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At least 91 records · Page 5

Can we safely go to 200 °C? An integrated approach to assessing impacts to the engineered barrier system in a high-temperature repository

Abstract. This presentation gives on overview of the complex thermo-hydro-mechanical-chemical (THMC) processes occurring during the disposal of heat-producing high-level radioactive waste in geologic repositories. A specific focus is on the role of compacted bentonite, which is commonly used as an engineered backfill material for emplacement tunnels because of its low permeability, high swelling pressure, and radionuclide retention capacity. Laboratory and field tests integrated with THMC modeling have provided an effective way to deepen our understanding of temperature-related perturbations in the engineered barrier system; however, most of this work has been conducted for maximum temperatures around 100 ∘C. In contrast, some international disposal programs have recently started investigations to understand whether local temperatures in the bentonite of up to 200 ∘C could be tolerated with no significant changes to safety relevant properties. Raising the maximum temperature is attractive for economical and safety reasons but faces the challenge of exposing the bentonite to significant temperature increases. Strong thermal gradients may induce complex moisture transport processes while geochemical processes, such as cementation and perhaps also illitization effects may occur, all of which could strongly affect the bentonite and near-field rock properties. Here, we present initial investigations of repository behavior exposed to strongly elevated temperatures. We will start discussing our current knowledge base for temperature effects in repositories exposed to a maximum temperature of 100 ∘C, based on data and related modeling analysis from a large heater experiment conducted for over 18 years in the Grimsel Test Site in Switzerland. We then show results from coupled THMC simulations of a nuclear waste repository in a clay formation exposed to a maximum temperature of 200 ∘C. We also explore preliminary data from a bench-scale laboratory mock-up experiment, which was designed to represent the strong THMC gradients occurring in a “hot” repository, and we finally touch on a full-scale field heater test to be conducted soon in the Grimsel Test Site underground research laboratory in Switzerland (referred to as HotBENT).

Birkholzer, Jens T. (ORCID:0000000279891912)↗

Use of Novel Diglycolamide Extractants in Liquid-liquid Separations of Light Rare Earths

Creation of a novel extractant that can improve rare earth separations both economically and environmentally will be pivotal for industry progression. Diglycolamide (DGA) extractants provide chemistries that support this goal by serving as an extractant with high affinity for lanthanides and improved separation factors for light rare earths as compared to current extractants like PC88A. Initial organic phase loading capacity and phase dispersion tests performed with various modified DGAs generated results that were unfavorable for industrial processing, but further modification of the DGA alkyl chain substituents have resulted in new structures with promising results. Dispersion time measurements taken in small scale batch contacts of the extractant with a simulated leach liquor containing La, Ce, Nd, and Pr support implementation in both mixer-settlers and centrifugal contactors for larger scale separations. Furthermore, this confirmation allowed for preliminary flowsheet design using extraction equilibria at various organic to aqueous flow ratios (O/A) for extraction, scrubbing, and stripping stages. These values along with expected product/effluent compositions for each section aid in the testing for specific distribution ratios and final flowsheet design. Implementation of the DGA extractant into solvent extraction equipment will provide essential information for the next steps of this project and how this extractant may be optimized for future applications.

42 ENGINEERING↗

Integrated Thermal Energy Storage and Brayton Cycle Equipment Demonstration (Integrated TESTBED) Project Design Basis

The Integrated Thermal Energy Storage and Brayton cycle Equipment Demonstration (Integrated TESTBED) project seeks to retire commercial-scale risks associated with the design, integration,and operation of a supercritical carbon dioxide (sCO2) power cycle and concentrating solar power (CSP) thermal energy storage (TES) system. This requires an understanding of commercial-scale collector system transient impacts on the TES system, the dynamics of heat exchange from theTES to the power cycle, and the control and operation of the power cycle to accommodate various dispatch strategies. In order to retire these risks, Heliogen has proposed to construct a 5 MWe CSP demonstration facility based on directly heated particle and sCO2 technology. The receivers, primary heat exchanger, and power cycle will be deployed at a full commercial scale based on Heliogen’s modular plant architecture to ensure actual system integration risks are validated during design, construction, and operation. This work summarizes the design basis for the Integrated TESTBED project demonstration facility including a design target for capacity factor to support test operations, hours of storage, particle silo arrangement, centrifugal article receivers, a diffusion bonded particle-sCO2 heat exchanger, and a 5 MWe (net) integrally geared sCO2 recompression Brayton cycle.

