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All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Neural Networks to Find the Optimal Forcing for Offsetting the Anthropogenic Climate Change Effects

Abstract Of great relevance to climate engineering is the systematic relationship between the radiative forcing to the climate system and the response of the system, a relationship often represented by the linear response function (LRF) of the system. However, estimating the LRF often becomes an ill-posed inverse problem due to high-dimensionality and nonunique relationships between the forcing and response. Recent advances in machine learning make it possible to address the ill-posed inverse problem through regularization and sparse system fitting. Here, we develop a convolutional neural network (CNN) for regularized inversion. The CNN is trained using the surface temperature responses from a set of Green’s function perturbation experiments as imagery input data together with data sample densification. The resulting CNN model can infer the forcing pattern responsible for the temperature response from out-of-sample forcing scenarios. This promising proof of concept suggests a possible strategy for estimating the optimal forcing to negate certain undesirable effects of climate change. The limited success of this effort underscores the challenges of solving an inverse problem for a climate system with inherent nonlinearity. Significance Statement Predicting the climate response for a given climate forcing is a direct problem, while inferring the forcing for a given desired climate response is often an inverse, ill-posed, problem, posing a new challenge to the climate community. This study makes the first attempt to infer the radiative forcing for a given target pattern of global surface temperature response using a deep learning approach. The resulting deeply trained convolutional neural network inversion model shows promise in capturing the forcing pattern corresponding to a given surface temperature response, with a significant implication on the design of an optimal solar radiation management strategy for curbing global warming. This study also highlights the technical challenges that future research should prioritize in seeking feasible solutions to the inverse climate problem.

Ren, Huiying↗
DOE OSTI2023

Laboratory Experiments Examining the Effect of Thermal and Mechanical Processes on Hydraulic Transmissivity Evolution

Using laboratory slide-hold-slide experiments, at temperatures from 22 to 200 degrees C, to examine effects of fracture reactivation and quasi-static loading on the evolution of fluid transport properties of simulated fractures in Westerly granite. At all temperatures, the in-plane hydraulic transmissivity consistently decays during hold periods resulting in an overall reduction in transmissivity. During the first three to fifteen hours of an experiment, transmissivity decreases rapidly due to the generation of wear products, development of a sliding surface, and compaction of the resulting gouge. Once the sliding surface has developed, the long-term transmissivity decay rate at 22 and 100 degrees C is significantly lower than the transmissivity decay rate during the initial 3-15 hours of the experiment. However, at 200 degrees C, the decay of hydraulic transmissivity remains high throughout the experiment. The long-term decay of hydraulic transmissivity can be fitted with a power law model with more rapid reduction of hydraulic transmissivity at higher temperature. Periods of sliding on the fracture surface result in transient increases in the transmissivity, due to shear dilation, as is expected for Coulomb materials. These transients are superimposed on the long-term decay. When sliding ceases and a new hold period commences, there is a rapid reduction in transmissivity and return to the long-term rate of transmissivity decay. The rate of decay of the transmissivity transients is inversely correlated with temperature, in contrast to the long-term decay and the expected behavior for processes like subcritical crack growth and indentation creep. The higher decay rates that are observed during the initial 3-15 hours of the tests and following sliding, are associated with times that the porosity of the gouge is expected to be high. The difference in decay rates suggests that when the gouge is driven far from equilibrium by active shearing, densification may be dominated by a different mechanism from long-term compaction.

15 GEOTHERMAL ENERGY↗
DOE OSTI2021

Nanomechanical mapping and strain rate sensitivity of microcrystalline cellulose

Nanoindentation provides a convenient and high-throughput means for mapping mechanical properties and for measuring the strain rate sensitivity of a material. Here, nanoindentation was applied to the study of microcrystalline cellulose. Here, constant strain rate nanoindentation revealed a depth dependence of nanohardness and modulus, mostly attributed to material densification. Nanomechanical maps of storage modulus and hardness resolved the shape and size of voids present in larger particles. In smaller, denser particles, however, where storage modulus varied little spatially, there was still some spatial dependence of hardness, which can be explained by cellulose’s structural anisotropy. Additionally, hardness changed with the indentation strain rate in strain rate jump tests. The resulting strain rate sensitivity values were found to be in agreement with those obtained by other techniques in the literature.

