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DOE OSTI2021

Al 2 O 3 Thin Films on Magnesium: Assessing the Impact of an Artificial Solid Electrolyte Interphase

Among the many emerging technologies under investigation as alternatives to the successful Lithium-ion battery, the magnesium battery is promising due to the wide availability of magnesium, its high volumetric capacity, and the possibility for safety improvements. One of the largest challenges facing rechargeable magnesium batteries is the formation of a passivation layer at the Mg metal anode interface when reactive species in the electrolyte are reduced at the electrode-electrolyte interface. To control the solid electrolyte interphase in Lithium batteries, protective layers called artificial solid electrolyte interphase (ASEI) layers have been successful in improving Li metal anode performance. The approach of protecting Mg metal anodes from electrolyte degradation has been demonstrated by fewer studies in the literature than Li systems. In this work, we discuss the properties of Al 2 O 3 thin films deposited using atomic layer deposition as an artificial solid electrolyte interphase at the Mg anode. Our results demonstrate that Al 2 O 3 does prevent electrolyte degradation due to the reductive nature of Mg. However, undesirable properties such as defects and layer breakdown lead to Mg growth that causes soft-shorting. The soft-shorting occurs with and without the protection layer, indicating the ALD layer does not prevent it and hinders Al 2 O 3 from being an ideal candidate for a protection layer. Crucial effects of this layer on Mg electrochemistry at the interface were observed, including growth of Mg deposits leading to soft-shorting of the cell whose morphology showed a dependence on the Al 2 O 3 layer. These results may provide guidelines for the future design and development of protective ASEI layers for Mg anodes.

25 ENERGY STORAGE↗

DOE OSTI2022

GEN3D Experimental and Numerical Development of GEN3 Durability Models

Understanding of the high temperature durability of particles and the materials that contain them is critical to next generation of concentrating solar power (CSP) technology. Here we studied the durability of particles and their containment materials under extreme UV cycling, thermal cycling, and in low-speed high temperature mechanical wear situations. The optical stability of seven candidate particles has been determined following exposure to the high temperature conditions present in a generation 3 particle-based CSP technology. Particle solar weighted absorptance and emittance measured periodically during 10,000 high solar irradiance exposure cycles and up to 400 hours of isothermal aging has been documented. The particle aging due to repeated exposure to concentrated solar flux represented the 30-year lifetime of a power plant. Models were fit to the absorptivity and emissivity data following the isothermal aging provides the projected optical degradation of the particles as a function of temperature. Mechanical wear was studied through the use of custom developed wear testing facilities for measuring high temperature impact wear, abrasion wear, and particle attrition. Additionally, a novel technique for measuring the high temperature mechanical properties of single particles was developed. Through these tests it was observed that high nickel alloys generally showed lower wear than comparable iron based steels, particularly at elevated temperatures of 800°C. Mechanical wear at these temperatures is a highly complex phenomenon combining both mechanical wear and oxidation. Additionally, the containment materials wear rates are influenced by the particles (both hardness and roundness), making the wear mechanisms complex. The initial wear test conducted in the abrasion test rig revealed a substantial amount of oxide materials in the particle bed after testing (in relative to later tests), and substantially more wear, likely indicating a need for concern in startup operation of particle facilities to not incur high wear from the presence of oxides. Particle attrition experiments have only been conducted for a single material but increase size distribution, reduction in circularity, and particle diameter is observed. Efforts to develop predictive models was limited due to a testing campaign that prioritized testing materials for particle pathway developers over building a comprehensive design of experiments. The results discussed in this report inform future CSP developers and researchers further de risking the technology and assisting in its future development. ParticleBased CSP development provides a path to dispatchable solar power generation with storage at a price competitive in the current energy market. Lowering the cost of CSP technology provides a carbon free power generation solution that can assist in the transition from fossil fuels to renewable sources of electricity.

