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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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At least 433 records · Page 24
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

High tensile alloy of copper to mitigate current collector deformation in silicon electrodes for lithium-ion batteries

The volumetric changes of silicon electrodes, along with the strong adhesive properties of certain binders, can lead to plastic deformation of the current collector and create damage in the electrode coating. Here, in this study, we report a detailed study of silicon coatings on a high-tensile alloy (HTA) foil of copper with strength over twice that of conventional copper foils. The HTA current collectors with high mechanical strength can mitigate plastic deformation upon continuous cycling. At moderate areal capacities (2.5–3 mAh cm −2 ), conventional copper foils show significant wrinkling after only a few electrochemical cycles, whereas the HTA foils remain intact. We demonstrate viability of the HTA foils in large format xx6395 pouch cells, in which the HTA current collectors remain intact even at an areal capacity of 4.5 mAh cm −2 ; in contrast, wrinkles form in conventional copper current collectors increasing the likelihood of lithium plating. Computational studies show that stresses generated during cycling of silicon electrodes are very high in the current collector and at the current collector-coating interface, explaining the wrinkling of conventional Cu foils. Our studies highlight importance of current collector to solve the electrochemical and chemo-mechanical performance challenges associated with high-loading silicon electrodes.

Chemo-mechanical degradation↗
DOE OSTI2016

Silicon-based anodes for lithium-ion batteries: Effectiveness of materials synthesis and electrode preparation

Lithium-ion batteries are widely used throughout the world for portable electronic devices and mobile phones and show great potential for more demanding applications like electric vehicles. Unfortunately, lithium-ion batteries still lack the required level of energy storage to completely meet the demands of such applications as electric vehicles. Among advanced materials being studied, silicon nanoparticles have demonstrated great potential as an anode material to replace the commonly used graphite. Silicon has been shown to have a high theoretical gravimetric capacity, approximately 4200 mA h/g, compared to only 372 mA h/g for graphite. Though silicon nanoparticles have remarkably high capacity, they suffer from rapid degradation with each cycle due to electrode volume expansion of approximately 400% during lithiation, placing a large strain on the material. With each cycle that strain creates cracks in the electrode particles and causes them to break down into smaller particles, which create void spaces between the particles and lead to poor contact as reflected in poor conductivity. In this review, we discuss exciting new research on silicon-based anodes conducted during the past couple of years. Besides stressing the importance of well-designed nanostructures of Si, we focus on optimization of the Si electrode and resulting performance enhancement by properly selecting binders and synergistically integrating them with various carbon materials during electrode design and fabrication. Importantly, although each improvement strategy has its own advantage, appropriate combination of them will yield much higher anode performance. We summarize the core issues in developing the silicon anode and effective strategies in yielding more promising results. (C) 2016 Elsevier Ltd. All rights reserved.

Casimir, Anix↗
DOE OSTI2018

A Novel Approach to Synthesize Micrometer-Sized Porous Silicon as a High Performance Anode for Lithium-Ion Batteries

Porous structured silicon (p-Si) has been recognized as one of the most promising anodes for Li-ion batteries. However, many available methods to synthesize p-Si are difficult to scale up due to their high production cost. Here we introduce a new scalable approach to obtain spherical micrometer-sized silicon with unique porous structure by using a microemulsion and magnesiothermic reduction method. The spherical micron-sized p-Si particles prepared by this approach consist of highly aligned nano-sized silicon and exhibit a tap density close to that of bulk Si particles. They have demonstrated significantly improved electrochemical stability compared to nano-Si. Well controlled void space and a highly graphitic carbon coating on the p-Si particles enable good stability of the structure and low overall resistance, thus resulting in a Si-based anode with high capacity (~1467 mAh g-1 at 1C), enhanced cycle life (200 cycles with 90% capacity retention), and high rate capability (~650 mAh g-1 at 5C). This scalable approach may also be generalized to prepare other hierarchical structured high capacity anode materials for constructing high energy density lithium ion batteries.

