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DOE OSTI2021

Self-powered Heating: Efficiency Analysis

Conventional fuel-fired heating devices such as furnaces, boilers, and water heaters have fuel efficiency less than 100% on the basis of higher heating value. They also require electricity from the electric grid to power parasitic loads such as blowers, pumps, fans, and ignitors. The primary energy efficiency of the device accounts for both fuel used on-site and primary energy used off-site to produce electric power used by the device. This work compares conventional fuel-fired heating devices to two types of self-powered devices. A self-powered device (SPD) integrates a power cycle onboard to eliminate consumption of grid electricity. We assume that all heat rejected by the onboard power cycle is added to the process fluid, so that, compared with a conventional device, the same amount of heat is provided to the process fluid and the same amount of fuel is consumed, but grid electricity consumption is eliminated. The first SPD type is the basic one: exactly the electricity required is generated. The second type considered is the SPD with heat pump (SPD-HP), in which the power cycle generates more electricity than needed for parasitic loads, and the excess electricity is used to power a heat pump. The heat pump extracts additional heat from the ambient to boost efficiency. Both SPD and SPD-HP self-consume all the generated electricity, in contrast to combined heat and power (CHP) systems that export electricity. In this work, equations are derived to express the efficiency of three classes of heating devices: conventional (consuming grid electricity), self-powered (consuming no grid electricity), and self-powered with heat pump. The efficiency of each is derived as a function of up to six factors: (1) the fraction of combustion heat captured, (2) the rate of parasitic power consumption, (3) the fraction of electric energy dissipated as useful heat, (4) the power cycle conversion efficiency, (5) the grid efficiency, when applicable, and (6) the heat pump COP, when applicable. Scenarios are identified in which it is possible to achieve efficiency greater than 100% on a higher heating value basis. Plausible configurations using existing technology options are outlined.

Gluesenkamp, Kyle↗

DOE OSTI2021

Process Heat for Chemical Industry

Process heating with nuclear energy can reduce greenhouse gas emissions by reducing combustion of fossil fuels in fired heaters as steam boilers. Light water reactors can replace the majority of steam duties used by industry; however, high temperature processes such as steam methane reforming require advanced high temperature reactors. Here, guidance on matching the scale of nuclear reactors with specific industries is provided. Principles of heat transport, temperature boosting, and substitution for hot combustion gases are also discussed in this section.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

DOE OSTI2025

Co-Firing Switchgrass and Waste Coal in A Power Plant: A Techno-Economic and Life Cycle Evaluation for The Ohio River Valley (SWITCH) (Final Technical Report for Ohio State/FE0032204)