14 SOLAR ENERGY↗

DOE OSTI2022

Operational Resilience of Nuclear-Renewable Integrated-Energy Microgrids

The increasing prevalence and severity of wildfires, severe storms, and cyberattacks is driving the introduction of numerous microgrids to improve resilience locally. While distributed energy resources (DERs), such as small-scale wind and solar photovoltaics with storage, will be major components in future microgrids, today, the majority of microgrids are backed up with fossil-fuel-based generators. Small modular reactors (SMRs) can form synergistic mix with DERs due to their ability to provide baseload and flexible power. The heat produced by SMRs can also fulfill the heating needs of microgrid consumers. This paper discusses an operational scheme based on distributed control of flexible power assets to strengthen the operational resilience of SMR-DER integrated-energy microgrids. A framework is developed to assess the operational resilience of SMR-DER microgrids in terms of system adaptive real-power capacity quantified as a response area metric (RAM). Month-long simulation results are shown with a microgrid developed in a modified Institute of Electrical and Electronics Engineers (IEEE)-30 bus system. The RAM values calculated along the operational simulation reflect the system resilience in real time and can be used to supervise the microgrid operation and reactor’s autonomous control.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

DOE OSTI2023

Enhancing the representation of water management in global hydrological models

Abstract. This study enhances an existing global hydrological model (GHM), Xanthos, by adding a new water management module that distinguishes between the operational characteristics of irrigation, hydropower, and flood control reservoirs. We remapped reservoirs in the Global Reservoir and Dam (GRanD) database to the 0.5∘ spatial resolution in Xanthos so that a single lumped reservoir exists per grid cell, which yielded 3790 large reservoirs. We implemented unique operation rules for each reservoir type, based on their primary purposes. In particular, hydropower reservoirs have been treated as flood control reservoirs in previous GHM studies, while here, we determined the operation rules for hydropower reservoirs via optimization that maximizes long-term hydropower production. We conducted global simulations using the enhanced Xanthos and validated monthly streamflow for 91 large river basins, where high-quality observed streamflow data were available. A total of 1878 (296 hydropower, 486 irrigation, and 1096 flood control and others) out of the 3790 reservoirs are located in the 91 basins and are part of our reported results. The Kling–Gupta efficiency (KGE) value (after adding the new water management) is ≥ 0.5 and ≥ 0.0 in 39 and 81 basins, respectively. After adding the new water management module, model performance improved for 75 out of 91 basins and worsened for only 7. To measure the relative difference between explicitly representing hydropower reservoirs and representing hydropower reservoirs as flood control reservoirs (as is commonly done in other GHMs), we use the normalized root mean square error (NRMSE) and the coefficient of determination (R2). Out of the 296 hydropower reservoirs, the NRMSE is > 0.25 (i.e., considering 0.25 to represent a moderate difference) for over 44 % of the 296 reservoirs when comparing both the simulated reservoir releases and storage time series between the two simulations. We suggest that correctly representing hydropower reservoirs in GHMs could have important implications for our understanding and management of freshwater resource challenges at regional-to-global scales. This enhanced global water management modeling framework will allow the analysis of future global reservoir development and management from a coupled human–earth system perspective.

13 HYDRO ENERGY↗

DOE OSTI2024

Life Cycle Greenhouse Gas Emissions of Coal-Biomass Co-Firing Power Plants with Carbon Capture and Storage

The United States has set a target to achieve the net-zero economy by 2050. Bioenergy with Carbon Capture and Sequestration (BECCS) is one of the promising negative-emission routes in the mitigation portfolio to help meet this goal. Coal-biomass co-firing with carbon capture and storage (CCS) is a key BECCS technology to realize the carbon mitigation at fossil-fuel power plants. The mitigation potential of co-firing option is affected by numerous critical factors, such as biomass properties, co-firing level, and carbon capture rate. The objectives of the study are to characterize and estimate the life cycle greenhouse gas (GHG) emissions and performance of coal-biomass co-firing power plants with CCS, determine the breakeven co-firing level at power plants necessary to achieve net-zero life cycle emissions, and quantify the variabilities and uncertainties in life cycle emissions. The scope of the life cycle assessment includes the fuel supply, combustion-based power generation, and CO2 transport and storage. A fuel-based life cycle module is developed and embedded in the Integrated Environmental Control Model (IECM), a fossil-fuel power plant modeling tool. This study then applies the enhanced IECM to conduct the process-based life cycle assessment for an array of biomass co-firing scenarios. Deterministic analysis indicates that reaching net-zero life cycle emissions in a biomass co-firing plant without CCS deployment is challenging. Combining biomass co-firing and CCS deployment can significantly lower the overall life cycle emissions of power plants. Net-zero life cycle emissions can be achieved with a 20 wt.% co-firing level and 90% CCS when the Powder River Basin coal is co-fired with energy crops or forestry residues. However, the breakeven co-firing level for net-zero emissions depend on the selected fuel properties. Fuel supply and plant operation are the critical stages influencing the life cycle emissions of power plants with 90% CCS. Deployment of deep CCS beyond 90% CO2 capture can remarkably reduce operational emissions and the breakeven co-firing level. With 99% CCS, the breakeven co-firing rate can be reduced to 12% on average. These findings highlight the trade-offs between technical performance and environmental impact of biomass co-firing at coal-fired power plants and emphasize the role of deep CCS in achieving a net-zero emissions future.