14 SOLAR ENERGY↗

Investigation on capacity loss mechanisms of lithium-ion pouch cells under mechanical indentation conditions

Capacity loss was observed in Li-ion cells after mechanical deformation approaching the onset of internal short circuit (ISCr). In this paper, a series of indentation tests were carried out on commercial Li-ion cells of three capacities (500, 1500 and 2000 mAh). Both in-situ and ex-situ methods were used to investigate the mechanisms of indentation-induced capacity loss. We note after indentation test, the cell capacity reduced by 0.5%–6% of its original value. The incremental capacity (IC) analysis results showed that IC curves generally shifted to lower voltage region, indicating the increase in cell internal resistance. In addition, the fitting results of electrochemical impedance spectroscopy (EIS) indicated that mechanical indentation can result in a reduction in ohmic resistance and the increase in polarization resistance. Scanning electron microscopy (SEM) and X-ray computed tomography (XCT) results showed crushing of graphite, mud cracking of copper current collectors and enlarged pores in separator, which is proposed to be the main reasons for the increase in polarization resistance and permanent capacity loss. The rapid capacity loss due to mechanical abuse was compared with the long-term capacity fading.

25 ENERGY STORAGE↗

Toward MBenes Battery Electrode Materials: Layered Molybdenum Borides for Li-Ion Batteries

Lithium-ion and sodium-ion batteries (LIBs and SIBs) are crucial in our shift toward sustainable technologies. In this work, the potential of layered boride materials (MoAlB and Mo 2 AlB 2 ) as novel, high-performance electrode materials for LIBs and SIBs, is explored. It is discovered that Mo 2 AlB 2 shows a higher specific capacity than MoAlB when used as an electrode material for LIBs, with a specific capacity of 593 mAh g -1 achieved after 500 cycles at 200 mA g -1 . It is also found that surface redox reactions are responsible for Li storage in Mo 2 AlB 2 , instead of intercalation or conversion. Moreover, the sodium hydroxide treatment of MoAlB leads to a porous morphology and higher specific capacities exceeding that of pristine MoAlB. When tested in SIBs, Mo 2 AlB 2 exhibits a specific capacity of 150 mAh g -1 at 20 mA g -1 . These findings suggest that layered borides have potential as electrode materials for both LIBs and SIBs, and highlight the importance of surface redox reactions in Li storage mechanisms.

25 ENERGY STORAGE↗

Facility Location Optimization Model for COVID-19 Resources

In response to anticipated resource shortfalls related to the treatment and testing of COVID-19, many communities are planning to build additional facilities to increase capacity. These facilities include field hospitals, testing centers, mobile manufacturing units, and distribution centers. In many cases, these facilities are intended to be temporary and are designed to meet an immediate need. When deciding where to place new facilities many factors need to be considered, including the feasibility of potential locations, existing resource availability, anticipated demand, and accessibility between patients and the new facility. In this project, a facility location optimization model was developed to integrate these key pieces of information to help decision makers identify the best place, or places, to build a facility to meet anticipated resource demands. The facility location optimization model uses the location of existing resources and the anticipated resource demand at each location to minimize the distance a patient must travel to get to the resource they need. The optimization formulation is presented below. The model was designed to operate at the county scale, where patients are grouped per county. This assumption can be modified to integrate other scales or include individual patients.

