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DOE OSTI2017

2016 Idaho National Laboratory Water Use Report and Comprehensive Well Inventory (Revision 25)

This 2016 Idaho National Laboratory Water Use Report and Comprehensive Well Inventory (Revision 25) provides water use information for production and potable water wells at the Idaho National Laboratory Site for Calendar Year 2016. It also provides detailed information for new, modified, and decommissioned wells. Four new wells were drilled and completed in Calendar Year 2016. Five storm water injection wells were decommissioned in Calendar Year 2016. Detailed construction and decommissioning information and location maps for the wells are provided. This report is being submitted in accordance with the Water Rights Agreement between the State of Idaho and the United States, for the United States Department of Energy (dated 1990), the subsequent Partial Decree for Water Right 34-10901 issued June 20, 2003, and the Final Unified Decree issued August 26, 2014.

2016 Water Use Report and Comprehensive Well Inven↗

DOE OSTI2023

Composite Analysis for Low-Level Waste Disposal in the Hanford Site Central Plateau (FY 2020) (Rev. 2)

This document provides an updated Hanford Site composite analysis (CA). A Hanford Site CA was prepared and issued in 1998 (PNNL-11800) with an addendum provided in 2002 (PNNL-11800 Addendum 1). The CA was approved in 2002 (Frei, 2002) and has been maintained (DOE/RL-2000-29 and subsequent revisions) to support low-level waste disposal performance assessments (PAs) and disposal authorizations for facilities at the Hanford Site, including the following: Continued operation of the Environmental Restoration Disposal Facility (ERDF) and the 200 East and 200 West Low-Level Burial Grounds; Construction of the Integrated Disposal Facility (IDF); Forthcoming closure of tank residual waste systems such as Waste Management Area (WMA) C. The CA maintenance program resulted in a determination in 2015 (DOE/RL-2015-66) that the Hanford Site CA needed an update for the following reasons: While the initial Hanford Site CA has been maintained since 2001, the accumulation of basis changes reported in the annual summary reports over the succeeding 14 years merit evaluation in an updated analysis; The U.S. Department of Energy (DOE) Headquarters requested in a memorandum in 2015 (Gilbertson and Marcinowski, 2015) that “as soon as the relevant PAs are complete, the CA will be revised to account for all of the new information.” This updated Hanford Site CA accounts for the following new information: 1. Inclusion of a detailed Hanford Site baseline disposition that projects remedial activities through site closure. There have been significant changes through decision making in the Comprehensive Environmental Response, Compensation, and Liability Act of 1980 (CERCLA) process that were not available when the original CA was produced; 2. Inclusion of an updated inventory basis, new modeling capabilities, and new decisions reached in the associated record of decision (ROD) that was provided by issuance of DOE/EIS-0391 in fiscal year (FY) 2013. Development of a Hanford Site groundwater model from the baseline provided in a technical transfer of models for the Final Tank Closure and Waste Management Environmental Impact Statement (DOE/EIS-0391) commenced in FY 2014 and resulted in the plateau-to-river (P2R) groundwater flow model that is used in this updated Hanford Site CA; 3. Accounting for pump and treat systems, which were not evaluated in the initial CA. Pump and treat systems have had significant impact on groundwater flow system behavior, contaminant transport, and contaminant removal from Hanford Site groundwater. This process is accounted for in the use of the P2R model for this updated Hanford Site CA; 4. Inclusion of water-level data collected since the initial CA was completed. Data collected as the unconfined aquifer water levels continue to recede since the cessation of large liquid discharges in the late 1990s have led to marked improvement in understanding of the flow system for future conditions, particularly regarding northward flow potential in the critical Gable Gap area. The calibration in the latest version of the P2R model accounts for this information; 5. Inclusion of results from the revised ERDF PA completed in 2013 (WCH-5209) that account for updated inventory and expansion of the ERDF facility to about twice the size that was evaluated in the original CA; 6. Use of updated geoframeworks to provide the structural basis for numerical fate and transport models in the groundwater pathway of this updated CA. The geologic basis for groundwater models has continued to improve with additional data collection and interpretation with the creation and maintenance of the Hanford South Geoframework and the Central Plateau Vadose Zone Geoframework tools; 7. Incorporation of updated tank residual inventory estimates. Tank residual inventory estimates have improved with the incorporation of tank retrieval inventory data for those tanks that have completed retrieval. The CA inventory data package includes this updated information; 8. Incorporation of WMA C PA results. Two additional PAs for tank farm closure decisions are in preparation during the period required to prepare an updated Hanford Site CA: WMA C (FY 2016) and WMA A-AX (in preparation). The WMA C PA results are incorporated into the updated Hanford Site CA, and its grouted residuals model is used as the basis for a release model to account for the other tank farm systems modeling in this updated CA; 9. An update to the IDF PA was submitted in FY 2017 and has been reviewed and approved. The results of the IDF PA are incorporated into this updated CA; 10. Updated risk assessment scenarios. The risk assessment scenarios currently in use for Hanford Site CERCLA and Resource Conservation and Recovery Act of 1976 (RCRA) analyses differ from those evaluated in the initial Hanford Site CA. The representative person exposure scenario evaluated in this updated Hanford Site CA is consistent with recent PAs and CERCLA and RCRA analyses as the Hanford Site. This updated Hanford Site CA provides the following: A comparison of the updated Hanford Site CA all-pathway dose results with the performance measures during the compliance period, which is assumed to begin with site closure in calendar 2070 with the last scheduled disposal action and continue for 1,000 years postclosure (to calendar year 3069); A comparison of Hanford Site CA all-pathway dose results with the performance measures during the postcompliance period to address potential peaks beyond the compliance period. This is accomplished by evaluating dose in the period for 9,000 years following the compliance period (i.e., from calendar year 3070 to 12070).