Wu, Wanying↗

DOE OSTI2025

Formation and fate of freshwater on an ice floe in the Central Arctic

The melt of snow and sea ice during the Arctic summer is a significant source of relatively fresh meltwater. The fate of this freshwater, whether in surface melt ponds or thin layers underneath the ice and in leads, impacts atmosphere–ice–ocean interactions and their subsequent coupled evolution. Here, we combine analyses of datasets from the Multidisciplinary drifting Observatory for the Study of Arctic Climate (MOSAiC) expedition (June–July 2020) for a process study on the formation and fate of sea ice freshwater on ice floes in the Central Arctic. Our freshwater budget analyses suggest that a relatively high fraction (58 %) is derived from surface melt. Additionally, the contribution from stored precipitation (snowmelt) outweighs by 5 times the input from in situ summer precipitation (rain). The magnitude and rate of local meltwater production are remarkably similar to those observed on the prior Surface Heat Budget of the Arctic Ocean (SHEBA) campaign, where the cumulative summer freshwater production totaled around 1 m during both. A relatively small fraction (10 %) of freshwater from melt remains in ponds, which is higher on more deformed second-year ice (SYI) compared to first-year ice (FYI) later in the summer. Most meltwater drains laterally and vertically, with vertical drainage enabling storage of freshwater internally in the ice by freshening brine channels. In the upper ocean, freshwater can accumulate in transient meltwater layers on the order of 0.1 to 1 m thick in leads and under the ice. The presence of such layers substantially impacts the coupled system by reducing bottom melt and allowing false bottom growth; reducing heat, nutrient, and gas exchange; and influencing ecosystem productivity. Regardless, the majority fraction of freshwater from melt is inferred to be ultimately incorporated into the upper ocean (75 %) or stored internally in the ice (14 %). Terms such as the annual sea ice freshwater production and meltwater storage in ponds could be used in future work as diagnostics for global climate and process models. For example, the range of values from the CESM2 climate model roughly encapsulate the observed total freshwater production, while storage in melt ponds is underestimated by about 50 %, suggesting pond drainage terms as a key process for investigation.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2024

Soil incubation methods lead to large differences in inferred methane production temperature sensitivity

Abstract Quantifying the temperature sensitivity of methane (CH 4 ) production is crucial for predicting how wetland ecosystems will respond to climate warming. Typically, the temperature sensitivity (often quantified as a Q 10 value) is derived from laboratory incubation studies and then used in biogeochemical models. However, studies report wide variation in incubation-inferred Q 10 values, with a large portion of this variation remaining unexplained. Here we applied observations in a thawing permafrost peatland (Stordalen Mire) and a well-tested process-rich model ( ecosys ) to interpret incubation observations and investigate controls on inferred CH 4 production temperature sensitivity. We developed a field-storage-incubation modeling approach to mimic the full incubation sequence, including field sampling at a particular time in the growing season, refrigerated storage, and laboratory incubation, followed by model evaluation. We found that CH 4 production rates during incubation are regulated by substrate availability and active microbial biomass of key microbial functional groups, which are affected by soil storage duration and temperature. Seasonal variation in substrate availability and active microbial biomass of key microbial functional groups led to strong time-of-sampling impacts on CH 4 production. CH 4 production is higher with less perturbation post-sampling, i.e. shorter storage duration and lower storage temperature. We found a wide range of inferred Q 10 values (1.2–3.5), which we attribute to incubation temperatures, incubation duration, storage duration, and sampling time. We also show that Q 10 values of CH 4 production are controlled by interacting biological, biochemical, and physical processes, which cause the inferred Q 10 values to differ substantially from those of the component processes. Terrestrial ecosystem models that use a constant Q 10 value to represent temperature responses may therefore predict biased soil carbon cycling under future climate scenarios.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2025

Stochastic Adaptive Droop Control in Frequency Regulation of Power Systems With Intermittent Generators

