolyte (SE). In addition to an enhancement of the effective diffusion within the anode, its dissolution is fundamentally changed from being 2D to 3D. By maintaining contact with the SE, the CNTs facilitate lithium transport to the interface, which yields more than 20 mAh cm −2 discharge capacity at 100 µ A cm −2 without the application of external stack pressure ( > 1 MPa). Conclusions drawn from electrochemical data on the anode microstructure are validated using cryo‐focused‐ion‐beam scanning electron microscopy and correlated with the mechanical properties. Micro‐indentation, acoustic analysis, and stress–strain testing show that mechanical properties of the anode, like yield strength and hardness, are adjustable. Overall, it is shown that the mechanical and electrochemical properties of Li–CNT composite electrodes can be tailored to suit the requirements of a practical cell.

Fuchs, Till↗

Impacts of Dissolved Ni 2+ on the Solid Electrolyte Interphase on a Graphite Anode

Transition metal (e.g. Ni) ions dissolved from layered-structured Ni-rich cathodes can migrate to the anode side and accelerate the failure of lithium-ion batteries. The investigations of the impact and distribution of Ni species on the solid electrolyte interphase (SEI) on the anode are crucial to understand the failure mechanism. Herein, we used time-of-flight secondary ion mass spectroscopy (TOF-SIMS) coupled with multivariate curve resolution (MCR) analysis to intuitively characterize the distribution of Ni species in the SEI. We find that the SEI on the graphite electrode using an EC-based electrolyte exhibits a multi-stratum structure. During accelerated aging of the LiNi 0.88 Co 0.08 Mn 0.04 O 2 /graphite full cell, the dissolution of Ni aggravates significantly upon cycling. A strong correlation between the dissolved-Ni and organic species in the SEI on graphite is illustrated. Here, the ion-exchange reaction between Ni 2+ and Li + ions in the SEI is demonstrated to be the main reason for the increase of SEI resistivity.

25 ENERGY STORAGE↗

Decoupling the degradation factors of Ni-rich NMC/Li metal batteries using concentrated electrolytes

Battery degradation results from multiple factors that usually correlate with each other. Electrochemical corrosion of the current collector is one of the main reasons for battery failure, leading to poor internal electrical contact and the dissolution of harmful ions into electrolytes. This phenomenon is especially evident in lithium bistrifluoromethanesulfonimidate (LiTFSI)-based electrolytes, although they have many advantages over conventional lithium hexafluorophosphate (LiPF 6 )-based electrolytes, such as low viscosity, good thermal stability, and stable to water. Recently, highly concentrated electrolytes are found hopeful of inhibiting aluminum's corrosion and boosting new electrolyte development. Here we discuss the solvation structures of liquid electrolytes and decouple the degradation mechanisms of using LiTFSI-based electrolytes in Li(Ni 0.8 Co 0.1 Mn 0.1 )O 2 /Li metal batteries. The results suggest although concentrated electrolytes inhibit the Al corrosion, the growth of lithium dendrites and the protection of the cathode-electrolyte interphase are not significantly improved. Furthermore, this paper provides a paradigm to evaluate the performance of electrolytes comprehensively.

25 ENERGY STORAGE↗

Impact of Charge Voltage on Factors Influencing Capacity Fade in Layered NMC622: Multimodal X-ray and Electrochemical Characterization

Ni-rich NMC is an attractive Li-ion battery cathode due to its combination of energy density, thermal stability, and reversibility. While higher delivered energy density can be achieved with a more positive charge voltage limit, this approach compromises sustained reversibility. Improved understanding of the local and bulk structural transformations as a function of charge voltage, and their associated impacts on capacity fade are critically needed. Through simultaneous operando synchrotron X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS) of cells cycled at 3–4.3 or 3–4.7 V, this study presents an in-depth investigation into the effects of voltage window on local coordination, bulk structure, and oxidation state. These measurements are complemented by ex situ X-ray fluorescence (XRF) mapping and scanning electrochemical microscopy mapping (SECM) of the negative electrode, X-ray photoelectron spectroscopy (XPS) of the positive electrode, and cell level electrochemical impedance spectroscopy (EIS). Initially, cycling between 3 and 4.7 V leads to greater delivered capacity due to greater lithium extraction, accompanied by increased structural distortion, moderately higher Ni oxidation, and substantially higher Co oxidation. Continued cycling at this high voltage results in suppressed Ni and Co redox, greater structural distortion, increased levels of transition metal dissolution, higher cell impedance, and 3× greater capacity fade.

capacity fading mechanisms↗

Elucidating Sodium-Sulfur Battery Chemistry using Operando Transmission X-ray Microscopy and X-ray Absorption Spectroscopy

Room-temperature sodium-sulfur (Na-S) batteries offer a beneficial and cost-effective solution for powering modern electric grids and devices. However, Na-S batteries suffer from performance decay during battery cycling due to the sluggish kinetics and polysulfide shuttling. Revealing the conversion mechanism of the Na-S chemistry is critical to designing high-capacity and stable Na-S batteries. In this study, we employed operando X-ray microscopy and operando X-ray absorption spectroscopy to elucidate the sulfur conversion in a carbon host using an ether-based electrolyte. We reveal the structural and chemical evolution of the sulfur cathode during cycling, which results in volume expansion and the dissolution of active material, ultimately affecting the battery performance. Our work provides fundamental insight into the sulfur reaction scheme, addressing the lingering challenges before establishing inexpensive Na-S batteries for broad applications, including portable electronics and large-scale energy storage.

