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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 343 records · Page 19
All sourcesNASA NTRSDOE OSTI
DOE OSTI2014

Synthesis and Characterization of Lithium Bis(fluoromalonato)borate (LiBFMB) for Lithium Ion Battery Applications

A new orthochelated salt, lithium bis(monofluoromalonato)borate (LiBFMB), has been synthesized and purified for the first time for application in lithium ion batteries. The presence of fluorine in the borate anion of LiBFMB increases its oxidation potential and also facilitates ion dissociation, as reflected by the ratio of ionic conductivity measured by electrochemical impedance spectroscopy ( exp) and that by ion diffusivity coefficients obtained using pulsed field gradient nuclear magnetic resonance (PFG-NMR) technique ( NMR). Half-cell tests using 5.0 V lithium nickel manganese oxide (LiNi0.5Mn1.5O4) as a cathode and EC/DMC/DEC as a solvent reveals that the impedance of the LiBFMB cell is much larger than those of LiPF6 and LiBOB based cells, which results in lower capacity and poor cycling performance of the former. XPS spectra of the cycled cathode electrode suggest that because of the stability of the LiBFMB salt, the solid electrolyte interphase (SEI) formed on the cathode surface is significantly different from those of LiPF6 and LiBOB based electrolytes, resulting in more solvent decomposition and thicker SEI layer. Initial results also indicate that using high dielectric constant solvent PC alters the surface chemistry, reduces the interfacial impedance, and enhances the performance of LiBFMB based 5.0V cell.

Liao, Chen↗
DOE OSTI2016

Lithium-air batteries, method for making lithium-air batteries

The invention provides a method for generating Li.sub.2O.sub.2 or composites of it, the method uses mixing lithium ions with oxygen ions in the presence of a catalyst. The catalyst comprises a plurality of metal clusters, their alloys and mixtures, each cluster consisting of between 3 and 18 metal atoms. The invention also describes a lithium-air battery which uses a lithium metal anode, and a cathode opposing the anode. The cathode supports metal clusters, each cluster consisting of size selected clusters, taken from a range of between approximately 3 and approximately 18 metal atoms, and an electrolyte positioned between the anode and the cathode.

25 ENERGY STORAGE↗
DOE OSTI2017

Heteroaromatic-based electrolytes for lithium and lithium-ion batteries

The present invention provides an electrolyte for lithium and/or lithium-ion batteries comprising a lithium salt in a liquid carrier comprising heteroaromatic compound including a five-membered or six-membered heteroaromatic ring moiety selected from the group consisting of a furan, a pyrazine, a triazine, a pyrrole, and a thiophene, the heteroaromatic ring moiety bearing least one carboxylic ester or carboxylic anhydride substituent bound to at least one carbon atom of the heteroaromatic ring. Preferred heteroaromatic ring moieties include pyridine compounds, pyrazine compounds, pyrrole compounds, furan compounds, and thiophene compounds.

25 ENERGY STORAGE↗
DOE OSTI2015

Electrolyte compositions for lithium and lithium-ion batteries

"The present invention provides an electrolyte composition for a lithium or lithium-ion battery comprising a lithium salt in a liquid carrier comprising (a) a linear alkyl carbonate solvent, a cyclic alkyl carbonate solvent, or a combination thereof, and (b) a glycerol carbonate derivative compound of Formula (I):wherein X is selected from O, O(CO)O, S, N, P, P(═O), B, and Si; n is 1 when X is O, O(CO)O, or S; n is 2 when x is N, P, P(═O), or B; n is 3 when X is Si; and each R independently is selected from alkyl, alkenyl, alkynyl, aryl, acyl, heteroaryl, a 5-member ring heterocyclic group, a 5-member ring heterocycle-substituted methyl group, trialkylsilyl, and any of the foregoing substituted with one or more fluoro substituents, provided that R is acyl only when X is O, S, or N, and R is not alkyl when X is O(CO)O."

