Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “LITHIUM”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 991 records · Page 55
All sourcesNASA NTRSDOE OSTI
DOE OSTI2013

Pyroelectric field assisted ion migration induced by ultraviolet laser irradiation and its impact on ferroelectric domain inversion in lithium niobate crystals

The impact of UV laser irradiation on the distribution of lithium ions in ferroelectric lithium niobate single crystals has been numerically modelled. Strongly absorbed UV radiation at wavelengths of 244–305 nm produces steep temperature gradients which cause lithium ions to migrate and result in a local variation of the lithium concentration. In addition to the diffusion, here the pyroelectric effect is also taken into account which predicts a complex distribution of lithium concentration along the c-axis of the crystal: two separated lithium deficient regions on the surface and in depth. The modelling on the local lithium concentration and the subsequent variation of the coercive field are used to explain experimental results on the domain inversion of such UV treated lithium niobate crystals.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Mechanical behavior of electroplated mossy lithium at room temperature studied by flat punch indentation

We report the Young’s modulus and deformation behavior of electroplated mossy lithium at room temperature investigated by flat punch indentation inside an argon-filled glovebox. The Young’s modulus of the mossy lithium with a porosity of about 62.3 % is measured to be about 2 GPa, which is smaller than that (~7.8 GPa) of bulk Li. Both the mossy and bulk lithium show clearly indentation creep behavior. Despite its highly porous microstructure, the impression creep velocity of the mossy lithium is less than one-thirtieth of that of bulk lithium under the same stress. We proposed possible mechanisms for the significantly higher deformation and creep resistance of the mossy lithium over bulk lithium. These findings are key to developing mechanical suppression approaches to improve the cycling stability of lithium metal electrodes.

25 ENERGY STORAGE↗
DOE OSTI2022

Observation of the surface layer of lithium metal using in situ spectroscopy

In this work, we have investigated the surface of lithium metal using x-ray photoemission spectroscopy and optical spectroscopic ellipsometry. Even if we prepare the surface of lithium metal rigorously by chemical cleaning and mechanical polishing inside a glovebox, both spectroscopic investigations show the existence of a few tens of nanometer-thick surface layers, consisting of lithium oxides and lithium carbonates. When lithium metal is exposed to room air (~50% moisture), in situ real-time monitoring of optical spectra indicates that the surface layer grows at a rate of approximately 24 nm/min, presumably driven by an interface-controlled process. Our results hint that surface-layer-free lithium metals are formidable to achieve by a simple cleaning/polishing method, suggesting that the initial interface between lithium metal electrodes and solid-state electrolytes in fabricated lithium metal batteries can differ from an ideal lithium/electrolyte contact.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Design principles for self-forming interfaces enabling stable lithium-metal anodes

Significance It is possible to nearly double the energy density of existing lithium-ion batteries by using lithium metal anodes. However, it has been known for decades that the lithium dendrites and mossy lithium formed during charging (electrodeposition) limit the cycle life of the batteries. It is important to change the growth behavior of lithium metal, which is closely related to the properties of the solid–electrolyte interface (SEI) formed via spontaneous reactions between the lithium metal and the electrolyte. In this experimental-modeling integrated study, we reveal the design principles of the SEI that facilitates the dendrite-free and dense deposition of lithium and demonstrate one of the best cycling performances of lithium metal anode to date under practically relevant conditions.

25 ENERGY STORAGE↗
DOE OSTI2020

Effect of lithium coating on long pulse high performance plasma discharges in EAST