Jagadeesan, Sathya Narayanan [SLAC National Accele↗

DECOVALEX-2023: Task E Final Report

This is the Task E final report for DECOVALEX-2023. Task E is focused on understanding thermal, two-phase hydrological, and mechanical (TH2M) processes, especially related to predicting brine migration in the excavation damaged zone around a heated excavation in salt. Salt is attractive as a disposal medium for radioactive waste because it is self-healing and is essentially impermeable and essentially non-porous in the far field (away from excavations). Investigation of the short-term (days to years) near-field (centimeters to tens of meters) behavior of salt is important for radioactive waste disposal because this early period strongly controls the amount of brine in a salt repository. Brine leads to corrosion of waste forms and waste packages, and possible dissolution of radionuclides with brine transport being a potential transport vector to the accessible environment. The main test case used in Task E is the ongoing Brine Availability Test in Salt (BATS) heater test located underground at the Waste Isolation Pilot Plant (WIPP) near Carlsbad, New Mexico, USA. The Task was divided into a series of Steps. Step 0 was an introduction to processes in salt, that included matching historical unheated brine inflow data from boreholes at WIPP and matching temperature observations during BATS heater test 1a. Step 1 included validation of models against a thermo-poroelastic analytical solution relevant to heated boreholes in salt, and two-phase flow around an excavation in salt. Step 2 required all the individual components covered in steps 0 and 1 to come together to match observed brine inflow behavior during the BATS 1a heater test. There were a range of approaches from the teams, from mechanistic to prescriptive. Given the uncertainties in the problem, some teams used one- or two-dimensional models of the processes, while other teams included more geometrical complexity in three-dimensional models. The key learning points from Task E have been: • Heat conduction through salt typically requires non-linear thermal conductivity (as a function of temperature), but most models do a good job matching observations, given appropriate adjustments to the applied power and some thermocouple locations. • Thermal pressurization requires coupled thermal-hydrological-mechanical (THM) responses that consider the thermal expansion of the fluid and solid phases. • Initialization of two-phase flow models around a borehole or excavation in salt are more realistically represented as “wetting up”, rather than “drying down” (i.e., the initial state after excavation is mostly dry, rather than mostly wet). • The BATS 1a heater test includes a significant release of brine after the end of heating, which requires a large increase in permeability to recreate. Task E has been a great learning experience for all the teams involved, and feedback from the modeling teams has led to changes in the design of follow-on BATS experiments, which are now ongoing underground at WIPP. There was a balance throughout the task between freedom to model phenomena how each team saw fit, and prescriptiveness in problem design to bring the modeling teams closer together to allow attribution of smaller differences between models to different modeling choices. The modeling approaches seem to go through two phases: an early phase of discovery or testing, and a later phase of refinement and improvement. In future modeling efforts, different field data could be used (e.g., BATS 2) and more time should be included in the processes for teams to make multiple model refinement or even significant changes to their conceptual model or setup, based on lessons learned from the modeling exercise.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Origins of wear-induced tungsten corrosion defects in semiconductor manufacturing during tungsten chemical mechanical polishing

During chemical mechanical polishing (CMP) process optimization, a unique corrosion defect was identified in the tungsten (W) contact plugs, which were investigated to develop practical solutions to improve CMP mass productivity. The corrosion defect occurred in the absence of external incident energy and was observed to occur only at the W plugs connected to the P + /n-well close to the wafer edge. To examine the root cause of the corrosion, a series of experiments was carried out at each W CMP step, using in-line defect inspection. Additional experiments were conducted using on-line inductively coupled plasma mass spectrometry (ICP-MS) to understand pH- and potential-dependent electrochemical dissolution behaviors of W. Experimentally, W corrosion was confirmed to be exacerbated if the surface oxide of the W plugs is removed by the deionized water (DIW) rinsing step under wafer pressurization, then exposed to DIW and alkaline cleaning solution. Although the DIW rinsing step is commonly performed to clean polishing pads right after the main polishing, a small amount of applied pressure (0.5 psi) without slurry supply can lead to corrosion defects. Finally, this wear-induced corrosion of the W plugs can be prevented by removing the applied pressure during the post DIW rinsing step of W CMP.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