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At least 235 records · Page 13

The Impact of Lithium Anode Interface on Capacity Fade in Polymer Electrolyte-Based Solid-State Batteries

This study investigates the Li stripping-plating morphology and failure mechanisms in full cells consisting of a solid polymer electrolyte (SPE) with two commercial Li anodes: Li chip and Li foil. The primary identified failure mechanism of the SPE cell is capacity fade, regardless of the Li manufacturer. While the cathode’s role in capacity fade is evident, the Li anode significantly influences cycling performance, with Li foil cells cycling 50% longer than Li chip cells, a statistical difference. Further, post-mortem scanning electron microscopy and X-ray photoelectron spectroscopy results attribute the Li chip’s faster capacity fade to a loss of contact and continuous growth of the solid electrolyte interphase (SEI). Conversely, Li foil maintains consistent contact with the solid polymer, displaying a thin and stable SEI. Additionally, failure mechanisms between a gel electrolyte in previous work and the dry SPE are compared.

25 ENERGY STORAGE↗

Modeling the influence of the solid electrolyte interphase on the sand’s time and dendrite formation on lithium metal electrodes

Lithium metal is a sought after battery material for its high energy density due to the low electrochemical potential and density. However, lithium metal is also highly reactive, which results in a strong propensity for dendrite formation. The Sand’s time has previously been used to predict the time of dendrite initiation on metals that do not form a solid-electrolyte interphase (SEI), but it has been shown that the Sand’s time is not accurate for lithium electrodes when using transport parameters associated with the electrolyte. Thus, we built a numerical model to simulate lithium ion transport through a growing SEI to predict the Sand’s time. The numerical model is shown to be more accurate than previous analytical solutions, especially for low current densities. We then analyze the sensitivity of the Sand’s time to different SEI properties and the chemical potential gradients present in the SEI, driving lithium transport. The results showed that high lithium concentration has a greater impact at high current density, while fast diffusivity is more important at low current density. Lastly, we modeled the influence of surface roughness on the plating evolution and chemical potential gradients when an SEI is present in comparison to the electrolyte. As a result, we demonstrate that the SEI plays a critical role in lithium electrode stability, and that improved characterization techniques are needed to better understand transport through the SEI and increase lithium metal utilization in energy storage devices.

Chemistry↗

The Critical Stack Pressure to Alter Void Generation at Li/Solid-Electrolyte Interfaces during Stripping

The lithium stripping process generates vacancies, which may accumulate as voids and lead to uneven current distribution and dendrite growth in the following plating cycles. A stack pressure is typically required during stripping, but how to optimize the stack pressure is not clear. In this work, extremely lithiophilic Li/Li 2 O and lithiophobic Li/LiF interfaces were used to reveal the combining effect of interface interaction and stack pressure induced lithium creep on the stripping critical current density (CCD). A multiscale simulation scheme with Density Functional Theory (DFT), kinetic Monte Carlo (KMC) simulations, and an analytical model was developed. The analytical model predicted lithiophobic interfaces require a higher stack pressure than lithiophilic interfaces to reach the same CCD. The KMC simulations also showed higher stack pressure is needed at lithiophobic interfaces to accelerate Li vacancy diffusion into the bulk and maintain a flat surface. This stack pressure needs to be high enough to alter the Li forward-and-backward hopping barriers at the interface. This multiscale simulation scheme illustrates the importance to include the chemical-mechanical effects during Li stripping morphology evolution. It can be used to design ideal interlayer coating materials to maintain a flat Li surface during cycling.