Control of impurities, fuel recycling and hydrogen content by lithium evaporative coatings and real-time lithium powder injection (LPI) in EAST are studied for high performance H-mode discharges of up to ~100 s. The results show that the lithium evaporative coatings significantly reduced both the low-Z impurity carbon and high-Z impurity tungsten as well as molybdenum concentration in the plasmas, and the impurities concentration significantly reduced with the accumulated lithium coatings and maintained well afterwards. Specifically the high-Z tungsten core impurity concentration was maintained between 3 ppm–15 ppm during the 101 s H-mode discharge, which is acceptable for the long pulse operation. In addition, real-time wall conditioning via LPI successfully reduced the core high-Z metal impurities by 50% during ~35 s long pulse H-mode discharge, exhibiting strong compatibility between real-time LPI with long pulse discharges. In addition, evaporative lithium coatings demonstrated fuel recycling control, with fuel recycling obviously reducing with lithium coatings and maintaining well afterwards. Also, the lithium evaporative coatings reduced the hydrogen minority species content, represented by the density ratio H/(H + D), from ~50% down to ~5% with accumulated lithium coatings; low hydrogen fraction improved the ICRF minority heating efficiency. Finally the real-time LPI reduced the recycling coefficient R global from 0.95 to 0.82. With these wall conditionings help, the plasma density controlled well during the 101 s long pulse H-mode discharge. Furthermore, these results provide valuable references on impurities, fuel recycling and hydrogen content control for future longer pulse high performance H-mode operation (≥400 s) in EAST and future fusion devices.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2023

Developing rapid electrochemical relithiation protocols for scalable relithiation of lithium-ion battery cathode materials

The recent and ongoing boom in electric vehicle sales has caused the circularity of the supply chain for electric vehicle battery materials to come under a great deal of scrutiny. Innovative recycling processes, or direct recycling, that offer the possibility of reducing the cost of recycling are one possible solution to regaining resources from end-of-life (EoL) electric vehicle batteries. Electrochemically shuttling lithium back into the cathode, or electrochemical relithiation, is a possible technique for restoring lithium content to NMC materials (EoL) in a direct recycling process. This study provides essential understanding towards developing an electrochemical relithiation protocol that will restore lithium loss in intercalation cathode materials that reach EoL by loss of lithium inventory (LLI) as opposed to other degradation mechanisms like loss of active material (LAM), cation mixing or phase transition. Electrochemically aged NMC cathode materials have been prepared and characterized to establish the extent of EoL material structural degradation and lithium loss. A model-informed experimental process is used to identify the optimal electrochemical relithiation protocol to minimize the time taken to relithiate EoL materials and maximize the amount of lithium restored. Protocols were evaluated based on their ability to enable rapid lithium intercalation, maintain structural uniformity in the EoL material and fully restore lithium content. An optimal protocol was identified at elevated temperatures utilizing a novel scanning voltage step.

25 ENERGY STORAGE↗
DOE OSTI2023

Cycling of block copolymer composites with lithium-conducting ceramic nanoparticles

Solid polymer and perovskite-type ceramic electrolytes have both shown promise in advancing solid-state lithium metal batteries. Despite their favorable interfacial stability against lithium metal, polymer electrolytes face issues due to their low ionic conductivity and poor mechanical strength. Highly conductive and mechanically robust ceramics, on the other hand, cannot physically remain in contact with redox-active particles that expand and contract during charge-discharge cycles unless excessive pressures are used. To overcome the disadvantages of each material, polymer-ceramic composites can be formed; however, depletion interactions will always lead to aggregation of the ceramic particles if a homopolymer above its melting temperature is used. In this study, we incorporate Li 0.33 La 0.56 TiO 3 (LLTO) nanoparticles into a block copolymer, polystyrene- b -poly (ethylene oxide) (SEO), to develop a polymer-composite electrolyte (SEO-LLTO). TEMs of the same nanoparticles in polyethylene oxide (PEO) show highly aggregated particles whereas a significant fraction of the nanoparticles are dispersed within the PEO-rich lamellae of the SEO-LLTO electrolyte. We use synchrotron hard x-ray microtomography to study the cell failure and interfacial stability of SEO-LLTO in cycled lithium-lithium symmetric cells. Three-dimensional tomograms reveal the formation of large globular lithium structures in the vicinity of the LLTO aggregates. Encasing the SEO-LLTO between layers of SEO to form a “sandwich” electrolyte, we prevent direct contact of LLTO with lithium metal, which allows for the passage of seven-fold higher current densities without signatures of lithium deposition around LLTO. We posit that eliminating particle clustering and direct contact of LLTO and lithium metal through dry processing techniques is crucial to enabling composite electrolytes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Operando Lithium Dynamics in the Li-Rich Layered Oxide Cathode Material via Neutron Diffraction