36 MATERIALS SCIENCE↗
DOE OSTI2022

In situ ion irradiation of amorphous TiO 2 nanotubes

Understanding of structural and morphological evolution in nanomaterials is critical in tailoring their functionality for applications such as energy conversion and storage. Here, we examine irradiation effects on the morphology and structure of amorphous TiO 2 nanotubes in comparison with their crystalline counterpart, anatase TiO 2 nanotubes, using high-resolution transmission electron microscopy (TEM), in situ ion irradiation TEM, and molecular dynamics (MD) simulations. Anatase TiO 2 nanotubes exhibit morphological and structural stability under irradiation due to their high concentration of grain boundaries and surfaces as defect sinks. On the other hand, amorphous TiO 2 nanotubes undergo irradiation-induced crystallization, with some tubes remaining only partially crystallized. The partially crystalline tubes bend due to internal stresses associated with densification during crystallization as suggested by MD calculations. Furthermore, these results present a novel irradiation-based pathway for potentially tuning structure and morphology of energy storage materials.

36 MATERIALS SCIENCE↗
DOE OSTI2020

FY20 Verification of BISON Using Analytic and Manufactured Solutions

In 2010, the U.S. Department of Energy created its first Energy Innovation Hub, which is focused on developing high-fidelity and high-resolution Modeling and Simulation (M&S) tools for modeling of Light Water Reactors (LWRs). This hub, Consortium for Advanced Simulation of LWRs (CASL), has developed an LWR simulation tool called Virtual Environment for Reactor Applications (VERA). The multi-physics capability of VERA is achieved through the coupling of single-physics codes, including BISON, CTF, MPACT, and MAMBA. BISON is a fuel performance code which models the thermo-mechanical behavior of nuclear fuel using high performance M&S. It is capable of modeling traditional LWR fuel rods, fuel plates, and TRi-structural ISOtropic (TRISO) fuel particles. It can employ three-dimensional Cartesian, two-dimensional axisymmetric cylindrical, or one-dimensional radial spherical geometry. It includes empirical models for a large variety of fuel physics: temperature- and burnup-dependent thermal properties, fuel swelling and densification, fission gas production, cladding creep, fracture, cladding plasticity, and gap/plenum models. This document details a series of code verification test problems that are used to test BISON. These problems add confidence that the BISON code is a faithful representation of its underlying mathematical model. The suite of verification tests are mapped to the underlying conservation equations solved by the code: heat conduction, mechanics, and species conservation. Twenty-two problems are added for the heat conduction solution, two for the mechanics solution, and none for species conservation. Method of Manufactured Solutions (MMS) capability is demonstrated with three problems, and temperature drops across the fuel gap are tested.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2020

VTO FY20Q4 quarterly report

Project Objective.This project has three objectives: (1) tuning microstructures of 3D-printed SSE separators,(2) determining material and processing compatibilities with cathode printing,and (3)3D printing of sintering-free SSE separators.Project Impact.All-solid-state lithium batteries are difficult to process due to the brittleness of ceramic materials, poor solid-solid contact, and electrolyte-electrode stability issues. As a result, the energy and power density and also cycling stability are far from satisfying. This project will address fabrication difficulties by using state-of-the-art 3D-printing techniques that can introduce 3D interfaces and architectures to enhance solid-solid contact and reduce charge transfer resistance. Success will benefit the DOE by establishing the best manufacturing methods for ASSBsto achieve VTO goals on the performance of beyond Li-ion batteries. Approach.The project employs 3D-printing techniques to manufacture SSEs and related components for ASSBs. The team starts with direct ink writing (DIW) to develop ink recipes with desired rheological properties and explore post-sintering approaches to achieve high densification. In parallel with DIW3D printing, the team also explores other 3D printing options, such as projection microstereolithography (PuSL). Both sintering and sintering-free approaches can gain benefit from 3D printing and therefore will be investigated.Out-Year Goals.The team will determine particle sizes and morphologies as well as post-processing conditions that deliver good ionic conductivity and charge transfer properties of LLZTO separators. They will examine co-sintering of LLZTO/cathode and determine the effects of material, particle size, surface coating, and sintering conditions.Collaborations.Microstructures, ionic conductivities, and mechanical properties will be provided to the LLNL simulation team, led by PI B. Wood, for establishing and validating phase-field modeling methods.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Improved Advanced Biomass Logistics Utilizing Woody and other Feedstocks in the Northeast and Pacific Northwest (Final Report)