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2016

Probabilistic precipitation and temperature downscaling of the Twentieth Century Reanalysis over France

This work proposes a daily high-resolution probabilistic reconstruction of precipitation and temperature fields in France over the 1871–2012 period built on the NOAA Twentieth Century global extended atmospheric reanalysis (20CR). The objective is to fill in the spatial and temporal data gaps in surface observations in order to improve our knowledge on the local-scale climate variability from the late nineteenth century onwards. The SANDHY (Stepwise ANalogue Downscaling method for HYdrology) statistical downscaling method, initially developed for quantitative precipitation forecast, is used here to bridge the scale gap between large-scale 20CR predictors and local-scale predictands from the Safran high-resolution near-surface reanalysis, available from 1958 onwards only. SANDHY provides a daily ensemble of 125 analogue dates over the 1871–2012 period for 608 climatically homogeneous zones paving France. Large precipitation biases in intermediary seasons are shown to occur in regions with high seasonal asymmetry like the Mediterranean. Moreover, winter and summer temperatures are respectively over- and under-estimated over the whole of France. Two analogue subselection methods are therefore developed with the aim of keeping the structure of the SANDHY method unchanged while reducing those seasonal biases. The calendar selection keeps the analogues closest to the target calendar day. The stepwise selection applies two new analogy steps based on similarity of the sea surface temperature (SST) and the large-scale 2 m temperature ( T ). Comparisons to the Safran reanalysis over 1959–2007 and to homogenized series over the whole twentieth century show that biases in the interannual cycle of precipitation and temperature are reduced with both methods. The stepwise subselection moreover leads to a large improvement of interannual correlation and reduction of errors in seasonal temperature time series. When the calendar subselection is an easily applicable method suitable in a quantitative precipitation forecast context, the stepwise subselection method allows for potential season shifts and SST trends and is therefore better suited for climate reconstructions and climate change studies. Furthermore, the probabilistic downscaling of 20CR over the period 1871–2012 with the SANDHY probabilistic downscaling method combined with the stepwise subselection thus constitutes a perfect framework for assessing the recent observed meteorological events but also future events projected by climate change impact studies and putting them in a historical perspective.