Jia, Haiping↗
DOE OSTI2020

A lithium-sulfur battery with a solution-mediated pathway operating under lean electrolyte conditions

Lithium-sulfur (Li-S) battery is one of the most promising candidates for the next generation energy storage systems. However, several barriers, including polysulfide shuttle effect, the slow solid-solid surface reaction pathway in the lower discharge plateau, and corrosion of Li anode still limit its practical applications, especially under the lean electrolyte condition required for high energy density applications. Here, we propose a solution-mediated sulfur reduction pathway to improve the capacity and reversibility of the sulfur cathode and suppress dendrite growth on the Li metal anode simultaneously. With this method, a high coulombic efficiency (99%) and stable cycle life over 100 cycles were achieved under application-relevant conditions (S loading: 6.2 mg cm-2; electrolyte to sulfur ratio: 3 mLE gs-1; sulfur weigh ratio: 72 wt%). This result is enabled by a specially designed Li2S4-rich electrolyte, in which Li2S is formed through a chemical disproportionation reaction instead of electrochemical routes. A diglyme solvent was used to obtain electrolytes with the optimum range of Li2S4 concentration. Operando X-ray absorption spectroscopy confirms the solution pathway in a practical Li-S cell. This solution pathway not only introduces a new electrolyte regime for practical Li-S batteries, but also provides a new perspective for bypassing the inefficient surface pathway for other electrochemical processes.

Wang, Hui↗
DOE OSTI2021

Mesoscale-architecture-based crack evolution dictating cycling stability of advanced lithium ion batteries

The cracking phenomenon of Ni-rich NMC (LiNixMnyCo1-x-yO2, x = 0.6) secondary particles is frequently discovered and believed to be one of critical reasons deteriorating the long-term cycling stability of NMC cathode in lithium ion batteries (LIBs). However, the initiation and evolution of those cracks is still controversial due to the limited quantification especially by in situ monitoring, leading to the challenge of identifying an efficient approach to inhibit the formation of the fractures during repeated cycling. Herein, the irreversible, anisotropic cycling lattice and mesoscale expansion/shrinkage of nano-grain during the first cycle, as revealed by in situ X-ray diffraction (XRD) and in situ atomic force microscopy (AFM), have been quantified and confirmed to be the dominant driving forces of microcracks initiation at the grain boundaries. These microcracks preferentially nucleates at the core region with random oriented nano-grains in early stage. The further growth and aggregation of microcracks into macrocrack eventually results in microfracture propagation radially outward to the periphery region with more uniform nano-grain orientation. This mesoscale nano-grain architecture controlled cracking process highlight the importance of predictive synthesis of cathode materials with controllable multiscale crystalline architecture for high-performance LIBs.

25 ENERGY STORAGE↗
DOE OSTI2013

Characteristics of Signals Originating near the Lithium-Diffused N+ Contact of High Purity Germanium P-Type Point Contact Detectors

A study of signals originating near the lithium-diffused n+ contact of p-type point contact (PPC) high purity germanium detectors (HPGe) is presented. The transition region between the active germanium and the fully dead layer of the n+ contact is examined. Energy depositions in this transition region are shown to result in partial charge collection. This provides a mechanism for events with a well defined energy to contribute to the continuum of the energy spectrum at lower energies. A novel technique to quantify the contribution from this source of background is introduced. Experiments that operate germanium detectors with a very low energy threshold may benefit from the methods presented herein.

Aguayo, E.↗
DOE OSTI2018

Development of a lithium fluoride zinc sulfide based neutron multiplicity counter

Past 3He shortages led to investigations into replacement options for neutron detectors in systems that previously used 3He-based technologies. The goal of this research was to investigate the feasibility of a full-scale lithium fluoride with silver activated zinc sulfide (LiF/ZnS) based neutron multiplicity counter. The LiF/ZnS based neutron multiplicity counter (LiNMC) was developed based on an iterative process between modeling and experimental measurements. Each active region of the LiNMC contains five sheets of LiF/ZnS sandwiched between six sheets of wavelength shifting plastic to form neutron detection stacks. The wavelength shifted scintillation light was collected by photomultiplier tubes located on each end of the stacks. Twelve such detector stacks were placed around a sample chamber in a square arrangement with lithiated high density polyethylene blocks in the corners to reflect high energy neutrons and capture low energy neutrons. Preliminary calibration with a 252Cf neutron source showed that the LiNMC was able to achieve 36% neutron detection efficiency (ε) and an 11.7 μs neutron die-away time (τ) for a doubles Figure-of-merit (ε2/ τ) of 109. This is the highest doubles Figure-of-merit performance measured to-date for a 3He-free neutron multiplicity counter system. By the end of this project, the LiNMC’s basic components were integrated into a single laboratory scale system capable of proof-of-concept measurements.