Willow and poplar short rotation woody crops (SRWC) have shown promise with regards to environmental benefits and rural development but wide adoption lags due to underdeveloped markets and supply systems. High costs associated with harvesting, handling and transportation (40-60% of delivered cost) have impeded expansion. A better understanding of these systems will create opportunities to improve efficiency, reduce costs, and realize environmental benefits and impacts. The project’s goal was to lower the delivered cost of hybrid poplar in the Northwest and willow in the Northeast by optimizing harvesting and logistics supply systems while maintaining or improving biomass quality along the supply chain. Over 3,400 Mg of biomass and 300 ha of willow and poplar were monitored over a range of crop and field conditions. Feedstock quality as affected by storage and preprocessing were shown to improve or maintain feedstock quality. Modeled harvesting costs ranged from $38–61 Mg -1 dry; when including delivery and preprocessing feedstock costs ranged between $79-83 Mg -1 dry for willow and $106-116 Mg -1 dry for poplar. Costs for willow minimized when hot water extraction and high-moisture densification preprocessing were used. Models also suggest that social and regional factors could further reduce costs. Results will give guidance to feedstock growers, harvesting and logistic operations, biorefinery project developers, and policy makers developing SRWC to support a growing bioeconomy.

, biomass↗
DOE OSTI2021

Binder Jet Printing of H13 Tool Steel

ORNL and Carpenter worked on evaluating H13 powders with different powder size distributions for deposition via binder jet additive manufacturing (AM). Binder jet AM has the potential to be a costeffective technique for fabrication of near net shaped tools with complex geometries and internal features such as cooling channels that can improve the production efficiency of injection/compression molding tools. However, a critical challenge in binder jet AM is the densification of the said tool for it to be usable. Powder size distribution can affect the process settings required to deposit the material and the subsequent sintering behavior. In this collaborative effort ORNL and Carpenter demonstrated that the process variables depend on the powder size distribution while the carbon pickup during sintering depends on the binder burnout atmosphere and temperature. On the other hand, there was no noticeable difference in the microstructural evolution of H13 deposited using the different powder size distributions.

42 ENGINEERING↗
DOE OSTI2021

Cold Sintered Ceramics and Cements for Part Encapsulation

In this project, ceramic encapsulation materials were studied for high temperature (>~°500 C) applications where typical polymer encapsulants are unstable. A new low temperature (<~°200 C) method of processing ceramics, the cold sintering process was examined. Additionally, commercially available high temperature ceramic cements were investigated. In both cases, the mechanical strengths of available materials are less than desired (i.e., desired strengths similar to Si 3 N 4 ), limiting applicability. Composite designs to increase mechanical strength are suggested. Additionally, non-uniformities in stresses and densification while embedding alumina sheets in encapsulants via cold sintering using uni-axial pressing led to fracture of sheets, and an alternative iso-static based approach is recommended for future studies.

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

Next Generation Logistics Systems for Delivering Optimal Biomass Feedstocks to Biorefining Industries in the Southeastern U.S.

The diverse portfolio of biomass sources that is available in the Southeastern U.S., including a significant supply of pine “residue”, represents a valuable strategic position for the region. Through blends formulated based on critical properties, this project will take full advantage of the range in biomass properties afforded by the portfolio to produce a consistent, high-performance feedstock for the industry, while lowering cost. Key developments being targeted to enable this potential include whole-tree transport to a state-of-the-art merchandising depot that will further access biomass from ongoing, forest industry operations. The approach will more effectively utilize the tree and distribute cost, while minimizing in-woods contamination of the woody biomass component. To implement this vision, information on the chemical composition and changes that are induced during multiple preprocessing steps (size reduction, moisture removal, densification, etc.) is needed. New NIR sensor technology will be developed for online monitoring of important biomass properties. The data will be incorporated into a statistical process control platform to improve process efficiency and meet required specifications. Advanced process models are being developed to inform the techno-economic and life-cycle assessment of the program’s impact. The new system will ultimately reduce operational risks from supply chain disruptions, and allow operation of larger-scale biorefineries.