54 ENVIRONMENTAL SCIENCES↗

NASA NTRS1979

Growth stage estimation

Of the three candidate approaches to adjustment of the crop calendar to account for year-to-year weather differences, the Robertson triquadratic unit, a function of a nonlinear function of maximum and minimum temperature and day length, best described the rate of phenological development of wheat. The adjustable crop calendar (ACC) as implemented for LACIE is used to calculate the daily increment of development through six physiological stages of growth. Topics covered include dormancy modeling, the spring restart model, spring wheat starter model, winter starter model, winter wheat starter model, inclusion of the moisture variable, and display of crop stage estimation results. Assessment of the ACC accuracy over the period of LACIE operation indicates that the adjustable crop calendars used provided more accurate information than would have been available using historical norms. The models performed best under the conditions from which they were derived (Canadian spring wheat) and most poorly for the dwarf varieties and Southern Hemisphere applications.

Whitehead, V. S.↗

NASA NTRS1981

Evaluation of spring wheat and barley crop calender models for the 1979 crop year

During the Large Area Crop Inventory Experiment, spring wheat planting date and crop development stage estimates based on historical normals were improved by the use of the Feyerherm planting date and Robertson spring wheat crop calendar models. The Supporting Research Crop Calendar Project element modified the Robertson model to reduce bias at cardinal growth stages within the growing season. These models were tested in 1980 along with a state-of-the-art barley model (Williams) against a ground-truth data set from 49 calendar year 1979 segments in the U.S. Great Plains spring wheat and barley region.

Nazare, C. V.↗

NASA NTRS2003

Monte Carlo Simulation of Sudden Death Bearing Testing

Monte Carlo simulations combined with sudden death testing were used to compare resultant bearing lives to the calculated hearing life and the cumulative test time and calendar time relative to sequential and censored sequential testing. A total of 30 960 virtual 50-mm bore deep-groove ball bearings were evaluated in 33 different sudden death test configurations comprising 36, 72, and 144 bearings each. Variations in both life and Weibull slope were a function of the number of bearings failed independent of the test method used and not the total number of bearings tested. Variation in L10 life as a function of number of bearings failed were similar to variations in lift obtained from sequentially failed real bearings and from Monte Carlo (virtual) testing of entire populations. Reductions up to 40 percent in bearing test time and calendar time can be achieved by testing to failure or the L(sub 50) life and terminating all testing when the last of the predetermined bearing failures has occurred. Sudden death testing is not a more efficient method to reduce bearing test time or calendar time when compared to censored sequential testing.

Vlcek, Brian L.↗

NASA NTRS2003

Development Efforts Expanded in Ion Propulsion: Ion Thrusters Developed With Higher Power Levels

The NASA Glenn Research Center was the major contributor of 2-kW-class ion thruster technology to the Deep Space 1 mission, which was successfully completed in early 2002. Recently, NASA s Office of Space Science awarded approximately $21 million to Glenn to develop higher power xenon ion propulsion systems for large flagship missions such as outer planet explorers and sample return missions. The project, referred to as NASA's Evolutionary Xenon Thruster (NEXT), is a logical follow-on to the ion propulsion system demonstrated on Deep Space 1. The propulsion system power level for NEXT is expected to be as high as 25 kW, incorporating multiple ion thrusters, each capable of being throttled over a 1- to 6-kW power range. To date, engineering model thrusters have been developed, and performance and plume diagnostics are now being documented. The project team-Glenn, the Jet Propulsion Laboratory, General Dynamics, Boeing Electron Dynamic Devices, the Applied Physics Laboratory, the University of Michigan, and Colorado State University-is in the process of developing hardware for a ground demonstration of the NEXT propulsion system, which comprises a xenon feed system, controllers, multiple thrusters, and power processors. The development program also will include life assessments by tests and analyses, single-string tests of ion thrusters and power systems, and finally, multistring thruster system tests in calendar year 2005. In addition, NASA's Office of Space Science selected Glenn to lead the development of a 25-kW xenon thruster to enable NASA to conduct future missions to the outer planets of Jupiter and beyond, under the High Power Electric Propulsion (HiPEP) program. The development of a 100-kW-class ion propulsion system and power conversion systems are critical components to enable future nuclear-electric propulsion systems. In fiscal year 2003, a team composed of Glenn, the Boeing Company, General Dynamics, the Applied Physics Laboratory, the Naval Research Laboratory, the University of Wisconsin, the University of Michigan, and Colorado State University will perform a 6-month study that will result in the design of a 25-kW ion thruster, a propellant feed system, and a power processing architecture. The following 2 years will involve hardware development, wear tests, single-string tests of the thruster-power circuits and the xenon feed system, and subsystem service life analyses. The 2-kW-class ion propulsion technology developed for the Deep Space 1 mission will be used for NASA's discovery mission Dawn, which involves maneuvering a spacecraft to survey the asteroids Ceres and Vesta. The 6-kW-class ion thruster subsystem technology under NEXT is scheduled to be flight ready by calendar year 2006. The less mature 25- kW ion thruster system under HiPEP is expected to be ready for a flight advanced development program in calendar year 2006.

