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Results for “Lithium distribution”

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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At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Inhomogeneous distribution of lithium and electrolyte in aged Li-ion cylindrical cells

Carbonate-based electrolytes in Li-ion batteries exhibit long range order in a frozen state, which enables their non-destructive analysis by diffraction methods. In the current study the spatial distribution of lithium and electrolyte inside the graphite anode was determined in cycled Li-ion cells using monochromatic spatially-resolved neutron diffraction measurements at 150 K. The results indicate a loss of lithium and electrolyte and their non-uniform distribution in the graphite anode in aged Li-ion cells. The observed lithium and electrolyte losses are directly correlated with two electrochemical performance degradation mechanisms, which are responsible for the cell capacity fade.

18650-type↗
NASA NTRS1971

Research, Development and Fabrication of Lithium Solar Cells

This report continues studies on cells made with low temperature (<400degC) single-cycle, lithium diffusion schedules. Measurements of concentration of lithium at the back surface showed that C(sub S) changes with time consisting of a build-up to a maximum value (above 10(exp 17) cm(exp -3)) with gradual decrease at longer diffusion times. Using the estimated C(sub S) values, theoretical lithium profiles were calculated. The calculated concentration near the PN junction was higher than those measured by the capacitance voltage (C-V) technique. The calculated concentration gradients were one-seventh of those measured by C-V methods. Both the concentration and its gradient were proportional to C(sub S). Estimates of C(sub S) obtained by extrapolating from C-V measured values of concentration and gradient near the PN junction, showed a decrease in C(sub S) for longer diffusion times. This fact supported the trend observed in Shipment C-13, where,, at longer times, the spread in values of V(sub oc), lithium concentration, and gradient became greater. The general conclusion was that the I-V characteristics were well controlled, with good cell output, but for longer diffusion times the lithium concentration gradient could have wider spread. The work described has led to greater insight into the lithium distribution dependence on the surface conditions. The surface conditions could be changed by varying the method used to apply lithium. Vacuum evaporation of lithium shows promise, and another exhaustive test of this method is in progress. Shipment C-13 is summarized, and the succeeding lots (C-14, C-15) are described. It is felt that improved monitoring of cell properties is at hand, and that the control of cell fabrication processes has advanced to where the effects of subtle differences in lithium distribution can now be seen. Evaluation is continuing on the best method to scale up the fabrication steps. A different sequence of fabrication is planned for Shipments C-14 and C-15.

Iles, Peter A.↗
DOE OSTI2023

Lithium Spatial Distribution and Split-Off Electronic Bands at Nanoscale V 2 O 5 /LiPON Interfaces

A combination of depth-resolved cathodoluminescence spectroscopy (DRCLS) and X-ray photoemission depth profiling (XPS) measured the pronounced changes in both the electronic density of states and lithium composition near the nanoscale LixV2O5/LiPON interface. DRCLS studies of electrochemically lithiated bare V2O5 and the sputterdeposited V2O5 plus LiPON overlayer electrochemically lithiated in stages both showed that in the bulk the luminescence intensity of the “split-off” hybridized bonding density of states was anticorrelated with XPSmeasured Li content, decreasing as the Li content increased. However, the LiPON overlayer was found to modify the band structure of the underlying LixV2O5 (LVO) to a depth of at least 30 nm beneath the V2O5 interface. DRCLS spectra near the electrochemically lithiated LiPON/ LVO interface showed a significant intensity of the split-off band, implying a low Li content. However, XPS depth profiling revealed a pronounced negative gradient of Li extending from a maximum Li content at the intimate LiPON boundary to its lowest content of ∼30 nm into the V2O5 in the same region, indicating a strong interaction between band structure and Li electrochemical potential near this heterojunction. These results provide evidence for substantial effects on the local band structure near an electrolyte/cathode interface and insights into the electrochemical interface behavior of solid-state batteries in general.