60 APPLIED LIFE SCIENCES↗

Conceptual Neutronics Scoping for Ramp Testing in the Advanced Test Reactor

With the closer of the Halden Boiling Water Reactor in 2018, the global capacity for in-reactor power ramp testing has been lost. As such tests provide valuable data for understanding pellet-cladding interaction (PCI) phenomena, finding new facilities for ramp testing is of interest to the United States Accident-Tolerant Fuel (ATF) Program. Several options at Idaho National Laboratory (INL) are being evaluated for adding ramp test capabilities. In the Transient Reactor Test Facility (TREAT), one option is testing inside a Transient Water Irradiation System in TREAT (TWIST) capsule. In the Advanced Test Reactor (ATR), one option under consideration is testing in an I-Loop toward the outer edge of the core. Another is testing in Loop-2A, located in the Center Flux Trap (CFT) of the ATR. In this paper, we examine the conceptual scoping for the Loop-2A experiment known as ATF-2Ramp.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Conceptual Neutronics Scoping for Ramp Testing in the Advanced Test Reactor

With the closure of the Halden Boiling Water Reactor in 2018, the global capacity for in-reactor power ramp testing has been lost. As such tests provide valuable data for understanding pellet-cladding interaction (PCI) phenomena, finding new facilities for ramp testing is of interest to the United States Accident-Tolerant Fuel (ATF) Program. Several options at Idaho National Laboratory (INL) are being evaluated for adding ramp test capabilities. In the Transient Reactor Test Facility (TREAT), one option is testing inside a Transient Water Irradiation System in TREAT (TWIST) capsule. In the Advanced Test Reactor (ATR), one option under consideration is testing in an I-Loop toward the outer edge of the core. Another is testing in Loop-2A, located in the Center Flux Trap (CFT) of the ATR. In this paper, we examine the conceptual scoping for the Loop-2A experiment known as ATF-2Ramp.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Use of Hydrogel Electrolyte in Zn-MnO2 Rechargeable Batteries: Characterization of Safety, Performance, and Cu2+ Ion Diffusion

Achieving commercially acceptable Zn-MnO2 rechargeable batteries depends on the reversibility of active zinc and manganese materials, and avoiding side reactions during the second electron reaction of MnO2. Typically, liquid electrolytes such as potassium hydroxide (KOH) are used for Zn-MnO2 rechargeable batteries. However, it is known that using liquid electrolytes causes the formation of electrochemically inactive materials, such as precipitation Mn3O4 or ZnMn2O4 resulting from the uncontrollable reaction of Mn3+ dissolved species with zincate ions. In this paper, hydrogel electrolytes are tested for MnO2 electrodes undergoing two-electron cycling. Improved cell safety is achieved because the hydrogel electrolyte is non-spillable, according to standards from the US Department of Transportation (DOT). The cycling of “half cells” with advanced-formulation MnO2 cathodes paired with commercial NiOOH electrodes is tested with hydrogel and a normal electrolyte, to detect changes to the zincate crossover and reaction from anode to cathode. These half cells achieved ≥700 cycles with 99% coulombic efficiency and 63% energy efficiency at C/3 rates based on the second electron capacity of MnO2. Other cycling tests with “full cells” of Zn anodes with the same MnO2 cathodes achieved ~300 cycles until reaching 50% capacity fade, a comparable performance to cells using liquid electrolyte. Electrodes dissected after cycling showed that the liquid electrolyte allowed Cu ions to migrate more than the hydrogel electrolyte. However, measurements of the Cu diffusion coefficient showed no difference between liquid and gel electrolytes; thus, it was hypothesized that the gel electrolytes reduced the occurrence of Cu short circuits by either (a) reducing electrode physical contact to the separator or (b) reducing electro-convective electrolyte transport that may be as important as diffusive transport.

25 ENERGY STORAGE↗

Low-Cost High-Power Anodes for Electric Vehicle Batteries

Saratoga Energy has developed a system for making graphite from carbon dioxide. LBNL has experience in benchmarking graphites for Li-ion battery applications. In half cells, we tested graphites for their reversible capacity and their rate capability. They used this data to support a phase II proposal that was funded by DOE to scale up their best material and test in larger cells.