Patterson, Michael J.↗

NASA NTRS2013

U.S. Naval Observatory VLBI Analysis Center

This report summarizes the activities of the VLBI Analysis Center at the United States Naval Observatory for the 2012 calendar year. Over the course of the year, Analysis Center personnel continued analysis and timely submission of IVS-R4 databases for distribution to the IVS. During the 2012 calendar year, the USNO VLBI Analysis Center produced two VLBI global solutions designated as usn2012a and usn2012b. Earth orientation parameters (EOP) based on this solution and updated by the latest diurnal (IVS-R1 and IVS-R4) experiments were routinely submitted to the IVS. Sinex files based upon the bi-weekly 24-hour experiments were also submitted to the IVS. During the 2012 calendar year, Analysis Center personnel continued a program to use the Very Long Baseline Array (VLBA) operated by the NRAO for the purpose of measuring UT1-UTC. Routine daily 1-hour duration Intensive observations were initiated using the VLBA antennas at Pie Town, NM and Mauna Kea, HI. High-speed network connections to these two antennas are now routinely used for electronic transfer of VLBI data over the Internet to a USNO point of presence. A total of 270 VLBA Intensive experiments were observed and electronically transferred to and processed at USNO in 2012.

Boboltz, David A.↗

NASA NTRS2020

Fuel Flexible Combustor for High-OPR Compact-Core N+3 Propulsion Engine

This document reports unlimited-rights data relating to technical work under NASA contract NNC14CA30C, performed throughout the full period of the effort. This period comprises Fiscal Years 2015 through 2019 (inclusive); this period includes the 4th Quarter of Calendar Year 2014, all of Calendar Years 2015 through 2018, and the first three Quarters of Calendar Year 2019. Limited-rights data relating to technical progress during this period are provided in a separate document, a Limited Rights version of this report having limited rights markings.

Smith, Lance L.↗

NASA NTRS2021

Sea Ice Extents Continue to Set New Records: Arctic, Antarctic, and Global Results

The multi-channel satellite passive-microwave record of Earth’s sea ice coverage, extending back to the late 1970s, has long revealed declining sea ice coverage in the Arctic but through 2015 revealed an overall increase rather than decrease in Antarctic sea ice coverage. Following major decreases in Antarctic sea ice since 2015, the 42-year 1979-2020 satellite dataset now shows losses in sea ice coverage in both hemispheres, and this is convincingly demonstrated by the enumeration of monthly and yearly record high and record low sea ice extents experienced over the course of the 42 years. In fact, one of the most convincing statistics on the declining Arctic sea ice cover is the fact that since 1986 the Arctic has not experienced a single monthly record high sea ice extent in any month but has experienced 93 monthly record lows. In contrast, all 12 calendar months have their 42-year Antarctic monthly record high sea ice extents in the period 2007-2015, while 8 of the 12 calendar months have had Antarctic record lows since 2015. Globally, every calendar month has registered a new monthly record low within the past 5 years. These results are complemented (and somewhat tempered) by quantification of the range of monthly and yearly sea ice extent values over the 42 years. For instance, although the Arctic’s lowest September monthly average sea ice extent (in 2012) is 53% lower than its highest September monthly average sea ice extent (in 1980), the other months have far smaller percent differences between their lowest and highest Arctic values. For yearly average sea ice extents, the Arctic’s lowest value (in 2020) is 18% lower than its highest value (in 1982), the Antarctic’s lowest value (in 2017) is 16% lower than its highest value (in 2014), and the global lowest value (in 2019) is only 12% lower than its highest value (in 1982).