25 ENERGY STORAGE↗

Dual Passivation of Cathode and Anode through Electrode–Electrolyte Interface Engineering Enables Long-Lifespan Li Metal–SPAN Batteries

The reliability and durability of lithium metal (Li 0 )–sulfur batteries are largely limited by the undesired Li 0 plating-stripping irreversibility and the detrimental polysulfide dissolution, yet approaches that can simultaneously address the above anodic and cathodic problems are scarce. In this study, we report the stable operation of a Li 0 -SPAN (sulfurized polyacrylonitrile) battery via an anode–cathode dual-passivation approach. By combination of a fluorinated localized high concentration electrolyte (LHCE) and a Li 3 N-forming additive (TMS-N 3 ), robust and highly conductive electrode passivation layers are formed in situ on the surface of both the Li 0 anode and the SPAN cathode. The resulting highly reversible, dendrite-free, and high-density Li 0 plating morphology enables a high Coulombic efficiency of 99.4%. Advanced tender energy X-ray spectroscopy also reveals the eliminated Li 2 S formation and minimized polysulfide dissolution in SPAN cathodes, leading to a high capacity of 580 mAh/g SPAN and stable cycling with negligible capacity decay (0.7%) for 800 cycles. This electrode–electrolyte interphase engineering strategy has tackled the major limitations of Li–S batteries in both ether- and carbonate-based electrolyte systems and under a wide temperature range from –10 to +50 °C, thus providing insightful guidelines for the rational design of highly durable and high-energy-density Li 0 -S batteries.

25 ENERGY STORAGE↗

The passivity of lithium electrodes in liquid electrolytes for secondary batteries

Rechargeable Li metal batteries are currently limited by electrolyte decomposition and rapid Li consumption. Li plating and stripping greatly depend on the solid electrolyte interphase formed at the Li metal-liquid electrolyte interface. This Review discusses the reactions occurring at this interface from a corrosion science perspective, highlighting the requirements for an ideal passivation layer. Rechargeable Li metal batteries are currently limited by safety concerns, continuous electrolyte decomposition and rapid consumption of Li. These issues are mainly related to reactions occurring at the Li metal-liquid electrolyte interface. Additionally, the formation of a passivation film (that is, a solid electrolyte interphase) determines ionic diffusion and the structural and morphological evolution of the Li metal electrode upon cycling. In this Review, we discuss spontaneous and operation-induced reactions at the Li metal-electrolyte interface from a corrosion science perspective. We highlight that the instantaneous formation of a thin protective film of corrosion products at the Li surface, which acts as a barrier to further chemical reactions with the electrolyte, precedes film reformation, which occurs during subsequent electrochemical stripping and plating of Li during battery operation. Finally, we discuss solutions to overcoming remaining challenges of Li metal batteries related to Li surface science, electrolyte chemistry, cell engineering and the intrinsic instability of the Li metal-electrolyte interface.

25 ENERGY STORAGE↗

Effects of Annealing Process on the Formability of Friction Stir Welded Al-Li Alloy 2195 Plates

Large rocket cryogenic tank domes have typically been fabricated using Al-Cu based alloys like Al-Cu alloy 2219. The use of aluminum-lithium based alloys for rocket fuel tank domes can reduce weight because aluminum-lithium alloys have lower density and higher strength than Al-Cu alloy 2219. However, Al-Li alloys have rarely been used to fabricate rocket fuel tank domes because of the inherent low formability characteristic that make them susceptible to cracking during the forming operations. The ability to form metal by stretch forming or spin forming without excessive thinning or necking depends on the strain hardening exponent "n". The stain hardening exponent is a measure of how rapidly a metal becomes stronger and harder. A high strain hardening exponent is beneficial to a material's ability to uniformly distribute the imposed strain. Marshall Space Flight Center has developed a novel annealing process that can achieve a work hardening exponent on the order of 0.27 to 0.29, which is approximately 50% higher than what is typically obtained for Al-Li alloys using the conventional method. The strain hardening exponent of the Al-Li alloy plates or blanks heat treated using the conventional method is typically on the order of 0.17 to 0.19. The effects of this novel annealing process on the formability of friction stir welded Al-Li alloy blanks are being studied at Marshall Space Flight Center. The formability ratings will be generated using the strain hardening exponent, strain rate sensitivity and forming range. The effects of forming temperature on the formability will also be studied. The objective of this work is to study the deformation behavior of the friction stir welded Al-Li alloy 2195 blank and determine the formability enhancement by the new annealing process.