25 ENERGY STORAGE↗
DOE OSTI2025

High spatial resolution neutron imaging of lithium-ion batteries: Correlating microstructure and lithium transport

Thick electrodes for lithium-ion batteries can increase the overall energy density, but increasing the electrode thickness introduces charge transport limitations. These limitations may be mitigated through proper electrode structuring. Here, high spatial resolution neutron imaging was used to understand the correlation between microstructure and lithium transport in lithium-ion anodes. Batteries with distinct graphite anode microstructures were produced and studied with high spatial resolution in operando neutron radiography to observe the effects of structure on transport. High spatial resolution neutron computed tomography was performed following in operando neutron radiography. X-ray computed tomography and scanning electron microscopy were used to observe the finer scale anode structure to complement neutron imaging. Solvent-free anodes containing a tightly-packed layered structure confined lithium movement close to the separator. This structure limited capacity, but supported better rate capability. Conversely, a more open pore structure in the wet cast anodes yielded higher capacity with reduced rate capability. Together, these results show that lithium distributions can be controlled by the macroscopic structure of the electrodes, the microstructural pore network, and the microscale active areas that support electrochemical reactions. Furthermore, multimodal imaging applying the complementary strengths of neutron and X-ray methods is shown as a tool for advancing battery design.

25 ENERGY STORAGE↗
DOE OSTI2021

Spatially Resolved Potential and Li-Ion Distributions Reveal Performance-Limiting Regions in Solid-State Batteries

The performance of solid-state electrochemical systems is intimately tied to the potential and lithium distributions across electrolyte–electrode junctions that give rise to interface impedance. Here, we combine two operando methods, Kelvin probe force microscopy (KPFM) and neutron depth profiling (NDP), to identify the rate-limiting interface in operating Si-LiPON-LiCoO 2 solid-state batteries by mapping the contact potential difference (CPD) and the corresponding Li distributions. The contributions from ions, electrons, and interfaces are deconvolved by correlating the CPD profiles with Li-concentration profiles and by comparisons with first-principles-informed modeling. Furthermore, we find that the largest potential drop and variation in the Li concentration occur at the anode–electrolyte interface, with a smaller drop at the cathode–electrolyte interface and a shallow gradient within the bulk electrolyte. Correlating these results with electrochemical impedance spectroscopy following battery cycling at low and high rates confirms a long-standing conjecture linking large potential drops with a rate-limiting interfacial process.

25 ENERGY STORAGE↗
DOE OSTI2021

Significant life extension of lithium-ion batteries using compact metallic lithium reservoir with passive control

Both traditional graphite-based lithium-ion batteries and next generation silicon-based chemistries suffer significant capacity fade from loss of cyclable lithium due to continued solid-electrolyte interphase growth. A possible engineering solution to maintaining the capacity of cells is incorporating a metallic lithium reservoir and discharging the reservoir into a working electrode to make up for lost cyclable lithium. Here, metallic lithium reservoirs are inserted into both pouch- and cylindrical-format cells. Significant capacity recovery and lifetime extension are demonstrated for traditional graphite and Si/graphite-based cells. In this work, a combination of post-mortem characterization and modeling provide insight into how the lithium distribution as a function of position from reservoir vary with recovery rate. The potential of using passive control to potentially eliminate the need for extra wiring for the third electrode is explored using a simple resistor.

25 ENERGY STORAGE↗
DOE OSTI2025

Strain-associated nanoscale fluctuating lithium transport within single-crystalline LiNi 1/3 Mn 1/3 Co 1/3 O 2 cathode particles

Solid-state lithium diffusion dynamics are critical for the rate capability and longevity of Li-ion batteries. Conventionally, nanoscale lithium diffusion within individual battery particles has been simplified as being primarily driven by concentration gradients, despite the associated processes inducing local lattice expansion, contraction, and strain fields. Using operando scanning transmission soft X-ray microscopy with high spatial resolution and chemical sensitivity to track nanoscale intraparticle lithium transport, and post-cycling Bragg coherent diffraction X-ray imaging to directly reveal three-dimensional intraparticle strain fields, we uncover strain-associated lithium transport dynamics within single-crystalline LiNi 1/3 Mn 1/3 Co 1/3 O 2 (scNMC) particles during cycling. Contrary to the expected thermodynamic solid-solution behavior of scNMC, our observations reveal near-uniform but fluctuating regions of lithium-dense and lithium-dilute areas during cycling. These fluctuations suggest that nanoscale lithium diffusion can proceed counter to concentration gradients. Additionally, we demonstrate that an increased presence of lithium-dilute regions near the surface enhances lithium surface insertion kinetics, emphasizing the importance of controlling surface lithium distribution to improve rate performance. Our study provides insights into nanoscale solid-state ion transport, with potential applications in batteries, solid-state fuel cells, and memristors.