sea ice↗

DOE OSTI2020

Acquisition and Implementation of a Comprehensive Environmental Permits Linking Tool at Savannah River Site - 20234

Historically, Savannah River Nuclear Solutions LLC (SRNS) tracked environmental regulatory commitments and the requirements from hundreds of permits at the Savannah River Site (SRS) using several separate methods, making integrated compliance assurance cumbersome and labor-intensive. When SRNS experienced an increase in environmental issues in 2017, SRNS management and U.S. Department of Energy - Savannah River (DOE-SR) management decided a single, proactive approach was needed to capture environmental permit information (including regulations, Consent Orders, DOE Orders, and any other state or federally issued statement of requirements), track the tasks necessary to ensure compliance with these requirements, and thereby mitigate the risk of noncompliance. SRNS developed a list of mandatory objectives that the tool must meet to function as a Comprehensive Environmental Permits Linking Tool (CEPLT). A key requirement was the ability to map Site permits to their governed locations and display the associated requirements at the compliance point (e.g., outfall, stack, waste unit, etc.). Several options included modifying existing onsite resources, building a custom onsite solution, purchasing an off-the-shelf solution, and contracting an offsite developer to build a custom solution. SRNS concluded an off-the-shelf solution with configuration and customization options would provide the flexibility to fit the unique needs of Savannah River Site (SRS) while taking advantage of industry-tested software and providing a reduced deployment timeline. SRNS chose Gensuite{sup R} a, a cloud-based solution that offers numerous a la carte applications in the environmental, health, and safety arenas, as the best candidate. SRNS selected three (3) integrated applications (Compliance Calendar, Permit Manager, and Mapper) to function as the CEPLT. The Compliance Calendar module allows for creation and tracking of regulatory commitment tasks assigned to responsible environmental professionals. Permit Manager organizes permits and other requirement documents, linking the commitments in each to Compliance Calendar tasks and/or implementing procedures. Mapper provides GIS capability for mapping the data from the other two modules to their physical onsite locations. The CEPLT was configured to allow for other SRS Site Tenants to eventually utilize the applications. Additionally, DOE-SR uses the CEPLT to provide an overview of contractor environmental compliance activities and to organize DOE-specific documents and tasks. The CEPLT fulfilled the requirement of meeting current compliance needs as well as providing the ability to grow as new organizations are incorporated and functionality is expanded. SRNS now uses the CEPLT to more effectively manage permit requirements, improve knowledge transfer, and increase the Site's overall protection of the environment, the Site worker, and the public. Possible future uses of the system include integration of mobile applications for timely communication of potential non-compliant conditions and DOE complex-wide deployment allowing for enhanced DOE site and Head Quarters oversight. Implementation of CEPLT will result in cost savings, both in terms of dollars and man-hours. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2019

Insights from incorporating reference electrodes in symmetric lithium-ion cells with layered oxide or graphite electrodes

Symmetric cells provide complementary means to probe electrochemical processes in lithium-ion batteries. Here, positive and negative electrodes harvested from conventional oxide/graphite cells are cross-paired, and the assembled reference-electrode-bearing symmetric cells are cycled/aged. For graphite symmetric cells, the electrode potentials and impedances remain nearly constant during calendar aging and the parasitic currents are typically small. However, at higher cell voltages when the “positive” graphite potential exceeds 1.0 V vs. Li/Li + , the capacity loss is higher, indicating that even a mild (but prolonged) overdischarge can damage the SEI. For the layered-oxide symmetric cells there are strong parasitic currents and a persistent slide of the electrode potential over time during calendar aging. Significant cell impedance rise, especially at higher hold voltages, is also observed. Curiously, the impedance rise in the “negative” oxide electrode, which experiences potentials below 4.0 V vs. Li/Li + , is greater than in the “positive” oxide electrode that experiences much higher potentials. We postulate that electrolyte oxidation is responsible for the behavior of these oxide symmetric cells, as it supplies electrons (that bind more Li + into the cathode, causing the potential slide) and protons (that contribute to impedance rise). Furthermore, these insights can guide the development of future lithium-ion cell chemistries.