09 BIOMASS FUELS↗
DOE OSTI2023

Laboratory-Scale Coal-Derived Graphene Process (Final Report)

The Energy & Environmental Research Center (EERC) conducted a laboratory-scale coal-derived graphene (CDG) project focused on developing a technological process for making graphene from four U.S. domestic coal or coal wastes, including lignite from North Dakota, subbituminous coal from Wyoming, bituminous coal from Utah, and anthracite from Pennsylvania. The project was divided into two performance or budget periods (BPs), with BP1 comprising the up-front laboratory experiments to make graphene materials from coal beginning on May 1, 2020, to April 30, 2022. BP2 was conducted from May 1, 2022, to April 30, 2023, and was focused on analyzing the CDG process economic feasibility and the technical gaps for technological scale-up and commercialization. During this project, a few different coal-derived high-value products have been demonstrated, including graphite, graphene oxide (GO), reduced graphene oxide (rGO), and graphene quantum dots (GQDs). A new graphite microstructure was discovered and named “croissant graphite” because of the exterior morphological and textural resemblance to croissant food items sold in commercial groceries stores. The new graphite structure and the associated preparation from coal or coal waste feedstocks has been the subject of a U.S. patent application. The systematic experimental processes involving coal cleaning, upgrading, and conversion to high-value carbon products culminated into a developed upgraded coal-to-products (UCP) technology that is being pursued for potential fast-track commercialization, if funding is available. It is envisioned that commercialization of the UCP technology would increase consumption of U.S. domestic coals or coal wastes to make environmentally sustainable high-value products for the electronics industry, high-energy-storage applications, and clean energy technologies such as electric vehicle (EV) lithium-ion batteries (LIBs), for which graphite has become a critical mineral commodity. Croissant graphite microstructures, when observed by field emission scanning electron microscopy (FESEM), display wavy surface morphology and often grow from a base that is made of graphitized particles with honeycomb-like layers, which are believed to be graphene layers. While more studies are needed to fully ascertain the mechanisms of the croissant graphite microstructure formation, it is postulated that their growth may begin from curling of the graphene sheets into ribbon-like structures, and continuous growth and densification of the ribbon-like structures forms croissant microstructures. Additional studies are ongoing to evaluate the electrochemical performance of croissant graphite for LIB applications and to determine the experimental conditions necessary to tune on/off croissant formation so that it can be either optimized or suppressed depending on performance evaluation results. In addition to the discovery of croissant graphite, the graphitization process from the four coal ranks in general was successful. X-ray diffraction (XRD) analysis showed that the degree of graphitization (DoG) ranged from 12% to 80% in an early sample set, and further optimization on lignite coal produces a DoG of about 92%, which was spectacular to see as lignite is the lowest-rank coal. Thus, it is expected that the graphitization performance for higher-rank coals will be similar or better when optimized as well. The coal-derived graphite was used to make GO and rGO. Analytical characterization, e.g., by methods such as Raman spectroscopy, XRD, Fourier transform infrared (FTIR) spectroscopy and FESEM, showed that the sequence of converting the coal to graphite, exfoliating it to GO, and then chemically reducing the GO to rGO was successful. Although coal naturally contains aromatic compounds and some relatively small-sized condensed aromatic units, it does not contain graphene sheets. In the UCP process, the aromatic domains in the coals, particularly low-rank coals, are concentrated and condensed further into graphene sheets, which are ordered into a 3D stack during graphitization. The synthesized graphite is then unpacked by methods such as exfoliation to various graphene products. GQDs were synthesized from all four coal types, and their optical properties were demonstrated to be tunable by the coal precursor preprocessing treatments. In all four coal types, enhanced optical properties were observed for the produced GDQs with incremental improvements made to the coal precursors. GQDs produced from raw coal samples displayed lower ultraviolet–visible (UV–Vis) spectroscopy absorbance intensity compared to those obtained from cleaned and upgraded coal residues. The photoluminescence (PL) intensities also varied with pretreatment conditions and with the concentration of GQDs in aqueous solutions. GQDs obtained from anthracite show longer emission wavelengths and can be excited by visible light as opposed to GQDs derived from the other coal ranks. UV fluorescence 3D maps and spectra revealed that the emission wavelength at which the GQDs solutions display the highest intensity was slightly redshifted based on the coal precursor pretreatments. In low-rank coal (lignite and subbituminous) samples, two clusters were observed in the maps for GQDs, which