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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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329 records · Page 19

Uncovering the Relationship between Diameter and Height of Electrodeposited Lithium Protrusions in a Rigid Electrolyte

A promising approach for enabling rechargeable batteries with significantly higher energy densities than current lithium-ion batteries is by deploying lithium-metal anodes. However, the growth of lithium protrusions during charging presents significant challenges. Since these protrusions are often branched and filamentous in conventional liquid electrolytes, this problem is referred to in the literature as the “dendrite problem”. While solid electrolytes have the potential to solve this problem, protrusions grow in all electrolytes when the current density exceeds a critical value. Fundamentally understanding the formation is necessary to develop a rational approach for increasing the critical current density, but it is challenging due to the complex interplay between electrochemical and material properties. The diameters and heights of protrusions on lithium-metal anodes stabilized by a rigid block copolymer electrolyte were measured in situ by synchrotron hard X-ray microtomography. The diameter of the shorting protrusions increased linearly with increasing electrolyte thickness. Further, a universal linear relationship between protrusion height and diameter of both shorting and non-shorting protrusions was observed. A model based on the concentrated solution theory was used to establish the electrochemical and mechanical sources for our observations. Here, the computational analysis indicates that elastic and plastic deformation of both the lithium metal and the polymer are important to describe protrusion growth. Both stress-induced current density effects due to the deformation of the electrolyte near the protrusion and plastic deformation of lithium metal combine to give the counterintuitive result: the fastest-growing protrusions have the largest diameter.

25 ENERGY STORAGE↗

Magnetohydrodynamics (MHD) Aerocapture System for Enabling Faster-Larger Planetary Science & Human Exploration Missions