25 ENERGY STORAGE↗

DOE OSTI2025

Quantifying the Reactivity of Isolated Li x Si Domains in Si Anodes Using Operando NMR

The use of Si anodes can greatly improve the energy density of Li-ion batteries. However, understanding and mitigation of calendar aging remains a barrier to commercialization. Here, in this short report, we utilize operando Nuclear Magnetic Resonance (NMR) spectroscopy to detect and quantify lithium silicides (Li x Si) as they form and react within Si anodes in pouch cells during calendar aging. We provide direct experimental evidence of complex aging phenomena in the Si anodes, including both SEI growth and dissolution during storage. Formation of electrochemically isolated Li x Si is also observed, as indicated by the partial persistence of highly lithiated phases after the cell is discharged. Remarkably, we show that these isolated domains can themselves self-discharge over time, suggesting that their detection can be challenging in post-mortem studies. Finally, we show that aging outcomes depend heavily on the type of silicon particles contained within the electrode, and that certain surface coatings can help decrease the reactivity between lithium silicides and the electrolyte.

Li-ion battery↗

DOE OSTI2023

The Effect of the SEI Layer Mechanical Deformation on the Passivity of a Si Anode in Organic Carbonate Electrolytes

The solid electrolyte interphase (SEI) on a Si negative electrode in carbonate-based organic electrolytes shows intrinsically poor passivating behavior, giving rise to unsatisfactory calendar life of Li-ion batteries. Moreover, mechanical strains induced in the SEI due to large volume changes of Si during charge-discharge cycling could contribute to its mechanical instability and poor passivating behavior. This study elucidates the influence that static mechanical deformation of the SEI has on the rate of unwanted parasitic reactions at the Si/electrolyte interface as a function of electrode potential. Further, the experimental approach involves the utilization of Si thin-film electrodes on substrates with disparate elastic moduli, which either permit or suppress the SEI deformation in response to Si volume changes upon charging-discharging. We find that static mechanical stretching and deformation of the SEI results in an increased parasitic electrolyte reduction current on Si. Furthermore, attenuated total reflection and near-field Fourier-transform infrared nanospectroscopy reveal that the static mechanical stretching and deformation of the SEI fosters a selective transport of linear carbonate solvent through, and nanoconfinement within, the SEI. These, in turn, promote selective solvent reduction and continuous electrolyte decomposition on Si electrodes, reducing the calendar life of Si anode-based Li-ion batteries. Finally, possible correlations between the structure and chemical composition of the SEI layer and its mechanical and chemical resilience under prolonged mechanical deformation are discussed in detail.

25 ENERGY STORAGE↗

DOE OSTI2012

2011 Idaho National Laboratory Water Use Report and Comprehensive Well Inventory (Revision 20)

This 2011 Idaho National Laboratory Water Use Report and Comprehensive Well Inventory (Revision 20) provides water use information (monthly annual average and total annual volume) for production and potable water wells at the Idaho National Laboratory for Calendar Year 2011. It also provides detailed information for new, modified, and abandoned (decommissioned) wells and holes. One new well was drilled and completed and one well was modified in Calendar Year 2011. A total of 14 wells and boreholes were reported as decommissioned. Detailed construction information for the new and modified wells is provided. Details are provided for the wells and boreholes that have been decommissioned, and if available, construction diagrams. Location maps are included, provided survey information was available. This report is being submitted in accordance with the Water Rights Agreement between the State of Idaho and the United States, for the United States Department of Energy (dated 1990) and the subsequent Partial Decree for Water Right 34-10901 issued June 20, 2003.