Chen, Po-Shou↗

Recent advances in plasma control and physics research in the Large Helical Device

The Large Helical Device (LHD), the largest superconducting helical system in the world, is equipped with advanced heating and diagnostic tools, facilitating plasma control and physics research. Data assimilation was employed for electron temperature control using a real-time Thomson scattering system and real time prediction code. A virtual LHD environment enabled visualization of escaping high-energy tritium ions and demonstrated that these ions impact the rear side of the divertor plate. Pioneering results crucial to plasma control have also been achieved. Real-time wall conditioning using Lithium granule dropping improved bulk ion energy and particle transport while simultaneously enhancing the heavy impurity transport. Progress has also been made in the investigation of turbulence-driven transport. At the confinement bifurcation, ion-scale turbulence decreased, while electron-scale turbulence increased. A change in the anisotropy of turbulent eddies was also observed at the confinement bifurcation. Coexistence of local and non-local turbulence was identified in electron-scale turbulence. Non-local turbulence exhibited the rapid spatial propagation of perturbations throughout the plasma, while local turbulence followed the temperature gradient. A transition between drift-wave turbulence and magnetohydrodynamics (MHD) turbulence was observed with the turbulence minimized at the transition condition. Machine learning analysis was employed to evaluate the temperate and density conditions of this turbulence transition. Then, real-time control of fueling and heating was applied to maintain the turbulence transition condition, improving the energy confinement enhancement factor by 20%. In addition, evidence was obtained for collisionless ion heating by energetic-ion-driven geodesic acoustic modes and MHD bursts. These achievements represent unique contributions to the development of fusion reactors.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

On the crystallography and reversibility of lithium electrodeposits at ultrahigh capacity

Abstract Lithium metal is a promising anode for energy-dense batteries but is hindered by poor reversibility caused by continuous chemical and electrochemical degradation. Here we find that by increasing the Li plating capacity to high values ( e.g ., 10–50 mAh cm −2 ), Li deposits undergo a morphological transition to produce dense structures, composed of large grains with dominantly (110) Li crystallographic facets. The resultant Li metal electrodes manifest fast kinetics for lithium stripping/plating processes with higher exchange current density, but simultaneously exhibit elevated electrochemical stability towards the electrolyte. Detailed analysis of these findings reveal that parasitic electrochemical reactions are the major reason for poor Li reversibility, and that the degradation rate from parasitic electroreduction of electrolyte components is about an order of magnitude faster than from chemical reactions. The high-capacity Li electrodes provide a straightforward strategy for interrogating the solid electrolyte interphase (SEI) on Li —with unprecedented, high signal to noise. We find that an inorganic rich SEI is formed and is primarily concentrated around the edges of lithium particles. Our findings provide straightforward, but powerful approaches for enhancing the reversibility of Li and for fundamental studies of the interphases formed in liquid and solid-state electrolytes using readily accessible analytical tools.

59 BASIC BIOLOGICAL SCIENCES↗

CRADA Final Report: Ultralong Cycle Life and Ultrafast Charging Batteries to Electrify High Duty-Cycle, Mobile Platforms

As part of the Cyclotron Road program, Tyfast Energy Corp. aimed to investigate the Li 3 V 2 O 5 (LVO) anode material for next generation lithium batteries. State of the art and fast charging lithium-ion batteries are based on the lithium titanate or Li 4 Ti 5 O 12 (LTO) anode chemistry. LTO cells demonstrate fast charging times (<6 mins), long cycle life (>20,000 cycles), but at the expense of very low energy density (<200Wh/L, <80Wh/kg). Silicon anodes have the promise of achieving fast charging times, however, issues with cycling stability in combination with fast charging is unknown. LVO has unique properties that enable new performance window for lithium batteries. First, LVO operates at an average potential of 0.6V vs. Li/Li + , well above the Li-metal plating region allowing ultrafast charge capability without sacrificing safety. Second, the LVO has a high specific capacity of 250 mAh/g making battery pack energy density equivalent with current high-energy Li-ion chemistries.