Neutron diffraction under operando battery cycling is used to study the lithium and oxygen dynamics of high Li-rich Li(Li x/3 Ni (3/8-3x/8) Co (1/4-x/4) Mn (3/8+7x/24) O 2 (x = 0.6, HLR) and low Li-rich Li(Li x/3 Ni (1/3-x/3) Co (1/3-x/3) Mn(1/3+x/3)O 2 (x = 0.24, LLR) compounds that exhibit different degrees of oxygen activation at high voltage. The measured lattice parameter changes and oxygen position show largely contrasting changes for the two cathodes where the LLR exhibits larger movement of oxygen and lattice contractions in comparison to the HLR that maintains relatively constant lattice parameters and oxygen position during the high voltage plateau until the end of charge. Density functional theory calculations show the presence of oxygen vacancy during the high voltage plateau; changes in the lattice parameters and oxygen position are consistent with experimental observations. Lithium migration kinetics for the Li-rich material is observed under operando conditions for the first time to reveal the rate of lithium extraction from the lithium layer, and transition metal layer is related to the different charge and discharge characteristics. At the beginning of charging, the lithium extraction predominately occurs within the lithium layer. The lithium extraction from the lithium layer slows down and extraction from the transition metal layer evolves at a faster rate once the high voltage plateau is reached.

25 ENERGY STORAGE↗
DOE OSTI2024

Transient Chemo‐Mechanical Model of Lithium Plating Impacted by External Pressure

Abstract Lithium anodes show great promise in commercial applications, but are hindered by lithium plating and dendrite growth which cause safety concerns during long‐term cell operation. Stack pressure is experimentally observed to improve cell lifetime; however, the relationship between stress and lithium deposition has remained difficult to elucidate. In this work, a transient, 3D, finite‐element model of the evolution of a lithium anode due to stripping and plating is developed. The evolution of a microscale protrusion on the anode surface is tracked over one charge‐discharge cycle with respect to stack pressure and lithium yield strength. Lithium plastic deformation, nonconformal anode‐separator contact, and separator porosity effects are accounted for. Over the course of several hours of stripping/plating, the anode surface evolves to a similar morphology under pressure regardless of the initial conditions due to lithium plastic deformation and hardening. The rate of this evolution highly depends on the applied pressure and assumed lithium yield strength.

25 ENERGY STORAGE↗
DOE OSTI2026

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↗
DOE OSTI2024

Study of Void Formation at the Lithium|Solid Electrolyte Interface

There is growing recognition of the critical role of void formation in lithium metal anodes in solid-state batteries and its impact on electrochemical performance. While experimental studies have demonstrated the challenges ensuing from void formation at the lithium metal interface with the solid electrolyte, there is a need to understand and quantify the role of intrinsic transport properties in lithium metal and the impact of external stimuli, such as temperature, pressure, and current density. Here, we develop this understanding by constructing a phase field-based model that captures the evolution of void domains at the lithium-solid electrolyte interface. Growth of the pores is driven by the fast removal of lithium from the interface during stripping at high current densities. Relative magnitudes of the bulk and surface lithium diffusivities, along with the applied current density, dictate the final pore morphology. Increasing the temperature results in faster diffusion, while external applied pressure causes creep flow of lithium, both of which help to mitigate the evolution of voids by quickly transporting metal from the bulk to the interface. Finally, a phase map as a function of temperature and pressure is developed as a guide to determine the regions that can lead to the stable cycling of lithium metal.