Modern power systems (MPSs), including microgrids (MGs), are increasingly incorporating multiple renewable energy sources (RESs) such as wind and solar power, as well as battery storage and controllable loads. While environmentally beneficial, these sources pose challenges for control and management due to their intermittent and stochastic nature, especially in maintaining frequency stability with multiple interconnected generators of varying capacities. Traditional droop control methods are effective in systems with generators that are dispatchable and have fixed generation capacities, but they fall short when applied to systems with RESs, where generation capacities are dynamic and affected by unpredictable environmental conditions. To address these challenges, this paper introduces a novel stochastic adaptive droop control (SADC) method for load frequency control (LFC). The proposed method adapts droop coefficients in real time, based on the measured stochastic data of power generation capacities, enabling more effective frequency regulation in systems with variable and intermittent power generation. Unlike traditional adaptive control methods, which assume constant or slowly-varying system parameters, this approach accounts for stochastic processes by modeling them as Markov chains, enabling robust performance under highly dynamic and unpredictable conditions. The key contributions of this work include the development of real-time droop coefficient adaptation algorithms, derivation of their stability and convergence properties, and the demonstration of the advantages of the method through simulations. Case studies highlight the improved performance of frequency regulation, particularly in addressing the impact of stochastic weather conditions and the benefits of reducing dependence on battery reserves in dealing with intermittency of RESs. Finally, this paper provides a comprehensive analysis of the theoretical foundations of the method, as well as practical implementation insights for future power systems with high penetration of RESs.

24 POWER TRANSMISSION AND DISTRIBUTION↗

DOE OSTI2025

Insights Into Thermal Runaway Mechanisms: Fast Tomography Analysis of Metal Agglomerates in Lithium-Ion Batteries

Thermal Runaway (TR) in lithium-ion batteries (LIB) is a critical technological and social concern. Whilst such events are rare, TR is characterized by uncontrollable heating leading to catastrophic failures. To deepen the understanding of the failure process and subsequently develop more accurate TR prediction models and as a result safer battery systems, we present in this work high-speed X-ray tomography for in-depth investigations of the copper current collector melting and agglomeration during TR. The melting process presents valuable real-time internal information about heat evolution during TR, previously challenging to access but crucially important for validating TR models. In this work, controlled failure studies combined with high-speed X-ray tomography were performed on two different commercial LIB models, subjecting them to both external heating and nail penetration to induce TR. Through real-time observation via high-speed tomography, followed by segmentation, rendering, and analysis, the formation of copper agglomerates was qualitatively and quantitatively characterized and visualized for the first time. Agglomerates tended to form either from the battery's outermost layers or centrally, depending on the method of TR initiation, and gives an indirect insight into the internal temperature evolution and distribution. Moreover, an initial comparative analysis between the battery models also revealed differences in agglomerate size, which has been linked to the thicker copper current collectors of one of the cell models. We further discuss the impact of larger copper agglomerates on heat distribution and safety. This study not only sheds light on the intricate dynamics of TR in LIBs but also underscores the pivotal role of 'gold-standard' imaging techniques in advancing battery safety, crucial for the robust modeling of TR and the future design of electric vehicle safety systems.

25 ENERGY STORAGE↗

DOE OSTI2024

An assessment of ocean alkalinity enhancement using aqueous hydroxides: kinetics, efficiency, and precipitation thresholds

Abstract. Ocean alkalinity enhancement (OAE) is a promising approach to marine carbon dioxide removal (mCDR) that leverages the large surface area and carbon storage capacity of the oceans to sequester atmospheric CO2 as dissolved bicarbonate (HCO3-). One OAE method involves the conversion of salt in seawater into aqueous alkalinity (NaOH), which is returned to the ocean. The resulting increase in seawater pH and alkalinity causes a shift in dissolved inorganic carbon (DIC) speciation toward carbonate and a decrease in the surface ocean pCO2. The shift in the pCO2 results in enhanced uptake of atmospheric CO2 by the seawater due to gas exchange. In this study, we systematically test the efficiency of CO2 uptake in seawater treated with NaOH at aquarium (15 L) and tank (6000 L) scales to establish operational boundaries for safety and efficiency in advance of scaling up to field experiments. CO2 equilibration occurred on the order of weeks to months, depending on circulation, air forcing, and air bubbling conditions within the test tanks. An increase of ∼0.7–0.9 mol DIC per mol added alkalinity (in the form of NaOH) was observed through analysis of seawater bottle samples and pH sensor data, consistent with the value expected given the values of the carbonate system equilibrium calculations for the range of salinities and temperatures tested. Mineral precipitation occurred when the bulk seawater pH exceeded 10.0 and Ωaragonite exceeded 30.0. This precipitation was dominated by Mg(OH)2 over hours to 1 d before shifting to CaCO3,aragonite precipitation. These data, combined with models of the dilution and advection of alkaline plumes, will allow the estimation of the amount of carbon dioxide removal expected from OAE pilot studies. Future experiments should better approximate field conditions including sediment interactions, biological activity, ocean circulation, air–sea gas exchange rates, and mixing zone dynamics.