Since our completing the NIAC Phase I NIAC on this Advanced Aerocapture System, NASA Langley Research Center has funded or supported a number of studies and code enhancements through its Center Innovation Fund (CIF) and NASA’s NSTGRO and Internship Programs to mature the analysis capabilities and quantify the merits of the MHD Aerocapture System technology. These efforts have resulted in a plug and play analysis capability for assessing MHD aerocapture system performance for arrival at many planetary bodies of interest. Our efforts have especially focused on the potential mass savings for improving the capacity for science observations at Neptune and Triton. A re-cent Forbes article published “‘Orbital mechanics is probably going to decide for us whether we go to Uranus or Neptune because we need to flyby Jupiter,’ said Kunio Sayanagi at Hampton University, Virginia, who also worked on the Neptune Odyssey proposal…. Exactly when a mission can be sent to Uranus, or Neptune, depends on the relative position of Jupiter, which can help give a spacecraft a gravitational slingshot. That drastically shortens the cruise phase.” [1] Since shortening the cruise phase is important for these science missions, any mass savings enabled by the MHD Aerocapture System could be reallocated to increasing Thermal Protection System mass to allow faster arrival speeds and/or for onboarding additional payloads such as science instruments, batteries, or propellant for conducting more science for longer durations in the desired orbits. The analysis steps and codes for conducting trades and sizing vehicles for aerocapture are as follows: Step 1 is to conduct aeroheating analysis using LAURA of the selected entry vehicle shape to identify locations on the forebody where ionization and flow velocity are sufficient for producing Lo-rentz forces. LAURA is a multiblock structured grid finite-volume CFD solver developed at the NASA Langley Research Center. [2] LAURA has been used for aerothermal analysis support of the entry, de-scent and landing (EDL) phase of interplanetary missions over the last three decades [3-7]. Step 2 is to port the LAURA results into CFDWARP to calcu-late electrical and thermal conductivities of ionized flow for sizing MHD patch system and calculating Lorentz forces needed for controls analysis. CFDWARP is a CFD code that uses advanced nu-merical methods that enable the simulation of the full coupling between the aerodynamics, the magne-tohydrodynamics, and the non-neutral plasma sheaths. CFDWARP has the unique capability to simulate efficiently the non-neutral sheaths (near the electrodes) in coupled form with the quasi-neutral bulk MHD flow [8-11]. Step 3 is to link re-sults from LAURA and CFDWARP into POST2 for calculating entry trajectories and comparing MHD control results with other aerodynamic control strategies. The Program to Optimize Simulated Tra-jectories II (POST2) is a generalized point mass, discrete parameter targeting and optimization pro-gram. POST2 provides the capability to target and optimize point mass trajectories for multiple pow-ered or un-powered vehicles near an arbitrary rotat-ing, oblate planet [12]. Step 4: TPS sizing was per-formed using the Fully Implicit Ablation and Ther-mal-response code (FIAT) tool which computes the transient one-dimensional thermal response and surface thermochemistry of a multilayer stackup of thermal protection, bonding, and structural materi-als subject to aeroheating on one surface [13]. The sizing and margining methodology used was based on the approach documented by Mahzari and Milos [14] for the dual-layered heatshield for extreme entry environment technology (DL-HEEET) TPS concept. TPS analysis utilizes trajectory information from POST2. Using this step-wise plug and play MHD Aerocapture performance assessment process, our analysis targets a Neptune aerocapture trajectory that will place the spacecraft in an observation orbit for Triton. [15]. Magnetohydrodynamic (MHD) control of a 4.5-meter diameter MSL-style capsule resulted in TPS mass savings of nearly 2000 kg when using an MHD system mass of under 200 kg. The flight path for a vehicle using the MHD control strategy has a much lower heat rate and heat load compared to the conventional aerodynamic aerocapture strategies known as bank angle con-trolled (BAC) and direct force controlled (DFC). Both BAC and DFC have heat rates significantly greater than 1500 W/cm2 typically used as an upper limit for PICA. Thus, DL-HEEET TPS concept was required for the BAC and DFC control strategies. However, considering the more benign environ-ments for the MHD case, additional TPS concepts with improved mass efficiency were also assessed. PICA was considered for the MHD controlled strat-egy since the maximum heat rate was well within the limits (<1500 W/cm2) of PICA. TPS sizing re-sulted in a significant mass reduction. The PICA layer for this sizing case was about 7.8 cm. As a point of reference, the Mars 2020 mission, which used this same PICA concept, had a PICA thickness of 3.18 cm [16]. The trajectories used for the TPS sizing originat-ed from the POST2 simulations. The current, I, to an electromagnet configuration can be manipulated to allow for active control of the vehicle. Manipula-tion of the current, I, changes the magnetic field, B, which affects the Lorentz force and therefore the MHD drag force on the vehicle. Our analysis in-cluded both open-loop and close-loop control. Closed-loop control will enable improved overall performance when taking into account mission level uncertainties, such as interplanetary delivery errors and atmospheric modeling uncertainties. The open-loop and closed-loop MHD control cases do not dip as deep into the atmosphere as the aerodynamic cases. Three types of aerodynamic-only approach-es are investigated: bank angle modulation (BAM), director force control (DFC), and Drag Modulated. BAM and DFC make use of vehicle aerodynamic angles to steer the vehicle. Thus, changing the aer-odynamic forces acting on the vehicle for control, aerodynamic drag modulated case requires a vary-ing drag area to modulate the drag force. The MHD drag modulated case modulates MHD generated drag force that adds to the aerodynamic drag. This higher atmospheric activation of drag forces by the MHD patch results in significantly less heat flux on the vehicle. The MHD technology will enable shorter cruise times and deceleration of larger payloads for increasing the capacity for science at the Ice Giants or for returning astronauts to Earth from cislunar space or from Mars. The purpose of this presentation is to provide more details about this work and to highlight plans for further research and development including a flight demonstration.