may suggest that there are potentially two types of fluorophores in solution or two main size populations. The ability to tune the properties of GQDs based on processing methods can be exploited to make GQDs for various optical display or optoelectronics applications. The results also highlight the importance of removing coal-borne impurities to improve the quality of the coal precursor for preparation of graphene products. Coal and/or coal wastes preprocessing methods were developed and applied to clean and upgrade the coal precursors prior to graphitization and subsequent conversion to graphene products. The preprocessing methods involve high specific-gravity separations, mineral acid cleaning (no hydrofluoric acid), and subsequent upgrading by reducing the coal-borne heteroatom (nitrogen, sulfur, and oxygen) content using proprietary chemical agents. Analytical characterization revealed that the preprocessing steps were successful, with ash reductions that range from 38% to 80% and residual ash content that was below the 5 wt% initial target. Based on proximate and ultimate analysis, the heteroatom reduction reactions produced upgraded coal residues with the oxygen content reduced by 8% to 24%, with additional reductions in the nitrogen and sulfur contents. An initial assessment of the waste streams from the UCP process shows very small to negligible environmental impact due to CO 2 , NO x , and SO x because most process steps are performed under inert atmosphere with argon. Consequently, reactive oxygen environments that tend to create these species are avoided. The inorganic and potentially hazardous species are released into aqueous waste streams that are easy to handle for proper disposal. The liquid waste streams were found to contain low-level concentrations of rare-earth elements (REEs), which could be concentrated and recovered as value-added by-products. Additionally, the volatile and gaseous fractions from carbonization and heat treatment contain useful organic compounds that can also be recovered as potential valuable by-products. Thus, the UCP technology is considered an environmentally sustainable and promising emerging technology for making high-value products from coal and coal wastes, with potential additional value-added by-products. Analysis of potential markets for the coal-derived carbon products shows a strong demand in both niche market sectors and across a wide variety of other industrial sectors. Graphite is currently considered a critical mineral commodity that has a large and growing demand in the LIB industry for EV applications. Based on data from Fortune Business Insights (2022) and Marketwatch (2023) reports, the average global graphite market is projected to reach about 33 billion by 2028, growing at a compound annual growth rate (CAGR) of about 7%, with much of this growth expected to be in the LIB industry. GO and rGO have strong market potentials in various application areas, such as coatings for anticorrosion, anti-icing, and antimicrobial protection, thermal barriers, wear resistance, sensors, additive manufacturing such as 3D inks, and others. GQDs are the emerging key player in the bioimaging, photovoltaics, and light-emitting diodes (LEDs) applications, with the potential to replace traditional semiconductor quantum dots (SQDs), which are based on metallic systems that are more toxic and more expensive. Biomedical applications of GQDs are becoming more attractive because of low to no toxicity and extremely low cost compared to SQDs. The major challenges for scale-up and commercialization of coal-derived carbon products such as graphene vary from the inherent attributes of graphene itself to reluctance to accept graphene in new manufacturing processes because of the uncertainty of the unknown. The 2D nature of graphene materials with a thickness of one atom presents significant challenges to proper handling/processing, and process scale-up becomes difficult because it requires high-end, expensive equipment, even for routine handling and analysis for quality assurance and control. Pristine graphene can also be extremely difficult to work into other matrices, thus hindering downstream processibility, especially at large scale. Currently, the cost of graphene and graphene products is still high and presents an economic risk that tends to slow down investment in scaling up emerging technologies. The lack of a standard for graphene materials for quality assurance and quality control poses a great challenge not only for the markets but also for commercialization efforts. A first-look economic feasibility analysis of the UCP technology provided valuable information that suggests the UCP process would be feasible, especially when it is scaled to a pilot scale and could be more competitive at the full scale. Graphitization was found to be the most energy-consuming and most capital-intensive step in the overall process. In small laboratory- and bench-scale experiments, labor is a significant contributor to the total process costs. Although these energy, capital, and labor constraints contribute to a higher selling price for the product, a preliminary economic model suggests that the process would be feasible at large scale when the process is fully integrated, optimized, and automated.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2023