Ringham, Mallory C. (ORCID:0000000348020185)↗

DOE OSTI2025

Enabling hydrogen chemisorption on charged graphene

Two-dimensional (2D) materials, including graphitic derivatives, have long been of interest for hydrogen storage applications, due to their high theoretical storage capacity, low weight, and other useful properties. However, poor kinetics for hydrogen adsorption and surface diffusion as part of the proposed spillover process for hydrogenation have limited their technological potential. Here, we use first-principles calculations to study electronic doping as a means to improve hydrogen chemisorption on graphene, which we use here as a proxy for graphitic derivatives more broadly. We find that positively charged graphene sheets have vastly improved kinetics for hydrogen diffusion and adsorption, while they limit unwanted hydrogen desorption. This combination of effects should favor hydrogen chemisorption via spillover. We connect these trends to the C–H bond, which introduces states near the Fermi level. These states are depopulated as electrons are removed, thereby lowering the bond energy and permitting more facile movement of hydrogen. Our results suggest that spillover mechanisms for hydrogen chemisorption should be revisited if strategies to apply a large charge to graphitic systems can be realized. Moreover, switchable application of the charge may lead to the reversible chemisorption of hydrogen. While the large magnitude of charging required suggests that graphene itself may not be suitable for reversible hydrogen chemisorption, the factors we identify and discuss could significantly boost the prospects of graphitic derivatives and other 2D or layered materials for hydrogen storage applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Exploring Multidimensional Spatial-Temporal Hydropower Operational Flexibilities by Modeling and Optimizing Water-Constrained Cascading Hydroelectric Systems

Because of unique characteristics such as clean and cost-competitive electricity as well as fast-ramping and storage abilities, the power industry continues to evolve its operation strategies for cascading hydroelectric (CHE) systems for providing enhanced values to the grid, especially under the deeper renewable resource integration. However, existing operation practices of CHEs predate the integration of renewables, which could prohibit the effective utilization of their inherent flexibilities in delivering maximum financial benefits and providing valuable grid services to the power system and electricity market operations. Indeed, modeling and optimizing these resource-limited while flexible CHE assets with uncertainties and imperfect information across multiple spatial-temporal dimensions present significant challenges. To facilitate CHE facility operators in effectively coordinating water usage and hydropower plant operations across multiple timescales, this project aims to fill the existing gaps by developing a suite of accurate water inflow (WI) forecast models as well as enhanced CHE modeling and optimization approaches with proper consideration of their unique characteristics, which would help explore their multidimensional spatial-temporal operational flexibility potentials. The developed approaches could better align reservoir operation strategies with variability and uncertainty of future water availability. They can also promote more effective utilization of multidimensional spatial-temporal hydropower operational flexibility potentials by designing long-term evacuation plans of reservoirs and short-term operation of CHEs, along with their coordination with other types of renewables. The project leverages various resources to facilitate the research and development activities, including actual characteristics data of CHE systems and a library of current and future cases of Portland General Electric (PGE). These realistic data enable the project team to study how to maximize the value of CHEs under current and future portfolios and evaluate opportunities to improve operation practices.

13 HYDRO ENERGY↗

DOE OSTI2024

Concept Study of Robotic Camera-Based Foreign Object Detection for EV Wireless Charging

Wireless charging of an electric vehicle (EV) is an emerging charging technology promising convenient, autonomous, and highly efficient EV charging without requiring heavy gauge cables. However, due to the strong electromagnetic field created by this process that surrounds the wireless charger, the presence of foreign objects can detrimentally interact with it, thus affecting wireless power transfer (WPT) performance or leading to harmful and unwanted safety risks. This paper presents the results for a concept study on a robotic camera-based foreign object detection (FOD) system, as a supplement to the industry-existing overlapped FOD coil array method, for EV wireless charging. A Raspberry PI 4 control board and compatible Raspberry PI Camera Module 2 are used to implement camera-based object detection. The FOD program was developed using a state-of-the-art deep learning object detection model with the OpenCV and Pytorch library and is compatible with camera module hardware. A dry-run test with Raspberry PI and a camera module was conducted and the preliminary FOD function was verified. The feasibility assessment is also validated by comparing the performance of five existing state-of-the-art deep learning object detection models for vehicles, animals, persons, and metals subsets, respectively. Satisfactory performance on the benchmark datasets is observed by the tests, but further improvements are needed in future work when detecting small-sized metallic objects. A programable robotic car is also under development as ongoing work for carrying the Raspberry PI and camera module while moving for the maintenance process.