2011 Idaho National Laboratory Water Use Report an↗

DOE OSTI2022

Suppressing Chemical Corrosions of Lithium Metal Anodes

In this study, the lithium metal anode is essential for next-generation high-energy-density rechargeable Li-metal batteries. Although extensive studies have been performed to prolong the cycle life of Li-metal batteries, the calendar life, which associates with the chemical corrosion of Li metal in liquid electrolytes, has not been quantitatively understood. Here, by combing the titration gas chromatography method and cryogenic focused ion beam, a quantitative relationship between the chemical corrosion rate and electrochemically deposited Li morphology in various liquid electrolyte systems is established. It has been identified that the corrosion rate is dominated by the porosity of the deposited Li. The larger the porosity of deposited Li has, the faster the corrosion rate will be. Strategies to mitigate the chemical corrosion on Li thus to extend the calendar life of Li-metal batteries are further proposed. By strictly controlling the stacking pressure during Li plating, Li deposits with ultra-low porosity can be achieved, suppressing the corrosion rate to 0.08 ± 0.16%/day compared with 1.71 ± 0.19%/day of the high-porosity Li.

25 ENERGY STORAGE↗

DOE OSTI2022

Evaluating the roles of electrolyte components on the passivation of silicon anodes

A protocol was recently developed to compare calendar life using a constant potential while monitoring the electrical current required to maintain the potential. Here, this calendar life protocol is used with electrolyte formulations containing various mole fractions of ethylene carbonate (EC), ethyl methyl carbonate (EMC), and LiPF 6 to elucidate the role each component plays in passivation for high silicon anodes. Together, EC and LiPF 6 lead to higher currents, and thus poorer passivation, whereas EMC acts as a spectator. The variation of the components' mole fraction also changes the solid-electrolyte interphase (SEI) composition, as measured by x-ray photoelectron spectroscopy. Importantly, higher LiPF 6 content leads to increased LiF as well as increased current, indicating that higher LiF content does not enhance the passivation of the silicon surface. Finding that EC did not yield a passivating SEI, instead ethylene sulfite, sulfolane, and propylene carbonate (PC) were used in place of EC. Using ethylene sulfite and sulfolane resulted in poorer passivation compared to EC, whereas PC resulted in superior passivation. As a result, the superior passivation may be related to more stable lithium-solvent complexes.

25 ENERGY STORAGE↗

DOE OSTI2020

Linking Hydrology and Dissolved Organic Matter Characteristics in a Subtropical Wetland: A Long-Term Study of the Florida Everglades

Dissolved organic matter (DOM) acts as an important biogeochemical component of aquatic ecosystems that controls nutrient cycling, influences water quality, and links terrestrial and oceanic carbon pools, yet long-term studies of how changing environmental drivers alter its abundance and composition are rare. Using a ten-year, spatially explicit dataset from Everglades National Park (ENP), a globally significant wetland, we investigated the relationships between DOM quality/quantity and hydrologic/climatic drivers along two contrasting marsh-estuarine transects based on generalized linear modeling and a cumulative sums analysis. Analyses revealed distinct spatial, seasonal, and interannual patterns in variability of DOC and optical properties. Landscape-scale seasonal patterns showed an enrichment in microbial-like and protein-like DOM during the dry season relative to the wet season. We found that, while some compositional constituents varied with the solar calendar, responsive to temperature and photoperiod, others varied with the hydrologic calendar. Independent water level and discharge effects indicated strong hydrologic control on DOM quality that differed between the two transects, evidencing differences in their connectivity to areas of high agricultural activity. Across all sites, a significant long-term increasing trend in the fluorescence index was observed, associated with a positive correlation with precipitation and also potential changes in agricultural inputs, with other features associated with drought and hurricanes. Lastly, the cumulative sums analysis revealed differences between the two transects in the sensitivity of DOM composition to decreased water levels associated with 30-year climate scenarios, with the less hydrologically dynamic transect exhibiting greater potential sensitivity.

54 ENVIRONMENTAL SCIENCES↗