25 ENERGY STORAGE↗

Aging Optimization of Aluminum-Lithium Alloy L277 for Application to Cryotank Structures

Compared with aluminum alloys such as 2219, which is widely used in space vehicle for cryogenic tanks and unpressurized structures, aluminum-lithium alloys possess attractive combinations of lower density and higher modulus along with comparable mechanical properties and improved damage tolerance. These characteristics have resulted in the successful use of the aluminum-lithium alloy 2195 for the Space Shuttle External Tank, and the consideration of newer U.S. aluminum-lithium alloys such as L277 and C458 for future space vehicles. A design of experiments aging study was conducted for plate and a limited study on extrusions. To achieve the T8 temper, Alloy L277 is typically aged at 290 F for 40 hours. In the study for plate, a two-step aging treatment was developed through a design of experiments study and the one step aging used as a control. Based on the earlier NASA studies on 2195, the first step aging temperature was varied between 220 F and 260 F. The second step aging temperatures was varied between 290 F and 310 F, which is in the range of the single-step aging temperature. For extrusions, two, single-step, and one two-step aging condition were evaluated. The results of the design of experiments used for the T8 temper as well as a smaller set of experiments for the T6 temper for plate and the results for extrusions will be presented.

Sova, B. J.↗

Process Model for Friction Stir Welding

Friction stir welding (FSW) is a relatively new process being applied for joining of metal alloys. The process was initially developed by The Welding Institute (TWI) in Cambridge, UK. The FSW process is being investigated at NASA/MSEC as a repair/initial weld procedure for fabrication of the super-light-weight aluminum-lithium shuttle external tank. The FSW investigations at MSFC were conducted on a horizontal mill to produce butt welds of flat plate material. The weldment plates are butted together and fixed to a backing plate on the mill bed. A pin tool is placed into the tool holder of the mill spindle and rotated at approximately 400 rpm. The pin tool is then plunged into the plates such that the center of the probe lies at, one end of the line of contact, between the plates and the shoulder of the pin tool penetrates the top surface of the weldment. The weld is produced by traversing the tool along the line of contact between the plates. A lead angle allows the leading edge of the shoulder to remain above the top surface of the plate. The work presented here is the first attempt at modeling a complex phenomenon. The mechanical aspects of conducting the weld process are easily defined and the process itself is controlled by relatively few input parameters. However, in the region of the weld, plasticizing and forging of the parent material occurs. These are difficult processes to model. The model presented here addresses only variations in the radial dimension outward from the pin tool axis. Examinations of the grain structure of the weld reveal that a considerable amount of material deformation also occurs in the direction parallel to the pin tool axis of rotation, through the material thickness. In addition, measurements of the axial load on the pin tool demonstrate that the forging affect of the pin tool shoulder is an important process phenomenon. Therefore, the model needs to be expanded to account for the deformations through the material thickness and the forging affect of the shoulder. The energy balance at the boundary of the plastic region with the environment required that energy flow away from the boundary in both radial directions. One resolution to this problem may be to introduce a time dependency into the process model, allowing the energy flow to oscillate across this boundary. Finally, experimental measurements are needed to verify the concepts used here and to aid in improving the model.