24 POWER TRANSMISSION AND DISTRIBUTION↗

DOE OSTI2024

HERO CarbonSAFE Phase 2 Project in the Columbia River Basalt Group

The Hermiston, Oregon Basalt CarbonSAFE Phase II project (HERO CarbonSAFE) seeks to accelerate the deployment of commercial carbon dioxide (CO2) storage projects in basaltic rocks. Basalt CO2 storage has several advantages to conventional saline storage reservoirs including 1. The potential for rapid mineralization of CO2, 2. Associated decreases in pressure and CO2 migration risks, 3. Reduced long-term monitoring requirements with respect to plume tracking, 4. Widespread geographic distribution and, 5. Large storage potential due to thickness, porosity, and CO2 interactions with basalt. And for locations such as the Pacific Northwest, Hawaii, Iceland, India and Japan, basalts may offer the only economically feasible option for local CO2 storage. However, there are limited field-scale assessments of CO2 storage in basalt, and current carbon capture utilization and storage (CCUS) permitting and regulatory frameworks were developed for conventional saline reservoirs. HERO CarbonSAFE is designed to address research gaps and uncertainties associated with basalt storage. Specifically, the project will assess the feasibility of CO2 injection in the deep layered basalts, long-term storage (mineralization), practical approaches for large-scale implementation (50+ million metric tons of CO2 over 30 years), lithology-specific risks, and the technoeconomic potential for CO2 storage in basalts. The HERO CarbonSAFE project will assess feasibility of developing a commercial-scale (50+ million metric tons of CO2) geological storage complex within the Columbia River Basalt Group (CRBG), a layered continental flood basalt complex that underlies Calpine’s natural gas-fired Hermiston Power Project (HPP) in Hermiston, OR (Figure 1). Under this 2-year CarbonSAFE Phase II project, the HERO team will conduct a data acquisition campaign that includes drilling a stratigraphic well to a total depth of ~1,500 m into the thick layered basalts proximal to HPP. A comprehensive well logging and hydrologic testing program will be augmented with new core collected from flow zones and sealing units, and comprehensive laboratory testing to help refine the kinetic rates of mineralization. The newly acquired information will be integrated with existing data from regional wells to correlate basalt injection zone properties to develop storage hub/commercial-scale models. Using these models, the project team will evaluate injection scenarios to define the technical and economic potential for storing a minimum of 50 million metric tons of CO2 over a 30-year period, along with a robust sensitivity analysis on key parameters governing reservoir viability for sustainable injection over a commercial project lifetime. Specific technical objectives of HERO are: (1) assessing the reservoir response of a series of stacked layered reservoir flowtop sequences occurring in this area of the CRBG to commercial-scale injection volumes; (2) extending prior efforts by the project team to characterize the deep layered basalts encountered in regional studies, to leverage prior investments by U.S. Department of Energy’s (DOE) Carbon Storage program; (3) leveraging DOE’s mineralization characterization efforts to advance model parametrization for commercial scale injection of CO2 in basalts; (4) conducting risk assessments associated with scaling up to commercial storage hub injection goals, while validating DOE’s National Risk Assessment Partnership (NRAP) tools, to identify potential constraints that would prevent the CRBG from serving as a commercial-scale storage complex; (5) developing mitigation plans to address identified risks; (6) developing a commercial-scale injection and monitoring, verification and accounting (MVA) strategy; (7) utilizing computational models to define and minimize, if possible, the Area of Review (AoR) under Class VI regulations; and (8) developing a robust CO2 management strategy for CRBG that also considers a regional source/sink approach that is responsive to stakeholder needs and industrial demand. Specific institutional objectives are: (1) identifying and developing plans to mitigate the nontechnical challenges associated with the build-out of a commercial-scale storage complex within the CRBG with integrated CO2 sources; (2) implementing the community outreach plan; (3) conducting regulatory research, including a survey of issues related to pore space ownership, MVA and long-term assurance of mineralization-based storage, to support an eventual application for a UIC Class VI permit; (4) advancing the project’s plan for CO2 liability management; and (5) continuing to refine and update the project’s economic model. The final objective is the preparation of a comprehensive Site Characterization Plan that draws upon the technical and institutional feasibility assessments to prepare the project for future commercialization efforts.