Development of Binder Jet Compatible Silicon Carbide Mixtures for Increased Sintered Density

Binder jet additive manufacturing can process a variety of ceramic powder feedstocks to manufacture near net shape green parts that are subsequently sintered to achieve densification. In particular, silicon carbide (SiC) is a promising ceramic material for heat exchangers in energy storage applications and binder jet is a well-suited process for manufacturing these heat exchangers due to the often geometrically complex designs. However, the need for good powder flowability in binder jet printing often limits the feedstock powder to be larger particles rather than that of ultra fine submicron powders used in conventional ceramic processing, which are more readily densified during sintering. The present work explores the use of various powder mixtures and sintering settings to identify strategies for achieving high density sintered parts in binder jet compatible systems without the use of infiltration. Liquid-phase sintering additives and bimodal powder mixtures are explored alongside different sintering temperatures, rates, atmospheres, and hold times. Two mixtures were found to be good candidates for further exploration: 1) 90 wt% 0.6 µm SiC + 6.25 wt% Al 2 O 3 + 3.75 wt% Y 2 O 3 mixture achieved the highest sintered relative density of 91.2%; and 2) a bimodal mixture comprised of 45 wt% 10 µm SiC + 45 wt% 0.6 µm SiC + 6.25 wt% Al 2 O 3 + 3.75 wt% Y 2 O 3 had the best powder flowability of the powders measured and a 75.1% sintered relative density.

25 ENERGY STORAGE↗
DOE OSTI2023

Progress on Producing an ODS Ferritic Alloy by High Deformation Processing of Reactive Powders

Oxide dispersion-strengthened (ODS) ferritic alloys, such as 14YWT, are considered as benchmarks for fuel cladding and core structural materials in advanced nuclear energy reactor systems that require high temperature strength and creep properties as well as resistance to radiation damage. Unfortunately, the popular processing method of mechanical alloying (MA) is time-consuming, incurs high manufacturing costs, and typically produces anisotropy in the microstructure and mechanical properties of ODS ferritic alloys. These considerations hinder their acceptance in many high-performance, high-temperature materials for advanced nuclear energy reactors. This work package is pursuing an alternative solid-state processing to MA involving high deformation at high temperatures for producing an ODS ferritic alloy for fuel cladding. This report summarizes the concept for this processing method and the progress toward selecting the reactive and ferritic alloy powders, preparing 316L stainless steel cans for filling with blended powder followed by degassing, and choosing the heat treatments and forging parameters for performing the first two forging experiments. The preliminary results of optical microscopy performed on polished samples that were cut in three orthogonal directions revealed remnant porosity in both samples. The analysis of the porosity using ImageJ revealed a lesser amount of ~2.49% in the HiLoMe-1 sample that was processed with the three heat treatments and forging parameters compared to ~5.70% for the Hi-1 sample that was processed with only the first sintering heat treatment and forging parameter. These initial results will provide insights that can be leveraged to improve the densification of the powders in future forging experiments that will be continued into FY24 for determining the optimum heat treatments and forging parameters coupled with detailed microstructure characterization studies for producing the ODS ferritic alloy.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2023

Proton-Conducting Solid Oxide Electrolysis Cells for Large-scale Hydrogen Production at Intermediate Temperatures