Abandoned coal mine lands (AMLs) represent one of the most persistent environmental challenges in the United States. Prior to the enactment of the Surface Mining Control and Reclamation Act (SMCRA) in 1977, coal mining operations were not legally required to reclaim disturbed lands, leaving behind approximately 500,000 AML sites nationwide. These sites pose severe environmental and health risks, including acid mine drainage, soil and water contamination, and spontaneous combustion of waste coal piles. Millions of Americans live within one mile of these AMLs, underscoring the urgency of remediation. Traditional reclamation practices, such as planting cool-season grasses, often fail to fully restore ecological function or leverage the economic potential of these lands. This project addressed these challenges by developing integrated strategies for resource recovery, land reclamation, and sustainable energy production. This project evaluated an integrated strategy to convert this liability into an opportunity by recovering waste coal and co-firing it with switchgrass (Panicum virgatum L.) cultivated on reclaimed or marginal AML areas in existing coal-fired power plants. Switchgrass not only provides a renewable feedstock but also aids in land reclamation and carbon sequestration. 1) Remote Sensing and Machine Learning for Waste Coal Identification Using Sentinel-2 satellite imagery and supervised classification, we applied four machine learning models to detect historical waste coal piles. Random Forest achieved the highest accuracy (precision: 86%, recall: 77%). Time-series analysis revealed gradual vegetation recovery since 1986, indicating natural reclamation processes in historical sites, while active mining areas showed ongoing disturbance. This workflow enables scalable monitoring and prioritization of reclamation efforts. 2) UAS-Based Stockpile Volume Estimation To quantify recoverable waste coal, we evaluated Unmanned Aerial Systems (UAS) equipped with Light Detection and Ranging (LiDAR) and multispectral sensors. Structure-from-Motion (SfM) photogrammetry combined with interpolated Digital Terrain Models (DTMs) achieved strong agreement with LiDAR reference volumes (Root Mean Square Error (RMSE) ≈147 m 3 , Mean Absolute Percentage Error (MAPE) ≈2%). Sensitivity analysis confirmed that spatial resolution significantly influences accuracy, emphasizing the need for high-resolution data for precise volume estimation. This approach offers a scalable, cost-effective, and accurate alternative to conventional ground-based surveys. 3) Switchgrass Cultivation for Bioenergy and Water Quality Improvement We assessed the hydrological and water quality impacts of converting AMLs to switchgrass production areas using the Soil and Water Assessment Tool (SWAT). Results showed that converting 10% of the watershed area into the switchgrass production zone reduced streamflow by 3.1%, total suspended solids by 18.1%, total nitrogen by 7.6%, and total phosphorus by 6.2%, while achieving biomass yields of 8.6–9.2 metric tons per hectare. These findings highlight switchgrass as a dual-benefit strategy for land reclamation and bioenergy feedstock production. 4) Integrated Co-Firing and CCS for Carbon-Negative Power Generation We modeled co-firing scenarios using the Power Plant Flexible Model (PPFM) to evaluate plant efficiency, greenhouse gas (GHG) emissions, and levelized cost of electricity (LCOE). Without carbon capture and storage (CCS), increasing switchgrass co-firing ratios reduced LCOE from $\$$150/MWh at 0% biomass to $\$$110/MWh at full substitution. Under CCS, costs remained higher (~$\$$250/MWh at 0% biomass) but decreased to $\$$200/MWh at 100% biomass, while enabling net-zero or carbon-negative electricity due to switchgrass sequestration benefits. Although CCS introduced efficiency penalties, pairing it with biomass co-firing offset these impacts and maximized climate benefits. Overall, optimizing co-firing ratios between 60-100%, supported by reliable logistics and storage strategies, emerged as a practical pathway to balance affordability, sustainability, and net-zero or negative GHG emissions while promoting productive reuse of AMLs.

01 COAL, LIGNITE, AND PEAT↗

NASA NTRS2010

CECE: Expanding the Envelope of Deep Throttling in Liquid Oxygen/Liquid Hydrogen Rocket Engines For NASA Exploration Missions

As one of the first technology development programs awarded by NASA under the Vision for Space Exploration, the Pratt & Whitney Rocketdyne (PWR) Deep Throttling, Common Extensible Cryogenic Engine (CECE) program was selected by NASA in November 2004 to begin technology development and demonstration toward a deep throttling, cryogenic engine supporting ongoing trade studies for NASA s Lunar Lander descent stage. The CECE program leverages the maturity and previous investment of a flight-proven hydrogen/oxygen expander cycle engine, the PWR RL10, to develop technology and demonstrate an unprecedented combination of reliability, safety, durability, throttlability, and restart capabilities in a high-energy cryogenic engine. The testbed selected for the deep throttling demonstration phases of this program was a minimally modified RL10 engine, allowing for maximum current production engine commonality and extensibility with minimum program cost. Three series of demonstrator engine tests, the first in April-May 2006, the second in March-April 2007 and the third in November-December 2008, have demonstrated up to 13:1 throttling (104% to 8% thrust range) of the hydrogen/oxygen expander cycle engine. The first two test series explored a propellant feed system instability ("chug") environment at low throttled power levels. Lessons learned from these two tests were successfully applied to the third test series, resulting in stable operation throughout the 13:1 throttling range. The first three tests have provided an early demonstration of an enabling cryogenic propulsion concept, accumulating over 5,000 seconds of hot fire time over 27 hot fire tests, and have provided invaluable system-level technology data toward design and development risk mitigation for the NASA Altair and future lander propulsion system applications. This paper describes the results obtained from the highly successful third test series as well as the test objectives and early results obtained from a fourth test series conducted over March-May 2010

Giuliano, Victor J.↗

DOE OSTI2025

Tritium Containment Vessel Response to Thermal and Mechanical Abuse Environments for Fire Safety Assessments

This report evaluates leakage behavior from tritium containment vessels under thermal abuse and combined thermal-mechanical abuse conditions to better understand safety implications for releases occurring in a fire scenario. Surrogate gases were used for all tests in this report. Leakage through the valves from thermal pressurization was observed when heating rates >0.8°C/s were sustained to >300°C. Gas plumes were visualized from vessels that were heated above 260°C and then dropped.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2020