Lee, Danwon [Seoul National Univ. (Korea, Republic↗
DOE OSTI2024

Liquid-like solid-state diffusion of lithium ions in super-halide-rich argyrodite

The development of solid electrolytes with high ionic conductivity is essential for advancing safer, high-energy-density solid-state batteries, where lithium site distribution in the sublattice strongly affects ion transport. Here, we report a super-halide-rich argyrodite, Li 5.3 PS 4.3 Cl 1.7 , with remarkable room-temperature ionic conductivity (11.4 ± 0.7 mS cm -1 ) due to population of two additional interstitial lithium sites induced by vacancy redistribution. Prominent lithium density between lithium sites and elevated atomic displacement parameters indicate liquid-like diffusive behavior resembling sublattice melting. Combining electrochemical impedance spectroscopy, pulsed-field gradient NMR, and T 1 relaxation methods, we demonstrate that the augmented conductivity partly arises from a low energy barrier (0.08 eV) at the local scale, attributed to a three-site lithium distribution that drives correlated lithium dynamics. This work advances our understanding of the structure-dynamics interplay in super-halide-rich argyrodites, and highlighting their potential as solid-state battery electrolytes in cells with a coated single-crystal NMC82 cathode that achieve 170 mAh/g capacity at a 0.2 C rate .

25 ENERGY STORAGE↗
NASA NTRS1990

Is there a classical Hyades lithium problem?

The distribution of surface lithium abundances in the Hyades cluster, as a function of effective temperature, has resisted a satisfactory theoretical explanation for more than two decades. Trends in the historically recomputed values of stellar opacity have stimulated a systematic investigation of the effects of larger opacities on lithium depletion during the premain-sequence evolution of low-mass stars. It is shown that the calculated depletion depends quite strongly on the opacities employed, and that both surface and interior opacities play an important role. By performing standard evolutionary calculations with parameterized increments in the opacities, the observed Hyades Li and T(eff) relation for G and K dwarfs have been determined in a manner consistent with the other observational constraints. The solution presented herein requires an increase in interior opacities at about 4 million K over older values by approximately less than 37 percent. Such a change is not incompatible with the historical trends in opacity computations and suggests that the resolution of this problem lies solely in the opacities, without recourse to other physical mechanisms such as turbulent diffusion or 'extra mixing'.

Swenson, Fritz J.↗
DOE OSTI2026

Mass spectral molecular mapping shows benefits of thermal evaporation in prelithiated silicon-based electrodes

Silicon based composites have become increasingly popular as potential anodes for lithium-ion batteries due to their large storage capacity and potential ability to generate batteries with energy densities greater than 350 Wh kg −1 . These anodes often see reduced initial columbic efficiency (ICE) due to disruptive volume expansionup to 300% and continuous solid electrolyte interphase (SEI) layer formation. Prelithiation, where an excess reservoir of Li is added to the electrode to compensate for irreversible SEI formation losses during their sample preparation, has proven to solve the issue of immediate capacity loss. Thermal evaporation is a prelithiation technique with limited studies on its effectiveness. In this study, time-of-flight secondary ion mass spectrometry (ToF-SIMS) is used to highlight the benefits of prelithiation via thermal evaporation. ToF-SIMS provides chemical mapping and spatial information in 2D and 3D visualizing the deposition of lithium, identifying Li x Si y alloy and Li x Si y O z silicate formation, and the distribution of lithium passivation into the electrodes. Passivation under different atmospheric conditions, such as inert Argon (Ar) and Ar/ carbon dioxide (CO 2 ), highlights the impact of the environment on the passivation effectiveness and formation of Li x Si y alloy and Li x Si y O z silicate. The ToF-SIMS molecular imaging and depth profiling results indicate that prelithiation via thermal evaporation effectively distributes lithium throughout the depth profile thickness of several hundred nanometers. It induces a greater degree of Li x Si y O z silicate formation over Li x Si y alloy. Our ToF-SIMS characterization results show the effectiveness of thermal evaporation in producing a more stable electrode and an electrode with an effective lithium reserve that can preserve its capacity.