Proton-conducting electrolyte based SOECs offer potential for operation at low to intermediate temperatures. Although yttrium-doped barium zirconate (BZY) and ceria-doped barium zirconate (BCY) have conductivity of 0.01 and 0.017 S.cm -1 respectively at 650C in comparison to the conductivity of 0.015 S.cm -1 for 8-YSZ at 850°C, there remains technology gaps and research needs related to understanding of chemical and structural stability in oxidizing and/or reducing atmospheres at intermediate temperatures, material processing and densification techniques, high polarization losses, and electrode poisoning due to intrinsic and extrinsic gas phase contaminants. Synthesis methods have produced proton-conducting materials and cells that met degradation rate targets, showcasing stable hydrogen production. Improved performance was evident in the HSOEC cell, achieving higher hydrogen production at a lower operating temperature compared to standard cells. Collaborations with multiple research facilities ensured scaling up of synthesis processes and milestone achievements for large-scale manufacturing. Assessment of contaminants revealed their adverse effects on electrode performance and structural stability. Contaminants like Cr and Si compounds, in high humidity, degraded electrodes by forming stable silicate and chromates, inhibiting active surface reactions. Getter materials showed promise in capturing contaminants, suggesting potential for mitigation.

08 HYDROGEN↗
DOE OSTI2024

Heteroatom-Modified and Compacted Zeolite-Templated Carbons for Gas Storage

Methane, the primary component of natural gas, is an energy-rich fuel by weight but exhibits lower energy density by volume than diesel and gasoline; efforts to increase its “volumetric” energy density have been focused on the design and synthesis of a porous scaffold that can bind the methane favorably. Novel approaches typically invoke the highly designable class of materials known as metal-organic frameworks (MOFs) owing to the relative difficulty of controlling carbon structure and composition precisely, without the use of a metal-based node. In this project, we instead explore the concept of carbon templating to achieve a porous scaffold with atomistically thin walls separated at a distance of ~1.2 nm, ideal for the formation of precisely two layers of methane per pore. This bottom-up templating approach permits the use of any small molecular precursor to build up the carbon scaffold, begging the question: which other elements (besides carbon) can be used to tune the surface for optimal methane binding without compromising the structure of the overall material? Boron and nitrogen were both explored and nitrogen was identified as the ideal agent for increasing methane binding to the optimal strength for use at near room temperature. Densification of the resulting materials by mechanical compaction was then explored to produce free-standing pellets with the highest methane “delivery” capacities of any known material. Here we define the amount “delivered” as the amount stored minus the amount remaining in the tank at 73 psi, the lowest useful pressure for vehicular transportation applications. The key features of the resulting methane storage system are rapid discharging and refueling speeds, extremely long cycle life (infinite cycle life for high-purity methane), a near-constant heat of refueling (making the heat generated upon refueling easier to manage), and a low maximum pressure of operation (<1500 psi), enabling the use of all-metal Type I cylinders and significantly reducing the costs of conversion of existing vehicles to cleaner burning, abundantly available natural gas). The technical effectiveness of this approach was further improved by exploring several cost-reduction strategies and investigating the reliability of such storage systems in the presence of “real” natural gas mixtures which contain a mixture of gaseous species.

03 NATURAL GAS↗
DOE OSTI2023

VTO FY23 Annual Progress Report on 3D Printing of All-Solid-State Lithium Batteries

All-solid-state lithium metal batteries (ASSLBs) have attracted attention due to their potential for mitigating safety issues and addressing energy density limitations of conventional lithium-ion batteries (LIBs). While solid state electrolytes (SSEs) with room-temperature ionic conductivities greater than that of their liquid electrolyte counterparts have been discovered, integration of the different solid components of ASSLBs is not trivial. Taking garnet Li 7 La 3 Zr 2 O 12 (LLZO) electrolyte as an example, problems for this SSE include brittleness, high temperature processing for densification, poor contact with electrodes, and lack of scalable manufacturing methods. These obstacles must be overcome before LLZO becomes commercially viable for ASSLB applications.