Techno-economic prospects for producing Fischer-Tropsch jet fuel and electricity from lignite and woody biomass with CO 2 capture for EOR

This work explores the prospective techno-economic performance of facilities that produce low- and net-negative-carbon liquid transportation fuels and electricity with CO 2 capture for enhanced oil recovery. The lignite and biomass-to-jet fuel process is based on KBR’s TRIG gasifier, Rectisol (for sulfur removal and CO 2 capture), fixed-bed low temperature Fischer-Tropsch synthesis of liquid fuels, and Brayton/Rankine combined cycles to convert synthesis/refining off-gases and waste heat to electricity. This work leverages a recent, highly-detailed assessment of a prospective first-of-a-kind (FOAK) demonstration facility to develop highly detailed Aspen Plus process simulations for nine prospective N th -of-a-kind (NOAK) plant equipment configurations. Component-level capital costs from the FOAK study are scaled and adjusted to reflective prospective learning-by-doing to estimate capital costs for the NOAK designs. NOAK plant economic performance is found to be largely insensitive to variations in plant configurations and electricity output fraction, but biomass input fraction significantly affects profitability. Facilities that consume only carbon–neutral biomass, with no lignite co-feed, have significantly net-negative carbon emissions and the most favorable prospective economics when carbon emissions are priced. For these facilities, the crude oil price required for plant economic viability falls rapidly from $\$$100/bbl as carbon emission prices increase above $\$$120/tonne CO 2eq . In general, plants that co-fire lignite with biomass are less profitable (than 100% biomass plants) due to their higher net greenhouse gas emissions.

09 BIOMASS FUELS↗

NASA NTRS1999

Robust Low Cost Aerospike/RLV Combustion Chamber by Advanced Vacuum Plasma Process

Next-generation, regeneratively cooled rocket engines will require materials that can withstand high temperatures while retaining high thermal conductivity. At the same time, fabrication techniques must be cost efficient so that engine components can be manufactured within the constraints of a shrinking NASA budget. In recent years, combustion chambers of equivalent size to the Aerospike chamber have been fabricated at NASA-Marshall Space Flight Center (MSFC) using innovative, relatively low-cost, vacuum-plasma-spray (VPS) techniques. Typically, such combustion chambers are made of the copper alloy NARloy-Z. However, current research and development conducted by NASA-Lewis Research Center (LeRC) has identified a Cu-8Cr-4Nb alloy which possesses excellent high-temperature strength, creep resistance, and low cycle fatigue behavior combined with exceptional thermal stability. In fact, researchers at NASA-LeRC have demonstrated that powder metallurgy (P/M) Cu-8Cr-4Nb exhibits better mechanical properties at 1,200 F than NARloy-Z does at 1,000 F. The objective of this program was to develop and demonstrate the technology to fabricate high-performance, robust, inexpensive combustion chambers for advanced propulsion systems (such as Lockheed-Martin's VentureStar and NASA's Reusable Launch Vehicle, RLV) using the low-cost, VPS process to deposit Cu-8Cr-4Nb with mechanical properties that match or exceed those of P/M Cu-8Cr-4Nb. In addition, oxidation resistant and thermal barrier coatings can be incorporated as an integral part of the hot wall of the liner during the VPS process. Tensile properties of Cu-8Cr-4Nb material produced by VPS are reviewed and compared to material produced previously by extrusion. VPS formed combustion chamber liners have also been prepared and will be reported on following scheduled hot firing tests at NASA-Lewis.

Holmes, Richard↗

DOE OSTI2023

Cost details from front-end engineering design of piperazine with the advanced stripper