Parker, Gabriel D. [Oak Ridge National Laboratory ↗
DOE OSTI2020

Direct observation of the momentum distribution and renormalization factor in lithium

We have measured the momentum distribution and renormalization factor $Z_{k_F}$ in liquid and solid lithium by high-resolution Compton scattering. High-resolution data over a wide momentum range exhibit a clear feature of the renormalization and a sharp drop of momentum densities at the Fermi momentum $k_F$. In this work, these results are compared with those computed by quantum Monte Carlo simulation performed both on a disordered crystal and a liquid exhibiting very good agreement. Asymptotic behavior of the experimental and theoretical momentum distributions are examined to estimate $Z_{k_F}$. The experimentally obtained $Z_{k_F} = 0.43^{+0.11}_{–0.01}$ for liquid Li and $0.54^{+0.11}_{–0.02}$ for solid Li are in good agreement with theoretical results of 0.54 ± 0.01 and 0.64 ± 0.01, respectively.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Comprehensive Insights into Nucleation, Autocatalytic Growth, and Stripping Efficiency for Lithium Plating in Full Cells

Synchrotron high-energy X-ray diffraction is used to enable nondestructive detection and quantification of heterogeneous lithium plating in working batteries. In this study a LiNi 0.5 Mn 0.3 Co 0.2 O 2 /graphite pouch cell was operated under 6C fast-charge rate for greater than 1200 cycles. The magnitude and spatial distribution of lithium plating, lithium stripping, and the effect of metallic lithium deposition on lithium intercalation into graphite were quantified. Fully intercalated graphite (LiC 6 ) was detected after discharge with a lateral distribution closely correlated with lithium plating, which can be used as a higher-sensitivity indicator for lithium plating. Over an extended cycle life, the overall metallic lithium concentration followed a sigmoidal curve indicating two-stage continuous nucleation and autocatalytic growth. The lithium stripping efficiency underwent an exponential decay as a function of cycle life as the buildup of metallic lithium hindered the efficient dissolution back into the electrolyte. The findings provide direct insights into the characteristics of lithium plating and stripping under realistic fast-charge conditions.

25 ENERGY STORAGE↗
DOE OSTI2021

Evidence of lithium mobility under neutron irradiation

Understanding the evolution of intermetallic materials in high-radiation environments is of great importance for fusion science and national security. Tritium ( 3 H) and lithium ( 6 Li, 7 Li) transport within neutron irradiated claddings coated with aluminide (FeAl3) has been investigated using state-of-the-art multimodal imaging. Specifically, scanning electron microscopy – focused ion beam (SEM-FIB) was used to prepare irradiated coating lift-out samples for follow-on microanalysis. Here, scanning transmission electron microscopy (STEM) was used to acquire atomic-scale information on the carbonaceous structure and elemental mapping. Atomic force microscopy (AFM) was used to determine lift-out dimensions nondestructively. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) spectral and depth profiling show unexpected lithium isotopic distributions in the irradiated cladding, raising an important evidence of possible light isotope mobility within the cladding under elevated temperature and irradiation. ToF-SIMS three-dimensional chemical mappings of mid- and bottom-cladding coatings show light isotopic (e.g., 3 H, 6 Li, 7 Li) distributions in the irradiated coating and give new insights into the fundamental mechanism related to transport mechanisms within the cladding. Multimodal imaging is power to link microstructure, chemistry, and nanoscale defects that impact reliability of these materials. Furthermore, chemical mapping offers observations of the microstructural evolution due to irradiation and provides insights into unexpected material transport under extreme conditions.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Plasma diagnostics and modeling of lithium-containing plasmas