25 ENERGY STORAGE↗
DOE OSTI2023

Smart Refractory Sensors Development for Corrosion and Erosion Monitoring in High Temperature Systems

To optimize the operation and functioning of high temperature systems such as slagging gasifiers, coal boilers and glass/steel melters, it is important to monitor corrosion and erosion of refractory used in such systems. Corrosion test strategies are generally based on continuous gravimetric and chemical reactivity monitoring at operational temperatures (750°-1500°C). Both thermocouples and failure sensors and arrays would be useful to monitor the health of any refractory or coatings in these systems. Many of such type of sensors are installed into the systems through open access ports within the refractory; however, there are some disadvantages of this approach where corrosive/erosive gas and molten materials can penetrate and compromise the system. The current work presents the development and performance demonstration of smart refractory with embedded high temperature sensors such as thermocouples, thermistors, and various spallation/crack monitoring sensors, which may be used within a variety of refractory brick in different high temperature processes and applications. The main feature of this technology is that electroceramic based sensors are embedded into smart refractory without significantly impact to the intrinsic properties of the refractory. This technology circumvents the need to insert an isolated monolithic, stand-alone sensor into the refractory via an access port. This technological approach guarantees the integrity and the chemical stability of the materials used in the sensor fabrication within the harsh environment and does not introduce molten material (such as slag) penetration pathways within the refractory. One interesting and important aspect of this innovation is that these embedded sensors can be used to in situ monitoring processes such as chemical reactions and at the same time give information and a deeper understanding of the corrosion and erosion process of the refractory within the system. As stated above, the objective of our work is to develop high-temperature sensors composed of electroceramic materials that are chemically stable at high temperatures (750°-1500°C) and high pressures (up to 1000 psi) that can be used in monitoring corrosion and erosion process in refractory used in high energy systems. The high-temperature sensors investigated in this work were composed of various oxide composites directly embedded into the refractory oxides. The composites used for this work were synthesized by a mixed-oxide route. Metal oxides were inserted within a matrix material composed of refractory oxides (Al2O3, ZrO2, etc.). The physical and electrical properties were specifically manipulated by altering the level of percolation of the conductive species (metal oxides) within the refractory constituent (refractory oxide). Prior to the development of the high-temperature sensors, the oxides composites developed in this study were sintered up to 1600°C under oxidizing atmosphere in order to investigate densification, microstructural evolution, phase development, and their thermoelectrical performance as a function of the composition. The 4-point DC conductivity measurements were performed between 100°-1500°C. The sensors were fabricated from the composite materials by 3D-printing or screen-printing methods into the refractory brick during the consolidation process. An example of one of these embedded sensors consisted of an electroceramic-based thermocouple fabricated with two separate oxide composite compositions which were patterned to produce a couple within the interior of a refractory matrix. The thermocouple successfully displayed thermoelectric voltage trend (as a function of temperature), and the voltage was 220.0 mV around 1400 °C. Corrosion tests on the refractory embedded sensors were performed. To evaluate corrosion in the refractory brick an in-house glass composition was prepared and pressed into pellets and delivered into a pre-cut cavity in the brick. Corrosion experiments results showed the glass penetrated the brick over a 90 h period, and the penetration of the glass through the brick could be monitored by both an amperometric and voltametric based sensor. With this experiment, it was demonstrated that the embedded sensor could dynamically monitor the corrosion process.

20 FOSSIL-FUELED POWER PLANTS↗
DOE OSTI2025

Multi-Scale Modeling of the Evolution of Structure and Properties in Materials for Nuclear Energy Applications [Slides]

Nuclear energy is an important component of an overall strategy to address climate change. Idaho National Laboratory (INL) is the U.S. Department of Energy’s primary facility for research and development in nuclear science and technology for energy generation, supporting the improvement and life extension of the existing reactor fleet and the development and licensing of new reactor designs. Computational modeling is an important component of these activities, particularly in the area of materials for nuclear applications, where experimental data can be very challenging and expensive to acquire, and where data is especially scarce for new reactor designs. INL has used multi-scale modeling – linking atomistic, mesoscale, and engineering scales – to improve the ability to predict the performance of materials for nuclear energy applications. In this talk, I will give an overview of the approach and tools used, and several examples of application, including performance of nuclear fuels, understanding radiation-driven formation of nanoscale void and gas bubble superlattices, and powder densification through electric field assisted sintering.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