This Front-End Engineering Design (FEED) was funded by the U.S. Department of Energy (DOE) to estimate the cost to capture and compress 90% of the CO 2 from an existing natural gas combined cycle (NGCC) in Denver City, Texas, USA. The FEED used the PZAS (Piperazine with the Advanced Stripper) 2G amine scrubbing technology developed and modeled by The University of Texas at Austin. This FEED is unique in providing more public cost details than other FEEDs funded by DOE. The primary objective of the FEED was to provide a comprehensive estimate for the total installed cost of the capture plant. The estimated capital cost of NGCC at the Mustang Station is $\$727$ million for a capacity of 460 MW and 1.6 million tonnes CO 2 /yr. This includes a contingency of $\$104.6$ million and a contractor’s profit of $\$60.1$ million. The total direct field cost is $\$384.1$ million. With an optimistic fuel value of $\$3$/MMBtu, the estimated cost of capture varies from $\$85$/t at 4% IRR/85% load to $\$170$/t at 10% IRR/52% load. Air cooling is technically feasible but expensive. The air cooling systems for the water wash and pump-around intercooling account for 23.4% of the direct cost. The gas-fired boilers represent only 4% of the direct costs, but steam extraction would reduce energy cost, free up cooling water, and reduce the direct costs of processing additional flue gas and CO 2 from the boilers. The absorbers represent 9.6% of the direct cost in this FEED with no direct contact cooler and only 7.6 m of packing. Furthermore, the solvent cross exchangers are less expensive than expected (2.5% of direct costs). Doubling the number of these exchangers could reduce the heat duty from 3.0 to 2.5 GJ/t CO 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS2002

Status of the RBCC Direct-Connect Mixer Combustor Experiment

The NASA Glenn Research Center is developing hydrogen based combined cycle propulsion technology for a single-stage-to-orbit launch vehicle application under a project called GTX. Rocket Based Combined Cycle (RBCC) propulsion systems incorporate one or more rocket engines into an airbreathing flow path to increase specific impulse as compared to an all rocket-powered vehicle. In support of this effort, an RBCC direct-connect test capability was established at the Engine Components Research Laboratory to investigate low speed, ejector ramjet, and initial ramjet operations and performance. The facility and test article enables the evaluation of two candidate low speed operating schemes; the simultaneous mixing and combustion (SMC) and independent ramjet stream (IRS). The SMC operating scheme is based on the fuel rich operations of the rocket where performance depends upon mixing between the rocket plume and airstream. In contrast, the IRS scheme fuels the airstream separately and uses the rocket plume to ignite the fuel-air mixture. This paper describes the test hardware and facility upgrades installed to support the RBCC tests. It also defines and discusses low speed technical challenges being addressed by the experiments. Finally, preliminary test results, including rocket risk mitigating tests, unfueled airflow tests, and the integrated system hot fire test will be presented.

Walker, James F.↗

NASA NTRS2002

Status of the RBCC Direct-Connect Mixer Combustor Experiment

Walker, James F.↗

NASA NTRS2001

Robust Low Cost Liquid Rocket Combustion Chamber by Advanced Vacuum Plasma Process

Next-generation, regeneratively cooled rocket engines will require materials that can withstand high temperatures while retaining high thermal conductivity. Fabrication techniques must be cost efficient so that engine components can be manufactured within the constraints of shrinking budgets. Three technologies have been combined to produce an advanced liquid rocket engine combustion chamber at NASA-Marshall Space Flight Center (MSFC) using relatively low-cost, vacuum-plasma-spray (VPS) techniques. Copper alloy NARloy-Z was replaced with a new high performance Cu-8Cr-4Nb alloy developed by NASA-Glenn Research Center (GRC), which possesses excellent high-temperature strength, creep resistance, and low cycle fatigue behavior combined with exceptional thermal stability. Functional gradient technology, developed building composite cartridges for space furnaces was incorporated to add oxidation resistant and thermal barrier coatings as an integral part of the hot wall of the liner during the VPS process. NiCrAlY, utilized to produce durable protective coating for the space shuttle high pressure fuel turbopump (BPFTP) turbine blades, was used as the functional gradient material coating (FGM). The FGM not only serves as a protection from oxidation or blanching, the main cause of engine failure, but also serves as a thermal barrier because of its lower thermal conductivity, reducing the temperature of the combustion liner 200 F, from 1000 F to 800 F producing longer life. The objective of this program was to develop and demonstrate the technology to fabricate high-performance, robust, inexpensive combustion chambers for advanced propulsion systems (such as Lockheed-Martin's VentureStar and NASA's Reusable Launch Vehicle, RLV) using the low-cost VPS process. VPS formed combustion chamber test articles have been formed with the FGM hot wall built in and hot fire tested, demonstrating for the first time a coating that will remain intact through the hot firing test, and with no apparent wear. Material physical properties and the hot firing tests are reviewed.