R. W. Moses↗

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↗

High Temperature Steam Electrolysis Process Performance and Cost Estimates

Technology readiness levels (TRLs) of electrolysis systems have dramatically increased in recent years as the interest in clean hydrogen production and decarbonization of transportation, industrial and other sectors increases across the globe. This is especially true of high temperature steam electrolysis (HTSE) / solid oxide electrolysis cell (SOEC) systems which show promise of much higher system efficiencies than other more developed electrolysis technologies. This possibility of higher efficiencies of HTSE / SOEC systems has been previously assumed to be theoretically possible but in recent years it has become less theoretical and more realistic as an increasing amount of suppliers complete lab and pilot tests showing very promising results. Research in the areas of manufacturing techniques, material selection, electrode and electrolyte compositions, and balance of plant size and integration continues at a fast pace as an increasing number of suppliers both internationally and domestically become involved. The advantages of HTSE become more pronounced when HTSE is coupled with nuclear power plants (NPPs). This is because thermal energy produced by the nuclear reactor can be used in a series of heat transfer loops and heat exchangers to vaporize HTSE feedwater, which drastically improves the economics of the process. Idaho National Laboratory (INL) has been very involved in the research and modeling of HTSE systems for a number of years, in collaboration with other national laboratories, academia, and industry stakeholders both on the hydrogen production as well as the hydrogen demand side. The modeling completed over the years on a large variety of projects has led to a wealth of knowledge at INL including in the area of the technoeconomic assessment (TEA) of HTSE systems. TEAs include process modeling of the HTSE systems to calculate system energy requirements and equipment sizing, followed by estimation of capital and operating costs to enable calculation of the levelized cost of hydrogen (LCOH). The TEA work performed has produced incremental improvements and tuning of the methods, assumptions, models, and results of the analyses as well as providing some opportunities for validating these results. The purpose of this document is to record the current baseline HTSE analyses led by INL to show the current status of assumptions and costs of these systems. Given the rapid development of this technology, the variety of suppliers entering the space, and the increasing attention government and industry are giving to such systems, this document may be updated on a periodic basis with updated analysis and assumptions. This document compiles various analyses results and approaches completed over a period of years into a single document to be used as a baseline going forward. It represents what the INL HTSE analysis group assumes to be the internal best estimate of the current operation, costs, and landscape of the HTSE industry state of the art capability for current SOEC technology in an Nth-of-a-Kind (NOAK) plant, which in this study is defined as existence of the manufacturing capacity to support previous deployment of N = 100 count of 25 MWe modular HTSE blocks (with modular equipment component cost reductions specified as following a 95% learning curve). That said, This is a public document and as such so no proprietary data was used or included in this report. There may be HTSE suppliers that have performance specifications, and cost estimates, and test data that differ from the analysis presented in this document. This document is meant to be a best conservative estimate of the technology and not an absolute reference.

08 HYDROGEN↗

High Temperature Steam Electrolysis Process Performance and Cost Estimates - DOE Hydrogen Program AMR Presentation

Technology readiness levels (TRLs) of electrolysis systems have dramatically increased in recent years as the interest in clean hydrogen production and decarbonization of transportation, industrial and other sectors increases across the globe. This is especially true of high temperature steam electrolysis (HTSE) / solid oxide electrolysis cell (SOEC) systems which show promise of much higher system efficiencies than other more developed electrolysis technologies. This possibility of higher efficiencies of HTSE / SOEC systems has been previously assumed to be theoretically possible but in recent years it has become less theoretical and more realistic as an increasing amount of suppliers complete lab and pilot tests showing very promising results. Research in the areas of manufacturing techniques, material selection, electrode and electrolyte compositions, and balance of plant size and integration continues at a fast pace as an increasing number of suppliers both internationally and domestically become involved. The advantages of HTSE become more pronounced when HTSE is coupled with nuclear power plants (NPPs). This is because thermal energy produced by the nuclear reactor can be used in a series of heat transfer loops and heat exchangers to vaporize HTSE feedwater, which drastically improves the economics of the process. Idaho National Laboratory (INL) has been very involved in the research and modeling of HTSE systems for a number of years, in collaboration with other national laboratories, academia, and industry stakeholders both on the hydrogen production as well as the hydrogen demand side. The modeling completed over the years on a large variety of projects has led to a wealth of knowledge at INL including in the area of the technoeconomic assessment (TEA) of HTSE systems. TEAs include process modeling of the HTSE systems to calculate system energy requirements and equipment sizing, followed by estimation of capital and operating costs to enable calculation of the levelized cost of hydrogen (LCOH). The TEA work performed has produced incremental improvements and tuning of the methods, assumptions, models, and results of the analyses as well as providing some opportunities for validating these results. The purpose of this document is to record the current baseline HTSE analyses led by INL to show the current status of assumptions and costs of these systems. Given the rapid development of this technology, the variety of suppliers entering the space, and the increasing attention government and industry are giving to such systems, this document may be updated on a periodic basis with updated analysis and assumptions. This document compiles various analyses results and approaches completed over a period of years into a single document to be used as a baseline going forward. It represents what the INL HTSE analysis group assumes to be the internal best estimate of the current operation, costs, and landscape of the HTSE industry state of the art capability for current SOEC technology in an Nth-of-a-Kind (NOAK) plant, which in this study is defined as existence of the manufacturing capacity to support previous deployment of N = 100 count of 25 MWe modular HTSE blocks (with modular equipment component cost reductions specified as following a 95% learning curve). That said, this is a public document and as such so no proprietary data was used or included in this report. There may be HTSE suppliers that have performance specifications, and cost estimates, and test data that differ from the analysis presented in this document. This document is meant to be a best conservative estimate of the technology and not an absolute reference.

08 HYDROGEN↗