25 ENERGY STORAGE↗
DOE OSTI2022

Onboard early detection and mitigation of lithium plating in fast-charging batteries

Fast-charging is considered as one of the most desired features needed for lithium-ion batteries to accelerate the mainstream adoption of electric vehicles. However, current battery charging protocols mainly consist of conservative rate steps to avoid potential hazardous lithium plating and its associated parasitic reactions. A highly sensitive onboard detection method could enable battery fast-charging without reaching the lithium plating regime. Here, we demonstrate a novel differential pressure sensing method to precisely detect the lithium plating event. By measuring the real-time change of cell pressure per unit of charge (dP/dQ) and comparing it with the threshold defined by the maximum of dP/dQ during lithium-ion intercalation into the negative electrode, the onset of lithium plating before its extensive growth can be detected with high precision. In addition, we show that by integrating this differential pressure sensing into the battery management system (BMS), a dynamic self-regulated charging protocol can be realized to effectively extinguish the lithium plating triggered by low temperature (0 °C) while the conventional static charging protocol leads to catastrophic lithium plating at the same condition. We propose that differential pressure sensing could serve as an early nondestructive diagnosis method to guide the development of fast-charging battery technologies.

25 ENERGY STORAGE↗
DOE OSTI2014

Quantifying the Promise of Lithium-Air Batteries for Electric Vehicles

Researchers worldwide view the high theoretical specific energy of the lithium-air or lithium-oxygen battery as a promising path to a transformational energy-storage system for electric vehicles. Here, we present a self-consistent material-to-system analysis of the best-case mass, volume, and cost values for the nonaqueous lithium-oxygen battery and compare them with current and advanced lithium-based batteries using metal-oxide positive electrodes. Surprisingly, despite their high theoretical specific energy, lithium-oxygen systems were projected to achieve parity with other candidate chemistries as a result of the requirement to deliver and purify or to enclose the gaseous oxygen reactant. The theoretical specific energy, which leads to predictions of an order of magnitude improvement over a traditional lithium-ion battery, is shown to be an inadequate predictor of systems-level cost, volume, and mass. This analysis reveals the importance of system-level considerations and identifies the reversible lithium-metal negative electrode as a common, critical high-risk technology needed for batteries to reach long-term automotive objectives. Additionally, advanced lithium-ion technology was found to be a moderate risk pathway to achieve the majority of volume and cost reductions.

Gallagher, KG↗
DOE OSTI2026

Variations in lithium vapor cave performance predictions due to radial transport and recycling assumptions

The lithium vapor cave is a detached divertor design that uses a single private flux region baffle to contain a dense cloud of lithium vapor to dissipate heat flux. Plasma flows are created via fuel gas puffing in order to minimize lithium contamination of the main plasma. Significant modeling using the 2D edge code SOLPS-ITER has already been performed, predicting that sufficient target heat flux reductions (q$^{max}_{Target}$ MW m −2 ) with ( $n$ Li /$n$ e ) LCFS < 0.05 is possible in a case with 90 MW m −2 unmitigated heat flux in NSTX-U. Low heat flux and low upstream concentration was found with a variety of combinations of divertor geometries, target recycling coefficients, upstream plasma parameters, lithium evaporation locations and deuterium fueling locations, with variations in performance found for each design choice. However, the most universal uncertainty of SOLPS-ITER simulations has until now remained unaddressed systematically, namely the cross-field anomalous particle and heat diffusivities. This article aims to bound the uncertainty in lithium concentration prediction as a result of the assumed deuterium cross-field transport and recycling. For the simulations presented here, a factor of 2.1 increase in the upstream lithium density prediction across a factor of four decrease to the assumed deuterium radial particle diffusivity is found. This result is compared across different assumed deuterium recycling coefficients, known to reduce with lithium injection. Upstream lithium density is found to vary by a factor of 2.4 across a feasible range of recycling coefficients at similar $n$$^{OMP,sep}_{e}$.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2018