Holmes, Richard↗

NASA NTRSDate not supplied

The Side Plume of Magnetically Shielded Hall Thrusters

A combination of near-thruster laser-induced fluorescence and far-field plasma probe measurements collected from two magnetically shielded Hall thrusters have shown that there exist an independent ion population of medium-energy (on average, 60-190 eV) exiting out the side (60° to 100° from firing axis) of the thrusters. Studying the trends with background pressure and known discrepancies between the laser-induced fluorescence and far-field plasma probe data suggest that at zero pressure the side plume is likely to exhibit higher energy and lower density than at facility background pressures. The possibility that these ions were produced by the modified two-stream instability is explored and while the agreement is good, there are areas of notable disagreement. Based on the idea that production of the side plume and channel exit striations are due to the same plasma wave actions, a theory was explored that explains why striations form under certain circumstances but not others. Another theory, based on the idea that side plume production only occurs over certain portion of the global discharge oscillation cycle, was also explored and areas of disagreement were identified. While the exact mechanism for side plume acceleration remains unclear, if the theory behind side plume production is correct, then side plume can be expected to be present in a wide range of magnetically-shielded as well as non-shielded Hall thrusters.

Hall thruster↗

NASA NTRSDate not supplied

The Side Plume of Magnetically Shielded Hall Thrusters

Electric propulsion↗

DOE OSTI2022

Integration of Superconducting Magnetic Energy Storage (SMES) Systems Optimized with Second-Generation, High-Temperature Superconducting (2G-HTS) Technology with a Major Fossil-Fueled Asset

Utility companies and fossil fueled generation assets are seeking combinations of “hybrid energy storage” to allow power to be provided in advance of, and to otherwise complement, peaking natural gas-fired generation. American Maglev Technology of Florida Inc. (AMT) learned during the Phase I program based on interactions with NRG Energy (NRG) that energy storage such as superconducting magnetic energy storage (SMES) can qualify as a Black Start unit in most markets, ensuring orderly re-start of grid operations and fossil fueled power plants and serving as an important asset of hybrid energy storage technology. In conjunction with the University of Houston (UH), AMT and NRG are working together to scale up low-cost, high- efficiency, second-generation high-temperature superconducting (2G-HTS) technology for deployment across several markets, with a primary focus on the commercial development of utility grid-scale SMES (g-SMES) systems. Ultimately the program confirmed that the novel g-SMES design can meet the performance and financial requirements of the fossil power plant industry, while exhibiting continuous grid-voltage regulation; cost-effective, peak-hour energy storage with almost infinite life; increased input/output efficiency; and the capability to undergo millions of charging cycles, without degradation, representing a significant improvement over lithium ion and other conventional storage technologies. We believe wide scale deployment of this technology is feasible and practical when compared to the higher life cycle cost and relatively short lifespan of chemical batteries. Based on these findings, the future for deployment of SMES at many fossil-fueled power plants exceeding 100MW capability is bright. Further de-risking g-SMES technology would pave the way for the construction of a subscale prototype. Eventually, scaled-down versions of SMES are expected to be competitive with the multi-billion-dollar lithium-ion market for a wide range of commercial, industrial, and transportation uses. There is long-term potential for commercialization and widespread deployment of this disruptive technology, which would spawn a new worldwide supply chain and create domestic, high-tech manufacturing jobs in the green industry.

20 FOSSIL-FUELED POWER PLANTS↗

DOE OSTI2023

Climate warming and elevated CO 2 alter peatland soil carbon sources and stability

Peatlands are an important carbon (C) reservoir storing one-third of global soil organic carbon (SOC), but little is known about the fate of these C stocks under climate change. Here, we examine the impact of warming and elevated atmospheric CO 2 concentration (eCO 2 ) on the molecular composition of SOC to infer SOC sources (microbe-, plant- and fire-derived) and stability in a boreal peatland. We show that while warming alone decreased plant- and microbe-derived SOC due to enhanced decomposition, warming combined with eCO 2 increased plant-derived SOC compounds. We further observed increasing root-derived inputs (suberin) and declining leaf/needle-derived inputs (cutin) into SOC under warming and eCO 2 . The decline in SOC compounds with warming and gains from new root-derived C under eCO 2 , suggest that warming and eCO 2 may shift peatland C budget towards pools with faster turnover. Together, our results indicate that climate change may increase inputs and enhance decomposition of SOC potentially destabilising C storage in peatlands.