Adams, Glynn↗

A Self-Healable Sulfide/Polymer Composite Electrolyte for Long-Life, Low-Lithium-Excess Lithium-Metal Batteries

Solid electrolyte-protected lithium-metal anodes promise energy-dense, safe cells. While sulfide solid electrolytes enable facile processability and fast ion transport, they suffer from complex chemo-mechanical issues, including Li plating-induced fracture and Li stripping-induced contact loss. To address these issues, a grafting approach is implemented to functionalize the sulfide solid electrolyte (Li 3,85 Sn 0.85 Sb 0.15 S 4 ) with a self-healing unit. This leads to a dynamic bonding between the solid electrolyte network and a mechanically robust polymer scaffold, which reversibly accommodates the volume changes of the lithium-metal anode. Thus, the approach improves the interfacial contact between the lithium-metal anode and the composite electrolyte, enabling stable cycling at a mild stack pressure (160 kPa). With a negative to positive capacity ratio equals to 1, pouch full cells with a high-nickel cathode (nickel content > 90%) and lithium-metal anode display 92% capacity retention for 140 cycles. Engineering the interface between solid electrolyte and the polymeric binder offers a promising pathway to address the chemo-mechanical issues.

36 MATERIALS SCIENCE↗

Modeling aluminum-lithium alloy welding characteristics

The purpose of this project was to develop a finite element model of the heat-affected zone in the vicinity of a weld line on a plate in order to determine an accurate plastic strain history. The resulting plastic strain increments calculated by the finite element program were then to be used to calculate the measure of damage D. It was hoped to determine the effects of varying welding parameters, such as beam power, efficiency, and weld speed, and the effect of different material properties on the occurrence of microfissuring. The results were to be compared first to the previous analysis of Inconel 718, and then extended to aluminum 2195.

Bernstein, Edward L.↗

Local Ultrasonic Resonance Spectroscopy of Lithium Metal Batteries for Aerospace Applications

As next-generation aircraft and vehicles continue to develop, so do their associated energy demands. Lithium metal batteries are a leading candidate to fulfill this energy requirement, but these batteries are prone to internal dendrite defects that can lead to catastrophic thermal runaway events. Current battery management systems are capable of mitigating such risks, but are unable to detect such defects until thermal runaway has already begun. Various nondestructive evaluation (NDE) techniques, particularly ultrasonic NDE, can directly monitor internal battery parameters giving them the potential to detect critical defects prior to catastrophic failure. However, most of the current battery NDE research has focused on improved battery state-of-charge (SOC) and stateof- health (SOH) monitoring with little emphasis on critical defect detection. Thus, a measurement technique sensitive to subtle battery defects is needed. In addition, the complex mechanics of ultrasound in porous, thin, multilayered batteries prompt the use of physics-based simulation to guide inspections. In this work, an ultrasonic NDE technique has been developed utilizing frequency domain analysis of local battery resonances to detect the presence of battery defects. This technique is a practical extension of local ultrasonic resonance spectroscopy (LURS) – which previously required non-contact laser ultrasonics – to measurements with piezoelectric contact and immersion scan transducers. To extend the technique to work with piezoelectric transducers, ultrasonic battery measurements were compared to a sans-battery calibration measurement. Then, a linear systems deconvolution was used to eliminate the transfer functions of extraneous factors such as the transducer and electronics, leaving only the frequency-dependent battery reflection coefficient. The LURS technique was first validated on stainless steel and aluminum plates, producing reflection coefficients in line with analytical and numerical finite element modeling (FEM) results. Functioning Li-metal pouch cells were then seeded with lithium chip defects prior to LURS measurements. The presence of these defects is shown to cause a measurable shift in the battery’s through-thickness local resonances. 2D, frequency-domain poroelastic models of ultrasonic propagation in a single-cell lithium metal pouch battery were created and corroborated these findings. Thus, this work has both extended and proven the feasibility of the LURS technique in the detection of local battery defects.