58 GEOSCIENCES↗

DOE OSTI2021

Energy flexibility of residential buildings: A systematic review of characterization and quantification methods and applications

With building electric demand becoming increasingly dynamic, and a growing percentage of intermittent renewable power generation from solar photovoltaics and wind turbines, the power grid is facing increasing challenge to manage the real time balance between the supply and demand. With advancements in smart sensing and metering, smart appliances, electric vehicles, and energy storage technologies, demand side management of residential buildings can help the grid to improve stability by optimizing flexible loads. This paper reviews recent studies on residential building demand side management, with a focus on characterization and quantification of energy flexibility covering various types of flexible loads, metrics, methods, and applications. The reviewed studies showed four levels of applications: building level (45%), district or community level (29%), system level (19%), and building sector level (7%). Shifting loads is the dominant flexibility type in 60% of applications, followed by shedding (19%), generation (16%), and modulating (6%). Depending on the technology and application scope, flexible operations have a wide range of performance, with peak power reductions of 1%~65%, energy savings up to 60%, operational cost reduction of 1%~48%, and greenhouse gas emission reductions of up to29%. More than half (51%) of the studies employed control strategies to achieve flexibility; among those 72% used optimal controls, while 28% used rule-based controls. About 58% of the studies used mathematical formulation to quantify energy flexibility. Most studies were based on simulation, while less than 15% of the studies had measurements from experiments or field tests. The review reveals research opportunities to address significant gaps in the existing literature: (1) establishing a common definition and performance metrics for energy flexibility of buildings that are technology and application agnostic, (2) developing an ontology to standardize representation of flexibility resources for interoperability, (3) integrating occupant impacts into the quantification and optimization of energy flexibility, and (4) developing requirements and credits of energy flexibility in building energy codes and standards. Findings from the review can inform future research and development of energy flexible buildings which are essential to a reliable and resilient power grid.

Li, H↗

DOE OSTI2020

Emerging Potassium Metal Anodes: Perspectives on Control of the Electrochemical Interfaces

Potassium metal acts as the anode in emerging potassium metal batteries (KMBs). It further serves as the counter-electrode for potassium ion battery (KIB) half-cells, with its reliable performance being critical for assessing the working electrode material. This first-of-its-kind critical review focuses on the dual challenge of controlling the potassium metal-substrate and the potassium metal-electrolyte interface so as to prevent dendrites. The discussion begins with a comparison of the physical and chemical properties of K metal anodes versus the much oft studied Li and Na metal anodes. Based on established descriptions for root causes of dendrites, the problem should be less severe for K than for Li or Na, while in fact the opposite is observed. The key reason that the K metal surface rapidly becomes dendritic in common electrolytes is its unstable solid electrolyte interphase (SEI). An unstable SEI layer is defined as being non self-passivating. No SEI is perfectly stable during cycling, and all SEI structures are heterogenous both vertically and horizontally relative to the electrolyte interface. The difference between a "stable" and an "unstable" SEI may be viewed as the relative degree to which during cycling it thickens and becomes further heterogeneous. The unstable SEI on K metal leads to a number of interrelated problems, such as low cycling Coulombic efficiency (CE), a severe impedance rise, large overpotentials, and possibly electrical shorting; all of which have been reported to occur as early as in the first ten plating/stripping cycles. Many of the traditional "interface fixes" employed for Li and Na metal anodes, such as various artificial SEIs, surface membranes, barrier layers, the secondary separators, etc. have not been attempted or optimized for the case of K. This is an important area for further exploration, with an understanding that success may come harder than with Li due to K-based SEI reactivity with both ether and ester solvents. The second critical problem with K metal anodes is that they do not thermally or electrochemically wet a standard (untreated) Cu foil current collector. Published experimental and modeling research directly highlights the weak bonding between the K atoms and a Cu surface. Existing surface treatment approaches that achieve improved K wetting are discussed, along with the general design rules for future studies. Also discussed are geometry-based methods to tune nucleation, as well dual approaches where nucleation and SEI structure are tuned through complementary schemes to achieve extended half-cell and full battery stability. We hypothesize that K metal never achieves a planar wetting morphology even at cycle one making the dendrites "baked-in". We propose that classical thin films growth models, Frank van der Merwe (F-M), Volmer Weber (V-W), and Stranski-Krastanov (S-K) can be employed to describe early stage plating behavior. It is demonstrated that island-like V-W growth is the applicable description for the natural plating behavior of K on pristine Cu. Moving forward, there are three inter-related thrusts to be pursued: First, K salt - based electrolyte formulations have to mature and become further tailored to handle the increased reactivity of a metal rather than an ion anode. Second, the K-based SEI structure needs to be further understood and ultimately tuned to be less reactive. Third, the energetics of the K metal - current collector interface must be controlled to promote planar wetting/dewetting throughout cycling.