Thin-film deposition from chemically reactive multi-component plasmas is complex, and the lack of electron collision cross-sections for even the most common metalorganic precursors and their fragments complicates their modeling based on fundamental plasma physics. This study focuses on understanding the plasma physics and chemistry in argon (Ar) plasmas containing lithium bis (trimethylsilyl) amide used to deposit Li x Si y thin films. These films are emerging as potential solid electrolytes for lithium-ion batteries, and the Li-to-Si ratio is a crucial parameter to enhance their ionic conductivity. We deposited Li x Si y films in an axial flow-through plasma reactor and studied the factors that determine the variation of the Li-to-Si ratio in films deposited at various points on a substrate spanning the entire reactor axis. While the Li-to-Si ratio is 1:2 in the precursor, the Li-to-Si ratio is as high as 3:1 in films deposited near the plasma entrance and decreases to 1:1 for films deposited downstream. Optical emission from the plasma is dominated by Li emission near the entrance, but Li emission disappears downstream, which we attribute to the complete consumption of the precursor. We hypothesized that the axially decreasing precursor concentration affects the electron energy distribution function in a way that causes different dissociation efficiencies for the production of Li and Si. We used Li line intensities to estimate the local precursor concentration and Ar line ratios to estimate the local reduced electric field to test this hypothesis. This analysis suggests that the mean electron energy increases along the reactor axis with decreasing precursor concentration. As a result, the decreasing Li-to-Si ratio with axially decreasing precursor concentration may be explained by Li release from the precursor having lower threshold energy than Si release.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2024

Visualizing the SEI formation between lithium metal and solid-state electrolyte

The solid electrolyte interphase (SEI) is regarded as the most important factor affecting the durability of lithium-metal anode in all-solid-state batteries (ASSBs). Despite its significance, the nucleation and growth mechanism of SEI is not yet well understood. Here, we elucidate the thermodynamics and kinetics governing SEI formation at the Li|β-Li 3 PS 4 interface at the atomic scale via thermodynamic phase equilibrium analysis and machine-learning-potential-assisted molecular dynamics (MD) simulations. An accurate moment tensor potential using the machine-learning method is developed for a reactive model of Li|β-Li 3 PS 4 . This potential enabled us to perform large-scale MD simulations with the model size expanded to the experimental dimensions (~40 nm) while maintaining the same level of accuracy as density functional theory calculations. The results reveal a four-stage evolution process at the Li|β-Li 3 PS 4 interface, namely (i) fast ion diffusion, (ii) nucleation, (iii) Li 2 S growth, and (iv) stabilization. Notably, we demonstrate that the SEI can be categorized into crystalline and amorphous regions. The simulated SEI thickness, structure, and composition closely match experimental findings, validating the accuracy of the MD simulations. We further disclose the significant impact of ion diffusion kinetic limitations on the phase formation and crystallization of interfacial products. Furthermore, we shed light on the detailed potential energy (PE) distribution of lithium along the direction perpendicular to the interface. Finally, this information is crucial for better understanding interfacial ion mobility.

25 ENERGY STORAGE↗
DOE OSTI2021

Challenges and future perspectives on sodium and potassium ion batteries for grid-scale energy storage

The energy crisis and environmental pollution require the advancement of large-scale energy storage techniques. Among the various commercialized technologies, batteries have attracted enormous attention due to their relatively high energy density and long cycle life. Nevertheless, the limited supply and uneven distribution of lithium minerals, as well as their high cost, has greatly hindered the application of lithium-ion batteries in large-scale energy storage. Therefore, building next-generation alternative rechargeable batteries that feature low cost, long service life, and high safety is of the utmost importance. Over the past several years, we have witnessed many successful research outcomes for sodium and potassium ion batteries (SIBs and PIBs) in regard to electrode and electrolyte materials. In this Perspective, we summarize the current developments on SIBs/PIBs and their challenges when facing practical applications, including their cost, energy density, ion diffusivity in solids/electrolytes/interphases, cycle life, and safety concerns. Furthermore, we provide an overview of strategies to overcome the remaining challenges for achieving better electrochemical performance. Finally, we outline several possible directions for the future development of these two battery chemistries, with the hope of aiding the transition from the laboratory to next-generation practical applications for SIBs/PIBs batteries in grid-scale energy storage.

Energy Storage↗