25 ENERGY STORAGE↗
DOE OSTI2020

TiO2 Nanocrystal-Framed Li 2 TiSiO 5 Platelets for Low-Voltage Lithium Battery Anode

Titanium-based anode materials are attracting considerable attention for use in high-performance lithium-ion batteries, but the compromised energy density caused by high voltage plateaus and unsatisfactory capacities severely retards their practical applications. Herein, a molten-salt synthesis of Li 2 TiSiO 5 crystalline platelets and a subsequent selective facet modification by in situ growth of TiO 2 nanocrystal frames are facilely achieved. The discharge voltage plateau at around 0.5 V renders the Li 2 TiSiO 5 anode safe compared with graphite and confers a high energy density compared with zero-strain Li 4 Ti 5 O 12 anode. With the optimized size, structure, and content of modified TiO2 nanocrystals associated with the exposed (001) plane of Li 2 TiSiO 5 , the Li 2 TiSiO 5 -based anodes can deliver a capacity of above 300 mAh g -1 , enhanced rate performance, and a capacity retention of 66% after 10 000 cycles. In situ X-ray diffraction and ex situ transmission electron microscopy have demonstrated the structural stability of the anodes upon charge/discharge. Further theoretical calculation reveals 3D migration paths of Li + ions in Li 2 TiSiO 5 . The selective modification of in situ grown TiO2 nanocrystals on certain facets of crystallites opens a new door for the development of electrode materials possessing superior electrochemical properties.

anodes↗
DOE OSTI2016

Extending the Life of Lithium-Based Rechargeable Batteries by Reaction of Lithium Dendrites with a Novel Silica Nanoparticle Sandwiched Separator

A reaction-protective separator that slows the growth of lithium dendrites penetrating into the separator is produced by sandwiching silica nanoparticles between two polymer separators. Here, the reaction between lithium dendrites and silica nanoparticles consumes the dendrites and can extend the life of the battery by approximately five times.

25 ENERGY STORAGE↗
DOE OSTI2019

A 3D Lithiophilic Mo 2 N–Modified Carbon Nanofiber Architecture for Dendrite–Free Lithium–Metal Anodes in a Full Cell

The pursuit for high-energy-density batteries has inspired the resurgence of metallic lithium (Li) as a promising anode, yet its practical viability is restricted by the uncontrollable Li dendrite growth and huge volume changes during repeated cycling. Herein, a new 3D framework configured with Mo 2 N-mofidied carbon nanofiber (CNF) architecture is established as a Li host via a facile fabrication method. The lithiophilic Mo 2 N acts as a homogeneously pre-planted seed with ultralow Li nucleation overpotential, thus spatially guiding a uniform Li nucleation and deposition in the matrix. The conductive CNF skeleton effectively homogenizes the current distribution and Li-ion flux, further suppressing Li-dendrite formation. As a result, the 3D hybrid Mo 2 N@CNF structure facilitates a dendrite-free morphology with greatly alleviated volume expansion, delivering a significantly improved Coulombic efficiency of ≈99.2% over 150 cycles at 4 mA cm –2 . Symmetric cells with Mo 2 N@CNF substrates stably operate over 1500 h at 6 mA cm –2 for 6 mA h cm –2 . Furthermore, full cells paired with LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NMC811) cathodes in conventional carbonate electrolytes achieve a remarkable capacity retention of 90% over 150 cycles. Finally, this work sheds new light on the facile design of 3D lithiophilic hosts for dendrite-free lithium-metal anodes.

25 ENERGY STORAGE↗
DOE OSTI2016

Lithium Fluoride Additives for Stable Cycling of Lithium Batteries at High Current Densities

The addition of LiF salt to a lithium battery electrolyte improves the surface diffusion of ions on the electrode surface, which leads to smooth electrodeposition. It also forms a protective layer on the electrode that prevents degradation of electrolyte by side reactions. This LiF additive can be effective in improving the capacity and lifetime of a commercial lithium metal battery.

25 ENERGY STORAGE↗
DOE OSTI2022

Over-Potential Tailored Thin and Dense Lithium Carbonate Growth in Solid Electrolyte Interphase for Advanced Lithium Ion Batteries

A stable solid electrolyte interphase (SEI) is highly desired to prevent parasitic reactions during normal operation of lithium-ion batteries (LIBs). Lithium carbonate (Li 2 CO 3 ) is one of the most significant components for smooth SEI passivation layers; while the formation mechanism and special distribution of the Li 2 CO 3 layer has not yet been illustrated. In this study, an over-potential tailored Li 2 CO 3 growth mechanism based on the typical hard carbon anode is demonstrated. With an increase in the over-potential, the size of Li 2 CO 3 decreases gradually as the amount increases. When the over-potential is large (potential at 0.01 V), a Li 2 CO 3 -rich thin and dense inorganic layer with the average thickness of 4.4 nm in the SEI is constructed. The special SEI the completely wraps the boundaries of the anode enables a larger Li-ion de-solvation energy barrier and a lower Li-ion diffusion energy barrier, which supports low self-discharge behavior and a fast kinetic rate at the anode. More generally, this Li 2 CO 3 growth mechanism is also applicable to commercialized graphite anodes and similar results are also obtained. Therefore, this work provides a new insight into the Li 2 CO 3 growth mechanism in SEIs, as well as a guideline for the design of stable artificial SEIs.