Ultrasound↗

Resource Adequacy and Capital Cost Considerations Pertaining to Large Electric Grids Powered by Wind, Solar, Storage, Gas, and Nuclear

The capacity and generation of wind, solar, storage, nuclear, and gas are estimated for large, idealized copper-plate electric grids. Wind and solar penetrations of 30% to 80% are considered together with different storage systems such as vanadium and lithium-ion batteries, pumped hydroelectric, compressed air, and hydrogen. In addition to a baseline dispatchable fleet without wind/solar, two bounding cases with wind/solar are analyzed: one without storage and one where the whole wind/solar fleet is connected to the storage system, hence providing a buffer between the wind/solar fleet and the grid. The reality will likely be somewhere between these bounding cases. The viability of a power grid with a large wind/solar penetration and no storage is not guaranteed but was nonetheless considered to provide a lower-bound capital cost estimate. Overall, the options that rely strongly on wind, solar, and storage could be significantly more capital-intensive than those that rely strongly on nuclear, depending on the amount of storage necessary to ensure grid stability. This is especially true in the long run because wind, solar, and storage assets have shorter lifetimes than nuclear plants and, consequently, need to be replaced more frequently. More analyses (e.g., grid stability and public acceptance) are necessary to determine which option is most likely to provide the path of least resistance to powering a clean, affordable, and reliable grid in a timely manner. Depending on the priorities, the path of least resistance may not necessarily be the one that is less capital intensive.

adequacy↗

Compatibility of molten salts with advanced solar dynamic receiver materials

Metal-coated graphite fibers are being considered as a thermal conductivity enhancement filler material for molten salts in solar dynamic thermal energy storage systems. The successful metal coating chosen for this application must exhibit acceptable wettability and must be compatible with the molten salt environment. Contact angle values between molten lithium fluoride and several metal, metal fluoride, and metal oxide substrates have been determined at 892 C using a modification of the Wilhelmy plate technique. Reproducible contact angles with repeated exposure to the molten LiF indicated compatibility.

Jaworske, D. A.↗

Production of aluminum-lithium near net shape extruded cylinders

In the late 1980's, under funding from the Advanced Launch System Program, numerous near net shape technologies were investigated as a means for producing high quality, low cost Aluminum-Lithium (Al-Li) hardware. Once such option was to extrude near net shape barrel panels instead of producing panels by machining thick plate into a final tee-stiffened configuration (which produced up to 90% scrap). This method offers a reduction in the volume of scrap and consequently reduces the buy-to-fly cost. Investigation into this technology continued under Shuttle-C funding where four Al alloys 2219, 2195, 2096, and RX 818 were extruded. Presented herein are the results of that program. Each alloy was successfully extruded at Wyman Gordon, opened and flattened at Ticorm, and solution heat treated and stretched at Reynolds Metals Company. The first two processes were quite successful while the stretching process did offer some challenges. Due to the configuration of the panels and the stretch press set-up, it was difficult to induce a consistent percentage of cold work throughout the length and width of each panel. The effects of this variation will be assessed in the test program to be conducted at a future date.

Hartley, Paula J.↗

Ion Conducting Polymer Interfaces for Lithium Metal Anodes: Impact on the Electrodeposition Kinetics

Electrochemical cells that utilize metals (e.g., lithium, sodium, zinc) as anodes are under intense investigation as they are projected to replace the current lithium-ion batteries to serve as a more energy-dense option for commercial applications. In addition, metal electrodes provide opportunities for fundamental research of different phenomena, such as ion transport and electrochemical kinetics, in the complex environment of reactive metal-electrodeposition. In this work, computationally and experimentally the competing effects related to transport and kinetics during the metal electrodeposition process are examined. Using Brownian dynamics simulations, it is shown that slower deposition kinetics results in a more compact and uniform Li morphology. This finding is experimentally implemented by designing ion-containing polymeric coatings on the electrodes that simultaneously provide pathways for lithium-ion transport, while impeding the charge transfer (Li + + e - → Li) at heterogeneous surfaces. It is further shown that these ionic polymer interfaces can significantly extend the cell-lifetime of a lithium metal battery in both ether-based and carbonate-based electrolytes. Through theoretical and experimental investigations, it is found that a low kinetic to transport rate ratio is a major factor in influencing the Li plating morphology. The plating morphology can be further fine-tuned by increasing ionic conductivity.

36 MATERIALS SCIENCE↗