25 ENERGY STORAGE↗

Predicting Li-Ion Battery Capacity Fade Using Early-Life Data and a Hybrid Data-Driven Gaussian Process-Bayesian Regression Approach

Accurately predicting Li-ion battery capacity trajectories using early-life data can dramatically improve battery-life understandings and be used to rapidly evaluate design/cost/performance trade-offs when developing new battery materials. Accurate early-life predictions enable researchers to quickly iterate over cell designs and material precursor properties without consistently cycling cells to failure. To this end, we present a toolbox that uses a combined Gaussian Process and Bayesian regression approach that capitalizes on signals other than just capacity (e.g., dQ/dV, voltage drops) to rapidly predict capacity-fade trajectories. The prediction tool uses Bayesian regression to fit functional forms, e.g., power law, sigmoids, etc., to predict capacity-fade dynamics. By fitting functional forms, the capacity fade can be interrogated at any point in the future, allowing for early cell-failure prediction. Additionally, Bayesian regression allows for accurate uncertainty estimates that account for cell-to-cell variability (aleatoric uncertainty) and the lack of observation data (epistemic uncertainty). By only using early cycle data to predict the capacity fade trajectory, uncertainty bounds at end-of-life can be extremely large. The large uncertainty bounds are further exacerbated because there is no systematic way to define the prior distribution of the functional forms' parameters. We improve our the predicted trajectory confidence interval of our predicted trajectory using two methods. First, we shows that a small amount of held-out cycling data is sufficientuse some train cells, that have been cycled to failure to derive information regarding the appropriate prior distributions for the functional forms' parameters of the functional form, effectively leading to data-driven priors.. We propose constructing the data-driven priors by first running a Bayesian regression starting with uninformed priors to generate intermediate cell-specific posterior parameter distributions. These posterior distributions are combined using a Ggaussian mixture model for each parameter to create the data-driven priors. These mixture models serve as the data-driven prior distributions for the parameters for. Second, we derive multiple features, e.g., C_dchg 0.5 DoD 0.5, log (|mean(dQ/dV_(w_3-w_0 ) (V)|), etc., from the train cellsheld-out cycling data, identify which the features are that best predicting capacity at early/mid-life cycles, and then create Ggaussian process regression models that are used for predicting capacity at early/mid-life cycles for the test cells (see blue dots with error bars in Fig 1b). Finally, these predicted data-points are used in addition to the actual early cycle data capacity fade to construct the Bayesian regression trajectory for the test cell s. Notably. We note that these two methods are complementary and can be combined with each other. We evaluate the performance of our proposed method on an testing open-source dataset from Iowa State University and Iowa Lakes Community College (ISU-ILCC). This dataset comprises of 251 nickel-manganese-cobalt/graphite Lithium-ion cells that are cycled under 63 different conditions. We compute the mean average percentage error (MAPE) and negative log predictive density (NLPD) to quantify the efficacy of our method. Our initial findings suggest that, when only few observations are available, for test cells, when using only Bayesian regression with uninformed priors, a power law functional provides the most accurate predictions. with very few data points. However, asHowever, a the number of data points increases, a twin sigmoidal function becomes more accurate as the number of observations further increases. We also find that using as little as 10% of the data set towards generating data-driven priors can lead to significant improvement in prediction accuracy when using early cycle data. Lastly, we found that augmenting early-cycle data with Gaussian process-predicted capacity data for Bayesian regression greatly improves the prediction accuracy. We will present a comprehensive comparison of our methods to other methods available in the literature and apply this method to additional battery datasets.

42 ENGINEERING↗

Sensitivity and history match analysis of a carbon dioxide “huff-and-puff” injection test in a horizontal shale gas well in Tennessee

Due to improvements in well development, shale gas production has gained importance recently, especially in the United States. To improve gas production and develop a better understanding of shale reservoirs, researchers are conducting field tests to monitor CO 2 storage and enhanced gas recovery. Reservoir simulations can then utilize these field results for sensitivity studies, uncertainty analysis, history matching, gas production forecasts, and CO 2 storage capacity estimations. One such field test was performed for the Chattanooga Shale formation in Morgan County, Tennessee. Approximately 463 tonnes (510 tons) of CO 2 was successfully injected into a hydraulically fractured horizontal well over a thirteen-day period in March 2014. The injection test was achieved in four steps: pre-injection, injection, soaking, and flowback. In this paper, those steps were modeled with a reservoir simulator to match the historic production and injection rates with gas component compositions and forecast the production for five years. The reservoir fluid was modeled as a multi-component gas, including CH 4 , C 2 H 6 , C 3 H 8 , N 2 , and CO 2 . Langmuir constants, reservoir pressure, and fracture network volume were adjusted to match simulation results with observed production rates and gas composition. Results showed that, under the same reservoir conditions, each gas component behaves differently by way of compositional changes in production. CH4 behaves like N2, while CO 2 behaves like heavier hydrocarbons such as C 2 H 6 and C 3 H 8 . CO 2 plume results showed that, after injection, the produced CO 2 is mostly derived from fractured limestone (i.e., Fort Payne Formation) because the injected CO 2 is not adsorbed in limestone but rather by shale formations.