25 ENERGY STORAGE↗
DOE OSTI2017

Lithium deintercalation/intercalation processes in cathode materials based on lithium iron phosphate with the olivine structure

This review describes the current state of the studies of lithium deintercalation/intercalation processes in cathode materials based on lithium iron phosphate with olivine structure. The limiting factors of LiFePO{sub 4} charge/discharge processes, as well as the main methods for their acceleration are considered. A partial replacement of iron cations in the structure improves the electrochemical characteristics of the cathode materials, including the discharge capacity, charge/discharge rate, and, in some cases, changes the charge/discharge mechanism. The use of nanoscale phosphate LiFePO{sub 4} with the olivine structure considerably increases the charge/discharge rate of cathode materials based on it by reducing the diffusion path length. Methods for LiFePO{sub 4} surface modification are considered. Particular attention is paid to the development of composite materials with electron-conducting additives. Combining of various approaches to the modification of the material in question makes it possible to obtain materials with a discharge capacity close to the theoretical value (170 mA h g{sup –1}) at a low charge/discharge rate and to considerably increase its capacity at high charge and discharge currents.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Chemo-Mechanical Instabilities in Lithium Cobalt Oxide at Higher State-Of-Charge in Li-Ion Batteries

Transition metal oxide cathodes are widely used in commercial Li-ion batteries. However, their practical charge capacity is limited due to severe chemo-mechanical instabilities at higher charge voltage, and state-of-charge condition. Here, in situ stress and strain measurements were synchronized to probe mechanical deformations in the lithium cobalt oxide (LCO) cathode via a multi-beam stress sensor and digital image correlation, respectively. In situ mechanical measurements revealed how Li removal from the electrode structure induces deformations on the LCO composite cathodes during cycling. The structure and morphology of the LCO cathodes were further investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM) studies. Two distinct electrochemical and mechanical behaviors were identified when the LCO was charged up to 4.65 V. The LCO undergoes a compressive stress generation when charged up to 4.2 V and surface fractures on the LCO particles were detected by SEM. LCO cathode experienced significantly large contractions (negative strains) when charged up to 4.65 V, where intergranular crack formation and phase transformation were detected on the LCO particles via SEM and XRD, respectively. Overall, the study bridges complicated structural deformations with in situ analysis of mechanical degradations in LCO cathodes charged at higher voltages. The correlation is vital to understanding instability mechanisms in transition metal oxides at high voltages for alkali metal ion batteries.

higher state-of-charge↗
DOE OSTI2018

Hydrogen retention in lithium and lithium oxide films

Pure lithium (Li) surfaces are difficult to maintain in fusion devices due to rapid oxide formation, therefore, parameterizing and understanding the mechanisms of hydrogen (H, D) retention in lithium oxide (Li 2 O) in addition to pure Li is crucial for Li plasma-facing material applications. To compare H retention in Li and Li 2 O films, measurements were made as a function of surface temperature (90–520 K) under ultrahigh vacuum (UHV) conditions using temperature programmed desorption (TPD). In both cases, the total retention dropped with surface temperature, from 95% at 90 K to 35% at 520 K Li 2 O films retained H in similar amounts as pure Li. Finally, Molecular Dynamics (MD) modeling was used to elucidate the mechanisms of H retention, and results were consistent with experiments in terms of both retention fraction and the drop of retention with temperature.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2017

Lithium recycling and cathode material regeneration from acid leach liquor of spent lithium-ion battery via facile co-extraction and co-precipitation processes