Engineering stable interfaces for three-dimensional lithium metal anodes

Lithium metal has long been considered one of the most promising anode materials for advanced lithium batteries (for example, Li-S and Li-O 2 ), which could offer significantly improved energy density compared to state-of-the-art lithium ion batteries. Despite decades of intense research efforts, its commercialization remains limited by poor cyclability and safety concerns of lithium metal anodes. One root cause is the parasitic reaction between metallic lithium and the organic liquid electrolyte, resulting in continuous formation of an unstable solid electrolyte interphase, which consumes both active lithium and electrolyte. Until now, it has been challenging to completely shut down the parasitic reaction. We find that a thin-layer coating applied through atomic layer deposition on a hollow carbon host guides lithium deposition inside the hollow carbon sphere and simultaneously prevents electrolyte infiltration by sealing pinholes on the shell of the hollow carbon sphere. By encapsulating lithium inside the stable host, parasitic reactions are prevented, resulting in impressive cycling behavior. In conclusion, we report more than 500 cycles at a high coulombic efficiency of 99% in an ether-based electrolyte at a cycling rate of 0.5 mA/cm 2 and a cycling capacity of 1 mAh/cm 2 , which is among the most stable Li anodes reported so far.

25 ENERGY STORAGE↗
DOE OSTI2022

Across-Depth Heterogeneity and Irreversibility of Fast-Charge-Driven Lithium Plating

Enabling fast charging in lithium-ion batteries (LIBs) is a key factor for resolving consumers’ “range anxiety” concerns in choosing an electric vehicle over a gasoline-powered one. The best-known issue in the fast charging of current LIBs (based on LiNi x Mn y Co 1–x–y O 2 /graphite) is lithium plating, which is barely reversible and is accompanied by capacity loss over time. Therefore, understanding the reasons for the irreversibility of lithium plating driven by fast charging is critical to enhancing the fast-charging capability of LIBs. Here, a study of the irreversibility and heterogeneity of lithium plating is carried out by using electrochemical analyses, inductively coupled plasma mass spectroscopy, and X-ray photoelectron spectroscopy. Further, the study shows that the majority of the lithium plated during fast charging remains inactive even with very slow discharging rates, implying that most of the plated lithium is irreversibly lost. The study also reveals that chemical compounds such as LiF, Li 2 O and Li 2 (CO 3 ) are formed heterogeneously within the lithium plating and are responsible for some of the irreversibility of the plated lithium.

33 ADVANCED PROPULSION SYSTEMS↗
DOE OSTI2018

Lithium Recovery from Aqueous Resources and Batteries: A Brief Review

The demand for lithium is expected to increase drastically in the near future due to the increased usage of rechargeable lithium-ion batteries (LIB) in electric vehicles, smartphones and other portable electronics. To alleviate the potential risk of undersupply, lithium can be extracted from raw sources consisting of minerals and brines or from recycled batteries and glasses. Aqueous lithium mining from naturally occurring brines and salt deposits is advantageous compared to extraction from minerals, since it may be more environmentally friendly and cost-effective. In this article, we briefly discuss the adsorptive behaviour, synthetic methodology and prospects or challenges of major sorbents including spinel lithium manganese oxide (Li-Mn-O or LMO), spinel lithium titanium oxide (Li-Ti-O or LTO) and lithium aluminium layered double hydroxide chloride (LiCl·2Al(OH) 3 ). Membrane approaches and lithium recovery from end-of-life LIB will also be briefly discussed.

25 ENERGY STORAGE↗
DOE OSTI2014

Neutronics Evaluation of Lithium-Based Ternary Alloys in IFE Blankets

Pre-conceptual fusion blanket designs require research and development to reflect important proposed changes in the design of essential systems, and the new challenges they impose on related fuel cycle systems. One attractive feature of using liquid lithium as the breeder and coolant is that it has very high tritium solubility and results in very low levels of tritium permeation throughout the facility infrastructure. However, lithium metal vigorously reacts with air and water and presents plant safety concerns. If the chemical reactivity of lithium could be overcome, the result would have a profound impact on fusion energy and associated safety basis. The overriding goal of this project is to develop a lithium-based alloy that maintains beneficial properties of lithium (e.g. high tritium breeding and solubility) while reducing overall flammability concerns. To minimize the number of alloy combinations that must be explored, only those alloys that meet certain nuclear performance metrics will be considered for subsequent thermodynamic study. The specific scope of this study is to evaluate the neutronics performance of lithium-based alloys in the blanket of an inertial confinement fusion (ICF) engine. The results of this study will inform the development of lithium alloys that would guarantee acceptable neutronics performance while mitigating the chemical reactivity issues of pure lithium.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