3He-free↗
DOE OSTI2019

Simulations of a high-density, highly-radiating lithium divertor

Results are presented for one- and two-dimensional (2D) edge plasma transport simulations for strong injection of lithium (Li) in the divertor region of a tokamak. The model includes the scrape-off layer and divertor regions, and, for 2D, a small region inside the magnetic separtrix. Equations are solved for the density and momentum of a deuterium/tritium (DT) species and all three charge states of Li, in addition to separate ion and electron energy equations via the UEDGE code. Equations are also included for the DT and Li gas species. Lithium gas is injected from the side walls or divertor plate, implying that these surfaces are evaporating liquid Li. For a range of Li gas input, steady-state, detached-plasma solutions are shown where greater than 90% of the exhaust power is radiated by Li, resulting in peak surface heat fluxes ~2 MW/m 2 on the divertor plate, outer wall, and private-flux wall. While Li ions dominate in the divertor leg, their density is in the range of 10% of the DT density at the midplane. The collisional parallel thermal force plays a key role in determining the midplane ion Li density, and sensitivity of results to different model assumptions are discussed. Here the key issue is possible dilution of the core DT fuel. A brief comparison of the Li neutral solution is made with that from the Direct Simulation Monte-Carlo (DSMC) SPARTA code.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2020

A direct recycling case study from a lithium-ion battery recall

Direct recycling of lithium-ion is a promising method for manufacturing sustainability. It is more efficient than classical methods because it recovers the functional cathode particle without decomposition into substituent elements or dissolution and precipitation of the whole particle. This case study of cathode-healing™ applied to a battery recall demonstrates an industrial model for recycling of lithium-ion, be it consumer electronic or electric vehicle (EV) batteries. The comprehensive process includes extraction of electrolyte with carbon dioxide, industrial shredding, electrode harvesting, froth flotation, cathode-healing™ and finally, building new cells with recycled cathode and anode. The final products demonstrated useful capability in the first full cells made from direct recycled cathodes and anodes from an industrial source. The lessons learned on recycling the prototypical chemistry are preliminarily applied to EV relevant chemistries.

Sloop, Steve↗
DOE OSTI2020

Long-Life, Ultrahigh-Nickel Cathodes with Excellent Air Storage Stability for High-Energy Density Lithium-Based Batteries

With increased energy density and cost advantage, ultrahigh-nickel layered oxides (LiNi x M 1-x O 2 , x = 0.9 - 1.0) are becoming front-runner as cathodes for next-generation lithium-based batteries, yet their commercialization is blocked both by severe capacity fade and exponentially aggravated air degradation. Thus, it is imperative to find effective solutions to address these issues simultaneously. Here, a significant enhancement in both the cycling and air storage stability of the ultrahigh-Ni cathode LiNi 0.94 Co 0.06 O 2 is achieved via a distinctive phosphoric acid treatment strategy. The modified cathode displays remarkably improved capacity retention (from 36 % to 80 % after 1,000 cycles) and rate capability (from 0 to 105 mA h g -1 at 30C rate) in pouch cells. Impressively, the modified cathode, after air storage for 450 days, maintains the morphology and 92% of the initial capacity of the fresh sample with excellent cyclability. Comprehensive interphase and structural analyses reveal that the enhanced electrochemical performance is due to a highly stabilized electrode/electrolyte interphase that suppresses electrode corrosion and lattice reconstruction. The excellent air stability results from an adsorption-buffering effect enabled by phosphoric acid to air attack. Finally, the study demonstrates an engineering pathway to improve the cycling and air stability, facilitating the practical viability of high-capacity, affordable, ultrahigh-Ni cathodes in lithium-based batteries.