03 NATURAL GAS↗

Long cycle and calendar life of Si-based Li-ion batteries enabled by localized high-concentration electrolytes and their surprising water tolerance

Silicon-based anodes promise an increase in energy density for Li-ion batteries, yet they suffer from a poor calendar life. Researchers have posited that fluorinated lithium salt forms reactive side products that destroy the solid electrolyte interphase (SEI), even without cycling. HF is one such reactive side product formed from trace water contamination in the electrolyte. Some electrolytes, such as localized high concentration electrolytes (LHCEs) may improve cell stability in highly reactive systems, such as Li metal and Si. In the present study, LHCEs containing 200-300 ppm of water retained up to 8% greater capacity (1200-1300 mAh/g Si) in calendar life tests over 200 days compared to dried electrolytes (< 20 ppm water). Calendar aging took place at 100% state of charge. Cells with 200-300 ppm water performed comparably to cells with 20 ppm water in cycle life tests (900-1000 mAh/g Si) . Even adding 1000 ppm water did not lead to rapid capacity fade in cells undergoing cycle life tests. Nano-FTIR spectroscopy revealed chemical and structural differences in the SEI for cells with 1000 ppm water compared to 200-300 ppm water. The SEI differences, including increased Li2O concentration, may have contributed to improved calendar life. This research reveals the capabilities of LHCEs to improve the calendar and cycle life of Si-based Li-ion batteries, despite the presence of a highly reactive contaminant.

25 ENERGY STORAGE↗

Pelletization with Spark Plasma Sintering and Characterization of Metal Iodides: An Assessment of Long-Term Radioiodine Immobilization Options

Four promising iodine “getter” materials (Ag, Cu, Bi, and Sn) for radioiodine capture were assessed in their pure metal-iodide (MI x ) pelletized forms to compare relative chemical durabilities. To study chemical durability, commercial MI x compounds of AgI, BiI 3 , BiOI, CuI, and SnI 4 were converted to dense monolithic pellets using spark plasma sintering. Semidynamic leach testing in the form of modified ASTM C1308 tests was then performed on the pellets in two different forms including unmounted (as-pressed) specimens (i.e., “U”) and epoxy-mounted specimens (i.e., “M”) with polished surfaces. The chemical durability results and sample characterizations showed that three of the five MI x compounds tested (i.e., AgI, CuI, and BiOI) displayed moderate to high leach resistances. Further, the remaining two MI x compounds (i.e., BiI 3 and SnI 4 ), which are both desirable iodine waste forms due to their high iodine loading capacities, readily decomposed during leach testing, indicated by crystallographic changes in the specimens as well as large amounts of iodine detected in the leachate solutions. The instabilities of BiI 3 and SnI 4 raise uncertainties for using the base metals/cations (i.e., Bi 0 /Bi 3+ and Sn 0 /Sn 4+ , respectively) as viable getters for radioiodine capture due to likely poor waste form chemical durabilities after capture and consolidation into waste forms.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

What are the Impacts on the HVAC System when it Provides Frequency Regulation? – A Comprehensive Case Study with a Multi-Zone Variable Air Volume (VAV) System