Highlights: • A novel process for combining Li and cathode material recycling is developed. • Ni, Co and Mn are co-extracted and separated with Li. • Li recovered as Li{sub 2}CO{sub 3} with the purity of 99.2% is achieved. • The spherical cathode material LiNi{sub 1/3}Co{sub 1/3}Mn{sub 1/3}O{sub 2} is directly regenerated. - Abstract: A novel process for extracting transition metals, recovering lithium and regenerating cathode materials based on facile co-extraction and co-precipitation processes has been developed. 100% manganese, 99% cobalt and 85% nickel are co-extracted and separated from lithium by D2EHPA in kerosene. Then, Li is recovered from the raffinate as Li{sub 2}CO{sub 3} with the purity of 99.2% by precipitation method. Finally, organic load phase is stripped with 0.5 M H{sub 2}SO{sub 4}, and the cathode material LiNi{sub 1/3}Co{sub 1/3}Mn{sub 1/3}O{sub 2} is directly regenerated from stripping liquor without separating metal individually by co-precipitation method. The regenerative cathode material LiNi{sub 1/3}Co{sub 1/3}Mn{sub 1/3}O{sub 2} is miro spherical morphology without any impurities, which can meet with LiNi{sub 1/3}Co{sub 1/3}Mn{sub 1/3}O{sub 2} production standard of China and exhibits good electrochemical performance. Moreover, a waste battery management model is introduced to guarantee the material supply for spent battery recycling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Li + -Desolvation Dictating Lithium-Ion Battery’s Low-Temperature Performances

Lithium (Li) ion battery (LIB) has penetrated almost every aspects of human life, from portable electronics, vehicles to grids, and its operation stability in extreme environments becomes increasingly important. Among these, sub-zero temperature presents a kinetic challenge to the electrochemical reactions required to deliver the stored energy. In this work, we attempted to identify the rate-determining process for Li+ migration under such low temperatures, so that an optimum electrolyte formulation could be designed to maximize the energy output. Substantial increase in available capacities from graphite||LiNi0.80Co0.15Al0.05O2 chemistry down to -40°C is achieved by reducing the solvent molecule that more tightly binds to Li+ and thus constitutes high desolvation energy barrier. The fundamental understanding is applicable universally to all electrochemical devices that have to operate in similar environments.

desolvation↗
DOE OSTI2015

Interfacial Effects on Lithium Superoxide Disproportionation in Li-O 2 Batteries

During the cycling of Li-O-2 batteries the discharge process gives rise to dynamically evolving agglomerates composed of lithium-oxygen nanostructures; however, little is known about their composition. In this paper, we present results for a Li-O-2 battery based on an activated carbon cathode that indicate interfacial effects can suppress disproportionation of a LiO2 component in the discharge product. High-intensity X-ray diffraction and transmission electron microscopy measurements are first used to show that there is a LiO2 component along with Li2O2 in the discharge product. The stability of the discharge product was then probed by investigating the dependence of the charge potential and Raman intensity of the superoxide peak with time. The results indicate that the LiO2 component can be stable for possibly up to days when an electrolyte is left on the surface of the discharged cathode. Density functional calculations on amorphous LiO2 reveal that the disproportionation process will be slower at an electrolyte/LiO2 interface compared to a vacuum/LiO2 interface. The combined experimental and theoretical results provide new insight into how interfacial effects can stabilize LiO2 and suggest that these interfacial effects may play an important role in the charge and discharge chemistries of a Li-O-2 battery.

interface↗
DOE OSTI2023

Purification of Lithium-Ion Battery Black Mass through Tailored Alkaline Corrosion

Obtaining high-purity material outputs is crucial to the viability of novel process aimed at direct recycling of lithium-ion batteries. Metallic impurities in recycled cathodes have been shown to inhibit performance, thereby threatening mainstream acceptance of recycled battery products. Thus, shredded black mass (BM) must be purified to remove metallic contaminants, and specifically Al and Cu originating from the electrode current collectors. We herein explore a process to ionize solid copper and aluminum to ionic form based on tailored alkaline chemistry, without incurring damage to the target cathode material (Li(NixMnyCo1-x-y)O2; NMC). Al and Cu corrosion may be enhanced through the addition of chloride salt, elevated temperatures, and the use of ultrasonication - all of which disrupt the formation of passivating films on the metallic surface, and thereby increase corrosion rate. We demonstrate optimized parameters for Al and Cu corrosion both from a kinetic and overall process cost perspective. Further, we analyze the impact of these conditions on the structural (XRD, SEM), chemical (EDS, ICP), and electrochemical (impedance, cycling, dQ/dV) properties of NMC, and suggest that the present purification method does not significantly disrupt NMC performance. Finally, we present preliminary results from a promising bench-scale demonstration of this purification process applied to a simulated black mass.

ADVANCED PROPULSION SYSTEMS,ENERGY STORAGE↗