25 ENERGY STORAGE↗

DOE OSTI2020

Cloud-based implementation of white-box model predictive control for a GEOTABS office building: A field test demonstration

Model predictive control (MPC) has been proven in simulations and pilot case studies to be a superior control strategy for large buildings. MPC can utilize the weather and occupancy schedule forecasts, together with the system model, to predict the future thermal behavior of the building and minimize the overall energy use and maximize thermal comfort. However, these advantages come with the cost of increased modeling effort, computational demands, communication infrastructure, and commissioning efforts. Thus a typical approach is to, often rapidly, simplify the building modeling and MPC optimization problem while paying a price of not reaching the full performance potential. It has been shown that by employing accurate physics-based models, MPC performance can be notably increased closer to its theoretical performance bound. However, implementation of such high-fidelity MPC in real buildings remains a challenge, resulting in a lack of successful field test studies. This work presents the methodology and field test demonstration of a computationally efficient implementation of the white-box MPC in an office building in Belgium. The detailed model of the building is based on first-principle physical equations. The deployment and supervision of MPC operation in a practical setting are supported by an automated cloud-based communication infrastructure. The motivating factor behind the cloud-based architecture is its compatibility with a commercially appealing control as a service concept. The building is equipped with a ground source heat pump (GSHP) and thermally activated building structures (TABS), where the combination of both is also known as GEOTABS. From a control perspective, GEOTABS buildings are particularly challenging systems due to large scale, complex heating, ventilation and air conditioning (HVAC) system, and slow dynamics with time delays. On the other hand, there is an increased potential for energy savings due to the high thermal mass, which acts as thermal storage. The MPC operation is demonstrated during the challenging transient seasons (switching between heating and cooling), and its performance is compared to a traditional rule-based controller (RBC). We provide a proof of concept of real MPC operation for the most difficult seasons with notable GSHP energy use savings equal to 53.5% and thermal comfort improvement by 36.9%. Other MPC applications found in the literature describe tests for only cooling or only heating, and up to now only for a black-box or a grey-box approach.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

DOE OSTI2023

Criterion validity of wrist accelerometry for assessing energy intake via the intake-balance technique

Background: Intake-balance assessments measure energy intake (EI) by summing energy expenditure (EE) with concurrent change in energy storage (ΔES). Prior work has not examined the validity of such calculations when EE is estimated via open-source techniques for research-grade accelerometry devices. The purpose of this study was to test the criterion validity of accelerometry-based intake-balance methods for a wrist-worn ActiGraph device. Methods: Healthy adults (n = 24) completed two 14-day measurement periods while wearing an ActiGraph accelerometer on the non-dominant wrist. During each period, criterion values of EI were determined based on ΔES measured by dual X-ray absorptiometry and EE measured by doubly labeled water. A total of 11 prediction methods were tested, 8 derived from the accelerometer and 3 from non-accelerometry methods (e.g., diet recall; included for comparison). Group-level validity was assessed through mean bias, while individual-level validity was assessed through mean absolute error, mean absolute percentage error, and Bland–Altman analysis. Results: Mean bias for the three best accelerometry-based methods ranged from -167 to 124 kcal/day, versus -104 to 134 kcal/day for the non-accelerometry-based methods. The same three accelerometry-based methods had mean absolute error of 323–362 kcal/day and mean absolute percentage error of 18.1-19.3%, versus 353–464 kcal/day and 19.5-24.4% for the non-accelerometry-based methods. All 11 methods demonstrated systematic bias in the Bland–Altman analysis. Conclusions: Accelerometry-based intake-balance methods have promise for advancing EI assessment, but ongoing refinement is necessary. We provide an R package to facilitate implementation and refinement of accelerometry-based methods in future research (see paulhibbing.com/IntakeBalance).

60 APPLIED LIFE SCIENCES↗