Heating, ventilation, and air-conditioning (HVAC) systems in commercial buildings have proven to be a great asset for providing secondary frequency regulation (FR) service to the power grid. However, how the provision of FR service affects the HVAC system Quality of Service (QOS) is still largely unknown. In particular, there exists a controversy regarding the energy efficiency impact. This paper investigates how a HVAC system performance and its associated controls are impacted during and after the FR service. For the assessment, we developed a dynamic Modelica-based medium office building model as a virtual testbed with the Air Handling Unit (AHU) fans providing the FR service. Different regulation capacities (demand levels) and standard test signals under various load profiles in the U.S. are considered. The results show that FR has little or no impact on the HVAC operation and occupant thermal comfort while the building is providing the service if an appropriate regulation capacity is pre-determined. However, if the regulation capacity is overestimated, the quality of the FR service provided by the HVAC system and the HVAC energy efficiency will be affected due to the equipment operating constraints. In addition, the AHU supply air temperature fluctuates, and the controller cannot maintain the desired setpoint as the FR magnitude is increased. After the FR service time, the system takes a certain period to return to normal operation. The recovery period extends with the increase in the FR magnitude. For this case study, there exists a control conflict between the FR control and the existing HVAC control (from ASHRAE Guideline 36-2018) during high load conditions, causing the fan speed to saturate. The fan power consumption could increase significantly; up to 77% increase compared to the baseline was observed. This case study demonstrates that the HVAC system controls need to be enhanced and adapted to minimize the interaction between the FR controller and the indoor environmental controls in order to preserve the HVAC system QOS while (during and after) providing satisfactory FR service.

Lu, Xing↗

Nonproliferation and Arms Control Research and Development (NPAC R&D) [Slides]

NPAC R&D focus areas include: Advancing U.S. capabilities to detect and characterize nuclear weapon development activities globally, including material production, the movement of special nuclear materials and nuclear weapons, and the testing or use of nuclear weapons, Supporting the development and testing of policy options and technical capabilities for international nuclear safeguards, arms control / treaty verification, nuclear export controls, and nonproliferation initiatives consistent with U.S. Government goals and objectives to enable monitoring and verification, Utilizing uranium, lithium, and high explosives (HE) materials expertise to support national-level activities in nuclear forensics and nuclear detection technology testing and evaluation, Providing unique training and capacity-building programs, particularly with the Nuclear Detection and Sensor Testing Center (NDSTC), and Engaging internationally to promote nonproliferation and arms control norms and best practices through bilateral and multilateral work.

36 MATERIALS SCIENCE↗

Hydroxyl Conducting Hydrogels Enable Low-Maintenance Commercially Sized Rechargeable Zn–MnO2 Batteries for Use in Solar Microgrids

Zinc (Zn)–manganese dioxide (MnO2) rechargeable batteries have attracted research interest because of high specific theoretical capacity as well as being environmentally friendly, intrinsically safe and low-cost. Liquid electrolytes, such as potassium hydroxide, are historically used in these batteries; however, many failure mechanisms of the Zn–MnO2 battery chemistry result from the use of liquid electrolytes, including the formation of electrochemically inert phases such as hetaerolite (ZnMn2O4) and the promotion of shape change of the Zn electrode. This manuscript reports on the fundamental and commercial results of gel electrolytes for use in rechargeable Zn–MnO2 batteries as an alternative to liquid electrolytes. The manuscript also reports on novel properties of the gelled electrolyte such as limiting the overdischarge of Zn anodes, which is a problem in liquid electrolyte, and finally its use in solar microgrid applications, which is a first in academic literature. Potentiostatic and galvanostatic tests with the optimized gel electrolyte showed higher capacity retention compared to the tests with the liquid electrolyte, suggesting that gel electrolyte helps reduce Mn3+ dissolution and zincate ion migration from the Zn anode, improving reversibility. Cycling tests for commercially sized prismatic cells showed the gel electrolyte had exceptional cycle life, showing 100% capacity retention for >700 cycles at 9.5 Ah and for >300 cycles at 19 Ah, while the 19 Ah prismatic cell with a liquid electrolyte showed discharge capacity degradation at 100th cycle. We also performed overdischarge protection tests, in which a commercialized prismatic cell with the gel electrolyte was discharged to 0 V and achieved stable discharge capacities, while the liquid electrolyte cell showed discharge capacity fade in the first few cycles. Finally, the gel electrolyte batteries were tested under IEC solar off-grid protocol. It was noted that the gelled Zn–MnO2 batteries outperformed the Pb–acid batteries. Additionally, a designed system nameplated at 2 kWh with a 12 V system with 72 prismatic cells was tested with the same protocol, and it has entered its third year of cycling. This suggests that Zn–MnO2 rechargeable batteries with the gel electrolyte will be an ideal candidate for solar microgrid systems and grid storage in general.

25 ENERGY STORAGE↗