54 ENVIRONMENTAL SCIENCES↗

NASA NTRS2013

Cu-Cr-Nb-Zr Alloy for Rocket Engines and Other High-Heat- Flux Applications

Rocket-engine main combustion chamber liners are used to contain the burning of fuel and oxidizer and provide a stream of high-velocity gas for propulsion. The liners in engines such as the Space Shuttle Main Engine are regeneratively cooled by flowing fuel, e.g., cryogenic hydrogen, through cooling channels in the back side of the liner. The heat gained by the liner from the flame and compression of the gas in the throat section is transferred to the fuel by the liner. As a result, the liner must either have a very high thermal conductivity or a very high operating temperature. In addition to the large heat flux (>10 MW/sq m), the liners experience a very large thermal gradient, typically more than 500 C over 1 mm. The gradient produces thermally induced stresses and strains that cause low cycle fatigue (LCF). Typically, a liner will experience a strain differential in excess of 1% between the cooling channel and the hot wall. Each time the engine is fired, the liner undergoes an LCF cycle. The number of cycles can be as few as one for an expendable booster engine, to as many as several thousand for a reusable launch vehicle or reaction control system. Finally, the liners undergo creep and a form of mechanical degradation called thermal ratcheting that results in the bowing out of the cooling channel into the combustion chamber, and eventual failure of the liner. GRCop-84, a Cu-Cr-Nb alloy, is generally recognized as the best liner material available at the time of this reporting. The alloy consists of 14% Cr2Nb precipitates in a pure copper matrix. Through experimental work, it has been established that the Zr will not participate in the formation of Laves phase precipitates with Cr and Nb, but will instead react with Cu to form the desired Cu-Zr compounds. It is believed that significant improvements in the mechanical properties of GRCop-84 will be realized by adding Zr. The innovation is a Cu-Cr-Nb-Zr alloy covering the composition range of 0.8 to 8.1 weight percent Cr, 0.7 to 7.2 weight percent Nb, 0.1 to 1.5 weight percent Zr, and balance Cu. The alloy combines two known strengthening mechanisms - dispersion strengthening by Cr2Nb precipitates (GRCop-84), and precipitation strengthening by CuxZr (AMZIRC) - to produce a synergistic increase in the capabilities of the alloy with the goal of achieving properties greater than either of the methods could achieve alone. The anticipated advantages of the alloy are higher strength at temperatures up to 700 C, improved creep strength, and significantly higher LCF lives relative to GRCop-84. The thermal expansion, thermal conductivity, and processing of the alloy are anticipated to remain largely unchanged relative to GRCop-84.