25 ENERGY STORAGE↗
DOE OSTI2021

Lowering the Activation Barriers for Lithium-Ion Conductivity through Orientational Disorder in the Cyanide Argyrodite Li6PS5CN

Rapid advancements in safe and high-energy-density energy storage are predicated on identifying new solid-state ion conductors with low activation energies and high ionic conductivities for all-solid-state battery technologies. Halide argyrodites are among some of the top candidates for solid-state electrolytes, as they can achieve ionic conductivities that approach liquid electrolytes. Incorporating dynamic pseudohalide species in argyrodite solid electrolytes presents an exciting opportunity to exploit lattice dynamics as a design principle to modulate the ion conduction properties of solid-state ion conductors. In the present study, we have prepared the new argyrodite Li 6 PS 5 CN containing orientationally disordered cyanide ions. The new cyanide argyrodite Li 6 PS 5 CN exhibits an activation barrier to Li-ion transport of 471 ± 25 meV and a room-temperature ionic conductivity of 6(2) × 10 –5 S cm –1 in comparison to the activation barrier of 502 ± 16 meV and an ionic conductivity of 2.3(1) × 10 –4 S cm –1 measured for the bromide analogue Li 6 PS 5 Br. Structural studies of both compounds by high-resolution X-ray diffraction indicate that Li 6 PS 5 CN and Li 6 PS 5 Br adopt nearly identical crystal structures with similar lattice parameters, which indicates that lower activation barriers in Li 6 PS 5 CN arise due to the cyanide ion itself rather than due to changes in the geometry of conduction pathways in the local lithium environment. The orientational disorder of the quadrupolar cyanide ion in Li 6 PS 5 CN points to a complex interplay of lattice polarizability and molecular dynamics that lower the activation barrier for lithium-ion conductivity in the cyanide argyrodite.

25 ENERGY STORAGE↗
DOE OSTI2017

Elucidating the Solvation Structure and Dynamics of Lithium Polysulfides Resulting from Competitive Salt and Solvent Interactions

Designing optimal electrolytes is key to enhancing the performance of energy storage devices,especially relating to cycle life, efficiency, and stability.1 Specifically, for future beyond-Li ion energy storage, there is still ample room for electrolyte improvements. Among the candidates for higher gravimetric energy storage, the Li-S battery is considered quite promising, owing to its theoretical specific energy density (2600 Wh/kg) and specific capacity (1675 mAh/g) and significantly lower cost as compared to state-of-art lithium-ion batteries.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Facilitating the Operation of Lithium-Ion Cells with High-Nickel Layered Oxide Cathodes with a Small Dose of Aluminum

Layered oxide cathodes with a high Ni content of >0.6 are promising for high-energy-density lithium-ion batteries. However, parasitic electrolyte oxidation of the charged cathode and mechanical degradation arising from phase transitions significantly deteriorate the cell performance and cycle life as the Ni content increases. Here we demonstrate here a significantly prolonged cycle life with superior cell performance by substituting a small-dose of Al (2 mol %) for Ni in LiNi 0.92 Co 0.06 Al 0.02 O 2 ; the capacity retention after operating a full cell fabricated with graphite anode for 1000 cycles increases from 47% to 83% on going from the Al-free LiNi 0.94 Co 0.06 O 2 to the Al-doped LiNi 0.92 Co 0.06 Al 0.02 O 2 cathode. Through in situ X-ray diffraction, we provide the operando evidence that the Al-doping tunes the H2–H3 phase transition process from a two-phase reaction to a quasi-monophase reaction, minimizing the mechanical degradation. Furthermore, secondary-ion mass spectrometry reveals considerably suppressed transition-metal dissolution with Al-doping, effectively preventing sustained parasitic reactions and active Li trapping due to chemical crossover on graphite anodes. This work offers a viable approach for adopting high-Ni cathodes in lithium-ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2023

Halide Substitution Effects on Lithium-Ion Diffusion in Protonated Antiperovskites