Ellis, David L.↗

DOE OSTI2025

Examples of X-Ray Characterization Techniques in Energy Storage Research

Lithium-ion batteries have revolutionized the portable electronics and transportation sectors. Their performance is often critically dependent on the crystal structures of the anode and cathode electrode materials, which must enable the transport and reversible storage of lithium ions into and out of the lattice. Because lithium is a low-Z element, characterization of materials for lithium-ion batteries can be particularly challenging. Regardless, X-ray techniques enable analysis of material structures to better understand how battery materials perform and degrade, particularly when combined with other materials characterization and electrochemical characterization techniques. While X-ray techniques are most often used in battery research for phase identification of crystal structures, X-ray characterization techniques are also used for a wide variety of other purposes. I will discuss several examples from my research with various collaborators on several projects that highlight the impact that X-ray characterization techniques can have on battery research. The first example will focus on low-temperature microwave-assisted solvothermal synthesis of vanadium-doped LiFePO4 cathode materials for lithium-ion batteries. (1,2) Through a combination of electrochemical and materials characterization, we determined that low temperature synthesis resulted in metastable phases that enabled incorporation of higher dopant levels than resulting from high-temperature synthesis of thermodynamically stable phases. Rietveld refinement of X-ray diffraction data enabled understanding of how lattice parameters changed with doping levels and synthesis temperature. X-ray absorption near edge spectroscopy enabled understanding of the vanadium and iron oxidation states to confirm how vacancies in the structure caused by doping were charge compensated. This was important to understand because the literature suggests doping can improve LiFePO4 electrical conductivity, which improves battery charge and discharge rates. The second example will focus on understanding residual strain in lithium metal anodes. Lithium-ion batteries typically use graphite anodes, but the charge-storage capacity can be theoretically improved ~10x by using lithium metal as the anode material instead. However, lithium anodes suffer from growth of high-aspect-ratio features, such as dendrites, that can pierce nanoporous polymer separators and lead to short circuits and fires. External pressure is commonly applied to cells to enable better morphological control. We hypothesized that applied pressure may promote strain and possibly work hardening during electrochemical cycling, which motivated us to look for evidence of residual strain in lithium metal cycled under applied pressure using X-ray diffraction and sin2(..psi..) analysis. We found that lithium electrodeposited under high pressure exhibited in-plane compressive strain and that that lithium electrodeposited under low pressure did not. (3) The residual strain that accompanies electrodeposition under high pressure may lead to work hardening, which may explain how a soft metal like lithium can puncture separators and why higher pressure does not always decrease short circuits. (4-6) References: 1) Harrison, K. L.; Manthiram, A. Microwave-Assisted Solvothermal Synthesis and Characterization of Metastable LiFe1- x (VO) x PO4 Cathodes. Inorganic chemistry 2011, 50(8), 3613-3620. 2) Harrison, K. L.; Bridges, C. A.; Paranthaman, M. P.; Segre, C. U.; Katsoudas, J.; Maroni, V. A.; Idrobo, J. C.; Goodenough, J. B.; Manthiram, A. Temperature Dependence of Aliovalent-Vanadium Doping in LiFePO4 Cathodes. Chemistry of Materials 2013, 25(5), 768-781. 3) Rodriguez, M. A.; Harrison, K. L.; Goriparti, S.; Griego, J. J.; Boyce, B. L.; Perdue, B. R. Use of a Be-Dome Holder for Texture and Strain Characterization of Li Metal Thin Films via Sin2 (..psi..) Methodology. Powder Diffraction 2020, 35(2), 89-97. 4) Jungjohann, K. L.; Gannon, R. N.; Goriparti, S.; Randolph, S. J.; Merrill, L. C.; Johnson, D. C.; Zavadil, K. R.; Harris, S. J.; Harrison, K. L. Cryogenic Laser Ablation Reveals Short-Circuit Mechanism in Lithium Metal Batteries. ACS Energy Letters 2021, 6(6), 2138-2144. 5) Harrison, K. L.; Merrill, L. C.; Long, D. M.; Randolph, S. J.; Goriparti, S.; Christian, J.; Warren, B.; Roberts, S. A.; Harris, S. J.; Perry, D. L. Cryogenic Electron Microscopy Reveals That Applied Pressure Promotes Short Circuits in Li Batteries. Iscience 2021, 24(12). 6) Harrison, K. L.; Goriparti, S.; Merrill, L. C.; Long, D. M.; Warren, B.; Roberts, S. A.; Perdue, B. R.; Casias, Z.; Cuillier, P.; Boyce, B. L. Effects of Applied Interfacial Pressure on Li-Metal Cycling Performance and Morphology in 4 M LiFSI in DME. ACS Applied Materials & Interfaces 2021, 13(27), 31668-31679.

batteries↗

DOE OSTI2024

The key role of forest disturbance in reconciling estimates of the northern carbon sink

Northern forests are an important carbon sink, but our understanding of the driving factors is limited due to discrepancies between dynamic global vegetation models (DGVMs) and atmospheric inversions. We show that DGVMs simulate a 50% lower sink (1.1 ± 0.5 PgC yr –1 over 2001–2021) across North America, Europe, Russia, and China compared to atmospheric inversions (2.2 ± 0.6 PgC yr –1 ). We explain why DGVMs underestimate the carbon sink by considering how they represent disturbance processes, specifically the overestimation of fire emissions, and the lack of robust forest demography resulting in lower forest regrowth rates than observed. We reconcile net sink estimates by using alternative disturbance-related fluxes. We estimate carbon uptake through forest regrowth by combining satellite-derived forest age and biomass maps. We calculate a regrowth flux of 1.1 ± 0.1 PgC yr –1 , and combine this with satellite-derived estimates of fire emissions (0.4 ± 0.1 PgC yr –1 ), land-use change emissions from bookkeeping models (0.9 ± 0.2 PgC yr –1 ), and the DGVM-estimated sink from CO 2 fertilisation, nitrogen deposition, and climate change (2.2 ± 0.9 PgC yr –1 ). The resulting ‘bottom-up’ net flux of 2.1 ± 0.9 PgC yr –1 agrees with atmospheric inversions. The reconciliation holds at regional scales, increasing confidence in our results.

54 ENVIRONMENTAL SCIENCES↗