Solid-state electrolytes (SSEs) for all-solid-state lithium-ion batteries are generating intense interest because these batteries can improve the safety and performance compared with devices fabricated with conventional, flammable liquid electrolytes. In these SSEs, it has been suggested that Li + ion diffusion in the grain boundaries is hindered and is a critical determinant of the overall ionic conductivity (σ). However, Li + ion diffusivities in the grain (D G ) and the grain boundary (D GB ) are difficult to determine experimentally, with few techniques capable of distinguishing the individual contributions. Here, we distinguished the D G and D GB for the protonated lithium antiperovskites (pLiAPs) SSEs: Li 2 OHCl, Li 2 OHBr, Li 2 OHF 0.1 Cl 0.9 , Li 2 OHF 0.1 Br 0.9 , and Li 2 OHCl 0.3 7Br 0.63 . The measurements were obtained directly from 7 Li pulsed-field gradient nuclear magnetic resonance (PFG-NMR) at 353 K. The 7 Li PFG-NMR echo profiles were composed of two primary components with additional secondary oscillatory components – the so-called NMR diffraction phenomenon. The length scale separating the two main components corresponds to a diffusion length of ~1.7 µm, which is thought to be the average grain size (by diameter). The short-range (≤ 1.7 µm) diffusion component associated with D G (≈10 -11 m 2 /s) varied minimally with halide substitution, while the long-range (≥ 1.7 µm) component D GB (≈10 -12 to 10 -15 m 2 /s) was highly sensitive to the substitution of halides and closely correlated with s. In addition, from the comparison of the ratio D GB /D G to D t (the Li + ion diffusion coefficient estimated from the rotational correlation time, t c ), it was determined that the contribution of D G to σ is negligible; 0.01 ~ 0.04 in the pLiAPs studied here. Finally, these insights provide fundamental understanding of the halide substitution effects on Li + ion grain versus grain boundary diffusion, and suggest that careful engineering of the grain boundaries at the microscopic level is necessary to achieve high-performance pLiAP SSEs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Reactivity at the Lithium–Metal Anode Surface of Lithium–Sulfur Batteries

Due to their high energy density and reduced cost, lithium–sulfur batteries are promising alternatives for applications such as electrical vehicles. However, a number of technical challenges need to be overcome in order to make them feasible for commercial uses. These challenges arise from the battery highly interconnected chemistry, which besides the electrochemical reactions includes side reactions at both electrodes and migration of soluble polysulfide (PS) species produced at the cathode to the anode side. The presence of such PS species alters the already complex reactivity of the Li anode. In this paper, interfacial reactions occurring at the surface of Li metal anodes due to electrochemical instability of the electrolyte components and PS species are investigated with density functional theory and ab initio molecular dynamics methods. It is found that the bis(trifluoromethane)sulfonimide lithium salt reacts very fast when in contact with the Li surface, and anion decomposition precedes salt dissociation. The anion decomposition mechanisms are fully elucidated. Two of the typical solvents used in Li–S technology, 1,3-dioxolane and 1,2-dimethoxyethane, are found stable during the entire simulation length, in contrast with the case of ethylene carbonate that is rapidly decomposed by sequential 2- or 4-electron mechanisms. Finally, on the other hand, the fast reactivity of the soluble PS species alters the side reactions because the PS totally decomposes before any of the electrolyte components forming Li 2 S on the anode surface.

25 ENERGY STORAGE↗
DOE OSTI2018

Internally Referenced DOSY-NMR: A Novel Analytical Method in Revealing the Solution Structure of Lithium-Ion Battery Electrolytes

Here, a novel methodology is reported on the use of internally referenced diffusion-ordered spectroscopy (IR-DOSY) in divulging the solution structure of lithium-ion battery electrolytes. Toluene was utilized as the internal reference for 1 H-DOSY analysis due to its exceptionally low donor number and reasonable solubility in various electrolytes. With the introduction of the internal reference, the solvent coordination ratio of different species in the electrolytes can be easily determined by 1 H-DOSY or 7 Li-DOSY. This new technique was applied to different carbonate electrolytes, and the results were consistent with a Fourier transform infrared (FTIR) analysis. Compared to conventional vibrational spectroscopy, this IR-DOSY technique avoids the complicated deconvolution of the spectrum and allows determination of the solvent coordination ratio of different species in electrolyte systems with two or more organic solvents.

25 ENERGY STORAGE↗